JP2003286388A - Epoxy resin composition and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin composition for sealing a semiconductor, which is excellent in flame retardancy although it contains neither a halogenated flame retardant nor an antimony compound, and is excellent in moldability, soldering resistance and high-temperature storage characteristics. <P>SOLUTION: The epoxy resin composition for sealing a semiconductor contains (A) an epoxy resin, (B) a phenolic resin, (C) a cure accelerator, (D) an inorganic filler, (E) a phosphoric ester represented by general formula (1) (wherein R's may be the same or different and are each an organic group), and (F) a polyorganosiloxane compound represented by general formula (2) (wherein R is a monovalent organic group, provided that 30-100 wt.% of the whole organic groups comprise each a phenyl group, and the remaining organic groups comprise one or more groups selected from the group consisting of vinylic groups, 1-6C alkylalkoxy groups, 1-6C alkyl groups, aminated groups, epoxy-containing groups, hydroxylated groups, and mercaptocontaining groups; and n is an average value and is a positive number of 5 to 100). <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin composition for semiconductor encapsulation and a semiconductor device which are excellent in flame retardancy without containing a halogen-based flame retardant and an antimony compound, and are also excellent in solder resistance and high temperature storage characteristics. It is about.

[0002]

2. Description of the Related Art Conventionally, electronic parts such as diodes, transistors and integrated circuits are mainly sealed with an epoxy resin composition. In order to impart flame retardancy, halogen-based flame retardants and antimony compounds such as antimony trioxide, antimony tetroxide and antimony pentoxide are usually blended in these epoxy resin compositions. However, with the increasing awareness of environmental protection worldwide, there is an increasing demand for an epoxy resin composition having flame retardancy without using a halogen-based flame retardant or an antimony compound. When the semiconductor device sealed with the epoxy resin composition containing the halogen-based flame retardant and the antimony compound is stored at high temperature,
It is known that the thermally decomposed halide is released from these flame retardant components, corrodes the joint part of the semiconductor element, and impairs the reliability of the semiconductor device.Halogen flame retardants and antimony compounds are used as flame retardants. There is a demand for an epoxy resin composition that can achieve V-0 of UL-94 as a flame-retardant grade.

As described above, the corrosion resistance of the joint portion (bonding pad portion) of the semiconductor element after the semiconductor device is stored at a high temperature (for example, 185 ° C.) is called a high temperature storage characteristic. As a method for improving the characteristics, a method using diantimony pentoxide (JP-A-55-
No. 146950), a method of combining antimony oxide and organic phosphine (Japanese Patent Laid-Open No. 61-53321), etc., and their effects have been confirmed, but recent high-temperature storage characteristics required for semiconductor devices have high required levels. On the other hand, some epoxy resin compositions are unsatisfactory. To meet these demands, various flame retardants have been investigated. For example, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, boron-based compounds have been studied, but if they are not blended in a large amount, the flame retardant effect will not be exhibited, and the curability tends to decrease. is there.

In the current situation where surface mounting of semiconductor devices has become common, cracked semiconductor devices may be generated due to explosive stress of vaporized water vapor when exposed to high temperatures during soldering. Alternatively, peeling occurs at the interface between the semiconductor element or the lead frame and the semiconductor encapsulating material, resulting in defects that greatly impair electrical reliability, and preventing these defects, that is, improving solder resistance is a major issue. Has become. Further, in response to recent environmental problems, there is a trend toward lead-free solder used for mounting semiconductor devices to lead-free solder, and the temperature of the soldering process is increasing accordingly, and the required solder resistance is It is expected to become more severe.

In order to improve the solder resistance, a large amount of an inorganic filler is added to the epoxy resin composition to reduce the moisture absorption, the thermal expansion and the strength of the semiconductor device obtained by using the inorganic filler. I am trying. For this reason, a low-viscosity type resin component or a crystalline epoxy resin that is crystalline at room temperature but has extremely low viscosity when the temperature exceeds the melting point is used, and the epoxy compound with the increase in the compounding amount of the inorganic filler is used. A common method is to prevent a decrease in fluidity at the time of molding the resin composition, or to use an epoxy resin or a phenol resin in which the resin skeleton itself is hydrophobic and the cured product also exhibits low hygroscopicity. Has become.

