JPH07188615A - Paste composition and semiconductor device using same - Google Patents

Abstract

PURPOSE:To obtain a paste composition whose cured products are excellent in stress relaxation, moisture resistance and heat resistance. CONSTITUTION:This composition comprises (A) 100 pts.wt. of a polyamide- silicone polymer obtained by polycondensation of an aromatic dicarboxylic acid or a reactive acid derivative thereof with a diamine containing diaminosiloxane as an essential component, or a polyamide imide-silicone polymer obtained by polycondensation of an aromatic tricarboxylic acid or a reactive derivative thereof with a diamine containing diaminosiloxane as an essential component, (B) 100-3, 500 pts.wt. of a silicon dioxide powder, (C) 50-700 pts.wt of a fine powder of a silicone rubber elastic body, and (D) 200-3, 500 pts.wt. of an organic solvent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a paste composition and a semiconductor device using the paste composition.

[0002]

2. Description of the Related Art Electronic components are becoming smaller and thinner, and chip-on-board (CO
Applications of B) and chip-on-glass (COG) have expanded. In this field, various liquid encapsulants, mainly epoxy resins, have been developed and put on the market.

Since these liquid encapsulating materials are used for directly encapsulating IC or LSI chips, high reliability is required. In particular, in recent years, chips have become larger and more highly integrated, and are more likely to be damaged by stress during or after resin curing, and there is a growing demand for lowering the stress of the resin itself.

In particular, in products such as IC cards and FAX thermal heads having a plurality of bare chips mounted on the same substrate, a slight stress during curing causes disconnection of wiring, warpage of the substrate, and distortion. Becomes

Epoxy liquid encapsulants have been conventionally used for the encapsulation of these products. However, this product has a large stress associated with shrinkage at the time of curing, and a heat cycle test after curing,
In the solder reflow test, disconnection of wiring and cracking of a cured product are problems. Against this background, there is an increasing demand for even lower stresses in the liquid encapsulating material.

[0006]

SUMMARY OF THE INVENTION The present invention has been made to solve these problems, and has little curing shrinkage at the time of coating and curing, and excellent relaxation of stress from the outside.
It is intended to provide a high heat resistant paste capable of obtaining a cured product having high humidity resistance and strong film strength.

[0007]

Means for Solving the Problems As a result of various studies to solve the above-mentioned problems, the inventors have used a resin having a low elasticity by introducing diaminosiloxane having rubber elasticity into the molecule. The present invention has been accomplished by finding a paste composition capable of obtaining a cured product having excellent flexibility and film strength by combining a silicon dioxide powder and a fine powder of a silicone rubber elastic body.

The present invention relates to (A) a polyamide-silicon polymer obtained by polycondensing an aromatic dicarboxylic acid or a reactive acid derivative thereof and a diamine containing diaminosiloxane as an essential component, or an aromatic tricarboxylic acid or a reactive derivative thereof. 100 parts by weight of a polyamide-imide silicone polymer obtained by polycondensing diamine having diaminosiloxane as an essential component and (D) a solvent used for dissolving the resin, for example, diethylene glycol dimethyl ether, N-methylpyrrolidone, or tri 200-350 polar solvents such as ethylene glycol dimethyl ether
(B) 100 to 3500 parts by weight of silicon dioxide powder, and (C) 50 to 700 parts by weight of fine powder of silicone rubber elastomer are added to a varnish dissolved in 0 parts by weight,
The present invention relates to a dispersed paste composition.

The present invention also relates to a semiconductor device having a protective film obtained by applying the paste composition onto the surface of a semiconductor component and drying it.

Next, the paste composition of the present invention will be described in detail. First, the (A) polyamide-silicone polymer and polyamide-imide silicone polymer in the present invention will be described. These polymers are obtained by polycondensing an aromatic dicarboxylic acid or aromatic tricarboxylic acid or a reactive acid derivative thereof and a diamine containing diaminosiloxane as an essential component. Here, as the (a) diaminosiloxane which is an essential component of the diamine, the following chemical formula 1 [general formula (I)]

[Chemical 1] (In the formula, Y ₁ represents a divalent hydrocarbon group, Y ₂ represents a monovalent hydrocarbon group, two Y ₁ may be the same or different, and a plurality of Y ₂ are the same as each other. However, they may be different, and m is preferably an integer of 1 or more).

