JP2005154694A - Flame-retardant epoxy resin composition for sealing semiconductor and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flame-retardant epoxy resin composition for sealing a semiconductor which contains neither a bromide such as a brominated epoxy resin nor an antimony compound such as antimony trioxide, exhibits excellent moldability and gives a cured product excellent in flame retardancy and moisture resistance reliability, and a semiconductor device sealed with the cured product of the resin composition. <P>SOLUTION: The flame-retardant epoxy resin composition for sealing the semiconductor comprises as essential ingredients (A) an epoxy resin, (B) a curing agent, and (E) a phosphazene compound represented by average composition formula (1) [wherein, A is O, S or NR<SP>3</SP>; R<SP>1</SP>, R<SP>2</SP>and R<SP>3</SP>are each a hydrogen atom or a 1-4C alkyl group; R is a substituted or unsubstituted monovalent hydrocarbon group containing no aliphatic unsaturated group; X is a divalent organic group; x, y, z and n are numbers satisfying the relations: 0<x<2n, 0<y<2n, x+y=2n, 0≤z≤400; and 3≤n≤1,000], and contains substantially neither a bromide nor an antimony compound. The semiconductor device is sealed with the cured product of the composition. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention has excellent moldability, flame retardancy and moisture resistance reliability, and can provide a cured product containing no brominated product such as brominated epoxy resin and antimony compound such as antimony trioxide. The present invention relates to a flame-retardant epoxy resin composition for semiconductor encapsulation suitable for stopping, and a semiconductor device sealed with a cured product of the resin composition.

  Currently, resin-encapsulated diodes, transistors, ICs, LSIs, and super LSIs are the mainstream semiconductor devices, but epoxy resins are more formable, adhesive, electrical, mechanical, and more than other thermosetting resins. Since it has excellent moisture resistance and the like, it is common to seal a semiconductor device with an epoxy resin composition. Since semiconductor devices are used everywhere in the living environment such as home appliances and computers, semiconductor devices are required to be flame retardant in preparation for an emergency fire.

  In the epoxy resin composition for semiconductor encapsulation, a halogenated epoxy resin and antimony trioxide are generally blended in order to enhance flame retardancy. The combination of the halogenated epoxy resin and antimony trioxide has a large radical trap and air blocking effect in the gas phase, and as a result, a high flame retardant effect can be obtained.

  However, halogenated epoxy resins have the problem of generating toxic gases when burned, and antimony trioxide is also powder toxic. Considering the effects on the human body and the environment, these flame retardants are contained in the resin composition. It is preferable that it is not contained at all.

In response to such demands, as a substitute for halogenated epoxy resin or antimony trioxide, conventionally, hydroxides such as Al (OH) ₃ and Mg (OH) ₂ , phosphorus-based difficulties such as red phosphorus and phosphate esters are used. Investigations such as flame retardants have been made. However, since hydroxides such as Al (OH) ₃ and Mg (OH) ₂ have a low flame retardant effect, a large amount of hydroxide must be added to the epoxy resin composition in order to obtain a flame retardant composition. As a result, there is a problem that the viscosity of the composition increases, and molding defects such as voids and wire flow occur during molding. On the other hand, when a phosphorus flame retardant such as red phosphorus or phosphate is added to the epoxy resin composition, when the semiconductor device is exposed to high temperature and high humidity conditions, the phosphorus flame retardant is hydrolyzed and phosphoric acid is generated. This phosphoric acid corrodes aluminum wiring or has a serious problem of reducing reliability such as ion migration in a copper frame or a silver plating frame.

In order to solve this problem, Japanese Patent No. 2843244 (Patent Document 1) proposes an epoxy resin composition using as a flame retardant a compound in which the surface of red phosphorus is coated with a coating layer comprising a Si _x O _y composition. However, at present, the moisture resistance reliability is not improved. Moreover, in Unexamined-Japanese-Patent No. 10-259292 (patent document 2), the quantity of a phosphorus atom becomes 0.2-3.0 mass% with respect to the total amount of a compounding component except a filler for a cyclic phosphazene compound. Although an epoxy resin composition using an amount is also proposed, it is necessary to add a considerable amount to the epoxy resin composition in order to obtain flame retardancy. There was a problem such as causing a decrease in electrical resistance.

Japanese Patent No. 2843244 JP-A-10-259292

  The present invention has been made in view of the above circumstances, does not contain brominated products such as brominated epoxy resins and antimony compounds such as antimony trioxide, has excellent moldability, and is excellent in flame retardancy and moisture resistance reliability. An object of the present invention is to provide a flame-retardant epoxy resin composition for semiconductor encapsulation capable of obtaining a product, and a semiconductor device encapsulated with a cured product of the resin composition.

  As a result of intensive studies to achieve the above object, the present inventors have found that (A) an epoxy resin, (B) a curing agent, (C) a phosphazene compound represented by the following average composition formula (1), and preferably (D) Inorganic filler, (E) Organopolysiloxane represented by the following average composition formula (2), (F) SiH group and alkenyl group-containing epoxy compound of the organopolysiloxane represented by the following average composition formula (2 ′) An epoxy resin composition containing a block copolymer obtained by addition reaction of an alkenyl group, or (G) a molybdenum compound obtained by supporting zinc molybdate on an inorganic filler and substantially free of bromide and antimony compound However, it is possible to obtain a cured product having excellent moldability, flame retardancy, and moisture resistance reliability, and a semiconductor encapsulated with the cured product of the epoxy resin composition Location is flame retardant, moisture resistance reliability, found that is excellent in high-temperature electric characteristics are those able to complete the present invention.

（式中、ＡはＯ、Ｓ又はＮＲ³であり、Ｒ¹、Ｒ²、Ｒ³は水素原子又は炭素数１〜４のアルキル基であり、Ｒは脂肪族不飽和基を含有しない置換又は非置換の一価炭化水素基であり、Ｘは二価の有機基であり、ｘ、ｙ、ｚ、ｎは、０＜ｘ＜２ｎ、０＜ｙ＜２ｎ、ｘ＋ｙ＝２ｎ、０≦ｚ≦４００、３≦ｎ≦１，０００を満たす数である。）

(In the formula, A is O, S or NR ³ , R ¹ , R ² and R ³ are hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, and R is a substituted or non-substituted aliphatic group. An unsubstituted monovalent hydrocarbon group, X is a divalent organic group, x, y, z, and n are 0 <x <2n, 0 <y <2n, x + y = 2n, 0 ≦ z ≦ 400, 3 ≦ n ≦ 1,000.)

R ⁴ _h R ⁵ _k Si (OR ⁶ ) _p (OH) _q O _{(4-hkpq) / 2} (2)
Wherein R ⁴ is a phenyl group, R ⁵ is a monovalent hydrocarbon group or hydrogen atom having 1 to ⁶ carbon atoms, R ⁶ is a monovalent hydrocarbon group having 1 to 4 carbon atoms, h , K, p, q are 0 ≦ h ≦ 2.0, 0 ≦ k ≦ 1.0, 0 ≦ p ≦ 2.5, 0 ≦ q ≦ 0.35, 0.92 ≦ h + k + p + q ≦ 2.8. The number of ranges to satisfy.)

H _r R ⁷ _s SiO _{(4-rs) / 2} (2 ')
Wherein R ⁷ is a substituted or unsubstituted monovalent hydrocarbon group containing no aliphatic unsaturated group, and r and s are 0.001 ≦ r ≦ 1, 1 ≦ s ≦ 3, 1.001 (It is a positive number satisfying ≦ r + s ≦ 3.)