Since a cured product of an epoxy resin composition using a crystalline epoxy resin, a hydrophobic epoxy resin or a hydrophobic phenol resin has a low glass transition temperature, when a halogen-based flame retardant and an antimony compound are used together, they are stored at high temperature. The characteristics tend to deteriorate, and in order to improve the characteristics, an epoxy resin composition that does not use a halogen-based flame retardant or an antimony compound is required. Further, the crystalline epoxy resin has a low viscosity and thus has a slow curability, and the hydrophobic epoxy resin and the hydrophobic phenol resin have a molecular structure with a long distance between cross-linking points. The cured product is soft, and it is difficult to use a flame retardant that inhibits the curing reaction of the epoxy resin in order to improve the mold releasability at the time of molding and improve the productivity. That is, maintaining flame retardancy,
There is a demand for an epoxy resin composition that is excellent in moldability, solder resistance, and high-temperature storage characteristics and that does not use a halogen-based flame retardant or an antimony compound.

[0007]

DISCLOSURE OF THE INVENTION The present invention provides a semiconductor encapsulation having excellent flame retardancy without containing a halogen-based flame retardant and an antimony compound, and having excellent moldability, solder resistance and high temperature storage characteristics. The present invention provides an epoxy resin composition for use and a semiconductor device obtained by encapsulating a semiconductor element using the epoxy resin composition.

[0008]

The present invention provides [1]
(A) Epoxy resin, (B) Phenolic resin, (C) Curing accelerator, (D) Inorganic filler, (E) Phosphate compound represented by general formula (1) and (F) General formula (2) An epoxy resin composition for semiconductor encapsulation, characterized by containing a polyorganosiloxane compound

[0009]

[Chemical 11] (R represents an organic group, which may be the same or different.)

[0010]

[Chemical 12] (R represents a monovalent organic group, and is 30 to 10 of all organic groups.
0% by weight is a phenyl group, and the remaining organic group is a vinyl group-containing group, a C1-6 alkylalkoxy group, a C1-6 alkyl group, an amino group-containing group, an epoxy group-containing group. One or more groups selected from the group consisting of a hydroxyl group-containing group and a mercapto group-containing group. n is an average value and is a positive number of 5 to 100. )

[2] The epoxy resin composition for semiconductor encapsulation according to the item [1], wherein R in the phosphate compound represented by the general formula (1) is a substituted or unsubstituted aryl group.
[3] The epoxy resin composition for semiconductor encapsulation according to the item [1] or [2], wherein the epoxy resin (A) is one or more selected from the group of general formulas (3) to (7). object,

[0012]

[Chemical 13] (R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, which may be the same or different.)

[0013]

[Chemical 14] (R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R1
Represents an alkyl group having 1 to 4 carbon atoms and may be the same or different from each other. a is 0 or an integer of 1 to 3. n
Is an average value and is a positive number from 1 to 10. )

[0014]

[Chemical 15] (R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R1
Represents an alkyl group having 1 to 4 carbon atoms and may be the same or different from each other. a is 0 or an integer of 1 to 3. n
Is an average value and is a positive number from 1 to 10. )

[0015]

[Chemical 16] (R represents an alkyl group having 1 to 4 carbon atoms and may be the same or different from each other. B is 1 or 2. n is an average value and is a positive number of 1 to 10.)

[0016]

[Chemical 17] (In the formula, n is an average value and is a positive number of 1 to 10.)

[4] The (B) phenolic resin is one or more selected from the phenolic resins represented by the general formulas (8) to (10), and the [1] to [3] are described. Epoxy resin composition for semiconductor encapsulation,

[0018]

[Chemical 18] (R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R1
Represents an alkyl group having 1 to 4 carbon atoms and may be the same or different from each other. a is 0 or an integer of 1 to 3. n
Is an average value and is a positive number from 1 to 10. )

[0019]

[Chemical 19] (R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R1
Represents an alkyl group having 1 to 4 carbon atoms and may be the same or different from each other. a is 0 or an integer of 1 to 3. n
Is an average value and is a positive number from 1 to 10. )

[0020]

[Chemical 20] (R represents an alkyl group having 1 to 4 carbon atoms and may be the same or different from each other. B is 1 or 2. n is an average value and is a positive number of 1 to 10.)

