JP2015093971A - Epoxy resin composition for sealing semiconductor and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy resin composition for sealing a semiconductor which can be used as a semiconductor device having excellent adhesiveness to CuLF or Ag plating and excellent reliability without breakage or corrosion of a Cu wire or a Cu wire/an Al pad junction when stored for a long period of time at a high temperature of 175 to 250°C, and to provide a semiconductor device.SOLUTION: There is provided an epoxy resin composition for sealing a semiconductor which comprises, as essential components, (A) an epoxy resin, (B) a curing agent, (C) an inorganic filler, (D) bismuth oxide or bismuth subcarbonate and (E) a phosphazene compound represented by the following average composition formula (1) [wherein, X is a single bond or a group selected from CH, C(CH), SO, S, O and O(CO)O; d,e,n are a number satisfying 0≤d≤0.25n, 0≤e<2n, 2d+e=2n and 3≤n≤1,000] and substantially contains no brominated product, red phosphorus, a phosphoric acid ester and an antimony compound.

Description

  The present invention is excellent in reliability when left at high temperature for a long period of time, has little peeling from a Cu lead frame (LF) or an Ag-plated portion, and does not cause corrosion or migration of Cu wire. And a semiconductor device sealed with the cured product.

  In recent years, environmental measures at the global level, such as measures against global warming and energy conversion from fossil fuels, have been promoted, and the number of automobiles produced is increasing. In addition, household electric appliances in emerging countries such as China and India are also increasing the number of models equipped with inverter motors as an energy saving measure.

  For the hybrid vehicle, electric vehicle, and inverter, a power semiconductor that plays a role of converting alternating current into direct current, converting direct current into alternating current, and transforming voltage is important. However, silicon (Si), which has been used as a semiconductor for many years, is approaching its performance limit, and it has become difficult to expect dramatic performance improvements. Therefore, attention has been focused on next-generation power semiconductors using materials such as silicon carbide (SiC), gallium nitride (GaN), and diamond. For example, a reduction in resistance of a power MOSFET is required in order to reduce a loss during power conversion, but it is difficult to significantly reduce the resistance in the current mainstream Si-MOSFET. Therefore, development of a low-loss power MOSFET using SiC, which is a semiconductor with a wide band gap (wide gap), is in progress. SiC and GaN have excellent characteristics that the band gap is about 3 times that of Si and the breakdown electric field strength is 10 times or more. In addition, there are also features such as high-temperature operation (SiC reports 650 ° C operation), high thermal conductivity (SiC is equivalent to Cu), and large saturated electron drift velocity. As a result, if SiC or GaN is used, the on-resistance of the power semiconductor can be lowered and the power loss of the power conversion circuit can be greatly reduced. However, since the temperature on the element is expected to generate heat at 175 ° C. or higher, heat resistance characteristics are required for the sealing material and other peripheral materials.

On the other hand, power semiconductors are generally protected by transfer molding with epoxy resin and potting sealing with silicone gel. Recently, transfer molding using an epoxy resin is becoming mainstream from the viewpoint of miniaturization and weight reduction (particularly for automobiles). Epoxy resins are well-balanced thermosetting resins with excellent moldability, adhesion to substrates, and mechanical strength, but their reliability characteristics in the temperature range exceeding 175 ° C. are questioned. Actually, when a semiconductor device sealed with an existing sealing material was left at a high temperature for 200 hours at 200 ° C., a case where a crack occurred in the sealing material, a case where peeling occurred at the interface between the sealing material and the Ag plating die pad part There are cases in which reliability is affected, such as a case in which an alloy layer of a Cu wire / Al pad is cracked.
In addition, the following literature is mentioned as a prior art relevant to this invention.

IEEE Transactions on Components and packing Technology, Vol.26, No.2, 367-374 SEMICON Singapore 2005, 35-43 Journal of Materials Science (2008) 43, 6038-6048

  The present invention has been made in view of such circumstances, and has excellent adhesion to CuLF and Ag plating even when stored at a high temperature of 175 to 250 ° C. for a long time, and bonding of Cu wire and Cu wire / Al pad. It is an object of the present invention to provide an epoxy resin composition for semiconductor encapsulation and a semiconductor device which can be a highly reliable semiconductor device free from disconnection and corrosion of parts.

