KR20060111851A - Semiconductor encapsulating epoxy resin composition and semiconductor device - Google Patents

Abstract

Provided are a semiconductor-encapsulating epoxy resin composition that has good fluidity, a small coefficient of linear expansion, and a high glass transition temperature and exhibits low water absorptivity and excellent crack resistance. The semiconductor-encapsulating epoxy resin composition comprises (a) a naphthalene type epoxy resin represented by the following formula 1, (b) a phenolic resin hardener having at least one substituted or unsubstituted naphthalene ring in a molecule, (c) an inorganic filler, and (d) at least one compound selected from rare earth oxides or hydrotalcite compounds. In the formula 1, m and n are 0 or 1, R represents a hydrogen atom, a C1-4 alkyl group, or a phenyl group, G represents a glycidyl-containing organic group, provided that 35-85 parts by mass of the resin(wherein, m=0 and n=0) and 1-35 parts by weight of the resin(wherein, m=1 and n=1) are contained in 100 parts by mass of the resin represented by the formula 1.

Description

Semiconductor Encapsulating Epoxy Resin Composition and Semiconductor Device

1 shows IR reflow conditions for reflowability measurement.

[Patent Document 1] Japanese Patent No. 3137202

[Patent Document 2] Japanese Patent Application Laid-Open No. 2005-15689

The present invention has a good fluidity, a low coefficient of linear expansion, high hygroscopicity, low hygroscopicity, excellent lead-free solder cracking resistance, heat resistance and moisture resistance reliability, and an epoxy resin composition for semiconductor sealing and the resin composition. A semiconductor device sealed with a cured product.

Conventionally, semiconductor devices mainly include resin-sealed diodes, transistors, ICs, LSIs, and ultra-LSIs, but epoxy resins have superior moldability, adhesiveness, electrical properties, mechanical properties, and moisture resistance compared to other thermosetting resins. It is common to seal a semiconductor device with an epoxy resin composition. However, in recent years, with the market trend of miniaturization, weight reduction, and high performance of electronic devices, not only high integration of semiconductor devices is progressed, but also epoxy resins that are used as semiconductor sealing materials as semiconductor device mounting technologies are promoted. The demand for them is becoming increasingly stringent, including lead-free.

For example, ball grid arrays (BGAs) or QFNs, which are excellent in high-density mounting, have become mainstream ICs or LSIs in recent years. However, since this package seals only one side, warpage after molding is a major problem. Conventionally, as one method for improving warpage, it is possible to increase the glass transition temperature by increasing the crosslinking density of the resin. However, not only the elastic modulus at high temperature is high but also the hygroscopicity is high due to the increase in the solder temperature due to the softening. Therefore, peeling at the epoxy resin hardened | cured material and a board | substrate interface, and peeling at a semiconductor element and a semiconductor resin paste interface became a problem after solder reflow. On the other hand, high filling of the inorganic filler using a resin having a low crosslinking density improves the low water absorption, low expansion rate, and low elastic modulus at high temperature, and thus the effect on downflow is expected. Fluidity is impaired. Moreover, since glass transition temperature is low, there exists a problem in reliability under high temperature.

Japanese Patent No. 3137202 (Patent Document 1) discloses 1,1-bis (2,7-diglycidyloxy-1-naphthyl) alkane as an epoxy resin in an epoxy resin composition comprising an epoxy resin and a curing agent. The epoxy resin composition characterized by using is disclosed. The cured product of this epoxy resin is not only excellent in heat resistance but also very excellent in moisture resistance, and generally overcomes the disadvantage of being hard and brittle in the cured product of a high heat resistant epoxy resin.

In addition, Japanese Patent Laid-Open No. 2005-15689 (Patent Document 2) discloses 1,1-bis (2,7-diglycidyloxy-1-naphthyl) alkane (a1) and 1- (2,7- Diglycidyloxy-1-naphthyl) -1- (2-glycidyloxy-1-naphthyl) alkane (a2) and 1,1-bis (2-glycidyloxy-1-naphthyl) It is an epoxy resin composition which consists of an epoxy resin (A) and a hardening | curing agent (B) containing an alkane (a3), and (a3) is added in 100 mass parts of said (a1), said (a2), and said (a3) in total. An epoxy resin composition is disclosed which contains 40 to 95 parts by mass. That is, from the fall of fluidity | liquidity and sclerosis | hardenability, it is described that it is preferable to contain 40 mass parts-95 mass parts of what is m = 0 and n = 0 in following formula (1a).