Y ₁ is preferably an alkylene group having 1 to 5 carbon atoms, a phenylene group or an alkyl-substituted phenylene group, and Y ₂ is preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group or a phenylene group. Alternatively, it is an alkyl-substituted phenyl group. In the general formula (I), m is 100.
The following are preferred. If m is too large, the ratio of the amide bond and the imide bond in the obtained polymer decreases, and the heat resistance tends to decrease.

When a compound represented by the general formula (I) in which m is 6 or more is used, the obtained polyamide silicon polymer or polyamide imide silicon polymer exhibits a low elastic modulus, and m is 16 or more. When used, the polymer exhibits low elastic modulus and improved heat resistance.

Examples of the diaminosiloxane represented by the general formula (I) include chemical formula 2 [general formula (II)], chemical formula 3 [general formula (III)], chemical formula 4 [general formula (IV)] and chemical formula 5 [general formula (V)], chemical formula 6 [general formula (VI)] and the like.

[Chemical 2]

[Chemical 3]

[Chemical 4]

[Chemical 5]

[Chemical 6]

In the above formula, m is a number in the range of 1-100. Among the diaminosiloxanes, in the above general formula (I),
LP-710 in which m is 1, average of 10, average of 20, average of 38, and average of 50 are respectively
0, X-22-161AS, X-22-161A, X-
22-161B and X-22-161C (both are trade names of Shin-Etsu Chemical Co., Ltd.). These diaminosiloxanes may be used alone or in combination of two or more.

The (a) diaminosiloxane can be synthesized, for example, by the method shown in US Pat. No. 3,185,719. Diaminosiloxane can effectively prevent a decrease in molecular weight and a decrease in heat resistance, and also an ether compound such as tetrahydrofuran, dioxane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, cyclohexanone, and 4-methylcyclohexanone. From the viewpoint of good solubility in general-purpose low-boiling point organic solvents such as the alicyclic ketone compound, it is preferably used in an amount of 0.1 to 40 mol% with respect to the total amount of diamines.

From the viewpoints of adhesion, heat resistance, transparency, molecular weight of product compound, elastic modulus, etc., it is more preferable that the diaminosiloxane (a) is used in an amount of 0.2 to 15 mol% based on the total amount of diamine. .

The diamine according to the present invention, wherein the above (a)
The diamine which can be used in combination with the diaminosiloxane is not particularly limited, but an aromatic diamine represented by the following (b) Chemical formula 7 [general formula (II)] or Chemical formula 9 [general formula (III)] is preferable.

[0018]

[Chemical 7] (In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represent hydrogen, a lower alkyl group, a lower alkoxy group or a halogen atom, X is a chemical bond, a single bond containing no element,
-O -, - S -, - C (= O) -, - SO 2 -, - S
(= O)-, the group of Chemical formula 8

[Chemical 8] Wherein R ₅ and R ₆ each independently represent hydrogen, a lower alkyl group, a trifluoromethyl group, a trichloromethyl group or a phenyl group)

[Chemical 9] (In the formula, X ′ is —O— or a group of Chemical formula 10

[Chemical 10] The expressed, wherein R _'4 and R' ₅ are each independently hydrogen, lower alkyl, trifluoromethyl group, trichloromethyl group or phenyl group, R _'1, R' ₂ and R _'3 are each independently Represents a lower alkyl group, a lower alkoxy group or halogen, x, y and z each represent the number of substituents and are integers of 0 to 4, two X's may be the same or different, and R ' _1, when R _'2 and R' ₃ are a plurality bond respectively, aromatic diamines in each, represented by may be the same or different).

When a diaminosiloxane represented by the general formula (I) having m of 16 or more is used, the reaction occurs when (b) the aromatic diamine represented by the general formula (II) or the general formula (III) is used in combination. Is advantageous because it is easy to proceed.

When a diaminosiloxane represented by the general formula (I) having m of 6 or more is used, when (b) an aromatic diamine represented by the general formula (II) or (III) is used in combination, This is advantageous because it is possible to simultaneously improve the properties of low elastic modulus and high heat resistance, which are generally contradictory properties.

