JP2007224125A - Epoxy resin composition and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel epoxy resin composition that gives a cured product excellent in thermal shock resistance and moisture resistance reliability and is suitably used as one for sealing a semiconductor that affords a semiconductor device assuring high reliability even when surface-mounted on a circuit board, and a semiconductor device sealed with a cured product of the resin composition. <P>SOLUTION: The epoxy resin composition comprises as essential ingredients (A) an epoxy resin, (B) a curing agent, (C) a silicone-modified phenolic resin represented by average compositional formula (1) (wherein R<SP>1</SP>is a hydrogen atom, a 1-4C alkyl group or a 1-6C organoxy group; X is a bivalent organic group; and Z is a bivalent organic group having an organosiloxane structure). The epoxy resin composition gives a cured product excellent in moldability as well as in thermal shock resistance and moisture resistance reliability. The semiconductor device sealed with the cured product of the epoxy resin composition exhibits excellent thermal shock resistance and moisture resistance reliability. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an epoxy resin composition suitably used for sealing a semiconductor device and a semiconductor device sealed with a cured product of the epoxy resin composition.

  Conventionally, epoxy resins have been widely used as various molding materials, powder coating materials, electrical insulating materials and the like as resin compositions obtained by adding a curing agent and an inorganic filler to the resin, and more recently, diodes, transistors, ICs, It is used in large quantities as a resin sealing material for resin-encapsulated semiconductor devices such as LSI and VLSI. This utilizes the property that epoxy resins are generally superior in moldability, adhesiveness, electrical properties, mechanical properties, moisture resistance, and the like as compared to other thermosetting resins.

  These semiconductor devices have recently been increasingly integrated and have larger chip dimensions. On the other hand, package dimensions have become smaller and thinner in response to demands for smaller and lighter electronic devices. Is progressing. Further, in the method of attaching a semiconductor component to a circuit board, surface mounting of the semiconductor component is performed in order to increase the density of components on the substrate and to reduce the thickness of the substrate.

  However, when a semiconductor substrate is surface-mounted on a circuit board, a general method is to immerse the entire semiconductor device in a solder bath or to pass a temperature zone where the solder melts. There has been a problem that cracks occur in the resin layer, and peeling occurs at the interface between the lead frame or chip and the sealing resin. Such cracks and delamination become even more prominent if the sealing resin layer of the semiconductor device absorbs moisture before the thermal shock of surface mounting, but in the actual work process, the moisture absorption of the sealing resin layer is For this reason, the reliability of the semiconductor device sealed with the epoxy resin after mounting may be greatly impaired.

  In order to solve these problems, generally, by adding a polysiloxane compound having plasticity to an epoxy resin, the elastic modulus of the molding material is lowered, and the internal stress is reduced. For example, a method of adding an organopolysiloxane to a curable epoxy resin (Patent Document 1: Japanese Patent Application Laid-Open No. 56-129246), a curable epoxy resin, a polyether organosiloxane, an amino-modified organopolysiloxane and an epoxy-modified organopoly A method using a reaction product with siloxane as a main agent (Patent Document 2: JP-A-4-41520), an epoxy resin, a curing agent, a mixture of polyetherorganosiloxane and polysiloxane containing both end epoxy groups, and aminosilane were reacted. Method using modified organopolysiloxane (Patent Document 3: JP-A-2-151621), adding epoxy group-containing polyether-modified polysiloxane, both terminal amino group-containing polysiloxane and / or both terminal mercapto-containing polysiloxane (Patent Document 4 JP-A-2-170819 publication), etc. have been proposed.

  However, among the above-mentioned sealing materials, in a system in which no polyether-modified polysiloxane is added, the compatibility between the matrix resin and the polysiloxane is poor, and the polysiloxane gradually bleeds out. There is a limit, a significant reduction in stress cannot be expected, and the mechanical strength is greatly reduced. In addition, the system using the polyether-modified polysiloxane is excellent in that the polysiloxane can be finely dispersed in the matrix resin. It is difficult to completely satisfy the demand for sealing high-density semiconductor devices.

