JPWO2015005275A1 - Semiconductor device manufacturing method and semiconductor device - Google Patents

Abstract

A preparation step of preparing an element mounting substrate (108) including a plurality of package areas (114) partitioned by a dicing region (112), and a semiconductor chip (in each of the package areas (114) of the element mounting substrate (108)) 116), a molding step of simultaneously molding the semiconductor chip (116) with the sealing epoxy resin composition, and dicing along the dicing region (112), and molding each semiconductor chip ( 116), and the sealing epoxy resin composition comprises (A) an epoxy resin, (B) a curing agent, (C) a silicone resin, and (D) an inorganic filler. (E) a curing accelerator, and the (C) silicone resin is a methylphenyl type thermoplastic silicone resin, and has the following general formula: a), (b), (c), (having repeating structural units represented by d), a branched structure silicone resin, a method of manufacturing a semiconductor device. (In the formula, * represents a bond to an Si atom in another repeating structural unit or the same repeating structural unit, R1a, R1b, R1c, and R1d are a methyl group or a phenyl group, and they are the same or different from each other. (The content of phenyl groups bonded to Si atoms is 50% by mass or more in one molecule, and the content of OH groups bonded to Si atoms is less than 0.5% by mass in one molecule.)

Description

  The present invention relates to a semiconductor device manufacturing method and a semiconductor device.

  In recent years, in the technical field of semiconductor packages, small packages such as CSP (Chip Size Package) and BGA are being used in order to meet demands for downsizing and multi-pinning.

  With regard to these packaging methods, a MAP (Mold Array Package) method is adopted, in which a semiconductor chip is modularized by a batch molding method, and the mounting area and manufacturing cost can be significantly reduced. The MAP method is a production method in which dozens of chips are arranged in a matrix on a large substrate, and dicing into individual packages after one-sided batch sealing (see, for example, Patent Document 1 and Patent Document 2).

  In recent years, electronic components have been highly integrated, densely packaged, or have high power, and accordingly, electronic components are required to operate in a high-temperature and high-humidity environment and have a long service life. Electronic components mounted in transmissions and engine compartments in vehicles are required to continue to operate well in harsh environments than general consumer electronic components, and the sealing resin (mold resin) for electronic components is heat resistant. The property which is excellent in property and oil resistance is required.

In order to improve such characteristics, attempts have been made to improve the characteristics of the sealing resin for electronic components using a silicone resin. Specific examples include the following.
Patent Document 3 describes an example of an epoxy resin composition for sealing in which an adduct of an aliphatic epoxy group-containing silicone resin, a third phosphine compound, and a quinone compound is combined as a curing accelerator. Since it is inferior in reactivity, it does not contribute to the crosslinking reaction of the resin component and deteriorates the water absorption rate of the sealing material. As a result, although the PKG warp was effective, the solder resistance was poor.
Patent Document 4 is an example of an epoxy resin composition for sealing in which a silicone resin containing an aliphatic epoxy group and a trisphenolmethane type phenol resin are combined. However, since an aliphatic epoxy group is inferior in reactivity, the resin component is crosslinked. It does not contribute to the reaction and deteriorates the water absorption rate of the sealing material. As a result, although the PKG warp was effective, the solder resistance was poor.
Patent Document 5 describes an example of an epoxy resin composition for sealing in which a silicone resin containing an aliphatic epoxy group and a bisphenol S type epoxy resin are combined. However, since an aliphatic epoxy group is inferior in reactivity, a resin component It does not contribute to the cross-linking reaction and deteriorates the water absorption rate of the sealing material. As a result, although the PKG warp was effective, the solder resistance was poor.
Patent Document 6 describes an example of a sealing epoxy resin composition in which a silicone resin containing a phenyl group and a hydroxyl group or a phenyl group and a propyl group and a phenyl aralkyl type, biphenyl type, or biphenyl aralkyl type epoxy resin are combined. When a large amount of hydroxyl groups were contained in the silicone resin, the silicone resin increased in molecular weight during molding, resulting in inferior moldability. Further, since the silicone resin contains a long-chain alkyl group such as a propyl group, the cured product has extremely poor flame resistance.

JP-A-8-222654 JP 2003-060126 A JP 2005-015559 A JP 2005-015561 A JP 2005-015565 A JP 2012-107209 A JP 2012-248774 A

In the MAP molding process described in Patent Document 1 or the like, when a semiconductor chip is mounted on an element mounting substrate and this semiconductor chip is sealed with a resin material, the element mounting substrate warps due to a difference in thermal expansion coefficient between them. May occur.
Particularly in recent years, there is a demand for thinning of the semiconductor package. There is a concern that by making the entire semiconductor package thinner, the warpage is likely to become obvious.
As one approach to eliminate such warpage, a method of relaxing stress caused by a difference in thermal expansion coefficient between the substrate, the element, and the sealing resin by using a resin material having excellent flexibility can be considered. . However, generally, a material having excellent flexibility tends to be inferior in heat resistance.
That is, there has been a demand for a resin material that does not generate warpage even in the MAP molding process, and that can maintain characteristics such as heat resistance and suppress warpage as a semiconductor device obtained after curing and dicing.

  The problems to be solved by the present invention are excellent in low melt viscosity and high fluidity during molding, and heat resistance, warpage resistance, solder crack resistance, temperature cycle resistance, and moisture resistance reliability when a semiconductor element is molded. An object of the present invention is to provide a method for manufacturing a semiconductor device having an excellent balance of properties.

（式中、＊は他の繰り返し構造単位または同一の繰り返し構造単位中のＳｉ原子への結合を示し、Ｒ^１ａとＲ^１ｂとＲ^１ｃとＲ^１ｄはメチル基またはフェニル基であり、それらは互いに同じでも異なっていても良い。Ｓｉ原子に結合したフェニル基の含有量は１分子中に５０質量％以上、Ｓｉ原子に結合したＯＨ基の含有量は１分子中に０．５質量％未満である。）
〔２〕 前記（Ｃ）シリコーンレジンが、更に下記一般式（ｅ）、（ｆ）で示される繰り返し構造単位を有するものである、〔１〕に記載の半導体装置の製造方法。

（式中、＊は他の繰り返し構造単位または同一の繰り返し構造単位中のＳｉ原子への結合を示し、Ｒ^１ｅはメチル基またはフェニル基である。Ｓｉ原子に結合した水素原子の含有量は１分子中に０．５質量％未満である。）
〔３〕 前記（Ｃ）シリコーンレジンの軟化点が６０℃以上、１００℃以下であり、数平均分子量が１０００以上、１００００以下である、〔１〕または〔２〕に記載の半導体装置の製造方法。
〔４〕 前記（Ｃ）シリコーンレジンの含有量が、全封止用エポキシ樹脂組成物中０．１質量％以上、５質量％以下である、〔１〕ないし〔３〕のいずれか一項に記載の半導体装置の製造方法。
〔５〕 前記（Ａ）エポキシ樹脂が、ビフェニル型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂、トリスフェノールメタン型エポキシ樹脂、ビスフェノール型エポキシ樹脂、擬アントラセン型エポキシ樹脂、から選ばれる１種以上である、〔１〕ないし〔４〕のいずれか一項に記載の半導体装置の製造方法。
〔６〕 前記（Ｂ）硬化剤が、フェノール系硬化剤である、〔１〕ないし〔５〕のいずれか一項に記載の半導体装置の製造方法。
〔７〕 前記フェノール系硬化剤が、フェノールアラルキル樹脂、またはトリスフェノールメタン骨格を有するフェノール樹脂の少なくとも一方を含むものである、〔６〕に記載の半導体装置の製造方法。
〔８〕 前記（Ｅ）硬化促進剤が、下記一般式（１）〜（３）で示される化合物から選ばれる１種以上である、〔１〕ないし〔７〕のいずれか一項に記載の半導体装置の製造方法。

（ただし、上記一般式（１）において、Ｐはリン原子を表す。Ｒ^２、Ｒ^３、Ｒ^４およびＲ^５は芳香族基またはアルキル基を表す。Ａはヒドロキシル基、カルボキシル基、チオール基から選ばれる官能基のいずれかを芳香環に少なくとも１つ有する芳香族有機酸のアニオンを表す。ＡＨはヒドロキシル基、カルボキシル基、チオール基から選ばれる官能基のいずれかを芳香環に少なくとも１つ有する芳香族有機酸を表す。ｘ、ｙは１〜３の数、ｚは０〜３の数であり、かつｘ＝ｙである。）

（ただし、上記一般式（２）において、Ｒ^６は炭素数１〜３のアルキル基、Ｒ^７はヒドロキシル基を表す。ａは０〜５の数であり、ｂは０〜４の数である。）

（ただし、上記一般式（３）において、Ｐはリン原子を表し、Ｓｉは珪素原子を表す。Ｒ^８、Ｒ^９、Ｒ^１０およびＲ^１１は、それぞれ、芳香環または複素環を有する有機基、あるいは脂肪族基を表し、互いに同一であっても異なっていてもよい。式中Ｒ^１２は、基Ｙ^２およびＹ^３と結合する有機基である。式中Ｒ^１３は、基Ｙ^４およびＹ^５と結合する有機基である。Ｙ^２およびＹ^３は、プロトン供与性基がプロトンを放出してなる基を表し、同一分子内の基Ｙ^２およびＹ^３が珪素原子と結合してキレート構造を形成するものである。Ｙ^４およびＹ^５はプロトン供与性基がプロトンを放出してなる基を表し、同一分子内の基Ｙ^４およびＹ^５が珪素原子と結合してキレート構造を形成するものである。Ｒ^１２とＲ^１３は互いに同一であっても異なっていてもよく、Ｙ^２、Ｙ^３、Ｙ^４、およびＹ^５は互いに同一であっても異なっていてもよい。Ｚ^１は芳香環または複素環を有する有機基、あるいは脂肪族基である。）
〔９〕 〔１〕ないし〔８〕のいずれか一項に記載の製造方法によって得られる半導体装置。Such an object is achieved by the present invention described in the following [1] to [9].
[1] A preparation step of preparing an element mounting substrate including a plurality of package areas partitioned by a dicing area;
A mounting step of mounting a semiconductor chip in each of the package areas of the element mounting substrate;
A molding step of simultaneously molding the semiconductor chip with an epoxy resin composition for sealing;
Dicing along the dicing region, and a singulation step of dividing each molded semiconductor chip,
Including
The sealing epoxy resin composition is
(A) epoxy resin,
(B) a curing agent,
(C) silicone resin,
(D) inorganic filler,
(E) a curing accelerator,
Including
The (C) silicone resin is a methylphenyl thermoplastic silicone resin, and has a repeating structural unit represented by the following general formulas (a), (b), (c), and (d): A method for manufacturing a semiconductor device.

(In the formula, * represents a bond to an Si atom in another repeating structural unit or the same repeating structural unit, R ^1a , R ^1b , R ^1c and R ^1d are a methyl group or a phenyl group, The content of phenyl groups bonded to Si atoms may be 50% by mass or more in one molecule, and the content of OH groups bonded to Si atoms may be less than 0.5% by mass in one molecule. is there.)
[2] The method for manufacturing a semiconductor device according to [1], wherein the (C) silicone resin further has a repeating structural unit represented by the following general formulas (e) and (f).

(In the formula, * represents a bond to an Si atom in another repeating structural unit or the same repeating structural unit, and R ^1e is a methyl group or a phenyl group. The content of a hydrogen atom bonded to the Si atom is 1) (It is less than 0.5% by mass in the molecule.)
[3] The method for producing a semiconductor device according to [1] or [2], wherein the softening point of the (C) silicone resin is 60 ° C. or higher and 100 ° C. or lower and the number average molecular weight is 1000 or more and 10,000 or less. .
[4] The content of the (C) silicone resin is 0.1% by mass or more and 5% by mass or less in the total sealing epoxy resin composition, according to any one of [1] to [3]. The manufacturing method of the semiconductor device of description.
[5] The (A) epoxy resin is at least one selected from a biphenyl type epoxy resin, a phenol aralkyl type epoxy resin, a trisphenol methane type epoxy resin, a bisphenol type epoxy resin, and a pseudo anthracene type epoxy resin. [1] A method for manufacturing a semiconductor device according to any one of [4].
[6] The method for manufacturing a semiconductor device according to any one of [1] to [5], wherein the (B) curing agent is a phenol-based curing agent.
[7] The method for manufacturing a semiconductor device according to [6], wherein the phenol-based curing agent includes at least one of a phenol aralkyl resin or a phenol resin having a trisphenolmethane skeleton.
[8] The hardening accelerator according to any one of [1] to [7], wherein the (E) curing accelerator is one or more selected from compounds represented by the following general formulas (1) to (3). A method for manufacturing a semiconductor device.

(However, in the above general formula (1), P is ^.R 2 representing the phosphorus ^atom, R 3, .A ^{R 4} and ^{R 5} representing an aromatic group or alkyl group is a hydroxyl group, a carboxyl group, a thiol group An anion of an aromatic organic acid having at least one of the selected functional groups in the aromatic ring, AH having at least one of the functional groups selected from a hydroxyl group, a carboxyl group, and a thiol group in the aromatic ring Represents an aromatic organic acid, where x and y are numbers from 1 to 3, z is a number from 0 to 3, and x = y.

(However, in the above general formula (2), ^{R 6} is an alkyl group having 1 to 3 carbon atoms, ^{R 7} is the number of .a 0-5 representing a hydroxyl group, b is the number of 0 to 4 .)

