KR101191537B1 - Semiconductor Encapsulating Epoxy Resin Composition and Semiconductor Device - Google Patents

Abstract

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) phosphazene compounds

It relates to an epoxy resin composition comprising a.

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 of the present invention provides a cured product having good fluidity, low coefficient of linear expansion, high glass transition temperature, low hygroscopicity, and excellent lead-free solder crackability.

Epoxy resin composition, inorganic filler, phosphazene compound, coefficient of linear expansion.

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 exhibits good hygroscopicity, low coefficient of linear expansion, high glass transition temperature, low hygroscopicity, excellent lead-free solder cracking, flame retardancy, and moisture resistance reliability, and the epoxy resin composition for semiconductor sealing and the hardness of the resin composition. A semiconductor device sealed with cargo.

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, by filling the inorganic filler with a resin having a low crosslinking density, it is possible to improve the low water absorption, low expansion rate and low elastic modulus at high temperature, and it is expected to have an effect on the reflow property, but due to high viscosity, fluidity during molding It is damaged.

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. It is said that 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 include 40-95 mass parts of things with m = 0 and n = 0 in following General formula (1a). However, further improvement is required.

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 and a resin composition for semiconductor encapsulation having excellent fluidity, low coefficient of linear expansion, high glass transition temperature, low hygroscopicity, and excellent lead-free solder cracking, flame retardancy and moisture resistance reliability. An object of the present invention is to provide a semiconductor device sealed with a cured product.

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 (3), the present invention has a good fluidity and a small and high linear expansion coefficient. Epoxy resin composition for semiconductor encapsulation, which has a glass transition temperature and exhibits low hygroscopicity, and provides a cured product having excellent flame resistance and moisture resistance reliability without using a brominated epoxy resin and antimony trioxide, by using a phosphazene compound represented by Formula 2 It discovered what was obtained and came to complete this invention.

Therefore,

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

(B) a phenol resin having one or more substituted or unsubstituted naphthalene rings in one molecule, preferably a phenol resin represented by the following formula (3),

(C) inorganic fillers, and

(D) the phosphazene compound represented by the following formula (2)

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 >

(Wherein 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, and G represents a glycidyl group-containing organic group, except that in 100 parts by mass of the compound of Formula 1) m = 0 and n = 0 contain 35 to 85 parts by mass, and m = 1 and n = 1 contain 1 to 35 parts by mass)

(Wherein R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an aryl group, and p is an integer of 0 to 10)

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, Y is OH, SH or NH ₂ , and R ¹ is An alkyl group having 1 to 4 carbon atoms and an alkoxy group, a group selected from NH ₂ , NR ² R ³ and SR ⁴ , and R ² , R ³ And R ⁴ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, d, e, f and a are 0 ≦ d ≦ 0.25a, 0 ≦ e ≦ 2a, 0 ≦ f ≦ 2a, 2d + e + f = 2a, 3≤a≤1,000)

BEST MODE FOR CARRYING OUT THE INVENTION [

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

[(A) Epoxy Resin]

Epoxy resin (A) used in the present invention contains the naphthalene type epoxy resin of the formula (1), 35 to 85 parts by mass, m = 1 and n in 100 parts by mass of the compound of formula (1) m = 0 and n = 0 It is necessary to contain 1 to 35 parts by mass of = 1.

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 deny it.

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 all the epoxy resins (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 one or more substituted or unsubstituted naphthalene ring in 1 molecule is used. use. Preferably it is a phenol resin represented by following formula (3).

<Formula 3>

In the formula, R ⁵ And R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an aryl group, and p is an integer of 0 to 10.

R ⁵ And R ⁶ includes 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 (4)-(7) is mentioned as a specific example of the phenol resin which has a naphthalene ring represented by General formula (3).