  Thus, development of a high-quality epoxy resin composition for a semiconductor device that can provide a highly reliable semiconductor device even when surface-mounted on a circuit board is desired.

As prior art documents related to the present invention, there are the following.
JP-A-56-129246 JP-A-4-41520 Japanese Patent Laid-Open No. 2-151621 Japanese Patent Laid-Open No. 2-170819

  The present invention has been made in view of the above circumstances, can be a cured product having excellent thermal shock resistance and moisture resistance reliability, and is suitable for semiconductor encapsulation that can provide a highly reliable semiconductor device even when surface-mounted on a circuit board. An object of the present invention is to provide a novel epoxy resin composition used in the invention and a semiconductor device encapsulated with a cured product of the resin composition.

  As a result of intensive studies to achieve the above object, the present inventors have found that an epoxy resin composition using a silicone-modified phenol resin represented by the following average composition formula (1) as a low stress agent is excellent in moldability. The present inventors have found that a cured product having excellent thermal shock resistance and moisture resistance reliability can be obtained. That is, the present invention provides (A) an epoxy resin, (B) a curing agent, and (C) a silicone-modified phenol resin represented by the following average composition formula (1):

（式中、Ｒ¹は水素原子又は炭素数１〜４のアルキル基又は炭素数１〜６のオルガノキシ基であり、Ｘは二価の有機基、Ｚはオルガノシロキサン構造を有する二価の有機基である。）
及び好ましくは（Ｄ）無機質充填剤を必須成分とするエポキシ樹脂組成物が、成形性に優れるとともに、耐熱衝撃性、耐湿信頼性に優れる硬化物となり得、また該エポキシ樹脂組成物の硬化物で封止された半導体装置が、耐熱衝撃性、特には耐熱衝撃クラック性、耐湿信頼性に優れるものであることを見出し、本発明をなすに至ったものである。

Wherein R ¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an organoxy group having 1 to 6 carbon atoms, X is a divalent organic group, and Z is a divalent organic group having an organosiloxane structure. .)
And preferably (D) an epoxy resin composition comprising an inorganic filler as an essential component is excellent in moldability, and can be a cured product excellent in thermal shock resistance and moisture resistance reliability, and is also a cured product of the epoxy resin composition. It has been found that the sealed semiconductor device is excellent in thermal shock resistance, in particular, thermal shock crack resistance and moisture resistance reliability, and has led to the present invention.

  The epoxy resin composition of the present invention is excellent in moldability and can provide a cured product excellent in thermal shock resistance and moisture resistance reliability. Moreover, the semiconductor device sealed with the cured product of the epoxy resin composition of the present invention is excellent in thermal shock resistance and moisture resistance reliability, and is particularly useful industrially.

Hereinafter, the present invention will be described in more detail.
The (A) epoxy resin which comprises the epoxy resin composition of this invention is not specifically limited. Common epoxy resins include novolak type epoxy resin, cresol novolac type epoxy resin, triphenolalkane type epoxy resin, aralkyl type epoxy resin, aralkyl type epoxy resin containing biphenyl skeleton, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin , Heterocyclic epoxy resins, naphthalene ring-containing epoxy resins, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, stilbene type epoxy resins and the like, and one or more of these can be used in combination.

  The epoxy resin has a hydrolyzable chlorine content of 1000 ppm or less, particularly 500 ppm or less, and preferably contains sodium and potassium in a content of 10 ppm or less. When hydrolyzable chlorine exceeds 1000 ppm and sodium or potassium exceeds 10 ppm, the moisture resistance may deteriorate if the semiconductor device is left under high temperature and high humidity for a long time.