(However, in the said General formula (3), P represents a phosphorus atom and Si represents a silicon atom. R < ⁸ >, R < ⁹ >, R < ¹⁰ > and R < ¹¹ > are respectively an organic group which has an aromatic ring or a heterocyclic ring, Alternatively, it represents an aliphatic group, which may be the same or different from each other, wherein R ¹² is an organic group bonded to the groups Y ² and Y ^{3. In the} formula, R ¹³ represents the groups Y ⁴ and Y. ⁵ and an organic group linked .Y ² and Y ³ represents a group proton donating group releases a proton, chelating structural groups Y ² and Y ³ in the same molecule are bonded to a silicon atom Y ⁴ and Y ⁵ each represent a group formed by releasing a proton from a proton donating group, and the groups Y ⁴ and Y ⁵ in the same molecule are bonded to a silicon atom to form a chelate structure. R ¹² and R ¹³ are the same as each other Y ² , Y ³ , Y ⁴ , and Y ⁵ may be the same or different from each other, Z ¹ is an organic group having an aromatic ring or a heterocyclic ring, or a fatty acid A group.)
[9] A semiconductor device obtained by the manufacturing method according to any one of [1] to [8].

In the method for manufacturing a semiconductor device of the present invention, an epoxy resin composition containing a specific silicone resin is used. Since this epoxy resin composition is excellent in low melt viscosity and high fluidity at the time of molding, the production efficiency at the time of semiconductor production can be improved. In addition, by providing a cured product obtained from the epoxy resin composition as a sealing material for sealing a semiconductor element, heat resistance, warpage resistance, solder crack resistance, temperature cycle resistance, moisture resistance reliability A semiconductor device with excellent balance can be provided.
Lowering the thermal expansion coefficient by increasing the amount of conventional inorganic fillers results in higher melt viscosity and lower fluidity. Conventional silicone resins have lower Tg, higher thermal expansion coefficient, lower flame resistance, and lower reliability of semiconductor devices. However, by using a specific silicone resin, it is possible to obtain a result with excellent balance without causing these trade-offs.

  The above-described object and other objects, features, and advantages will become more apparent from the preferred embodiments described below and the accompanying drawings.

It is process sectional drawing which shows the manufacturing procedure of the semiconductor device in 1st Embodiment. It is a process top view which shows the manufacture procedure of the semiconductor device in 1st Embodiment. It is process sectional drawing which shows the manufacturing procedure of the semiconductor device in 1st Embodiment. It is a longitudinal cross-sectional view which shows an example of the electronic component module in 2nd Embodiment.

  Hereinafter, a semiconductor device manufacturing method and a semiconductor device of the present invention will be described in detail based on preferred embodiments.

<First Embodiment>
The manufacturing method of the semiconductor device 100 of this embodiment is called a “MAP method” and includes the following steps. First, the element mounting substrate 108 including a plurality of package areas 114 partitioned by the dicing region 112 is prepared (hereinafter referred to as a preparation process). Next, the semiconductor chip 116 is mounted in each package area 114 of the element mounting substrate 108 (hereinafter referred to as a mounting process). Next, the semiconductor chip 116 is simultaneously molded with a sealing epoxy resin composition (hereinafter referred to as a molding process). Dicing is performed along the dicing region 112 to divide each molded semiconductor chip 116 (hereinafter referred to as a singulation process).
The sealing epoxy resin composition of the present embodiment includes (A) an epoxy resin, (B) a curing agent, (C) a silicone resin, (D) an inorganic filler, and (E) a curing accelerator. C) The silicone resin is a methylphenyl type thermoplastic silicone resin, and is a branched structure silicone resin having repeating structural units represented by the following general formulas (a), (b), (c), and (d). .

（式中、＊は他の繰り返し構造単位または同一の繰り返し構造単位中のＳｉ原子への結合を示し、Ｒ^１ａとＲ^１ｂとＲ^１ｃとＲ^１ｄはメチル基またはフェニル基であり、それらは互いに同じでも異なっていても良い。Ｓｉ原子に結合したフェニル基の含有量は１分子中に５０質量％以上、Ｓｉ原子に結合したＯＨ基の含有量は１分子中に０．５質量％未満である。）

(In the formula, * represents a bond to an Si atom in another repeating structural unit or the same repeating structural unit, R ^1a , R ^1b , R ^1c and R ^1d are a methyl group or a phenyl group, The content of phenyl groups bonded to Si atoms may be 50% by mass or more in one molecule, and the content of OH groups bonded to Si atoms may be less than 0.5% by mass in one molecule. is there.)

  Hereinafter, each process is explained in full detail.

(Preparation process)
In this preparation step, the element mounting substrate 108 is prepared. The element mounting substrate can be set as appropriate as long as the object of the invention is not impaired. For example, a case of an organic substrate is exemplified.

(Mounting process)
Next, the mounting process of this embodiment will be described.
FIG. 2 is a process top view of the mounting process. FIG. 1A is a cross-sectional view taken along the line AA ′ of FIG.
As shown in FIG. 2, a plurality of semiconductor chips 116 are arranged on the element mounting surface 110 of the element mounting substrate 108. On the element mounting surface 110, a package area 114 partitioned by a dicing region 112 is formed. The package area 114 is arranged at a predetermined interval. One semiconductor chip 116 may be formed in one package area 114, or a plurality of semiconductor chips 116 may be formed. In this embodiment, an example in which one semiconductor chip 116 is arranged in one package area 114 will be described. The outer edge of the semiconductor chip 116 corresponds to the outer edge of the package area 114.

  In the present embodiment, the distance between the center package areas 114 that are closest to the center position is L1, and the distance between the center package area 114 and the outer package area 114 disposed outside the center package area 114 is L2. L2 may be the same as L1, or may be larger than L1. By setting L2 = L1, the semiconductor chips 116 can be arranged with high density. Further, by setting L2> L1, the difference between the linear expansion coefficient of the element mounting surface 110 and the linear expansion coefficient on the opposite surface side can be reduced outside the element mounting substrate 108. Thereby, especially the curvature of the outer side of the element mounting board | substrate 108 can be made small.

  As shown in FIG. 1A, the element mounting substrate 108 and the semiconductor chip 116 are electrically connected via, for example, solder bumps 118 and a wiring layer (not shown). In addition, the electrode of the element mounting substrate 108 and the semiconductor chip 116 may be connected by a bonding wire.

The element mounting substrate 108 and the semiconductor chip 116 are connected as follows, for example.
First, after temporarily fixing the semiconductor chip 116 to the element mounting substrate 108 with an adhesive, these are thermocompression bonded. In the present embodiment, the adhesive may be liquid or sheet-like. The adhesive may have a flux activator.
Next, the semiconductor chip 116 and the element mounting substrate 108 are solder-bonded by heating the laminated body including the semiconductor chip 116 and the element mounting substrate 108 at a temperature equal to or higher than the melting point of the solder bump 118. Thereby, the semiconductor chip 116 and the element mounting substrate 108 are connected to each other.

  The semiconductor chip 116 is not particularly limited, but preferably has a chip size package structure, for example.

(Molding process)
Then, the molding process of this Embodiment is demonstrated.
As shown in FIG. 1B, the semiconductor chip 116 on the element mounting substrate 108 is simultaneously molded with a sealing material. The entire semiconductor chip 116 is covered with a mold resin layer 120. Thereby, a semiconductor package is formed. In the semiconductor package, the gap between the semiconductor chips 116 is embedded with a mold resin layer 120.

  In the molding step, the mold resin layer 120 is formed on the element mounting substrate 108 on which the semiconductor chip 116 is mounted using a sealing epoxy resin composition containing a specific silicone resin.

（式中、＊は他の繰り返し構造単位または同一の繰り返し構造単位中のＳｉ原子への結合を示し、Ｒ^１ａとＲ^１ｂとＲ^１ｃとＲ^１ｄはメチル基またはフェニル基であり、それらは互いに同じでも異なっていても良い。Ｓｉ原子に結合したフェニル基の含有量は１分子中に５０質量％以上、Ｓｉ原子に結合したＯＨ基の含有量は１分子中に０．５質量％未満である。）Hereinafter, the epoxy resin composition for sealing will be described.
<Epoxy resin composition for sealing>
The epoxy resin composition for sealing of this embodiment is
(A) epoxy resin,
(B) a curing agent,
(C) silicone resin,
(D) inorganic filler,
(E) a curing accelerator,
Including
The (C) silicone resin is a methylphenyl thermoplastic silicone resin, and has a repeating structural unit represented by the following general formulas (a), (b), (c), and (d): It is.

(In the formula, * represents a bond to an Si atom in another repeating structural unit or the same repeating structural unit, R ^1a , R ^1b , R ^1c and R ^1d are a methyl group or a phenyl group, The content of phenyl groups bonded to Si atoms may be 50% by mass or more in one molecule, and the content of OH groups bonded to Si atoms may be less than 0.5% by mass in one molecule. is there.)

Hereinafter, each component contained in the epoxy resin composition for sealing of this embodiment is demonstrated sequentially.
[Epoxy resin]
The epoxy resin (A) in this embodiment is a phenol aralkyl type epoxy resin (a phenol aralkyl type epoxy resin having a biphenylene skeleton, a phenol aralkyl type epoxy resin having a phenylene skeleton, etc.), a biphenyl type epoxy resin, or a trisphenol methane type epoxy resin. , Bisphenol-type epoxy resin (bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, etc.), pseudo anthracene-type epoxy resin, and these may be used alone or in combination of two or more. Also good.

  The content of the epoxy resin (A) used in the sealing epoxy resin composition of the present embodiment is not particularly limited, but is 3% by mass or more and 20% by mass or less in the total epoxy resin composition for sealing. Preferably, 5 mass% or more and 15 mass% or less are more preferable, and especially 6 mass% or more and 10 mass% or less are the most preferable.

  (A) By making content of the whole epoxy resin more than the said lower limit, the fluidity | liquidity at the time of the fusion | melting of the epoxy resin composition for sealing improves. Moreover, the solder resistance of a molded product can be improved by setting it as the said upper limit or less.

（式中、Ｒ^１４、Ｒ^１５は水素原子又は炭素数１〜４の有機基であり、互いに同一でも異なっていてもよい。ｃは０〜３の数、ｄは０〜４の数である。ｎは平均値として１〜５の数である。）<Phenol aralkyl type epoxy resin having biphenylene skeleton>
Examples of the phenol aralkyl type epoxy resin having a biphenylene skeleton in the present embodiment include those containing a resin having a structure represented by the following general formula (4).

(Wherein R ¹⁴ and R ¹⁵ are a hydrogen atom or an organic group having 1 to 4 carbon atoms, and may be the same or different from each other. C is a number from 0 to 3, and d is a number from 0 to 4. N is an average value of 1 to 5)

R <^14> , R < ¹⁵ > in General formula (4) is a C1-C4 alkyl group, such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a methoxy group, and an ethoxy group , A C 1-4 alkoxy group such as a propoxy group and a butoxy group, etc., among which a hydrogen atom or a methyl group is preferable. As the phenol aralkyl type epoxy resin having a biphenylene skeleton in the present embodiment, an epoxy resin having n = 1 as a main component is more preferable. For example, NC-3000L (trade name, manufactured by Nippon Kayaku Co., Ltd.) is commercially available. It is available as a product. When the phenol aralkyl type epoxy resin having the biphenylene skeleton is used, the distance between the cross-linking points is increased, so that the elastic modulus of the cured product can be reduced and the solder resistance is improved.

<Biphenyl type epoxy resin>
Examples of the biphenyl type epoxy resin in this embodiment include those containing a resin having a structure represented by the following general formula (5).

（式中、Ｒ^１６〜Ｒ^２３は水素原子又は炭素数１〜４の有機基であり、互いに同一でも異なっていてもよい。）

(In formula, R < ¹⁶ > -R < ²³ > is a hydrogen atom or a C1-C4 organic group, and may mutually be same or different.)

R ^{16 to} R ²³ in the general formula (5) are each a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group or other alkyl group having 1 to 4 carbon atoms, a methoxy group, or an ethoxy group. , A C 1-4 alkoxy group such as a propoxy group and a butoxy group, etc., among which a hydrogen atom or a methyl group is preferable. As the biphenyl type epoxy resin in the present invention, 4,4′-bis (2,3-epoxypropoxy) biphenyl or 4,4′-bis (2,3-epoxypropoxy) -3,3 ′, 5,5 ′ -Epoxy resin mainly composed of tetramethylbiphenyl, epoxy resin obtained by reacting epichlorohydrin with 4,4'-biphenol or 4,4 '-(3,3', 5,5'-tetramethyl) biphenol Among them, an epoxy resin mainly composed of 4,4′-bis (2,3-epoxypropoxy) -3,3 ′, 5,5′-tetramethylbiphenyl is more preferable. For example, YX— 4000K, YX-4000H (both are trade names manufactured by Mitsubishi Chemical Corporation) and the like are commercially available. When this biphenyl type epoxy resin is used, the adhesion to the circuit board and the lead frame is improved, so that the solder resistance is improved.

<Phenol aralkyl type epoxy resin having a phenylene skeleton>
Examples of the phenol aralkyl type epoxy resin having a phenylene skeleton in the present embodiment include those containing a resin having a structure represented by the following general formula (6).

（式中、Ｒ^２４、Ｒ^２５は水素原子又は炭素数１〜４の有機基であり、互いに同一でも異なっていてもよい。ｅは０〜３の数、ｆは０〜４の数である。ｎは平均値として１〜５の数である。）

(In the formula, R ²⁴ and R ²⁵ are a hydrogen atom or an organic group having 1 to 4 carbon atoms, and may be the same or different from each other. E is a number from 0 to 3, and f is a number from 0 to 4. N is an average value of 1 to 5)

R ²⁴ and R ²⁵ in the general formula (6) are each a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group or other alkyl group having 1 to 4 carbon atoms, a methoxy group, or an ethoxy group. , A C 1-4 alkoxy group such as a propoxy group and a butoxy group, etc., among which a hydrogen atom or a methyl group is preferable. As the phenol aralkyl type epoxy resin having a phenylene skeleton in the present embodiment, an epoxy resin having n = 1 as a main component is more preferable. For example, NC-2000 (trade name, manufactured by Nippon Kayaku Co., Ltd.) is commercially available. It is available as a product. When the phenol aralkyl type epoxy resin having the phenylene skeleton is used, the distance between the crosslinking points is widened, so that the elastic modulus of the cured product can be reduced and the solder resistance is improved.

