JP2006233149A - Resin composition for sealing low-dielectric film forming element and semiconductor apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a resin composition for semiconductor sealing, which provides a cured product having remarkably excellent adhesiveness to an element surface in sealing an element having a formed low-dielectric film and excellent reliability in a solder crack resistance test and a temperature cycle resistance test and to provide a semiconductor apparatus sealed by the cured product. <P>SOLUTION: The resin composition for semiconductor sealing is a material for sealing a low-dielectric film forming element and has ≤2,100 MPa storage elastic modulus of cured product at 150°C, ≤700 MPa storage elastic modulus of cured product at 260°C, ≤1.0×10<SP>-5</SP>/°C coefficient of linear expansion at -55°C to 50°C, ≤5.0×10<SP>-5</SP>/°C coefficient of linear expansion at 150°C to 200°C and ≤0.15% molding shrinkage percentage molded at 175°C. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention provides a cured product that is remarkably excellent in adhesion to an element surface when sealing an element on which a low dielectric film is formed, and excellent in reliability when subjected to a solder crack resistance test and a temperature resistance cycle test. The present invention relates to a semiconductor sealing resin composition to be applied, and a semiconductor device sealed with a cured product thereof.

Semiconductor devices have dramatically reduced package size. Integrated circuits have evolved according to the 2 year / 0.5 times size rule, commonly referred to as Moore's Law, in other words, the number of devices on a chip doubles every 2 years. . Currently, devices with feature sizes of 0.18 μm and even 0.13 μm are being produced, but nano-level processes have also been developed, and devices of 90 and 70 nanoprocesses will also be produced. I will. Along with the shrinking process, the response speed of semiconductors is also increasing. To further reduce the device size on an integrated circuit, it is necessary to weaken the electrostatic coupling between adjacent metal lines by using a conductive material having a low resistivity and an insulator having a low dielectric constant. . That is, a low dielectric film is applied to the element surface as an insulating layer on the element surface. However, black diamond, silsesquioxane, fluorine-based film, porous SiO _2, etc., which are generally applied as a low dielectric film, are very brittle and are affected by internal stress generated from the sealing material. There is a problem that cracks and peeling are likely to occur during temperature cycling and solder mounting.

In addition, the following is mentioned as a prior art relevant to this invention.
JP 2004-359854 A JP 2004-359855 A

  The present invention has been made in view of the above circumstances, and when sealing an element on which a low dielectric film is formed, it is remarkably excellent in adhesion to the element surface, and when subjected to a solder crack resistance test and a temperature resistance cycle test. An object of the present invention is to provide a resin composition for encapsulating a semiconductor that gives a cured product with excellent reliability, and a semiconductor device encapsulated with the cured product.

As a result of intensive studies to achieve the above object, the present inventors have found that the cured product has a storage elastic modulus at 150 ° C. of 2,100 MPa or less, a storage elastic modulus at 260 ° C. of 700 MPa or less, and −55 ° C. to 50 ° C. The linear expansion coefficient is up to 1.0 × 10 ⁻⁵ / ° C., the linear expansion coefficient up to 150 to 200 ° C. is up to 5.0 × 10 ⁻⁵ / ° C., and the molding shrinkage ratio when molded at 175 ° C. The resin composition for encapsulating a semiconductor having a content of 0.15% or less is excellent in adhesiveness, moldability, reliability at high temperature, reflow crack resistance, and crack resistance as a sealing material for a low dielectric film forming element. I found out. In this case, as the resin composition that gives such a cured product, (A) an epoxy resin represented by the following general formula (1) or (2), (B) a curing agent, particularly the following general formula (3) or ( In addition to the phenol resin represented by 4) and (C) the inorganic filler, (D) it is found effective to use a resin composition containing a silicone polymer represented by the following general formula (5), It came to make this invention.

