JP2003020337A - Bisnadimide-polysiloxane alternating copolymer or its derivative and epoxy resin composition for electronic material containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a bisnadimide-polysiloxane alternating copolymer which is a novel compound; its derivative; a method for producing the same; and an epoxy resin composition which contains the same, exhibits a lowered stress and an improved resistance to heat hysteresis while retaining its inherent mechanical strengths, adhesive properties, and heat resistance, and is used for electronic materials, especially for semiconductor sealing. SOLUTION: There are provided a bisnadimide-polysiloxane alternating copolymer produced by the hydrosilylation of (A) an unsaturated-group-containing bisnadimide with (B) a polysiloxane having SiH groups at both molecular ends; a derivative of the copolymer; and an epoxy resin composition for electronic materials, especially for semiconductor sealing, prepared by compounding the alternating copolymer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel bisnadiimide-polysiloxane alternating copolymer or a derivative thereof, a method for producing the same, and a resin composition for an electronic material or a semiconductor encapsulant containing the same, More specifically, it is effective for lowering stress and improving resistance to heat history without damaging mechanical strength, adhesiveness, adhesiveness and heat resistance of the epoxy resin composition, and particularly for electronic materials, especially semiconductor encapsulation. Novel bisnadiimide-polysiloxane alternating copolymer useful as an additive for antistatic epoxy resin composition, method for producing the same,
And a resin composition for an electronic material or a semiconductor encapsulating material containing the same.

[0002]

2. Description of the Related Art Conventionally, various silicone compounds have been proposed and widely used as a stress-reducing agent for electronic materials, especially for epoxy resin compositions for semiconductor encapsulation. For example, when dimethylpolysiloxane oil is blended, it is effective as a stress reducing agent, but there is a problem that the dispersibility and heat resistance are poor. Further, JP-A-60-13841 discloses that a polysiloxane molecule has an epoxy group, an amino group, a hydroxyl group, a carboxy group, a carboxylic acid ester group, etc., which reacts with an epoxy resin at both ends, It has been proposed to use a modified dimethyl polysiloxane in which a polyalkylene oxide is pendantly bonded to a part of linear dimethyl siloxane units of a siloxane molecule. This has a considerably superior effect compared to the case of using conventional dimethylpolysiloxane, but unreacted polyalkylene oxide remains, which is heat resistance, adhesion, moisture resistance, metal corrosion resistance. In addition, there is a problem that heat resistance, moisture resistance, electrical characteristics and mechanical characteristics are not sufficiently exhibited due to deterioration of stress relaxation property and properties derived from the entire chemical structure. Further, Japanese Patent No. 3043838 discloses that the present applicant has developed
Dimethylpolysiloxane having hydrogen groups directly bonded to silicon atoms as both end groups, and (meth) as both end groups
Dimethylpolysiloxane obtained by hydrosilylation reaction with an allyl group-containing polyalkylene oxide-
Disclosed is an epoxy resin composition for semiconductor encapsulation, which comprises an alternating copolymer having a repeating unit of polyalkylene oxide as a stress reducing agent. In addition, Japanese Patent Publication No. 6-74320 proposes a maleic acid imide-modified polysiloxane.

However, in recent years, electronic components have become highly integrated and miniaturized, and the usage conditions thereof are becoming severer.
With conventional epoxy resin compositions containing a stress-reducing agent, satisfactory performance is no longer being obtained. For example, in a conventional epoxy resin composition containing a stress-reducing agent, when used as an encapsulant for electronic components that have recently become highly integrated and miniaturized, thermal history after molding, for example, during soldering in a later process There is a problem that deterioration occurs due to repeated heating of the semiconductor, heating during use of the semiconductor and cooling after use, and bleeding out. Further, it has been proposed that a polyimide-based compound be blended for the purpose of improving heat resistance, but sufficient stress reduction has not been achieved. It is strongly desired to solve these problems.

[0004]

In view of the above-mentioned problems, the present invention is effective in reducing the stress of the epoxy resin composition and improving the resistance to heat history, and has the mechanical strength, adhesion, adhesiveness and It is an object of the present invention to provide a novel compound useful as an additive that does not impair heat resistance, a method for producing the same, and a resin composition for an electronic material or a semiconductor encapsulant having the above properties, which is obtained by mixing the compound. .

[0005]

As a result of intensive studies to solve the above problems, the inventors of the present invention produced a novel bisnadiimide-polysiloxane alternating copolymer having a specific chemical structure or a derivative thereof. When it was blended with an epoxy resin composition, they found that the above problems could be solved, and completed the present invention.

That is, according to the first aspect of the present invention,
The average number of repeating units represented by the following general formula (1) is 1
A bisnadiimide-polysiloxane alternating copolymer having 100 to 100,000 or a derivative thereof is provided.