（式中、Ｒ^２６は、水素原子又は炭素数１〜４の有機基であり、互いに同一でも異なっていてもよい。ｎは平均値として１〜１０の数、ｇは０〜３の数、ｈは０〜４の数である。）<Trisphenol methane type epoxy resin>
Examples of the trisphenolmethane type epoxy resin in the present embodiment include those containing a resin having a structure represented by the following general formula (7).

(In the formula, R ²⁶ is a hydrogen atom or an organic group having 1 to 4 carbon atoms, and may be the same or different. N is an average value of 1 to 10, g is a number of 0 to 3, h is a number from 0 to 4.)

R ²⁶ in the general formula (7) is a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group or other alkyl group having 1 to 4 carbon atoms, a methoxy group, an ethoxy group, or a propoxy group. , Selected from an alkoxy group having 1 to 4 carbon atoms such as a butoxy group, among which a hydrogen atom or a methyl group is preferable. As the trisphenolmethane type epoxy resin in the present embodiment, an epoxy resin having n = 1 as a main component is more preferable. (Trade name, manufactured by Co., Ltd.), EPPN-501, EPPN-502 (trade name, manufactured by Nippon Kayaku Co., Ltd.) and the like are commercially available. When this trisphenol methane type epoxy resin is used, Tg can be improved by increasing the crosslinking density, and solder resistance is improved.

（式中、Ｒ^２７は水素原子又は炭素数１〜４の有機基であり、互いに同じでも異なっていても良い。ｉは０〜４の数であり、ｎは平均値として０〜５の数である。）<Bisphenol A type epoxy resin>
Examples of the bisphenol A type epoxy resin in this embodiment include those containing a resin having a structure represented by the following general formula (8).

(In the formula, R ²⁷ is a hydrogen atom or an organic group having 1 to 4 carbon atoms, and may be the same or different. I is a number from 0 to 4, and n is a number from 0 to 5 as an average value. .)

R ²⁷ in the general formula (8) is a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an alkyl group having 1 to 4 carbon atoms such as an isobutyl group, a methoxy group, an ethoxy group, a propoxy group , Selected from an alkoxy group having 1 to 4 carbon atoms such as a butoxy group, among which a hydrogen atom or a methyl group is preferable. As the bisphenol A type epoxy resin in the present embodiment, an epoxy resin having n = 0 as a main component is more preferable, and for example, Epicoat YL6810 (trade name, manufactured by Mitsubishi Chemical Corporation) is available as a commercial product. . When this bisphenol A type epoxy resin is used, the distance between cross-linking points is widened, so that the elastic modulus of the cured product can be reduced and the solder resistance is improved.

（式中、Ｒ^２８は水素原子又は炭素数１〜４の有機基であり、互いに同じでも異なっていても良い。ｊは０〜８の数であり、ｎは平均値として０〜５の数である。）<Pseudoanthracene type epoxy resin>
Examples of the pseudo anthracene type epoxy resin in the present embodiment include those containing a resin having a structure represented by the following general formula (9).

(In the formula, R ²⁸ is a hydrogen atom or an organic group having 1 to 4 carbon atoms, and may be the same or different. J is a number from 0 to 8, and n is a number from 0 to 5 as an average value. .)

R ²⁸ in the general formula (9) is a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group or other alkyl group having 1 to 4 carbon atoms, a methoxy group, an ethoxy group, or a propoxy group. , Selected from an alkoxy group having 1 to 4 carbon atoms such as a butoxy group, among which a hydrogen atom or a methyl group is preferable. As the pseudo-anthracene-type epoxy resin represented by the general formula (9), an epoxy resin mainly composed of n = 0 is more preferable. For example, YX8800 (trade name manufactured by Mitsubishi Chemical Corporation), YL7310 (Mitsubishi Chemical) (Trade name, manufactured by Co., Ltd.) is available as a commercial product. When this pseudo anthracene type epoxy resin is used, the distance between cross-linking points becomes long, so that the elastic modulus of the cured product can be reduced and the solder resistance is improved.

[Curing agent]
The (B) curing agent in the present embodiment is not particularly limited as long as it is generally used in an epoxy resin composition for sealing. For example, a phenol-based curing agent, an amine-based curing agent, and an acid anhydride system are used. Examples thereof include a curing agent and a mercaptan curing agent. Among these, a phenolic curing agent is preferable from the viewpoint of balance of flame resistance, moisture resistance, electrical characteristics, curability, storage stability, and the like.
<Phenolic curing agent>
The phenolic curing agent is not particularly limited as long as it is generally used in an epoxy resin composition for sealing. For example, phenol novolac resin, cresol novolac resin, phenol, cresol, resorcin, catechol , Phenols such as bisphenol A, bisphenol F, phenylphenol and aminophenol and / or naphthols such as α-naphthol, β-naphthol and dihydroxynaphthalene and a compound having an aldehyde group such as formaldehyde in an acidic catalyst or Resin obtained by cocondensation, phenol aralkyl resin having biphenylene skeleton synthesized from phenol and / or naphthol and dimethoxyparaxylene or bis (methoxymethyl) biphenyl, having phenylene skeleton Phenol aralkyl resins, phenol resins having a trisphenolmethane skeleton, and the like may be used, and these may be used alone or in combination of two or more.

<Amine-based curing agent>
Examples of amine curing agents include aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), and metaxylylene diamine (MXDA), diaminodiphenylmethane (DDM), m-phenylenediamine (MPDA), and diaminodiphenylsulfone. In addition to aromatic polyamines such as (DDS), polyamine compounds including dicyandiamide (DICY), organic acid dihydrazide, and the like may be used, and these may be used alone or in combination of two or more.
<Acid anhydride curing agent>
Examples of acid anhydride curing agents include alicyclic acid anhydrides such as hexahydrophthalic anhydride (HHPA), methyltetrahydrophthalic anhydride (MTHPA) and maleic anhydride, trimellitic anhydride (TMA) and pyromellitic anhydride. (PMDA), benzophenone tetracarboxylic acid (BTDA), aromatic acid anhydrides such as phthalic anhydride, etc. may be mentioned, and these may be used alone or in combination of two or more.
<Mercaptan-based curing agent>
Examples of the mercaptan-based curing agent include trimethylolpropane tris (3-mercaptobutyrate), trimethylolethane tris (3-mercaptobutyrate), and these may be used alone or in combination of two or more. Also good.
<Other curing agents>
Examples of other curing agents include isocyanate compounds such as isocyanate prepolymers and blocked isocyanates, and organic acids such as carboxylic acid-containing polyester resins. These may be used alone or in combination of two or more. .
Moreover, you may use combining 2 or more types of the said different type | system | group hardening | curing agent.

  (B) When the curing agent is a phenolic curing agent, the equivalent ratio of (A) epoxy resin and (B) curing agent, that is, the number of moles of epoxy groups in the epoxy resin / the moles of phenolic hydroxyl groups in the phenolic curing agent The ratio of the numbers is not particularly limited, but in order to obtain an epoxy resin composition excellent in moldability and reflow resistance, a range of 0.5 to 2 is preferable, and a range of 0.6 to 1.5 is preferable. A range of 0.8 to 1.2 is most preferable.

（式中、＊は他の繰り返し構造単位または同一の繰り返し構造単位中のＳｉ原子への結合を示し、Ｒ^１ａとＲ^１ｂとＲ^１ｃとＲ^１ｄはメチル基またはフェニル基であり、それらは互いに同じでも異なっていても良い。Ｓｉ原子に結合したフェニル基の含有量は１分子中に５０質量％以上、Ｓｉ原子に結合したＯＨ基の含有量は１分子中に０．５質量％未満である。）[Silicone resin]
The (C) silicone resin in the present embodiment is a methylphenyl type thermoplastic silicone resin, and has a branched structure having repeating structural units represented by the following general formulas (a), (b), (c), and (d). It is a silicone resin.

(In the formula, * represents a bond to an Si atom in another repeating structural unit or the same repeating structural unit, R ^1a , R ^1b , R ^1c and R ^1d are a methyl group or a phenyl group, The content of phenyl groups bonded to Si atoms may be 50% by mass or more in one molecule, and the content of OH groups bonded to Si atoms may be less than 0.5% by mass in one molecule. is there.)

（式中、＊は他の繰り返し構造単位または同一の繰り返し構造単位中のＳｉ原子への結合を示し、Ｒ^１ｅはメチル基またはフェニル基である。Ｓｉ原子に結合した水素原子の含有量は１分子中に０．５質量％未満である。）
（Ｃ）シリコーンレジンの軟化点は６０℃以上、１００℃以下が好ましい。軟化点が６０℃未満だと、ガラス転移温度が低下し、作動時（高温）と停止時（常温）の電子部品の反り変動が大きくなり、電子部品の寿命が短くなる。軟化点が１００℃より高いと、レジン成分との相溶性が悪化するため、反り制御能力が十分発揮されず、電子部品表面の汚れも発生する。
（Ｃ）シリコーンレジンの数平均分子量は１０００以上、１００００以下であることが好ましい。数平均分子量が１０００未満だと、揮発成分が増加し、電子部品内部にボイドが発生しやすくなる。数平均分子量が１００００より大きいと、レジン成分との相溶性が悪化するため、反り制御能力が十分発揮されず、電子部品表面の汚れも発生する。
（Ｃ）シリコーンレジンは、ジクロロジメチルシラン、ジクロロジフェニルシラン、ジクロロメチルフェニルシラン、トリクロロメチルシラン、トリクロロフェニルシラン、クロロトリメチルシラン、クロロトリフェニルシランを、目標とする分岐構造量、フェニル基含有量、分子量に応じた配合比で配合し、加水分解させ、生成したシラノール基を脱水縮合、精製して得ることができる。（Ｃ）シリコーンレジンの市販品としては、ＫＲ−４８０（信越化学工業（株）社製商品名）、２３３ＦＬＡＫＥ（東レダウコーニング（株）社製商品名）、２４９ＦＬＡＫＥ（東レダウコーニング（株）社製商品名）等が入手可能であるが、封止用エポキシ樹脂組成物に用いるためには、脱塩素のために洗浄等によって精製して用いることが好ましい。
これらの（Ｃ）シリコーンレジンは単独で用いても２種類以上を併用しても良い。By containing 50% by mass or more of a phenyl group in one molecule, compatibility with an epoxy resin or a phenol-based curing agent is enhanced, flame resistance is enhanced, and water absorption of the cured resin can be reduced. .
(C) The silicone resin further has a content of OH groups bonded to Si atoms and hydrogen atoms bonded to Si atoms each represented by a repeating structure of the following general formulas (e) and (f). It is preferably less than 0.5% by mass in the molecule. When the amount is 0.5% by mass or more, the increase in the melt viscosity and the decrease in fluidity of the epoxy resin composition for sealing progress due to the increase in the molecular weight of the silicone resin during the molding of the epoxy resin composition for sealing. This may cause molding defects such as unfilling and wire deformation.

(In the formula, * represents a bond to an Si atom in another repeating structural unit or the same repeating structural unit, and R ^1e is a methyl group or a phenyl group. The content of a hydrogen atom bonded to the Si atom is 1) (It is less than 0.5% by mass in the molecule.)
(C) The softening point of the silicone resin is preferably 60 ° C or higher and 100 ° C or lower. When the softening point is less than 60 ° C., the glass transition temperature decreases, the warpage fluctuation of the electronic component during operation (high temperature) and stop (normal temperature) increases, and the life of the electronic component is shortened. When the softening point is higher than 100 ° C., the compatibility with the resin component is deteriorated, so that the warpage control ability is not sufficiently exhibited, and the electronic component surface is stained.
(C) The number average molecular weight of the silicone resin is preferably 1000 or more and 10,000 or less. When the number average molecular weight is less than 1000, volatile components increase and voids are likely to be generated inside the electronic component. When the number average molecular weight is greater than 10,000, the compatibility with the resin component is deteriorated, so that the warpage control ability is not sufficiently exhibited, and the electronic component surface is stained.
(C) Silicone resin is dichlorodimethylsilane, dichlorodiphenylsilane, dichloromethylphenylsilane, trichloromethylsilane, trichlorophenylsilane, chlorotrimethylsilane, chlorotriphenylsilane, the target branched structure amount, phenyl group content, It can be obtained by blending at a blending ratio according to molecular weight, hydrolyzing, and dehydrating condensation and purification of the produced silanol group. (C) As a commercial product of silicone resin, KR-480 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), 233FLAKE (trade name, manufactured by Toray Dow Corning), 249 FLAKE (Toray Dow Corning) Product name) etc. are available, but in order to be used for the epoxy resin composition for sealing, it is preferable to use after purification by washing or the like for dechlorination.
These (C) silicone resins may be used alone or in combination of two or more.

  (C) The content of the silicone resin is preferably 0.1% by mass or more and 5% by mass or less, more preferably 0.5% by mass or more and 2% by mass or less in the total epoxy resin composition for sealing, 0.5 mass% or more and 1 mass% or less are especially preferable. By making the content within the above range, good moldability, good warp characteristics and peeling resistance of the semiconductor device can be obtained. If it is less than 0.1% by mass, the contained effect is difficult to obtain, and the glass transition temperature of the cured product is lowered, the coefficient of thermal expansion is increased, and the warpage is increased. If it exceeds 5% by mass, the dispersion state in the epoxy resin deteriorates, and due to an increase in melt viscosity and a decrease in fluidity, defective molding such as poor adhesion, poor filling, and wire deformation occurs.