（式中、Ｒ¹は水素原子又は炭素数１〜４のアルキル基であり、Ｑ＝０〜１０の数である。）

（式中、Ｒ¹は水素原子又は炭素数１〜４のアルキル基、Ｇｒはグリシジル基である。）
（Ｂ）下記一般式（３）又は（４）で表されるフェノール樹脂、又はその併用物、

（式中、Ｒ²は水素原子、炭素数１〜４のアルキル基又はフェニル基であり、ｒ＝０〜１０の数である。）

（ｓ＝１〜５の整数である。）
（Ｃ）無機質充填剤、
（Ｄ）下記一般式（５）で示されるシリコーン変性エポキシ樹脂

（式中、Ｒ¹は水素原子又は炭素数１〜４のアルキル基であり、Ｒは脂肪族不飽和結合を含有しない置換又は非置換の一価炭化水素基であり、Ｘは二価の有機基である。ｋ、ｍは０≦ｋ≦１００、０＜ｍ≦１００、０＜ｋ＋ｍ≦２００を満たす正数であり、ｎは０≦ｎ≦４００を満たす整数である。）
を含有することを特徴とする半導体封止用エポキシ樹脂組成物。
［３］（Ｃ）成分である無機質充填剤がシリカであり、（Ａ）成分のエポキシ樹脂と（Ｂ）成分の硬化剤の合計量１００質量部に対し、７００〜１，１００質量部配合されてなることを特徴とする［２］記載の半導体封止用樹脂組成物。
［４］低誘電膜形成素子が［１］〜［３］のいずれかに記載の半導体封止用樹脂組成物で封止された半導体装置。 Accordingly, the present invention provides the following semiconductor sealing resin composition and semiconductor device.
[1] A sealing material for a low dielectric film forming element, wherein the cured product has a storage elastic modulus at 150 ° C. of 2,100 MPa or less, a storage elastic modulus at 260 ° C. of 700 MPa or less, and a line from −55 ° C. to 50 ° C. The expansion coefficient is 1.0 × 10 ⁻⁵ / ° C. or lower, the linear expansion coefficient from 150 to 200 ° C. is 5.0 × 10 ⁻⁵ / ° C. or lower, and the molding shrinkage ratio when molded at 175 ° C. is 0.00. A resin composition for encapsulating a semiconductor, which is 15% or less.
[2] (A) An epoxy resin represented by the following general formula (1) or (2), or a combination thereof,

(In the formula, R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Q = 0 to 10)

(In the formula, R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Gr is a glycidyl group.)
(B) a phenol resin represented by the following general formula (3) or (4), or a combination thereof,

(In the formula, R ² is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and r = 0 to 10)

(S is an integer of 1 to 5)
(C) inorganic filler,
(D) Silicone-modified epoxy resin represented by the following general formula (5)

Wherein R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R is a substituted or unsubstituted monovalent hydrocarbon group containing no aliphatic unsaturated bond, and X is a divalent organic group. K and m are positive numbers that satisfy 0 ≦ k ≦ 100, 0 <m ≦ 100, and 0 <k + m ≦ 200, and n is an integer that satisfies 0 ≦ n ≦ 400.)
An epoxy resin composition for encapsulating a semiconductor, comprising:
[3] The inorganic filler as component (C) is silica, and is blended in an amount of 700 to 1,100 parts by mass with respect to 100 parts by mass of the total amount of the epoxy resin as component (A) and the curing agent as component (B). The resin composition for semiconductor encapsulation as described in [2], wherein
[4] A semiconductor device in which the low dielectric film forming element is sealed with the semiconductor sealing resin composition according to any one of [1] to [3].

  When a low dielectric film forming element is encapsulated with the epoxy resin composition for semiconductor encapsulation of the present invention, internal stress generated from the resin can be suppressed, and cracks and peeling of the low dielectric film can be suppressed. It becomes.

The low dielectric film forming element encapsulated in the present invention is an element to which black diamond, silsesquioxane, fluorine-based film, porous SiO ₂ or the like is applied, and the low dielectric film has a thickness of 0. It is 05-2 μm and is applied in a single layer or multiple layers. Further, a protective layer such as SiO ₂ , Si ₃ N ₄ , or polyimide may be further provided on the low dielectric film layer. Furthermore, although the dielectric constant of the conventional element is 4.0 to 4.5, an element called a low dielectric film having a dielectric film of 1.5 to 3.5 is defined as a low dielectric film forming element.

