JP2011132337A - Epoxy resin composition and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin composition with an excellent molding property and heat resistance capable of providing a low elasticity cured product and to provide a semiconductor device formed with a cured product of the composition. <P>SOLUTION: The epoxy resin composition includes, as essential components, (A) a silicone-modified epoxy resin including a siloxane unit represented by formula (1), (wherein R<SP>1</SP>s are each independently a 1-10C monovalent hydrocarbon group, and n is an integer of 5 to 100), (B) a curing agent, 3 to 50 pts.mass of (C) an organopolysiloxane having a straight chain diorganopolysiloxane unit -[-(R<SP>2</SP>)Si(R<SP>3</SP>)-O-]<SB>m</SB>- with respect to 100 pts.mass of the total amount of the (A) component and the (B) component, and 0.01 to 10 pts.mass of (E) a curing accelerator with respect to 100 pts.mass of the total amount of the (A) component and the (B) component, (wherein R<SP>2</SP>, R<SP>3</SP>are rach independently OH, 1-3C alkyl, cyclohexyl, vinyl, phenyl or allyl; and m is an integer from 5 to 70). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an epoxy resin composition for semiconductor devices, and more particularly to an epoxy resin composition that is excellent in moldability and heat resistance and gives a low-elasticity cured product, and a semiconductor device molded from a cured product of the composition.

In recent years, higher integration of semiconductors has progressed year by year, and the size of molding packages such as MAP (Matrix Array Package) has been increased. In addition, the abolition of lead, which is a harmful substance, is required by the Rhos directive. However, the melting point of lead-free solder is higher than that of the conventional product, and a problem arises that a crack occurs in the resin part during mounting due to an increase in mounting temperature.

The epoxy resin composition for semiconductor encapsulation having good crack resistance is required to have low moisture absorption and low stress. It has been widely practiced to improve low moisture absorption and low stress (ie, low elastic modulus) by high filling with an inorganic filler such as fused silica powder, which has a great effect on improving solder crack resistance. However, since high fluidity of the inorganic filler impairs the fluidity at the time of molding, the epoxy resin composition for the sealing material has been required to have a low melt viscosity. Patent Documents 1 to 3 report a semiconductor sealing epoxy resin composition that has a low melt viscosity and gives a cured product excellent in low hygroscopicity and low stress.

JP 2002-212268 A JP 2003-128748 A JP 2003-277467 A

  However, when the viscosity of the epoxy resin and the phenol resin is reduced, the molecular weight of the resin becomes small and the molecule easily moves. Therefore, a curing accelerator such as 1,8-diazabicyclo (5,4,0) undecene-7 or triphenylphosphine is used. When used, there is a problem that a part of the cross-linking reaction proceeds rapidly at the time of resin kneading and the predetermined fluidity is not exhibited. In addition, the curing reaction gradually proceeds even at room temperature, and the storage stability of the resin composition at room temperature is lowered, and the continuous moldability is poor. Therefore, development of an epoxy resin composition that has good heat resistance and good moldability and gives a low-elasticity cured product that exhibits low warpage during MAP-type package molding is required.

SUMMARY OF THE INVENTION An object of the present invention is to provide an epoxy resin composition that is excellent in moldability and heat resistance and gives a low-elasticity cured product, and a semiconductor device molded from the cured product of the composition.

  As a result of intensive studies to solve the above problems, the present inventor has found that an epoxy resin composition containing a silicone-modified epoxy resin, which is an addition reaction product of a specific aromatic polymer and organopolysiloxane, has crack resistance and heat resistance. The present invention has been found that a cured product having excellent elasticity and low elasticity can be obtained.