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

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

  Here, the blending amount of (A) the epoxy resin and (B) the curing agent is not particularly limited. However, when a phenol resin is used as the curing agent, the curing agent and the later-described are used with respect to 1 mol of the epoxy group contained in the epoxy resin. (C) It is preferable that the molar ratio of the phenolic hydroxyl group contained in the silicone-modified phenolic resin is 0.5 to 1.5, particularly 0.8 to 1.2. When the molar ratio is 0.5 or less and 1.5 or more, it is not preferable because the crosslinking density is lowered and the reliability may be lowered.

  The epoxy resin composition of the present invention uses a silicone-modified phenol resin represented by the following average composition formula (1) as the component (C).

（式中、Ｒ¹は水素原子又は炭素数１〜４のアルキル基又は炭素数１〜６のオルガノキシ基であり、Ｘは二価の有機基、Ｚはオルガノシロキサン構造を有する二価の有機基である。）

Wherein R ¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an organoxy group having 1 to 6 carbon atoms, X is a divalent organic group, and Z is a divalent organic group having an organosiloxane structure. .)

Here, R ¹ in the above formula is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group. Or an alkoxy group having 1 to 6 carbon atoms such as a methoxy group or an ethoxy group or a phenoxy group.

  X is a divalent organic group, an alkylene group in which an oxygen atom may be interposed, an arylene group, a group in which an alkylene group in which an oxygen atom may be interposed and an arylene group are bonded, or a part of these hydrogen atoms Or the group etc. which all were substituted by the halogen atom, the hydroxyl group, etc. are mentioned, A C1-C15, especially 2-10 thing is preferable. For example, the group shown below can be mentioned.

As the divalent organic group having an organosiloxane structure of Z represented by the general formula (1), the hydrogen atom of the SiH group is added to the Y double terminal bond of the phenol resin in the organohydrogensiloxane. Thus, the hydrogen atom of the SiH group is an organohydrogensiloxane residue in a desorbed state, and is preferably a divalent group represented by the following general formula.

（但し、Ｒは同種又は異種の脂肪族不飽和基を含有しない置換又は非置換の一価炭化水素基であり、ｎは０≦ｎ≦４００を満たす整数である。）

(However, R is a substituted or unsubstituted monovalent hydrocarbon group that does not contain the same or different aliphatic unsaturated groups, and n is an integer that satisfies 0 ≦ n ≦ 400.)

Here, R is a substituted or unsubstituted monovalent hydrocarbon group not containing an aliphatic unsaturated group having 1 to 15 carbon atoms, particularly 1 to 10 carbon atoms, and specifically includes a methyl group, an ethyl group, and a propyl group. , Isopropyl group, butyl group, isobutyl group, tert-butyl group, hexyl group, cyclohexyl group, octyl group, decyl group and other alkyl groups, phenyl group, xylyl group, tolyl group and other aryl groups, benzyl group, phenylethyl group , Aralkyl groups such as phenylpropyl groups, etc., and halogens such as chloromethyl groups, bromoethyl groups, trifluoropropyl groups, etc. in which some or all of the hydrogen atoms of these hydrocarbon groups are replaced by halogen atoms such as chlorine, fluorine, bromine, etc. Examples thereof include substituted monovalent hydrocarbon groups.
Note that n is an integer satisfying 0 to 400, preferably 5 to 100.

  Therefore, the silicone-modified phenol resin whose Z is the formula (1a) is represented by the following average composition formula (1 ′).

（式中、Ｒ¹、Ｒ、Ｘ、ｎは上記の通りである。）

(Wherein R ¹ , R, X, and n are as described above.)

  Specific examples of such silicone-modified phenolic resins include the following.