  As a result of intensive studies to achieve the above object, the present inventors have (A) an epoxy resin, (B) a curing agent, (C) an inorganic filler, (D) bismuth hydroxide or bismuth carbonate, and (E) An epoxy resin composition for encapsulating a semiconductor containing a phosphazene compound represented by the following average composition formula (1) as an essential component and substantially free of bromide, red phosphorus, phosphate ester and antimony compound is A cured product having excellent reliability when stored for a long period of time and having excellent flame resistance and moisture resistance reliability can be obtained, and a semiconductor device encapsulated with the cured product of the composition is flame retardant, high temperature It has been found that it is excellent in unreliable reliability, and has led to the present invention.

［式中、Ｘは単結合、又はＣＨ₂、Ｃ（ＣＨ₃）₂、ＳＯ₂、Ｓ、Ｏ、及びＯ（ＣＯ）Ｏから選ばれる基であり、ｄ，ｅ，ｎは０≦ｄ≦０．２５ｎ、０≦ｅ＜２ｎ、２ｄ＋ｅ＝２ｎ、３≦ｎ≦１，０００を満たす数である。］
を必須成分とし、臭素化物、赤リン、リン酸エステル及びアンチモン化合物を実質的に含まないことを特徴とする半導体封止用エポキシ樹脂組成物。
〔２〕
（Ｄ）水酸化ビスマス又は次炭酸ビスマスの添加量が、（Ａ），（Ｂ）成分の合計１００質量部に対し、３〜１０質量部であることを特徴とする〔１〕に記載のエポキシ樹脂組成物。
〔３〕
（Ａ）エポキシ樹脂のエポキシ当量が２１０未満であることを特徴とする〔１〕又は〔２〕に記載のエポキシ樹脂組成物。
〔４〕
（Ａ）エポキシ樹脂が、下記一般式（２）で示されるエポキシ樹脂であることを特徴とする〔１〕〜〔３〕のいずれかに記載のエポキシ樹脂組成物。

（式中、ａは１〜１０の整数である。）
〔５〕
〔１〕〜〔４〕のいずれかに記載のエポキシ樹脂組成物の硬化物で封止した半導体装置。 Accordingly, the present invention provides the following epoxy resin composition for semiconductor encapsulation and semiconductor device.
[1]
(A) epoxy resin,
(B) a curing agent,
(C) inorganic filler,
(D) bismuth hydroxide or bismuth subcarbonate,
(E) A phosphazene compound represented by the following average composition formula (1)

[Wherein, X is a single bond or a group selected from CH ₂ , C (CH ₃ ) ₂ , SO ₂ , S, O, and O (CO) O, and d, e, and n are 0 ≦ d ≦ 0.25n, 0 ≦ e <2n, 2d + e = 2n, 3 ≦ n ≦ 1,000. ]
Is an essential component, and is substantially free of bromide, red phosphorus, phosphate ester and antimony compound.
[2]
(D) The epoxy according to [1], wherein the addition amount of bismuth hydroxide or bismuth carbonate is 3 to 10 parts by mass with respect to 100 parts by mass in total of the components (A) and (B). Resin composition.
[3]
(A) The epoxy resin composition according to [1] or [2], wherein an epoxy equivalent of the epoxy resin is less than 210.
[4]
(A) The epoxy resin composition according to any one of [1] to [3], wherein the epoxy resin is an epoxy resin represented by the following general formula (2).

(In the formula, a is an integer of 1 to 10.)
[5]
A semiconductor device sealed with a cured product of the epoxy resin composition according to any one of [1] to [4].

  The epoxy resin composition for semiconductor encapsulation of the present invention is excellent in moldability and can provide a cured product excellent in flame retardancy and high-temperature standing reliability. In addition, since brominated products such as brominated epoxy resins and antimony compounds such as antimony trioxide are not contained in the epoxy resin composition, there are no adverse effects on the human body and the environment. Furthermore, the epoxy resin composition for semiconductor encapsulation of the present invention has superior hot water extraction characteristics and moisture resistance reliability compared to an epoxy resin composition to which a phosphorus-based flame retardant such as red phosphorus or phosphate is added. A particularly excellent cured product can be obtained. Moreover, the semiconductor device sealed with the cured product of the epoxy resin composition for semiconductor sealing of the present invention is excellent in flame retardancy and high temperature storage reliability, and is particularly useful industrially.

