JPH0335059A - Paste composition and semiconductor device using the same - Google Patents

Abstract

PURPOSE:To obtain a paste composition which is suitably used as a protecting material for semiconductor parts, because it can be coated in a thick film, being excellent in stress absorption, adhesion, humidity resistance or the like, by adding an organic solvent and a silicon dioxide powder to a specific polyamide (imide) silicone polymer. CONSTITUTION:(A) 100 pts.wt. of a polyamide silicon polymer obtained by polycondensation reaction of an aromatic dicarboxylic acid or its reactive derivative and a diamine containing a diaminosiloxane of the formula (Y1 is a divalent hydrocarbon group; Y2 is a monovalent hydrocarbon group, m is 1 or more) as an essential component or a polyamideimide silicon polymer obtained by polycondensation reaction between an aromatic tricarboxylic acid or its reactive acid derivative and a diamine containing a diaminosiloxane as an essential component are compounded with (B) 200 to 3,500 pts.wt. of an organic solvent such as acetamide and (C) 100 to 3,500 pts.wt. of silicon dioxide of 0.1 to 40mum average particle size.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a paste composition and a semiconductor device using the paste composition.

[Prior Art] Generally, it is known that the characteristics of semiconductor components are significantly deteriorated due to moisture absorption or adhesion of contaminants. It is also known that external stress and heat generated during operation can cause serious defects such as changes in characteristics, wire breakage, and destruction of the board and case. As a countermeasure against these problems, a method of providing a protective material on the surface of the semiconductor component has been proposed, and silicone resin, epoxy resin, polyimide resin, etc. are used.

Silicone rubber and silicone gel, which are commonly used as silicone resins, have stress absorbing properties and are effective against external stress and thermal stress during operation, but they have high moisture permeability and are difficult to use as a base material. Moisture resistance is insufficient due to poor adhesion to mold materials. Further, epoxy resins have disadvantages in that they tend to cause stress due to thermal contraction during curing, and polyimide resins require high temperatures and long periods of time to cure, which tends to cause element deterioration.

In recent years, demands for improved reliability, higher density, and multifunctionality of semiconductor components have become stronger, and conventional surface protection materials are no longer able to meet these demands.

As a solution to the above problems, materials using polyamide polymers or polyamideimide polymers similar to thermoplastic resins have been proposed for semiconductor junction coatings (Japanese Patent Application No. 103214/1989, 62-
However, since these polymers have long chains, it is difficult to dissolve more than 30% in a solvent, and the disadvantage is that thick films cannot be applied because they are lost during film formation. be.

[Problem to be solved by the invention]

The present invention can be applied to the surface of semiconductor components, reduces loss when drying, can be applied as a thick film, has excellent stress absorption properties, has good adhesion to base materials and mold materials, and is moisture resistant. The purpose of the present invention is to provide a paste composition with excellent properties.

Another object of the present invention is to provide a semiconductor device which has excellent moisture resistance and stress relaxation properties and improved reliability by applying and drying the paste composition of the present invention to the surface of a semiconductor component to form a protective film. do.

[Means for Solving the Problems] The present invention provides (A) a polyamide obtained by a polycondensation reaction of an aromatic dicarboxylic acid or its reactive acid derivative and a diagonal having cyanosiloxane as an essential component; 100 parts by weight of a polyamideimide silicone polymer obtained by polycondensation reaction of a silicone polymer or an aromatic tricarboxylic acid or its reactive acid derivative with a diamine whose essential component is diaminosiloxane, (B) 200 to 3,500 parts by weight of an organic solvent and (C) 100 to 3,500 parts by weight of silicon dioxide powder.

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

First, the (A) polyamide silicone polymer and polyamide silicone polymer in the present invention will be explained.

These polymers are obtained by polycondensation reaction of aromatic dicarboxylic acids, aromatic tricarboxylic acids, or their reactive acid derivatives and diamines containing diaminosiloxane as an essential acid component.