（Ｒ^１は、互いに独立に、炭素数１〜１０の１価の炭化水素基であり、ｎは５〜１００の整数である）
（Ｂ）硬化剤
（Ｃ）下記式（２）で表される直鎖状ジオルガノポリシロキサン単位を有するオルガノポリシロキサン （Ａ）成分及び（Ｂ）成分の合計量１００質量部に対して３〜５０質量部

（Ｒ^２及びＲ^３は、互いに独立に、水酸基、炭素数１〜３のアルキル基、シクロヘキシル基、ビニル基、フェニル基及びアリル基から選ばれる基であり、ｍは５〜７０の整数である）
（Ｅ）硬化促進剤 （Ａ）成分及び（Ｂ）成分の合計量１００質量部に対して０．０１〜１０質量部
及び、該エポキシ樹脂組成物を用いた半導体装置を提供する。 That is, the present invention provides an epoxy resin composition comprising the following components as essential components (A) and a silicone-modified epoxy resin containing a siloxane unit represented by the following formula (1)

(R ¹ is each independently a monovalent hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 5 to 100)
(B) Curing agent
(C) Organopolysiloxane having a linear diorganopolysiloxane unit represented by the following formula (2): 3 to 50 parts by mass with respect to 100 parts by mass of the total amount of component (A) and component (B)

(R ² and R ³ are each independently a group selected from a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, a cyclohexyl group, a vinyl group, a phenyl group, and an allyl group, and m is an integer of 5 to 70. )
(E) Curing accelerator 0.01 to 10 parts by mass relative to 100 parts by mass of the total amount of component (A) and component (B)
And the semiconductor device using this epoxy resin composition is provided.

The composition of the present invention includes an epoxy resin having a linear siloxane unit of a predetermined length, thereby providing a cured product having excellent adhesion and crack resistance after temperature cycling and heat resistance. Can do. In addition, it is possible to form a sealed body that has a small amount of moisture absorption and excellent reflow resistance.

(A) Silicone-modified epoxy resin The silicone-modified epoxy resin of the component (A) is a silicone-modified epoxy resin containing a siloxane unit represented by the following formula (1). By including the siloxane unit, the stress characteristics of the epoxy resin composition can be improved.

R ¹ independently of each other is a monovalent hydrocarbon group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a tert-butyl group. , Pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, decyl group and other alkyl groups, vinyl group, allyl group, propenyl group, butenyl group and other alkenyl groups, phenyl group, tolyl group and other aryl groups, benzyl Groups, aralkyl groups such as phenylethyl groups, and halogen-substituted monovalent hydrocarbon groups in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted with halogen atoms or the like. Preferably, it is a methyl group or a phenyl group. n is an integer of 5 to 100, preferably 10 to 80.

  The component (A) is a silicone-modified epoxy resin containing a silicone-modified epoxy resin (A-1) obtained by addition reaction of an aromatic polymer and an organohydrogenpolysiloxane.

Ｘは水素原子又は臭素原子であり、ｐは０〜５０、特に好ましくは１〜２０の整数である。ｑは０〜５の整数、特に好ましくは０または１である。） Examples of the aromatic polymer include alkenyl group-containing compounds represented by the following formula (3).

X is a hydrogen atom or a bromine atom, and p is an integer of 0 to 50, particularly preferably 1 to 20. q is an integer of 0 to 5, particularly preferably 0 or 1. )

（式中、Ｒ^１及びｎは上記したとおりである。） Examples of the organohydrogenpolysiloxane include a compound represented by the following formula (4).

(In the formula, R ¹ and n are as described above.)

  In the above formula (4), the number of silicon atoms in one molecule is 5 to 100, preferably 5 to 90, more preferably 10 to 80. Below the lower limit, the silicone-modified resin is dissolved in the epoxy resin, and a fine sea-island structure using the epoxy resin as a matrix cannot be taken. As a result, sufficient impact resistance cannot be obtained, resulting in a resin composition lacking in stress characteristics. Further, if the value exceeds the upper limit, the silicone-modified resin is phase-separated from the epoxy resin, resulting in a problem that the strength of the cured product is weakened and the fluidity is lowered. The organohydrogenpolysiloxane is preferably a straight-chain one, but it may be one partially containing a branched structure.

  Conditions conventionally used in this field can be used as the addition reaction conditions for the aromatic polymer and the organohydrogenpolysiloxane. For example, a silicone-modified epoxy resin can be obtained by subjecting an aromatic polymer and an organopolysiloxane to an addition reaction in the presence of a platinum-based catalyst. The organohydrogenpolysiloxane is preferably reacted in an amount such that the SiH group is 0.1 to 2.0 mol, preferably 0.5 to 1.2 mol, with respect to 1 mol of the alkenyl group in the epoxy resin. .