［式中、Ｘは単結合、又はＣＨ₂、Ｃ（ＣＨ₃）₂、ＳＯ₂、Ｓ、Ｏ、及びＯ（ＣＯ）Ｏから選ばれる基であり、ｄ，ｅ，ｎは０≦ｄ≦０．２５ｎ、０≦ｅ＜２ｎ、２ｄ＋ｅ＝２ｎ、３≦ｎ≦１，０００を満たす数である。］
を必須成分とし、臭素化物、赤リン、リン酸エステル及びアンチモン化合物を実質的に含まないものである。
ここで、実質的に含まないとは、組成物中に意図的に添加していないという意味で、工業的にはコンタミで混入する可能性を許容するものである。 Hereinafter, the present invention will be described in more detail.
The epoxy resin composition for semiconductor encapsulation of the present invention is
(A) epoxy resin,
(B) a curing agent,
(C) inorganic filler,
(D) bismuth hydroxide or bismuth subcarbonate,
(E) A phosphazene compound represented by the following average composition formula (1)

[Wherein, X is a single bond or a group selected from CH ₂ , C (CH ₃ ) ₂ , SO ₂ , S, O, and O (CO) O, and d, e, and n are 0 ≦ d ≦ 0.25n, 0 ≦ e <2n, 2d + e = 2n, 3 ≦ n ≦ 1,000. ]
Is an essential component and does not substantially contain bromide, red phosphorus, phosphate ester and antimony compound.
Here, “substantially free” means that it is not intentionally added to the composition, and industrially allows the possibility of contamination by contamination.

  The (A) epoxy resin which comprises the epoxy resin composition of this invention is not specifically limited. Common epoxy resins include novolak-type epoxy resins, cresol novolak-type epoxy resins, triphenolalkane-type epoxy resins, aralkyl-type epoxy resins, biphenyl-skeleton-containing aralkyl-type epoxy resins, biphenyl-type epoxy resins, dicyclopentadiene-type epoxy resins. , Heterocyclic epoxy resin, naphthalene ring-containing epoxy resin, bisphenol A-type epoxy compound, bisphenol F-type epoxy compound, stilbene-type epoxy resin, etc., one of which is used alone or in combination of two or more Can do. In the present invention, a brominated epoxy resin is not blended.

  Among these, for semiconductor devices that require insulation at high temperatures and mechanical strength, a cured product having a high glass transition temperature is generally preferred, and such a cured product has a high crosslinking density. An epoxy resin having a high epoxy group concentration, that is, a low epoxy equivalent is preferably used. The epoxy equivalent is preferably less than 210, more preferably less than 170. The triphenolalkane type represented by the following general formula (2) has an epoxy equivalent of 168.

（式中、ａは１〜１０の整数である。）

(In the formula, a is an integer of 1 to 10.)

  The epoxy resin has a hydrolyzable chlorine content of 1,000 ppm or less, particularly 500 ppm or less, and preferably contains sodium and potassium in a content of 10 ppm or less. When the hydrolyzable chlorine exceeds 1,000 ppm or the sodium or potassium exceeds 10 ppm, the moisture resistance may deteriorate if the semiconductor device is left under high temperature and high humidity for a long time.

  The (B) curing agent used in the present invention is not particularly limited. As a general curing agent, a phenol resin is preferable. Specifically, a phenol novolak resin, a naphthalene ring-containing phenol resin, an aralkyl type phenol resin, a triphenol alkane type phenol resin, a biphenyl skeleton-containing aralkyl type phenol resin, a biphenyl type. Examples include phenolic resins, alicyclic phenolic resins, heterocyclic phenolic resins, naphthalene ring-containing phenolic resins, bisphenol A type resins, bisphenol F type resins, and other bisphenol type phenol resins. Two or more kinds can be used in combination.

  As for the said hardening | curing agent, it is preferable to make content of sodium and potassium into 10 ppm or less similarly to an epoxy resin, respectively. When sodium or potassium exceeds 10 ppm, moisture resistance may deteriorate if the semiconductor device is left under high temperature and high humidity for a long time.

  Here, although the compounding quantity of an epoxy resin and a hardening | curing agent is not restrict | limited in particular, The molar ratio of the phenolic hydroxyl group contained in a hardening | curing agent is 0.5-1.5 with respect to 1 mol of epoxy groups contained in an epoxy resin. In particular, a range of 0.7 to 1.2 is preferable.