[0007]

[Chemical 8] (In the formula, R ¹ is an organic group containing a divalent aromatic ring or a divalent aliphatic residue, and R ² is a divalent aliphatic residue having 2 to 10 carbon atoms, The right end of R ² is 1, 2,
It is bonded at any one of the 3 and 4 positions, and R ² '
Represents a divalent aliphatic residue having 2 to 10 carbon atoms,
The left end of R ² 'is bound at any one of the 1', 2 ', 3', 4'positions in the formula, and R ³ is independently of each other a hydrocarbon having 1 to 24 carbon atoms. Represents a group, a hydroxyl group, an alkoxy group having 1 to 5 carbon atoms or a trimethylsiloxy group, and x represents a number of 0 to 10,000 on average. )

According to the second aspect of the present invention, the first aspect
In the invention described above, R ¹ in the general formula (1) is any of the following groups, and a bisnadiimide-polysiloxane alternating copolymer is provided.

[0009]

[Chemical 9]

[0010]

[Chemical 10]

According to the third aspect of the present invention, the first aspect
In the invention, the weight average molecular weight is 1,000 to 1,0.
Bisnadiimide-characterized in that it is 0,000
Alternating polysiloxane copolymers are provided.

According to the fourth aspect of the present invention, bisnadiimide (A) represented by the following general formula (2) and SiH at both ends of the molecule represented by the following general formula (3) are provided. The method for producing a bisnadiimide-polysiloxane alternating copolymer according to claim 1, wherein the hydrosilylation reaction is carried out with the group-containing polysiloxane (B).

[0013]

[Chemical 11] (In the formula, R ¹ is an organic group containing a divalent aromatic ring or a divalent aliphatic residue, and R ⁴ and R ⁵ are each a carbon atom having 2 to 1 carbon atoms.
A terminal unsaturated aliphatic group-containing organic group of 0, which is any one of the 1, 2, 3, and 4 positions in the formula and 1 ′, 2 ′,
Substitution is made at any one of the 3'and 4'positions. )

[0014]

[Chemical 12] (In the formula, R ⁶ independently represents a hydrocarbon group having 1 to 24 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 5 carbon atoms, or a trimethylsiloxy group, and x is 0 to 0 on average.
Represents a number of 10,000. )

According to the fifth aspect of the present invention, the fourth aspect
In the invention described above, R ¹ in the general formula (2) is any of the following groups, and a method for producing a bisnadiimide-polysiloxane alternating copolymer is provided.

[0016]

[Chemical 13]

[0017]

[Chemical 14]

According to the sixth aspect of the present invention, the fourth aspect
Bisnadiimide-A polysiloxane (B) is reacted in a molar ratio of 1.0: 0.5 to 1.0: 2.0 in the invention of claim 2, wherein the bisnadiimide-polysiloxane alternating copolymerization A method of making a coalescence is provided.

Further, according to the seventh invention of the present invention, in the resin composition for an electronic material containing an epoxy resin as a main component, the invention according to any one of the first to third inventions is applied to 100 parts by weight of the composition. There is provided a resin composition for electronic materials, which comprises 0.01 to 50 parts by weight of the described bisnadiimide-polysiloxane alternating copolymer.

According to the eighth aspect of the present invention, in the semiconductor encapsulating material containing an epoxy resin as a main component, 3 to 20 parts by weight of the epoxy resin and 2 to 2 parts of the phenol novolac resin are used.
In addition to 15 parts by weight and 60 to 80 parts by weight of inorganic powder, the first
The present invention provides a semiconductor encapsulating material obtained by blending 0.01 to 50 parts by weight of the bisnadiimide-polysiloxane alternating copolymer according to any one of claims 1 to 3.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION The bisnadiimide of the present invention is described below.
A polysiloxane alternating copolymer, a method for producing the same, and an epoxy resin composition for electronic materials containing the same,
Each item will be described in detail.

1. Unsaturated group-containing group-substituted bisnadiimide (A) The unsaturated group-containing group-substituted bisnadiimide (A) used as one of the raw materials in the production of the bisnadiimide-polysiloxane alternating copolymer of the present invention is represented by the following general formula (2). It is represented by.

[0023]

[Chemical 15] In the formula, R ¹ is an organic group containing a divalent aromatic ring or a divalent aliphatic residue, and specific examples thereof are the same as those shown in Chemical formulas 9 and 10.

R ⁴ and R ⁵ are each an organic group containing a terminal unsaturated aliphatic group having 2 to 10 carbon atoms, and are represented by any one of the 1, 2, 3, and 4 positions in the formula and 1 ′, 2 ',
Substitution is made at any one of the 3'and 4'positions. R
⁴ and R ⁵ are a terminal unsaturated aliphatic group-containing organic group having 2 to 10 carbon atoms, and specific examples thereof include groups represented by the following, and an allyl group or a methallyl group is particularly preferable. .