  As the epoxy resin used as the raw material for the aromatic polymer, it is preferable to use an epoxy resin in which the hydrolyzable chlorine remaining in the purification process is 1000 ppm or less, particularly 500 ppm or less, and sodium and potassium are each 10 ppm or less. . The semiconductor device is sealed with an epoxy resin composition comprising a silicone-modified epoxy resin prepared from an epoxy resin with hydrolyzable chlorine exceeding 1000 ppm or sodium and potassium exceeding 10 ppm, and the semiconductor device is kept under high temperature and high humidity for a long time. If the semiconductor device is left unattended, the moisture resistance may deteriorate.

（Ｒ⁶はグリシジル基、Ｒ^７は−ＯＣＨ_２−ＣＨ（ＯＨ）−Ｏ−ＣＨ_２ＣＨ_２ＣＨ_２−、ｎは上述の通り。） Specific examples of (A-1) include silicone-modified epoxy resins represented by the following formula.

(R ⁶ is a glycidyl group, R ⁷ is —OCH ₂ —CH (OH) —O—CH ₂ CH ₂ CH ₂ —, and n is as described above.)

（式中、ｋは１または２の整数） In addition to the silicone-modified epoxy resin (A-1), the component (A) of the present invention can be further mixed with another epoxy resin (A-2). As this epoxy resin, a well-known thing can be used and it does not restrict | limit in particular. For example, novolak type, bisphenol type, biphenyl type, phenol aralkyl type, dicyclopentadiene type, naphthalene type, amino group-containing type and the like can be mentioned. Among these, a phenol aralkyl type epoxy resin represented by the following formula (5) is preferable. The compounding amount of the epoxy resin (A-2) is (A-1) / (A-2) = 100/1 to 100/30, preferably 100/2 to 100 with respect to the silicone-modified epoxy resin (A-1). It is good to mix | blend in the quantity used as / 15 (weight ratio).

(Wherein k is an integer of 1 or 2)

(B) Curing Agent (B) The curing agent is a curing agent for epoxy resin, and any known one can be used without particular limitation. Specific examples include phenolic resin-based curing agents, amine-based curing agents, acid anhydride-based curing agents, and the like, and among these, phenolic resin-based curing agents are preferably used.

  As the phenol resin curing agent, it is preferable to use a phenol resin having at least two phenolic hydroxyl groups in one molecule. Specific examples of such curing agents include novolak-type phenol resins such as phenol novolak resins and cresol novolak resins, paraxylylene-modified novolak resins, metaxylylene-modified novolak resins, orthoxylylene-modified novolak resins, bisphenols such as bisphenol A and bisphenol F. Type resin, biphenyl type phenol resin, resol type phenol resin, phenol aralkyl resin, biphenyl skeleton-containing aralkyl type phenol resin, triphenol alkane type resin and polymers thereof, naphthalene ring-containing phenol resin, dicyclopentadiene modified phenol Resins, alicyclic phenol resins, heterocyclic phenol resins and the like are exemplified, and these can be used alone or in combination of two or more.

  The phenol resin-based curing agent preferably has a softening point of 60 to 150 ° C, particularly 70 to 130 ° C. Moreover, as a hydroxyl equivalent, the thing of 90-250 is preferable. Moreover, it is preferable to use the phenol resin whose sodium and potassium which remain | survived in the refinement | purification process are 10 ppm or less as a phenol resin type hardening | curing agent. When a semiconductor device is sealed using a material exceeding 10 ppm and the semiconductor device is left standing for a long time under high temperature and high humidity, deterioration of moisture resistance may be promoted.

  The compounding amount of the curing agent is not particularly limited as long as it is an effective amount for curing the epoxy resin. Preferably, the reactive functional group (included in the curing agent with respect to 1 mol of the epoxy group contained in the epoxy resin). For example, it is preferable that the molar ratio with a phenolic hydroxyl group is 0.4 to 2.0, particularly 0.6 to 1.8.