The aromatic diamine having an ether bond represented by the general formula (II) is, for example, 2,2-bis [4- (4-aminophenoxy) phenyl] propane or 2,2-bis [3. -Methyl-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4
-Aminophenoxy) phenyl] butane, 2,2-bis [3-methyl-4- (4-aminophenoxy) phenyl] butane, 2,2-bis [3,5-dimethyl-4-]
(4-Aminophenoxy) phenyl] butane, 2,2-
Bis [3,5-dibromo-4- (4-aminophenoxy) phenyl] butane, 1,1,1,3,3-hexafluoro-2,2-bis [3-methyl-4- (4-aminophenoxy) ) Phenyl] propane, 1,1-bis [4-
(4-aminophenoxy) phenyl] cyclohexane,
1,1-bis [4- (4-aminophenoxy) phenyl] cyclopentane, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] ether, bis [4 -(3-Aminophenoxy) phenyl] sulfone, 4,4'-carbonylbis (p-phenyleneoxy) dianiline, 4,4 '
-Bis (4-aminophenoxy) biphenyl and the like.
Of these, 2,2-bis [4-aminophenoxy) phenyl] propane is particularly preferable.

Examples of the aromatic diamine represented by the general formula (III) include 1,3-bis (3-aminophenoxy) benzene and 1,3-bis (4-aminophenoxy).
Benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4 '-[1,3-phenylenebis (1-methylethylidene)] bisaniline, 4,4'-[1,4-
Examples include phenylene bis (1-methylethylidene)] bisaniline and 3,3 ′-[1,3-phenylenebis (1-methylethylidene)] bisaniline.

(C) Aromatic diamines other than the above (a) and (b) include, for example, 4,4'-diaminophenyl ether, 4,4'-diaminodiphenylmethane,
4,4'-diamino-3,3 ', 5,5,'-tetramethyldiphenyl ether, 4,4'-diamino-3,
3 ', 5,5'-tetradimethylphenylmethane, 4,
4'-diamino-3,3 ', 5,5'-tetraethyldiphenyl ether, 2,2- [4,4'-diamino-
3,3 ', 5,5'-tetramethyldiphenyl] propane, metaphenylenediamine, paraphenylenediamine, 3,3'-diaminodiphenylsulfone and the like,
This can also be used together.

(D) Except for the above (a), (b) and (c), examples of the diamine include, for example, piberazine, hexamethylenediamine, heptamethylenediamine, tetramethylenediamine, p-xylylenediamine and m-xylyl. There are aliphatic diamines such as diamine and 3-methylheptamethylenediamine, and these can be used together.

The aromatic diamines (b) and (c) are preferably used in combination for improving heat resistance, and the total amount of (b) and (c) is 0.1 with respect to the total amount of diamine.
It is preferable to use it so as to be ˜99.9 mol%.

Next, an example will be shown for the composition of the preferable composition of the diamine. (1) Diaminosiloxane of (a) 0.1 to 100 mol% and diamine other than (b), (c) or (d) 99.9 to 0 mol%, such that the total amount becomes 100 mol%. (2) Diaminosiloxane (a) 0.1 to 99.9 mol% (b) or (c) aromatic diamine 0.1 to 99.9 mol% and (d) diamine 99.8 to 0 mol Formulated so that the total is 100 mol% in%. (3) Diaminosiloxane of (a) 0.1-40 mol% (b) or (c) aromatic diamine 99.9-60 mol% and (d) diamine 39.9-0 mol% Formulated to be 100 mol%. (4) Diaminosiloxane of (a) 0.2 to 15 mol% Aromatic diamine of (b) or (c) 99.8 to 85 mol% and diamine of (d) 14.8 to 0 mol% Formulated to be 100 mol%. (5) Diaminosiloxane of (a) 0.1-40 mol% Aromatic diamine of (b) 99.9-60 mol% Aromatic diamine of (c) 39.9-0 mol% and diamine of (d) Formulated such that the total amount of 39.9 to 0 mol% is 100 mol%.

The aromatic dicarboxylic acid in the present invention is one in which two carboxyl groups are bound to the aromatic nucleus, and the aromatic tricarboxylic acid is one in which three carboxyl groups are blended in the aromatic nucleus, and 3 Two of the carboxyl groups are attached to adjacent carbon atoms. Of course, this aromatic ring may have a hetero atom introduced, or the aromatic rings may be bonded to each other with an alkylene group, oxygen, a carbonyl group or the like. Further, a substituent such as an alkoxy group, an allyloxy group, an alkylamino group, or a halogen that does not participate in the condensation reaction may be introduced into the aromatic ring.

Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid-4,4 ', diphenyl sulfonecarboxylic acid-
4,4 ', diphenyldicarboxylic acid-4,4', naphthalenedicarboxylic acid-1,5 and the like can be mentioned, but terephthalic acid and isophthalic acid are preferred because they are easily available and inexpensive. In particular, the use of a mixture of terephthalic acid and isophthalic acid is desirable from the viewpoint of solubility of the resulting polymer. The reactive derivative of an aromatic dicarboxylic acid in the present invention means a dihalide of the above aromatic dicarboxylic acid, for example, dichloride, dibromide, diester or the like.

As the aromatic tricarboxylic acid, trimellitic acid, 3,3,4'-benzophenone tricarboxylic acid, 2,3,4'-diphenyltricarboxylic acid,
2,3,6-pyridinetricarboxylic acid, 3,4,4'-
Benzanilide tricarboxylic acid, 1,4,5-naphthalene tricarboxylic acid, 2'-methoxy-3,4,4'-diphenyl ether tricarboxylic acid, 2'-chlorobenzanilide-3,4,4'-tricarboxylic acid, etc. be able to.

The above-mentioned reactive derivative of aromatic tricarboxylic acid means an acid anhydride, halide, ester, amide, ammonium salt or the like of the aromatic tricarboxylic acid. Examples of these are trimellitic anhydride, trimellitic anhydride monochloride, 1,4 dicarboxy-3-N, N-dimethylcarbamoylbenzene, 1,4
-Dicarbomethoxy-3-carboxybenzene, 1,4
-Dicarboxy-3-carbophenoxybenzene, 2,
6-dicarboxy-3-carbomethoxypyridine, 1,
Examples thereof include 6-dicarboxy-5-carbamoylnaphthalene, ammonium salts of the above aromatic tricarboxylic acids and ammonia, dimethylamine, triethylamine and the like. Of these, trimellitic anhydride and trimellitic anhydride monochloride are preferable because they are easily available and inexpensive.

In the present invention, the aromatic dicarboxylic acid, aromatic tricarboxylic acid or reactive derivative thereof is preferably used in a total amount of 80 to 120 mol% based on 100 mol% of the total amount of diamine. It is particularly preferable to use 95 to 105 mol%. The highest molecular weight product is obtained when the total amount of these diamines is equimolar to the total amount. If the aromatic dicarboxylic acid, aromatic tricarboxylic acid or their reactive derivative is too much or too little with respect to the diamine, the molecular weight tends to decrease and mechanical strength, heat resistance and the like tend to decrease.

The polyamide silicon polymer or polyamide imide silicon polymer obtained by polycondensing an aromatic dicarboxylic acid, an aromatic tricarboxylic acid or a reactive derivative thereof with a diamine as described above is dimethylformamide 0.2. The reduced viscosity at 30 ° C. in the weight% solution is preferably 0.2 to 2.0 dl / g. If this reduced viscosity is too small, heat resistance and mechanical strength decrease,
If it is too large, the solubility in organic solvents tends to decrease.

The polyamide-silicone polymer or the polyamide-imide-silicone polymer can be dissolved in an organic solvent to form a varnish. Examples of the (D) organic solvent used in the present invention include acetamide, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-
A polar solvent such as diethylformamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, nitrobenzene and glycol carbonate, an ether compound such as tetrahydrofuran, dioxane, 1,2-dimethoxyethane and polyethylene glycol dimethyl ether, 2 Examples thereof include alicyclic ketone compounds such as cyclohexanone and 4-methyl-2-cyclohexanone.

The silicon dioxide powder (B) used in the present invention preferably has an average particle size of 0.1 to 40 μm. 40
If it exceeds 0.1 μm, the sedimentation property becomes large, and the stability of the paste composition with time may be poor, and if it is 0.1 μm or less, the surface area may become large, so that the filling rate may not be increased. You may combine and mix 2 or more types from which a particle size differs. In order to suppress the spreadability of the paste composition, silicon dioxide powder having an average particle size of 0.1 μm or less may be used in an amount of 10% by weight or less based on the paste composition.

As the silicon dioxide powder, spherical or crushed particles can be used alone or in combination in consideration of workability and characteristics such as wettability and spreadability.

As the fine powder of the silicone rubber elastic body (C) used in the present invention, spherical fine particles having an average particle diameter of 0.1 to 20 μm are used. Average particle size is 20 μm
If it exceeds, the surface of the coating film becomes rough and the coating strength decreases. On the other hand, if it is less than 0.1 μm, sufficient dispersion cannot be achieved, leading to deterioration in stability of the paste over time.