  The method for producing a silicone-modified phenolic resin according to the present invention comprises the following average composition formula (2):

（式中、Ｒ¹は上記したと同様の基であり、Ｙは末端に二重結合を有する有機基である。）で表されるフェノール樹脂のＹの末端二重結合と、下記平均組成式（３）
Ｈ_aＲ² _bＳｉＯ_(4-a-b)/2 （３）
（式中、Ｒ²は脂肪族不飽和基を含有しない置換もしくは非置換の一価炭化水素基、水酸基又はアルコキシ基を示し、ａ、ｂは０．０１≦ａ≦１、１≦ｂ≦３、１．０１≦ａ＋ｂ＜４を満足する正数である。また１分子中の珪素原子の数は２〜４０２、特に好ましくは２０〜１００の整数である。）で示される有機珪素化合物のＳｉＨ基とを付加反応させてなるものである。

(Wherein R ¹ is the same group as described above, and Y is an organic group having a double bond at the terminal), and the following average composition formula: (3)
H _a R ² _b SiO _{(4-ab) / 2} (3)
(Wherein R ² represents a substituted or unsubstituted monovalent hydrocarbon group, hydroxyl group or alkoxy group not containing an aliphatic unsaturated group, and a and b are 0.01 ≦ a ≦ 1, 1 ≦ b ≦ 3, respectively. 1.01 ≦ a + b <4, and the number of silicon atoms in one molecule is 2 to 402, particularly preferably an integer of 20 to 100). It is formed by addition reaction with a group.

In the phenol resin represented by the average composition formula (2), R ¹ can be exemplified by the same ones as described above. Y is an organic group having a double bond at the terminal, and is not particularly limited as long as it has a double bond at the terminal. Examples of the organic group having a double bond at the terminal include those containing an alkenyl group such as a vinyl group and an allyl group at the terminal, and an alkenyloxy group such as an allyloxy group. Examples thereof include those having a double bond at the end, and examples thereof include the following groups.

これらの中でも、特にアリル基が好ましい。

Among these, an allyl group is particularly preferable.

  Specific examples of the phenol resin represented by the average composition formula (2) include those represented by the following formulas (2-i) to (2-iii).

The organosilicon compound having an SiH group added to a phenol resin and containing an organic group having a double bond at the terminal is represented by the above average composition formula (3).
Here, examples of the substituted or unsubstituted monovalent hydrocarbon group not containing the aliphatic unsaturated group of R ² in the above formula (3) are the same as those of R described above. Examples of the valent hydrocarbon group include a chloropropyl group, a chloromethyl group, and a glycidylpropyl group. Examples of the unsubstituted monovalent hydrocarbon group include a methyl group, an ethyl group, a phenyl group, and a benzyl group. Furthermore, examples of the alkoxy group for R ² include a methoxy group and an ethoxy group. a and b are positive numbers satisfying 0.01 ≦ a ≦ 1, 1 ≦ b ≦ 3, 1.01 ≦ a + b <4, preferably 0.01 ≦ a ≦ 0.5, 1.5 ≦ b It is a positive number satisfying ≦ 2.5 and 1.51 ≦ a + b ≦ 3.0.

  Specific examples of the organosilicon compound represented by the average composition formula (3) include those represented by the following formulas (3-i) and (3-ii).

（式中、Ｒ³は、上述したＲと同様の脂肪族不飽和基を含有しない置換又は非置換の一価炭化水素基、水酸基、又はメトキシ基、エトキシ基等のアルコキシ基、ｐ、ｑ、ｒ、ｓ、ｔ、ｕ、ｖは２≦ｐ＋ｑ＋ｔ＋ｒ×ｕ、０≦ｓ＋ｔ＋ｕ×ｖ＋ｕ≦４００、ｘ、ｙは２≦ｙ、３≦ｘ＋ｙ≦８を満たす整数である。）

(In the formula, R ³ is a substituted or unsubstituted monovalent hydrocarbon group, hydroxyl group, or alkoxy group such as methoxy group and ethoxy group, which does not contain an aliphatic unsaturated group similar to R described above, p, q, r, s, t, u, and v are integers that satisfy 2 ≦ p + q + t + r × u, 0 ≦ s + t + u × v + u ≦ 400, and x and y satisfy 2 ≦ y and 3 ≦ x + y ≦ 8.

  In the present invention, the organosilicon compound represented by the average composition formula (3) is represented by the following general formula (3 ′) represented by p = q = 1 and t = u = 0 in (3-i). It is preferably a linear organopolysiloxane having both ends monohydroxylated.