[0025]

[Chemical 16] (In the formula, R ⁷ represents a direct bond or a divalent hydrocarbon group, particularly an alkyl group having 1 to 8 carbon atoms, and R ⁸ represents a hydrogen atom group or an alkyl group having 1 to 8 carbon atoms. )

Unsaturated group-containing group-substituted bisnadiimide (A)
Are those in which R ¹ is a divalent aliphatic residue,
N'-ethylene-bis (allylbicyclo [2.2.1]
Hept-5-ene-2,3-dicarboximide),
N, N'-trimethylene-bis (allylbicyclo [2.
2.1] Hept-5-ene-2,3-dicarboximide), N, N'-hexamethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyl) Imido), N, N'-dodecamethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-
Dicarboximide) and the like, and those in which R ¹ is an organic group containing a divalent aromatic ring include N, N′-p-phenylene-bis (allylbicyclo [2.2.1] hept-5-
Ene-2,3-dicarboximide), N, N'-m-
Phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), bis {4- (allylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximido) phenyl} methane,
Bis {4- (allylbicyclo [2.2.1] hept-5
-Ene-2,3-dicarboximido) phenyl} ether, N, N'-p-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N'-m-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-
Dicarboximide) and the like. The chemical formulas of some of them are as follows:
To (12).

[0027]

[Chemical 17]

[0028]

[Chemical 18]

[0029]

[Chemical 19]

Unsaturated group-containing group-substituted bisnadiimide (A)
Can be produced by a known method. For example, JP-A-59-
80662, JP-A-60-178862, JP-A-6
No. 1,187,61, JP-A No. 63-170358, and JP-A No. 7-53516, the corresponding alkenyl-substituted nadic acid anhydrides, such as alkenyl-substituted bicyclo [2,2,1] hept-5. It can be produced by reacting an ene-2,3-dicarboxylic anhydride derivative with a diamine. Also, BANI- from Maruzen Petrochemical Co., Ltd.
It is also possible to use those commercially available as M, BANI-H, and BANI-X.

2. Polysiloxane having SiH groups at both ends of molecule (B) Polysiloxane having SiH groups at both ends of the molecule used as one of raw materials in the production of the bisnadiimide-polysiloxane alternating copolymer of the present invention (B) ) Is represented by the following general formula (3).

[0032]

[Chemical 20] In the formula, R ⁶ independently represents a hydrocarbon group having 1 to 24 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 5 carbon atoms, or a trimethylsiloxy group, but a methyl group, an ethyl group and a phenyl group are preferable. The methyl group is particularly preferable. x represents a number of 0 to 10,000 on average. When x is 10,000 or more, the effect of improving the resistance of the epoxy resin to the heat history cannot be obtained. In order to obtain the effect of improving the resistance to heat history, x is preferably 100 or less, and in order to further enhance the effect of reducing the stress of the epoxy resin, x is preferably 5 or more. The hydroorganopolysiloxane of the general formula (3) can be prepared, for example, by R
^When all ⁶ are alkyl groups, tetraalkyldisiloxane and octaalkylcyclotetrasiloxane are obtained by various ring-opening polymerization at room temperature for several hours in the presence of an acid catalyst such as sulfuric acid. You can

3. Method for Producing Alternating Copolymer of Bisnadiimide-Polysiloxane By subjecting the above-mentioned unsaturated group-containing group-substituted bisnadiimide (A) to polysiloxane (B) having SiH groups at both ends of the molecule, a hydrosilylation reaction is carried out. A bisnadiimide-polysiloxane alternating copolymer can be obtained. The use of catalysts is preferred in order to carry out the reaction rapidly and at relatively low temperatures. As the catalyst, a known substance as a hydrosilylation catalyst, for example, a compound such as platinum, ruthenium, rhodium, palladium, osmium or iridium can be used. Particularly, platinum compounds are useful because of their high activity. Examples of platinum compounds include chloroplatinic acid, simple substance of platinum, alumina,
A solid platinum supported on a carrier such as silica or carbon black, a platinum-vinyl siloxane complex, a platinum-phosphine complex, a platinum-phosphite complex, a platinum alcoholate catalyst and the like can be used. In the hydrosilylation reaction, the platinum catalyst is used in an amount of 0.0001 to 0.1% by weight as platinum.

In the hydrosilylation reaction, a solvent may be used if necessary. Examples of usable solvents include ethers; ketones such as acetal and cyclohexanone; esters; phenols; hydrocarbons; halogenated hydrocarbons; and dimethylpolysiloxane. When a catalyst is used, the hydrosilylation reaction is 20 to 150 ° C.
For about 10 minutes to 8 hours at a temperature of about 40 ° C. to 120 ° C.

The terminal of the copolymer of the present invention is not limited.
When produced by the above method, the terminal copolymer of the alternating copolymer has a terminal unsaturated aliphatic group-containing organic group or SiH group. When the terminal is an organic group containing a terminal unsaturated aliphatic group, Si-such as trimethoxysilane and methyldimethoxysilane
It may be further hydrosilylated with a H-containing compound or saturated by hydrogenation. When the terminal is a SiH group, allyl glycidyl ether, allylamine, 1-octene, vinyltrimethoxysilane and the like may be further added by a hydrosilylation reaction.

3. Bisnadiimide-Polysiloxane Alternating Copolymer The bisnadiimide-polysiloxane alternating copolymer or derivative thereof of the present invention has bisnadiimide first, and then polysiloxane bonded next, as represented by the following general formula (1). The average number of repeating units is 1 to 100,000
It has 0.