In formula, m and n are 0 or 1, R represents a hydrogen atom, a C1-C4 alkyl group, or a phenyl group, G represents a glycidyl group containing organic group.

The present invention provides an epoxy resin composition for semiconductor encapsulation and a resin having excellent fluidity, low coefficient of linear expansion, high glass transition temperature, low hygroscopicity, and excellent lead-free solder cracking, heat and reliability. It is an object to provide a semiconductor device sealed with a cured product of the composition.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said objective, when using the combination of the specific epoxy resin of the following general formula (1) and the specific phenol resin, especially the compound of general formula (2), the present invention has a good fluidity | liquidity and a small and high linear expansion coefficient. In addition to exhibiting low hygroscopicity with a glass transition temperature, by using at least one or more compounds selected from rare earth oxides or hydrotalcite compounds, ionic impurities are reduced during long-term storage at high temperature, and heat and reliability It discovered that the epoxy resin composition for semiconductor sealing which provides the outstanding hardened | cured material was obtained, and came to complete this invention.

Therefore, the present invention

(A) a naphthalene type epoxy resin represented by following General formula (1),

(B) a phenol resin curing agent having at least one substituted or unsubstituted naphthalene ring in one molecule,

(C) inorganic fillers, and

(D) at least one compound selected from rare earth oxides or hydrotalcite compounds

It is sealed with the epoxy resin composition for semiconductor sealing, and its hardened | cured material, Preferably, a semiconductor element is mounted in one side of a resin substrate or a metal substrate, The resin substrate surface in which this semiconductor element is mounted, or Provided is a semiconductor device in which only one side of the metal substrate surface side is sealed.

<Formula 1>

In the formula, m and n are 0 or 1, R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, G represents a glycidyl group-containing organic group, provided that m in 100 parts by mass of the compound of Formula 1 35 to 85 parts by mass for = 0 and n = 0, and 1 to 35 parts by mass for m = 1 and n = 1.

Preferably, it is the above-mentioned epoxy resin composition containing the phenol resin (B) hardener represented by following General formula (2).

In formula, R <^1> and R <^2> respectively independently represents a hydrogen atom, a C1-C4 alkyl group, or a phenyl group, p is an integer of 0-10.

Best Mode for Carrying Out the Invention

Hereinafter, the present invention will be described in more detail.

[(A) Epoxy Resin]

The epoxy resin (A) used in the present invention contains the naphthalene type epoxy resin of the above formula (1), and in the mass of 100 parts by mass of the compound of the formula (1), m = 0 and n = 0 are 35 to 85 parts by mass, m = 1 and n = 1 needs to contain 1-35 mass parts.

When the content of m = 0 and n = 0 is less than 35 parts by mass in 100 parts by mass of the total compound of the formula (1), the viscosity of the resin composition is increased and the fluidity is lowered. When the content of the compound composition exceeds 85 parts by mass, the crosslinking density of the resin composition is extremely Since it falls, since curability or glass transition temperature falls, it is unpreferable. And when m = 1 and n = 1 exceed 35 mass parts, crosslinking density will become high and a glass transition temperature will rise, but since the elasticity modulus at high temperature also becomes high, it is unpreferable. Moreover, since the curability, heat resistance, and high elastic modulus of the epoxy resin composition obtained are excellent, the content of the thing of m = 0 and n = 0 is 45-70 mass parts, and the content of the thing of m = 1 and n = 1 is 5-30 mass. It is desirable to disclaim.

Japanese Laid-Open Patent Publication No. 2005-15689 describes that it is preferable to include 40 parts by mass to 95 parts by mass of m = 0 and n = 0 from the deterioration of fluidity and curability. However, although the epoxy resin (A) used in the present invention also has a naphthalene structure as described above, by defining the content of m = 1 and n = 1 in the general formula (1), the fluidity is good and the linear expansion coefficient is small. It was found that not only exhibits low hygroscopicity while having a high glass transition temperature, but also excellent solder cracking resistance.

As such an epoxy resin, the following are mentioned specifically ,.

However, R and G are as above-mentioned.

Specific examples of R include an alkyl group such as a hydrogen atom, a methyl group, an ethyl group, and a propyl group, or a phenyl group. Specific examples of G glycidyl group-containing organic groups include groups represented by the following formulae.