（式中、ＡはＯ、Ｓ又はＮＲ³であり、Ｒ¹、Ｒ²、Ｒ³は水素原子又は炭素数１〜４のアルキル基であり、Ｒは脂肪族不飽和基を含有しない置換又は非置換の一価炭化水素基であり、Ｘは二価の有機基であり、ｘ、ｙ、ｚ、ｎは、０＜ｘ＜２ｎ、０＜ｙ＜２ｎ、ｘ＋ｙ＝２ｎ、０≦ｚ≦４００、３≦ｎ≦１，０００を満たす数である。）
を必須成分とし、臭素化物及びアンチモン化合物を実質的に含まないことを特徴とする半導体封止用難燃性エポキシ樹脂組成物。
〔２〕 （Ａ）エポキシ樹脂と（Ｂ）硬化剤との総量１００質量部に対し、（Ｃ）ホスファゼン化合物の添加量が１〜５０質量部であることを特徴とする〔１〕記載の半導体封止用難燃性エポキシ樹脂組成物。
〔３〕 更に、（Ｄ）無機質充填剤を（Ａ）エポキシ樹脂と（Ｂ）硬化剤との総量１００質量部に対して４００〜１，２００質量部配合してなることを特徴とする〔１〕又は〔２〕記載の半導体封止用難燃性エポキシ樹脂組成物。
〔４〕 更に、（Ｅ）下記平均組成式（２）
Ｒ⁴ _hＲ⁵ _kＳｉ（ＯＲ⁶）_p（ＯＨ）_qＯ_{(4-h-k-p-q)/2} ・・・（２）
（式中、Ｒ⁴はフェニル基であり、Ｒ⁵は炭素数１〜６の一価炭化水素基又は水素原子であり、Ｒ⁶は炭素数１〜４の一価炭化水素基であり、ｈ，ｋ，ｐ，ｑは、０≦ｈ≦２．０、０≦ｋ≦１．０、０≦ｐ≦２．５、０≦ｑ≦０．３５、０．９２≦ｈ＋ｋ＋ｐ＋ｑ≦２．８を満たす範囲の数である。）
で表されるオルガノポリシロキサンを配合することを特徴とする〔１〕〜〔３〕のいずれかに記載の半導体封止用難燃性エポキシ樹脂組成物。
〔５〕 更に、（Ｆ）下記平均組成式（２’）
Ｈ_rＲ⁷ _sＳｉＯ_(4-r-s)/2 ・・・（２’）
（式中、Ｒ⁷は脂肪族不飽和基を含有しない置換又は非置換の一価炭化水素基であり、ｒ，ｓは、０．００１≦ｒ≦１、１≦ｓ≦３、１．００１≦ｒ＋ｓ≦３を満足する正数である。）
で示されるオルガノポリシロキサンのＳｉＨ基とアルケニル基含有エポキシ化合物のアルケニル基を付加反応させたブロック共重合体を配合することを特徴とする〔１〕〜〔４〕のいずれかに記載の半導体封止用難燃性エポキシ樹脂組成物。
〔６〕 更に、（Ｇ）モリブデン酸亜鉛を無機質充填剤に担持してなるモリブデン化合物を配合することを特徴とする〔１〕〜〔５〕のいずれかに記載の半導体封止用難燃性エポキシ樹脂組成物。
〔７〕 （Ａ）エポキシ樹脂と（Ｂ）硬化剤との総量１００質量部に対し、（Ｇ）モリブデン化合物の添加量が３〜１００質量部であることを特徴とする〔６〕記載の半導体封止用難燃性エポキシ樹脂組成物。
〔８〕 〔１〕〜〔７〕のいずれかに記載の半導体封止用難燃性エポキシ樹脂組成物の硬化物で封止した半導体装置。 Accordingly, the present invention provides the following flame-retardant epoxy resin composition for semiconductor encapsulation and a semiconductor device.
[1] (A) Epoxy resin (B) Curing agent (C) Phosphazene compound represented by the following average composition formula (1)

(In the formula, A is O, S or NR ³ , R ¹ , R ² and R ³ are hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, and R is a substituted or non-substituted aliphatic group. An unsubstituted monovalent hydrocarbon group, X is a divalent organic group, x, y, z, and n are 0 <x <2n, 0 <y <2n, x + y = 2n, 0 ≦ z ≦ 400, 3 ≦ n ≦ 1,000.)
Is a flame retardant epoxy resin composition for semiconductor encapsulation, characterized in that it contains essentially bromine and an antimony compound.
[2] The semiconductor according to [1], wherein the addition amount of (C) phosphazene compound is 1 to 50 parts by mass with respect to 100 parts by mass of the total amount of (A) epoxy resin and (B) curing agent. Flame-retardant epoxy resin composition for sealing.
[3] Further, (D) an inorganic filler is blended in an amount of 400 to 1,200 parts by mass with respect to 100 parts by mass of the total amount of (A) epoxy resin and (B) curing agent [1] ] Or the flame-retardant epoxy resin composition for semiconductor encapsulation according to [2].
[4] Furthermore, (E) the following average composition formula (2)
R ⁴ _h R ⁵ _k Si (OR ⁶ ) _p (OH) _q O _{(4-hkpq) / 2} (2)
Wherein R ⁴ is a phenyl group, R ⁵ is a monovalent hydrocarbon group or hydrogen atom having 1 to ⁶ carbon atoms, R ⁶ is a monovalent hydrocarbon group having 1 to 4 carbon atoms, h , K, p, q are 0 ≦ h ≦ 2.0, 0 ≦ k ≦ 1.0, 0 ≦ p ≦ 2.5, 0 ≦ q ≦ 0.35, 0.92 ≦ h + k + p + q ≦ 2.8. The number of ranges to satisfy.)
The flame retardant epoxy resin composition for semiconductor encapsulation according to any one of [1] to [3], wherein an organopolysiloxane represented by the formula:
[5] Furthermore, (F) the following average composition formula (2 ′)
H _r R ⁷ _s SiO _{(4-rs) / 2} (2 ')
Wherein R ⁷ is a substituted or unsubstituted monovalent hydrocarbon group containing no aliphatic unsaturated group, and r and s are 0.001 ≦ r ≦ 1, 1 ≦ s ≦ 3, 1.001 (It is a positive number satisfying ≦ r + s ≦ 3.)
A block copolymer obtained by addition-reacting a SiH group of an organopolysiloxane represented by formula (II) and an alkenyl group of an alkenyl group-containing epoxy compound is blended, and the semiconductor encapsulation according to any one of [1] to [4] A flame retardant epoxy resin composition for stopping.
[6] The flame retardant for semiconductor encapsulation according to any one of [1] to [5], further comprising (G) a molybdenum compound obtained by supporting zinc molybdate on an inorganic filler. Epoxy resin composition.
[7] The semiconductor according to [6], wherein the amount of (G) molybdenum compound added is 3 to 100 parts by mass with respect to 100 parts by mass of the total amount of (A) epoxy resin and (B) curing agent. Flame-retardant epoxy resin composition for sealing.
[8] A semiconductor device encapsulated with a cured product of the flame-retardant epoxy resin composition for encapsulating a semiconductor according to any one of [1] to [7].