In the paste composition of the present invention, the organic solvent is 200 to 3 with respect to 100 parts by weight of the total amount of the polyamide silicon polymer or the polyamide imide silicon polymer.
500 parts by weight are used. The organic solvent is preferably used in an amount of 200 to 1000 parts by weight, more preferably 300 to 600 parts by weight, based on 100 parts by weight of the total amount of the polymer.

In the paste composition of the present invention, 100 to 100 parts by weight of the above polymer is contained in an amount of 100 to 100 parts by weight of silicon dioxide powder.
3500 parts by weight are used, preferably 200 to 3000 parts by weight, more preferably 800 to 1200 parts by weight.

In the paste composition of the present invention, 10 to 700 parts by weight of a fine powder of a silicone rubber elastic body is used, preferably 20 to 300 parts by weight, and 80 to 120 parts by weight based on 100 parts by weight of the above polymer. The use of parts by weight is more preferred.

The silicon dioxide powder and the fine powder of the silicone rubber elastic material are mixed and used at the time of making a paste.
When the organic solvent is less than 200 parts by weight during preparation of the paste, the ratio of the solid content is high, so that the coating property is poor and it becomes difficult to maintain the coating surface at a constant thickness. When the amount of the organic solvent exceeds 3500 parts by weight, the viscosity is so low that it becomes difficult to disperse the silicon dioxide powder and the fine powder of the silicone rubber elastic body.
It becomes difficult to settle, the stability over time as a paste deteriorates, and since the solid content decreases, thick film coating becomes impossible. If the amount of silicon dioxide is less than 100 parts by weight, thixotropy is insufficient and it becomes difficult to form a thick film. If it exceeds 3500 parts by weight, the strength and moisture resistance of the resulting coating film will be poor.

The paste composition of the present invention is, for example, (A)
Polyamide silicon polymer obtained by polycondensing aromatic dicarboxylic acid or its reactive acid derivative and diamine containing diaminosiloxane as an essential component, or aromatic tricarboxylic acid or its reactive derivative and diaminosiloxane as an essential component A polymer varnish obtained by dissolving 100 parts by weight of a polyamide-imide silicon polymer obtained by polycondensation with a diamine in 200 to 3,500 parts by weight of an organic solvent (D) (B) 100 to 350 silicon dioxide powder.
0 parts by weight and (C) fine powder of silicone rubber elastic body 1
0-700 parts by weight is added, and a raider machine, 3 rolls,
It can be produced by mixing and kneading with a ball mill or the like.

When producing the paste composition of the present invention, a coloring agent or a coupling agent may be added and used. Carbon black, organic dyes, inorganic pigments and the like can be used as the coloring material.

As the coupling agent, a silane coupling agent or a titanate coupling agent can be used, and it is added in an amount of 30 parts by weight or less based on 100 parts by weight of the above polyamide silicon polymer or polyamide imide silicon polymer. It

The semiconductor device of the present invention can be manufactured, for example, by applying the paste composition on the surface of a semiconductor component and drying it to form a protective film. The coating and drying can be performed by a known method. The linear expansion coefficient of the formed protective film is 6 × 10 ⁻⁶ from the viewpoint of warpage and crack resistance of the substrate.
It is preferably 1.0 × 10 ⁻⁵ 1 / ° C., and the elastic modulus is preferably 50 Kgf / mm ² or less.

The paste composition of the present invention is prepared by dissolving a polyamide-silicon polymer or a polyamide-imide silicone polymer, which is a heat-resistant thermoplastic resin, in a solvent, and dispersing silicon dioxide powder and fine powder of a silicone rubber elastic body in this. It was obtained by Therefore, a coating film can be easily formed only by heating and drying after coating and volatilizing the solvent, and there is no curing reaction during drying. In addition, since the silicon group contained in the polyamide-silicon polymer or the polyamide-imide silicone polymer has a high affinity for the silicon dioxide powder and the fine powder of the silicone rubber elastic body, the content of both of them in the paste should be controlled. It is possible to increase the thickness, and it becomes possible to apply a thick film, and as a result, moisture resistance can be improved. Also, the addition of fine powder of the silicone rubber elastic body imparts flexibility to the cured product and makes it possible to reduce the elastic modulus. Furthermore, by using a low-elasticity polyamide-silicone polymerization or polyamide-imide-silicone polymer obtained by using a long-chain diaminosiloxane, it is possible to impart flexibility to the cured product, which is particularly excellent in stress relaxation property. A protective film material for semiconductor components can be formed.