  In the present invention, it is preferable to use a curing accelerator in order to accelerate the curing reaction between the epoxy resin and the curing agent. The curing accelerator is not particularly limited as long as it accelerates the curing reaction. For example, triphenylphosphine, tributylphosphine, tri (p-methylphenyl) phosphine, tri (nonylphenyl) phosphine, triphenylphosphine-trimethyl. Phosphorus compounds such as phenylborane, tetraphenylphosphine / tetraphenylborate, adducts of triphenylphosphine and benzoquinone, triethylamine, benzyldimethylamine, α-methylbenzyldimethylamine, 1,8-diazabicyclo (5.4.0) Tertiary amine compounds such as undecene-7, imidazole compounds such as 2-methylimidazole, 2-phenylimidazole, and 2-phenyl-4-methylimidazole can be used.

  The blending amount of the curing accelerator is an effective amount, but the curing accelerator for promoting the curing reaction between the epoxy compound such as the phosphorus compound, the tertiary amine compound, and the imidazole compound and the curing agent (phenol resin) is ( It is preferable to set it as 0.1-5 mass parts with respect to 100 mass parts of total amounts of A) and (B) component, especially 0.5-2 mass parts.

  As the inorganic filler (C) blended in the epoxy resin composition of the present invention, those usually blended in the epoxy resin composition can be used. Examples thereof include silicas such as fused silica and crystalline silica, alumina, silicon nitride, aluminum nitride, boron nitride, titanium oxide, glass fiber and the like.

  The average particle diameter and shape of these inorganic fillers and the filling amount of the inorganic filler are not particularly limited, but in order to increase the flame retardancy, the amount is as large as possible within the range that does not impair the moldability in the epoxy resin composition. Is preferably filled. In this case, spherical fused silica having an average particle diameter of 5 to 30 μm is particularly preferable as the average particle diameter and shape of the inorganic filler, and the filling amount of the inorganic filler of the component (C) is (A), (B ) 400 to 1,200 parts by weight, particularly 500 to 1,000 parts by weight, based on 100 parts by weight of the total component.

  In addition, in order to strengthen the bond strength of resin and an inorganic filler, it is preferable to use what was surface-treated with coupling agents, such as a silane coupling agent and a titanate coupling agent, as an inorganic filler. As such a coupling agent, epoxy silane such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N -Β (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, aminosilane such as N-phenyl-γ-aminopropyltrimethoxysilane, mercaptosilane such as γ-mercaptopropyltrimethoxysilane, etc. It is preferable to use one kind or two or more kinds of silane coupling agents. Here, the blending amount of the coupling agent used for the surface treatment and the surface treatment method are not particularly limited.

The epoxy resin composition for semiconductor encapsulation of the present invention uses (D) bismuth hydroxide or bismuth subcarbonate.
The effects of bismuth compounds so far include an effect as an inorganic ion exchanger for exchanging anions derived from phosphate esters when used in combination with a phosphate ester flame retardant (JP 2003-147169 A), laser A marking property improving effect (JP-A-6-84601), a combination with a brominated epoxy resin, a halogenated gas trap effect in a high-temperature atmosphere (JP-A-11-240937), and the like are known.

  In the present invention, among bismuth compounds, only bismuth hydroxide and bismuth carbonate are supplemented with organic acids other than halogens and do not release corrosive anions. It was found that the properties were maintained, and disconnection, corrosion, etc. of the joint portion of Cu wire and Cu wire / Al pad were not caused. Among epoxy resins, resins having a low epoxy equivalent, for example, a triphenolalkane type epoxy resin represented by the above general formula (2), have a high concentration of organic acid generated by thermal decomposition, so that bismuth hydroxide and bismuth carbonate can be used in combination. It is valid.

  (D) The amount of bismuth hydroxide or bismuth carbonate added is preferably 3 to 10 parts by weight, more preferably 3 to 8 parts by weight, based on 100 parts by weight of the total amount of components (A) and (B). If it is less than 3 parts by mass, the characteristics may not be sufficiently exhibited. If it exceeds 10 parts by mass, it may cause a decrease in fluidity and poor curing.

  In addition, as an impurity in bismuth hydroxide and bismuth carbonate, nitrate ion is preferably 10% by mass or less.