(C) The organopolysiloxane (C) component is an organopolysiloxane having a linear diorganopolysiloxane unit (hereinafter referred to as siloxane unit (a)) represented by the following formula (2).

In the formula, R ² and R ³ are each independently a group selected from a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, a cyclohexyl group, a vinyl group, a phenyl group and an allyl group, preferably a methyl group and a phenyl group. It is. m is an integer of 5 to 70, preferably 8 to 60, and more preferably 10 to 50. If m is less than the lower limit, the cured product is poor in flexibility (crack resistance) and may cause warping of the apparatus. On the other hand, if m exceeds the upper limit, the viscosity of the organopolysiloxane increases, so that there is a tendency not to melt at the time of producing the composition.

  At least one siloxane unit (a) may be present in the organopolysiloxane (C), but generally 20 to 60% by weight, particularly 30 to 50% by weight in the organopolysiloxane (C). It is preferable that it exists in the ratio. If the content of the siloxane unit (a) is less than the lower limit value, it is not preferable because the effect of lowering elasticity does not work, and if it exceeds the upper limit value, it cannot be solidified and is difficult to handle.

The component (C) of the present invention further has a trifunctional siloxane unit (hereinafter referred to as siloxane unit (b)) represented by the following formula (6).

In the formula, R ⁴ represents a substituted or unsubstituted aryl or alkaryl group having 6 to 12 carbon atoms. For example, phenyl group, tolyl group, xylyl group, ethylphenyl group, chlorophenyl group, bromophenyl group, cyanophenyl group , 4-methylphenyl group, 2,4-diethylphenyl group, and the like. In the present invention, R ⁴ is preferably a phenyl group.

  At least one siloxane unit (b) may be present in the organopolysiloxane (C), but generally 30 to 80% by weight, particularly 40 to 60% by weight in the organopolysiloxane (C). Is preferably present. If the content of the siloxane unit (b) is less than the lower limit, solids cannot be formed, which is not preferable. If the content exceeds the upper limit, the elasticity cannot be reduced.

（ｘは１〜３の整数である。） The component (C) of the present invention may be an organopolysiloxane in which at least one molecular terminal is blocked with a siloxane unit (c) represented by the following formula (7).

(X is an integer of 1 to 3)

In said formula (7), R < ² > is group chosen from a hydroxyl group, a C1-C3 alkyl group, a cyclohexyl group, a vinyl group, a phenyl group, and an allyl group, Preferably they are a methyl group and a phenyl group. R ⁵ is an alkenyl group having 2 to 8 carbon atoms or a hydroxyl group, and examples thereof include vinyl, allyl, propenyl, butenyl, hexenyl and the like. The siloxane unit (c) is preferably present in the organopolysiloxane (C) in a proportion of 1 to 10% by weight, preferably 2 to 9% by weight. The siloxane unit (c) gives a crosslinking point to the organopolysiloxane (C), and the crosslinking density of a cured product obtained by curing the epoxy resin composition of the present invention can be adjusted.

In addition to the siloxane units (a) to (c), the component (C) is a D unit (R ₂ SiO ₁ ) in which m is outside the range of 5 to 50 (where R is a hydroxyl group, a methyl group) , An ethyl group, a propyl group, a cyclohexyl group, a phenyl group, a vinyl group, or an allyl group).

The organopolysiloxane of component (C) can be represented by the following average composition formula.

In the above formula, R ^{2 to} R ⁵ , R, m, and x are as described above. a is 0.01 to 0.2, preferably 0.02 to 0.15, b is 0.6 to 0.95, preferably 0.7 to 0.9, c is 0 to 0.3, preferably 0 to 0.2 and d is a number from 0 to 0.2, preferably 0 to 0.1, provided that the sum is 1.

  (C) It is preferable that the polystyrene conversion weight average molecular weights by gel permeation chromatography (GPC) of a component are 3,000-1,000,000, More preferably, it is 10,000-100,000. Within this range, the polymer is solid or semi-solid and is suitable from the viewpoint of workability and curability.