Here, (a) cyanosiloxane, which is an essential acid component of diamine, is expressed by the general formula (I) (wherein, Yl is a divalent hydrocarbon group, and Y represents a -valent hydrocarbon group. , two Y's may be the same or different, and multiple Y's may be the same or different from each other.<<m is an integer of 1 or more). preferable.

YI is preferably an alkylene group having 1 to 5 carbon atoms,
is a phenylene group or an alkyl-substituted phenylene group, and Y
t is preferably an alkyl group or alkoxy group having 1 to 5 carbon atoms, a phenyl group, or an alkyl-substituted phenyl group. General formula (where m is preferably 100 or less 0
If m is too large, the ratio of amide bonds and imide bonds in the obtained polymer will decrease, and the heat resistance will tend to decrease.

In the compound represented by the general formula (I), when m is 6 or more, the resulting polyamide silicone polymer or polyamitimide silicone polymer shows a low elastic modulus, and when m is 16 or more, When used, the polymer exhibits a low modulus of elasticity and improved heat resistance.

As the diaminosiloxane represented by the general formula (I),
Examples include compounds such as: In the above formula, m is a number ranging from 1 to 100. Among the diaminosiloxanes, in the general formula (I), those with m of 1, those with an average of 10, and those with an average of 20
those with an average of 38 and those with an average of 50, respectively.
LP-7100, X-22-161AS, X-22-1
61A%X-22-161B and X-22-16IC (
Both are commercially available as Shin-Etsu Chemical (trade name).

One or more types of these diaminosiloxanes can be used.

(a) Diaminosiloxane is described, for example, in U.S. Pat.
185.719 can be used. Diaminosiloxane can effectively prevent a decrease in molecular weight and heat resistance, and is also compatible with ether compounds such as tetrahydrofuran, dioxane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether, as well as cyclohexanone and 4-methylcyclohexanone. From the viewpoint of good solubility in general-purpose low-boiling point organic solvents such as alicyclic ketone compounds, it is preferable to use 0.1 to 40 mol % based on the total amount of diamino.

From the viewpoints of adhesion, heat resistance, transparency, and molecular weight of the resulting compound, (a) diaminosiloxane is more preferably used in an amount of 0.2 to 15 mol % based on the total amount of diamine.

Among the diamines in the present invention, the diamino that can be used in combination with the above (a) diaminosiloxane is not particularly limited, but the aromatic diamino represented by the following (b) general formula (U) or general formula (III) is preferable.

General formula (If) (wherein R1, Rs, Rs and R4 each independently represent hydrogen, a lower alkyl group, a lower alkoxy group or a halogen atom, X is a chemical bond, -0-R3 and R1 each independently represents hydrogen, lower alkyl group, trifluoromethyl group, trichloromethyl group or phenyl group) or general formula (II) (wherein, X' represents -〇- or S4 ■ -C-, where R represents R14 and R1 each independently represent hydrogen, a lower alkyl group, a trifluoromethyl group, a trichloromethyl group, or a phenyl group, and R11, R and R each independently represent a lower alkyl group, a lower alkoxy group, or a halogen. , x, y and 2 each indicate the number of substituents, and 0
An integer of ~4, the two X's may be the same or different, and when R'Yo, R12 and R1 are bonded in multiple numbers, each of them may be the same or different) Aromatic diamino represented by.

Diaminosiloxane represented by general formula (I) where m is 16
When using the above, (b) in combination with aromatic diamine represented by general formula (n) or general formula (II),
This is advantageous because the reaction progresses easily. General formula (I)
When a cyaminosiloxane represented by m is 6 or more is used, (b) general formula (It) or general formula (I
The combined use of aromatic diamino represented by II) is advantageous because it is possible to simultaneously improve the properties of low elastic modulus and high heat resistance, which are generally contradictory properties.