Moreover, in this invention, another epoxy resin can also be used together other than the said specific epoxy compound (A) as an epoxy resin component. It does not specifically limit as another epoxy resin, A conventionally well-known epoxy resin, for example, a novolak-type epoxy resin, such as a phenol novolak-type epoxy resin and a cresol novolak-type epoxy resin, a triphenol methane type epoxy resin, and a triphenol propane type Triphenol alkane type epoxy resins, such as an epoxy resin, a biphenyl type epoxy resin, a phenol aralkyl type epoxy resin, a biphenyl aralkyl type epoxy resin, a heterocyclic type epoxy resin, a naphthalene ring containing epoxy resin other than the above, bisphenol A type epoxy resin, and Bisphenol-type epoxy resins, such as a bisphenol F-type epoxy resin, a stilbene type epoxy resin, a halogenated epoxy resin, etc. are mentioned, Among these, 1 type, or 2 or more types can be used.

In this case, it is preferable that the compounding quantity of the said specific epoxy resin (A) is 50-100 mass%, especially 70-100 mass% with respect to an epoxy resin (the said specific epoxy resin (A) + other epoxy resin). When the compounding quantity of the said naphthalene type epoxy resin is less than 50 mass%, sufficient heat resistance, reflow property, a moisture absorption characteristic, etc. may not be obtained.

[(B) Curing Agent]

The phenol resin which is (B) component of the epoxy resin composition of this invention acts as a hardening | curing agent of the epoxy resin which is (A) component, and in this invention, the phenol resin which has at least 1 or more substituted naphthalene rings in 1 molecule. Use Preferably it is a phenol resin represented by following General formula (2).

<Formula 2>

In formula, R <^1> and R <^2> respectively independently represents a hydrogen atom, a C1-C4 alkyl group, or a phenyl group, p is an integer of 0-10.

Examples of R ¹ and R ² include an alkyl group or a phenyl group such as a hydrogen atom, a methyl group, an ethyl group and a propyl group.

By using the phenol resin curing agent having such a naphthalene ring, the epoxy resin of the present invention is obtained because the coefficient of linear expansion is small, the glass transition temperature is high, the low elastic modulus and the low water absorption hardened product are obtained in the temperature range above the glass transition temperature. When the composition is used as a sealing material of a semiconductor device, not only the crack resistance at the time of thermal shock is improved, but also the curvature of the package is improved. The following compound (3)-(6) is mentioned as a specific example of the phenol resin which has a naphthalene ring represented by General formula (2).

Moreover, the phenol resin which is (B) component of the epoxy resin composition of this invention can also use together another phenol resin other than the said specific phenol compound. It does not specifically limit as another phenol resin, Conventionally well-known phenol resin, For example, novolak-type phenol resins, such as a phenol novolak resin and a cresol novolak resin, a phenol aralkyl type phenol resin, a biphenyl aralkyl type phenol resin, biphenyl Biphenols such as triphenolalkane phenol resins, alicyclic phenol resins, heterocyclic phenol resins, bisphenol A phenol resins, and bisphenol F phenol resins such as a phenol resin, a triphenol methane phenol resin, and a triphenol propane phenol resin Type phenol resin etc. can be mentioned, Among these, 1 type, or 2 or more types can be used.

In this case, the compounding quantity of the specific phenol resin (B) of the said Formula (2) is 25-100 mass%, especially 40-80 mass% with respect to a phenol resin (specific phenol resin (B) + other phenol resin of the said Formula 2). desirable. When the compounding quantity of the said naphthalene type phenol resin is less than 25 mass%, sufficient heat resistance, a moisture absorption characteristic, a bending characteristic, etc. may not be obtained.

Although it does not restrict | limit especially about the compounding ratio of (A) component epoxy resin and (B) component phenol resin in this invention, 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, it is preferable that it is the range of 0.8-1.2.

[(C) Inorganic Filler]

As an inorganic filler which is (C) component mix | blended in the epoxy resin composition of this invention, what is mix | blended with an epoxy resin composition can be used normally. For example, silica, such as fused silica and crystalline silica, alumina, silicon nitride, aluminum nitride, boron nitride, titanium oxide, glass fiber, antimony trioxide, etc. are mentioned. The average particle diameter or shape of these inorganic fillers and the amount of the inorganic fillers are not particularly limited, but in order to increase lead-free solder cracking resistance and flame retardancy, it is preferable to fill the epoxy resin composition in as much amount as possible without impairing moldability. desirable.