[Inorganic filler]
The inorganic filler generally used in the said field | area can be used for (D) inorganic filler in this embodiment. Specific examples include fused crushed silica, fused spherical silica, crystalline silica, alumina, silicon nitride, and aluminum nitride. These inorganic fillers may be used alone or in combination. Preferably, fused spherical silica is used.

(D) It is preferable that the average particle diameter of an inorganic filler is 0.01 micrometer or more and 150 micrometers or less from a viewpoint of a filling property. The average particle size can be measured using a laser diffraction / scattering particle size distribution meter.
(D) The content of the inorganic filler in the total sealing epoxy resin composition is preferably 75% by mass or more and 93% by mass or less, more preferably 80% by mass or more and 91% by mass or less, More preferably, it is 85 mass% or more and 90 mass% or less. Within the above range, it is possible to obtain peeling resistance because it is sufficiently adhered to a semiconductor element at a high temperature and warpage is reduced and no great stress is applied to the element. When the content is less than the lower limit value, good solder crack resistance cannot be obtained, the weight reduction rate at high temperature is increased, the linear expansion coefficient is increased, warpage is increased, and peeling resistance is decreased. When content exceeds an upper limit, the fluidity | liquidity and moldability of the epoxy resin composition for sealing will fall.

  Moreover, it is preferable to contain simultaneously the inorganic filler (D1) with an average particle diameter of 7 micrometers or more and 50 micrometers or less, and the inorganic filler (D2) with an average particle diameter of 1 micrometer or less. The content of (D1) is preferably 60% by mass or more and 85% by mass or less, more preferably 65% by mass or more and 83% by mass or less in the total sealing epoxy resin composition, and the content of (D2) is In the total sealing epoxy resin composition, 1% by mass to 25% by mass is preferable, and 3% by mass to 20% by mass is more preferable. Within the above range, since it is sufficiently adhered to a semiconductor element at a high temperature and does not give a large stress to the element, it is possible to obtain warpage resistance and peeling resistance.

  In addition, when using inorganic flame retardants such as metal hydroxides such as aluminum hydroxide and magnesium hydroxide, zinc borate, zinc molybdate and antimony trioxide described later, these inorganic flame retardants and the above The total amount of inorganic filler is preferably within the above range.

[Curing accelerator]
(E) A hardening accelerator has a function which accelerates | stimulates the reaction of the epoxy groups of an epoxy resin, and the reaction of an epoxy resin and a hardening | curing agent, and the hardening accelerator generally used is used.

  Specific examples of the (E) curing accelerator include phosphorus atom-containing compounds such as organic phosphines, tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, and adducts of phosphonium compounds and silane compounds; Amidines and tertiary amines exemplified by 1,8-diazabicyclo (5,4,0) undecene-7, benzyldimethylamine, 2-methylimidazole and the like, and further nitrogen atoms such as quaternary salts of the amidine and amine A compound is mentioned and 1 type or 2 types or more of these can be used in combination. Among these, a phosphorus atom-containing compound is preferable from the viewpoint of curability, and an adduct of a phosphobetaine compound and a phosphine compound and a quinone compound is particularly preferable from the viewpoint of solder resistance and fluidity. In terms of mild contamination, phosphorus-containing compounds such as tetra-substituted phosphonium compounds and adducts of phosphonium compounds and silane compounds are particularly preferred.

  Examples of the organic phosphine that can be used in the epoxy resin composition for sealing include a first phosphine such as ethylphosphine and phenylphosphine; a second phosphine such as dimethylphosphine and diphenylphosphine; trimethylphosphine, triethylphosphine, tributylphosphine, and triphosphine. A third phosphine such as phenylphosphine can be mentioned.

  Examples of the tetra-substituted phosphonium compound that can be used in the sealing epoxy resin composition include compounds represented by the following general formula (1).

（ただし、上記一般式（１）において、Ｐはリン原子を表す。Ｒ^２、Ｒ^３、Ｒ^４およびＲ^５は芳香族基またはアルキル基を表す。Ａはヒドロキシル基、カルボキシル基、チオール基から選ばれる官能基のいずれかを芳香環に少なくとも１つ有する芳香族有機酸のアニオンを表す。ＡＨはヒドロキシル基、カルボキシル基、チオール基から選ばれる官能基のいずれかを芳香環に少なくとも１つ有する芳香族有機酸を表す。ｘ、ｙは１〜３の数、ｚは０〜３の数であり、かつｘ＝ｙである。）

(However, in the above general formula (1), P is ^.R 2 representing the phosphorus ^atom, R 3, .A ^{R 4} and ^{R 5} representing an aromatic group or alkyl group is a hydroxyl group, a carboxyl group, a thiol group An anion of an aromatic organic acid having at least one of the selected functional groups in the aromatic ring, AH having at least one of the functional groups selected from a hydroxyl group, a carboxyl group, and a thiol group in the aromatic ring Represents an aromatic organic acid, where x and y are numbers from 1 to 3, z is a number from 0 to 3, and x = y.

Although the compound represented by General formula (1) is obtained as follows, for example, it is not limited to this. First, a tetra-substituted phosphonium halide, an aromatic organic acid and a base are mixed in an organic solvent and mixed uniformly to generate an aromatic organic acid anion in the solution system. Then, when water is added, the compound represented by the general formula (1) can be precipitated. In the compound represented by the general formula (1), R ² , R ³ , R ⁴ and R ⁵ bonded to the phosphorus atom are phenyl groups, and AH is a compound having a hydroxyl group in an aromatic ring, that is, phenols. And A is preferably an anion of the phenol. Examples of the phenols in the present embodiment include monocyclic phenols such as phenol, cresol, resorcin, and catechol, condensed polycyclic phenols such as naphthol, dihydroxynaphthalene, and anthraquinol, bisphenol A, bisphenol F, and bisphenol S. Examples thereof include polycyclic phenols such as bisphenols, phenylphenol and biphenol.

  Examples of the phosphobetaine compound include compounds represented by the following general formula (2).

（ただし、上記一般式（２）において、Ｒ^６は炭素数１〜３のアルキル基、Ｒ^７はヒドロキシル基を表す。ａは０〜５の数であり、ｂは０〜４の数である。）

(However, in the above general formula (2), ^{R 6} is an alkyl group having 1 to 3 carbon atoms, ^{R 7} is the number of .a 0-5 representing a hydroxyl group, b is the number of 0 to 4 .)

  The compound represented by the general formula (2) is obtained, for example, as follows. First, it is obtained through a step of bringing a triaromatic substituted phosphine, which is a third phosphine, into contact with a diazonium salt and replacing the triaromatic substituted phosphine with a diazonium group of the diazonium salt. However, the present invention is not limited to this.

  Examples of the adduct of a phosphine compound and a quinone compound include compounds represented by the following general formula (10).

（ただし、上記一般式（１０）において、Ｐはリン原子を表す。Ｒ^２９、Ｒ^３０およびＲ^３１は炭素数１〜１２のアルキル基または炭素数６〜１２のアリール基を表し、互いに同一であっても異なっていてもよい。Ｒ^３２、Ｒ^３３およびＲ^３４は水素原子または炭素数１〜１２の炭化水素基を表し、互いに同一であっても異なっていてもよく、Ｒ^３３とＲ^３４が結合して環状構造となっていてもよい。）

(However, in the general formula (10), P is ^{.R 29, R 30} and ^{R 31} representing a phosphorus atom is an alkyl group or an aryl group having 6 to 12 carbon atoms having 1 to 12 carbon atoms, identical to one another R ³² , R ³³ and R ³⁴ each represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and may be the same or different from each other, and R ³³ and R ³⁴ may be different from each other. May be combined to form a ring structure.)

  Examples of the phosphine compound used as an adduct of a phosphine compound and a quinone compound include an aromatic ring such as triphenylphosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, trinaphthylphosphine, and tris (benzyl) phosphine. Those having a substituent or a substituent such as an alkyl group and an alkoxyl group are preferred, and examples of the substituent such as an alkyl group and an alkoxyl group include those having 1 to 6 carbon atoms. From the viewpoint of availability, triphenylphosphine is preferable.

  Moreover, as a quinone compound used for the adduct of a phosphine compound and a quinone compound, a benzoquinone and anthraquinones are mentioned, Especially, p-benzoquinone is preferable from the point of storage stability.

  As a method for producing an adduct of a phosphine compound and a quinone compound, the adduct can be obtained by contacting and mixing in a solvent capable of dissolving both organic tertiary phosphine and benzoquinone. The solvent is preferably a ketone such as acetone or methyl ethyl ketone, which has low solubility in the adduct. However, the present invention is not limited to this.

In the compound represented by the general formula (10), R ²⁹ , R ³⁰ and R ³¹ bonded to the phosphorus atom are phenyl groups, and R ³² , R ³³ and R ³⁴ are hydrogen atoms, ie, 1, A compound in which 4-benzoquinone and triphenylphosphine are added is preferable in that it reduces the thermal elastic modulus of the cured product of the sealing epoxy resin composition.

  Examples of the adduct of a phosphonium compound and a silane compound include compounds represented by the following general formula (3).

（ただし、上記一般式（３）において、Ｐはリン原子を表し、Ｓｉは珪素原子を表す。Ｒ^８、Ｒ^９、Ｒ^１０およびＲ^１１は、それぞれ、芳香環または複素環を有する有機基、あるいは脂肪族基を表し、互いに同一であっても異なっていてもよい。式中Ｒ^１２は、基Ｙ^２およびＹ^３と結合する有機基である。式中Ｒ^１３は、基Ｙ^４およびＹ^５と結合する有機基である。Ｙ^２およびＹ^３は、プロトン供与性基がプロトンを放出してなる基を表し、同一分子内の基Ｙ^２およびＹ^３が珪素原子と結合してキレート構造を形成するものである。Ｙ^４およびＹ^５はプロトン供与性基がプロトンを放出してなる基を表し、同一分子内の基Ｙ^４およびＹ^５が珪素原子と結合してキレート構造を形成するものである。Ｒ^１２とＲ^１３は互いに同一であっても異なっていてもよく、Ｙ^２、Ｙ^３、Ｙ^４、およびＹ^５は互いに同一であっても異なっていてもよい。Ｚ^１は芳香環または複素環を有する有機基、あるいは脂肪族基である。）

(However, in the said General formula (3), P represents a phosphorus atom and Si represents a silicon atom. R < ⁸ >, R < ⁹ >, R < ¹⁰ > and R < ¹¹ > are respectively an organic group which has an aromatic ring or a heterocyclic ring, Alternatively, it represents an aliphatic group, which may be the same or different from each other, wherein R ¹² is an organic group bonded to the groups Y ² and Y ^{3. In the} formula, R ¹³ represents the groups Y ⁴ and Y. ⁵ and an organic group linked .Y ² and Y ³ represents a group proton donating group releases a proton, chelating structural groups Y ² and Y ³ in the same molecule are bonded to a silicon atom Y ⁴ and Y ⁵ each represent a group formed by releasing a proton from a proton donating group, and the groups Y ⁴ and Y ⁵ in the same molecule are bonded to a silicon atom to form a chelate structure. R ¹² and R ¹³ are the same as each other Y ² , Y ³ , Y ⁴ , and Y ⁵ may be the same or different from each other, Z ¹ is an organic group having an aromatic ring or a heterocyclic ring, or a fatty acid A group.)

In the general formula (3), examples of R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ include a phenyl group, a methylphenyl group, a methoxyphenyl group, a hydroxyphenyl group, a naphthyl group, a hydroxynaphthyl group, a benzyl group, and a methyl group. , Ethyl group, n-butyl group, n-octyl group, cyclohexyl group and the like, among these, alkyl groups such as phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group, hydroxynaphthyl group, and alkoxy groups An aromatic group having a substituent such as a hydroxyl group or an unsubstituted aromatic group is more preferable.

In the general formula ^{(3), R 12} is an organic group bonded to ^{Y 2} and ^{Y 3.} Similarly, R ¹³ is an organic group that binds to groups Y ⁴ and Y ⁵ . Y ² and Y ³ are groups formed by proton-donating groups releasing protons, and groups Y ² and Y ³ in the same molecule are combined with a silicon atom to form a chelate structure. Similarly, Y ⁴ and Y ⁵ are groups formed by proton-donating groups releasing protons, and groups Y ⁴ and Y ⁵ in the same molecule are combined with a silicon atom to form a chelate structure. The groups R ¹² and R ¹³ may be the same or different from each other, and the groups Y ² , Y ³ , Y ⁴ , and Y ⁵ may be the same or different from each other. In such a group represented by —Y ² —R ¹² —Y ³ — and Y ⁴ —R ¹³ —Y ⁵ — in the general formula (3), the proton donor releases two protons. The proton donor is preferably an organic acid having at least two carboxyl groups or hydroxyl groups in the molecule, and further has a carboxyl group or hydroxyl group on the adjacent carbon constituting the aromatic ring. An aromatic compound having at least two is preferable, and an aromatic compound having at least two hydroxyl groups on adjacent carbons constituting the aromatic ring is more preferable. For example, catechol, pyrogallol, 1,2-dihydroxynaphthalene, 2,3-dihydroxy Naphthalene, 2,2′-biphenol, 1,1′-bi-2-naphthol, salicylic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy Roxy-2-naphthoic acid, chloranilic acid, tannic acid, 2-hydroxybenzyl alcohol, 1,2-cyclohexanediol, 1,2-propanediol, glycerin, and the like, among these, catechol, 1,2- Dihydroxynaphthalene and 2,3-dihydroxynaphthalene are more preferable.