[5] Furthermore, the compound represented by the general formula (11), the compound represented by the general formula (12) or one or more ion scavengers selected from zinc oxide is added to the total epoxy resin composition in an amount of 0. Item [1] containing 0.01 to 1.0% by weight of
The epoxy resin composition for semiconductor encapsulation according to the item [4], Mg _a Al _b (OH) _{2a + 3b-2c} (CO ₃ ) _c · dH ₂ O (11) (0 <b / a ≦ 1, 0 ≦ c / b <1.5, d is 0 or a positive number BiO _a (OH) _b (NO ₃ ) _c (HSiO ₃ ) _d (12) (a = 0.9 to 1.1, b = 0. 6 to 0.8, c + d =
0.2-0.4, and d / c = 0-2.0. [6] A semiconductor device comprising a semiconductor element encapsulated with the epoxy resin composition for semiconductor encapsulation according to any one of items [1] to [5].

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION The epoxy resin used in the present invention refers to all monomers, oligomers and polymers having two or more epoxy groups in one molecule, and its molecular weight and molecular structure are not particularly limited. For example, biphenyl type epoxy resin, bisphenol type epoxy resin, stilbene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenol methane type epoxy resin, alkyl modified triphenol methane type epoxy resin, triazine nucleus-containing epoxy resin, Dicyclopentadiene-modified phenol type epoxy resin, phenol aralkyl type epoxy resin (having phenylene skeleton, diphenylene skeleton, etc.), naphthol aralkyl type epoxy resin (having phenylene skeleton, diphenylene skeleton, etc.) ), Naphthol type epoxy resins, and the like. These no problem be used singly or in admixture. Among these epoxy resins, the crystalline epoxy resin represented by the general formula (3), which has a low viscosity when melted, can be highly filled with an inorganic filler, and thus low moisture absorption and flame retardancy are easily obtained, and thus it is preferable. Further, since the epoxy resins represented by the general formulas (4) to (7) include a hydrophobic structure in the resin skeleton, a cured product of the epoxy resin composition using the epoxy resin exhibits low hygroscopicity and is cured. Since the distance between the cross-linking points of the product becomes long, the elastic modulus at the soldering processing temperature is small, and therefore the stress generated is low and the adhesion is excellent, so that the solder resistance is improved, which is preferable. In particular, the epoxy resins represented by the general formulas (4) to (6) have a high aromatic ring content in the resin skeleton, a high flame retardancy of the resin itself, and a low flame retardant content. Have.

As the phenol resin used in the present invention,
Monomers, oligomers and polymers having two or more phenolic hydroxyl groups in one molecule are generally mentioned, and the molecular weight and the molecular structure thereof are not particularly limited. For example, phenol novolac resin, cresol novolac resin, dicyclopentadiene modified phenol resin , Terpene modified phenol resin, triphenol methane type resin, phenol aralkyl resin (having phenylene skeleton, diphenylene skeleton, etc.), naphthol aralkyl resin (having phenylene skeleton, diphenylene skeleton, etc.), naphthol resin, etc. However, they can be mixed and used. In particular, since the phenol resin represented by the general formula (8) to the general formula (10) contains a hydrophobic structure in the resin skeleton, the cured product of the epoxy resin composition using the resin exhibits low hygroscopicity and is cured. Since the distance between the cross-linking points of the product becomes long, the elastic modulus at the soldering processing temperature is small, and therefore the stress generated is low and the adhesion is excellent, so that the solder resistance is improved, which is preferable. Further, the phenolic resins represented by the general formulas (8) to (10) have a high aromatic ring content in the resin skeleton, the flame retardancy of the resin itself is high, and the compounding amount of the flame retardant can be kept low. It has the feature that it can.

As the blending amount of these, it is preferable that the equivalent ratio of the number of epoxy groups of all epoxy resins and the number of phenolic hydroxyl groups of all phenol resins is in the range of 0.8 to 1.3. If the equivalent ratio is less than 0.8, the curability and the heat resistance of the cured product of the epoxy resin composition decrease, the moisture absorption rate increases,
If it exceeds 1.3, the heat resistance and the flame resistance of the cured product of the epoxy resin composition may decrease, which is not preferable.