As the aromatic diamino having an ether bond represented by the general formula (II), for example, 2,2-bis[4-(
4-aminophenoxy)phenyl]propane, 2.2-
Bis[3-methyl-4-(4-aminophenoxy)phenyl]propane, 2゜2-bis(4-(4-aminophenoxy)phenylcobutane, 2.2-bis[3-methyl-4-(4 -aminophenoxy)phenylcobutane, 2
゜2-bis[3,5-dimethyl-4-(4-aminophenoxy)phenylcobutane, 2.2-bis[3,5-dibromo-4-(4-aminophenoxy)phenylcobutane, 1.1 .1.3,3.3-hexafluoro-2,2
-bis[3-methyl-4-(4-aminophenoxy)phenyl]propane, 1.1-bis(4-(4-aminophenoxy)phenylcocyclohexane, 1.1-bis[
4-(4-aminophenoxy)phenylcocyclopentane, 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, etc. Among these, 2,2-bis(4- (4-Aminophenoxy)phenyl]propane is particularly preferred.

As the aromatic diamino represented by general formula (III),
For example, 1.3-bis(3-aminophenoxy)benzene, 1.3-bis(4-aminophenoxy)benzene,
1,4-bis(4-aminophenoxy)benzene, 4.
4'-(I,3-phenylenebis(I-methylethylidene))]bisaniline, 4.4'-(I,4-phenylenebis(I-methylethylidene))bisaniline, 3
．． Examples include 3'[1,3-phenylenebis(I-methylethylidene)]bisaniline.

(c) Aromatic diamines other than the above (a) and (b) include, for example, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'
-cyamino-3,3', 5゜5'-tetramethyldiphenyl ether, 4,4'-diamino-3,3', 5
．． 5'-tetramethyldiphenylmethane, 4,4'-
Cyamino-3,3'5.5'-tetraethyldiphenyl ether, 2゜2-(4,4'-cyaξ)-3,3'
, 5.5'-tetramethyldiphenyl]propane, metaphenylenediamine, paraphenylenediamine, 3゜3
Examples include 1-diaminodiphenylsulfone, which can also be used in combination.

(d) Diamines other than the above (a), (b) and (c) include, for example, piperazine, hexamethylene diamino, heptamethylene diamine, tetramethylene diamine, p-xylylene cyamon, m-xylylene diamino,
There are aliphatic diamino such as 3-methylhebutamethylene diamino, and these can also be used together.

The aromatic diamines (b) and (C) are preferably used in combination in order to improve heat resistance, and the total amount of (b) and (C) is 0.1 to 99.9 with respect to the total amount of diamines. It is preferable to use it so that it becomes mol%.

Next, an example of a preferred composition of diamine will be shown.

(I) Diaminosiloxane of (a) 0.1 to 100
Mol% and diamine other than (b), (c) or (d) 99.9-0
The composition is such that the total mol% is 100 mol%.

(2) (a) Diaminosiloxane 0.1-99.9 mol% (b) or (c) aromatic diamine 0.1-99.9 mol% and (d) diamino 99.8-0 mol %, the total is 100 mol%.

(3) (a) Cyaminosiloxane 0.1-40 mol% (b) or (c) aromatic diamino 99.9-60 mol% and (d) diamine 39.9-0 mol% as a whole The composition is such that the amount is 100 mol%.

(4) (a) Diaminosiloxane 0.2 to 15 mol% (b) or (c) aromatic diamine 99.8 to 85 mol% and (d) diamino 14.8 to 0 mol% to form a total The composition is 100 mol%.

(5) (a) Diaminosiloxane 0.1-40 mol% (b) Aromatic diamine 99.9-60 mol% (C) Aromatic diamino 39.9-0 mol% and (d) Diamine The composition is 39.9 to 0 mol% and the total is 100 mol%.