Z ¹ in the general formula (3) represents an organic group or an aliphatic group having an aromatic ring or a heterocyclic ring. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, Aliphatic hydrocarbon groups such as hexyl group and octyl group, aromatic hydrocarbon groups such as phenyl group, benzyl group, naphthyl group and biphenyl group, glycidyloxy groups such as glycidyloxypropyl group, mercaptopropyl group and aminopropyl group Reactive groups such as mercapto groups, alkyl groups having amino groups, and vinyl groups. Among these, methyl groups, ethyl groups, phenyl groups, naphthyl groups, and biphenyl groups are preferred from the viewpoint of thermal stability. More preferable.

  As a method for producing an adduct of a phosphonium compound and a silane compound, a silane compound such as phenyltrimethoxysilane and a proton donor such as 2,3-dihydroxynaphthalene are added to a flask containing methanol and dissolved, and then room temperature. Sodium methoxide-methanol solution is added dropwise with stirring. Furthermore, when a solution prepared by dissolving a tetra-substituted phosphonium halide such as tetraphenylphosphonium bromide in methanol in methanol is added dropwise with stirring at room temperature, crystals are precipitated. The precipitated crystals are filtered, washed with water, and vacuum dried to obtain an adduct of a phosphonium compound and a silane compound. However, it is not limited to this.

  (C) Although silicone resin like a component raises the melt viscosity of the epoxy resin composition for sealing, and may worsen a moldability, the said general formula (1)-(3) and (3) and ( By using the compound represented by 10), it becomes easy to ensure good fluidity at the time of molding. Further, from the viewpoint of sufficiently adhering to a semiconductor element at a high temperature, an adduct of a phosphine compound and a quinone compound and an adduct of a phosphonium compound and a silane compound are particularly preferable. The reason for this is not clear, but the epoxy resin represented by the general formulas (4) to (9) in the present invention, the aromatic group having a plurality of hydroxyl groups contained in the structure derived from the phenolic curing agent, and the curing acceleration. The agent exhibits unique behavior at the interface of the semiconductor device at the time of curing and at the high operating temperature of the device, so that it may exhibit not only excellent fluidity, adhesion properties, warping behavior but also good moisture resistance reliability properties. Conceivable.

  (E) 0.1 mass% or more and 1 mass% or less are preferable in the epoxy resin composition for whole sealing, and, as for content of a hardening accelerator, 0.11 mass% or more and 0.7 mass% or less are more preferable. 0.12 mass% or more and 0.65 mass% or less is most preferable. (E) When the content of the curing accelerator is within the above range, sufficient curability and fluidity can be obtained, and further, the warp resistance and peel resistance are the best characteristics. It has a unique effect.

[Other ingredients]
Moreover, the component as shown below may be contained in the epoxy resin composition for sealing of this embodiment as needed.

[Compounds in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting an aromatic ring]
In this embodiment, a compound (F) in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting an aromatic ring can be used. Compound (F) is an epoxy resin for sealing, even when a phosphorus atom-containing curing accelerator having no latent property is used as a curing accelerator that promotes a crosslinking reaction between a phenolic curing agent and an epoxy resin. Reaction during melt kneading of the composition can be suppressed.

  By including such a compound (F), it becomes possible to form a sealing material under higher shear conditions, improve the flow characteristics of the epoxy resin composition for sealing, and raise the package surface release component in continuous molding. Or it is preferable at the point which has the effect of lengthening the cleaning cycle of a metal mold | die by suppressing accumulation | storage of the mold release component on the metal mold | die surface.

  The compound (F) has the effect of lowering the melt viscosity of the sealing epoxy resin composition and improving the fluidity, and also has the effect of improving the solder resistance, although the detailed mechanism is unknown.

  As the compound (F), a monocyclic compound represented by the following general formula (11) or a polycyclic compound represented by the following general formula (12) can be used. It may have a substituent.

（ただし、上記一般式（１１）において、Ｒ^３５、Ｒ^３９は少なくともどちらか一方が水酸基であり、片方が水酸基のとき他方は水素原子、水酸基または水酸基以外の置換基のいずれかである。Ｒ^３６、Ｒ^３７およびＲ^３８は水素原子、水酸基または水酸基以外の置換基である。）

(However, in the general formula (11), at least one of R ³⁵ and R ³⁹ is a hydroxyl group, and when one is a hydroxyl group, the other is either a hydrogen atom, a hydroxyl group, or a substituent other than a hydroxyl group. ³⁶ , R ³⁷ and R ³⁸ are a hydrogen atom, a hydroxyl group or a substituent other than a hydroxyl group.)

（ただし、上記一般式（１２）において、Ｒ^４０、Ｒ^４６は少なくともどちらか一方が水酸基であり、片方が水酸基のとき他方は水素原子、水酸基または水酸基以外の置換基のいずれかである。Ｒ^４１、Ｒ^４２、Ｒ^４３、Ｒ^４４およびＲ^４５は水素原子、水酸基または水酸基以外の置換基のいずれかである。）

(However, in the general formula (12), at least one of R ⁴⁰ and R ⁴⁶ is a hydroxyl group, and when one is a hydroxyl group, the other is either a hydrogen atom, a hydroxyl group or a substituent other than a hydroxyl group. ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ and R ⁴⁵ are either a hydrogen atom, a hydroxyl group or a substituent other than a hydroxyl group.)

  Specific examples of the monocyclic compound represented by the general formula (11) include catechol, pyrogallol, gallic acid, gallic acid ester, and derivatives thereof.

  Specific examples of the polycyclic compound represented by the general formula (12) include 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, and derivatives thereof. Among these, a compound in which a hydroxyl group is bonded to each of two adjacent carbon atoms constituting an aromatic ring is preferable because of easy control of fluidity and curability. In consideration of volatilization in the kneading step, it is more preferable that the mother nucleus is a compound having a low volatility and a highly stable weighing naphthalene ring. In this case, specifically, the compound (F) can be a compound having a naphthalene ring such as 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene and derivatives thereof. These compounds (F) may be used alone or in combination of two or more.

  The content of the compound (F) is preferably 0.01% by mass or more and 1% by mass or less, more preferably 0.03% by mass or more, 0.8% in the total sealing epoxy resin composition. It is 0.05 mass% or less, Most preferably, it is 0.05 mass% or more and 0.5 mass% or less. When content of a compound (F) is smaller than a lower limit, the melt viscosity of the epoxy resin composition for sealing will rise and fluidity | liquidity will fall. Moreover, when content of a compound (F) is larger than an upper limit, the sclerosis | hardenability of the epoxy resin composition for sealing will fall, the intensity | strength of hardened | cured material will fall, and a linear expansion coefficient will rise.

[Coupling agent]
The coupling agent has a function to improve the adhesion between the epoxy resin and the inorganic filler when an inorganic filler is included in the sealing epoxy resin composition. For example, a silane coupling agent, etc. Is used.

  As the silane coupling agent, various materials such as anilinosilane can be used.

  The lower limit of the content of the coupling agent such as a silane coupling agent is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, particularly preferably 0 in the total epoxy resin composition for sealing. .1% by mass or more. If content is more than a lower limit, the interface strength of an epoxy resin and an inorganic filler will not fall, and the favorable solder crack resistance in an electronic component apparatus can be obtained. Moreover, as an upper limit of content of coupling agents, such as a silane coupling agent, 1 mass% or less is preferable in the epoxy resin composition for total sealing, More preferably, it is 0.8 mass% or less, Most preferably, it is 0. .6% by mass or less. If content is below an upper limit, the interface strength of an epoxy resin and an inorganic filler will not fall, and the favorable solder crack resistance in an apparatus can be obtained. In addition, if the content of the coupling agent such as a silane coupling agent is within the above range, the water absorption of the cured epoxy resin composition does not increase, and good solder resistance in electronic component devices. Cracking properties can be obtained.

[Inorganic flame retardant]
An inorganic flame retardant has a function which improves the flame retardance of the epoxy resin composition for sealing, and the generally used inorganic flame retardant is used.

  Specifically, metal hydroxides that inhibit the combustion reaction by dehydrating and absorbing heat during combustion, and composite metal hydroxides that can shorten the combustion time are preferably used.

  Examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, and zirconia hydroxide.

  The composite metal hydroxide is a hydrotalcite compound containing two or more metal elements, wherein at least one metal element is magnesium, and the other metal elements are calcium, aluminum, tin, titanium, iron Any metal element selected from cobalt, nickel, copper, or zinc may be used, and as such a composite metal hydroxide, a magnesium hydroxide / zinc solid solution is commercially available.

  Of these, aluminum hydroxide and magnesium hydroxide / zinc solid solution are preferable from the viewpoint of the balance between solder resistance and continuous moldability.

  An inorganic flame retardant may be used independently or may be used 2 or more types. Further, for the purpose of reducing the influence on the continuous moldability, a surface treatment may be performed with a silicon compound such as a silane coupling agent or an aliphatic compound such as wax.

[Release agent]
Here, the mold release agent has a function of releasing the molded product from the mold when molding with a transfer molding machine or the like.
Although it will not specifically limit if it is a mold release agent well-known to those skilled in the art as a mold release agent in this embodiment as an epoxy resin composition for semiconductor sealing, For example, a carnauba is mentioned.
These release agents may be used alone or in combination of two or more.
The lower limit of the content of the release agent is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more in the epoxy resin composition for total sealing. is there. If content of a mold release agent is more than a lower limit, hardened | cured material can be released from a metal mold | die at the time of shaping | molding. Moreover, as an upper limit of the content rate of a mold release agent, 1 mass% or less is preferable in the epoxy resin composition for all sealing, More preferably, it is 0.8 mass% or less, Most preferably, it is 0.5 mass% or less. is there. If content of a mold release agent is below an upper limit, the stain | pollution | contamination by a mold release agent oozing out on the molded article surface can be suppressed.
In addition to the other components described above, components known to those skilled in the art, such as colorants such as carbon black, bengara, and titanium oxide, may be appropriately contained.

  In addition, the epoxy resin composition for sealing of the present invention as described above is prepared by uniformly mixing a curing agent, an epoxy resin, and other components at room temperature using, for example, a mixer. Accordingly, it is possible to adjust to a desired degree of dispersion, fluidity, and the like by melt-kneading using a kneader such as a heating roll, a kneader, or an extruder, and subsequently cooling and pulverizing as necessary.

<Thickness of each component>
Although the dimension of a semiconductor package is not specifically limited, It is preferable to satisfy | fill the following conditions (1)-(3).
(1) The chip height (thickness H1) is preferably 50 μm or more and 500 μm or less, and more preferably 200 μm or more and 400 μm or less.
(2) The thickness H2 of the sealing material is preferably 100 μm or more and 1000 μm or less, and more preferably 200 μm or more and 800 μm or less.
(3) The thickness H3 of the element mounting substrate is preferably 100 μm or more and 3000 μm or less, and more preferably 300 μm or more and 2000 μm or less.
The thickness H1 to the thickness H3 may be an average thickness, for example.
When the dimensions of the semiconductor package satisfy all of the above conditions (1) to (3), it is possible to reduce warpage in the thin semiconductor package. That is, when the element mounting substrate 108 and the mold resin layer 120 are thin layers, the remaining warpage at the time of mounting is likely to occur in the semiconductor package. On the other hand, in this embodiment, even in such a thin semiconductor package, it is possible to reduce the remaining warp during mounting.

(Individualization process)
Subsequently, as shown in FIG. 3A, solder bumps 128 are formed on the opposite surface side of the element mounting substrate 108. Thereafter, as shown in FIG. 3B, the semiconductor chip 116 is separated into pieces using a dicing saw 130 or the like. For example, dicing is performed along the dicing region 112 shown in FIG. 2 to separate each molded semiconductor chip 116 into individual pieces. Thereby, the semiconductor device 100 can be obtained.
Since the semiconductor device 100 of this embodiment is sealed using the specific epoxy resin composition, warping is suppressed even after being singulated, and heat resistance, solder crack resistance, Excellent properties such as temperature cycleability and moisture resistance reliability.
Note that an electronic device can be obtained by mounting the semiconductor device 100 on a motherboard or the like.

<Second Embodiment>
In the first embodiment, a method of manufacturing a semiconductor device referred to as a so-called “MAP method” has been described. However, an electronic component module (package or PKG) exemplified below as an example of the epoxy resin composition for sealing is described. Can also be applied).

That is, Patent Document 7 shows an example of a vehicle-mounted single-side sealed electronic component module, in which an electronic component is mounted on one side of a circuit board and electrically connected to a lead frame terminal with a wire. The other side of the circuit board is bonded to the heat sink via an adhesive layer. A mold package is disclosed in which the terminals of these circuit boards, electronic components, heat sinks, and lead frames are sealed with a mold resin, and attempts have been made to prevent peeling by designing the module structure.
However, in the electronic parts as described above, when the electronic parts are enlarged, the influence of thermal stress or the like becomes large, and the electronic parts themselves are warped, so that peeling occurs at each interface formed between the mold resin and other members. There is a problem that is likely to occur. As a method for solving such a problem, by reducing the linear expansion coefficient of the mold resin, the difference in the linear expansion coefficient between the sealing resin and other members (for example, a heat sink, a circuit board, etc.) is reduced, thereby reducing stress. Such a method is conceivable. There is a method of increasing the content of the inorganic filler as a method of lowering the linear expansion coefficient of the mold resin, but there are problems such as an increase in melt viscosity and deterioration of fluidity.

  That is, in this embodiment, when producing such an electronic component module, an epoxy resin composition containing a specific silicone resin is applied. As a result, the linear expansion coefficient can be set in an appropriate range without causing high melt viscosity or low fluidity, and as a result, warpage of the entire electronic component can be suppressed.