[0037]

[Chemical 21] In the above formula, R ¹ is a divalent aromatic ring-containing organic group or a divalent aliphatic residue.
Is the same as that shown in.

R^TwoIs a divalent fat having 2 to 10 carbon atoms
Group residue, R^TwoThe right end of the is 1, 2, 3, 4
Bound at any one of the positions, R^Two’Is carbon
Represents a divalent aliphatic residue having 2 to 10 atoms, R^Two’Left
The side end is one of the 1 ', 2', 3 ', and 4'positions in the formula
Is bonded at the position^ThreeAre carbon sources independent of each other
No hydrocarbon groups with 1 to 24 children, hydroxyl groups, 1 carbon atoms
Table 5 shows the alkoxy or trimethylsiloxy groups of
However, x represents a number of 0 to 10,000 on average. R
^TwoAnd R^Two’Is-(CH_Two)_Two-,-(C
H_Three)_Two-,-(CH _Four)_Two-,-(CH₆)_Two-,-
(CH₈)_Two-,-(CH₁₀)_Two-, -CH _TwoCH
(CH_Three) CH_Two-, -CH_TwoCH (CH_Three) CH_TwoC
H_Two-, -CH_TwoCH (CH_Three) CH_TwoCH_TwoCH
_Two-, -CH_TwoCH (CH_Three) CH_TwoCH_TwoCH_TwoCH
_TwoCH_Two-, -CH_TwoCH (CH_Three) CH_TwoCH_TwoCH
_TwoCH_TwoCH_TwoCH_TwoCH_Two-, -CH_TwoCH (C
H_Three) CH_TwoCH_TwoCH_TwoCH_TwoCH_TwoCH _TwoCH_TwoC
H_TwoCH_Two-, Etc. are illustrated. Bisnadiimide of the present invention
Left end of polysiloxane alternating copolymer or derivative thereof
In the repeating unit of, that is, the copolymer or its
In the repeating unit of the polymerization initiation point of the derivative, bisna
R at the left end of the diimide part^TwoIs -CH = CHCH_Two
-, -CH = C (CH_Three) CH_Two-And the like. R
^ThreeAre hydrocarbons having 1 to 24 carbon atoms independently of each other.
Groups, hydroxyl groups, alkoxy groups having 1 to 5 carbon atoms,
Represents a trimethylsiloxy group. x is 0-10 on average
000, preferably 1 to 2000
However, the number is more preferably 3 to 20. y is 1 on average
~ 10,000, preferably 1-200, more preferably
Represents a number of 2 to 20.

The degree of polymerization of the alternating copolymer of the present invention is not particularly limited, but its weight average molecular weight is 1,000 to 1.0.
Those having an amount of 0,000, particularly 2,000 to 100,000 can be preferably used. Here, the weight average molecular weight means gel permeation chromatography (GP
It is a value calculated from the measurement result of the polystyrene reduced molecular weight according to C). If the weight average molecular weight is smaller than this range, the effect of lowering the stress of the resin is small, which is not preferable, and if it is larger, the viscosity of the resin is high and the fluidity is impaired, which is not preferable. The bisnadiimide-polysiloxane alternating copolymer of the present invention or a derivative thereof has a repeating unit represented by the above general formula (1),
The terminal group is uniquely determined by the charging ratio of (A) and (B), and the terminal unsaturated aliphatic group-containing organic group and / or SiH group may be used as it is as the terminal group. It may be reacted with a compound.

As a case which is uniquely determined by the charging ratio of (A) and (B), for example, when the compound (A) and the compound (B) are charged at a molar ratio of 2/1, ABA
An alternating copolymer having an average structure of is obtained, the left end is blocked with a -H group, and the right end group is an ethylene group when the terminal unsaturated group in R ⁴ which is the left end group of the compound (A) is an ethylene group. It is blocked by the group changed to. When the compound (A) and the compound (B) are charged in a molar ratio of 1/2, an alternating copolymer having an average structure of BAB is obtained, and the left terminal group is the right terminal group of the compound (B). Is −
It is blocked by the compound (B) residue excluding the H group, and the right terminal group is blocked by the -H group. When the compound (A) and the compound (B) have a molar ratio of 3/2 and 4/3, respectively, they have an average structure of ABABA and ABABABA, respectively, and the left end is blocked with a -H group, and the right end group is the compound ( The terminal unsaturated group in R ⁴ , which is the left side terminal group of A), is blocked by a group converted to an ethylene group.

As the molar ratio of the compound (A) to the compound (B) approaches 1: 1, the compound is composed of only the repeating units of AB, and the number of repeating units also increases, and both ends are --H groups. . When the compound (A) and the compound (B) are in a molar ratio of 2/3 and 3/4, BABAB and BAB, respectively.
It becomes an average structure of ABAB, the left end is blocked by a -H group, and the right end group is blocked by a group in which the terminal unsaturated group in R ⁴ which is the left end group of the compound (A) is changed to an ethylene group. ing.

The derivative of the bisnadiimide-polysiloxane alternating copolymer of the present invention means the above-mentioned bisnadiimide-
It is obtained by reacting another compound with the terminal unsaturated aliphatic group-containing organic group having 2 to 10 carbon atoms and / or the SiH group, which is the terminal group of the polysiloxane alternating copolymer.