［式中、Ｘは単結合、又はＣＨ₂、Ｃ（ＣＨ₃）₂、ＳＯ₂、Ｓ、Ｏ、及びＯ（ＣＯ）Ｏから選ばれる基であり、ｄ，ｅ，ｎは０≦ｄ≦０．２５ｎ、０≦ｅ＜２ｎ、２ｄ＋ｅ＝２ｎ、３≦ｎ≦１，０００を満たす数である。］ The epoxy resin composition for semiconductor encapsulation of the present invention uses (E) a phosphazene compound represented by the following average composition formula (1).

[Wherein, X is a single bond or a group selected from CH ₂ , C (CH ₃ ) ₂ , SO ₂ , S, O, and O (CO) O, and d, e, and n are 0 ≦ d ≦ 0.25n, 0 ≦ e <2n, 2d + e = 2n, 3 ≦ n ≦ 1,000. ]

  The epoxy resin composition for semiconductor encapsulation of the present invention to which the phosphazene compound represented by the above formula (1) is added is compared with the epoxy resin composition to which a phosphorus-based flame retardant such as red phosphorus or phosphate is added, A cured product having excellent hot water extraction characteristics and particularly excellent moisture resistance reliability can be obtained.

  Here, in Formula (1), n is 3-1,000, However, A more preferable range is 3-10. Particularly preferably n = 3 in terms of synthesis.

  The ratios of d and e are 0 ≦ d ≦ 0.25n, 0 ≦ e <2n, and 2d + e = 2n. When 0.25n <d, since there are many intermolecular crosslinks of the phosphazene compound, the softening point becomes high, it is difficult to be compatible with the epoxy resin, and the expected flame retardant effect cannot be obtained. The ratio of e is 0 ≦ e <2n, but it is desirable that 1.5n ≦ e ≦ 1.97n in order to achieve both high flame retardance.

で表される。 In addition, when X is a single bond,

It is represented by

  The addition amount of the phosphazene compound is preferably 1 to 10 parts by mass, particularly 3 to 7 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). When the addition amount is less than 1 part by mass, a sufficient flame retardant effect may not be obtained, and when it exceeds 10 parts by mass, the fluidity and the glass transition temperature may be lowered.

  Various additives can be further blended in the epoxy resin composition for semiconductor encapsulation of the present invention as necessary. For example, low stress agents such as thermoplastic resins, thermoplastic elastomers, organic synthetic rubbers, silicones, waxes such as carnauba wax, higher fatty acids, synthetic waxes, colorants such as carbon black, additives such as hydrotalcite It can be added and blended within a range that does not impair the object of the present invention.

  The epoxy resin composition for semiconductor encapsulation of the present invention comprises, for example, an epoxy resin, a curing agent, an inorganic filler, bismuth hydroxide or bismuth hydroxide, a phosphazene compound, and other additives in a predetermined composition ratio. Can be sufficiently uniformly mixed with a mixer or the like, then subjected to a melt mixing process using a hot roll, a kneader, an extruder or the like, then cooled and solidified, and pulverized to an appropriate size to obtain a molding material.

  The thus obtained epoxy resin composition for semiconductor encapsulation of the present invention can be effectively used for encapsulation of various semiconductor devices. In this case, the most common method of encapsulation is low-pressure transfer molding Law. In addition, as for the shaping | molding temperature of the epoxy resin composition for semiconductor sealing of this invention, it is desirable to carry out for 30 to 180 second at 150-180 degreeC, and for 2 to 16 hours at 150-180 degreeC.

  Hereinafter, although the Example and comparative example of an epoxy resin composition are shown and this invention is shown concretely, this invention is not restrict | limited to the following Example.

[Synthesis Example A]
Under a nitrogen atmosphere, 4.8 g (119 mmol) of sodium hydride (NaOH) was suspended in 50 ml of tetrahydrofuran (THF) at 0 ° C., and then 10.2 g (108 mmol) of phenol, 0.44 of 4,4′-sulfonyldiphenol. A solution of 45 g (1.8 mmol) in 50 ml of THF was added dropwise. After stirring for 30 minutes, a solution of 12.5 g (36.0 mmol) of hexachlorotriphosphazene in 50 ml of THF was added dropwise, and the mixture was heated to reflux for 5 hours. Separately, 5.2 g (130 mmol) of sodium hydride was suspended in 50 ml of THF at 0 ° C., and a solution of phenol 11.2 g (119 mmol) in 50 ml of THF was added dropwise thereto, and the mixture was further heated and refluxed for 19 hours. After distilling off the solvent under reduced pressure, chlorobenzene was added and dissolved, followed by extraction with 5% by weight NaOH aqueous solution 200 ml × 2, 5% by weight sulfuric acid aqueous solution 200 ml × 2, 5% by weight sodium hydrogen carbonate aqueous solution 200 ml × 2, and water 200 ml × 2. went. The solvent was distilled off under reduced pressure to obtain 20.4 g of yellow-brown crystalline phosphazene compound A (phosphorus atomic weight: 13.36% by mass) represented by the following formula.