When sealing this low dielectric film forming element, the properties of the resin composition are that the cured product has a storage elastic modulus at 150 ° C. of 2,100 MPa or less, a storage elastic modulus at 260 ° C. of 700 MPa or less, and −55 ° C. to 50 ° C. The linear expansion coefficient is up to 1.0 × 10 ⁻⁵ / ° C., the linear expansion coefficient up to 150 to 200 ° C. is up to 5.0 × 10 ⁻⁵ / ° C., and the molding shrinkage ratio when molded at 175 ° C. Is 0.15% or less. The storage elastic modulus is measured by a dynamic elasticity measuring device, and the device is not particularly specified. For example, DMS6100 or DMS120 manufactured by Seiko Instruments Inc. is used. The linear expansion coefficient is measured by thermomechanical analysis, and the apparatus is not particularly limited. For example, TMA8140C manufactured by Rigaku Corporation is used. The method of measuring the molding shrinkage rate is not particularly limited, but, for example, a cold bar / cold mold method is used.

When the storage elastic modulus at 150 ° C. of the cured product of the resin composition of the present invention is greater than 2,100 MPa, or the storage elastic modulus at 260 ° C. is greater than 700 MPa, during temperature cycling or solder mounting at 260 ° C., Stress applied to the low dielectric element may increase, and cracks on the chip surface may occur. Further, the cured product of the resin composition of the present invention has a linear expansion coefficient from −55 ° C. to 50 ° C. of greater than 1.0 × 10 ⁻⁵ / ° C., and a linear expansion coefficient from 150 to 200 ° C. of 5.0. When the molding shrinkage ratio is greater than × 10 ⁻⁵ / ° C. or less and molding at 175 ° C. is greater than 0.15%, the chip is clamped during molding or a temperature cycle test at −55 ° C. to 200 ° C. The stress increases, and the low dielectric film on the chip surface may crack or peel off.

More preferably, the storage elastic modulus of the cured product at 150 ° C. is 2,100 MPa or less, particularly 2,000 MPa or less, and the storage elastic modulus at 260 ° C. is 700 MPa or less, particularly 600 MPa or less. The lower limit is not particularly limited, but usually, the storage elastic modulus at 150 ° C. is 400 MPa or more, particularly 600 MPa or more, and the storage elastic modulus at 260 ° C. is 100 MPa or more, particularly 200 MPa or more. Further, a more preferable linear expansion coefficient from −55 ° C. to 50 ° C. is 1.0 × 10 ⁻⁵ / ° C. or less, particularly 0.9 × 10 ⁻⁵ / ° C. or less, and a more preferable linear expansion coefficient from 150 to 200 ° C. Is 5.0 × 10 ⁻⁵ / ° C. or less, particularly 4.5 × 10 ⁻⁵ / ° C. or less. The lower limit is not particularly limited, but usually the linear expansion coefficient from −55 ° C. to 50 ° C. is 0.4 × 10 ⁻⁵ / ° C. or more, particularly 0.5 × 10 ⁻⁵ / ° C. or more, to 150 to 200 ° C. The linear expansion coefficient is 3.0 × 10 ⁻⁵ / ° C. or higher, particularly 3.5 × 10 ⁻⁵ / ° C. or higher. Further, a more preferable molding shrinkage when molding at 175 ° C. is 0.15% or less, particularly 0.12% or less, and the lower limit thereof is usually 0.05% or more, particularly 0.06% or more. However, it is not limited to this.

  Examples of the resin composition for encapsulating a semiconductor that give the cured product properties as described above include (A) an epoxy resin, (B) a curing agent, (C) an inorganic filler, and (D) a composition containing a silicone polymer. Can be mentioned.

（式中、Ｒ¹は各々独立に水素原子、炭素数１〜４のメチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ−ブチル基等のアルキル基であり、Ｑ＝０〜１０の数である。）

（式中、Ｒ¹は水素原子又は炭素数１〜４のアルキル基、Ｇｒはグリシジル基である。）
上記式（１）で表されるエポキシ樹脂は、ビフェニルアラルキル骨格を有するため、熱分解開始温度が他のエポキシ樹脂に比べて高く、熱分解速度が緩やかであり、耐熱性に優れるものである。上記式（１）で表されるエポキシ樹脂の具体例としては、以下のものが例示される。 Here, as the epoxy resin of component (A), an epoxy resin represented by the following general formula (1) or (2) is used.