In this case, spherical fused silica having an average particle diameter of 3 to 30 µm, particularly 5 to 25 µm, is particularly preferred as the average particle diameter and shape of the inorganic filler. Here, an average particle diameter can be calculated | required as a weight average value (or median diameter) etc. using the particle size distribution measuring apparatus etc. by the laser light diffraction method etc., for example. In addition, it is preferable to mix | blend the said inorganic filler previously surface-treated with coupling agents, such as a silane coupling agent and a titanate coupling agent, in order to strengthen the bond strength of resin and an inorganic filler.

Examples of the coupling agent include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-ureidopropyltriethoxysilane and β- (3, Epoxy silanes such as 4-epoxycyclohexyl) ethyltrimethoxysilane; Aminosilanes such as N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane and N-phenyl-γ-aminopropyltrimethoxysilane: γ-mercaptopropyl Mercaptosilanes such as trimethoxysilane; It is preferable to use silane coupling agents such as a reactant of an imidazole compound and γ-glycidoxypropyltrimethoxysilane. These may be used individually by 1 type, or may be used in combination of 2 or more type.

In addition, there is no restriction | limiting in particular about the compounding quantity of the coupling agent used for surface treatment, and a surface treatment method.

The filling amount of the inorganic filler is preferably from 200 to 1,100 parts by mass, in particular from 500 to 800 parts by mass, with respect to 100 parts by mass of the total amount of the (A) epoxy resin and the (B) curing agent (phenol resin). As the coefficient increases, the warpage of the package increases, and the stress applied to the semiconductor device increases, which may lead to deterioration of device characteristics. In addition, the amount of resin to the whole composition increases, so that the moisture resistance is significantly lowered and cracking resistance is achieved. It also deteriorates. On the other hand, when it exceeds 1,100 mass parts, the viscosity at the time of shaping | molding becomes high and moldability may deteriorate. Moreover, it is preferable to set this inorganic filler as content of 75-91 mass%, especially 78-89 mass% of the whole composition, and it is more preferable to set it as content of 83-87 mass%.

[(D) Rare Earth Oxides or Hydrotalcite Compounds]

The at least one compound selected from (D) rare earth oxides or hydrotalcite compounds used in the present invention is used for the purpose of trapping ionic impurities and for neutralizing the acidity of the cured product.

Hydrotalcite can use a conventionally well-known thing. Specifically, Japanese Patent Nos. 2501820, 2519277, 2712898, 3167853, Japanese Patent Publication No. 06-051826, Japanese Patent Publication No. 09-118810, Japanese Patent Publication No. 10-158360, Japan Japanese Patent Laid-Open No. 11-240937, Japanese Patent Laid-Open No. 11-310766, Japanese Patent Laid-Open No. 2000-159520, Japanese Patent Laid-Open No. 2000-230110 and Japanese Patent Laid-Open No. 2002-080566 It may be any one of them, and they have been observed to improve moisture resistance and heat resistance.

In particular, the compound represented by the following formula (7) is preferable because numerous examples of use can be cited as the ion trapping material of the semiconductor sealing material.

_{Mg x Al y (OH) 2x} + 3y + 2z (CO 3) 2 and mH ₂ O

In the formula, x, y and z each have a relationship of 0 <y / x≤1, 0≤z / y <1.5, and m represents an integer.

The rare earth oxide not only has excellent trapping ability such as phosphate ions and organic acid ions, but also does not elute metal ions even under high temperature and high humidity. Moreover, it does not affect the hardenability of an epoxy resin composition.

Examples of the rare earth oxides include lanthanum oxide, gadolinium oxide, samarium oxide, thulium oxide, europium oxide, neodymium oxide, erbium oxide, terbium oxide, prasedium oxide, dysprosium oxide, yttrium oxide, ytterbium oxide and holmium oxide.

In this invention, it is preferable to use 1 or more types, preferably 2 or more types from the above-mentioned hydrotalcite compound and rare earth oxide. Although there is no restriction | limiting in particular as addition amount, It is preferable that it is 2-20 mass parts with respect to 100 mass parts of total amounts of (A) and (B) component, Especially 3-10 mass parts is preferable. If the added amount is less than 2 parts by mass, not only a sufficient ion trap effect may be obtained, but if it exceeds 20 parts by mass, the fluidity may be lowered.