[Examples 1 to 5, Comparative Examples 1 to 7]
The components shown in Tables 1 and 2 were uniformly melt-mixed with two hot rolls, cooled and pulverized to obtain an epoxy resin composition for semiconductor encapsulation. Using these compositions, the following properties (i) to (iv) were measured, and the results are shown in Tables 1 and 2.

(I) Flame retardancy Based on the UL-94 standard, the flame retardancy of a 1/16 inch thick plate was examined. A 1/16 inch thick plate was prepared by molding at a temperature of 175 ° C., a molding pressure of 6.9 N / mm ² and a molding time of 120 seconds, and post-curing at 180 ° C. for 4 hours.

(Ii) Adhesiveness with Cu / Ag plating lead frame stored at high temperature 100pin-QFP frame (Cu alloy C7025, die pad part Ag plating) with epoxy resin composition at temperature 175 ° C., molding pressure 6.9 N / mm ² , molding time Molding was performed under conditions of 120 seconds and post-curing was performed at 180 ° C. for 4 hours. Package size 14 x 20 x 2.7 mm. Twenty of these packages were stored in a 250 ° C. atmosphere for 96 hours, and then examined for the presence or absence of peeling using an ultrasonic flaw detector. Those in which peeling was observed in an area of 20% or more were regarded as defective, and the number of defects was examined.

(Iii) High temperature reliability of Cu wire A 7 × 7 mm silicon chip formed with aluminum wiring is bonded to a 100 pin-QFP frame (Cu alloy C7025, die pad Ag plating), and the aluminum electrode on the chip surface and lead frame And an epoxy resin composition were molded under the conditions of a temperature of 175 ° C., a molding pressure of 6.9 N / mm ² and a molding time of 120 seconds, and post-cured at 180 ° C. for 4 hours. Package size 14 x 20 x 2.7 mm. After 20 packages were left in an atmosphere of 200 ° C. for 1,000 hours, the resistance value was measured, and those having a value 10 times or more of the initial value were regarded as defective, and the number of defects was examined.

(Iv) Cu wire package, moisture resistance reliability A 7 × 7 mm silicon chip formed with aluminum wiring is bonded to a 100 pin-QFP frame (Cu alloy C7025, die pad portion Ag plating), and an aluminum electrode on the chip surface After wire bonding to the lead frame with a 25 μmφ Cu wire, the epoxy resin composition was molded to this at a temperature of 175 ° C., a molding pressure of 6.9 N / mm ² , a molding time of 120 seconds, and post-cured at 180 ° C. for 4 hours. did. Package size 14 x 20 x 2.7 mm. Twenty of these packages were allowed to stand in an atmosphere of 130 ° C. and 85% RH for 1,000 hours, and the resistance value was measured.

