JP2008094896A - Resin composition for sealing semiconductor and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for sealing a semiconductor excellent in solder resistance, flame retardance and flowability, and also excellent in moistureproof reliability or low warpage property. <P>SOLUTION: This resin for sealing the semiconductor contains (A) an epoxy resin expressed by general formula (1) [wherein, R1s are each a 1-20C hydrocarbon which may be the same or different; R2 is a 1-4C alkyl; (nl) is 0 to 5 integer and the mean value of the total is 0 or <5 positive number; and (m1) is 0 to 6 integer], (B) a compound containing ≥2 phenolic hydroxy, (C) an inorganic filler and (D) a curing accelerator. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a semiconductor sealing resin composition and a semiconductor device.

  In recent years, electronic devices have become more and more compact in size, light weight, and high in performance, and semiconductor elements (hereinafter referred to as “elements” and “chips”) have been increasingly integrated, and semiconductor devices (hereinafter “ The demand for a resin composition for encapsulating a semiconductor (hereinafter also referred to as “encapsulant” or “encapsulant”) is becoming increasingly severe as surface mounting of a package is also promoted. It has become to. In particular, surface mounting of semiconductor devices has become common, and moisture-absorbed semiconductor devices are exposed to high temperatures during soldering, and cracks are generated in the semiconductor devices due to the explosive stress of vaporized water vapor, or semiconductors Delamination occurs at the interface between the element or lead frame and the cured resin composition for semiconductor encapsulation, resulting in defects that greatly impair the electrical reliability of the semiconductor device. Improvement of solderability is a major issue. Furthermore, the use of lead-free solder, which has a higher melting point than before, has been increasing due to the abolition of the use of lead. By using this lead-free solder, it is necessary to increase the mounting temperature by about 20 ° C. compared to the conventional case, and there has been a problem that the reliability of the semiconductor device after mounting is significantly reduced compared to the current situation. Moreover, the request | requirement which provides flame resistance, without using flame retardants, such as a Br compound and antimony oxide, from the environmental problem is also increasing. For improving solder resistance and flame resistance, the former can reduce water absorption and the latter can reduce flammable resin by increasing the filling of the inorganic filler, which is effective as an improved technique for both. Against this background, the recent trend of resin compositions for semiconductor encapsulation is to apply low-viscosity crystalline epoxy resin and maintain more inorganic filling in order to maintain low viscosity and high fluidity during molding. The tendency to mix | blend an agent has become strong (for example, refer patent document 1).

  On the other hand, a large number of semiconductor devices are installed in outdoor equipment such as automobiles, and reliability that can withstand a severer environment than that used in indoor equipment is required. Under high temperature or high humidity, ionic impurities such as chlorine ions contained in the epoxy resin are likely to move. Therefore, corrosion of aluminum wiring on the semiconductor element is likely to proceed. There was a difficulty in moisture resistance reliability which is an essential requirement item. Ionic impurities such as chlorine ions contained in the epoxy resin that cause poor moisture resistance reliability are attributed to glycidyl etherification of phenol with epihalohydrin in the epoxy resin production process. The conventional cresol novolac type epoxy resin has high solubility in a solvent, so that it can be washed with water, and a lower chlorine (high purity) epoxy resin can be obtained. Since the low-viscosity crystalline epoxy resin used has poor solubility in a solvent, it is difficult to obtain a high-purity epoxy resin (see, for example, Patent Document 2).

In order to capture the ionic impurities contained in the resin composition for encapsulating semiconductors, which causes poor moisture resistance reliability, an anionic impurity using an ion scavenger or hydrotalcite compound containing a Bi-based inorganic compound Has been proposed (see, for example, Patent Documents 3, 4, and 5), but a sufficient effect of improving moisture resistance reliability has not been obtained.
As described above, in the lead frame package, there has been a demand for a technology capable of satisfying the requirement of moisture resistance reliability without impairing fluidity, and consequently solder resistance and flame resistance, even when the inorganic filler is highly filled. .

Furthermore, in the market trend of downsizing, weight reduction, and high functionality of electronic devices, semiconductors have been increasingly integrated and the surface mounting of semiconductor packages has been promoted. Developed and starting to migrate from traditionally structured packages.
The area surface mount type semiconductor package is typically a ball grid array (hereinafter referred to as “BGA”) or a chip size package (hereinafter referred to as “CSP”) in pursuit of further miniaturization. These are high-pin counts that are approaching the limit in conventional surface mount packages such as quad flat packages (hereinafter referred to as “QFP”) and small outline packages (hereinafter referred to as “SOP”).・ It was developed to meet the demand for higher speed. The structure is one side of a rigid circuit board typified by bismaleimide triazine (hereinafter referred to as “BT”) resin / copper foil circuit board or a flexible circuit board typified by polyimide resin film / copper foil circuit board. A semiconductor element is mounted on the element, and only the element mounting surface, that is, one side of the substrate is molded and sealed with a resin composition for semiconductor sealing. In addition, solder balls are formed in parallel in a lattice pattern on the surface opposite to the element mounting surface of the substrate, and the package is bonded to a second board for surface mounting. Furthermore, a structure using a metal substrate such as a lead frame in addition to the organic circuit substrate has been devised as a substrate on which elements are mounted.

  The structure of these area surface mount type semiconductor packages is in the form of single-side sealing in which only the element mounting surface of the substrate is sealed with a resin composition for semiconductor sealing, and the solder ball forming surface side is not sealed. In rare cases, when a metal substrate such as a lead frame is used as a substrate on which an element is mounted, a sealing resin layer of about several tens of μm may exist on the solder ball formation surface, but on the element mounting surface, Since a sealing resin layer of about 100 μm to several mm is formed, it is substantially single-side sealed. For this reason, due to mismatch of thermal expansion / shrinkage between the organic substrate or metal substrate and the cured resin composition for semiconductor encapsulation, or due to curing shrinkage during molding / curing of the semiconductor encapsulation resin composition. Due to the influence, the area surface mount type semiconductor package is likely to warp immediately after molding. In addition, when solder bonding is performed on a second board for mounting an area surface mount type semiconductor package, a heating process of 200 ° C. or higher is performed, but at this time, warpage of the package occurs, and a large number of solder balls do not become flat. In some cases, the second board on which the package is mounted floats up and the reliability of electrical connection decreases.

In a package in which only one surface on a substrate such as the area surface mount semiconductor package is sealed with a resin composition for semiconductor encapsulation, the shrinkage of the resin composition for semiconductor encapsulation is reduced in order to reduce warpage. Two methods for reducing the linear expansion coefficient of the substrate and the linear expansion coefficient of the cured resin composition for semiconductor encapsulation are important.
In the organic substrate, resins having a high glass transition temperature such as BT resin and polyimide resin are widely used, and these have a Tg higher than around 170 ° C. which is the molding temperature of the resin composition for semiconductor encapsulation. Accordingly, these organic substrates thermally shrink only in the region where the linear expansion coefficient of the organic substrate is α1 during the cooling process from the molding temperature of the resin composition for semiconductor encapsulation to room temperature. Therefore, if the Tg of the cured product of the resin composition for semiconductor encapsulation is high, the α1 of the cured product is about the same as that of the circuit board, and the cure shrinkage is zero, the warping of the package becomes almost zero. Conceivable. For this reason, a technique has been proposed in which Tg is increased by a combination of a triphenolmethane type epoxy resin and a triphenolmethane type phenol resin, and the curing shrinkage of the resin composition for semiconductor encapsulation is reduced (for example, Patent Document 6). reference.). On the other hand, a method of matching α1 with a substrate by increasing the blending amount of the inorganic filler using a resin having a low melt viscosity has been proposed (see, for example, Patent Document 7). However, although these semiconductor sealing resin compositions are unlikely to warp, the cured product has a high water absorption rate, so that cracks are likely to occur during solder processing, and the flame resistance is also practical without using a flame retardant. There was no case.
Based on the above, there is a need for a technology that can meet the requirements for low warpage in area surface-mount semiconductor packages without sacrificing fluidity, and consequently solder resistance and flame resistance, even if the inorganic filler is highly filled. It was done.
As described above, both the lead frame package and the area surface mount type semiconductor package satisfy the required high level of solder resistance and flame resistance, as well as high fluidity, moisture resistance reliability, and low warpage. Development of a sealing material has been desired.

JP-A-7-130919 JP-A-2-187420 Japanese Patent Laid-Open No. 11-240937 JP-A-9-157497 JP-A-9-169830 Japanese Patent Laid-Open No. 11-147940 Japanese Patent Laid-Open No. 11-1541

  The present invention provides a resin composition for encapsulating a semiconductor excellent in solder resistance, flame resistance and fluidity, and excellent in moisture resistance reliability or low warpage, and a semiconductor device using the same.

The present invention
[1] An epoxy resin (A) represented by the following general formula (1), a compound (B) containing two or more phenolic hydroxyl groups, an inorganic filler (C), a curing accelerator (D), A resin composition for semiconductor encapsulation, comprising:

（ただし、上記一般式（１）において、Ｒ１は炭素数１ないし２０の炭化水素基であり、互いに同じであっても異なっていても良い。Ｒ２は炭素数１ないし４のアルキル基である。ｎ１は０ないし５の整数であり、全体の平均値は０、又は５より小さい正数である。ｍ１は０ないし６の整数である。）

(However, in the above general formula (1), R1 is a hydrocarbon group having 1 to 20 carbon atoms and may be the same or different from each other. R2 is an alkyl group having 1 to 4 carbon atoms. n1 is an integer of 0 to 5, and the overall average value is 0 or a positive number smaller than 5. m1 is an integer of 0 to 6.)