(In the formula, each R ¹ is independently a hydrogen atom, an alkyl group such as a methyl group having 1 to 4 carbon atoms, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, or a tert-butyl group; It is a number from 0 to 10.)

(In the formula, R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Gr is a glycidyl group.)
Since the epoxy resin represented by the above formula (1) has a biphenylaralkyl skeleton, the thermal decomposition starting temperature is higher than that of other epoxy resins, the thermal decomposition rate is slow, and the heat resistance is excellent. Specific examples of the epoxy resin represented by the above formula (1) include the following.

（式中、ｐは０．５〜１．５である。）

(In the formula, p is 0.5 to 1.5.)

が例示される。 As the resin represented by the above formula (2),

Is exemplified.

  Epoxy resins (1) and (2) are used alone or in combination.

  The epoxy resin composition of the present invention can be used in combination with other epoxy resins as necessary. The epoxy resins used in combination include novolak type epoxy resins, cresol novolac type epoxy resins, triphenolalkane type epoxy resins, heterocyclic type epoxy resins, naphthalene ring-containing epoxy resins, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, and stilbene. Type epoxy compounds and the like, and one of them can be used alone or two or more of them can be used in combination. Of these, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, stilbene type epoxy compounds and the like that have low viscosity when melted are preferred.

  When other epoxy resins are used in combination, the amount of the epoxy resins of the above formulas (1) and (2) is the total amount of the epoxy resin (the sum of the epoxy resins of the formulas (1) and (2) and the above other epoxy resins. 50) to 100% by mass, and more preferably 70 to 100% by mass.

（式中、Ｒ²は水素原子、炭素数１〜４のアルキル基又はフェニル基であり、ｒ＝０〜１０の数である。）

（ｓ＝１〜５の整数である。） Next, the component (B) in the epoxy resin composition of the present invention is a phenol resin curing agent having two or more phenolic hydroxyl groups in one molecule, and is represented by the following general formulas (3) and (4). Used phenolic resin.

(In the formula, R ² is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and r = 0 to 10)

(S is an integer of 1 to 5)

  The phenol resin represented by the above formulas (3) and (4) is also a resin having a biphenyl aralkyl skeleton, and is excellent in heat resistance, like the epoxy resin of the present invention. Specific examples of the phenol resin represented by the above formula (3) include the following.

（式中、ｍは平均０．５〜１．５である。）

(In the formula, m is an average of 0.5 to 1.5.)

  The phenol resins represented by the above formulas (3) and (4) are other phenol resin curing agents such as phenol novolac resins, naphthalene ring-containing phenol resins, phenol aralkyl type phenol resins, and triphenylalkane type phenol resins. , Biphenyl type phenol resin, alicyclic phenol resin, heterocyclic type phenol resin, naphthalene ring-containing epoxy resin, bisphenol A type phenol resin, bisphenol F type phenol resin, etc. The amount of the phenol resin curing agent represented by (4) is 50 to 100% by mass of the total amount of the phenol resin curing agent (the total of the phenol resin of the formulas (3) and (4) and the other phenol resin curing agent). Preferably, it is 70-100 mass%.

  The mixing ratio of the (A) epoxy resin and the (B) phenol resin curing agent is not particularly limited, but the total amount of epoxy groups contained in the (A) epoxy resin and the (D) silicone-modified epoxy resin described later is 1 mol. On the other hand, the total molar ratio of the phenolic hydroxyl groups contained in the (B) phenol resin curing agent is preferably 0.5 to 1.5, particularly preferably 0.8 to 1.2. When the molar ratio of the phenolic hydroxyl group is less than 0.5, the curability at the time of molding may deteriorate, and when it exceeds 1.5, the water absorption of the cured product may increase.

  As the inorganic filler (C) used in the present invention, those usually blended in the resin composition can be used. Specific examples include silica such as spherical fused silica, crushed fused silica, crystalline silica, alumina, mullite, silicon nitride, aluminum nitride, boron nitride, titanium oxide, glass fiber, and the like. Among these, silica, particularly spherical fused silica is desirable, and the average particle size thereof is 5 to 30 μm, and the particle size exceeding 75 μm measured by the wet sieving method is 0.2% by mass or less. More desirable from the viewpoint of fluidity.