  Thus, the epoxy resin composition of the present invention is substantially free of bromide and antimony compound. In general, a brominated epoxy resin and antimony trioxide are blended in the epoxy resin composition in order to achieve flame retardancy, but the epoxy resin composition of the present invention is mixed with the brominated epoxy resin and the three. The flame retardant standards UL-94 and V-0 can be achieved without using antimony oxide.

Here, as an alternative to brominated epoxy resin or antimony trioxide, conventionally, hydroxides such as Al (OH) ₃ and Mg (OH) ₂ , phosphorus-based flame retardants such as red phosphorus and phosphate esters, etc. have been studied. ing. However, these known alternative flame retardants have the common disadvantage that the water resistance is particularly weak at high temperatures, and the flame retardant itself dissolves and decomposes to increase impurity ions in the extracted water. For this reason, if a semiconductor device sealed with a conventional flame retardant epoxy resin composition substantially free of bromide and antimony compound is left under high temperature and high humidity for a long time, the aluminum wiring of the semiconductor device corrodes, There was a problem that the moisture resistance reliability deteriorated.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that an epoxy resin composition for semiconductor encapsulation using the phosphazene compound (C) represented by the average composition formula (1) as a flame retardant is more preferable. As a flame retardant, phosphazene compound (C) represented by average composition formula (1), (E) organopolysiloxane represented by average composition formula (2), and (F) represented by average composition formula (2 ′) Encapsulation using a block copolymer obtained by addition reaction of an alkenyl group of an organopolysiloxane and an alkenyl group-containing epoxy compound or a molybdenum compound (G) in which zinc molybdate is supported on an inorganic filler As described above, the epoxy resin composition for use has a hard mold having excellent moldability, flame retardancy and moisture resistance reliability without increasing impurity ions in the extracted water. It has been found that it is possible to obtain the objects.

  In this case, the composition using these two or more flame retardants in combination has high water resistance and does not have an effect of increasing impurity ions in the extracted water. However, a composition using these flame retardants (E) and (F) alone has insufficient flame retardancy, the fluidity of the epoxy resin composition is reduced, or the curability is low. The flame retardant epoxy resin composition of the present invention has a phosphazene compound (C) represented by an average composition formula (1) and (E) an average composition formula (2) as a flame retardant. ), (F) a block copolymer obtained by addition reaction of SiH group of organopolysiloxane represented by average composition formula (2 ′) and alkenyl group of alkenyl group-containing epoxy compound, and (G) molybdenum By using together with a compound selected from molybdenum compounds formed by supporting zinc acid on an inorganic filler, the amount of each added can be minimized, as described above. No problem during molding, yet is capable of obtaining a particularly excellent cured flame retardancy and moisture resistance reliability.

The flame-retardant epoxy resin composition for semiconductor encapsulation of the present invention is excellent in moldability and can provide a cured product excellent in flame retardancy and moisture resistance reliability. In addition, since brominated products such as brominated epoxy resins and antimony compounds such as antimony trioxide are not contained in the epoxy resin composition, there are no adverse effects on the human body and the environment.
Moreover, the semiconductor device sealed with the hardened | cured material of the flame-retardant epoxy resin composition for semiconductor sealing of this invention is excellent in a flame retardance and moisture resistance reliability, and is especially useful industrially.

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

  The epoxy resin preferably has a hydrolyzable chlorine content of 1,000 ppm or less, particularly 500 ppm or less, and preferably contains sodium and potassium in a content of 10 ppm or less. When the hydrolyzable chlorine exceeds 1,000 ppm or the sodium or potassium exceeds 10 ppm, the moisture resistance may deteriorate if the semiconductor device is left under high temperature and high humidity for a long time.

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

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

  Here, the blending amount of the epoxy resin and the curing agent is not particularly limited, but when a phenol resin is used as the curing agent, the phenolic hydroxyl group contained in the curing agent with respect to 1 mol of the epoxy group contained in the epoxy resin. It is preferable that the molar ratio is in the range of 0.5 to 1.5, particularly 0.8 to 1.2.

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

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

（式中、ＡはＯ、Ｓ又はＮＲ³であり、Ｒ¹、Ｒ²、Ｒ³は水素原子又は炭素数１〜４のアルキル基であり、Ｒは脂肪族不飽和基を含有しない置換又は非置換の一価炭化水素基であり、Ｘは二価の有機基であり、ｘ、ｙ、ｚ、ｎは、０＜ｘ＜２ｎ、０＜ｙ＜２ｎ、ｘ＋ｙ＝２ｎ、０≦ｚ≦４００、３≦ｎ≦１，０００を満たす数である。） The epoxy resin composition of the present invention uses (C) a phosphazene compound represented by the following average composition formula (1).

(In the formula, A is O, S or NR ³ , R ¹ , R ² and R ³ are hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, and R is a substituted or non-substituted aliphatic group. An unsubstituted monovalent hydrocarbon group, X is a divalent organic group, x, y, z, and n are 0 <x <2n, 0 <y <2n, x + y = 2n, 0 ≦ z ≦ 400, 3 ≦ n ≦ 1,000.)

  Since the phosphazene compound represented by the above formula (1) has a silicone skeleton, it has both flame retardancy and moisture resistance reliability. Moreover, the flame-retardant epoxy resin composition for semiconductor encapsulation of the present invention to which the phosphazene compound represented by the above formula (1) is added is an epoxy resin composition to which a phosphorus-based flame retardant such as red phosphorus or phosphate is added. In comparison with the above, a cured product having excellent hot water extraction characteristics and particularly excellent moisture resistance reliability can be obtained. Further, the phosphazene compound represented by the above formula (1) is converted into (E) an organopolysiloxane represented by an average composition formula (2), and (F) an SiH group of an organopolysiloxane represented by an average composition formula (2 ′). By using together with a block copolymer in which an alkenyl group of an alkenyl group-containing epoxy compound is subjected to an addition reaction, or (G) a molybdenum compound, an even higher flame retardant effect can be obtained.

Here, in the formula (1), R ¹ , R ² , and R ³ are hydrogen atoms, methyl groups, ethyl groups, propyl groups, isopropyl groups, n-butyl groups, sec-butyl groups, tert-butyl groups, and the like. An alkyl group having 1 to 4 carbon atoms, and R is a substituted or unsubstituted monovalent hydrocarbon group not containing an aliphatic unsaturated group, and specifically includes a methyl group, an ethyl group, a propyl group, and an isopropyl group. Group, butyl group, isobutyl group, tert-butyl group, hexyl group, cyclohexyl group, octyl group, alkyl group such as decyl group, aryl group such as phenyl group, xylyl group, tolyl group, benzyl group, phenylethyl group, phenylpropylene Aralkyl groups such as ruthenium groups, and chloromethyl groups or bromoethyl groups in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted with halogen atoms such as chlorine, fluorine or bromine. Group, 1 to 15 carbon atoms, such as a halogen-substituted monovalent hydrocarbon groups such as trifluoropropyl group, particularly 1-10 monovalent hydrocarbon groups are exemplified.

X is a divalent organic group, and is preferably an alkylene group having 2 to 15 carbon atoms, particularly 2 to 5 oxygen atoms, which may be interposed, —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, A group represented by —OCH ₂ CH ₂ CH ₂ — and the like can be exemplified.