Examples of the bisnadiimide-polysiloxane alternating copolymer of the present invention include the following general formula (13).
The compounds represented by (17) to (17) are mentioned. General formula (1
3) corresponds to the ABA type alternating copolymer, and has the general formula (1
4) corresponds to the BAB type alternating copolymer and has the general formula (1
5) corresponds to the (AB) ₉ type alternating copolymer, the general formula (16) corresponds to the (AB) ₁₉ A type alternating copolymer,
The general formula (17) corresponds to a B (AB) ₆ type alternating copolymer. These are characterized in that they have a repeating unit of AB, although various groups can be selected as the both terminal groups.
That is, the physical properties of the repeating unit of bisnadiimide-polysiloxane is effective in lowering stress and improving resistance to heat history without impairing the mechanical strength, adhesiveness, adhesiveness and heat resistance of the epoxy resin composition. The terminal group of the copolymer has little influence on the physical properties of the epoxy resin composition. Therefore, as a general formula of the bisnadiimide-polysiloxane alternating copolymer of the present invention, the repeating unit of bisnadiimide-polysiloxane, which is a characteristic part, is shown and both end groups are omitted, but both end groups cannot be specified by the chemical formula. It has not been omitted, and since it can be specified as described in detail for each case above, it has been omitted for the sake of brevity.

[0044]

[Chemical formula 22]

[0045]

[Chemical formula 23]

[0046]

[Chemical formula 24]

[0047]

[Chemical 25]

[0048]

[Chemical formula 26]

Examples of the derivative of the bisnadiimide-polysiloxane alternating copolymer of the present invention include compounds represented by the following general formulas (18) to (22).

[Chemical 27]

[0050]

[Chemical 28]

[0051]

[Chemical 29]

[0052]

[Chemical 30]

[0053]

[Chemical 31]

4. Use of bisnadiimide-polysiloxane alternating copolymer and its derivative When the bisnadiimide-polysiloxane alternating copolymer and its derivative of the present invention are compounded in various resin compositions, the effect of reducing the stress of the resin and improving the resistance to heat history is improved. It is useful because it does not impair mechanical strength, adhesion, adhesiveness and heat resistance. Therefore, when it is blended with the epoxy resin composition and used for semiconductor encapsulation, it can exhibit its characteristics most. Epoxy resin composition and bisnadiimide-
An epoxy resin composition for semiconductor encapsulation comprising a polysiloxane alternating copolymer or a derivative thereof is also an aspect of the present invention.

4.1 Epoxy resin composition for electronic materials The epoxy resin composition for electronic materials in the present invention is a resin composition based on epoxy resin, which is used for adhesion, sealing, insulation, and structural materials of electronic and electric devices. It refers to all things that can be used. Specifically, a known composition composed of an epoxy resin, a curing agent, a curing accelerator, an inorganic filler and other additives can be used. The epoxy resin refers to all monomers, oligomers and polymers having two or more epoxy groups in one molecule and is not particularly limited. For example, orthocresol novolac type epoxy resin, phenol novolac type epoxy resin,
Dicyclopentadiene modified phenolic epoxy resin,
Examples thereof include bisphenol type epoxy resin, biphenyl type epoxy resin, stilbene type epoxy resin, naphthol type epoxy resin, triphenolmethane type epoxy resin, triazine nucleus-containing epoxy resin, and modified resins thereof. You may use. For curability, the epoxy equivalent is 150 to 300 g / eq.
A degree is preferable. The amount of the epoxy resin compounded in the epoxy resin composition is 3 to 20% by weight, and particularly 5 to 1%.
0% by weight is preferred.

As a curing agent, a phenol resin having two or more phenolic hydroxyl groups in one molecule is typical. More specifically, phenol novolac resin,
Examples thereof include dicyclopentadiene-modified phenol resin, phenol aralkyl resin, triphenol methane resin, and modified resins thereof, and these may be used alone or in combination. For curability, the hydroxyl equivalent is 80-
About 250 g / eq is preferable. When a phenol resin is used as the curing agent, the molar ratio of the epoxy group in the epoxy resin to the phenolic hydroxyl group in the phenol resin is 0.5.
The blending amount is preferably in the range of -1.5, particularly 0.8-1.2. As the inorganic filler, for example, fused silica,
Examples thereof include spherical silica, crystalline silica, secondary agglomerated silica, porous silica, secondary agglomerated silica, silica obtained by pulverizing porous silica, alumina, and the like, and these may be used alone or in combination. The particle shape may be crushed or spherical, but spherical fused silica having well-balanced flow characteristics, mechanical strength, and thermal characteristics is preferably used. Further, these inorganic fillers may be surface-treated with a silane coupling agent or the like. The compounding amount of the inorganic filler is 100 to 12 with respect to 100 parts by weight of the epoxy resin.
00 parts by weight, particularly 400 to 1000 parts by weight are preferred. If it is less than 100 parts by weight, the expansion coefficient of the resin becomes large, and when used as a sealing material, excessive stress is applied to the semiconductor element, which may cause deterioration of the element. Also, 120
If it exceeds 0 parts by weight, the viscosity of the resin increases and the moldability deteriorates.