Aromatic dicarboxylic acids in the present invention have two carboxyl groups bonded to an aromatic nucleus, and aromatic tricarboxylic acids have three carboxyl groups bonded to an aromatic nucleus and three carboxyl groups. Two of the groups are bonded to adjacent carbon atoms. Of course, this aromatic ring may have a hetero atom introduced therein, or the aromatic rings may be bonded to each other with an alkylene group, oxygen, carbonyl group, etc. Furthermore, the aromatic ring may have an alkoxy group, an allyloxy group, etc. , an alkyla main group, a halogen, and other substituents that do not participate in the condensation reaction may be introduced.

Examples of aromatic dicarboxylic acids include terephthalic acid,
Isophthalic acid, diphenyl ether dicarboxylic m-4,
a', diphenylsulfonedicarboxylic acid-4,4',
Examples include diphenyldicarboxylic acid-4゜4' and naphthalene dicarboxylic acid-1,5-, but terephthalic acid and isophthalic acid are preferred because they are easily available and inexpensive, especially a mixture of terephthalic acid and isophthalic acid. The use of is desirable from the viewpoint of solubility of the resulting polymer.

In addition, the reactive derivative of aromatic dicarboxylic acid in the present invention means a civalide of the aromatic dicarboxylic acid, such as dichloride, dichloride, diester, etc.

Further, 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′-benzanilidetricarboxylic acid, ■.

4.5-Naphthalenetricarboxylic acid, 2'-methoxy-
3,4,4'-diphenyl ethertricarboxylic acid,
Examples include ゛2'-chlorobenzanilide 3.4゜4'-tricarboxylic acid.

In addition, the above-mentioned reactive derivative of aromatic tricarboxylic acid is
It means acid anhydrides, halides, esters, amides, ammonium salts, etc. of the aromatic tricarboxylic acids. Examples of these include 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°6-dicarboxybenzene Examples include carboxy-5-carbamoylnaphthalene, and ammonium salts made of the above-mentioned aromatic tricarboxylic acids and ammonia, dimethylamine, triethylamine, and the like.

Among these, trimellitic anhydride and trimellitic anhydride monochloride are preferred because they are easily available and inexpensive.

In the present invention, aromatic dicarboxylic acids, aromatic tricarboxylic acids, or reactive derivatives thereof are used in a total amount of diamine 1
It is preferable to use a total amount of 80 to 120 mol%, particularly preferably 95 to 105 mol%, based on 00 mol%.The highest molecular weight is obtained when these are used in an equal mole amount to the total amount of diamines. You can get the following. Even if the amount of aromatic dicarboxylic acid, aromatic tricarboxylic acid, or their reactive derivatives is too much or too little relative to the diamine,
There is a tendency for the molecular weight to decrease and mechanical strength, heat resistance, etc. to decrease.

The polyamide silicone polymer or polyamideimide silicone polymer obtained by polycondensation reaction of the above aromatic dicarboxylic acid, aromatic tricarboxylic acid, or a reactive derivative thereof and a diamine is a dimethylformamide ξ.
Reduced viscosity at 30°C in 2% by weight solution is 0.2-2
．． The reduced viscosity is preferably 0 dl/g. If the reduced viscosity is too small, the heat resistance and mechanical strength will decrease, and if it is too large, the solubility in solvents will tend to decrease.

A polyamide silicone polymer or a polyamideimide silicone polymer is dissolved in an organic solvent to form a varnish.

Examples of organic solvents include acetamide and N.

N-dimethylformamide, N,N-dimethylacedo1do, N,N-diethylformamide, N.

Polar solvents such as N-diethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, nitrobenzene, glycol carbonate, ether compounds such as tetrahydrofuran, dioxane, 1,2-dimethoxyethane, polyethylene glycol dimethyl ether, 2-cyclohexanone, 4- Alicyclic ketone compounds such as methyl-2-cyclohexanone are used.

The silicon dioxide powder used in the present invention preferably has an average particle size of 0.1 to 40 μm. If the particle size exceeds 40 μm, sedimentation may become large and the stability over time as a paste composition may deteriorate. If it is less than 0.1 am, the surface area becomes large and it may become impossible to increase the filling rate.