[Other Blended Ingredients]

Various additives can be mix | blended with the sealing resin composition of this invention further as needed. For example, curing catalysts such as imidazole compounds, tertiary amine compounds and phosphorus compounds, zinc molybdate-supported zinc oxide, zinc molybdate-supported talc, phosphazene compounds, flame retardants such as magnesium hydroxide and aluminum hydroxide, thermoplastic resins, thermoplastic elastomers And low stress agents such as organic synthetic rubbers and silicones, waxes such as carnauba wax, polyethylene oxide and montan ester, and coloring agents such as carbon black and Ketjen black can be added and blended.

Moreover, in this invention, in order to accelerate | stimulate the hardening reaction of an epoxy resin and a hardening | curing agent, it is preferable to use a hardening accelerator. There is no restriction | limiting in particular if this hardening accelerator accelerates hardening reaction, For example, a triphenyl phosphine, a tributyl phosphine, a tri (p-methylphenyl) phosphine, a tri (nonylphenyl) phosphine, a triphenyl phosphine. Phosphorus compounds such as triphenylborane, tetraphenylphosphine tetraphenylborate and triphenylphosphine-benzoquinone adduct, triethylamine, benzyldimethylamine, α-methylbenzyldimethylamine and 1,8-diazabicyclo ( Tertiary amine compounds such as 5,4,0) undecene-7, imidazole compounds such as 2-methylimidazole, 2-phenylimidazole and 2-phenyl-4-methylimidazole, and the like can be used. Can be.

Although the compounding quantity of a hardening accelerator is an effective amount, the hardening accelerator for hardening reaction of epoxy resins, such as the said phosphorus compound, a tertiary amine compound, and an imidazole compound, and a hardening | curing agent (phenol resin) is with respect to 100 mass parts of total amounts of an epoxy resin and a hardening | curing agent. , 0.1 to 3 parts by mass, particularly preferably 0.5 to 2 parts by mass.

The mold release agent component is not particularly limited and all known ones can be used. For example, carnauba wax, rice wax, polyethylene, polyethylene oxide, montanic acid, montan wax which is an ester compound of montanic acid and saturated alcohol, 2- (2-hydroxyethylamino) -ethanol, ethylene glycol and glycerin, etc. ; Stearic acid, stearic acid ester, stearic acid amide, ethylene bis stearic acid amide, copolymer of ethylene and vinyl acetate, etc. are mentioned, These may be used individually by 1 type, or may be used in combination of 2 or more type.

As a mixing ratio of a mold release agent, it is preferable that it is 0.1-5 mass parts with respect to 100 mass parts of total amounts of (A) and (B) component, More preferably, it is 0.3-4 mass parts.

[Production of epoxy resin composition, etc.]

As a general method in the case of producing the sealing resin composition of the present invention as a molding material, an epoxy resin, a curing agent, an inorganic filler, and other additives are blended in a predetermined composition ratio, and the mixture is sufficiently uniformly mixed with a mixer or the like, followed by a heat roll or a kneader. And a melt mixing process using an extruder or the like, followed by solidification by cooling and grinding to an appropriate size to obtain a molding material.

Moreover, when mixing a composition sufficiently uniformly with a mixer etc., in order to improve storage stability, it is preferable to surface-treat etc. previously with a silane coupling agent etc. as a wetting agent.

Here, as the silane coupling agent, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, γ- Methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxy Silane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γaminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane , Bis (triethoxypropyl) tetrasulfide and γ-isocyane A bit propyltriethoxysilane and the like can be mentioned silane. Here, the amount of the silane coupling agent used for the surface treatment and the surface treatment method are not particularly limited.

Thus, the resin composition for semiconductor sealing of this invention obtained can be effectively used for sealing of various semiconductor devices, In this case, the low pressure transfer method is mentioned as the most common method of sealing. Moreover, it is preferable to perform shaping | molding temperature of the resin composition for sealing of this invention at 150-185 degreeC-30-180 second, and postcure 2 to 20 hours at 150-185 degreeC.

In this case, the epoxy resin composition of this invention is effective in sealing only one surface of the resin substrate surface or metal substrate surface side in which this semiconductor element was mounted in the semiconductor device in which the semiconductor element was mounted in one surface of the resin substrate or the metal substrate. For this reason, it is preferably used for sealing a package such as a ball grid array or a QFN.