  The component (C) can be synthesized by combining the compounds used as raw materials for the above units in the resulting polymer so as to have a required molar ratio, for example, hydrolysis and condensation in the presence of an acid. . For example, a copolymer (C) having a bifunctional silane such as chloro-terminated dichloropolysiloxane having a degree of polymerization of 5 to 50 in an organic solvent such as toluene, phenyltrichlorosilane, and, if necessary, methylphenyldichlorosilane. ) At a molar ratio corresponding to. An organopolysiloxane (C) can be produced by adding this solution to toluene in which water is sufficiently dispersed and performing cohydrolysis.

（ここで、ｍ＝３〜４８の整数（平均値）、ｎ＝０〜４８の整数（平均値）、かつｍ＋nが３〜４８（平均値）） Here, the following can be mentioned as a raw material of a siloxane unit (a).

(Here, an integer (average value) of m = 3 to 48, an integer (average value) of n = 0 to 48, and m + n of 3 to 48 (average value))

Examples of the raw material for the R ⁴ SiO _3/2 unit (siloxane unit (b)) include chlorosilanes such as PhSiCl ₃ , tolyltrichlorosilane, and ethylphenyltrichlorosilane, and alkoxysilanes such as methoxysilanes corresponding to these chlorosilanes. Examples can be given.

As raw materials for R ² _3-x R ⁵ _x SiO _1/2 unit (siloxane unit (c)) and D unit (R ₂ SiO ₁ ), Me ₂ ViSiCl, Ph ₂ ViSiCl, PhVi ₂ SiCl, and MePhSiCl _{2 are used.} And chlorosilanes such as MeViSiCl ₂ and PhViSiCl ₂ , and alkoxysilanes such as methoxysilane corresponding to each of these chlorosilanes. Here, Me represents a methyl group, Ph represents a phenyl group, and Vi represents a vinyl group.

  These raw materials can be combined in a predetermined molar ratio and obtained, for example, by the following reaction. 100 parts by mass of phenylmethyldichlorosilane, 2100 parts by mass of phenyltrichlorosilane, 2400 parts by mass of chlordimethylsilicone oil having 21 Si atoms, and 3000 parts by mass of toluene are added and mixed, and the mixed silane is dropped into 11000 parts by mass of water. Cohydrolyze at 30-50 ° C. for 1 hour. Thereafter, after aging at 50 ° C. for 1 hour, water is added for washing, followed by azeotropic dehydration, filtration, and vacuum stripping.

When manufacturing by the said cohydrolysis and condensation, the siloxane unit which has a silanol group may be contained. The organopolysiloxane of component (C) usually contains 0 to 10 mol%, preferably 0 to 5 mol%, of the mole number of silanol group-containing siloxane units relative to the total number of moles of all siloxane units. Is preferred. Examples of the silanol group-containing siloxane units include R (HO) SiO units, R (HO) ₂ SiO _1/2 units, and R ₂ (HO) SiO _1/2 units (R is not a hydroxyl group).

(C) The compounding quantity of a component becomes like this. Preferably it is 3-50 mass parts with respect to a total of 100 mass parts of (A) component and (B) component, More preferably, it is 6-20 mass parts. If the amount added is small, the adhesion to the metal substrate is small and the elasticity cannot be reduced. When the addition amount is large, the viscosity of the composition increases, which may hinder molding.

(D) Inorganic filler As an inorganic filler, what is normally mix | blended with an epoxy resin composition can be used. Examples thereof include silica such as spherical fused silica, crushed fused silica, crystalline silica, alumina, silicon nitride, aluminum nitride, boron nitride, titanium oxide, magnesium oxide, aluminum hydroxide, glass fiber, and the like. Among these, at least one selected from the group consisting of silica, alumina, magnesium oxide, aluminum hydroxide, and titanium oxide is preferable, and silica, particularly spherical fused silica is preferable. The average particle size of the inorganic filler is 1 to 75 μm, preferably 5 to 53 μm, and the particle size exceeding 75 μm measured by the wet sieving method is 0.2% by mass or less. More desirable. In the present invention, the average particle diameter can be obtained by, for example, particle size distribution measurement by a laser light diffraction method or the like, and can be obtained as a weight average value (or median diameter) or the like.