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 (3) is 25-100 mass%, especially 40-80 mass% with respect to all phenol resins (specific phenol resin (B) + other phenol resin of the said Formula 3). It is preferable. 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, as the average particle diameter and shape of the inorganic filler, spherical fused silica having an average particle diameter of 3 to 30 µm, particularly 5 to 25 µm is particularly preferable, wherein the average particle diameter is, for example, particle size distribution measurement by laser light diffraction method or the like. It can obtain | require as a weight average value (or median diameter) etc. using an apparatus etc. 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 element increases, leading to deterioration of the device characteristics. In addition, since the amount of resin to the whole composition increases, the moisture resistance is significantly lowered and cracking resistance is achieved. It also degrades. 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) phosphazene compound]

The epoxy resin composition for semiconductor encapsulation of the present invention to which the (D) phosphazene compound represented by the following general formula (2) used in the present invention is added, compared with the epoxy resin composition to which a phosphorus flame retardant such as red phosphorus and phosphate ester is added, and extracting hot water Hardened | cured material which is excellent in a characteristic and especially excellent in moisture resistance can be obtained.

<Formula 2>

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, Y is OH, SH or NH ₂ , and R ¹ is carbon number Alkyl group and alkoxy group of 1 to 4, NH ₂ , NR ² R ³ and SR ⁴ is selected from group, R ² , R ³ and R ⁴ is a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, d, e, f And a is a number satisfying 0 ≦ d ≦ 0.25a, 0 ≦ e ≦ 2a, 0 ≦ f ≦ 2a, 2d + e + f = 2a, and 3 ≦ a ≦ 1,000.

In Formula 2, a is 3 to 1,000, but more preferably 3 to 10. In the synthesis, particularly preferably a = 3.

The ratios of d, e and f are 0 ≦ d ≦ 0.25a, 0 ≦ e ≦ 2a, 0 ≦ f ≦ 2a and 2d + e + f = 2a. At 0.25 a <d, the softening point becomes high because of the intermolecular crosslinking of the phosphazene compound, and the expected flame retardant effect is not obtained because it is difficult to be used in the epoxy resin. The ratio of d is preferably 0 ≦ d ≦ 0.15a.

X, Y and R ¹ are as described above, and R ¹ is an electron donating group. When there is no substitution of an electron donating group, since nucleophilicity of Y falls, reactivity with an epoxy group becomes low. Therefore, when the addition amount of the phosphazene compound represented by the said Formula (2) is increased, curability fall and electrical resistance fall at high temperature generate | occur | produce. Moreover, when sclerosis | hardenability deteriorates, since it is easy to thermally decompose, flame retardance also falls.

In addition, in an alkyl group and an alkoxy group having R ¹ of 5 or more carbon atoms, the flame retardance decreases when the carbon number increases. Therefore, methyl group, methoxy group, amino group and dimethylamino group are preferable.

In addition, when X is a single bond,

.

Although there is no restriction | limiting in particular as addition amount, It is preferable that it is 1-50 mass% with respect to 100 mass% of total amounts of (A) and (B) component, Especially 2-20 mass% is preferable. If the added amount is less than 1% by mass, not only a sufficient flame retardant effect may not be obtained, but if it exceeds 50% 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, flame retardants such as magnesium hydroxide and aluminum hydroxide, thermoplastic resins, thermoplastic elastomers, organic synthetic rubbers And low stress agents such as 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.

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

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-isocyanai Tpropyl triethoxysilane etc. are mentioned. 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.

<Examples>

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

[Synthesis Examples A and B, Examples 1 to 6, Comparative Examples 1 to 5]

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 used raw material is shown below.

Synthesis Example A

Under nitrogen atmosphere, 8.6 g (214 mmol) of sodium hydride was suspended in 50 mL of THF at 0 ° C, and a 75 mL solution of THF 75 mL of 19.8 g (211 mmol) of phenol was added dropwise thereto. After stirring for 30 minutes, a 75 ml solution of 12.0 g (34.5 mmol) of THF in hexachlorotriphosphazene was added dropwise and heated to reflux for 18 hours. The solvent was distilled off under reduced pressure, methanol was added, and the precipitated crystals were washed with methanol and water to obtain 23.8 g of white crystals.