<Example>

Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited to the following Example. In addition, in the following example, all parts are mass parts.

[Examples 1 to 6 and Comparative Examples 1 to 4]

The components shown in Table 2 were melt-mixed uniformly with the heat | fever biaxial roll, and it cooled and pulverized, and obtained the epoxy resin composition for semiconductor sealing. The raw materials used are shown below.

(Epoxy resin)

를 나타낸다. With respect to the epoxy resins (i) to (iii) represented by the following structures by the values of m and n in the epoxy resin of the formula (1), the compounding ratio of the epoxy resins (A) to (D) as shown in Table 1, and (E) Biphenyl aralkyl type epoxy resin (NC3000: Nippon Kayaku Co., Ltd. brand name) was used. G is

Indicates.

Epoxy resin (i) (m = 0 and n = 0)

Epoxy resin (ii) (m = 1 and n = 0 or m = 0 and n = 1)

Epoxy resin (iii) (m = 1, n = 1)

(Phenolic resin)

Phenolic resin (bar): Phenolic resin represented by the following chemical formula

Phenolic resin (company): Phenolic resin represented by the following chemical formula

Novolak-type phenol resin (a): TD-2131 (product name made by Dai Nippon Ink Chemical Co., Ltd.)

(Mineral filler)

Spherical Fused Silica (trade name, manufactured by Tatsumori Co., Ltd.)

(Ion trap material)

Ion trapping material: Hydrotalcite compound DHT-4A-2 (Kyogawa Chemical Co., Ltd. brand name)

Ion trap material (tea): Lanthanum oxide (III) (brand name made by Shin-Etsu Chemical Co., Ltd.)

Ion trap material (ka): Yttrium (III) (brand name made by Shin-Etsu Chemical Co., Ltd.)

Ion trap material (other): Bismuth type compound IXE-500 (product made by Toagosei Co., Ltd.)

(Other additives)

Curing accelerator: Triphenyl phosphine (trade name of Fuko Chemical Co., Ltd.)

Release agent: Carnauba wax (brand name made by Nikko Fine Products Co., Ltd.)

Silane coupling agent: KBM-403, γ-glycidoxypropyltrimethoxysilane (trade name: manufactured by Shin-Etsu Chemical Co., Ltd.)

The following various characteristics were measured about these compositions. The results are shown in Table 2.

(a) Spiral flow value

It measured on the conditions of 175 degreeC, 6.9 N / mm <2>, and molding time 120 second using the metal mold | die according to EMMI standard.

(b) melt viscosity

Using a solid flow tester, the viscosity was measured at a temperature of 175 ° C. using a nozzle of diameter 1 mm under pressure of 10 kgf / cm 2.

(c) glass transition temperature and coefficient of linear expansion

It measured on the conditions of 175 degreeC, 6.9 N / mm <2>, and molding time 120 second using the metal mold | die according to EMMI standard.

(d) water absorption

A disk having a diameter of 50 × 3 mm was formed under conditions of 175 ° C., 6.9 N / mm 2 and a molding time of 2 minutes, and after curing at 180 ° C. for 4 hours, the resultant was left to stand at 85 ° C./85%RH in a constant temperature and humidity chamber for 168 hours. Absorption rate was measured.

(e) Package curvature

Using a 0.40 mm thick BT resin substrate, the package size was 32 × 32 mm, 1.2 mm thick, 10 × 10 × 0.3 mm silicon chip mounted at 175 ° C., 6.9 N / mm 2, and a curing time of 2 minutes. Molded under transfer conditions, and then subjected to post-curing at 175 ° C. for 5 hours to produce a package having a size of 32 × 32 mm and a thickness of 1.2 mm, using a laser three-dimensional measuring instrument and displacement of the height in the diagonal direction of the package. Was measured and the value with the largest displacement difference was defined as the amount of warpage.

(f) downflowability

After the package used in the measurement of the package warpage amount was absorbed by standing in a constant temperature and humidity chamber of 85 ° C./60%RH for 168 hours, and passed through the IR reflow condition shown in FIG. 1 three times using an IR reflow apparatus. The ultrasonic cracking device was used to observe the occurrence of internal cracking and peeling.