[2] The semiconductor sealing resin composition according to [1], wherein R2 of the epoxy resin (A) represented by the general formula (1) is a methyl group. Resin composition,
[3] In the resin composition for encapsulating a semiconductor according to [1] or [2], the total chlorine content in the epoxy resin (A) represented by the general formula (1) is 300 ppm. A resin composition for semiconductor encapsulation, characterized by:

（ただし、上記一般式（２）において、−Ｒ３−はフェニレン基、ビフェニレン基又はナフチレン基である。−Ｒ４（ＯＨ）−はヒドロキシフェニレン基又は１−ヒドロキシナフチレン基、２−ヒドロキシナフチレン基である。Ｒ５、Ｒ６は、それぞれＲ４、Ｒ３に導入される基で、炭素数１ないし１０の炭化水素基であり、それらは互いに同じであっても異なっていても良い。ｎ２の平均値は１以上、１０以下の正数、ｋ２は０ないし５の整数、ｍ２は０ないし８の整数である。） [4] In the resin composition for encapsulating a semiconductor according to any one of [1] to [3], the compound (B) containing two or more phenolic hydroxyl groups is represented by the following general formula (2). A resin composition for encapsulating a semiconductor, comprising a compound represented by:

(In the general formula (2), -R3- is a phenylene group, a biphenylene group, or a naphthylene group. -R4 (OH)-is a hydroxyphenylene group, a 1-hydroxynaphthylene group, or a 2-hydroxynaphthylene group. R5 and R6 are groups introduced into R4 and R3, respectively, which are hydrocarbon groups having 1 to 10 carbon atoms, which may be the same or different from each other. A positive number of 1 or more and 10 or less, k2 is an integer of 0 to 5, and m2 is an integer of 0 to 8.)

[5] In the resin composition for semiconductor encapsulation according to any one of [1] to [4], the compound (B) containing two or more phenolic hydroxyl groups is represented by the following general formula (3). A resin composition for encapsulating a semiconductor, comprising a compound represented by:

（ただし、上記一般式（３）において、Ｒ５、Ｒ６は、炭素数１ないし１０の炭化水素基であり、それらは互いに同じであっても異なっていても良い。ｎ３の平均値は１以上、１０以下の正数、ｋ３は０ないし３の整数、ｍ３は０ないし４の整数である。）

(In the above general formula (3), R5 and R6 are hydrocarbon groups having 1 to 10 carbon atoms, and they may be the same or different from each other. The average value of n3 is 1 or more, A positive number of 10 or less, k3 is an integer of 0 to 3, and m3 is an integer of 0 to 4.)

[6] In the resin composition for semiconductor encapsulation according to any one of [1] to [4], the compound (B) containing two or more phenolic hydroxyl groups is represented by the following general formula (4). A resin composition for encapsulating a semiconductor, comprising a compound represented by:

（ただし、上記一般式（４）において、Ｒ５、Ｒ６は、炭素数１ないし１０の炭化水素基であり、それらは互いに同じであっても異なっていても良い。ｎ４の平均値は１以上、１０以下の正数、ｋ４は０ないし５の整数、ｍ４は０ないし４の整数である。）

(However, in the general formula (4), R5 and R6 are hydrocarbon groups having 1 to 10 carbon atoms, and they may be the same or different. The average value of n4 is 1 or more, A positive number of 10 or less, k4 is an integer of 0 to 5, and m4 is an integer of 0 to 4.)

[7] In the resin composition for semiconductor encapsulation according to any one of [1] to [6], the curing accelerator (D) is a compound represented by the following general formula (5): A semiconductor represented by the following general formula (6), a compound represented by the following general formula (7), and a compound represented by the following general formula (8): Sealing resin composition,

（ただし、上記一般式（５）において、Ｐはリン原子を表す。Ｒ７、Ｒ８、Ｒ９及びＲ１０は芳香族基、又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。ａ、ｂは１ないし３の整数、ｃは０ないし３の整数であり、かつａ＝ｂである。）

(However, in the said General formula (5), P represents a phosphorus atom. R7, R8, R9, and R10 represent an aromatic group or an alkyl group. A is a function chosen from a hydroxyl group, a carboxyl group, and a thiol group. An anion of an aromatic organic acid having at least one of the groups in the aromatic ring AH represents an aromatic organic having at least one functional group selected from a hydroxyl group, a carboxyl group, and a thiol group in the aromatic ring. Represents an acid, a and b are integers of 1 to 3, c is an integer of 0 to 3, and a = b.

（ただし、上記一般式（６）において、Ｐはリン原子を表す。Ｘ１は水素又は炭素数１ないし３のアルキル基、Ｙ１は水素又はヒドロキシル基を表す。ｍ６、ｎ６は１ないし３の整数。）

(However, in the said General formula (6), P represents a phosphorus atom. X1 represents hydrogen or a C1-C3 alkyl group, Y1 represents hydrogen or a hydroxyl group. M6 and n6 are integers of 1-3. )

（ただし、上記一般式（７）において、Ｐはリン原子を表す。Ｒ１１、Ｒ１２及びＲ１３は炭素数１ないし１２のアルキル基又は炭素数６ないし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。Ｒ１４、Ｒ１５及びＲ１６は水素原子又は炭素数１ないし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、Ｒ１４とＲ１５が結合して環状構造となっていてもよい。）

(In the above general formula (7), P represents a phosphorus atom. R11, R12 and R13 each represents an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, and may be the same as each other). R14, R15 and R16 each represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms and may be the same or different from each other, and R14 and R15 are bonded to form a cyclic structure. May be.)

（ただし、上記一般式（８）において、Ａ１は窒素原子又はリン原子を表す。Ｓｉは珪素原子を表す。Ｒ１７、Ｒ１８、Ｒ１９及びＲ２０は、それぞれ、芳香環又は複素環を有する有機基、或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。Ｘ２は、基Ｙ２及びＹ３と結合する有機基である。Ｘ３は、基Ｙ４及びＹ５と結合する有機基である。Ｙ２及びＹ３は、プロトン供与性置換基がプロトンを放出してなる基であり、それらは互いに同一であっても異なっていてもよく、同一分子内の基Ｙ２、及びＹ３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。Ｙ４及びＹ５は、プロトン供与性置換基がプロトンを放出してなる基であり、同一分子内の基Ｙ４及びＹ５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。Ｘ２、及びＸ３は互いに同一であっても異なっていてもよく、Ｙ２、Ｙ３、Ｙ４、及びＹ５は互いに同一であっても異なっていてもよい。Ｚ１は芳香環又は複素環を有する有機基或いは脂肪族基を表す。）

(In the above general formula (8), A1 represents a nitrogen atom or a phosphorus atom. Si represents a silicon atom. R17, R18, R19 and R20 are each an organic group having an aromatic ring or a heterocyclic ring, or Represents an aliphatic group, which may be the same or different from each other, X2 represents an organic group bonded to the groups Y2 and Y3, and X3 represents an organic group bonded to the groups Y4 and Y5. Y3 is a group formed by releasing a proton from a proton-donating substituent, which may be the same or different from each other, and the groups Y2 and Y3 in the same molecule are bonded to a silicon atom to form a chelate. Y4 and Y5 are groups formed by proton-donating substituents releasing protons, and groups Y4 and Y5 in the same molecule are combined with a silicon atom to form a chelate structure. X2 and X3 may be the same or different from each other, and Y2, Y3, Y4 and Y5 may be the same or different from each other, and Z1 is an organic having an aromatic ring or a heterocyclic ring. Represents a group or an aliphatic group.)

[8] In the resin composition for encapsulating a semiconductor according to any one of [1] to [7], the silane coupling agent (E) and two or more adjacent members constituting an aromatic ring A resin composition for encapsulating a semiconductor, comprising a compound (F) in which a hydroxyl group is bonded to each carbon atom,
[9] In the resin composition for encapsulating a semiconductor according to [8], the compound (F) is a compound in which a hydroxyl group is bonded to each of two adjacent carbon atoms constituting an aromatic ring. A resin composition for encapsulating a semiconductor,
[10] In the semiconductor sealing resin composition described in [8], the compound (F) is a compound in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting a naphthalene ring. A resin composition for encapsulating a semiconductor,
[11] In the resin composition for encapsulating a semiconductor according to [8], the compound (F) is a compound in which a hydroxyl group is bonded to each of two adjacent carbon atoms constituting a naphthalene ring. A resin composition for encapsulating a semiconductor,
[12] In the resin composition for encapsulating a semiconductor according to any one of [8] to [11], the compound (F) is contained in an amount of 0.01% by weight or more based on the total amount of the resin composition. A resin composition for encapsulating a semiconductor, comprising:
[13] In the resin composition for semiconductor encapsulation according to any one of [8] to [12], the silane coupling agent (E) is 0.01% by weight of the resin composition as a whole. Or more, 1 wt% or less, a semiconductor sealing resin composition,
[14] In the resin composition for semiconductor encapsulation according to any one of [1] to [13], the inorganic filler (C) is 80% by weight or more of the total resin composition, 92 A resin composition for encapsulating a semiconductor, comprising:
[15] A semiconductor device comprising a semiconductor element sealed with a cured product of the semiconductor sealing resin composition according to any one of [1] to [14].
[16] A semiconductor device used for an electronic component that is required to have moisture resistance reliability under high temperature and high humidity at a temperature of 80 to 150 ° C. and a relative humidity of 80 to 100%. A semiconductor device characterized by sealing a semiconductor element with a cured product of a sealing resin composition;
[17] A semiconductor element is mounted on one side of the substrate, and substantially only one side of the substrate side on which the semiconductor element is mounted is sealed with a cured product of the resin composition for semiconductor sealing described in the above [6]. Area surface mount semiconductor device characterized by being stopped,
It is.