The curing accelerator used in the present invention may be any one as long as it accelerates the curing reaction between the epoxy group and the phenolic hydroxyl group, and those generally used for sealing materials can be used. For example, 1,8-diazabicyclo (5,4,
0) Undecene-7, triphenylphosphine, 2-methylimidazole, tetraphenylphosphonium / tetraphenylborate and the like can be mentioned, and these may be used alone or in combination. The amount of the curing accelerator compounded is
0.05 to 1.0, more preferably 0.15 to 0.6% by weight is desirable in the total epoxy resin composition.

As the inorganic filler used in the present invention, those generally used for sealing materials can be used. Examples thereof include fused silica, crystalline silica, talc, alumina, silicon nitride and the like, and these may be used alone or in combination. The blending amount of the inorganic filler is 6 in the total epoxy resin composition from the balance of moldability and solder resistance.
0 to 95% by weight is preferred. If it is less than 60% by weight, the solder resistance will be lowered due to the increase of the moisture absorption rate, and if it exceeds 95% by weight, problems such as wire sweep and pad shift will be caused, which is not preferable.

The phosphoric acid ester compound represented by the general formula (1) used in the present invention promotes carbonization by phosphorus, that is, forms a non-combustible carbonized layer on the surface of a cured product of an epoxy resin composition to give a cured product surface. It is presumed that high flame retardancy will be imparted by protecting the material and blocking oxygen.
R's in the formula represent the same or different organic groups, but a substituted or unsubstituted aryl group is preferable from the viewpoint of heat resistance and moisture resistance. Specific examples of the phosphoric acid ester compound represented by the general formula (1) include triphenyl phosphate,
Trixylenyl phosphate, tricresinyl phosphate, cresyl diphenyl phosphate, resorcinol bis (diphenyl) phosphate, bisphenol A
Examples thereof include bis (diphenyl) phosphate.

The phosphoric acid ester compound used in the present invention includes
A compound having a structure in which a plurality of phosphoric acid ester compounds represented by the general formula (13) are bonded via a divalent organic group (R1) is also included. The divalent organic group that bonds the phosphate ester compounds to each other is preferably a residue obtained by removing two hydrogen atoms from the hydroxyl group of a bifunctional phenol compound such as hydroquinone, 4,4′-biphenol and bisphenol A. The phosphoric acid ester compounds bonded may be the same or different.

[0029]

[Chemical 21]

The compounding amount of the phosphoric acid ester compound of the present invention is
The total epoxy resin composition content is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight. 0.
If it is less than 01% by weight, flame retardancy is insufficient, and if it exceeds 10% by weight, curability, heat resistance and moisture resistance reliability are deteriorated and moisture absorption rate is increased, which is not preferable. These phosphoric acid ester compounds may be used alone or in combination.

The polyorganosiloxane compound represented by the general formula (2) used in the present invention acts as a flame retardant aid. Polyorganosiloxane requires a large amount of blending to achieve the flame retardancy of the epoxy resin composition when blended alone, so the curability of the epoxy resin composition decreases, the moisture absorption rate increases, the strength decreases, etc. However, when used in combination with a phosphoric acid ester compound, higher flame retardancy can be obtained with a small amount of compounding.

R in the polyorganosiloxane represented by the general formula (2) is a monovalent organic group, and 3 of all organic groups are included.
0 to 100% by weight is a phenyl group, and the remaining organic group is a vinyl group-containing group, an alkylalkoxy group having 1 to 6 carbon atoms,
The polyorganosiloxane comprises one or more groups selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an amino group-containing group, an epoxy group-containing group, a hydroxyl group-containing group, and a mercapto group-containing group. It is a liquid compound with a molecular weight.

Since the siloxane skeleton has a phenyl group, it can be easily dissolved in the resin component and plasticized, so that the epoxy resin composition can be easily adhered to various metals and the adhesion can be modified. Further, 30 to 100% by weight of all the organic groups are phenyl groups, and the phenyl groups contribute to the improvement of flame retardancy. In the case of polydimethylsiloxane which has been conventionally used in the epoxy resin composition for semiconductor encapsulation, a polyalkylene oxide component is introduced in order to make it compatible with the resin component, but since this polyalkylene oxide component is a hydrophilic group, it is water resistant. However, the semiconductor device sealed with the epoxy resin composition containing this polyorganosiloxane tends to have a high moisture absorption rate and a reduced solder resistance. However, since the polyorganosiloxane represented by the general formula (2) does not contain polyalkylene oxide, the problem of high moisture absorption does not occur.