Synthesis Example B

Under nitrogen atmosphere, 4.6 g (114 mmol) of sodium hydride are suspended in 50 mL of THF at 0 ° C, and 9.7 g (104 mmol) of phenol, 0.40 g (1.7 mmol) of THF 50 of 4,4'-sulfonyldiphenol are added thereto. ML solution was added dropwise. After stirring for 30 minutes, a solution of 12.5 g (36.0 mmol) of THF 50 ml of hexachlorotriphosphazene was added dropwise and heated to reflux for 5 hours. After distilling off the solvent under reduced pressure, 150 mL of cyclohexane and 57.3 g (345 mmol) of methylhydroquinone were added thereto, and 27.3 g (345 mmol) of pyridine was added dropwise thereto. After heating to reflux for 18 hours, the lower yellow syrup-like substance obtained by decanting was dissolved in 80 ml of 80% acetic acid, and transferred to 500 ml of water to obtain crystals. This crystal was dissolved in methanol and transferred to water to obtain a crystal. This operation was repeated until water became neutral, and 25.8g of dark brown crystals were obtained.

(Epoxy resin)

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.

를 나타낸다. 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 made by Dai Nippon Ink Chemical Industries, Ltd.)

(Mineral filler)

Spherical Fused Silica (Tatsumori Co., Ltd.)

(Flame retardant)

Flame Retardant (Phosphorus): Phosphagen Compound of Synthesis Example A

Flame retardant (tea): phosphazene compound of Synthesis Example B

Flame Retardant (K): Magnesium Hydroxide KISMA 8N (manufactured by Kyowa Chemical Co., Ltd.)

(Other additives)

Curing accelerator: triphenylphosphine (manufactured by Fuko Chemical Co., Ltd.)

Release agent: Carnauba wax (manufactured by Nikko Fine Products Co., Ltd.)

Silane coupling agent: KBM-403, γ-glycidoxypropyltrimethoxysilane (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

The viscosity was measured at the temperature of 175 degreeC using the solid flow tester using the nozzle of diameter 1mm under the 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 absorbing the package used in the package warping amount measurement in a constant temperature and humidity chamber of 85 ℃ / 60% RH for 168 hours, and then passed through the IR reflow condition of Figure 1 three times using an IR reflow apparatus, ultrasonic exploration Using the apparatus, the occurrence of internal cracks and the occurrence of peeling were observed.

(g) flame retardant

Based on the UL-94 standard, a 1/16 inch thick plate was molded at molding conditions of 175 ° C., 6.9 N / mm 2, and a molding time of 120 seconds, and the flame retardancy of the post-cured product at 180 ° C. for 4 hours was investigated.

(h) 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 has a good fluidity, a low linear expansion coefficient, high glass transition temperature, low hygroscopicity and excellent crack resistance, and provides a cured product having excellent flame resistance and moisture resistance reliability. will be. Therefore, the semiconductor device sealed by hardening of the epoxy resin composition for semiconductor sealing of this invention is especially useful industrially.

Claims (5)

(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) the phosphazene compound represented by the following formula (2) / RTI &gt; The said phenol resin (B) contains 25-100 mass parts of phenol resins represented by following formula (3) in 100 mass parts of total phenol resins, The epoxy resin composition characterized by the above-mentioned. &Lt; Formula 1 >

<Formula 2>

<Formula 3>

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 = 0 and n = 0 contain 35 to 85 parts by mass, and m = 1 and n = 1 contain 1 to 35 parts by mass, X is a single bond or a group selected from CH ₂ , C (CH ₃ ) ₂ , SO ₂ , S, O and O (CO) O, Y is OH, SH or NH ₂ , and R ¹ has 1 to 4 carbon atoms Is an alkyl group and an alkoxy group, NH ₂ , NR ² R ³ and SR ⁴ is selected from group, R ² , R ³ and R ⁴ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, d, e, f and a are 0≤d≤0.25a, 0≤e≤2a, 0≤f≤2a, 2d + e + f = 2a, 3≤a≤1,000 R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group or an aryl group having a carbon number of 1 to 4, p is an integer from 0 to 10. delete delete The semiconductor device sealed with the hardened | cured material of the epoxy resin composition of Claim 1. The semiconductor device according to claim 4, 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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