[0046]

EXAMPLES Next, the present invention will be described in more detail by way of examples, which should not be construed as limiting the invention.

(Synthesis Example 1) 2,2-bis [4- (4-aminophenoxy) was used as a diamine under a nitrogen gas atmosphere in a four-necked flask equipped with a thermometer, a stirrer, a nitrogen introducing tube and a cooling tube. Phenyl] propane 65.6 g (160 mmol)

[Chemical 11] 36 g (40 mmol) (80 mol% / 20 mol% in terms of molar ratio) of the diaminosiloxane of was added and dissolved in 335 g of diethylene glycol dimethyl ether.

The solution was cooled to -10.degree. C. and at this temperature 40.6 g (200 mmol) of isophthalic acid dichloride were added so that the temperature did not exceed -5.degree. Then, 23.2 g of propylene oxide was added, 96 g of diethylene glycol dimethyl ether was added, and stirring was continued at room temperature for 3 hours. The polymer was isolated by pouring the reaction solution into methanol. After drying this, it was again dissolved in dimethylformamide and poured into methanol to purify the polyamide-silicon polymer (I).

(Synthesis Example 2) 2,2-bis [4- (4-aminophenoxy) as diamine in a four-necked flask equipped with a thermometer, a stirrer, a nitrogen introducing tube and a cooling tube under a nitrogen gas atmosphere. Phenyl] propane 174.3 g (425
12)

[Chemical 12] 225 g (75 mmol) (85 mol% / 15 mol% in terms of molar ratio) of the diaminosiloxane of was added and dissolved in 1177 g of diethylene glycol dimethyl ether.

The solution was cooled to -10 ° C and 101.5 g (500 mmol) of isophthalic acid dichloride was added at this temperature so that the temperature did not exceed -5 ° C. After the addition, 87 g of propylene oxide was added, and stirring was continued at room temperature for 3 hours. When the viscosity of the reaction liquid increased and the liquid became transparent, diethylene glycol methyl ether 841
g was added, and stirring was continued for another 1 hour, and then the obtained reaction solution was poured into a large amount of a mixed solvent of n-hexane / methanol = 1/1 (weight ratio) to isolate the polymer. . After drying this, it was dissolved in N, N-dimethylformamide, poured into methanol to purify the polyamide-silicon polymer (II), and dried under reduced pressure.

(Synthesis Example 3) 2,2-bis [4- (4-aminophenoxy) phenyl was used as a diamine under a nitrogen gas atmosphere in a four-necked flask equipped with a thermometer, a stirrer, a nitrogen introducing tube and a cooling tube. ] Propane 174.3 g (425 mmol)

[Chemical 13] 225 g (75 mmol) of diaminosiloxane (85 mol% / 15 mol% in terms of molar ratio) was added and dissolved in 1177 g of diethylene glycol dimethyl ether.

This solution was cooled to -10 ° C., and at this temperature, 105.3 g of trimellitic anhydride monochloride (5
00 mmol) was added so that the temperature did not exceed -5 ° C. After the addition, 87 g of propylene oxide was added, and stirring was continued at room temperature for 3 hours. When the viscosity of the reaction solution increased and the solution became transparent, 841 g of diethylene glycol methyl ether was added, and the mixture was further stirred for 1 hour. ,
128 g of acetic anhydride and 64 g of pyridine were added, and stirring was continued at 60 ° C. for one day. The obtained reaction solution is n-hexane /
The polymer was isolated by pouring it into a large amount of a mixed solvent of methanol = 1/1 (weight ratio). After drying this, N,
It was dissolved in N-dimethylformamide, poured into methanol to purify the polyamide-imide silicon polymer, and dried under reduced pressure.

(Synthesis Example 4) Except that the diaminosiloxane of Synthesis Example 1 was excluded and 2,2-bis [4- (4-aminophenoxy) phenyl] propane was 100 mol%,
A polyamide polymer was produced according to Synthesis Example 1.