R in the polyorganosiloxane represented by the general formula (2) is a monovalent organic group, and 3 of all the organic groups are included.
It is essential that 0 to 100% by weight is a phenyl group. If it is less than 30% by weight, the compatibility with the resin component, the contribution to the improvement of flame retardance, and the high temperature storage property are deteriorated. N in General formula (2) is an average value and is 5-100. When n is less than 5, the vapor pressure at a high temperature is high, the vapor pressure evaporates at the molding temperature of the epoxy resin composition and does not remain in the semiconductor device, and when it exceeds 100, the melt viscosity of the epoxy resin composition increases and molding occurs. Sex decreases.

The remaining organic groups other than the phenyl group are preferably vinyl group-containing groups and one or more groups selected from alkylalkoxy groups having 1 to 6 carbon atoms. Less than 50% by weight of the group is desirable. If the amount exceeds 50% by weight, the amount of phenyl groups is relatively small, and the contribution to the improvement of flame retardance tends to be small. From the viewpoint of improving flame retardancy, a vinyl group-containing group that promotes a radical reaction during combustion and an alkylalkoxy group having 1 to 6 carbon atoms that chemically reacts with silica during combustion are desirable.

In the present invention, it is particularly preferable to incorporate an ion trapping agent that traps phosphate ions and phosphite ions generated from the phosphate ester compound and immobilizes these ions, especially in terms of moisture resistance reliability and lead frame. It is effective from the viewpoint of preventing a decrease in adhesion at the interface with the cured product of the epoxy resin composition. The ion scavenger preferably contains at least one selected from the hydrotalcite compound represented by the general formula (11), the bismuth-based metal compound represented by the general formula (12), and zinc oxide.

The amount of these compounds is preferably 0.01 to 1% by weight, more preferably 0.1 to 0.9% by weight, based on the total epoxy resin composition. 0.01
If it is less than wt%, phosphate ions and phosphite ions cannot be captured, and the moisture resistance reliability is not sufficiently improved, which is not preferable. If it exceeds 1% by weight, curability and adhesiveness are deteriorated and solder resistance is deteriorated, which is not preferable.

The epoxy resin composition of the present invention comprises (A)-
In addition to the component (F), a flame retardant such as a brominated epoxy resin or antimony trioxide may be contained if necessary, but the stability of the electrical characteristics of the semiconductor device at a high temperature of 150 to 200 ° C. For required applications, the content of bromine atom and antimony atom is preferably less than 0.1% by weight in the total epoxy resin composition, and more preferably not contained at all. If the content of either bromine atom or antimony atom is 0.1% by weight or more, the resistance value of the semiconductor device increases with time when the semiconductor device is left under high temperature, and finally the gold wire of the semiconductor element is broken. There is a risk that defects may occur. Also from the viewpoint of environmental protection, bromine atom,
It is desirable that the content of each antimony atom is less than 0.1% by weight and that the content of antimony atoms is as small as possible.

The epoxy resin composition of the present invention comprises (A)-
If necessary, a silane coupling agent other than the component (F),
Various additives such as colorants such as carbon black, release agents such as natural wax and synthetic wax, and low stress additives such as silicone oil and rubber may be appropriately blended. Further, the epoxy resin composition of the present invention comprises (A) to (F)
It can be obtained by sufficiently uniformly mixing the components and other additives with a mixer or the like, further melt-kneading with a hot roll or a kneader, cooling and pulverizing.

As a method of sealing various electronic parts such as semiconductor elements using the epoxy resin composition of the present invention, curing molding may be carried out by a conventional molding method such as transfer molding, compression molding or injection molding. . As a method of manufacturing a semiconductor device using the epoxy resin composition of the present invention, a known method can be used.

[0041]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. The mixing ratio is parts by weight. Example 1 7.0 parts by weight of epoxy resin 1 containing the formula (14) as a main component (melting point: 105 ° C., epoxy equivalent: 19 1 g / eq.)