  In the above formula, R is a substituted or unsubstituted monovalent hydrocarbon group that does not contain the same or different aliphatic unsaturated groups, examples of which are the same as those of R described above, and n is 0 ≦ n ≦ 400, Preferably, it is an integer of 5 ≦ n ≦ 100.

  Specific examples of such organopolysiloxanes include those represented by the following formula.

（式中、Ｍｅはメチル基、Ｐｈはフェニル基である。）

(In the formula, Me is a methyl group and Ph is a phenyl group.)

  Here, when the phenol resin and the organosilicon compound are subjected to an addition reaction, each of the phenol resin and the organosilicon compound may be used alone or in combination of two or more.

  In this addition reaction, the mixing ratio of the phenol resin and the organosilicon compound is the molar ratio of the terminal double bond of Y in the phenol resin to the hydrogen atom (SiH group) bonded to the silicon atom in the organosilicon compound ( The terminal double bond / SiH) is preferably added in an amount of 1.01 to 3.0 mol / mol, particularly 1.5 to 2.0 mol / mol.

  Moreover, as a method of addition reaction, it can carry out according to a conventionally well-known addition reaction method. That is, in the addition reaction, conventionally known addition reaction catalysts such as platinum black, chloroplatinum chloride, chloroplatinic acid, a reaction product of chloroplatinic acid and a monohydric alcohol, a complex of chloroplatinic acid and an olefin, platinum Platinum catalysts such as bisacetoacetate, palladium catalysts such as tetrakis (triphenylphosphine) palladium and dichlorobis (triphenylphosphine) palladium, rhodium catalysts such as chlorotris (triphenylphosphine) rhodium and tetrakis (triphenylphosphine) rhodium It is preferable to use a platinum group metal catalyst such as The addition amount of the addition reaction catalyst can be a catalyst amount, and the solution concentration is usually 20 to 60% by mass, and the catalyst concentration is 10 to 100 ppm in terms of platinum group metal with respect to the reaction product.

  The addition reaction is desirably performed in an organic solvent, and it is preferable to use an inert solvent such as benzene, toluene, or methyl isobutyl ketone as the organic solvent.

  Although the addition reaction conditions are not particularly limited, it is usually preferable to react at 60 to 120 ° C. for 30 minutes to 10 hours.

  The amount of addition of the silicone-modified phenolic resin as component (C) is 0.1 to 50 parts by weight, particularly 5 to 30 parts by weight, based on 100 parts by weight of the total amount of (A) epoxy resin and (B) curing agent. preferable. If the addition amount is less than 0.1 parts by mass, improvement in thermal shock resistance and crack resistance may not be obtained, and if it exceeds 50 parts by mass, the molding hardness may be lowered and molding may be difficult.

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

  The average particle size and shape of these inorganic fillers and the amount of the inorganic filler are not particularly limited, but in order to increase flame retardancy and thermal conductivity, in order to further reduce the linear expansion coefficient, an epoxy resin composition It is preferable to fill in as much as possible as long as the moldability is not impaired. In this case, spherical fused silica having an average particle size of 5 to 30 μm is particularly preferable as the average particle size and shape of the inorganic filler, and the filling amount of the inorganic filler is (A) an epoxy resin and (B) a curing agent. It is preferable to set it as 400-1200 mass parts with respect to 100 mass parts in total with 500-1000 mass parts especially.

  In the present invention, the average particle diameter can be determined, for example, as a weight average value (or median diameter) by a laser light diffraction method or the like.

  In order to increase the bond strength between the resin and the inorganic filler, the inorganic filler is preferably blended in advance with a surface treatment with a coupling agent such as a silane coupling agent or a titanate coupling agent. As such a coupling agent, epoxy silane such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N Silane cups such as aminosilanes such as -β (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and mercaptosilanes such as γ-mercaptosilane It is preferable to use a ring agent. Here, the blending amount of the coupling agent used for the surface treatment and the surface treatment method are not particularly limited.