  According to the present invention, it is possible to obtain a resin composition for encapsulating a semiconductor which is excellent in solder resistance, flame resistance and fluidity, and also excellent in moisture resistance reliability and low warpage.

The present invention relates to an epoxy resin (A) represented by the general formula (1), a compound (B) containing two or more phenolic hydroxyl groups, an inorganic filler (C), a curing accelerator (D), Thus, a resin composition for encapsulating a semiconductor excellent in high solder resistance, flame resistance and fluidity, and excellent in moisture resistance reliability or low warpage can be obtained.
Hereinafter, each component will be described in detail.

  The epoxy resin (A) represented by the following general formula (1) used in the present invention contains a naphthalene skeleton in the molecule, so that the linear expansion of a cured product of the resin composition for semiconductor encapsulation using the epoxy resin (A) There is an effect that an area surface mount type semiconductor device having a small coefficient and excellent in low warpage can be obtained. Moreover, since the naphthalene skeleton contained in the epoxy resin (A) represented by the following general formula (1) is also excellent in heat stability, the flame resistance of the cured product of the resin composition for semiconductor encapsulation using the same It also has the effect of improving. In the epoxy resin (A) represented by the following general formula (1), the bonding positions of —O— to the naphthalene ring are the 2nd and 7th positions, which is a conventional naphthalene type epoxy resin. Compared with the epoxy resin in which the bonding position of O- to the naphthalene ring is 1-position and 6-position, for example, 1,6-diglycidyl ether naphthalene (manufactured by Dainippon Ink & Chemicals, Inc., HP-4032), It is excellent in that it can be crystallized and has excellent handling properties at room temperature.

  In the epoxy resin (A) represented by the following general formula (1), n1 is a mixture of compounds having an integer of 0 to 5, preferably a mixture in which a compound having a value of n1 of 0 is a main component. It is desirable. When the compound whose n1 value is 0 is the main component, the epoxy resin has a low molecular weight comparable to that of the conventional biphenyl type epoxy resin, and exhibits a considerably low viscosity. High fluidity can be imparted to the resin composition for semiconductor encapsulation at the time of molding even if the amount is made high. Thereby, the moisture absorption rate of the hardened | cured material of the resin composition for semiconductor sealing can be reduced. Moreover, when the compound whose n1 value is 0 is the main component, since the compound whose n1 value is 0 is a bifunctional epoxy resin, the elasticity of the cured product of the resin composition for semiconductor encapsulation The rate can be lowered. As described above, when the compound whose n1 value is 0 is the main component, the resin composition for semiconductor encapsulation using the epoxy resin can reduce the hygroscopicity of the cured product, Since the elastic modulus of the cured product can be reduced, a semiconductor device having excellent solder resistance can be obtained. In addition, when the compound whose n1 value is 0 is the main component, the inorganic filler can be highly filled in the resin composition for semiconductor encapsulation by reducing the viscosity of the epoxy resin. The linear expansion coefficient of the cured product of the stopping resin composition can be reduced, and a semiconductor device excellent in low warpage can be obtained.

  R1 in the following general formula (1) is a hydrocarbon group having 1 to 20 carbon atoms and is preferably a hydrocarbon group containing an alkyl group or an aromatic group, which may be the same or different from each other. It is preferably a hydrocarbon group containing a group. Thereby, in addition to the naphthalene skeleton, aromatic carbon is further increased, and the cured product of the resin composition for semiconductor encapsulation using this has an effect of being particularly excellent in flame resistance. R2 in the following general formula (1) is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group. As in the past, when dihydroxynaphthalene is converted to glycidyl ether with normal epichlorohydrin, it becomes highly reactive at low molecular weight, and it becomes an epoxy resin that can cause sensitization and mutagenicity. By introducing a lower alkyl group such as the above, the reactivity of the resulting epoxy resin can be moderately suppressed, and the above-mentioned problems can be improved as compared with conventional epoxy resins. As described above, the epoxy resin (A) represented by the general formula (1) in which R2 is a lower alkyl group having 1 to 4 carbon atoms can realize a low viscosity of the resin composition for semiconductor encapsulation. It is an industrially useful epoxy resin.

  Moreover, since the epoxy resin (A) represented by the following general formula (1) is a high-level low-chlorine resin, it is extremely excellent in moisture resistance reliability. The total amount of chlorine contained in the epoxy resin (A) represented by the following general formula (1) is preferably 300 ppm or less, and more preferably 200 ppm or less. If the total chlorine content is within the above range, the moisture resistance reliability of the semiconductor device is improved. In addition, although it does not specifically limit about the measuring method of the chlorine content contained in an epoxy resin (A), For example, it can measure according to JISK7243-3.

  Examples of the epoxy resin (A) represented by the following general formula (1) used in the present invention include a compound represented by the following formula (9). There is no particular limitation. Moreover, although it does not specifically limit about the manufacturing method of the epoxy resin (A) represented by following General formula (1) used by this invention, For example, 2, 7- dihydroxy naphthalene is used as a raw material phenol compound. , Β-methylepichlorohydrin or the like as an epoxidizing agent can be obtained by a method of synthesis according to a known epoxidation process.

（ただし、上記一般式（１）において、Ｒ１は炭素数１ないし２０の炭化水素基であり、互いに同じであっても異なっていても良い。Ｒ２は炭素数１ないし４のアルキル基である。ｎ１は０ないし５の整数であり、全体の平均値は０、又は５より小さい正数である。ｍ１は０ないし６の整数である。）

(However, in the above general formula (1), R1 is a hydrocarbon group having 1 to 20 carbon atoms and may be the same or different from each other. R2 is an alkyl group having 1 to 4 carbon atoms. n1 is an integer of 0 to 5, and the overall average value is 0 or a positive number smaller than 5. m1 is an integer of 0 to 6.)

（ただし、上記式（９）において、ｎ９は０ないし５の整数であり、全体の平均値は０、又は５より小さい正数である。）

(However, in the above formula (9), n9 is an integer of 0 to 5, and the average value of the whole is 0 or a positive number smaller than 5.)

In this invention, another epoxy resin can be used together in the range by which the effect by using the epoxy resin (A) represented by the said General formula (1) is not impaired. Examples of epoxy resins that can be used in combination include biphenyl type epoxy resins, bisphenol type epoxy resins, stilbene type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, triphenolmethane type epoxy resins, and phenol aralkyl type epoxy resins having a phenylene skeleton. Resin, phenol aralkyl type epoxy resin having biphenylene skeleton, naphthol type epoxy resin, alkyl modified triphenol methane type epoxy resin, triazine nucleus-containing epoxy resin, dicyclopentadiene modified phenol type epoxy resin, dihydroanthrahydroquinone glycidyl etherified epoxy resin Etc. In consideration of moisture resistance reliability as a resin composition for semiconductor encapsulation, it is preferable that Na ions and Cl ions, which are ionic impurities, be as small as possible. From the viewpoint of curability, the epoxy equivalent is 100 g / eq or more and 500 g / eq or less. Are preferred.
The blending ratio of the epoxy resin (A) represented by the general formula (1) when used in combination is preferably 10% by weight or more, more preferably 30% by weight or more, particularly with respect to the total epoxy resin. Preferably it is 50 weight% or more. When the blending ratio of the epoxy resin (A) is within the above range, the moisture resistance reliability and the low warpage improving effect can be obtained.

  In the present invention, a compound (B) containing two or more phenolic hydroxyl groups is used as a curing agent from the viewpoints of flame resistance, moisture resistance, electrical properties, curability, storage stability, and the like. The compound (B) containing two or more phenolic hydroxyl groups is a monomer, oligomer or polymer in general having two or more phenolic hydroxyl groups in one molecule, and its molecular weight and molecular structure are not particularly limited. For example, phenol novolak resin, cresol novolak resin, triphenolmethane type phenol resin, terpene modified phenol resin, dicyclopentadiene modified phenol resin, phenol aralkyl resin having phenylene skeleton and / or biphenylene skeleton, phenylene and / or biphenylene skeleton A naphthol aralkyl resin, a bisphenol compound, etc. are mentioned, These may be used individually by 1 type, or may use 2 or more types together. Among these, the hydroxyl equivalent is preferably 90 g / eq or more and 300 g / eq or less from the viewpoint of curability.

Moreover, in this invention, it is preferable that the compound represented by following General formula (2) is included as a compound (B) containing two or more phenolic hydroxyl groups. Since the compound represented by the following general formula (2) has an aralkyl group (—CH ₂ —R 3 —CH ₂ —) containing a phenylene, biphenylene, or naphthylene skeleton, the distance between cross-linking points as compared with a novolak type phenol resin. Therefore, since the cured product of the resin composition for semiconductor encapsulation using these has a low elastic modulus at high temperature and the content of phenolic hydroxyl groups is small, the resin composition for semiconductor encapsulation using these is used. The water absorption of the cured product can also be reduced. The manifestation of these characteristics can contribute to the improvement of solder resistance. Further, in a compound containing a naphthylene skeleton, low warpage in an area surface mount type semiconductor package due to an increase in Tg due to rigidity due to the naphthalene ring and a decrease in linear expansion coefficient due to intermolecular interaction due to its planar structure. Can be improved. In the compound represented by the following general formula (2), the aromatic group (-R4 (OH)-) containing a phenolic hydroxyl group may be a hydroxyphenylene group, 1-hydroxynaphthylene group, 2-hydroxynaphthylene. Any of the ren groups may be used, but particularly in the case of a hydroxy naphthylene group, similarly to the compound containing a naphthylene skeleton, an increase in Tg or a line in a cured product of a resin composition for semiconductor encapsulation using the naphthylene skeleton is used. By reducing the expansion coefficient, the effect of improving the low warpage is obtained, and since it has a lot of aromatic carbon, the improvement of the flame resistance in the cured product of the resin composition for semiconductor encapsulation using the same is also realized. Can do.
Examples of the compound represented by the following general formula (2) used in the present invention include a phenol aralkyl resin containing a phenylene skeleton, a phenol aralkyl resin containing a biphenylene skeleton represented by the following general formula (3), and naphthylene. Examples thereof include a phenol aralkyl resin containing a skeleton and a naphthol aralkyl resin containing a phenylene skeleton represented by the following general formula (4). However, the structure is not particularly limited as long as the structure is the following general formula (2).