  In this case, n is from 3 to 1,000, more preferably from 3 to 10, and particularly preferably 3 in view of synthesis. X, y, and z are as described above. In order to achieve both flame retardancy and moisture resistance reliability, 1.2n ≦ x ≦ 1.8n, 0.2n ≦ y ≦ 0.8n, It is preferable that 5 ≦ z ≦ 100.

（式中、Ｒ¹は水素原子又は炭素数１〜４のアルキル基であり、Ｙは末端に二重結合を有する有機基である。）
で表されるフェノールと、（ＩＩＩ）下記一般式（５）

（式中、ＡはＯ、Ｓ又はＮＲ³であり、Ｒ²、Ｒ³は水素原子又は炭素数１〜４のアルキル基である。）
で表されるベンジル基含有化合物とを反応させ、得られた反応物中のＹの末端二重結合と、下記一般式（６）

（式中、Ｒは脂肪族不飽和基を含有しない置換又は非置換の一価炭化水素基であり、ｚは０≦ｚ≦４００である。）
で示される（ＩＶ）有機珪素化合物のＳｉＨ基とを付加反応させることにより得ることができる。 More specifically, the silicone-modified phosphazene compound has the following general formula (3):
(NPCl ₂ ) _m (3)
(In the formula, m is 3 to 100, preferably 3 to 10.)
(I) a chlorophosphazene compound represented by the formula (II):

(In the formula, R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Y is an organic group having a double bond at the terminal.)
And (III) the following general formula (5)

(In the formula, A is O, S or NR ³ , and R ² and R ³ are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)
And a terminal double bond of Y in the resulting reaction product, and the following general formula (6):

(In the formula, R is a substituted or unsubstituted monovalent hydrocarbon group not containing an aliphatic unsaturated group, and z is 0 ≦ z ≦ 400.)
(IV) It can obtain by carrying out addition reaction with the SiH group of the organosilicon compound.

（式中、Ｒ¹は水素原子又は炭素数１〜４のアルキル基であり、Ｙは末端に二重結合を有する有機基である。） The phenol as the component (II) is represented by the following general formula (4).

(In the formula, R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Y is an organic group having a double bond at the terminal.)

In the above formula (4), R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, can be exemplified the same as R ¹ described above. Y is an organic group having a double bond at the end, and is not particularly limited as long as it has a double bond at the end, but particularly those having 2 to 15 carbon atoms, especially 2 to 5 carbon atoms. Preferable examples include alkenyl groups such as vinyl group and allyl group, and alkenyloxy groups such as allyloxy group, among which allyl group is preferable.

  Specific examples of the phenol represented by the formula (4) include allylphenol and allyloxyphenol. In the present invention, these one kind may be used alone or two or more kinds may be used in combination. it can.

（式中、ＡはＯ、Ｓ又はＮＲ³であり、Ｒ²、Ｒ³は水素原子又は炭素数１〜４のアルキル基である。） Moreover, the benzyl group containing compound of (III) component is represented by the following general formula (5).

(In the formula, A is O, S or NR ³ , and R ² and R ³ are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

In the above formula (5), R ^2, R ³ is an alkyl group having 1 to 4 carbon hydrogen atom or a carbon, can be exemplified the same as R ^2, R ³ described above.

  Specific examples of the benzyl group-containing compound represented by the formula (5) include benzylamine, methylbenzylamine, benzyl alcohol, methylbenzyl alcohol, α-toluenethiol, methyl-α-toluenethiol, N- Examples thereof include methylbenzylamine and N-ethylbenzylamine. In the present invention, these one kind can be used alone or two or more kinds can be used in combination.

  In the present invention, (I) chlorophosphazene compound, (II) phenol containing an organic group having a double bond at the end, and (III) benzyl group-containing compound are mixed in a ratio of (I) chloro P-Cl bond in phosphazene compound: (II) phenolic hydroxyl group equivalent in phenol containing an organic group having a double bond at the end and (III) amine equivalent, OH equivalent or SH equivalent in benzyl group-containing compound = 1 : 1 to 1:50, particularly 1: 1.1 to 1:10.

  In addition, the mixing ratio of (II) phenol containing a double bond organic group and (III) benzyl group-containing compound used for the reaction is (II) phenol containing a double bond organic group. Phenolic hydroxyl group equivalent in: (III) Amine equivalent, OH equivalent or SH equivalent in the benzyl group-containing compound is preferably 1: 1 to 1: 100, and more preferably 1: 2 to 1:20.

  In the present invention, it is preferable to use a catalyst when the chlorophosphazene compound is reacted with a phenol containing an organic group having a double bond at the terminal and a benzyl group-containing compound. Examples of the catalyst include tertiary amine compounds such as diazabicycloundecene (DBU), triethylamine, benzyldimethylamine, and α-methylbenzyldimethylamine, 2-methylimidazole, 2-phenylimidazole, and 2-phenyl-4. -Imidazole compounds such as methylimidazole and the like.

  The addition amount of the catalyst is an effective amount and is not particularly limited, but is preferably 1.2 to 2.0 equivalents (molar ratio) with respect to all P—Cl bonds of the chlorophosphazene compound.

  The reaction in reacting a chlorophosphazene compound with a phenol containing an organic group having a double bond at the end and a benzyl group-containing compound is usually carried out in an organic solvent. Examples of such an organic solvent include THF, Examples include toluene and acetone.

  As this reaction method, for example, a chlorophosphazene compound, a phenol containing an organic group having a double bond at the end, and a catalyst are reacted in an organic solvent, a benzyl group-containing compound is added thereto, and further reacted. By crystallization, a phosphazene compound containing an organic group having a double bond at the end can be obtained. The reaction temperature is preferably from room temperature to 150 ° C., particularly from 50 to 100 ° C. in terms of yield and production efficiency, and the reaction time is preferably from 1 to 48 hours, particularly preferably from 3 to 20 hours.

  Next, after reacting the above-mentioned chlorophosphazene compound, a phenol containing an organic group having a double bond at the end, and a benzyl group-containing compound, the terminal double bond of Y of this reaction product, A silicone-modified phosphazene compound can be obtained by addition reaction with the SiH group of the organosilicon compound represented by (6).

上記式中、Ｒは脂肪族不飽和基を含有しない置換又は非置換の一価炭化水素基であり、上述したＲと同様のものが例示でき、ｚは０≦ｚ≦４００、特に５≦ｚ≦１００である。

In the above formula, R is a substituted or unsubstituted monovalent hydrocarbon group containing no aliphatic unsaturated group, and examples thereof are the same as those described above for R, and z is 0 ≦ z ≦ 400, particularly 5 ≦ z. ≦ 100.

（式中、Ｍｅはメチル基、Ｐｈはフェニル基である。） Specific examples of such organopolysiloxanes include those represented by the following formula.

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

  Here, when the phosphazene compound having an organic group having a double bond at the terminal and an organosilicon compound are subjected to an addition reaction, the phosphazene compound and the organic silicon compound having an organic group having a double bond at the terminal are each one kind. May be used alone or in combination of two or more.

  In this addition reaction, the mixture ratio of the phosphazene compound containing an organic group having a double bond at the terminal and the organosilicon compound is bonded to the silicon atom in the organosilicon compound with respect to the Y double bond in the phosphazene compound. The hydrogen atom (SiH group) mole ratio is preferably 0.2 to 1.0 mol / mol, and more preferably 0.4 to 0.95 mol / mol.