  Moreover, in this invention, in order to accelerate | stimulate hardening reaction with an epoxy resin and a hardening | curing agent, it is preferable to use a hardening accelerator as (E) component. The curing accelerator is not particularly limited as long as it accelerates the curing reaction. For example, triphenylphosphine, tributylphosphine, tri (p-methylphenyl) phosphine, tri (nonylphenyl) phosphine, triphenylphosphine / triphenyl. Phosphorus compounds such as borane, tetraphenylphosphine and tetraphenylborate, tertiary amine compounds such as triethylamine, benzyldimethylamine, α-methylbenzyldimethylamine, 1,8-diazabicyclo (5,4,0) undecene-7 Imidazole compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and the like can be used.

  (E) Although the compounding quantity of a hardening accelerator is an effective amount, it is 0.1-5 mass parts with respect to 100 mass parts of total amounts of (A) epoxy resin and (B) hardening | curing agent, Especially 0.5-2. It is preferable to set it as a mass part.

  The epoxy resin composition of the present invention is a flame retardant, for example, a phosphoric acid ester, triphenyl phosphate, ammonium polyphosphate, a phosphorus compound such as red phosphorus, aluminum hydroxide, and the like within the range in which the objects and effects of the present invention can be expressed. Hydroxides such as magnesium hydroxide and inorganic compounds such as zinc borate, zinc stannate, and zinc molybdate can also be added.

  Various additives can be further blended in the epoxy resin composition of the present invention as necessary. For example, thermoplastic resins, thermoplastic elastomers, organic synthetic rubbers, silicone-based low stress agents, carnauba waxes, higher fatty acids, release agents composed of waxes such as synthetic waxes, colorants such as carbon black, halogen trapping agents, etc. These additives can be added and blended.

  In the epoxy resin composition of the present invention, an epoxy resin, a curing agent, a silicone-modified epoxy resin, if necessary, an inorganic filler, and other additives are blended at a predetermined composition ratio, and this is mixed sufficiently uniformly by a mixer or the like. Thereafter, it can be melt-mixed by a hot roll, a kneader, an extruder, etc., then cooled and solidified, and pulverized to an appropriate size to obtain a molding material.

  Moreover, the epoxy resin composition of this invention can be mixed using an organic solvent. An epoxy resin, a curing agent, an inorganic filler, and other additives are blended at a predetermined composition ratio, mixed uniformly using an organic solvent, the organic solvent is removed by distillation under reduced pressure, and then cooled and solidified. It can be crushed into a size to form a molding material. Furthermore, only an epoxy resin and a curing agent are used in the same manner using an organic solvent. After adding an inorganic filler and other additives to the mixture and mixing them sufficiently uniformly with a mixer, etc., a heat roll, a kneader, an extruder, etc. It is also possible to carry out a melt mixing process according to the above, then to cool and solidify, and pulverize to an appropriate size to obtain a molding material. It can also be used as a varnish. Examples of such an organic solvent include toluene, MEK, THF, acetone and the like.

  In addition, when mixing the composition sufficiently uniformly with a mixer or the like, it is preferable to perform surface treatment or the like in advance with a silane coupling agent or the like as a wetter in order to improve storage stability.

  Here, as the silane coupling agent, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, γ- Methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, N-β (aminoethyl) ) Γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminop Pyrtriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, bis (triethoxypropyl) tetrasulfide, γ-isocyanatopropyltriethoxysilane, etc. Is mentioned. Here, the amount of the silane coupling agent used for the surface treatment and the surface treatment method are not particularly limited.

  The epoxy resin composition of the present invention thus obtained can be effectively used for sealing various semiconductor devices. In this case, the most common method for sealing is a low-pressure transfer molding method. . The epoxy resin composition of the present invention is preferably molded at a temperature of 150 to 180 ° C. for 30 to 180 seconds, and post-cured at 150 to 180 ° C. for 2 to 16 hours.