  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.

  As a compounding quantity of this inorganic filler, it is preferable to set it as 700-1100 mass parts with respect to 100 mass parts of total amounts of (A) epoxy resin and (B) phenol resin. If it is less than 700 mass parts, the ratio of resin is high and a linear expansion coefficient may not become the target value. 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.

  The inorganic filler is preferably blended in advance with a silane coupling agent or the like in order to increase the bonding strength between the resin and the surface of the inorganic filler. Here, the amount of the coupling agent used for the surface treatment and the surface treatment method are not particularly limited.

  In the semiconductor sealing resin composition of the present invention, a silicone-modified epoxy resin is blended as the component (D). As the silicone-modified epoxy resin of component (D), a silicone-modified epoxy resin represented by the following general formula (5) is particularly preferably used.

（式中、Ｒ¹は水素原子又は炭素数１〜４のアルキル基であり、Ｒは脂肪族不飽和結合を含有しない置換又は非置換の一価炭化水素基であり、Ｘは二価の有機基である。ｋ、ｍは０≦ｋ≦１００、０＜ｍ≦１００、０＜ｋ＋ｍ≦２００を満たす正数であり、ｎは０≦ｎ≦４００を満たす整数である。）

Wherein R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R is a substituted or unsubstituted monovalent hydrocarbon group containing no aliphatic unsaturated bond, and X is a divalent organic group. K and m are positive numbers that satisfy 0 ≦ k ≦ 100, 0 <m ≦ 100, and 0 <k + m ≦ 200, and n is an integer that satisfies 0 ≦ n ≦ 400.)

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. And R is a substituted or unsubstituted monovalent hydrocarbon group containing no aliphatic unsaturated group, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group Alkyl groups such as tert-butyl group, hexyl group, cyclohexyl group, octyl group and decyl group, aryl groups such as phenyl group, xylyl group and tolyl group, aralkyl groups such as benzyl group, phenylethyl group and phenylpropyl group Or a chloromethyl group, a bromoethyl group, a trifluoro group in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted with a halogen atom such as chlorine, fluorine, or bromine. 1 to 15 carbon atoms, such as a halogen-substituted monovalent hydrocarbon groups such as propyl group, are exemplified in particular 1-10 monovalent hydrocarbon group.

  X is a divalent organic group, specifically, 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 these groups And a group in which some or all of the hydrogen atoms are substituted with a halogen atom, a hydroxyl group, or the like, and those having 1 to 15 carbon atoms, particularly those having 2 to 10 carbon atoms are preferred. For example, the group shown below can be mentioned.

  K and m are positive numbers satisfying 0 ≦ k ≦ 100, 0 <m ≦ 100, and 0 <k + m ≦ 200, preferably 0.2 ≦ k ≦ 10, 0.2 ≦ m ≦ 10, 0. It is a positive number satisfying 4 ≦ k + m ≦ 20. n is an integer satisfying 0 to 400, preferably 5 to 100.

  Specific examples of such silicone-modified epoxy resins include those shown below (in the following formula, Me represents a methyl group).

（式中、Ｒ¹は水素原子又は炭素数１〜４のアルキル基であり、Ｙは末端に二重結合を有する有機基である。ｋ、ｍは０≦ｋ≦１００、０＜ｍ≦１００、０＜ｋ＋ｍ≦２００を満たす正数である。）
で表されるエポキシ樹脂のＹの末端二重結合と、（Ｂ）下記平均組成式（ｉｉ）

（式中、Ｒは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、特に５≦ｎ≦１００の整数である。）
で示される有機珪素化合物のＳｉＨ基を白金系触媒の存在下に常法に従って、付加反応させることにより得ることができる。 The method for producing the silicone-modified epoxy resin is as follows: (A) The following average composition formula (i)

(In the formula, R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Y is an organic group having a double bond at the terminal. K and m are 0 ≦ k ≦ 100, 0 <m ≦ 100. , 0 <k + m ≦ 200 is a positive number.)
And the terminal double bond of Y of the epoxy resin represented by formula (B) and the following average composition formula (ii)

(In the formula, R is a substituted or unsubstituted monovalent hydrocarbon group containing no aliphatic unsaturated group, and n is an integer of 0 ≦ n ≦ 400, particularly 5 ≦ n ≦ 100.)
In the presence of a platinum catalyst, the SiH group of the organosilicon compound can be obtained by addition reaction according to a conventional method.