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

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

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

  Moreover, the addition amount of the phosphazene compound which is (C) component is 1-50 mass parts with respect to 100 mass parts of total amounts of (A) epoxy resin and (B) hardening | curing agent, Especially 2-30 mass parts is preferable. When the addition amount is less than 1 part by mass, a sufficient flame retardant effect may not be obtained, and when it exceeds 50 parts by mass, fluidity may be lowered.

  The epoxy resin composition of this invention can mix | blend (D) inorganic filler. As this inorganic filler, those usually blended in an epoxy resin composition can be used. For example, silica such as fused silica and crystalline silica, alumina, silicon nitride, aluminum nitride, boron nitride, oxidation Titanium, glass fiber, etc. are mentioned.

  The average particle diameter and shape of these inorganic fillers and the filling amount of the inorganic filler are not particularly limited, but in order to increase the flame retardancy, the amount is as large as possible within the range that does not impair the moldability in the epoxy resin composition. Is preferably filled. In this case, as the average particle diameter and shape of the inorganic filler, spherical fused silica having an average particle diameter of 5 to 30 μm is particularly preferable, and the filling amount in the case of using the inorganic filler is (A) an epoxy resin (B) It is preferable to set it as 400-1,200 mass parts with respect to 100 mass parts of total amounts with a hardening | curing agent, especially 500-1,000 mass parts.

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

  The flame-retardant epoxy resin composition for semiconductor encapsulation of the present invention can contain (E) an organopolysiloxane represented by the average composition formula (2).

R ⁴ _h R ⁵ _k Si (OR ⁶ ) _p (OH) _q O _{(4-hkpq) / 2} (2)
(Wherein R ⁴ is a phenyl group, R ⁵ is a monovalent hydrocarbon group such as an alkyl group or alkenyl group having 1 to 6 carbon atoms (excluding the phenyl group) or a hydrogen atom, and R ⁶ is A monovalent hydrocarbon group such as an alkyl group having 1 to 4 carbon atoms or an alkenyl group, and h, k, p, and q are 0 ≦ h ≦ 2.0, 0 ≦ k ≦ 1.0, and 0 ≦ p ≦. 2.5, 0 ≦ q ≦ 0.35, 0.92 ≦ h + k + p + q ≦ 2.8.

  The reason why the resin composition of the present invention exhibits good flame retardancy is not clear, but when the resin composition of the present invention containing the silicone compound represented by the above average composition formula (2) is burned, an alkoxy group By the oxidative degradation crosslinking, the organosiloxane and especially the epoxy resin containing aromatics are bonded and fixed around the burning part, and the phenyl group contained in the organosiloxane in a high content is particularly between the epoxy resin containing aromatic rings. It is considered that a nonflammable Si-C ceramic layer is easily formed by coupling each aromatic ring, and a high flame retardant effect is exhibited. In order that this flame retardant mechanism works effectively, the preferable alkoxy group content is p in the average composition formula of the organosiloxane, that is, the number of moles of alkoxy groups per mole of Si atoms is preferably 0.42 to 2.5. It is. If it is less than 0.42, the crosslinkability is too low to be fixed around the combustion part, and if it exceeds 2.5, only low molecular weight organosiloxane can be obtained, and it is vaporized by heat before being fixed during combustion. Since the loss rate by doing so becomes high, in any case, the flame retarding effect may be reduced. A more preferable alkoxy group content is 0.5 to 2.3 moles per mole of Si atoms.

R ⁶ in the average composition formula (2) is preferably selected from alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, and butyl groups, and an alkyl group having 5 or more carbon atoms is an alkoxy group. The reactivity is low, and the flame retardant effect cannot be expected.

  On the other hand, the silanol group contained in the organosiloxane also has low reactivity and hardly contributes to flame retardancy. However, in terms of storage stability and workability, the value of q in the organosiloxane average composition formula is 0. .35 or less is preferable.

  The phenyl group content, which is another element necessary for the above-described flame retardant mechanism to work effectively, is h in the average composition formula, that is, the number of moles of phenyl groups per mole of Si atoms, and is preferably about 0.00. 5 to 2.0. If it is less than 0.5, the number of phenyl groups may be too small to obtain a flame retarding effect. If it exceeds 2.0, the phenyl group content is sufficiently high, but since the bulky phenyl group contains many structures densely packed on one Si, the steric hindrance is large and the spatial freedom of the polyorganosiloxane molecule is reduced. However, it becomes difficult for the aromatic rings to overlap each other, which is necessary for the flame retardant mechanism due to the mutual coupling of the aromatic rings to act, thereby reducing the flame retardant effect. A more preferable value of h is 0.6 to 1.8.

The substituent bonded to Si by the Si—C bond may include a substituent R ⁵ other than the phenyl group. This substituent is not directly related to the flame-retarding effect, so if the content is increased, the reverse effect will be obtained, but by containing the proper amount, the steric hindrance of the organosiloxane molecule having a high bulky phenyl group content is alleviated. In some cases, the degree of spatial freedom is improved, the phenyl groups are easily overlapped, and the flame retarding effect is enhanced. The content of R ⁵ at which this effect can be expected is 1.0 or less in terms of k in the average composition formula. Preferably, the ratio of k to h + k in the average composition formula, k / (h + k), is in the range of 0 to 0.3, and if it exceeds 0.3, the relative phenyl group content decreases and the flame retardant effect May not be sufficiently obtained.

R ⁵ is a monovalent hydrocarbon group having 1 to 6 carbon atoms or a hydrogen atom, preferably an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms. For example, alkyl groups such as methyl, ethyl, propyl, butyl, and hexyl groups, and alkenyl groups such as vinyl, propenyl, and butenyl groups are exemplified. In particular, a methyl group and a vinyl group are preferred from the viewpoint of reducing steric hindrance and industrially.

The organopolysiloxane of component (E) of the present invention has the following formula (7)
R ⁸ SiZ ₃ (7)
(However, R ⁸ in the formula represents the same organic group as R ⁴ or R ⁵ , Z represents —OH, —OR ^9, or a siloxane residue, and among the three Z bonded to one Si atom, At least one contains a siloxane bond.)
It is preferable to contain 50 mol% or more of siloxane units represented by This trifunctional siloxane unit imparts resinous properties by forming a three-dimensional crosslinked structure and strengthening the organosiloxane molecular structure, and improves dispersibility and processability in the epoxy resin composition. In addition, organosiloxanes with a linear molecular structure containing many monofunctional and bifunctional siloxane units can easily escape from the system by forming volatile low molecular weight siloxanes by rearrangement of siloxane bonds that occurs during combustion. On the other hand, an organosiloxane containing a large amount of trifunctional siloxane units having high cross-linking reactivity further increases in molecular weight and stops in the system, contributing to flame retardancy. If the trifunctional siloxane unit is less than 50 mol%, these effects may be reduced. More preferably, the organosiloxane containing 60 mol% or more of the trifunctional siloxane unit exhibits a high flame retardancy effect.

R ^{8 in the} formula (7) is the same as R ⁴ or R ^5, and is an alkyl group, an alkenyl group, an aryl group, etc., for example, an alkyl group such as methyl, ethyl, propyl, butyl, hexyl group, vinyl, propenyl , An alkenyl group such as a butenyl group, and an aryl group such as a phenyl group. Particularly, a phenyl group, a methyl group, and a vinyl group are industrially preferable.