（ただし、上記一般式（２）において、−Ｒ３−はフェニレン基、ビフェニレン基又はナフチレン基である。−Ｒ４（ＯＨ）−はヒドロキシフェニレン基又は１−ヒドロキシナフチレン基、２−ヒドロキシナフチレン基である。Ｒ５、Ｒ６は、それぞれＲ４、Ｒ３に導入される基で、炭素数１ないし１０の炭化水素基であり、それらは互いに同じであっても異なっていても良い。ｎ２の平均値は１以上、１０以下の正数、ｋ２は０ないし５の整数、ｍ２は０ないし８の整数である。）

(In the general formula (2), -R3- is a phenylene group, a biphenylene group, or a naphthylene group. -R4 (OH)-is a hydroxyphenylene group, a 1-hydroxynaphthylene group, or a 2-hydroxynaphthylene group. R5 and R6 are groups introduced into R4 and R3, respectively, which are hydrocarbon groups having 1 to 10 carbon atoms, which may be the same or different from each other. A positive number of 1 or more and 10 or less, k2 is an integer of 0 to 5, and m2 is an integer of 0 to 8.)

（ただし、上記一般式（３）において、Ｒ５、Ｒ６は、炭素数１ないし１０の炭化水素基であり、それらは互いに同じであっても異なっていても良い。ｎ３の平均値は１以上、１０以下の正数、ｋ３は０ないし３の整数、ｍ３は０ないし４の整数である。）

(In the above general formula (3), R5 and R6 are hydrocarbon groups having 1 to 10 carbon atoms, and they may be the same or different from each other. The average value of n3 is 1 or more, A positive number of 10 or less, k3 is an integer of 0 to 3, and m3 is an integer of 0 to 4.)

（ただし、上記一般式（４）において、Ｒ５、Ｒ６は、炭素数１ないし１０の炭化水素基であり、それらは互いに同じであっても異なっていても良い。ｎ４の平均値は１以上、１０以下の正数、ｋ４は０ないし５の整数、ｍ４は０ないし４の整数である。）

(However, in the general formula (4), R5 and R6 are hydrocarbon groups having 1 to 10 carbon atoms, and they may be the same or different. The average value of n4 is 1 or more, A positive number of 10 or less, k4 is an integer of 0 to 5, and m4 is an integer of 0 to 4.)

  In the present invention, the mixing ratio of the compound represented by the general formula (2) is not particularly limited, but is preferably 10 with respect to the total amount of the compound (B) containing two or more phenolic hydroxyl groups. % By weight or more, more preferably 30% by weight or more, and particularly preferably 50% by weight or more. When the compounding ratio of the compound represented by the general formula (2) is within the above range, an effect of improving the flame resistance can be obtained.

  The blending ratio of the total amount of the epoxy resin used in the present invention and the total amount of the compound (B) containing two or more phenolic hydroxyl groups is the phenol of the compound containing the number of epoxy groups (EP) of the epoxy resin and two or more phenolic hydroxyl groups. The ratio (EP / OH) to the number of functional hydroxyl groups (OH) is preferably 0.6 or more and 1.5 or less, and more preferably 0.8 or more and 1.3 or less. When the equivalent ratio is within the above range, there is little possibility that the curability of the resin composition for semiconductor encapsulation is lowered. Further, when the equivalent ratio is within the above range, the cured product of the resin composition for encapsulating a semiconductor is less likely to cause a decrease in glass transition temperature, a decrease in moisture resistance reliability, and the like.

  As the inorganic filler (C) used in the present invention, those generally used in a resin composition for semiconductor encapsulation can be used. For example, fused silica, spherical silica, crystalline silica, alumina, silicon nitride And aluminum nitride. The particle size of the inorganic filler (C) is preferably 0.01 μm or more and 150 μm or less in consideration of the filling property to the mold. In addition, the content of the inorganic filler (C) is preferably 80% by weight or more and 92% by weight or less, more preferably 82% by weight or more and 91% by weight or more, particularly preferably, based on the entire resin composition for semiconductor encapsulation. Is 84% by weight or more and 90% by weight or more. When the content of the inorganic filler (C) is within the above range, there is little risk of causing a decrease in solder resistance due to an increase in water absorption of the cured product of the resin composition for semiconductor encapsulation and a decrease in strength. . Further, when the content of the inorganic filler (C) is within the above range, there is little possibility of causing defects on the molding surface due to the loss of fluidity.

  The curing accelerator (D) used in the present invention is not limited as long as it accelerates the reaction between the epoxy group of the epoxy resin and the phenolic hydroxyl group of the compound (B) containing two or more phenolic hydroxyl groups. What is used for the resin composition for sealing can be utilized. Specific examples include organic phosphines, tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, phosphorus atom-containing compounds such as phosphonium compounds and silane compounds, 1,8-diazabicyclo (5,4,0 ) Nitrogen-containing compounds such as undecene-7, benzyldimethylamine, 2-methylimidazole and the like. Among these, a phosphorus atom-containing compound is preferable, and a tetra-substituted phosphonium compound is particularly preferable in consideration of fluidity, and a phosphobetaine compound in consideration of a low elastic modulus at the time of heat of a cured resin composition for semiconductor encapsulation. An adduct of a phosphine compound and a quinone compound is preferable, and an adduct of a phosphonium compound and a silane compound is preferable in consideration of latent curing properties.

  Examples of the organic phosphine include a first phosphine such as ethylphosphine and phenylphosphine, a second phosphine such as dimethylphosphine and diphenylphosphine, and a third phosphine such as trimethylphosphine, triethylphosphine, tributylphosphine, and triphenylphosphine.

  Examples of the tetra-substituted phosphonium compound include compounds represented by the following general formula (5).

（ただし、上記一般式（５）において、Ｐはリン原子を表す。Ｒ７、Ｒ８、Ｒ９及びＲ１０は芳香族基、又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。ａ、ｂは１ないし３の整数、ｃは０ないし３の整数であり、かつａ＝ｂである。）

(However, in the said General formula (5), P represents a phosphorus atom. R7, R8, R9, and R10 represent an aromatic group or an alkyl group. A is a function chosen from a hydroxyl group, a carboxyl group, and a thiol group. An anion of an aromatic organic acid having at least one of the groups in the aromatic ring AH represents an aromatic organic having at least one functional group selected from a hydroxyl group, a carboxyl group, and a thiol group in the aromatic ring. Represents an acid, a and b are integers of 1 to 3, c is an integer of 0 to 3, and a = b.

  The compound represented by the general formula (5) is obtained as follows, for example, but is not limited thereto. 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. Subsequently, when water is added, the compound represented by the general formula (5) can be precipitated. In the compound represented by the general formula (5), R7, R8, R9 and R10 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.

（ただし、上記一般式（６）において、Ｐはリン原子を表す。Ｘ１は水素又は炭素数１ないし３のアルキル基、Ｙ１は水素又はヒドロキシル基を表す。ｍ６、ｎ６は１ないし３の整数。） Examples of the phosphobetaine compound include compounds represented by the following general formula (6).

(However, in the said General formula (6), P represents a phosphorus atom. X1 represents hydrogen or a C1-C3 alkyl group, Y1 represents hydrogen or a hydroxyl group. M6 and n6 are integers of 1-3. )

  The compound represented by the general formula (6) 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.

（ただし、上記一般式（７）において、Ｐはリン原子を表す。Ｒ１１、Ｒ１２及びＲ１３は炭素数１ないし１２のアルキル基又は炭素数６ないし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。Ｒ１４、Ｒ１５及びＲ１６は水素原子又は炭素数１ないし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、Ｒ１４とＲ１５が結合して環状構造となっていてもよい。） Examples of the adduct of the phosphine compound and the quinone compound include a compound represented by the following general formula (7).

(In the above general formula (7), P represents a phosphorus atom. R11, R12 and R13 each represents an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, and may be the same as each other). R14, R15 and R16 each represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms and may be the same or different from each other, and R14 and R15 are bonded to form a cyclic structure. May be.)

Examples of the phosphine compound used for the adduct of the phosphine compound and the quinone compound include triphenylphosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, trinaphthylphosphine, and tris (benzyl) phosphine. Those having a substituent or a substituent such as an alkyl group or an alkoxyl group are preferred, and examples of the organic group of the alkyl group and the alkoxyl group include those having 1 to 6 carbon atoms. From the viewpoint of availability, triphenylphosphine is preferable.
Examples of the quinone compound used for the adduct of the phosphine compound and the quinone compound include o-benzoquinone, p-benzoquinone, and anthraquinones. Among them, p-benzoquinone is preferable from the viewpoint of storage stability.
As a method for producing the adduct of the phosphine compound and the quinone compound, the adduct can be obtained by contacting and mixing in a solvent in which both the organic tertiary phosphine and the benzoquinone can be dissolved. 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 (5), R11, R12 and R13 bonded to the phosphorus atom are phenyl groups, and R14, R15 and R16 are hydrogen atoms, that is, 1,4-benzoquinone and tri A compound to which phenylphosphine has been added is preferable in that it reduces the thermal modulus of the cured resin thermal composition.