Component (D) is added in an amount of 1 to 70 parts by weight, particularly 2 to 50 parts by weight, based on 100 parts by weight of the total amount of components (A) and (B). If the addition amount is small, the effect of lowering the storage elastic modulus may be thinned. If the addition amount is large, the viscosity of the resin composition increases, which may hinder molding.
In addition to the component (D), other low stress agents such as thermoplastic resins, thermoplastic elastomers, organic synthetic rubbers and other silicone polymers may be used in combination.

  In the composition of the present invention, for example, 2-methylimidazole, 2-ethyl-4-methylimidazole, triphenylphosphine, tetraphenylphosphonium / tetraphenylborate and the like are used as a curing catalyst.

  Moreover, the epoxy resin composition for semiconductor sealing of this invention can mix | blend various additives as needed other than an epoxy resin, a phenol resin hardening | curing agent, an inorganic filler, and the said silicone polymer. For example, low stress agents such as thermoplastic resins, thermoplastic elastomers, organic synthetic rubbers, silicones, waxes such as carnauba wax, colorants such as carbon black, difficulty in halogenated resins, antimony oxides, molybdates, etc. Additives such as a flame retardant and a halogen trap agent can be added and blended within a range not impairing the object of the present invention.

  As a general method when preparing the epoxy resin composition for semiconductor encapsulation of the present invention as a molding material, an epoxy resin, a phenol resin curing agent, an inorganic filler, a silicone-modified epoxy resin and, if necessary, a curing catalyst, After blending other additives at a predetermined composition ratio and mixing them sufficiently uniformly with a mixer, etc., perform a melt mixing process with a hot roll, a kneader, an extruder, etc., and then cool and solidify to an appropriate size. It can be pulverized into a molding material.

  The thus obtained resin composition for encapsulating a semiconductor of the present invention can be effectively used for encapsulating various semiconductor devices having an element on which a low dielectric film is formed. A typical method is a low-pressure transfer molding method. The molding temperature of the epoxy resin composition for semiconductor encapsulation of the present invention is 160 to 185 ° C. for 30 to 180 seconds, preferably 40 to 90 seconds, and post-curing is desirably 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 concretely, this invention is not restrict | limited to the following Example. In addition, in the following example, a part shows a mass part.

[Examples 1 to 5, Comparative Examples 1 to 4]
The low dielectric film forming element was sealed with a semiconductor sealing resin composition having the composition shown in Table 1 and having the cured product characteristics shown in Table 2 to obtain a semiconductor component. The evaluation results of the semiconductor parts are shown in Table 3. The characteristics of the composition and the evaluation of semiconductor parts were carried out by the following methods.
In addition, the component of the composition shown in Table 1 was melt-mixed on the conditions of 100 degreeC with the continuous kneader, and the composition for semiconductor sealing was obtained.

<Storage modulus>
A cured product of 100 × 10 × 4 mm was molded under the conditions of a temperature of 175 ° C., a molding pressure of 6.9 N / mm ² and a molding time of 120 seconds, and post-cured at 180 ° C. for 4 hours. Thereafter, the storage elastic modulus at 150 ° C. and 260 ° C. was measured with a DMS6100 manufactured by Seiko Instruments Inc. Temperature rising speed 10 ° C / min, measurement frequency 5Hz, distance between bending mode fulcrums 20mm.
<Linear expansion coefficient>
A cured product of 5 × 5 × 15 mm was molded under the conditions of a temperature of 175 ° C., a molding pressure of 6.9 N / mm ² and a molding time of 120 seconds, and post-cured at 180 ° C. for 4 hours. Thereafter, linear expansion coefficients of −55 ° C. to 50 ° C. and 150 to 200 ° C. were measured with TMA8140C manufactured by Rigaku Corporation. Temperature rising speed 5 ° C / min.
《Mold shrinkage》
A cured product of 100 × 10 × 4 mm was molded under the conditions of a temperature of 175 ° C., a molding pressure of 6.9 N / mm ² and a molding time of 90 seconds, and the length (a) in the longitudinal direction when cooled to room temperature was measured. The cavity length (b) of the mold at room temperature was measured. The shrinkage was measured from the formula of ((ab) / a) × 100. A caliper was used as the measuring device.
《Spiral Flow》
Using a mold conforming to the EMMI standard, measurement was performed under conditions of a temperature of 175 ° C., a pressure of 70 kgf / cm ² , and a molding time of 90 seconds.