Z in the formula (7) represents —OH, —OR ⁹ , or a siloxane residue, and at least one of Z bonded to one Si atom must contain a siloxane unit. Note that a siloxane residue and a siloxane bond indicate -O- (Si≡) (provided that Si≡ in parentheses is bonded to an adjacent Si atom). R ⁹ represents an alkyl group having 1 to 3 carbon atoms.

  The organopolysiloxane of component (E) contains a difunctional siloxane unit, a monofunctional siloxane unit, or a tetrafunctional siloxane unit as a constituent unit other than the trifunctional siloxane unit as long as it does not affect the characteristics. May be. In particular, tetrafunctional siloxane units form a three-dimensional cross-linked structure to strengthen the organopolysiloxane molecular structure, and high cross-linking reactivity promotes high molecular weight and stops in the system, contributing to flame resistance. To do. On the other hand, when the content of the tetrafunctional siloxane unit is increased, the dispersibility in the epoxy resin is lowered, so that the preferable content is 50 mol% or less.

  Moreover, it is preferable that the average degree of polymerization of organopolysiloxane which is (E) component is a 2.5-20 mer. The degree of polymerization is an important factor that determines the flame retardant effect. Organopolysiloxanes in this degree of polymerization range disperse well during melt mixing, move and move with heat during combustion, and gather around the combustion area. You can also. This ease of movement also improves the flame retarding effect by facilitating the overlap of phenyl groups. For low molecular weight organosiloxanes with an average degree of polymerization of less than 2.5, the flame retardancy effect decreases due to heat vaporization during combustion, and when it exceeds 20, the ease of movement during combustion is lost and the flame retardancy effect decreases. In addition, dispersibility in the epoxy resin may deteriorate. More preferably, the average degree of polymerization is 2.5 to 15-mer, and even more preferably the average molecular weight is in the range of 410 to less than 2,000.

  Such an organopolysiloxane can be produced by a known method. For example, the organochlorosilane capable of forming the siloxane unit is reacted with excess alcohol that reacts with all chloro groups and water to form an alkoxy group-containing organosilane, and unreacted alcohol, And the reaction by-product, hydrogen chloride, is removed to obtain the desired product. In order to prepare the target alkoxy group content and average molecular weight, the amount of alcohol and water to be reacted is adjusted. If water is the theoretical amount at which the target average molecular weight is achieved and the alcohol is in excess of the theoretical amount to achieve the target amount of alkoxy groups, an organopolysiloxane close to the target structure can be obtained.

  If an alkoxysilane capable of forming the above siloxane unit is available, a method of performing a partial hydrolysis-condensation reaction by adding a theoretical amount of water that can achieve the target average molecular weight is also possible. In this case, it is desirable to add an acid, a base, or an organometallic compound as a catalyst for promoting the reaction. By-product alcohol is removed by atmospheric distillation or vacuum strip to obtain the desired product. When it is necessary to further improve the storage stability, the added reaction catalyst may be removed by a method such as neutralization. In any method, an organic solvent can be blended for the purpose of suppressing the generation of gel and the spread of molecular weight distribution.

  The addition amount in the case of using the organopolysiloxane which is the component (E) in the present invention is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the total amount of the (A) epoxy resin and the (B) curing agent. More preferably, it is 2-20 mass parts. If the amount is less than 0.1 parts by mass, the flame retardancy may not be sufficiently imparted. If the amount exceeds 50 parts by mass, the viscosity during molding increases, and the appearance and strength of the molded product may be adversely affected. .

  The flame-retardant epoxy resin composition for semiconductor encapsulation of the present invention is a block obtained by addition-reacting an SiH group of an organopolysiloxane represented by the following average composition formula (2 ′) and an alkenyl group of an alkenyl group-containing epoxy compound. A copolymer (F) can also be used.

H _r R ⁷ _s SiO _{(4-rs) / 2} (2 ')
Wherein R ⁷ is a substituted or unsubstituted monovalent hydrocarbon group containing no aliphatic unsaturated group, and r and s are 0.001 ≦ r ≦ 1, 1 ≦ s ≦ 3, 1.001 (It is a positive number satisfying ≦ r + s ≦ 3.)

Here, in the formula (2 ′), the monovalent hydrocarbon group for R ⁷ is preferably a group having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms, and preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group. Alkyl groups such as isobutyl group, tert-butyl group, hexyl group, cyclohexyl group, octyl group, decyl group, aryl groups such as phenyl group, xylyl group, tolyl group, benzyl group, phenylethyl group, phenylpropyl group, etc. Aralkyl groups, etc., and halogen-substituted monovalent hydrocarbon groups such as chloromethyl groups, trifluoropropyl groups, bromoethyl groups, etc., in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted with halogen atoms such as chlorine, fluorine, bromine, etc. And so on.

  In the formula (2 ′), more preferable ranges of s and r are 0.01 ≦ r ≦ 0.5, 1.5 ≦ s ≦ 2.5, 1.51 ≦ r + s ≦ 3.0, The number of silicon atoms in one molecule of the organopolysiloxane of the formula (2 ′) is preferably 2 to 1,000, particularly preferably 10 to 200, and the number of hydrogen atoms (SiH groups) directly connected to the silicon atom is 1 to 10 is preferred, especially 1-5. Further, the organopolysiloxane content in the block copolymer is preferably 5 to 50% by mass, particularly preferably 10 to 20% by mass.

  The production method of the copolymer of the present invention is already known (Japanese Examined Patent Publication No. 63-60069, Japanese Examined Publication No. 63-60070, etc.), an alkenyl group of an alkenyl group-containing epoxy compound, and the above formula (2 ′) It can obtain by addition reaction with SiH group of organopolysiloxane shown by these. Specific examples of the block copolymer include a structure represented by the following formula (8).

（上記式中、Ｒ⁷は上記と同じ、Ｒ¹⁰は水素原子又は炭素数１〜４のアルキル基、Ｒ¹¹は−ＣＨ₂ＣＨ₂ＣＨ₂−、−ＯＣＨ₂−ＣＨ（ＯＨ）−ＣＨ₂−Ｏ−ＣＨ₂ＣＨ₂ＣＨ₂−又は−Ｏ−ＣＨ₂ＣＨ₂ＣＨ₂−である。ｕは１〜２００、好ましくは１０〜１００の整数、ｔ、ｖは１〜１００、好ましくは１〜２０の整数である。）

(In the above formula, R ⁷ is the same as above, R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹¹ is —CH ₂ CH ₂ CH ₂ —, —OCH ₂ —CH (OH) —CH _2. -O-CH ₂ CH ₂ CH ₂ -or -O-CH ₂ CH ₂ CH _2- , u is an integer of 1 to 200, preferably 10 to 100, t and v are 1 to 100, preferably 1 to (It is an integer of 20.)

  In the present invention, the organopolysiloxane content in the (F) block copolymer is preferably 5 to 50% by mass, particularly preferably 10 to 20% by mass.

  As content when using the block copolymer which is (F) component, 0.1-50 mass parts is preferable with respect to 100 mass parts of total amounts of (A) epoxy resin and (B) hardening | curing agent, More preferably, it is 2-20 mass parts. Moreover, as organopolysiloxane content in a copolymer, 0.1-10 mass parts is preferable at a diorganopolysiloxane unit with respect to 100 mass parts of total amounts of (A) epoxy resin and (B) hardening | curing agent. More preferably, the content is 0.5 to 8 parts by mass.

  In the flame-retardant epoxy resin composition for semiconductor encapsulation of the present invention, (G) a molybdenum compound obtained by supporting zinc molybdate on an inorganic filler can be used.