（ただし、上記一般式（８）において、Ａ１は窒素原子又はリン原子を表す。Ｓｉは珪素原子を表す。Ｒ１７、Ｒ１８、Ｒ１９及びＲ２０は、それぞれ、芳香環又は複素環を有する有機基、或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。Ｘ２は、基Ｙ２及びＹ３と結合する有機基である。Ｘ３は、基Ｙ４及びＹ５と結合する有機基である。Ｙ２及びＹ３は、プロトン供与性置換基がプロトンを放出してなる基であり、それらは互いに同一であっても異なっていてもよく、同一分子内の基Ｙ２、及びＹ３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。Ｙ４及びＹ５は、プロトン供与性置換基がプロトンを放出してなる基であり、同一分子内の基Ｙ４及びＹ５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。Ｘ２、及びＸ３は互いに同一であっても異なっていてもよく、Ｙ２、Ｙ３、Ｙ４、及びＹ５は互いに同一であっても異なっていてもよい。Ｚ１は芳香環又は複素環を有する有機基或いは脂肪族基を表す。） Examples of the adduct of the phosphonium compound and the silane compound include compounds represented by the following general formula (8).

(In the above general formula (8), A1 represents a nitrogen atom or a phosphorus atom. Si represents a silicon atom. R17, R18, R19 and R20 are each an organic group having an aromatic ring or a heterocyclic ring, or Represents an aliphatic group, which may be the same or different from each other, X2 represents an organic group bonded to the groups Y2 and Y3, and X3 represents an organic group bonded to the groups Y4 and Y5. Y3 is a group formed by releasing a proton from a proton-donating substituent, which may be the same or different from each other, and the groups Y2 and Y3 in the same molecule are bonded to a silicon atom to form a chelate. Y4 and Y5 are groups formed by proton-donating substituents releasing protons, and groups Y4 and Y5 in the same molecule are combined with a silicon atom to form a chelate structure. X2 and X3 may be the same or different from each other, and Y2, Y3, Y4 and Y5 may be the same or different from each other, and Z1 is an organic having an aromatic ring or a heterocyclic ring. Represents a group or an aliphatic group.)

In the general formula (8), examples of R17, R18, R19, and R20 include phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group, naphthyl group, hydroxynaphthyl group, benzyl group, methyl group, and ethyl group. , N-butyl group, n-octyl group, cyclohexyl group and the like, among these, an aromatic group having a substituent such as phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group, hydroxynaphthyl group, or the like An unsubstituted aromatic group is more preferable.
Moreover, in the said General formula (8), X2 is an organic group couple | bonded with Y2 and Y3. Similarly, X3 is an organic group bonded to the groups Y4 and Y5. Y2 and Y3 are groups formed by proton-donating substituents releasing protons, and groups Y2 and Y3 in the same molecule are bonded to a silicon atom to form a chelate structure. Similarly, Y4 and Y5 are groups formed by proton-donating substituents releasing protons, and groups Y4 and Y5 in the same molecule are combined with a silicon atom to form a chelate structure. The groups Y2 and Y3 may be the same or different from each other, and the groups Y2, Y3, Y4, and Y5 may be the same or different from each other.
The groups represented by -Y2-X2-Y3- and -Y4-X3-Y5- in general formula (8) are formed by releasing two protons from a bivalent or higher proton donor. Examples of divalent or higher proton donors include catechol, pyrogallol, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,2′-biphenol, 1,1 ′. -Bi-2-naphthol, salicylic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, chloranilic acid, tannic acid, 2-hydroxybenzyl alcohol, 1,2-cyclohexanediol, 1,2- Propanediol, glycerin, etc. are mentioned, among these, catechol, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene More preferable.

  Z1 in the general formula (8) 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, and a hexyl group. Reactions of aliphatic hydrocarbon groups such as octyl and octyl groups, aromatic hydrocarbon groups such as phenyl, benzyl, naphthyl and biphenyl, glycidyloxypropyl, mercaptopropyl, aminopropyl and vinyl Among them, a methyl group, an ethyl group, a phenyl group, a naphthyl group, and a biphenyl group are more preferable from the viewpoint of thermal stability.

  As a method for producing an adduct of the phosphonium compound and the silane compound, a silane compound such as phenyltrimethoxysilane and a bivalent or higher proton donor such as 2,3-dihydroxynaphthalene are added to a flask containing methanol. Then, sodium methoxide-methanol solution is added dropwise with stirring at room temperature. 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.

  As for the compounding quantity of the hardening accelerator (D) used for this invention, 0.1 to 1 weight% is preferable in the resin composition for whole semiconductor sealing. There is little possibility of causing curability fall that the compounding quantity of a hardening accelerator (D) exists in the said range. Moreover, there is little possibility of causing a fluid fall as the compounding quantity of a hardening accelerator (D) exists in the said range.

  The silane coupling agent (E) that can be used in the present invention is preferably epoxy silane, amino silane, ureido silane, mercapto silane, etc., but is not particularly limited thereto, and reacts between the epoxy resin and the inorganic filler. Any material that improves the interface strength between the epoxy resin and the inorganic filler may be used. Further, the compound (F) (hereinafter also referred to as “compound (F)”) in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting an aromatic ring described later is the silane coupling agent (E). The silane coupling agent (E) is also effective for obtaining the effect of the compound (F) sufficiently because it has the effect of lowering the viscosity of the resin composition for encapsulating semiconductors and improving the fluidity. It is. Examples of the epoxy silane include γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane. Examples of aminosilanes include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, and N-β (aminoethyl) γ. -Aminopropylmethyldimethoxysilane, N-phenylγ-aminopropyltriethoxysilane, N-phenylγ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-6- (amino (Hexyl) 3-aminopropyl Examples include trimethoxysilane and N- (3- (trimethoxysilylpropyl) -1,3-benzenedimethanane. Examples of ureidosilane include γ-ureidopropyltriethoxysilane and hexamethyldisilazane. Examples of the mercaptosilane include γ-mercaptopropyltrimethoxysilane, etc. These silane coupling agents (E) may be used alone or in combination of two or more. The amount of the silane coupling agent (E) that can be used in the present invention is preferably 0.01% by weight or more and 1% by weight or less, more preferably 0.05% by weight, based on the resin composition for encapsulating all semiconductors. The content of the silane coupling agent (E) is 0.8% by weight or less, particularly preferably 0.1% by weight or more and 0.6% by weight or less. Within the range, due to the synergistic effect with the compound (F), it is possible to obtain a sufficient viscosity reduction and fluidity improving effect of the resin composition for semiconductor encapsulation, and the silane coupling agent (E). If the blending amount is within the above range, there is little risk of causing a decrease in solder resistance in the semiconductor device due to a decrease in the interface strength between the epoxy resin and the inorganic filler. If the amount is within the above range, there is little fear of causing a decrease in solder resistance due to an increase in water absorption of the cured product of the semiconductor sealing resin composition.

  A compound (F) (hereinafter also referred to as “compound (F)”) in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting an aromatic ring that can be used in the present invention is used. The resin composition for semiconductor encapsulation has the effect of lowering the melt viscosity and improving fluidity. As the compound (F), a monocyclic compound represented by the following general formula (10) or a polycyclic compound represented by the following general formula (11) can be used. It may have a substituent.

（ただし、上記一般式（１０）において、Ｒ２１、Ｒ２５は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、水酸基又は水酸基以外の置換基である。Ｒ２２、Ｒ２３、及びＲ２４は水素、水酸基又は水酸基以外の置換基である。）

(However, in the general formula (10), one of R21 and R25 is a hydroxyl group, and when one is a hydroxyl group, the other is hydrogen, a hydroxyl group or a substituent other than a hydroxyl group. R22, R23, and R24 are hydrogen. , A hydroxyl group or a substituent other than a hydroxyl group.)

（ただし、上記一般式（１１）において、Ｒ２６、Ｒ３２は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、水酸基又は水酸基以外の置換基である。Ｒ２７、Ｒ２８、Ｒ２９、Ｒ３０及びＲ３１は水素、水酸基又は水酸基以外の置換基である。）

(In the general formula (11), one of R26 and R32 is a hydroxyl group, and when one is a hydroxyl group, the other is hydrogen, a hydroxyl group or a substituent other than a hydroxyl group. R27, R28, R29, R30 and R31 is hydrogen, a hydroxyl group or a substituent other than a hydroxyl group.)

  Specific examples of the monocyclic compound represented by the general formula (10) include catechol, pyrogallol, gallic acid, gallic acid ester, and derivatives thereof. Specific examples of the polycyclic compound represented by the general formula (11) 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 individually by 1 type, or may use 2 or more types together.

  The compounding amount of the compound (F) is preferably 0.01% by weight or more and 1% by weight or less, more preferably 0.03% by weight or more, 0.8% in the total semiconductor sealing resin composition. % By weight or less, particularly preferably 0.05% by weight or more and 0.5% by weight or less. When the compounding amount of the compound (F) is within the above range, a sufficient viscosity reduction and fluidity improvement effect of the resin composition for semiconductor encapsulation can be obtained by a synergistic effect with the silane coupling agent (E). it can. Moreover, when the compounding quantity of a compound (F) exists in the said range, there is little possibility of causing the fall of sclerosis | hardenability of a resin composition for semiconductor sealing, and the fall of cured | curing material property.