《Gelification time》
The composition was spread thinly on a hot plate heated to 175 ° C., the resin was scraped off with a spatula, and the point at which the resin was peeled off from the hot plate surface was defined as the gel time.
<Melt viscosity>
The minimum melt viscosity when measured by applying a load of 5 kgf at 175 ° C. using a 1 mmφ × 10 mm die using a Shimadzu Corporation Koka type flow tester.
"Adhesiveness"
A 10 × 10 mm low dielectric film forming element was molded with the above resin composition at a temperature of 175 ° C., a molding pressure of 70 kgf / cm ² , and a molding time of 60 seconds to produce a test piece for bonding. This was post-cured at 180 ° C. for 4 hours, and then the adhesive strength at room temperature and 260 ° C. was measured. The bonding area between the frame of the test piece and the resin is 10 mm ² . The low dielectric forming element is obtained by applying four layers of SiO ₂ : 200 nm and black diamond 400 nm on a Si chip, and further applying SiO ₂ : 150 nm and SiN: 100 nm.

《Reflow crack resistance test》
A 10 × 10 × 0.3 mm low dielectric film forming element is mounted on a lead frame plated with Pd, and molded under the conditions of a temperature of 175 ° C., a pressure of 70 kgf / cm ² , a molding time of 45 seconds, and a post at 180 ° C. for 4 hours. Curing was performed to obtain a LQFP package of 14 × 20 × 1.4 mm. 10 pieces of each of these packages were placed in a 85 ° C./85% RH constant temperature and humidity chamber for 168 hours to absorb moisture, and then the ultrasonic wave was removed from the element surface when passed through an IR reflow oven at 260 ° C. Observation was performed using a flaw detector.
<Temperature resistance cycle test>
A 12 × 12 × 0.3 mm low dielectric film forming element is mounted on a BT resin coated with an epoxy resist, and molded under conditions of a temperature of 175 ° C., a pressure of 70 kgf / cm ² , and a molding time of 60 seconds. Time post cure was performed to obtain a 35 × 35 mm PBGA package. Each of the 10 packages was subjected to 100 cycles of 260 ° C. solder bath / 30 seconds and −196 ° C./60 seconds of thermal shock to examine the occurrence of chip surface cracks. The raw materials used are shown below.

Silicone-modified epoxy resin Silicone-modified epoxy resin represented by the following formula: epoxy equivalent 510

（ロ）：ビフェニル型エポキシ樹脂：ＹＸ４０００ＨＫ（油化シェル社製、エポキシ当量
１９０）
（ハ）：多官能型エポキシ樹脂：ＥＰＰＮ５０１（日本化薬（株）製、エポキシ当量１６
５） Epoxy resin (A): Epoxy resin represented by the following formula: NC3000P (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 272)

(B): Biphenyl type epoxy resin: YX4000HK (manufactured by Yuka Shell, epoxy equivalent)
190)
(C): Multifunctional epoxy resin: EPPN501 (Nippon Kayaku Co., Ltd., epoxy equivalent 16)
5)

（ホ）：フェノールアラルキル樹脂：ＭＥＨ７８００ＳＳ（明和化成（株）製、フェノー
ル性水酸基当量１７５、１５０℃におけるＩＣＩ溶融粘度１００ｍＰａ・ｓ） Curing agent (d): phenol resin represented by the following formula (8): MEH7851L (manufactured by Meiwa Kasei Co., Ltd., phenolic hydroxyl group equivalent 199, ICI melt viscosity at 150 ° C. 80 mPa
・ S)

(E): Phenol aralkyl resin: MEH7800SS (Maywa Kasei Co., Ltd., phenolic hydroxyl group equivalent of 175, ICI melt viscosity at 150 ° C. of 100 mPa · s)