(Examples 1 to 3) 100 parts by weight of the polyamide-silicon polymer obtained in Synthesis Example 1 was dissolved in 230 parts by weight of diethylene glycol dimethyl ether to form a varnish. To this, 500 to 1000 parts by weight of spherical silicon dioxide powder having an average particle diameter of 13 μm (“FB-35” manufactured by Denki Kagaku Co., Ltd.) was added, and fine powder of a silicone rubber elastic body having an average particle diameter of 2 μm (Toray Dow Corning Silicone 50-100 parts by weight of "Trefil E601" manufactured by the company) was added, and the mixture was kneaded with three rolls to prepare a paste composition.

After defoaming the obtained composition, the paste was thinly spread on a Teflon plate, preheated at 70 ° C. for 30 minutes, and further dried by heating at 150 ° C. for 60 minutes to obtain a film-like cured product (film). A thickness of 200 μm) was obtained. The linear expansion coefficient, elastic modulus, and film strength were measured using the obtained cured product. The coefficient of linear expansion is calculated by Seiko Denshi Thermal Analysis System SS
It measured using C-5000TMA100 type. Also,
The dynamic viscoelasticity was measured in air using a spectrometer manufactured by Iwamoto Seisakusho at a temperature rising rate of 2 ° C./min and a frequency of 10 Hz. The film strength was measured using a tensile tester manufactured by Imada Seisakusho.

Further, the paste was applied on a ceramic substrate of 20 × 200 mm and thickness of 0.6 mm, width 5 mm and length 150 m.
The coating was applied over m, heat-cured under the same heating conditions as described above (film thickness of cured product 0.8 to 1.0 mm), and warpage of the substrate was observed based on the following criteria. ○: No warp on the board △: Warp on the board is visible ×: Warp on the board is remarkable

On the other hand, in order to examine the crack resistance, a certain amount of the paste was dropped on a silica substrate and dried and cured (10 mmφ × 1.2 mm) under the above-mentioned drying conditions to obtain a heat cycle test (-40 ° C./30). Min → 150 ° C / 30 min,
After 500 cycles, the presence or absence of cracks after the test was examined.

Example 4 A paste was prepared according to Example 3 except that the polyamide silicon polymer obtained in Synthesis Example 2 was used. The characteristic evaluation results are shown in Table 1.

Example 5 A paste was prepared according to Example 3 except that the polyamideimide silicon polymer obtained in Synthesis Example 3 was used. The characteristic evaluation results are shown in Table 1.

Comparative Example 1 A paste composition was prepared in the same manner as in Example 1 except that the fine powder of the silicone rubber elastic body was not added. Table 1 shows the evaluation results of the characteristics.

Comparative Example 2 A paste composition was prepared in the same manner as in Example 1 except that the amount of fine powder of silicone rubber elastic material was 800 parts by weight. The evaluation results of the characteristics are shown in Table 1.

Comparative Example 3 A paste composition was prepared in the same manner as in Example 3 except that the polymer obtained in Synthesis Example 4 was used.
Table 1 shows the evaluation results of the characteristics.

Comparative Example 4 A paste composition was prepared in the same manner as in Example 3 except that the polymer obtained in Synthesis Example 4 was used and the fine powder of silicone rubber elastic material was not added.
Table 1 shows the evaluation results of the characteristics.

[0064]

EFFECTS OF THE INVENTION The paste composition according to the present invention can provide a cured product which is flexible, uniform and excellent in strength. Since the cured product has high heat resistance and low elasticity, it has excellent stress relaxation property. Therefore, it is suitable as a protective film material for semiconductor products to which thermal stress is applied. Further, since there is almost no curing shrinkage as compared with the epoxy liquid encapsulant used conventionally, there is no stress on the base material, and it is possible to sufficiently cope with miniaturization and thinning of electronic parts. A semiconductor product using this has high reliability with excellent moisture resistance, resistance to external stress, and thermal shock resistance.

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Claims (2)

[Claims] 1. A polyamide-silicon polymer obtained by polycondensing an aromatic dicarboxylic acid or a reactive acid derivative thereof and a diamine containing diaminosiloxane as an essential component, or an aromatic tricarboxylic acid or a reactive derivative thereof. Polyamideimide silicon polymer obtained by polycondensing diamine having diaminosiloxane as an essential component 100 parts by weight (b) Silicon dioxide powder 100 to 3500 parts by weight (c) Silicone rubber elastic powder 50 to 700 parts by weight (D) A paste composition containing 200 to 3500 parts by weight of an organic solvent. 2. A semiconductor device comprising a protective film obtained by applying and drying the paste composition according to claim 1 on the surface of a semiconductor component.