<Electronic component module>
FIG. 4 is a longitudinal sectional view showing an example of the electronic component module of the present embodiment.

  An electronic component module 1 shown in FIG. 4 is an in-vehicle electronic control device that is mounted, for example, in a transmission room of an automobile and controls the operation of the transmission. As shown in FIG. 4, a heat sink 5 and a lead frame terminal 2 are mainly used. A mold resin (sealing epoxy resin) 8, a circuit board 3, and the like.

  The circuit board 3 is made of, for example, a bismaleimide / triazine resin having excellent heat resistance and moisture resistance. The circuit board 3 is capable of supplying an external current, inputting a signal, or outputting a signal to the outside via the lead frame terminal 2 and the wire 6. For example, an electronic component mounted on the circuit board 3 7 performs electronic control of the transmission. Here, a bismaleimide / triazine resin substrate is illustrated as the circuit board 3, but the circuit board 3 may be formed of a ceramic substrate whose surface is coated with a polyimide resin or the like.

  The heat sink 5 is configured, for example, in a plate shape and in a rectangular shape (rectangular shape in plan view) that is slightly larger than the circuit board 3, and heat generated in the circuit board 3 and the lead frame terminal 2 is transmitted to the outside. It has a function to dissipate heat. The heat sink 5 is made of, for example, a material having high thermal conductivity and easy to process. Specific examples of the heat sink 5 include a sintered body of Al and SiC (Al-SiC), SiC, and carbon. Used for. In addition, the material of the heat sink 5 is not limited to these, You may use the other material which functions heat dissipation. Also, the thickness, size, shape, etc. can be variously changed.

  Further, the heat sink 5 and the circuit board 3 are bonded by a substrate adhesive 4. The substrate adhesive 4 that bonds the circuit board 3 and the heat sink 5 is made of, for example, a known resin adhesive.

  The lead frame terminal 2 is electrically connected to an electrode formed on the circuit board 3 and is made of, for example, a metal material. In the electronic component module 1 of the present embodiment, a plurality of lead frame terminals 2 are arranged around the circuit board 3, and each lead frame terminal 2 is, for example, directly or indirectly via a wire 6. Are connected to the electrodes of the circuit board 3. These lead frame terminals 2 are formed by cutting a plate-shaped metal material, and each function as a metal terminal (lead frame terminal).

  In the present embodiment, the direction orthogonal to the plate surface of the circuit board 3 is defined as the vertical direction, the mounting surface side of the electronic component 7 is defined as the upper side, and the heat sink 5 side is defined as the lower side.

The mold resin (sealing resin) 8 integrally seals the circuit board 3, the electronic component 7, the heat sink 5, and one end side portion (the portion on the circuit board 3 side) of the lead frame 2. The circuit board 3 and the joint portion between the circuit board 3 and another member are protected.
As this mold resin (sealing resin) 8, the epoxy resin composition containing the specific silicone resin shown as 1st Embodiment is applicable. As a result, the linear expansion coefficient can be set within an appropriate range without increasing the melt viscosity or reducing the fluidity, and as a result, the warpage of the electronic component module 1 as a whole can be suppressed.

  The entire mounting surface side and the entire side surface of the circuit board 3 are covered with the mold resin 8, and the side edge portion of the substrate adhesive 4 that covers the substrate surface of the circuit board 3 is also covered with the mold resin 8. Therefore, the circuit board 3 is sealed by the mold resin 8 and the board adhesive 4. The entire outer peripheral edge of the heat sink 5 is also covered with the mold resin 8, and the joint portion formed by joining the lead frame terminal 2 and the heat sink 5 is also covered with the mold resin 8 so as not to be exposed to the outside. Since the circuit board 3 is sealed by the mold resin 8 and the waterproofness is enhanced, for example, when the electronic component module 1 is mounted on the transmission unit, a liquid such as ATF oil may be discharged from the circuit board 3 and the electronic circuit. It is protected so as not to enter the vicinity of the component 7.

  Further, in the present embodiment, the electronic component of the present invention is not limited to the case described in the above description, but can be applied to various semiconductor packages in a single-side sealed form. For example, a ball grid array ( BGA), quad flat packed non-lead (QFN), matrix array package ball grid array (MAPBGA). In addition to the single-side sealed package, dual in-line package (DIP), chip carrier with plastic lead (PLCC), quad flat package (QFP), low profile quad flat package ( LQFP), Small Outline Package (SOP), Small Outline J Lead Package (SOJ), Thin Small Outline Package (TSOP), Thin Quad Flat Package (TQFP), Tape Carrier Package ( TCP), chip size package (CSP), chip stacked chip size package and other memory and logic devices, and power transistors and other power devices A package such as O-220 can be preferably applied.

  Although the method for manufacturing a semiconductor device and the semiconductor device of the present invention have been described above, the present invention is not limited to these.

  For example, an optional component that can exhibit the same function may be added to the sealing epoxy resin composition used in the method for manufacturing a semiconductor device of the present invention.

  Moreover, the structure of each part of the electronic component device of the present invention can be replaced with an arbitrary one that can exhibit the same function, or an arbitrary structure can be added.

（式中、＊は他の繰り返し構造単位または同一の繰り返し構造単位中のＳｉ原子への結合を示し、Ｒ^１ａとＲ^１ｂとＲ^１ｃとＲ^１ｄはメチル基またはフェニル基であり、それらは互いに同じでも異なっていても良い。Ｓｉ原子に結合したフェニル基の含有量は１分子中に５０質量％以上、Ｓｉ原子に結合したＯＨ基の含有量は１分子中に０．５質量％未満である。）
［１−２］前記（Ｃ）シリコーンレジンが、更に下記一般式（ｅ）、（ｆ）で示される繰り返し構造単位を有するものである、［１−１］に記載の封止用エポキシ樹脂組成物。

（式中、＊は他の繰り返し構造単位または同一の繰り返し構造単位中のＳｉ原子への結合を示し、Ｒ^１ｅはメチル基またはフェニル基である。Ｓｉ原子に結合した水素原子の含有量は１分子中に０．５質量％未満である。）
［１−３］前記（Ｃ）シリコーンレジンの軟化点が６０℃以上、１００℃以下であり、数平均分子量が１０００以上、１００００以下である、［１−１］または［１−２］に記載の封止用エポキシ樹脂組成物。
［１−４］前記（Ｃ）シリコーンレジンの含有量が、全封止用エポキシ樹脂組成物中０．１質量％以上、５質量％以下である、［１−１］ないし［１−３］のいずれか一項に記載の封止用エポキシ樹脂組成物。
［１−５］前記（Ａ）エポキシ樹脂が、ビフェニル型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂、トリスフェノールメタン型エポキシ樹脂、ビスフェノール型エポキシ樹脂、擬アントラセン型エポキシ樹脂、から選ばれる１種以上である、［１−１］ないし［１−４］のいずれか一項に記載の封止用エポキシ樹脂組成物。
［１−６］前記（Ｂ）硬化剤が、フェノール系硬化剤である、［１−１］ないし［１−５］のいずれか一項に記載の封止用エポキシ樹脂組成物。
［１−７］前記フェノール系硬化剤が、フェノールアラルキル樹脂、またはトリスフェノールメタン骨格を有するフェノール樹脂の少なくとも一方を含むものである、［１−６］に記載の封止用エポキシ樹脂組成物。
［１−８］前記（Ｅ）硬化促進剤が、下記一般式（１）〜（３）で示される化合物から選ばれる１種以上である、［１−１］ないし［１−７］のいずれか一項に記載の封止用エポキシ樹脂組成物。

（ただし、上記一般式（１）において、Ｐはリン原子を表す。Ｒ^２、Ｒ^３、Ｒ^４およびＲ^５は芳香族基またはアルキル基を表す。Ａはヒドロキシル基、カルボキシル基、チオール基から選ばれる官能基のいずれかを芳香環に少なくとも１つ有する芳香族有機酸のアニオンを表す。ＡＨはヒドロキシル基、カルボキシル基、チオール基から選ばれる官能基のいずれかを芳香環に少なくとも１つ有する芳香族有機酸を表す。ｘ、ｙは１〜３の数、ｚは０〜３の数であり、かつｘ＝ｙである。）

（ただし、上記一般式（２）において、Ｒ^６は炭素数１〜３のアルキル基、Ｒ^７はヒドロキシル基を表す。ａは０〜５の数であり、ｂは０〜４の数である。）

（ただし、上記一般式（３）において、Ｐはリン原子を表し、Ｓｉは珪素原子を表す。Ｒ^８、Ｒ^９、Ｒ^１０およびＲ^１１は、それぞれ、芳香環または複素環を有する有機基、あるいは脂肪族基を表し、互いに同一であっても異なっていてもよい。式中Ｒ^１２は、基Ｙ^２およびＹ^３と結合する有機基である。式中Ｒ^１３は、基Ｙ^４およびＹ^５と結合する有機基である。Ｙ^２およびＹ^３は、プロトン供与性基がプロトンを放出してなる基を表し、同一分子内の基Ｙ^２およびＹ^３が珪素原子と結合してキレート構造を形成するものである。Ｙ^４およびＹ^５はプロトン供与性基がプロトンを放出してなる基を表し、同一分子内の基Ｙ^４およびＹ^５が珪素原子と結合してキレート構造を形成するものである。Ｒ^１２とＲ^１３は互いに同一であっても異なっていてもよく、Ｙ^２、Ｙ^３、Ｙ^４、およびＹ^５は互いに同一であっても異なっていてもよい。Ｚ^１は芳香環または複素環を有する有機基、あるいは脂肪族基である。）
［１−９］［１−１］ないし［１−８］のいずれか一項に記載の封止用エポキシ樹脂組成物からなる、半導体封止用エポキシ樹脂組成物。
［１−１０］［１−９］に記載の半導体封止用エポキシ樹脂組成物の硬化物を、封止樹脂として備えることを特徴とする電子部品。The present invention also includes the following aspects.
[1-1]
(A) epoxy resin,
(B) a curing agent,
(C) silicone resin,
(D) inorganic filler,
(E) a curing accelerator,
Including
The (C) silicone resin is a methylphenyl thermoplastic silicone resin, and has a repeating structural unit represented by the following general formulas (a), (b), (c), and (d): Is,
An epoxy resin composition for sealing.

(In the formula, * represents a bond to an Si atom in another repeating structural unit or the same repeating structural unit, R ^1a , R ^1b , R ^1c and R ^1d are a methyl group or a phenyl group, The content of phenyl groups bonded to Si atoms may be 50% by mass or more in one molecule, and the content of OH groups bonded to Si atoms may be less than 0.5% by mass in one molecule. is there.)
[1-2] The epoxy resin composition for sealing according to [1-1], wherein the (C) silicone resin further has a repeating structural unit represented by the following general formulas (e) and (f): object.

(In the formula, * represents a bond to an Si atom in another repeating structural unit or the same repeating structural unit, and R ^1e is a methyl group or a phenyl group. The content of a hydrogen atom bonded to the Si atom is 1) (It is less than 0.5% by mass in the molecule.)
[1-3] The softening point of the (C) silicone resin is 60 ° C. or more and 100 ° C. or less, and the number average molecular weight is 1000 or more and 10,000 or less, described in [1-1] or [1-2]. An epoxy resin composition for sealing.
[1-4] The content of the (C) silicone resin is 0.1% by mass or more and 5% by mass or less in the total sealing epoxy resin composition, [1-1] to [1-3]. The epoxy resin composition for sealing as described in any one of these.
[1-5] The (A) epoxy resin is at least one selected from a biphenyl type epoxy resin, a phenol aralkyl type epoxy resin, a trisphenol methane type epoxy resin, a bisphenol type epoxy resin, and a pseudo anthracene type epoxy resin. [1-1] thru | or the epoxy resin composition for sealing as described in any one of [1-4].
[1-6] The epoxy resin composition for sealing according to any one of [1-1] to [1-5], wherein the (B) curing agent is a phenol-based curing agent.
[1-7] The epoxy resin composition for sealing according to [1-6], wherein the phenol-based curing agent includes at least one of a phenol aralkyl resin or a phenol resin having a trisphenolmethane skeleton.
[1-8] Any of [1-1] to [1-7], wherein the (E) curing accelerator is at least one selected from compounds represented by the following general formulas (1) to (3): The epoxy resin composition for sealing according to claim 1.

(However, in the above general formula (1), P is ^.R 2 representing the phosphorus ^atom, R 3, .A ^{R 4} and ^{R 5} representing an aromatic group or alkyl group is a hydroxyl group, a carboxyl group, a thiol group An anion of an aromatic organic acid having at least one of the selected functional groups in the aromatic ring, AH having at least one of the functional groups selected from a hydroxyl group, a carboxyl group, and a thiol group in the aromatic ring Represents an aromatic organic acid, where x and y are numbers from 1 to 3, z is a number from 0 to 3, and x = y.

(However, in the above general formula (2), ^{R 6} is an alkyl group having 1 to 3 carbon atoms, ^{R 7} is the number of .a 0-5 representing a hydroxyl group, b is the number of 0 to 4 .)