  The resin composition for encapsulating a semiconductor of the present invention contains the components (A) to (F) as main components, but in addition to this, if necessary, natural wax such as carnauba wax, synthetic wax such as polyethylene wax, Mold release agents such as higher fatty acids such as stearic acid and zinc stearate and metal salts thereof or paraffin; colorants such as carbon black and bengara; low-stress additives such as silicone oil and silicone rubber; bismuth oxide hydrate, etc. Additives such as inorganic ion exchangers; metal hydroxides such as aluminum hydroxide and magnesium hydroxide, flame retardants such as zinc borate, zinc molybdate, and phosphazene;

  The resin composition for semiconductor encapsulation of the present invention is obtained by mixing the components (A) to (F) and other additives uniformly at room temperature using, for example, a mixer, and then heating roll, kneader Or what knead | mixed and kneaded using kneading machines, such as an extruder, and cooled and grind | pulverized subsequently, etc., what adjusted dispersion degree, fluidity | liquidity, etc. suitably can be used as needed.

  To manufacture a semiconductor device by sealing a semiconductor element with a cured product of the resin composition for semiconductor encapsulation of the present invention, for example, after installing a lead frame or the like on which the semiconductor element is mounted in a mold cavity, The epoxy resin composition may be molded and cured by a molding method such as a transfer mold, a compression mold, or an injection mold.

The semiconductor element that performs sealing in the present invention is not particularly limited, and examples thereof include an integrated circuit, a large-scale integrated circuit, a transistor, a thyristor, a diode, and a solid-state imaging element.
The form of the semiconductor device of the present invention is not particularly limited. For example, the dual in-line package (DIP), the plastic lead chip carrier (PLCC), the quad flat package (QFP), the small outline, and the like. Package (SOP), Small Outline J Lead Package (SOJ), Thin Small Outline Package (TSOP), Thin Quad Flat Package (TQFP), Tape Carrier Package (TCP), Ball Grid Examples include an array (BGA), a chip size package (CSP), and the like.
A semiconductor device sealed by a molding method such as the above transfer mold is completely cured at a temperature of about 120 ° C. to 200 ° C. for about 10 minutes to 10 hours, and then mounted on an electronic device or the like. Is done.

  FIG. 1 is a view showing a cross-sectional structure of an example of a semiconductor device using the resin composition for encapsulating a semiconductor according to the present invention. The semiconductor element 1 is fixed on the die pad 3 via the die bond material cured body 2. The electrode pad of the semiconductor element 1 and the lead frame 5 are connected by a gold wire 4. The semiconductor element 1 is sealed with a cured body 6 of a sealing resin composition.

  FIG. 2 is a view showing a cross-sectional structure of an example of a single-sided sealing type semiconductor device using the semiconductor sealing resin composition according to the present invention. The semiconductor element 1 is fixed on the substrate 8 through the die bond material cured body 2. The electrode pad of the semiconductor element 1 and the electrode pad on the substrate 8 are connected by a gold wire 4. Only the single side | surface side in which the semiconductor element 1 of the board | substrate 8 was mounted is sealed by the hardening body 6 of the resin composition for sealing. The electrode pads on the substrate 8 are bonded to the solder balls 9 on the non-sealing surface side on the substrate 8 inside.

EXAMPLES Hereinafter, although this invention is demonstrated concretely in an Example, this invention is not limited at all by these Examples. The blending ratio is parts by weight.
<Evaluation of encapsulant for lead frame>
Example 1

Epoxy resin 1: an epoxy resin represented by the following formula (9) (an epoxy resin represented by the general formula (1) prepared by the method described above. Epoxy equivalent 169, melting point 103 ° C. n9 in the following formula (9) An integer of 0 to 5, the average value is 0.2, and the chlorine content measured according to JIS K 7243-3 is 150 ppm.) 5.82 parts by weight

溶融球状シリカ（平均粒径３０μｍ） ８６．００重量部
硬化促進剤１：トリフェニルホスフィン ０．２０重量部
シランカップリング剤１：γ−グリシドキシプロピルトリメトキシシラン
０．３０重量部
２，３−ジヒドロキシナフタレン ０．２０重量部
カルナバワックス ０．２０重量部
カーボンブラック ０．３０重量部
をミキサーにて常温混合し、８０℃以上、１００℃以下の加熱ロールで溶融混練し、冷却後粉砕し、エポキシ樹脂組成物を得た。得られたエポキシ樹脂組成物を用いて以下の方法で評価した。評価結果を表１に示す。 Curing agent 1: Compound 1 represented by the following formula (12) (Maywa Kasei Co., Ltd., MEH-7851SS. Hydroxyl equivalent: 203, softening point: 66 ° C. In general formula (2) -R3-: biphenylene group, -R4 (OH)-: a hydroxyphenylene group, a compound having k2: 0 and m2: 0, an average value of n12 in the following formula (12): 1.5.) 6.98 parts by weight

Fused spherical silica (average particle size 30 μm) 86.00 parts by weight Curing accelerator 1: 0.20 parts by weight of triphenylphosphine Silane coupling agent 1: γ-glycidoxypropyltrimethoxysilane
0.30 parts by weight 2,3-dihydroxynaphthalene 0.20 parts by weight Carnauba wax 0.20 parts by weight Carbon black 0.30 parts by weight is mixed at room temperature with a mixer and melted with a heating roll at 80 ° C. or higher and 100 ° C. or lower. The mixture was kneaded, cooled and pulverized to obtain an epoxy resin composition. It evaluated by the following method using the obtained epoxy resin composition. The evaluation results are shown in Table 1.

-Spiral flow: Using a low-pressure transfer molding machine (KTS-15, manufactured by Kotaki Seiki Co., Ltd.), a mold for spiral flow measurement conforming to EMMI-1-66, mold temperature 175 ° C, injection pressure 6.9 MPa The epoxy resin composition was injected under the condition of a holding 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. The unit is cm.

-Moisture absorption rate: An epoxy resin composition is injection-molded using a low-pressure transfer molding machine (KTS-30, manufactured by Kotaki Seiki Co., Ltd.) at a mold temperature of 175 ° C, an injection pressure of 7.4 MPa, and a curing time of 120 seconds. A test piece having a diameter of 50 mm and a thickness of 3 mm was prepared and post-cured at 175 ° C. for 8 hours. Thereafter, the obtained test piece was humidified for 168 hours in an environment of 85 ° C. and 85% relative humidity, and the weight change before and after the humidification treatment was measured to obtain the moisture absorption rate. The unit is% by weight.

Flame resistance: Epoxy resin using a low-pressure transfer molding machine (KTS-30, KTS-30) under conditions of a mold temperature of 175 ° C., an injection pressure of 9.8 MPa, an injection time of 15 seconds, and a curing time of 120 seconds. The composition was injection molded to produce a 3.2 mm thick flame resistant test piece. Using the prepared test piece, a flame resistance test was performed in accordance with the standard of the UL94 vertical method to determine the flame resistance. The table shows the fire resistance rank after judgment.

Solder resistance 1: Epoxy resin composition using a low-pressure transfer molding machine (Daiichi Seiko Co., Ltd., GP-ELF) under conditions of a mold temperature of 180 ° C., an injection pressure of 7.4 MPa, and a curing time of 120 seconds. The lead frame on which the silicon chip is mounted is sealed and molded, and an 80-pin quad flat package (80 pQFP; Cu lead frame, package size is 14 x 20 mm x thickness 2.00 mm, silicon chip The size is 7 × 7 mm × thickness 0.35 mm, and the bonding pad of the chip and the circuit board is bonded with a gold wire with a diameter of 25 μm). Six packages heat treated at 175 ° C. for 4 hours as post-cure were humidified for 168 hours at 85 ° C. and 60% relative humidity, and then IR reflow treatment (260 ° C., according to JEDEC / Le1el2 conditions) was performed. The inside of the package after the treatment and the presence or absence of cracks were observed with an ultrasonic scratcher (manufactured by Hitachi Construction Machinery Finetech, mi-scope 10), and any one of the peeling or cracking was regarded as defective. When the number of defective packages is n, n / 6 is displayed.

・ Moisture resistance reliability: TEG chip (3.5mm x 3.5mm x 350μm thickness, exposed aluminum circuit without protective film) bonded to 16pSOP frame 42 alloy, and aluminum pad and lead frame are bonded. Wire bonded. Using a low-pressure transfer molding machine (KTS-125, manufactured by Kotaki Seiki Co., Ltd.), with a mold temperature of 175 ° C., an injection pressure of 9.8 MPa, and a curing time of 120 seconds, a 16-pin small outline package ( 16pSOP; package size 11.2mm x 7.2mm x thickness 1.8mm), heat treated at 175 ° C for 8 hours as post cure, then HAST test (high acceleration high temperature high compliant with IEC68-6-2) Wet test). Test conditions were 130 ° C., 85% RH, and application of 20 V to measure the presence or absence of circuit disconnection failure. If there are 4 terminals per package and the circuit breaks even with 1 terminal, it was considered defective. The number of defects in 15 packages is shown.