  In order to obtain a sufficient flame retardant effect, it is preferable to uniformly disperse zinc molybdate in the epoxy resin composition. In order to improve dispersibility, zinc molybdate is preliminarily filled with inorganic substances such as silica and talc. The one supported on the agent is optimal.

Examples of the inorganic filler for supporting zinc molybdate include silicas such as fused silica and crystalline silica, talc, alumina, silicon nitride, aluminum nitride, boron nitride, titanium oxide, zinc oxide, and glass fiber. In this case, the average particle size of the inorganic filler is preferably 0.1 to 40 μm, more preferably 0.5 to 15 μm. Moreover, it is preferable that a specific surface area is 0.5-50 m < ² > / g, More preferably, it is 0.7-10 m < ² > / g.

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

  Further, the content of zinc molybdate in the molybdenum compound in which zinc molybdate is supported on the inorganic filler is preferably 5 to 40% by mass, particularly preferably 10 to 30% by mass. If the content of zinc molybdate is too small, a sufficient flame retardant effect may not be obtained, and if it is too large, fluidity and curability during molding may be deteriorated.

  Examples of the molybdenum compound formed by supporting such zinc molybdate on an inorganic filler include KEGGARD 1260, 1261, 911B, and 911C manufactured by SHERWIN-WILLIAMS.

  As an addition amount when using the molybdenum compound which made the inorganic filler which is (G) component carry | support zinc molybdate, it is 3 with respect to 100 mass parts of total amounts of (A) epoxy resin and (B) hardening | curing agent. It is preferable that it is -100 mass parts, and it is especially preferable that it is 5-100 mass parts. If it is less than 3 parts by mass, a sufficient flame retardant effect may not be obtained, and if it exceeds 100 parts by mass, fluidity and curability may be lowered. In this case, the amount of zinc molybdate itself in the molybdenum compound is 0.1 to 40 parts by weight, particularly 0.2 to 40 parts per 100 parts by weight of the total amount of (A) epoxy resin and (B) curing agent. Part by mass is preferred. If the amount is less than 0.1 parts by mass, a sufficient flame retardant effect may not be obtained. If the amount exceeds 40 parts by mass, fluidity and curability may be deteriorated.

  The epoxy resin composition of the present invention has other flame retardants such as phosphoric acid esters, triphenyl phosphate, ammonium polyphosphate, phosphorous compounds such as red phosphorus, hydroxylation, etc. Hydroxides such as aluminum and magnesium hydroxide, and inorganic compounds such as zinc borate and zinc stannate can also be added. However, antimony compounds such as antimony trioxide are not blended.

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

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

  In addition, the epoxy resin composition of the present invention can be mixed with each component using an organic solvent, and an epoxy resin, a curing agent, a phosphazene compound, and if necessary, an inorganic filler and other additives are added at a predetermined composition ratio. And then uniformly mixed with an organic solvent, the organic solvent is removed by distillation under reduced pressure, then cooled and solidified, and pulverized to an appropriate size to obtain a molding material. Further, a mixture is obtained in the same manner using only an epoxy resin and a curing agent using an organic solvent, and after adding a phosphazene compound, and if necessary, an inorganic filler and other additives, and mixing sufficiently uniformly with a mixer or the like, a heat roll It is possible to carry out a melt mixing process using a kneader, an extruder, etc., then to cool and solidify, and pulverize to an appropriate size to obtain a molding material. It can also be used as a varnish. Examples of such an organic solvent include toluene, MEK, THF, acetone and the like.

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

  Hereinafter, although the synthesis example of a phosphazene compound, an organopolysiloxane, and the Example and comparative example of an epoxy resin composition are shown and this invention is shown concretely, this invention is not restrict | limited to the following Example. In the formula, Me is a methyl group.

[Synthesis Example 1] Synthesis of Compound A 11.3 g of DBU in a mixture of 25.7 g (73.9 mmol) of hexachlorocyclotriphosphazene, 10.3 g (111 mmol) of 2-allylphenol and 250 g of toluene at room temperature under a nitrogen atmosphere. (739 mmol) was added dropwise. After stirring at 80 ° C. for 5 hours, a solution of 55.3 g (517 mmol) of benzylamine in 120 g of toluene was added dropwise, and the mixture was further stirred at 100 ° C. for 6 hours. Then, 5% aqueous solution of hydrogen chloride 500ml x 2 times, 5% aqueous solution of sodium hydroxide 500ml x 3 times, 5% aqueous solution of ammonium chloride 500ml x 2 times, pure water 500ml x 3 times, and 50g of sodium sulfate were added. By drying and distilling off the solvent under reduced pressure, 49.5 g of compound a represented by the following formula (9) was obtained.

  In a 500 ml four-necked flask equipped with a reflux condenser, a thermometer, a stirrer, and a dropping funnel, 100 g of toluene and 10 g of an alkenyl group-containing phosphazene compound (compound a) represented by the above formula (9) were placed under a nitrogen atmosphere. And azeotropic dehydration was carried out for 2 hours. The system was cooled to 80 ° C., 0.1 g of platinum chloride catalyst was added, and then a solution of 20.2 g of an organosilicon compound represented by the following formula (10) dissolved in 80.8 g of toluene was added dropwise over 2 hours. did. The system was stirred and aged for 6 hours while maintaining the inside of the system at 90 to 100 ° C., and then cooled to room temperature. Thereafter, the solvent was distilled off under reduced pressure to obtain 27.6 g of a silicone-modified phosphazene compound (Compound A) represented by the following average composition formula (11).

As a result of measuring ¹ H-NMR and IR of the obtained reaction product, ¹ H-NMR was -0.5-0.5, 4.2-4.4, 7.2-7.8, 7. 9-8.2ppm to a peak, IR is derived P-N in 700-950,1200-1400cm ^-1, and a peak derived from Si-Me around 1255cm ^-1. Thereby, it was found that a compound A represented by the following formula was obtained.

(Compound A)

[Synthesis Example 2] Synthesis of Compound B Under nitrogen atmosphere, 4.8 g (119 mmol) of sodium hydride was suspended in 50 ml of THF at 0 ° C., and 10.2 g (108 mmol) of phenol and 4,4′-sulfonyldiphenol were suspended therein. A solution of 0.45 g (1.8 mmol) in 50 ml of THF was added dropwise. After stirring for 30 minutes, a solution of 12.5 g (36.0 mmol) of hexachlorotriphosphazene in 50 ml of THF was added dropwise, and the mixture was heated to reflux for 5 hours. Separately, 5.2 g (130 mmol) of sodium hydride was suspended in 50 ml of THF at 0 ° C., and a solution of 11.2 g (119 mmol) of phenol in 50 ml of THF was added dropwise thereto, and the mixture was further heated to reflux for 19 hours. After the solvent was distilled off under reduced pressure, chlorobenzene was added and dissolved, and 5% aqueous sodium hydroxide solution 200 ml x 2 times, 5% sulfuric acid aqueous solution 200 ml x 2 times, 5% aqueous sodium hydrogen carbonate solution 200 ml x 2 times, water 200 ml x 2 times. Extraction was performed. The solvent was distilled off under reduced pressure to obtain 20.4 g of tan crystals (compound B) represented by the following formula (12).