(g) Extraction water ionic impurity concentration after long-term high temperature storage

Five disks of 50 × 3 mm in diameter were molded under conditions of 175 ° C., 6.9 N / mm 2, and molding time of 2 minutes, and those which were post-cured at 180 ° C. for 4 hours were stored at 175 ° C. for 1000 hours. Thereafter, the resultant was pulverized with a disk mill, and 50 g of ion-exchanged water was added to 10 g of a pulverized product of a mesh sieve 75 µm ON and 150 µm PASS, and extracted at 125 ° C. for 20 hours in a pressure vessel. The electrical conductivity, pH, and various impurity ion concentrations of the filtrate were measured by ion chromatography, atomic absorption method, and the like.

(h) heat resistance reliability

In addition to bonding a 6 × 6 mm silicon chip with a 5 μm wide, 5 μm spaced aluminum wire to a 14 pin-DIP frame (42 alloy), the aluminum electrode and lead frame on the chip surface are 25 μm After wire bonding with the gold wire of, the epoxy resin composition was molded to 175 ° C., 6.9 N / mm 2, and molding time 120 seconds to postcure at 180 ° C. for 4 hours. After 20 packages were left for 1,000 hours by applying a DC bias voltage of -10V in an atmosphere of 175 ° C, the average value of the resistance values was examined.

(i) Moisture resistance reliability

In addition to bonding a 6 × 6 mm silicon chip with a 5 μm wide, 5 μm spaced aluminum wire to a 14 pin-DIP frame (42 alloy), the aluminum electrode and lead frame on the chip surface are 25 μm After wire bonding with the gold wire of, the epoxy resin composition was molded to 175 ° C., 6.9 N / mm 2, and molding time 120 seconds to postcure at 180 ° C. for 4 hours. After 20 packages were left for 500 hours by applying a DC bias voltage of -20 V in an atmosphere of 130 ° C / 85% RH, the number of packages in which aluminum corrosion occurred was examined.

The epoxy resin composition for semiconductor encapsulation of the present invention exhibits good hygroscopicity, low linear expansion coefficient, high glass transition temperature, low hygroscopicity and excellent crack resistance, and reduces ionic impurities during long-term storage at high temperatures. Therefore, the hardened | cured material which is excellent also in heat resistance reliability and moisture resistance reliability is provided. Therefore, the semiconductor device sealed by hardening of the epoxy resin composition for semiconductor sealing of this invention is especially useful industrially.

Claims (7)

(A) a naphthalene type epoxy resin represented by following General formula (1), (B) a phenol resin curing agent having at least one substituted or unsubstituted naphthalene ring in one molecule, (C) inorganic fillers, and (D) at least one compound selected from rare earth oxides or hydrotalcite compounds Epoxy resin composition comprising a. <Formula 1>

In the formula, m and n are 0 or 1, R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, G represents a glycidyl group-containing organic group, provided that m in 100 parts by mass of the compound of Formula 1 35 to 85 parts by mass for = 0 and n = 0, and 1 to 35 parts by mass for m = 1 and n = 1. The epoxy resin composition according to claim 1, wherein the phenol resin (B) contains a phenol resin represented by the following formula (2). <Formula 2>

In formula, R <^1> and R <^2> respectively independently represents a hydrogen atom, a C1-C4 alkyl group, or a phenyl group, p is an integer of 0-10. The epoxy resin composition according to claim 1 or 2, wherein 25 to 100 parts by mass of the phenol resin of the formula (2) is contained in 100 parts by mass of the entire phenol resin. The epoxy resin composition according to claim 1 or 2, wherein the component (D) is a compound represented by the following general formula (7). <Formula 7> _{Mg x Al y (OH) 2x} + 3y + 2z (CO 3) 2 and mH ₂ O In the formula, x, y and z each have a relationship of 0 <y / x≤1, 0≤z / y <1.5, and m represents an integer. (D) Component is lanthanum oxide, gadolinium oxide, samarium oxide, thulium oxide, europium oxide, neodymium oxide, erbium oxide, terbium oxide, prasedium oxide, dysprosium oxide, yttrium oxide of Claim 1 or 2 And a rare earth oxide selected from ytterbium oxide and holmium oxide. The semiconductor device sealed with the hardened | cured material of the epoxy resin composition of Claim 1 or 2. The semiconductor device according to claim 6, wherein a semiconductor element is mounted on one surface of the resin substrate or the metal substrate, and substantially only one surface of the resin substrate surface or the metal substrate surface side on which the semiconductor element is mounted is sealed. .

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