Examples 2 to 17, Comparative Examples 1 to 3
According to the composition of Tables 1 and 2, an epoxy resin composition was produced in the same manner as in Example 1, and evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 1 and 2.
Components used in Examples other than Example 1 are shown below.
Epoxy resin 2: phenol aralkyl type epoxy resin having a biphenylene skeleton (manufactured by Nippon Kayaku Co., Ltd., NC-3000, epoxy equivalent 274, softening point 58 ° C.)
Epoxy resin 3: Cresol novolac type epoxy resin (Dainippon Ink & Chemicals, Inc., Epicron N660. Epoxy equivalent 196, softening point 60 ° C.)
Epoxy resin 4: Biphenyl type crystalline epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., YX4000K. Epoxy equivalent 185, melting point 105 ° C.)
Curing agent 3: Phenol aralkyl resin having a phenylene skeleton (Mitsui Chemical Co., Ltd., XLC-4L. Hydroxyl equivalent 165, softening point 65 ° C. In the general formula (2), -R3-: phenylene group, -R4 (OH)- : Hydroxyphenylene group, k2: 0, m2: 0, average value of n2: 3.5.)
Curing agent 4: Phenol novolac resin (manufactured by Sumitomo Bakelite, PR-HF-3, hydroxyl equivalent 104, softening point 80 ° C.)
Curing accelerator 2: 1,8-diazabicyclo (5,4,0) undecene-7
Curing accelerator 3: Curing accelerator represented by the following formula (13)

硬化促進剤４：下記式（１４）で表される硬化促進剤

Curing accelerator 4: Curing accelerator represented by the following formula (14)

硬化促進剤５：下記式（１５）で表される硬化促進剤

Curing accelerator 5: Curing accelerator represented by the following formula (15)

Curing accelerator 6: Curing accelerator represented by the following formula (16)

Silane coupling agent 2: γ-mercaptopropyltrimethoxysilane 1,2-dihydroxynaphthalene catechol pyrogallol

  In Examples 1 to 17, the epoxy resin (A) represented by the general formula (1) is used as an epoxy resin, the compounding ratio of the epoxy resin (A), a compound containing two or more phenolic hydroxyl groups ( B) type and mixing ratio, inorganic filler (C) mixing ratio, curing accelerator (D) type, silane coupling agent (E) type and mixing ratio, and two or more constituting the aromatic ring These include compounds with different types and blending ratios of compounds (F) in which hydroxyl groups are bonded to adjacent carbon atoms, all of which exhibit good low moisture absorption, flame resistance and solder resistance, and high fluidity. (Spiral flow), good moisture resistance reliability was obtained.

On the other hand, in Comparative Example 1 in which a cresol novolac type epoxy resin was used as the epoxy resin and a phenol novolac resin was used as the compound (B) containing two or more phenolic hydroxyl groups, good moisture resistance reliability was obtained. As a result, the fluidity, flame resistance and solder resistance were poor. Further, Comparative Example 2 which is different from Example 17 only in that a phenol aralkyl type epoxy resin having a biphenylene skeleton is used as an epoxy resin has good results in terms of low hygroscopicity, flame resistance, solder resistance and moisture resistance reliability. However, the fluidity was remarkably inferior to that of Example 17. Furthermore, in Comparative Example 3 using a low-viscosity crystalline biphenyl type epoxy resin as an epoxy resin and a phenol aralkyl resin as a compound (B) containing two or more phenolic hydroxyl groups, the resin composition for semiconductor encapsulation is low. Since it is a viscosity, it is possible to mix a large amount of an inorganic filler, and therefore the moisture absorption rate is low, but the moisture resistance reliability, flame resistance and solder resistance are inferior.
From the above results, it was found that Examples 1 to 17 were excellent in low moisture absorption, flame resistance, solder resistance, high fluidity, and good moisture resistance reliability.

<Evaluation of sealing material for BGA>
Example 18
Epoxy resin 1: an epoxy resin represented by the following formula (9) (an epoxy resin represented by the general formula (1) prepared by the method described above. Epoxy equivalent 169, melting point 103 ° C. n9 in the following formula (9) An integer of 0 to 5, the average value is 0.2, the chlorine content measured according to JIS K 7243-3 is 150 ppm.) 4.82 parts by weight

Curing agent 2: Compound 2 represented by the following formula (17) (manufactured by Nippon Steel Chemical Co., Ltd., SN-485. Hydroxyl equivalent 210, softening point 85 ° C. In the general formula (2), -R3-: phenylene group, -R4 (OH)-: 2-hydroxynaphthylene group, k2: 0, m2: 0, average value of n17 in the following formula (17): 1.5.) 5.98 parts by weight

Fused spherical silica (average particle size 30 μm) 88.00 parts by weight Curing accelerator 1: 0.20 parts by weight of triphenylphosphine Silane coupling agent 1: γ-glycidoxypropyltrimethoxysilane
0.30 parts by weight 2,3-dihydroxynaphthalene 0.20 parts by weight Carnauba wax 0.20 parts by weight Carbon black 0.30 parts by weight is mixed at room temperature with a mixer and melted with a heating roll at 80 ° C. or higher and 100 ° C. or lower. The mixture was kneaded, cooled and pulverized to obtain a semiconductor sealing resin composition. The evaluation results are shown in Table 3.

-Spiral flow: Using a low-pressure transfer molding machine (KTS-15, manufactured by Kotaki Seiki Co., Ltd.), a mold for spiral flow measurement conforming to EMMI-1-66, mold temperature 175 ° C, injection pressure 6.9 MPa The epoxy resin composition was injected under the condition of a holding 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. The unit is cm.

-Moisture absorption rate: An epoxy resin composition is injection-molded using a low-pressure transfer molding machine (KTS-30, manufactured by Kotaki Seiki Co., Ltd.) at a mold temperature of 175 ° C, an injection pressure of 7.4 MPa, and a curing time of 120 seconds. A test piece having a diameter of 50 mm and a thickness of 3 mm was prepared and post-cured at 175 ° C. for 8 hours. Thereafter, the obtained test piece was humidified for 168 hours in an environment of 85 ° C. and 85% relative humidity, and the weight change before and after the humidification treatment was measured to obtain the moisture absorption rate. The unit is% by weight.

Flame resistance: Epoxy resin using a low-pressure transfer molding machine (KTS-30, KTS-30) under conditions of a mold temperature of 175 ° C., an injection pressure of 9.8 MPa, an injection time of 15 seconds, and a curing time of 120 seconds. The composition was injection molded to produce a 3.2 mm thick flame resistant test piece. Using the prepared test piece, a flame resistance test was performed in accordance with the standard of the UL94 vertical method to determine the flame resistance. The table shows the fire resistance rank after judgment.

Solder resistance 2: Silicone is injected by injecting an epoxy resin composition using a low-pressure transfer molding machine (manufactured by TOWA, Y series) under conditions of a mold temperature of 180 ° C., an injection pressure of 7.4 MPa, and a curing time of 120 seconds. A circuit board on which the chip is mounted is encapsulated, and a 225-pin ball grid array (225pBGA; board is 0.36mm thick, bismaleimide triazine / glass cloth board, package size is 24x24mm, thick The silicon chip is 9 × 9 mm in size, the thickness is 0.35 mm, and the chip and the bonding pad of the circuit board are bonded with a gold wire with a diameter of 25 μm. The average gold wire length is 5 mm. . Eight packages heat treated at 175 ° C. for 8 hours as post-cure were humidified for 168 hours at 85 ° C. and 60% relative humidity, and then IR reflow treatment (260 ° C., according to JEDEC Level 2 conditions) was performed. The inside of the package after the treatment and the presence or absence of cracks were observed with an ultrasonic scratcher (manufactured by Hitachi Construction Machinery Finetech, mi-scope 10), and any one of the peeling or cracking was regarded as defective. When the number of defective packages is n, n / 8 is displayed.

-Thermal expansion amount: An epoxy resin composition was injected using a low-pressure transfer molding machine (KTS-30, manufactured by Kotaki Seiki Co., Ltd.) under conditions of a mold temperature of 175 ° C, an injection pressure of 7.5 MPa, and a curing time of 120 seconds. Molded to prepare a test piece (4 mm × 5 mm × 15 mm). From the chart when the obtained test piece was measured at a measurement temperature range of 0 ° C. to 320 ° C. and a temperature increase rate of 5 ° C./min using a thermomechanical analyzer (manufactured by Seiko Denshi Kogyo Co., Ltd., TMA100), 30 The amount of thermal expansion in the range from ℃ to 175 ℃ was calculated. Units%.

Package warpage amount: Using a low-pressure transfer molding machine (manufactured by TOWA, Y series), a silicon chip was mounted with an epoxy resin composition under conditions of a mold temperature of 180 ° C., an injection pressure of 7.4 MPa, and a curing time of 120 seconds. Circuit board, etc. is sealed and molded, and 225-pin ball grid array (225pBGA; board is 0.36mm thick, bismaleimide triazine / glass cloth board, package size is 24x24mm, thickness is 1.17mm The silicon chip was 9 × 9 mm in size and 0.35 mm in thickness, and the chip and the bonding pad of the circuit board were bonded with a 25 μm diameter gold wire. The obtained package was further heat treated at 175 ° C. for 8 hours as a post cure. After cooling to room temperature, the displacement in the height direction was measured using a surface roughness meter in the diagonal direction from the gate of the package, and the value with the largest displacement difference was taken as the amount of warpage. The unit is μm.

Examples 19 to 34, Comparative Examples 4 and 5
The resin composition for semiconductor encapsulation was produced in the same manner as in Example 18 according to the formulations in Tables 3 and 4, and evaluated in the same manner as in Example 18. The evaluation results are shown in Tables 3 and 4.
Components used in Examples other than Example 18 are shown below.
Epoxy resin 4: Biphenyl type crystalline epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., YX-4000K. Epoxy equivalent 185, melting point 105 ° C.)
Epoxy resin 5: Triphenolmethane type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., E-1032H60. Epoxy equivalent 171, softening point 60 ° C.)
Curing agent 4: Phenol novolac resin (manufactured by Sumitomo Bakelite, PR-HF-3, hydroxyl equivalent 104, softening point 80 ° C.)
Curing agent 5: Triphenolmethane type phenol resin (Maywa Kasei Co., Ltd., MEH-7500. Hydroxyl equivalent 97, softening point 110 ° C.)
Curing accelerator 2: 1,8-diazabicyclo (5,4,0) undecene-7
Curing accelerator 3: Curing accelerator represented by the following formula (13)

硬化促進剤４：下記式（１４）で表される硬化促進剤

Curing accelerator 4: Curing accelerator represented by the following formula (14)

硬化促進剤５：下記式（１５）で表される硬化促進剤

Curing accelerator 5: Curing accelerator represented by the following formula (15)

Curing accelerator 6: Curing accelerator represented by the following formula (16)

Silane coupling agent 2: γ-mercaptopropyltrimethoxysilane 1,2-dihydroxynaphthalene catechol pyrogallol

In Examples 18 to 34, the epoxy resin (A) represented by the general formula (1) was used as an epoxy resin, and the compounding ratio of the epoxy resin (A) and a compound containing two or more phenolic hydroxyl groups ( B) type and mixing ratio, inorganic filler (C) mixing ratio, curing accelerator (D) type, silane coupling agent (E) type and mixing ratio, and two or more constituting the aromatic ring These include compounds with different types and blending ratios of compounds (F) in which hydroxyl groups are bonded to adjacent carbon atoms, all of which have good fluidity (spiral flow), low moisture absorption, flame resistance and solder resistance. In addition, good results were obtained that the thermal expansion amount and the package warpage amount were low.