As the curing accelerator, those generally used in electronic materials can be widely used. As a typical example, for example, 1,8-diazabicyclo (5,4,0)
Undecene-7, triphenylphosphine, tetraphenylphosphonium / tetraphenylborate, tetraphenylphosphonium / tetranaphthoic acid borate, benzyldimethylamine, 2-methylimidazole and the like can be mentioned, and these may be used alone or in combination. . These curing accelerators may be dry blended into the epoxy resin composition, melt blended, or a combination of both. The addition amount of the curing accelerator is preferably 0.01 to 5 parts by weight, particularly 0.1 to 3 parts by weight with respect to 100 parts by weight of the epoxy resin. Compounding amount 0.0
If it is less than 1 part by weight, the action as a curing accelerator is not sufficiently exhibited, and if it exceeds 5 parts by weight, the curing rate becomes excessively high, which may cause a problem in moldability of the resin. Other additives include coupling agents such as silane coupling agents, brominated epoxy resins, flame retardants such as antimony trioxide, colorants such as carbon black, mold release agents such as natural wax and synthetic wax, silicone oil, Examples thereof include low stress additives such as rubber. The bisnadiimide-polysiloxane alternating copolymer of the present invention or its derivative is added in an amount of 0.01 to 50 parts by weight, preferably 0.1 to 20 parts by weight, per 100 parts by weight of the epoxy resin composition for electronic materials. If the blending amount is less than 0.01 parts by weight, it does not contribute to lowering the stress and improving the resistance to heat history of the epoxy resin composition for electronic materials, and if it exceeds 50 parts by weight, it does not contribute to other epoxy resin compositions. The composition ratio of the components becomes too small, and due to the characteristics of epoxy resin such as adhesiveness, mechanical strength, sealing property, moldability, low hygroscopicity, electrical characteristics, and the heat resistance and low thermal expansion coefficient of the inorganic filler. Crack resistance and the like are not expressed, which is not preferable.

The epoxy resin composition is obtained by thoroughly and uniformly mixing the above components at room temperature with a mixer or the like, further melt-kneading them with a hot roll or a kneader, cooling and pulverizing. The bisnadiimide-polysiloxane alternating copolymer may be mixed and kneaded together when the respective components are mixed,
You may mix and knead after mixing the said component previously. INDUSTRIAL APPLICABILITY The epoxy resin composition of the present invention can be used for electronic materials such as semiconductor encapsulants, laminates and electronic substrates, and is particularly useful for semiconductor encapsulation. By using the epoxy resin composition of the present invention to seal electronic components such as semiconductor elements and to manufacture semiconductor devices, transfer molding, compression molding, injection molding, or other conventional molding methods may be used for curing and molding. Good.

4.2 Semiconductor Encapsulating Material The bisnadiimide-polysiloxane alternating copolymer of the present invention and its derivative are particularly useful as a modifier for simultaneously improving the elastic modulus and thermal stability of an epoxy resin-based semiconductor encapsulating material. Is. Its composition is 3 to 20 parts by weight of epoxy resin, 0.01 to 50 parts by weight of bisnadiimide-polysiloxane alternating copolymer, 2 to 2 parts of phenol novolac resin.
It is preferable to use 15 parts by weight and 60 to 80 parts by weight of inorganic powder as essential components. As a compounding agent other than the essential components, flame retardants such as antimony trioxide and hexalomobenzene, carnauba wax, release agents such as higher fatty acids (metal salts), 3-glycidoxypropyltrimethoxysilane, epoxysilane, etc. Coupling agents, colorants such as carbon black and titanium oxide may be used as appropriate.

[0060]

EXAMPLES Next, the present invention will be specifically described based on examples, but the present invention is not limited to these examples, and all the embodiments utilizing the technical idea of the present invention are as follows. It is included in the scope of the invention. In the following examples, a synthesis example of a bisnadiimide-polysiloxane alternating copolymer will be described first, and then, a production example of a resin composition for semiconductor encapsulation in which it is blended and evaluation results of respective characteristics thereof will be described. explain.

Measuring Method Molecular Weight Measuring Method: Both the number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured by gel permeation chromatography (GPC). Device: GPC measurement system (JASCO Corporation) Column: Showa Denko KK Shodex-803L Detector: Refractive index (RI) detector RL540R (GL Science KK) Calibration curve: Showa Denko KK Made using 10 kinds of standard polystyrene (molecular weight 1.2 × 103 to 2.75 × 106) Measurement: Chloroform 1.0m at a temperature of 40 ° C
Flow at a rate of 1 / min and add 10% of sample (concentration 0.3 wt%) to it.
0 μl was injected.