The blending amount of the inorganic filler is 300 to 1,100 parts by mass, preferably 500 to 1,100 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B). If it is less than 300 mass parts, the ratio of resin is high and sufficient reflow crack resistance and a linear expansion coefficient may not be obtained. On the other hand, if the amount exceeds 1,100 parts by mass, the viscosity becomes high and there is a possibility that molding cannot be performed.

(E) Curing accelerator The curing accelerator is used to accelerate the curing reaction between the epoxy resin and the curing agent, and is not particularly limited, and conventionally known ones can be used. Examples of the organic phosphorus compound include triphenylphosphine, tributylphosphine, tridecylphosphine, triphenylphosphine / triphenylborane, tetraphenylphosphonium / tetraphenylborate, and dimethyl. Examples include tetraphenyldiphosphine. Examples of amine compounds include benzyldimethylamine (BDMA), dimethylaminomethylphenol (DMP-10), tris (dimethylaminomethyl) phenol (DMP-30), 1,8-diazabicyclo (5,4,0) undecene-7. (DBU) and the like. Examples of the imidazole compound include 2-methyl-4-ethylimidazole (2E4MZ), 2-phenylimidazole (2PZ), 2-methylimidazole (2MZ), 1-benzyl-2-phenylimidazole (1B2PZ), and the like. These curing accelerators may be used alone or in combination of two or more.

  The compounding quantity of a hardening accelerator is 0.01-10 mass parts with respect to a total of 100 mass parts of (A) component and (B) component, Preferably it is 0.1-6 mass parts. Within the said range, sclerosis | hardenability is favorable and the storage stability of a composition is also good.

(F) Silane coupling agent A silane coupling agent is mix | blended in order to strengthen the bond strength of an epoxy resin and an inorganic filler. Examples of such a coupling agent include epoxy functions such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Functional alkoxysilanes such as N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and γ-mercapto It is preferable to use a mercapto functional alkoxysilane such as propyltrimethoxysilane. In addition, about the compounding quantity of a coupling agent, it does not restrict | limit in particular. The compounding quantity of a silane coupling agent is 0.1-2.0 mass parts with respect to a total of 100 mass parts of (A) component and (B) component, Preferably it is 0.5-1.5 mass parts.

Other Additives Various additives can be further blended in the epoxy resin composition of the present invention as necessary. For example, whisker, silicone powder, thermoplastic resin, thermoplastic elastomer, organic synthetic rubber and other additives, fatty acid esters and glyceric acid to improve the properties of ionic impurity traps and resins that can cause electrical failure An internal mold release agent such as an ester, a phenol-based, phosphorus-based, or sulfur-based antioxidant can be added and blended within a range that does not impair the effects of the present invention.

  As a method for producing the epoxy resin composition of the present invention, a silicone-modified epoxy resin, a curing agent, an organopolysiloxane, an inorganic filler, a curing accelerator, a silane coupling agent, and other additives are blended at a predetermined composition ratio. Then, after mixing it sufficiently uniformly with a mixer or the like, it is melt mixed with a hot roll, kneader, extruder, etc., then cooled and solidified, and pulverized to an appropriate size to obtain a molding material for the epoxy resin composition be able to.

The most common molding method for the epoxy resin composition includes a transfer molding method and a compression molding method. In the transfer molding method, it is preferable to use a transfer molding machine at a molding pressure of 5 to 20 N / mm ² and 120 to 190 ° C. for 30 to 500 seconds, particularly 150 to 185 ° C. for 30 to 180 seconds. In the compression molding method, a compression molding machine is used, and the molding temperature is preferably 120 to 190 ° C. for 30 to 600 seconds, particularly 130 to 160 ° C. for 120 to 300 seconds. Further, in any molding method, post-curing may be performed at 150 to 185 ° C. for 2 to 20 hours.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated in detail, this invention is not restrict | limited to the following Example.