Two or more types of particles with different particle sizes may be mixed in combination.In order to suppress the wetting and spreading properties of the paste composition, 10% by weight of silicon dioxide powder with a particle size of 0.1 m or less is added to the paste composition. It can also be used in the following amounts.

As the silicon dioxide powder, spherical or crushed silicon dioxide powder can be used alone or in combination, taking into consideration workability and properties such as wetting and spreading properties.

A silane coupling agent can also be added to the paste composition to improve adhesion to the substrate. As the silane coupling agent, a silane compound having a functional group such as an amino group, a vinyl group, an epoxy group, a mercapto group, an alkoxy group, chlorine, or bromine can be used, such as γ-glycidoxypropyltrimethoxysilane, T -(2-aminoethyl)a[nopropyltrimethoxysilane, r-(2-aminoethyl)aminopropylmethyldimethoxysilane,
T-methacryloxypropyltrimethoxysilane, T-
Mercaptopropyltrimethoxysilane, methylmethoxysilane, methyltriethoxysilane, vinyltriacetoxysilane, T-chloropropyltrimethoxysilane, hexamethyldisilazane, T-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, T-chloro Propylmethyldimethoxysilane, T-mercaptopropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, T-aminopropyltriethoxysilane, hinyltriethoxysilane, vinyltrichlorosilane, vinyltri(β-methoxyethoxy)silane, etc. can be mentioned.

When using a silane coupling agent, the above polymer 1
It is added in an amount of 0.1 to 30 parts by weight per 00 parts by weight. If it is less than 0.1 part by weight, sufficient adhesion cannot be imparted, and if it is used in excess of 30 parts by weight, the adhesion will not improve any further and will instead cause oozing onto the surface, so it is preferable. do not have.

In the paste composition of the present invention, the total amount of polyamide silicone polymer or polyamideimide silicone polymer is 1
200 to 3500 parts by weight of the organic solvent are used per 00 parts by weight. It is preferable to use 200 to 1000 parts by weight of the organic solvent based on 100 parts by weight of the total amount of the polymer. In the paste composition of the present invention, the above polymer 1
00 parts by weight of silicon dioxide powder is 100 to 3500 parts by weight.
If the solvent is used in an amount of 200 to 3000 parts by weight, preferably less than 200 parts by weight, the solid content will be high, resulting in poor coating properties and difficulty in maintaining the coated surface at a constant thickness. When the organic solvent exceeds 3500 parts by weight,
Since the viscosity is low, it becomes difficult to disperse the silicon dioxide powder, making it prone to sedimentation, resulting in poor stability over time as a paste, as well as a decrease in the solid content, making thick film coating impossible. If the amount of silicon dioxide powder is less than 100 parts by weight, thixotropy will be insufficient and it will be difficult to form a thick film. 35
If it exceeds 0.00 parts by weight, the resulting coating film will have poor strength and moisture resistance.

Pace of the present invention) [Paraboloid is, for example, a boria 4 dosilicon polymer obtained by polycondensation reaction of (A) aromatic dicarboxylic acid or its reactive acid derivative and a diamine having cyanosiloxane as an essential component. Alternatively, 100 parts by weight of a boria ξ toy ξ dosilicon polymer obtained by polycondensation reaction of an aromatic tricarboxylic acid or its reactive acid derivative and cyanosiloxane containing cyaminosiloxane as an essential component (B
) 100-3500 parts of silicon dioxide powder (C) is added to a polymer varnish prepared by dissolving 200-3500 parts by weight of an organic solvent.
It can be produced by adding parts by weight and mixing and kneading in a mill, three-roll mill, ball mill, etc. Further, the semiconductor device of the present invention can be manufactured by, for example, applying and drying the paste composition on the surface of a semiconductor component to form a protective film.