Synthesis Example 1 Bisallylnadiimide compound (R in the general formula 2¹= -Ph
-CH_Two-Ph-, R ^Four= R⁵= Allyl group, chemical name: bi
Su {4- (allylbicyclo [2.2.1] hept-5-
Ene-2,3-dicarboximido) phenyl} meta
Manufactured by Maruzen Petrochemical Co., Ltd., product name "BANI-
M ") 50 parts, both-end hydrogen straight-chain dimethyl silo
Xan (R in the general formula 3⁶= Methyl group, x = 17) 80
Parts, toluene 130 parts 500mL separable flask
, Heated to 80 ° C, refluxed at 200 mmHg for 1 hour
Then, as a catalyst, 0.3% tetravinyltetramethyl
Rucyclotetrasiloxane-platinum complex / toluene solution
Hydrosilylation by adding 10 ppm of the reaction product as platinum
The reaction was carried out. After 12 hours there are unreacted SiH groups
After confirming that there was no yellow toluene, the toluene
A mushy solid was obtained. This is referred to as a copolymer A. Both ends of raw material
End hydrogen straight chain dimethyl siloxane and product
The offspring amount was measured by the following method. The maximum peak molecular weight is
Terminal hydrogen linear dimethyl siloxane has Mn = 1
624, Mw = 3764 (peak 3), the product is Mn
= 4965, Mw = 12375 (peak 2).
The molecular weight of the bisallylnadiimide compound used is 570
Therefore, the copolymer represented by (AB) 2.7A is produced.
You can see that it is done. Each GPC chart
Shown in FIGS. 1 and 2.

Synthesis Example 2 As a bisallyl nadiimide compound, 1,6-bis (ari
Rubicyclo [2.2.1] hept-5-ene-2,3-
Dicarboximide) hexane (R in the general formula 2 ¹=-
(CH_Two)₆-, R^Four= R⁵= Allyl group ,. Maruzen Petrochemical
Gaku Co., Ltd., trade name "BANI-H") 43 parts
A yellow viscous liquid was obtained in the same manner as in Example 1 except that
Got This is referred to as a copolymer B.

Synthesis Example 3 1,3-bis {(allylbicyclo [2.2.1] hept-5-ene-2,3 as a bisallylnadiimide compound
- dicarboximide) methyl} benzene (Formula 2 ^{_{R 1 = -CH 2 -C 6 H}} 4 -CH 2 -., R 4 = R 5 = allyl, Maruzen Petrochemical Co., Ltd., trade name: "BANI
-X ") was performed in the same manner as in Example 1 except that 45 parts was used, and a pale yellow gum-like solid was obtained. This is referred to as a copolymer C.

Example 1-For electronic materials (for semiconductor encapsulation)
Production of resin composition-Epoxy resin (orthocresol novolac type epoxy resin (epoxy equivalent 208 g / eq)), curing agent (phenol novolac resin (hydroxyl equivalent 105 g / e)
q)), triphenylphosphine, silica powder, carnauba wax, antimony trioxide, carbon black, 3
-A compound containing glycidoxypropyltrimethoxysilane and any of the above-mentioned copolymers A to C in the content (parts by weight) shown in Table 1 is uniformly melt-kneaded with a heating biaxial roll. The epoxy resin composition of the present invention was manufactured. Similarly, a composition in which a polyether silicone represented by the following general formula (23) is blended in place of any one of the copolymers A to C is set as Comparative Example 1, and the copolymers A to C are not blended. The composition was designated as Comparative Example 2. The properties of these compositions were measured by the following methods, and the results are shown in Table 1.

[0066]

[Chemical 32]

[0067]

[Table 1] As is clear from the results shown in Table 1, the resin composition of the present invention has a markedly improved mechanical strength deterioration rate due to heat history and is excellent in other physical properties as compared with the resin compositions of Comparative Examples. Therefore, it is a very excellent semiconductor encapsulant.

Evaluation method of each characteristic 1) Spiral flow EMMI standard mold is used at 175 ° C., 70
It was measured under the condition of kg / cm ² . 2) Mechanical strength (bending strength, bending elastic modulus) 175 ° C., 70 kg / according to JIS K-6911
A test piece of 10 × 10 × 4 mm was prepared under the condition of cm ² and a molding time of 2 minutes, post-cured at 180 ° C. for 4 hours, and then the strength was measured at a temperature of 215 ° C. 3) Deterioration rate of mechanical strength due to heat history (bending strength, bending elastic modulus) 175 ° C, 70 kg / in accordance with JIS K-6911
A test piece of 10 × 10 × 4 mm was prepared under the conditions of cm ² and a molding time of 2 minutes, post-cured at 180 ° C. for 4 hours, and then cooled to 25 ° C. Further, after repeating a cycle of 180 ° C.-25 ° C. 100 times, the strength was measured at a temperature of 215 ° C. The deterioration rate (%) was determined from the measured value and the mechanical strength value measured in 2) from the following formula. 100 × (measured value) / (mechanical strength value) 4) 1 under the conditions of glass transition temperature, expansion coefficient 175 ° C., 70 kg / cm ² , and molding time 2 minutes
A test piece of 0 × 10 × 4 mm was prepared, post-cured at 180 ° C. for 4 hours, and then 5 ° C./at a dilatometer.
It was measured at a temperature rising rate of min. 5) Resistance to solder cracking A silicon chip having a size of 10.0 × 8.0 × 0.3 mm was adhered to a 64PIN-QFP frame (42 alloy), and the epoxy resin composition was applied thereto under molding conditions of 175 ° C. and 7 ° C.
Molded at 0kg / cm ² and molding time 2 minutes, 180 ℃ × 4
I post-cured for an hour. This package is 85 ℃ / 8
After leaving it in a 5% RH atmosphere for 72 hours, it was passed through an infrared reflow furnace at 260 ° C., and a crack of the generated package was observed under a microscope (n = 10).