(Compound B)

[Synthesis Example 3] Synthesis of Compound C A 1 L flask equipped with a stirrer, a cooling device, and a thermometer was charged with 211 g (1 mol) of phenyltrichlorosilane and 143 g of toluene, 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 at an internal temperature of 40 ° C. with stirring for 1 hour. Next, 12 g (0.7 mol) of water is charged into the dropping funnel and added dropwise to the flask with stirring for 1 hour, and the reaction proceeds while removing hydrogen chloride gas generated during the hydrolysis-condensation reaction out of the system. It was. After completion of the dropwise addition, the mixture was further aged at an internal temperature of 40 ° C. for 1 hour. Subsequently, toluene, excess methanol, unreacted water and hydrogen chloride were removed by distillation under reduced pressure to remove liquid methoxy group-containing organopolysiloxane ( 151 g of compound C) was obtained.

When the obtained organopolysiloxane is represented by R ⁴ _h R ⁵ _k Si (OR ⁶ ) _p (OH) _q O _{(4-hkpq) / 2} , h = 1.0, k = 0, k / (k + h ) = 0 and 100 mol% of organic substituents bonded by Si—C bonds on Si atoms are phenyl groups, p = 1.5, R ⁶ = methyl group, q = 0.2, trifunctional It contained 100 mol% of siloxane units, and the appearance was a colorless and transparent liquid, and the average degree of polymerization was 3 (average molecular weight was 500).

[Examples 1 to 9, Comparative Examples 1 to 4]
The components shown in Tables 1 and 2 were uniformly melt-mixed with two hot rolls, cooled and pulverized to obtain an epoxy resin composition for semiconductor encapsulation. With respect to these compositions, the following properties (I) to (VIII) were measured. The results are shown in Tables 3 and 4.

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

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

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

(IV) High-temperature electrical resistance characteristics A 70φ × 3 mm disc was molded under the conditions of a temperature of 175 ° C., a molding pressure of 6.9 N / mm ² and a molding time of 120 seconds, and post-cured at 180 ° C. for 4 hours. Thereafter, the volume resistivity was measured in a 150 ° C. atmosphere.

(V) Flame retardance Based on the UL-94 standard, a 1/32 inch thick plate was molded under conditions of a temperature of 175 ° C., a molding pressure of 6.9 N / mm ² and a molding time of 120 seconds, and 180 ° C. for 4 hours. The post-cured material was examined for flame retardancy.

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

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

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

Epoxy resin: o-cresol novolac type epoxy resin, EOCN1020-55 (manufactured by Nippon Kayaku, epoxy equivalent 200)
Curing agent: phenol novolac resin, DL-92 (Maywa Kasei, phenolic hydroxyl group equivalent 110)
Phosphazene compounds: Compounds of Synthesis Examples 1 and 2 (Compounds A and B)
Inorganic filler: Spherical fused silica (manufactured by Tatsumori, average particle size 20 μm)
Organopolysiloxane: Polysiloxane of Synthesis Example 3 (Compound C)
Block copolymer obtained by addition reaction of organopolysiloxane and alkenyl group-containing epoxy compound: block copolymer represented by the following formula, organopolysiloxane content 16 mass%, epoxy equivalent 238

Molybdenum compound: Zinc molybdate, KEMGARD911C (SHERWIN-WI
LLIAMS, zinc molybdate content 18% by mass, core material: talc, average particle size 2
. 0 μm, specific surface area 2.0 m ² / g)
Curing catalyst: Triphenylphosphine (manufactured by Hokuko Chemical)
Mold release agent: Carnauba wax (Nikko Fine Products)
Carbon black: Denka Black (manufactured by Denki Kagaku Kogyo)
Silane coupling agent: γ-glycidoxypropyltrimethoxysilane, KBM-403
(Shin-Etsu Chemical Co., Ltd.)

As is clear from the results of Tables 3 and 4, the flame-retardant epoxy resin composition for semiconductor encapsulation of the present invention is excellent in curability, excellent in flame retardancy and moisture resistance reliability, and excellent in high-temperature electrical resistance characteristics. The semiconductor device which can obtain hardened | cured material and was sealed with the hardened | cured material of the epoxy resin composition of this invention is excellent in a flame retardance and moisture resistance reliability. In addition, since the bromide such as brominated epoxy resin and the antimony compound such as antimony trioxide are not contained in the resin composition, there is no adverse effect on the human body and the environment.

Claims (8)

(A) Epoxy resin (B) Curing agent (C) Phosphazene compound represented by the following average composition formula (1)

(In the formula, A is O, S or NR ³ , R ¹ , R ² and R ³ are hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, and R is a substituted or non-substituted aliphatic group. An unsubstituted monovalent hydrocarbon group, X is a divalent organic group, x, y, z, and n are 0 <x <2n, 0 <y <2n, x + y = 2n, 0 ≦ z ≦ 400, 3 ≦ n ≦ 1,000.)
Is a flame retardant epoxy resin composition for semiconductor encapsulation, characterized in that it contains essentially bromine and an antimony compound.   2. The semiconductor sealing device according to claim 1, wherein the amount of (C) phosphazene compound added is 1 to 50 parts by mass with respect to 100 parts by mass of the total amount of (A) epoxy resin and (B) curing agent. Flame retardant epoxy resin composition.   Further, (D) 400 to 1,200 parts by mass of (D) inorganic filler is blended with respect to 100 parts by mass of the total amount of (A) epoxy resin and (B) curing agent. The flame-retardant epoxy resin composition for semiconductor sealing of description. Furthermore, (E) the following average composition formula (2)
R ⁴ _h R ⁵ _k Si (OR ⁶ ) _p (OH) _q O _{(4-hkpq) / 2} (2)
Wherein R ⁴ is a phenyl group, R ⁵ is a monovalent hydrocarbon group or hydrogen atom having 1 to ⁶ carbon atoms, R ⁶ is a monovalent hydrocarbon group having 1 to 4 carbon atoms, h , K, p, q are 0 ≦ h ≦ 2.0, 0 ≦ k ≦ 1.0, 0 ≦ p ≦ 2.5, 0 ≦ q ≦ 0.35, 0.92 ≦ h + k + p + q ≦ 2.8. The number of ranges to satisfy.)
The flame retardant epoxy resin composition for semiconductor encapsulation according to claim 1, wherein an organopolysiloxane represented by the formula: Further, (F) the following average composition formula (2 ′)
H _r R ⁷ _s SiO _{(4-rs) / 2} (2 ')
Wherein R ⁷ is a substituted or unsubstituted monovalent hydrocarbon group containing no aliphatic unsaturated group, and r and s are 0.001 ≦ r ≦ 1, 1 ≦ s ≦ 3, 1.001 (It is a positive number satisfying ≦ r + s ≦ 3.)
A block copolymer obtained by adding an SiH group of an organopolysiloxane represented by the above formula and an alkenyl group of an alkenyl group-containing epoxy compound is added. Flame retardant epoxy resin composition.   The flame retardant epoxy resin composition for semiconductor encapsulation according to any one of claims 1 to 5, further comprising (G) a molybdenum compound obtained by supporting zinc molybdate on an inorganic filler. .   7. The semiconductor sealing device according to claim 6, wherein the addition amount of (G) molybdenum compound is 3 to 100 parts by mass with respect to 100 parts by mass of the total amount of (A) epoxy resin and (B) curing agent. Flame retardant epoxy resin composition. The semiconductor device sealed with the hardened | cured material of the flame-retardant epoxy resin composition for semiconductor sealing of any one of Claims 1 thru | or 7.