・ Inorganic filler: spherical fused silica with an average particle size of 10 μm and coarse particles with a particle size exceeding 53 μm is 0.1% by mass. ・ Curing catalyst: tetraphenylphosphonium, tetraphenylborate, carbon black: electrified black (Electrochemical Industry Co., Ltd.) ) Made)
・ Ion trap agent: KW2200 (manufactured by Kyowa Chemical Industry Co., Ltd.)
-Mold release agent: Carnauba wax (manufactured by Nikko Fine Products Co., Ltd.)
Silane coupling agent: KBM803 (manufactured by Shin-Etsu Chemical Co., Ltd., mercapto group-containing trimethoxysilane)

  From the results in the above table, it can be seen that the semiconductor component encapsulated with the resin composition of the present invention has excellent adhesion to the low dielectric film forming element and exhibits excellent solder reflow properties and temperature cycle properties.

[Reference Example] Synthesis of silicone-modified epoxy resin 400 g of toluene in an 2 L four-necked flask equipped with a reflux condenser, a thermometer, a stirrer, and a dropping funnel, an allyl group-containing epoxy resin represented by the following formula (iii) 10 g of (epoxy equivalent 310) was added, and azeotropic dehydration was performed for 2 hours in a nitrogen atmosphere. Thereafter, the system is cooled to 80 ° C., 1.00 g of platinum chloride catalyst is added, and a solution obtained by dissolving 48.5 g of an organosilicon compound represented by the following formula (iv) in 194.1 g of toluene is dropped over 2 hours. did. The system was stirred for 6 hours while maintaining the system at 90 to 100 ° C., aged, and then cooled to room temperature. Thereafter, the solvent was distilled off under reduced pressure to obtain 56.2 g of the target silicone-modified epoxy resin.

アリル基含有エポキシ樹脂組成
ｓ＝０、ｔ＝１ …５５モル％
ｓ＝１、ｔ＝１ …３５モル％
ｓ＝２、ｔ＝１ …１０モル％

Allyl group-containing epoxy resin composition s = 0, t = 1... 55 mol%
s = 1, t = 1 ... 35 mol%
s = 2, t = 1 ... 10 mol%

As a result of measuring ¹ H-NMR and IR of the obtained reaction product, ¹ H-NMR was -0.5-0.5, 3.6-3.9, 6.6-7.2, 8. A peak was shown at 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 a compound represented by the following average composition formula (6) was obtained.

Claims (4)

A sealing material for a low dielectric film forming element, wherein the cured product has a storage elastic modulus at 150 ° C. of 2,100 MPa or less, a storage elastic modulus at 260 ° C. of 700 MPa or less, and a linear expansion coefficient from −55 ° C. to 50 ° C. 1.0 × 10 ⁻⁵ / ° C. or less, linear expansion coefficient from 150 to 200 ° C. is 5.0 × 10 ⁻⁵ / ° C. or less, and molding shrinkage when molded at 175 ° C. is 0.15% or less. A resin composition for encapsulating a semiconductor, characterized in that (A) An epoxy resin represented by the following general formula (1) or (2), or a combination thereof,

(In the formula, R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Q = 0 to 10)

(In the formula, R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Gr is a glycidyl group.)
(B) a phenol resin represented by the following general formula (3) or (4), or a combination thereof,

(In the formula, R ² is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and r = 0 to 10)

(S is an integer of 1 to 5)
(C) inorganic filler,
(D) Silicone-modified epoxy resin represented by the following general formula (5)

Wherein R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R is a substituted or unsubstituted monovalent hydrocarbon group containing no aliphatic unsaturated bond, and X is a divalent organic group. K and m are positive numbers that satisfy 0 ≦ k ≦ 100, 0 <m ≦ 100, and 0 <k + m ≦ 200, and n is an integer that satisfies 0 ≦ n ≦ 400.)
An epoxy resin composition for encapsulating a semiconductor, comprising:   The inorganic filler as component (C) is silica, and is blended in an amount of 700 to 1,100 parts by mass with respect to 100 parts by mass of the total amount of the epoxy resin of component (A) and the curing agent of component (B). The resin composition for semiconductor encapsulation according to claim 2, wherein: A semiconductor device in which a low dielectric film forming element is sealed with a resin composition for sealing a semiconductor according to any one of claims 1 to 3.