[0042]

[Chemical formula 22]

[0043]   Phenolic resin 1 represented by formula (15) (softening point 77 ° C., hydroxyl equivalent 174 g / Eq. ) 6.3 parts by weight

[0044]

[Chemical formula 23]

[0045]   0.5 parts by weight of phosphoric acid ester compound 1 represented by formula (16)

[0046]

[Chemical formula 24] 0.5 parts by weight of polyorganosiloxane 1 represented by formula (17)

[0047]

[Chemical 25]

The fused spherical silica (average particle size 20 [mu] m) 84.0 parts by weight of _{Mg 4.3 Al 2 (OH) 12.6} (CO 3) 3 · 3.5H 2 O 0.5 part by weight of triphenylphosphine and 0.3 parts by weight epoxy Silane (γ-glycidoxypropyltrimethoxysilane) 0.2 parts by weight Carbon black 0.3 parts by weight Carnauba wax 0.4 parts by weight After mixing at room temperature with a mixer, the surface temperature is 90
The mixture was kneaded using two rolls at 45 ° C and 45 ° C, cooled, and then pulverized to obtain an epoxy resin composition. The obtained epoxy resin composition was evaluated by the following methods. The results are shown in Table 1.

Evaluation method Spiral flow: Using a mold for spiral flow measurement according to EMMI-1-66, mold temperature 175 ° C.
It was measured at an injection pressure of 6.9 MPa and a curing time of 120 seconds.
The unit is cm. Curing: Mold temperature 1 using low pressure transfer molding machine
Molding was performed at 75 ° C., injection pressure of 6.9 MPa, and curing time of 120 seconds. The surface hardness of the runner 10 seconds after the mold was opened was measured with a Bacol hardness meter # 935. The Bacol hardness is an index of curability, and the larger the value, the better the curability. Moisture absorption rate: Mold temperature 1 using low pressure transfer molding machine
A disc having a diameter of 50 mm and a thickness of 3 mm was molded at 75 ° C., an injection pressure of 6.9 MPa, and a curing time of 120 seconds, and then molded at 175 ° C., 8
Post-cured in 1 hour, under an environment of 85 ° C and 85% relative humidity
After standing for 68 hours, the weight change was measured to determine the moisture absorption rate.
The unit is% by weight. Bending strength under heat: JIS K 6911 (5.17.1)
The molding material was measured according to the test conditions. The test piece (length 80 mm, height 4 mm, width 10 mm) had a mold temperature of 17
A transfer molding machine was used for molding at 5 ° C., an injection pressure of 9.8 MPa, and a curing time of 120 seconds, and the resin was post-cured at 175 ° C. for 8 hours to prepare. This test piece was set on a measuring table (distance between fulcrums 64 mm), preheated in a tank kept at 240 ° C. for 6 minutes, and then measured. The unit is MPa. Flame resistance: Mold temperature 1 using low pressure transfer molding machine
A test piece (127 mm × 12.7 mm, thickness 3.2 mm) was molded at 75 ° C., an injection pressure of 9.8 MPa, and a curing time of 120 seconds, post-cured at 175 ° C. for 8 hours, and then UL-94.
The flame retardancy was determined by measuring according to the vertical method.