(However, in the said General formula (3), P represents a phosphorus atom and Si represents a silicon atom. R < ⁸ >, R < ⁹ >, R < ¹⁰ > and R < ¹¹ > are respectively an organic group which has an aromatic ring or a heterocyclic ring, Alternatively, it represents an aliphatic group, which may be the same or different from each other, wherein R ¹² is an organic group bonded to the groups Y ² and Y ^{3. In the} formula, R ¹³ represents the groups Y ⁴ and Y. ⁵ and an organic group linked .Y ² and Y ³ represents a group proton donating group releases a proton, chelating structural groups Y ² and Y ³ in the same molecule are bonded to a silicon atom Y ⁴ and Y ⁵ each represent a group formed by releasing a proton from a proton donating group, and the groups Y ⁴ and Y ⁵ in the same molecule are bonded to a silicon atom to form a chelate structure. R ¹² and R ¹³ are the same as each other Y ² , Y ³ , Y ⁴ , and Y ⁵ may be the same or different from each other, Z ¹ is an organic group having an aromatic ring or a heterocyclic ring, or a fatty acid A group.)
[1-9] An epoxy resin composition for encapsulating a semiconductor, comprising the epoxy resin composition for encapsulating according to any one of [1-1] to [1-8].
[1-10] An electronic component comprising a cured product of the epoxy resin composition for semiconductor encapsulation according to [1-9] as a sealing resin.

Next, specific examples of the present invention will be described.
In addition, this invention is not limited to description of these Examples at all.

1. Preparation of raw materials First, raw materials used in the sealing epoxy resin compositions of the examples and comparative examples are shown below.
Unless otherwise specified, the amount of each component is part by mass.

(The components used in Examples 1 to 15 and Comparative Examples 1 to 5 are shown below.
(A) Component epoxy resin:
Epoxy resin 1: A phenol aralkyl type epoxy resin having a biphenylene skeleton having an epoxy equivalent of 276 g / eq and a softening point of 52 ° C. (trade name “NC-3000L” manufactured by Nippon Kayaku Co., Ltd.). In the general formula (4) ^are those having the structure R 14 ^{to R 15} is a hydrogen atom.
Epoxy resin 2: Biphenyl type epoxy resin having an epoxy equivalent of 185 g / eq and a melting point of 108 ° C. (trade name “YX-4000K” manufactured by Mitsubishi Chemical Corporation). In General formula (5), R <^16> , R <^17> , R <^22> , R < ²³ > is a methyl group, R <^18> , R <^19> , R <^20> , R <^21> is a hydrogen atom.
Epoxy resin 3: Phenol aralkyl type epoxy resin having a phenylene skeleton having an epoxy equivalent of 238 g / eq and a softening point of 52 ° C. (trade name “NC-2000”, manufactured by Nippon Kayaku Co., Ltd.). In the general formula (6), R ²⁴ and R ²⁵ have a structure of a hydrogen atom.
Epoxy resin 4: Trisphenolmethane type epoxy resin having an epoxy equivalent of 171 g / eq and a softening point of 59 ° C. (product name “1032H-60” manufactured by Mitsubishi Chemical Corporation). In the general formula (7), R ²⁶ is a hydrogen atom.
Epoxy resin 5: bisphenol A type epoxy resin having an epoxy equivalent of 172 g / eq and a softening point of 45 ° C. (trade name “Epicoat YL6810” manufactured by Mitsubishi Chemical Corporation). In the general formula (8), R ²⁷ is a hydrogen atom.
Epoxy resin 6: Pseudoanthracene skeleton type epoxy resin having an epoxy equivalent of 168 g / eq and a softening point of 115 ° C. (trade name “Epicoat YL7310” manufactured by Mitsubishi Chemical Corporation). In the general formula (9), R ²⁸ is a hydrogen atom.

(B) Component phenolic curing agent:
Phenol-based curing agent 1: phenol aralkyl resin having a biphenylene skeleton having a hydroxyl group equivalent of 198 g / eq and a softening point of 64.5 ° C. (trade name “GPH-65” manufactured by Nippon Kayaku Co., Ltd.). In the general formula (13), R ⁴⁷ has a structure of 4,4′-dimethylenebiphenyl.
Phenol-based curing agent 2: a phenol resin having a trisphenolmethane skeleton having a hydroxyl group equivalent of 97 g / eq and a softening point of 110 ° C. (product name “MEH-7500” manufactured by Meiwa Kasei Co., Ltd.). In the general formula (13), R ⁴⁷ has a structure of hydroxyphenylmethylene.
Phenol-based curing agent 3: a phenol aralkyl resin having a phenylene skeleton having a hydroxyl group equivalent of 175 g / eq and a softening point of 66.5 ° C. (product name “MEH-7800SS” manufactured by Meiwa Kasei Co., Ltd.). In the general formula (13), R ⁴⁷ has a structure of p-xylylene.

Component (D) inorganic filler:
Inorganic filler 1: fused spherical silica (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name “FB560”, average particle size 30 μm). In addition, the average particle diameter in this invention was measured using Shimadzu Corporation laser diffraction scattering type particle size distribution analyzer SALD-7000.
Inorganic filler 2: fused spherical silica (manufactured by Admatechs Co., Ltd., trade name “SO-25R”, average particle size 0.5 μm).
(E) Component curing accelerator:
As the hardening accelerator 1, the hardening accelerator shown by following formula (14) was prepared.

[Method of synthesizing curing accelerator 1]
A separable flask equipped with a stirrer was charged with 37.5 g (0.15 mol) of 4,4′-bisphenol S and 100 ml of methanol, dissolved by stirring at room temperature, and 4.0 g of sodium hydroxide in 50 ml of methanol in advance while stirring. A solution in which (0.1 mol) was dissolved was added. Next, a solution in which 41.9 g (0.1 mol) of tetraphenylphosphonium bromide was previously dissolved in 150 ml of methanol was added. After stirring for a while and adding 300 ml of methanol, the solution in the flask was added dropwise to a large amount of water with stirring to obtain a white precipitate. The precipitate was filtered and dried to obtain white crystal curing accelerator 1.

As the curing accelerator 2, a curing accelerator represented by the following formula (15) was prepared.

[Method of synthesizing curing accelerator 2]
A separable flask equipped with a condenser and a stirrer was charged with 12.81 g (0.080 mol) of 2,3-dihydroxynaphthalene, 16.77 g (0.040 mol) of tetraphenylphosphonium bromide and 100 ml of methanol, and dissolved uniformly. It was. When a sodium hydroxide solution prepared by previously dissolving 1.60 g (0.04 ml) of sodium hydroxide in 10 ml of methanol was gradually dropped into the flask, crystals were deposited. The precipitated crystals were filtered, washed with water, and vacuum-dried to obtain a curing accelerator 2.

As the hardening accelerator 3, the hardening accelerator shown by following formula (16) was prepared.

[Method of synthesizing curing accelerator 3]
In a flask containing 1800 g of methanol, 249.5 g of phenyltrimethoxysilane and 384.0 g of 2,3-dihydroxynaphthalene were added and dissolved, and then 231.5 g of 28% sodium methoxide-methanol solution was added dropwise with stirring at room temperature. Furthermore, when a solution prepared by dissolving 503.0 g of tetraphenylphosphonium bromide prepared in advance in 600 g of methanol was added dropwise with stirring at room temperature, crystals were deposited. The precipitated crystals were filtered, washed with water, and vacuum-dried to obtain a pinky white crystal hardening accelerator 3.

As the curing accelerator 4, a compound in which 1,4-benzoquinone and triphenylphosphine represented by the following formula (17) were added was prepared.

[Synthesis Method of Curing Accelerator 4]
A separable flask equipped with a condenser and a stirrer was charged with 6.49 g (0.060 mol) of benzoquinone, 17.3 g (0.066 mol) of triphenylphosphine and 40 ml of acetone, and reacted at room temperature with stirring. The precipitated crystals were washed with acetone, filtered and dried to obtain dark green crystal curing accelerator 4.

(Silane coupling agent)
As the silane coupling agent 1, N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM-573”) was prepared.

Silicone resin (C): The following silicone resins 1 to 7 were washed with water at 100 ° C. for 2 hours and sufficiently dried before use.
Silicone resin 1: methyl phenyl having a content of phenyl groups bonded to Si atoms of 55% by mass, a content of OH groups bonded to Si atoms of 0.3% by mass, and a content of hydrogen atoms bonded to Si atoms of 0.1% Type silicone resin (synthesized by the following synthesis method: number average molecular weight 2900, softening point 90 ° C.)
[Synthesis Method of Silicone Resin 1]
In a 1 L flask equipped with a stirrer, a cooling device, and a thermometer, 87.0 g (0.39 mol) of phenyltrichlorosilane, 45.2 g (0.18 mol) of diphenyldichlorosilane, and 37.4 g (0.25 of methyltrichlorosilane) Mol), 23.0 g (0.18 mol) of dimethyldichlorosilane and 150 g of toluene were charged and heated to an internal temperature of 40 ° C. in an oil bath. Methanol (64 g, 2 mol) was charged into the dropping funnel and added dropwise to the flask with stirring for 1 hour, and the reaction was advanced while removing hydrogen chloride gas generated during the alkoxylation reaction out of the system. After completion of the dropwise addition, the mixture was further aged by continuing stirring at an internal temperature of 40 ° C. for 1 hour. Next, 12 g (0.7 mol) of water was charged into the dropping funnel and dropped into the flask with stirring for 1 hour, and the reaction was advanced while removing hydrogen chloride gas generated during the hydrolysis condensation reaction out of the system. . After completion of the dropwise addition, stirring is further continued for 1 hour at an internal temperature of 40 ° C., and the dehydration condensation reaction of the produced silanol group is advanced and ripened. Subsequently, toluene, excess methanol, unreacted water and hydrogen chloride are removed by vacuum distillation. Removal of 102 g of solid silicone resin 1 was obtained.
Silicone resin 2: methyl having a phenyl group content of 57% by mass bonded to Si atoms, a content of OH groups bonded to Si atoms of 0.3% by mass, and a content of hydrogen atoms bonded to Si atoms of 0.07% by mass Phenyl type silicone resin (manufactured by Toray Dow Corning Co., Ltd., trade name “233FLAKE”, number average molecular weight 1500 (weight average molecular weight 2200), softening point 80 ° C.)
Silicone resin 3: methyl having a phenyl group content of 54% by mass bonded to Si atoms, a content of OH groups bonded to Si atoms of 0.3% by mass, and a content of hydrogen atoms bonded to Si atoms of 0.06% by mass Phenyl type silicone resin (manufactured by Toray Dow Corning Co., Ltd., trade name “249FLAKE”, number average molecular weight 1600 (weight average molecular weight 3400), softening point 85 ° C.)
Silicone resin 4: methyl content of phenyl group bonded to Si atom 45% by mass, content of OH group bonded to Si atom 0.3% by mass, content of hydrogen atom bonded to Si atom 0.06% by mass Phenyl type silicone resin (manufactured by Toray Dow Corning Co., Ltd., trade name “220FLAKE”, number average molecular weight 3000, softening point 100 ° C.)
Silicone resin 5: dimethyl type silicone rubber having a phenyl group content of 0% by mass bonded to Si atoms and an OH group content of 0.1% by mass bonded to Si atoms (made by Toray Dow Corning Co., Ltd., trade name “ CF2152 ")
Silicone Resin 6: A methylphenyl type silicone resin having a phenyl group content of 57% by mass bonded to Si atoms and an OH group content of 6% by mass bonded to Si atoms (manufactured by Toray Dow Corning Co., Ltd., trade name “217FLAKE”) ”Number average molecular weight 1100, softening point 75 ° C.)
Silicone Resin 7: Propylphenyl type silicone resin having a phenyl group content of 54% by mass bonded to Si atoms and an OH group content of 0.3% by mass bonded to Si atoms (manufactured by Toray Dow Corning Co., Ltd., trade name) “SH6018”, number average molecular weight 1700, softening point 100 ° C.)

(Release agent)
As the mold release agent 1, carnauba (manufactured by Nikko Fine Co., Ltd., trade name “Nikko Carnauba”) was prepared.

(Coloring agent)
As the colorant 1, carbon black (manufactured by Mitsubishi Chemical Corporation, trade name “MA600”) was prepared.

2. Production of epoxy resin composition for sealing [Example 1]
Epoxy resin 1 (8.00 parts by mass), phenolic curing agent 1 (5.00 parts by mass), inorganic filler 1 (75.00 parts by mass), inorganic filler 2 (10.00 parts by mass), curing acceleration Agent 4 (0.20 parts by mass), Silane coupling agent 1 (0.20 parts by mass), Release agent 1 (0.20 parts by mass), Silicone resin 1 (1.00 parts by mass), Colorant 1 ( 0.40 parts by mass) were weighed and mixed using a mixer, and then kneaded using two rolls having surface temperatures of 95 ° C. and 25 ° C. to obtain a kneaded product. Next, the kneaded product was pulverized after cooling to obtain the sealing epoxy resin composition of Example 1.

[Examples 2 to 15, Comparative Examples 1 to 5]
Except having changed the kind and the compounding quantity of raw materials as shown in Table 1 and Table 2, it carried out similarly to the said Example 1, and carried out the epoxy resin composition for sealing of Examples 2-15 and Comparative Examples 1-5. Obtained.

3. Evaluation The epoxy resin compositions for sealing of each Example and each Comparative Example were evaluated by the following methods.

3-1. Evaluation of Spiral Flow (SF) Using a low-pressure transfer molding machine (“KTS-15” manufactured by Kotaki Seiki Co., Ltd.), a spiral flow measurement mold according to ANSI / ASTM D 3123-72 was applied at 175 ° C. The sealing epoxy resin composition of each example and each comparative example was injected under the conditions of an injection pressure of 6.9 MPa and a holding pressure time of 120 seconds, and the flow length was measured.

  The spiral flow is a fluidity parameter, and the larger the value, the better the fluidity. In order to seal the module when applied to an in-vehicle semiconductor package, it is preferably 100 cm or more.

3-2. Evaluation of Melt Viscosity Using a Koka type flow tester (manufactured by Shimadzu Corporation, trade name “CFT-500D”), the sample is put into the cylinder, and the plunger is lowered at a pressure of 40 kgf / cm ^2. Was allowed to flow out of a nozzle die (nozzle 1 mmφ, thickness 1 mm) and the Koka type viscosity was measured. The unit is Pa · s.