  Synthesis Examples, Examples and Comparative Examples are shown below to describe the present invention more specifically. However, the present invention is not limited to the following examples.

[Synthesis Example 1] Synthesis of Compound A Into a 2 L four-necked flask equipped with a reflux condenser, a thermometer, a stirrer, and a dropping funnel, 150 g of toluene, an allyl group-containing phenol resin represented by the following formula (4) (phenol) 100 g of a functional hydroxyl group equivalent 164) was added, and azeotropic dehydration was performed for 2 hours in a nitrogen atmosphere. Thereafter, the system was cooled to 90 ° C., 1.00 g of a platinum chloride catalyst (toluene solution) was added, and a solution obtained by dissolving 221.3 g of an organosilicon compound represented by the following formula (5) in 332 g of toluene was taken over 2 hours. And dripped. The system was stirred for 6 hours while maintaining the temperature at 100 to 110 ° C., aged, and then cooled to room temperature. Thereafter, the solvent was distilled off under reduced pressure to obtain 315 g of the desired silicone-modified phenol resin (Compound A).

As a result of measuring ¹ H-NMR and IR after separating and purifying the obtained reaction product, ¹ H-NMR was -0.5-0.5, 1.8-2.6, 3.6-3. A peak was shown at 9,6.4-7.2, 8.0-8.2 ppm, and IR showed a peak derived from Si-Me in the vicinity of 1255 cm ⁻¹ . ²⁹ Si-NMR also showed a peak in the vicinity of 9.5 ppm. Thereby, it was found that the compound A represented by the following average composition formula (6) was obtained.

Silicone modified phenolic resin A

[Examples 1 to 3, Comparative Example 1]
The components shown in Table 1 were uniformly melt-mixed with two hot rolls, cooled and pulverized to obtain an epoxy resin composition for semiconductor encapsulation. With respect to these compositions, the following properties (I) to (VI) were measured. The results are shown in Table 2.

(I) Spiral Flow Value Using a mold conforming to the EMMI standard, measurement was performed under conditions of a temperature of 175 ° C., a molding pressure of 6.9 N / mm ² , and a molding time of 120 seconds.

(II) Gelation time The gelation time of the composition was measured on a hot plate at 175 ° C.

(III) Molding hardness According to JIS-K6911, the bar hardness is the hot hardness when a 10 × 4 × 100 mm rod is molded under conditions of a temperature of 175 ° C., a molding pressure of 6.9 N / mm ² , and a molding time of 90 seconds. Measured with a meter.

(IV) Moisture resistance A 6 × 6 mm silicon chip with aluminum wiring is bonded to a 14 pin-DIP frame (42 alloy), and the aluminum electrode on the chip surface and the lead frame are wire bonded with a 30 μmφ gold wire. After that, the epoxy resin composition was molded on this under the conditions of a temperature of 175 ° C., a molding pressure of 6.9 N / mm ² and a molding time of 120 seconds, and post-cured at 180 ° C. for 4 hours. Each of the 20 packages was left in a 140 ° C./85% RH atmosphere with a DC bias voltage of −5 V for 500 hours, and then the number of packages in which aluminum corrosion occurred was examined.

(V) High-temperature storage reliability A 6 × 6 mm silicon chip formed with aluminum wiring is bonded to a 14 pin-DIP frame (42 alloy), and the aluminum electrode on the chip surface and the lead frame are connected with a 30 μmφ gold wire. After wire bonding, the epoxy resin composition was molded on this under the conditions of a temperature of 175 ° C., a molding pressure of 6.9 N / mm ² and a molding time of 120 seconds, and post-cured at 180 ° C. for 4 hours. Each of the 20 packages was left in a 200 ° C. atmosphere for 500 hours, and then dissolved and opened with fuming nitric acid, and the gold wire tensile strength was measured. Those having a tensile strength of 70% or less of the initial value were regarded as defective, and the number of defects was examined.