（式中、ａは１〜１０の整数である。）
硬化剤：フェノールノボラック樹脂、ＤＬ−９２（明和化成製、フェノール性水酸基当量１１０、ナトリウム量１ｐｐｍ、カリウム量１ｐｐｍ）
無機質充填剤：球状溶融シリカ（龍森製、平均粒径２０μｍ）
水酸化ビスマス（日本化学産業製、硝酸イオン量６．０質量％）
次炭酸ビスマス（日本化学産業製、硝酸イオン量０．５質量％）
ホスファゼン化合物：合成例Ａで得られたホスファゼン化合物Ａ
酸化ビスマス（和光純薬製）
ビスマス系無機イオン交換体：ＩＸＥ−５００（東亞合成製）
三酸化アンチモン：ＰＡＴＯＸ ＣＺ（日本精鉱製）
水酸化アルミニウム：ハイジライト３２０Ｉ（昭和電工製）
酸化アルミニウム：ＡＯ−４１Ｒ（アドマテックス製）
ハイドロタルサイト：ＤＨＴ−４Ａ−２（協和化学製）
硬化促進剤：トリフェニルホスフィン（北興化学製）
離型剤：カルナバワックス（日興ファインプロダクツ製）
カーボンブラック：デンカブラック（電気化学工業製）
シランカップリング剤１：ＫＢＭ−４０３、γ−グリシドキシプロピルトリメトキシシラン（信越化学工業製）
シランカップリング剤２：ＫＢＭ−８０３Ｐ、γ−メルカプトプロピルトリメトキシシラン（信越化学工業製） Epoxy resin 1: o-cresol novolac type epoxy resin, Epicron N-665-EXP-S (DIC, epoxy equivalent 200)
Epoxy resin 2: Epoxy resin represented by the following formula (2), EPPN-502H (manufactured by Nippon Kayaku, epoxy equivalent 168, hydrolyzable chlorine content 500 ppm, sodium content 1 ppm, potassium content 1 ppm)

(In the formula, a is an integer of 1 to 10.)
Curing agent: phenol novolak resin, DL-92 (Maywa Kasei, phenolic hydroxyl group equivalent 110, sodium 1 ppm, potassium 1 ppm)
Inorganic filler: Spherical fused silica (manufactured by Tatsumori, average particle size 20 μm)
Bismuth hydroxide (manufactured by Nippon Chemical Industry Co., Ltd., nitrate ion content 6.0% by mass)
Bismuth carbonate (manufactured by Nippon Chemical Industry Co., Ltd., nitrate content 0.5% by mass)
Phosphazene compound: Phosphazene compound A obtained in Synthesis Example A
Bismuth oxide (made by Wako Pure Chemical Industries)
Bismuth-based inorganic ion exchanger: IXE-500 (manufactured by Toagosei)
Antimony trioxide: PATOX CZ (manufactured by Nippon concentrate)
Aluminum hydroxide: Heidilite 320I (made by Showa Denko)
Aluminum oxide: AO-41R (manufactured by Admatechs)
Hydrotalcite: DHT-4A-2 (manufactured by Kyowa Chemical)
Curing accelerator: Triphenylphosphine (manufactured by Hokuko Chemical)
Mold release agent: Carnauba wax (Nikko Fine Products)
Carbon black: Denka Black (manufactured by Denki Kagaku Kogyo)
Silane coupling agent 1: KBM-403, γ-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)
Silane coupling agent 2: KBM-803P, γ-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)

As is clear from the results in Tables 1 and 2, the semiconductor device molded with the cured product of the epoxy resin composition for semiconductor encapsulation of the present invention has adhesion with CuLF and Ag plating even when stored for a long time at a high temperature. Excellent reliability with no disconnection at the joint of Cu wire or Cu wire / Al pad.
In addition, brominated products such as Br-epoxy epoxy resins and antimony compounds such as antimony trioxide are not contained in the resin composition, so that there is no adverse effect on the human body and the environment.

Claims (5)

(A) epoxy resin,
(B) a curing agent,
(C) inorganic filler,
(D) bismuth hydroxide or bismuth subcarbonate,
(E) A phosphazene compound represented by the following average composition formula (1)

[Wherein, X is a single bond or a group selected from CH ₂ , C (CH ₃ ) ₂ , SO ₂ , S, O, and O (CO) O, and d, e, and n are 0 ≦ d ≦ 0.25n, 0 ≦ e <2n, 2d + e = 2n, 3 ≦ n ≦ 1,000. ]
Is an essential component, and is substantially free of bromide, red phosphorus, phosphate ester and antimony compound.   (D) The epoxy according to claim 1, wherein the addition amount of bismuth hydroxide or bismuth carbonate is 3 to 10 parts by mass with respect to 100 parts by mass in total of the components (A) and (B). Resin composition.   (A) The epoxy equivalent of an epoxy resin is less than 210, The epoxy resin composition of Claim 1 or 2 characterized by the above-mentioned. The epoxy resin composition according to any one of claims 1 to 3, wherein the epoxy resin (A) is an epoxy resin represented by the following general formula (2).

(In the formula, a is an integer of 1 to 10.)   The semiconductor device sealed with the hardened | cured material of the epoxy resin composition of any one of Claims 1-4.