Moisture resistance reliability: Using a low-pressure transfer molding machine, a mold temperature of 175 ° C., an injection pressure of 9.8 MPa, and a curing time of 120 seconds were used to mold 16 pSOP (using a simulated element TEG3, wiring width 20 μm) at 175 ° C. After post-curing for 8 hours, moisture resistance reliability evaluation (140 ° C / 85% relative humidity)
%, And applied with an applied voltage of 10 V) to confirm an open defect between wirings. With respect to 15 packages, the number of defective packages after 500 hours and 1000 hours after the treatment is shown as a percent defective as a percentage. Units%. Solder resistance: 80 pQFP (thickness: 2 mm, chip size: 9.0 mm) at a mold temperature of 175 ° C., an injection pressure of 8.3 MPa, and a curing time of 120 seconds using a low-pressure transfer molding machine.
× 9.0 mm) was molded, post-cured at 175 ° C. for 8 hours, left at 85 ° C. and 85% relative humidity for 168 hours, and then immersed in a solder bath at 240 ° C. for 10 seconds. Observed with a microscope, crack occurrence rate [(crack occurrence rate) = {(number of external crack occurrence packages) / (total number of packages)} x 1
00]. Units%. Moreover, the peeling area at the interface between the semiconductor element and the cured product of the epoxy resin composition was measured using an ultrasonic flaw detector, and the peeling rate [(peeling rate) = {(peeling area) / (semiconductor element area)} × 100]. Units%. High temperature storage characteristics: 16 pDIP (chip size 3.0 mm x 3.5 mm) at a mold temperature of 175 ° C, a pressure of 9.8 MPa, and a curing time of 120 seconds using a low pressure transfer molding machine.
After being molded and post-cured at 175 ° C. for 8 hours, a high temperature storage test (185 ° C., 1000 hours) was performed, and a package in which the electrical resistance between wirings increased by 20% with respect to the initial value was determined to be defective. The percentage of defective packages (defective rate) out of 15 packages is shown in percentage. Units%.

Examples 2 to 5, Comparative Examples 1 to 5 According to the formulations shown in Table 1, the phosphoric acid ester compound 1 of Example 1 was changed to phosphoric acid ester compounds 2 to 5, and the polyorganosiloxane 1 was changed to polyorganosiloxane 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 Table 1. Example 2 below
The structural formulas of the phosphoric acid ester compounds 2 to 4 and the polyorganosiloxane 2 used in Examples 1 to 5 are shown below. Phosphoric acid ester compound 2 (phosphoric acid ester compound of formula (18)) Phosphoric acid ester compound 3 (phosphoric acid ester compound of formula (19)) Phosphoric acid ester compound 4 (phosphoric acid ester compound of formula (20)) Polyorganosiloxane 2 (formula (21 ) Polyorganosiloxane)

[0052]

[Chemical formula 26]

[0053]

[Chemical 27]

[0054]

[Chemical 28]

[0055]

[Chemical 29]

The brominated bisphenol A type epoxy resin used in Comparative Example 4 had an epoxy equivalent of 365 g / eq. The bromine atom content is 48% by weight.

Examples 6 to 12 and Comparative Examples 6 to 11 The epoxy resin and the phenol resin of Example 1 were changed as shown in Table 2, and an epoxy resin composition was obtained in the same manner as in Example 1 and carried out. Evaluation was carried out in the same manner as in Example 1. The results are shown in Table 2. Ortho-cresol novolac type epoxy resin (softening point 5
5 ° C., epoxy equivalent 200 g / eq. ) The structural formulas of the epoxy resins 2 to 6 and the phenol resins 2 and 3 used in Examples 6 to 12 and Comparative examples 6 to 11 are shown below. Epoxy resin 2 (Epoxy resin of formula (22), softening point 6
0 ° C., epoxy equivalent 270 g / eq. ) Epoxy resin 3 (epoxy resin of formula (23), softening point 8
1 ° C., epoxy equivalent 265 g / eq. ) Epoxy resin 4 (epoxy resin of formula (24), softening point 6
2 ° C., epoxy equivalent 227 g / eq. ) Epoxy resin 5 (epoxy resin of formula (25), softening point 7
3 ° C., epoxy equivalent 269 g / eq. ) Epoxy resin 6 (epoxy resin of formula (26), softening point 5
8 ° C., epoxy equivalent 244 g / eq. ) Phenolic resin 2 (phenolic resin of formula (27), softening point 73 ° C, hydroxyl group equivalent weight 199 g / eq.) Phenolic resin 3 (phenolic resin of formula (28), softening point 87 ° C, hydroxyl group equivalent weight 210 g / eq.)