On the other hand, in Comparative Example 4, which differs from Example 34 only in that a low-viscosity crystalline biphenyl type epoxy resin was used as the epoxy resin, the thermal expansion amount and package warpage amount were small and good, but flame resistance and solder resistance The result was in terms of sex. In Comparative Example 5 in which a triphenolmethane type epoxy resin was used as the epoxy resin and a triphenolmethane type phenol resin was used as the compound (B) containing two or more phenolic hydroxyl groups, the thermal expansion amount and the package warpage amount were small and good. However, the moisture absorption rate was high, and the fluidity, flame resistance, and solder resistance were poor.
From the above results, it was found that Examples 18 to 34 were excellent in fluidity, low moisture absorption, flame resistance and solder resistance, had a low thermal expansion amount, and had a good package warpage.

  According to the present invention, it is possible to obtain a resin composition for encapsulating a semiconductor that is excellent in solder resistance, flame resistance, and fluidity, and excellent in moisture resistance reliability or low warpage. Is preferred. From the viewpoint of excellent low warpage, it is also suitable for an area mounting type semiconductor device package.

It is the figure which showed the cross-sectional structure about an example of the semiconductor device using the resin composition for semiconductor sealing which concerns on this invention. It is the figure which showed the cross-sectional structure about an example of the single-side sealing type semiconductor device using the resin composition for semiconductor sealing which concerns on this invention.

DESCRIPTION OF SYMBOLS 1 Semiconductor element 2 Die-bonding material hardening body 3 Die pad 4 Gold wire 5 Lead frame 6 Curing body of the resin composition for sealing 7 Resist 8 Substrate 9 Solder ball

Claims (17)

An epoxy resin (A) represented by the following general formula (1);
A compound (B) containing two or more phenolic hydroxyl groups;
An inorganic filler (C);
A curing accelerator (D);
A resin composition for encapsulating a semiconductor, comprising:

(However, in the above general formula (1), R1 is a hydrocarbon group having 1 to 20 carbon atoms and may be the same or different from each other. R2 is an alkyl group having 1 to 4 carbon atoms. n1 is an integer of 0 to 5, and the overall average value is 0 or a positive number smaller than 5. m1 is an integer of 0 to 6.)   The resin composition for semiconductor encapsulation according to claim 1, wherein R2 of the epoxy resin (A) represented by the general formula (1) is a methyl group.   In the resin composition for semiconductor sealing of Claim 1 or Claim 2, the total chlorine amount contained in the epoxy resin (A) represented by General formula (1) is 300 ppm or less, It is characterized by the above-mentioned. Semiconductor sealing resin composition. The resin composition for semiconductor encapsulation according to any one of claims 1 to 3, wherein the compound (B) containing two or more phenolic hydroxyl groups contains a compound represented by the following general formula (2). A resin composition for semiconductor encapsulation.

(In the general formula (2), -R3- is a phenylene group, a biphenylene group, or a naphthylene group. -R4 (OH)-is a hydroxyphenylene group, a 1-hydroxynaphthylene group, or a 2-hydroxynaphthylene group. R5 and R6 are groups introduced into R4 and R3, respectively, which are hydrocarbon groups having 1 to 10 carbon atoms, which may be the same or different from each other. A positive number of 1 or more and 10 or less, k2 is an integer of 0 to 5, and m2 is an integer of 0 to 8.) The resin composition for semiconductor encapsulation according to any one of claims 1 to 4, wherein the compound (B) containing two or more phenolic hydroxyl groups contains a compound represented by the following general formula (3). A resin composition for semiconductor encapsulation.

(In the above general formula (3), R5 and R6 are hydrocarbon groups having 1 to 10 carbon atoms, and they may be the same or different from each other. The average value of n3 is 1 or more, A positive number of 10 or less, k3 is an integer of 0 to 3, and m3 is an integer of 0 to 4.) The resin composition for semiconductor encapsulation according to any one of claims 1 to 4, wherein the compound (B) containing two or more phenolic hydroxyl groups contains a compound represented by the following general formula (4). A resin composition for semiconductor encapsulation.

(However, in the general formula (4), R5 and R6 are hydrocarbon groups having 1 to 10 carbon atoms, and they may be the same or different. The average value of n4 is 1 or more, A positive number of 10 or less, k4 is an integer of 0 to 5, and m4 is an integer of 0 to 4.) The resin composition for semiconductor sealing in any one of Claims 1 thru | or 6 WHEREIN: The said hardening accelerator (D) is a compound represented by following General formula (5), and following General formula (6) A resin composition for encapsulating a semiconductor, which is at least one selected from a compound represented by the following formula, a compound represented by the following general formula (7), and a compound represented by the following general formula (8).

(However, in the said General formula (5), P represents a phosphorus atom. R7, R8, R9, and R10 represent an aromatic group or an alkyl group. A is a function chosen from a hydroxyl group, a carboxyl group, and a thiol group. An anion of an aromatic organic acid having at least one of the groups in the aromatic ring AH represents an aromatic organic having at least one functional group selected from a hydroxyl group, a carboxyl group, and a thiol group in the aromatic ring. Represents an acid, a and b are integers of 1 to 3, c is an integer of 0 to 3, and a = b.

(However, in the said General formula (6), P represents a phosphorus atom. X1 represents hydrogen or a C1-C3 alkyl group, Y1 represents hydrogen or a hydroxyl group. M6 and n6 are integers of 1-3. )

(In the above general formula (7), P represents a phosphorus atom. R11, R12 and R13 each represents an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, and may be the same as each other). R14, R15 and R16 each represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms and may be the same or different from each other, and R14 and R15 are bonded to form a cyclic structure. May be.)

(In the above general formula (8), A1 represents a nitrogen atom or a phosphorus atom. Si represents a silicon atom. R17, R18, R19 and R20 are each an organic group having an aromatic ring or a heterocyclic ring, or Represents an aliphatic group, which may be the same or different from each other, X2 represents an organic group bonded to the groups Y2 and Y3, and X3 represents an organic group bonded to the groups Y4 and Y5. Y3 is a group formed by releasing a proton from a proton-donating substituent, which may be the same or different from each other, and the groups Y2 and Y3 in the same molecule are bonded to a silicon atom to form a chelate. Y4 and Y5 are groups formed by proton-donating substituents releasing protons, and groups Y4 and Y5 in the same molecule are combined with a silicon atom to form a chelate structure. X2 and X3 may be the same or different from each other, and Y2, Y3, Y4 and Y5 may be the same or different from each other, and Z1 is an organic having an aromatic ring or a heterocyclic ring. Represents a group or an aliphatic group.)   8. The resin composition for encapsulating a semiconductor according to claim 1, wherein a hydroxyl group is further bonded to each of the silane coupling agent (E) and two or more adjacent carbon atoms constituting the aromatic ring. The resin composition for semiconductor sealing characterized by including the compound (F) which carried out.   9. The resin composition for semiconductor encapsulation according to claim 8, wherein the compound (F) is a compound in which a hydroxyl group is bonded to each of two adjacent carbon atoms constituting an aromatic ring. Resin composition for stopping.   9. The semiconductor sealing resin composition according to claim 8, wherein the compound (F) is a compound in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting a naphthalene ring. Resin composition for sealing.   9. The resin composition for semiconductor encapsulation according to claim 8, wherein the compound (F) is a compound in which a hydroxyl group is bonded to each of two adjacent carbon atoms constituting a naphthalene ring. Resin composition for stopping.   The resin composition for semiconductor encapsulation according to any one of claims 8 to 11, wherein the compound (F) is contained in an amount of 0.01% by weight or more and 1% by weight or less of the total resin composition. A semiconductor sealing resin composition.   The resin composition for semiconductor encapsulation according to any one of claims 8 to 12, wherein the silane coupling agent (E) is contained in an amount of 0.01% by weight or more and 1% by weight or less of the entire resin composition. A resin composition for encapsulating a semiconductor.   The resin composition for semiconductor encapsulation according to any one of claims 1 to 13, wherein the inorganic filler (C) is contained in an amount of 80% by weight or more and 92% by weight or less of the entire resin composition. A semiconductor sealing resin composition.   A semiconductor device comprising a semiconductor element sealed with a cured product of the resin composition for semiconductor encapsulation according to claim 1.   6. A resin composition for encapsulating a semiconductor according to claim 5, wherein the semiconductor device is used in an electronic component that requires moisture resistance reliability under high temperature and high humidity at a temperature of 80 to 150 ° C. and a relative humidity of 80 to 100%. A semiconductor device, wherein a semiconductor element is sealed with a cured product.   A semiconductor element is mounted on one surface of the substrate, and substantially only one surface on the substrate surface side on which the semiconductor element is mounted is sealed with a cured product of the semiconductor sealing resin composition according to claim 6. An area surface mount type semiconductor device characterized by the above.

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