[Synthesis Example 1]
(A-1) Synthesis of Silicone Modified Epoxy Resin 37 g of the epoxy compound of the following formula (8) and 17 g of the organopolysiloxane of the following formula (9) were mixed (SiH / SiVi = 0.5 mol%), and the platinum concentration was 0.00. 5% 2-ethylhexanol-modified chloroplatinic acid solution (0.15 g) was added, and the mixture was heated and stirred at 110 ° C. for 3 hours to obtain a silicone-modified epoxy resin (A-1) represented by the following formula (10) (siloxane content). 15 wt%, epoxy equivalent 299).

（ｎ＝８）

（ｎ＝８）

(N = 8)

(N = 8)

[Synthesis Example 2]
(C) Synthesis of organopolysiloxane 100 parts by weight of phenylmethyldichlorosilane, 2100 parts by weight of phenyltrichlorosilane, 2400 parts by weight of chlorodimethylsilicone oil having 21 Si atoms, 3000 parts by weight of toluene, and 11000 parts by weight of water The silane mixed therein is dropped and cohydrolyzed at 30 to 50 ° C. for 1 hour. Then, after aging at 50 ° C. for 1 hour, water is added for washing, and then azeotropic dehydration, filtration, and vacuum stripping are performed, and the melt viscosity at 150 ° C. is 5 Pa.s, colorless and transparent. The indicated organopolysiloxane (C) was obtained.
(Weight average molecular weight 45,000)

  The raw materials used in Examples and Comparative Examples are shown below.

（ｋ＝１または２）
(A-2) Epoxy resin (NC-3000: Nippon Kayaku Co., Ltd. trade name, epoxy equivalent 273)

(K = 1 or 2)

(B) Curing agent phenolic resin (MEH-7851SS Meiwa Kasei Co., Ltd. trade name, hydroxyl group equivalent 203)

(D) Inorganic filler fused spherical silica (MSR-4500TN: trade name, manufactured by Tatsumori Co., Ltd., average particle diameter of 45 microns)

(E) Curing accelerator triphenylphosphine (made by Hokuko Chemical Co., Ltd.)

(F) Silane coupling agent γ-mercaptopropyltrimethoxysilane (KBM-803: trade name, manufactured by Shin-Etsu Chemical Co., Ltd.)

[Examples 1-5, Comparative Examples 1-5]
In the formulation shown in Table 1, (A-1) silicone-modified epoxy resin, (A-2) epoxy resin, (B) curing agent, (C) organopolysiloxane, (D) inorganic filler, (E) curing acceleration An agent and (F) a silane coupling agent were blended, manufactured by roll mixing, cooled and pulverized to obtain an epoxy resin composition.

  The following properties were measured for these compositions. The results are shown in Table 1.

Spiral flow value was measured under the conditions of 175 ° C., 6.9 N / mm ² , and molding time of 120 seconds using a mold conforming to the EMMI standard.

Bending strength and flexural modulus Using a mold conforming to the EMMI standard, molding was performed under the conditions of 175 ° C., 6.9 N / mm ² , molding time of 120 seconds, and then secondarily cured at 180 ° C. for 4 hours. The bending strength and the flexural modulus were measured according to JIS K6911 with an autograph measuring device AGS-50 (manufactured by Shimadzu Corporation).

A QFP package (Pd frame) having a crack resistance thickness of 1.4 mm was sealed under conditions of 175 ° C., 6.9 N / mm ² and a molding time of 120 seconds, and obtained after secondary curing at 180 ° C. for 4 hours. The cured product was stored in an environment of 85 ° C. and 85% for 168 hours, passed through an IR reflow once at a peak temperature of 260 ° C., and observed with an ultrasonic flaw detector to confirm the presence or absence of cracks (n = 6).

A disk with a diameter of 50Φ and a thickness of 3mm was molded under conditions of a water absorption of 175 ° C, 6.9N / mm ² , and a molding time of 120 seconds. After secondary curing at 180 ° C for 4 hours, the environment was 85 ° C and humidity was 85%. Under storage for 1000 hours, the amount of water absorption was observed.

A MAP type package (Pd frame) having a warpage amount of 50 × 50 mm was molded under the conditions of 175 ° C., 6.9 N / mm ² and a molding time of 120 seconds, and the warpage amount was observed.