[0069]

INDUSTRIAL APPLICABILITY The present invention provides a bisnadiimide-polysiloxane alternating copolymer which is a novel compound, and the novel compound has a mechanical strength when blended with an epoxy resin composition for electronic materials, especially for semiconductor encapsulation. , Is effective in reducing stress and improving resistance to heat history without impairing adhesion, adhesiveness and heat resistance.

[0070]

[Brief description of drawings]

FIG. 1 is a GPC chart of linear dimethylsiloxane having hydrogen at both ends.

FIG. 2 is a GPC chart of a bisallylnadimide compound.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H01L 23/31 H01L 23/30 R // (C08L 63/00 83:14) F term (reference) 4J002 CC04X CC06X CC07X CD03W CD05W CD06W CD07W CD13W CE00X CP193 DJ016 FA086 FA096 FB166 FD016 FD090 FD130 FD14X FD150 GJ02 GQ01 4J035 BA01 CA062 GB03 HA03 HA06 HB02 LA03 LB03 4J036 AA01 FA01 FB07 FB16 JA07 4M109 AA01 BA01 CA21 EA02 EB03 EB12 EB19 EC04 EC05

Claims (8)

[Claims] 1. A bisnadiimide-polysiloxane alternating copolymer or a derivative thereof, which has an average of 1 to 100,000 repeating units represented by the following general formula (1). [Chemical 1] (In the formula, R ¹ is an organic group containing a divalent aromatic ring or a divalent aliphatic residue, and R ² is a divalent aliphatic residue having 2 to 10 carbon atoms, The right end of R ² is 1, 2,
It is bonded at any one of the 3 and 4 positions, and R ² '
Represents a divalent aliphatic residue having 2 to 10 carbon atoms,
The left end of R ² 'is bound at any one of the 1', 2 ', 3', 4'positions in the formula, and R ³ is independently of each other a hydrocarbon having 1 to 24 carbon atoms. Represents a group, a hydroxyl group, an alkoxy group having 1 to 5 carbon atoms or a trimethylsiloxy group, and x represents a number of 0 to 10,000 on average. ) 2. The bisnadiimide-polysiloxane alternating copolymer according to claim 1, wherein R ¹ in the general formula (1) is any of the following groups. [Chemical 2] [Chemical 3] 3. A weight average molecular weight of 1,000 to 1,000
The bisnadiimide-polysiloxane alternating copolymer according to claim 1, characterized in that it is 50,000. 4. A bisnadiimide (A) represented by the following general formula (2) and a polysiloxane (B) having SiH groups at both ends of a molecule represented by the following general formula (3) are hydrolyzed. The method for producing a bisnadiimide-polysiloxane alternating copolymer according to claim 1, wherein a silylation reaction is carried out. [Chemical 4] (In the formula, R ¹ is an organic group containing a divalent aromatic ring or a divalent aliphatic residue, and R ⁴ and R ⁵ are each a carbon atom having 2 to 1 carbon atoms.
A terminal unsaturated aliphatic group-containing organic group of 0, which is any one of the 1, 2, 3, and 4 positions in the formula and 1 ′, 2 ′,
Substitution is made at any one of the 3'and 4'positions. ) [Chemical 5] (In the formula, R ⁶ independently represents a hydrocarbon group having 1 to 24 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 5 carbon atoms, or a trimethylsiloxy group, and x is 0 to 0 on average.
Represents a number of 10,000. ) 5. The method for producing a bisnadiimide-polysiloxane alternating copolymer according to claim 4, wherein R ¹ in the general formula (2) is any of the following groups. [Chemical 6] [Chemical 7] 6. The bisnadiimide (A) and the polysiloxane (B) are reacted in a molar ratio of 1.0: 0.5 to 1.0: 2.0. Method for producing alternating bisnadiimide-polysiloxane copolymer. 7. In a resin composition for an electronic material, which comprises an epoxy resin as a main component, 0.01 to 100 parts by weight of the bisnadiimide-polysiloxane alternating copolymer according to claim 1 to 100 parts by weight of the composition. A resin composition for electronic materials, comprising 50 parts by weight. 8. A semiconductor encapsulating material containing an epoxy resin as a main component, wherein the epoxy resin is 3 to 20 parts by weight, the phenol novolac resin is 2 to 15 parts by weight, and the inorganic powder is 60 to 80.
The bisnadiimide according to claims 1 to 3 in addition to parts by weight.
A semiconductor encapsulant containing 0.01 to 50 parts by weight of a polysiloxane alternating copolymer.