(VI) Thermal shock crack resistance A 6 × 6 mm silicon chip with aluminum wiring formed is bonded to a 14 pin-DIP frame (42 alloy), and the aluminum electrode on the chip surface and the lead frame are attached with a 30 μmφ gold wire. After wire bonding, the epoxy resin composition was molded on this under the conditions of a temperature of 175 ° C., a molding pressure of 6.9 N / mm ² and a molding time of 120 seconds, and post-cured at 180 ° C. for 4 hours. Five of these packages were each subjected to 100 cycles of a thermal shock of 260 ° C. solder bath / 30 seconds and −196 ° C./60 seconds, and the defect rate (%) was examined assuming that a crack occurred.

(A) Epoxy resin o-cresol novolac type epoxy resin represented by the following formula: EOCN1020-55 (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 200)

(B) Phenol-based curing agent Phenol novolak resin represented by the following formula: DL-92 (trade name, manufactured by Meiwa Kasei Co., Ltd., phenolic hydroxyl group equivalent 110)

(C) Silicone-modified phenol resin: Compound of Synthesis Example 1 (Compound A)
(D) Inorganic filler: Spherical fused silica (manufactured by Tatsumori Co., Ltd., average particle size 20 μm)
(E) Curing catalyst: Triphenylphosphine (made by Hokuko Chemical Co., Ltd.)

Other additive release agent: Carnauba wax NP-1S (manufactured by Nikko Rica Co., Ltd.)
Carbon black: Denka Black (manufactured by Denki Kagaku Kogyo Co., Ltd.)
Silane coupling agent: γ-glycidoxypropyltrimethoxysilane, KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.)

  As is apparent from the results in Table 1, the epoxy resin composition of the present invention has excellent moldability, a cured product excellent in thermal shock resistance and moisture resistance reliability, and the cured epoxy resin composition of the present invention. A semiconductor device sealed with an object is excellent in thermal shock resistance, in particular, thermal shock crack resistance and moisture resistance reliability.

Claims (8)

(A) Epoxy resin (B) Curing agent (C) Silicone-modified phenolic resin represented by the following average composition formula (1)

Wherein R ¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an organoxy group having 1 to 6 carbon atoms, X is a divalent organic group, and Z is a divalent organic group having an organosiloxane structure. .)
An epoxy resin composition characterized by comprising an essential component.   The addition amount of (C) silicone-modified phenol resin is 0.1 to 50 parts by mass with respect to 100 parts by mass of the total amount of (A) epoxy resin and (B) curing agent. Epoxy resin composition.   (B) The epoxy resin composition according to claim 1 or 2, wherein the curing agent is a phenol resin.   (A) The molar ratio of the phenolic hydroxyl group contained in (B) the phenol resin curing agent and (C) the silicone-modified phenol resin relative to 1 mol of the epoxy group contained in the epoxy resin is 0.5 to 1. The epoxy resin composition according to claim 3, which is blended so as to be in the range of 5. 5. (C) Silicone modified phenolic resin is shown by the following average compositional formula (1 '), The epoxy resin composition of any one of Claims 1 thru | or 4 characterized by the above-mentioned.

(In the formula, R ¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms such as methoxy, ethoxy, or phenoxy, and R is a substituted or non-substituted group containing no aliphatic unsaturated group. A substituted monovalent hydrocarbon group, X is a divalent organic group, and n is an integer satisfying 0 ≦ n ≦ 400.   Furthermore, 400-1200 mass parts is mix | blended with the inorganic filler as (D) component with respect to 100 mass parts of total amounts of (A) epoxy resin and (B) hardening | curing agent, The 1 thru | or 5 characterized by the above-mentioned. The epoxy resin composition according to any one of the above.   Furthermore, 0.1-5 mass parts is mix | blended with respect to 100 mass parts of total amounts of (A) epoxy resin and (B) hardening | curing agent as a (E) component, The hardening accelerator is characterized by the above-mentioned. The epoxy resin composition of any one of thru | or 6.   The semiconductor device sealed with the hardened | cured material of the epoxy resin composition of any one of Claims 1 thru | or 7.