[0058]

[Chemical 30]

[0059]

[Chemical 31]

[0060]

[Chemical 32]

[0061]

[Chemical 33]

[0062]

[Chemical 34]

[0063]

[Chemical 35]

[0064]

[Chemical 36]

[0065]

[Table 1]

[0066]

[Table 2]

[0067]

Industrial Applicability The epoxy resin composition of the present invention does not contain a halogen-based flame retardant and an antimony compound, and a semiconductor device sealed by using the composition has flame retardancy, moisture resistance reliability, solder resistance and high temperature. It has excellent storage characteristics and moldability during molding.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H01L 23/29 H01L 23/30 R 23/31 F term (reference) 4J002 CD04W CD05W CP03X DE146 DF016 DJ016 DJ046 DK006 EW047 FD016 FD13X FD137 GQ00 4J036 AA02 AA04 AD07 AD08 AD11 AE05 DA01 DA02 DA05 DC41 DC46 DD07 FA03 FA12 FB08 GA08 JA07 4M109 AA01 BA01 CA21 EA02 EB03 EB04 EB07 EB12 EC05

Claims (6)

[Claims] 1. (A) Epoxy resin, (B) Phenolic resin, (C) Curing accelerator, (D) Inorganic filler, (E) Phosphate compound represented by the general formula (1) and (F) General. An epoxy resin composition for semiconductor encapsulation, comprising a polyorganosiloxane compound represented by the formula (2). [Chemical 1] (R represents an organic group, which may be the same or different from each other.) (R represents a monovalent organic group, and is 30 to 10 of all organic groups.
0% by weight is a phenyl group, and the remaining organic group is a vinyl group-containing group, a C1-6 alkylalkoxy group, a C1-6 alkyl group, an amino group-containing group, an epoxy group-containing group. One or more groups selected from the group consisting of a hydroxyl group-containing group and a mercapto group-containing group. n is an average value and is a positive number of 5 to 100. ) 2. The epoxy resin composition for semiconductor encapsulation according to claim 1, wherein R of the phosphoric acid ester compound represented by the general formula (1) is a substituted or unsubstituted aryl group. 3. The epoxy resin (A) has the general formula (3) to
It is 1 or more types chosen from the group of General formula (7).
Or the epoxy resin composition for semiconductor encapsulation according to 2. [Chemical 3] (R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, which may be the same or different from each other.) (R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R1
Represents an alkyl group having 1 to 4 carbon atoms and may be the same or different from each other. a is 0 or an integer of 1 to 3. n
Is an average value and is a positive number from 1 to 10. ) [Chemical 5] (R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R1
Represents an alkyl group having 1 to 4 carbon atoms and may be the same or different from each other. a is 0 or an integer of 1 to 3. n
Is an average value and is a positive number from 1 to 10. ) [Chemical 6] (R represents an alkyl group having 1 to 4 carbon atoms and may be the same or different from each other. B is 1 or 2. n is an average value and is a positive number of 1 to 10.) (In the formula, n is an average value and is a positive number of 1 to 10.) 4. The phenolic resin (B) has the general formula (8):
~ The epoxy resin composition for semiconductor encapsulation according to claims 1 to 3, which is one or more selected from the phenol resins represented by the general formula (10). [Chemical 8] (R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R1
Represents an alkyl group having 1 to 4 carbon atoms and may be the same or different from each other. a is 0 or an integer of 1 to 3. n
Is an average value and is a positive number from 1 to 10. ) [Chemical 9] (R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R1
Represents an alkyl group having 1 to 4 carbon atoms and may be the same or different from each other. a is 0 or an integer of 1 to 3. n
Is an average value and is a positive number from 1 to 10. ) [Chemical 10] (R represents an alkyl group having 1 to 4 carbon atoms and may be the same or different from each other. B is 1 or 2. n is an average value and is a positive number of 1 to 10.) 5. A compound represented by the general formula (11), a compound represented by the general formula (12), or at least one ion-trapping agent selected from zinc oxide in an amount of 0.1. The epoxy resin composition for semiconductor encapsulation according to any one of claims 1 to 4, which comprises 0. Mg _a Al _b (OH) _{2a + 3b-2c} (CO ₃ ) _c · dH ₂ O (11) (0 <b / a ≦ 1, 0 ≦ c / b <1.5, d is 0 or a positive number. BiO _a (OH) _b (NO ₃ ) _c (HSiO ₃ ) _d (12) (a = 0.9 to 1.1, b = 0.6 to 0.8, c + d =
0.2-0.4, and d / c = 0-2.0. ) 6. A semiconductor device comprising a semiconductor element encapsulated with the epoxy resin composition for semiconductor encapsulation according to claim 1.