3-3. Evaluation of glass transition temperature (hereinafter referred to as Tg), linear expansion coefficient α1 (linear expansion coefficient in a temperature region below Tg), α2 (linear expansion coefficient in a temperature region above Tg) Sealing of each example and each comparative example The epoxy resin composition for stopping is 15 mm × 4 mm × 3 mm with a mold temperature of 175 ° C., an injection pressure of 6.9 MPa, and a curing time of 90 seconds using a transfer molding machine (50 ton transfer press manufactured by Towa Seiki Co., Ltd.). The test piece was molded and post-cured at 175 ° C. for 4 hours. The glass transition temperature, the linear expansion coefficient α1, and the linear expansion coefficient α2 of the test piece were measured using a thermomechanical analyzer (trade name “TMA-120” manufactured by Seiko Electronics Co., Ltd., heating rate 5 ° C./min). Measured. Tg was the intersection of 30 ° C. and 280 ° C. tangent. The unit of the linear expansion coefficient α is (/ ° C.).

3-4. Warpage evaluation (thick package)
Using a transfer molding machine (30 ton transfer press manufactured by Kotaki Seiki Co., Ltd.), the mold temperature is 175 ° C., the injection pressure is 6.9 MPa, the curing time is 2 minutes, and the in-vehicle semiconductor device (mold part 75 mm × 65 mm, thickness 6.7 mm, circuit board is 55 mm x 55 mm, 1.6 mm thick FR-4 (Frame Regentant Type 4) board, heat sink is 60 mm x 60 mm, 1.5 mm thick Al, copper lead frame and circuit board The bonding pad was bonded with a 150 μm diameter aluminum wire) to obtain a semiconductor device. After cooling the obtained 10 semiconductor devices to room temperature, the displacement in the height direction was measured using a surface roughness meter in the diagonal direction of the mold part of the semiconductor device, and the value with the largest variation difference was taken as the amount of warpage. . Furthermore, after post-curing at 175 ° C. for 4 hours, the amount of warpage was measured in the same manner. The unit is μm. A case of 100 μm or more was judged as defective.
(Thin package)
A semiconductor element having a size of 10 mm × 9 mm and a thickness of 294 μm is assigned to each individual unit of 14 mm × 14 mm arranged on a multi-sided printed wiring board having a thickness of 300 μm and arranged in 4 × 13 pieces (vertical × horizontal). The element mounting substrate placed in this manner is put into a mold of a compression molding machine (compression mold press manufactured by TOWA Co., Ltd.), and a sealing material is put into a cavity forming a sealing portion of the mold, and the temperature is 175 ° C. A batch sealing substrate was obtained by performing compression molding in a curing time of 2 minutes.
The obtained collective sealing substrate had a sealing portion size of 55 mm × 190 mm (length × width) and a sealing portion thickness of 500 μm.
After cooling the resulting encapsulated substrate to room temperature, measure the displacement in the height direction using a surface roughness meter in the diagonal direction of the mold part of the encapsulated substrate, and set the maximum amount of variation difference as the amount of warpage. It was.
The obtained collective sealing substrate was cut using a dicing saw (manufactured by DISCO) and divided (diced) into individual pieces. A plurality of separated semiconductor devices were obtained. For the individual semiconductor device, the displacement in the height direction was measured using a surface roughness meter, and the value with the largest variation difference was taken as the amount of warpage.

3-5. Evaluation of solder crack resistance 80pQFP (copper lead frame, package outer dimensions: 14mm x 20mm x 2mm thickness) TEG (TEST ELEMENT GROUP) chip (6.0mm x 6.0mm x 0.35mm thick) with aluminum electrode pads , Pad size: 6.5 mm × 6.5 mm) and bonding the aluminum electrode pad of the TEG chip and the electrode pad of the substrate using copper wire 4N (copper purity 99.99% by weight) did. Using a low-pressure automatic transfer molding machine (trade name “GP-ELF” manufactured by Daiichi Seiko Co., Ltd.), the mold temperature is 175 ° C., the injection pressure is 9.8 MPa, and the curing time is 70 seconds. Sealing molding was performed with the sealing epoxy resin composition of any of Examples 1 to 15 or Comparative Examples 1 to 5, and post-curing was performed at 175 ° C. for 4 hours to obtain 80 pQFP.
Six 80pQFP were humidified for 168 hours at 60 ° C. and 60% relative humidity, and then subjected to IR reflow treatment at 260 ° C. for 10 seconds. Peeling and cracks inside the package were confirmed with an ultrasonic flaw detector (trade name “mi-scopehyper II” manufactured by Hitachi Construction Machinery Finetech Co., Ltd.), no cracks, no chip circuit surface peeling, Those with a peeled area of 5% or less were accepted and the number of rejected semiconductor devices was counted.

3-6. Evaluation of temperature cycle resistance Ten thick packages same as warpage evaluation were produced, and the package was put into a temperature cycle tester (trade name “THEMAL SHOCK CHAMBER TSA-101S” manufactured by ESPEC Co., Ltd.). A temperature cycle treatment of 1000 cycles was performed with 30 ° C. and −55 ° C. for 30 minutes as one cycle. The inside of the semiconductor device was checked for cracks and cracks using an ultrasonic flaw detector (trade name “mi-scope hyper II” manufactured by Hitachi Construction Machinery Finetech Co., Ltd.). None of the islands with a peeled area of 5% or less was accepted and the number of rejected semiconductor devices was counted.

3-7. Evaluation of Moisture Resistance (HAST) TEG (TEST ELEMENT GROUP, 1 chip 3 circuit) chip (3.0 × 3.5 mm) with aluminum electrode pad is 16 pSOP (copper lead frame, package outer dimension: 7.2 mm × 11.5mm x 1.95mm thick) is bonded to the island part, and copper wire 4N (copper purity 99.99 wt%) is connected so that the aluminum electrode pad of the TEG chip and the electrode pad of the substrate are connected in a daisy chain. Used for wire bonding. Using the low-pressure transfer molding machine (trade name “KTS-125” manufactured by Kotaki Seiki Co., Ltd.), this was performed under the conditions of a mold temperature of 175 ° C., an injection pressure of 6.9 MPa, and a curing time of 2 minutes. Sealing molding was performed using the sealing epoxy resin composition of any one of 1 to 15 or Comparative Examples 1 to 5 to produce a 16pSOP package. This package was post-cured at 175 ° C. for 4 hours to obtain a semiconductor device.
A HAST test was conducted according to IEC68-2-66 using six 16pSOPs. Test conditions are 140 ° C 85% RH, DC20V applied, 40 hours, 80 hours, 120 hours, 160 hours, 200 hours, and 240 hours. (10 packages × 3 circuits = 30 circuits were detected), an average failure time (MTTF: Mean Time To Failure; hereinafter referred to as MTTF) was determined, and an average value of six 16pSOPs was determined.

3-8. Evaluation of Flame Resistance Test Using a transfer molding machine (30 ton transfer press manufactured by Kotaki Seiki Co., Ltd.), a test piece (127 mm × 12.7 mm × 3. 3) at a molding temperature of 175 ° C., a pressure of 6.9 MPa, and a curing time of 120 seconds. 2mm), and post-curing was performed at 175 ° C for 4 hours to obtain a test piece. The test piece was subjected to a combustion test according to the UL-94 test method, and the total after flame time of the five test pieces was evaluated as the total after flame time.

  The evaluation results in the epoxy resin compositions for sealing of Examples and Comparative Examples obtained as described above are shown in Tables 1 and 2 below, respectively.

  As shown in Tables 1 and 2, the epoxy resin composition for sealing of each example containing (C) silicone resin has low viscosity, high flow characteristics (spiral flow), and sealing. The cured epoxy resin composition has a high glass transition temperature (Tg), a low coefficient of thermal expansion (α2), sufficient flame resistance, and an excellent balance. Furthermore, the epoxy resin composition for sealing The semiconductor device encapsulated in (1) exhibited an excellent balance of small room temperature warpage and reliability (solder crack resistance, temperature cycle resistance, moisture resistance reliability).

  In contrast, Comparative Example 1 does not contain (C) a silicone resin and instead uses an increased amount of inorganic filler. Therefore, although high Tg, α1, α2, warping behavior is good, fluidity The melt viscosity, solder crack resistance, temperature cycle resistance, and moisture resistance reliability were inferior. In Comparative Example 2 and Comparative Example 3, since a silicone resin in which the phenyl group bonded to the Si atom contained in one molecule is less than 50% by mass is used, the fluidity is equal to that of the example. , Α1, α2, warpage, solder crack resistance, temperature cycle resistance, and moisture resistance reliability were poor. In Comparative Example 4, since a methylphenyl type silicone resin containing a large amount of OH groups bonded to Si atoms is used, the increase in melt viscosity is large, resulting in poor solder crack resistance, temperature cycle resistance, and moisture resistance reliability. Met. In Comparative Example 5, since a propylphenyl type silicone resin was used, the fluidity and warpage control characteristics were good, but the results were poor in flame resistance.

  This application claims the priority on the basis of Japanese application Japanese Patent Application No. 2013-145061 for which it applied on July 11, 2013, and takes in those the indications of all here.

Claims (9)

Preparing a device mounting substrate having a plurality of package areas partitioned by a dicing region; and
A mounting step of mounting a semiconductor chip in each of the package areas of the element mounting substrate;
A molding step of simultaneously molding the semiconductor chip with an epoxy resin composition for sealing;
Dicing along the dicing region, and a singulation step of dividing each molded semiconductor chip,
Including
The sealing epoxy resin composition is
(A) epoxy resin,
(B) a curing agent,
(C) silicone resin,
(D) inorganic filler,
(E) a curing accelerator,
Including
The (C) silicone resin is a methylphenyl thermoplastic silicone resin, and has a repeating structural unit represented by the following general formulas (a), (b), (c), and (d): A method for manufacturing a semiconductor device.

(In the formula, * represents a bond to an Si atom in another repeating structural unit or the same repeating structural unit, R ^1a , R ^1b , R ^1c and R ^1d are a methyl group or a phenyl group, The content of phenyl groups bonded to Si atoms may be 50% by mass or more in one molecule, and the content of OH groups bonded to Si atoms may be less than 0.5% by mass in one molecule. is there.) The method for manufacturing a semiconductor device according to claim 1, wherein the (C) silicone resin further has a repeating structural unit represented by the following general formulas (e) and (f).

(In the formula, * represents a bond to an Si atom in another repeating structural unit or the same repeating structural unit, and R ^1e is a methyl group or a phenyl group. The content of a hydrogen atom bonded to the Si atom is 1) (It is less than 0.5% by mass in the molecule.)   The method for manufacturing a semiconductor device according to claim 1, wherein the softening point of the (C) silicone resin is 60 ° C. or more and 100 ° C. or less, and the number average molecular weight is 1000 or more and 10,000 or less.   4. The semiconductor device according to claim 1, wherein the content of the (C) silicone resin is 0.1% by mass or more and 5% by mass or less in the total sealing epoxy resin composition. Production method.   The (A) epoxy resin is at least one selected from a biphenyl type epoxy resin, a phenol aralkyl type epoxy resin, a trisphenol methane type epoxy resin, a bisphenol type epoxy resin, and a pseudo anthracene type epoxy resin. 5. The method for manufacturing a semiconductor device according to claim 4.   The method for manufacturing a semiconductor device according to claim 1, wherein the (B) curing agent is a phenol-based curing agent.   The method for manufacturing a semiconductor device according to claim 6, wherein the phenol-based curing agent includes at least one of a phenol aralkyl resin or a phenol resin having a trisphenolmethane skeleton. The method for manufacturing a semiconductor device according to claim 1, wherein the (E) curing accelerator is one or more selected from compounds represented by the following general formulas (1) to (3). .

(However, in the above general formula (1), P is ^.R 2 representing the phosphorus ^atom, R 3, .A ^{R 4} and ^{R 5} representing an aromatic group or alkyl group is a hydroxyl group, a carboxyl group, a thiol group An anion of an aromatic organic acid having at least one of the selected functional groups in the aromatic ring, AH having at least one of the functional groups selected from a hydroxyl group, a carboxyl group, and a thiol group in the aromatic ring Represents an aromatic organic acid, where x and y are numbers from 1 to 3, z is a number from 0 to 3, and x = y.

(However, in the above general formula (2), ^{R 6} is an alkyl group having 1 to 3 carbon atoms, ^{R 7} is the number of .a 0-5 representing a hydroxyl group, b is the number of 0 to 4 .)

(However, in the said General formula (3), P represents a phosphorus atom and Si represents a silicon atom. R < ⁸ >, R < ⁹ >, R < ¹⁰ > and R < ¹¹ > are respectively an organic group which has an aromatic ring or a heterocyclic ring, Alternatively, it represents an aliphatic group, which may be the same or different from each other, wherein R ¹² is an organic group bonded to the groups Y ² and Y ^{3. In the} formula, R ¹³ represents the groups Y ⁴ and Y. ⁵ and an organic group linked .Y ² and Y ³ represents a group proton donating group releases a proton, chelating structural groups Y ² and Y ³ in the same molecule are bonded to a silicon atom Y ⁴ and Y ⁵ each represent a group formed by releasing a proton from a proton donating group, and the groups Y ⁴ and Y ⁵ in the same molecule are bonded to a silicon atom to form a chelate structure. R ¹² and R ¹³ are the same as each other Y ² , Y ³ , Y ⁴ , and Y ⁵ may be the same or different from each other, Z ¹ is an organic group having an aromatic ring or a heterocyclic ring, or a fatty acid A group.)   A semiconductor device obtained by the manufacturing method according to claim 1.

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