As shown in Table 1, the cured product of the resin composition consisting only of an epoxy resin not containing a siloxane unit has a high elastic modulus, resulting in cracks when exposed to high temperature and high humidity for a long time (Comparative Example). 1-4). On the other hand, the cured product made of the composition containing the silicone-modified epoxy resin of the present invention has a low elastic modulus and does not crack even when exposed to high temperature and high humidity for a long time, and is excellent in moldability. Moreover, it is excellent in low hygroscopicity and low stress property by highly filling the inorganic filler.

  The epoxy resin composition of the present invention is excellent in moldability and heat resistance, and can provide a cured product having low elasticity, low moisture absorption and low stress, and therefore provides a sealed body excellent in reflow resistance. In particular, it can be advantageously used as a sealing resin composition for MAP type package molding.

Claims (12)

An epoxy resin composition comprising the following components as essential components.
(A) Silicone-modified epoxy resin containing a siloxane unit represented by the following formula (1)

(R ¹ is each independently a monovalent hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 5 to 100)
(B) Curing agent
(C) Organopolysiloxane having a linear diorganopolysiloxane unit represented by the following formula (2): 3 to 50 parts by mass with respect to 100 parts by mass of the total amount of component (A) and component (B)

(R ² and R ³ are each independently a group selected from a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, a cyclohexyl group, a vinyl group, a phenyl group, and an allyl group, and m is an integer of 5 to 70. )
(E) Curing accelerator 0.01 to 10 parts by mass relative to 100 parts by mass of the total amount of component (A) and component (B) (A) component is an aromatic polymer represented by the following formula (3);

(However, R ⁶ is a glycidyl group represented by the following formula:

X is a hydrogen atom or a bromine atom, p is an integer of 0 to 50, and q is an integer of 0 to 5)
Organohydrogenpolysiloxane represented by the following formula (4)

(R ¹ is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 5 to 100).
2. The epoxy resin composition according to claim 1, comprising a silicone-modified epoxy resin (A-1) which is an addition reaction product of Component (A) is a phenyl aralkyl type epoxy resin (A-2) represented by the following formula (5)

(K is an integer of 1 or 2)
The epoxy resin composition according to claim 2, comprising: (C) The component is a linear diorganopolysiloxane unit (siloxane unit (a)) represented by the following formula (2), and

(In the formula, R ² and R ³ are each independently a group selected from a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, a cyclohexyl group, a vinyl group, a phenyl group, and an allyl group; Is an integer)
Siloxane unit (b) represented by the following formula (6)

(Wherein R ⁴ represents a substituted or unsubstituted aryl group or alkaryl group having 6 to 12 carbon atoms)
The epoxy resin composition according to any one of claims 1 to 3, wherein the epoxy resin composition is an organopolysiloxane. The epoxy resin according to any one of claims 1 to 4, wherein the component (C) is an organopolysiloxane having at least one molecular end blocked with a siloxane unit (c) represented by the following formula (7). Composition.

(Wherein R ² is the same as above, R ⁵ is an alkenyl group or hydroxyl group having 2 to 8 carbon atoms, and x is an integer of 1 to 3) The epoxy resin composition according to any one of claims 1 to 5, wherein the component (B) is a phenol resin curing agent. The epoxy resin according to claim 6, wherein the blending amount of the component (B) is such that the phenol group in the component (B) is 0.4 to 2.0 mol with respect to 1 mol of the epoxy group in the component (A). Composition. (D) The inorganic filler is further included in an amount of 300 to 1,100 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B). Epoxy resin composition. The epoxy resin composition according to claim 8, wherein the component (D) is at least one selected from the group consisting of silica, alumina, magnesium oxide, aluminum hydroxide, and titanium oxide. (F) Any one of Claims 1-9 which further contain a silane coupling agent in the quantity used as 0.1-2.0 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component. The epoxy resin composition according to item.   The epoxy resin hardened | cured material formed by hardening | curing the epoxy resin composition of any one of Claims 1-10. A semiconductor device having the cured epoxy resin according to claim 11.