[Effect]

The polyamide silicone polymer or polyamideimide silicone polymer of the present invention is a heat-resistant thermoplastic resin that has excellent mechanical strength and adhesion, and the silicon group in the polymer skeleton has a high affinity for silicon dioxide powder. Because of this property, the content of silicon dioxide powder can be increased, thick film coating is possible, and moisture resistance can be improved. Furthermore, when using a low-elasticity polyamide silicone polymer or boria-imide silicone polymer obtained using a long-chain cyanosiloxane, the elastic modulus can be kept low even if the content of silicon dioxide powder is increased. Therefore, it has excellent stress relaxation properties and is particularly excellent as a protective film material for semiconductor components.

〔Example〕

Next, the present invention will be explained in more detail by examples.
The present invention is not limited to these.

Synthesis Example 1 In a four-bottle flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube, 1 liter of sodium hydroxide was added under a nitrogen gas atmosphere.
7.2 g was dissolved in 80 d of water, then 2.2
63.5 g of -bis(4-(4-aminophenoxy)phenyl)propane and 40 g of 1,3-bis(anobrovir)tetramethyldisiloxane (molar ratio = 90 mol%/
10 mol%) was dissolved in 340 g of cyclohexanone, poured into the flask, and cooled to -2°C. Meanwhile, 18.2 g of terephthalic acid dichloride and 18.2 g of isophthalic acid dichloride were mixed with 240 g of cyclohexanone.
The acid chloride solution was injected into the flask from the dropping funnel, and the reaction was allowed to proceed for 3 hours while ensuring that the reaction temperature did not exceed 10°C.

The reaction solution was poured into methanol to isolate the polymer. After drying this, dissolve it again in dimethylformago,
This was poured into methanol to purify the polyamide silicone polymer.

Synthesis Example 2 2. Diamine was added under a nitrogen gas atmosphere into a four-bottle flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube.
65.6 g (60 mmol) of 2-bis(4-(4-aminophenoxy)phenyl)propane and formula % (formula %) (80 mol%, 720 mol% in molar ratio) were dissolved in 335 g of diethylene glycol dimethyl ether. This solution was cooled to -10°C, and at this temperature 40.6 g (200 mmol) of isophthaloyl dichloride was added at a temperature of -15°C.
It was added so as not to exceed ℃. Thereafter, 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 resulting reaction solution was treated in the same manner as in Synthesis Example 1 to monopolize the polyamide silicone polymer. Separated and purified.

Synthesis Example 3 2.
174.3 g (425 mmol) of 2-bis(4-(4-aminophenoxy)phenyl)propane and formula % (85 mol %/15 mol % in molar ratio) were added and dissolved in 1177 g of diethylene glycol dimethyl ether.

The solution was cooled to -10°C and at this temperature 101.5 g (500 mmol) of isophthaloyl dichloride were added such that the temperature did not exceed 15°C. After the addition, 87 g of propylene oxide was added, stirring was continued for 3 hours at room temperature, and when the viscosity of the reaction liquid increased and the liquid became transparent, 841 g of diethylene glycol dimethyl ether was added,
After continuing stirring for an additional hour, the resulting reaction solution was poured into a large amount of a mixed solvent of n-hexane/methanol=1/1 (weight: 1) to isolate the polymer. After drying this, it was dissolved in N,N-dimethylformamide, poured into methanol to purify the polyamide silicone polymer, and dried under reduced pressure.

Synthesis Example 4 2. Diamine was added under a nitrogen gas atmosphere into a four-hole flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube.
147.6 g (360 mmol) of 2-bis(4-(4-aminophenoxy)phenyl)propane and 9-92 g of 1,3-bis(aminopropyl)tetramethyldisiloxane
g (40 mmol) (90 mol%/10 mol% in molar ratio
), propylene oxide 34.8g (600 mmol)
and dissolved in 564 g of N,N-dimethylacetamide. The solution was cooled to 0°C, and at this temperature 84.2 g (400 mmol) of trimellitic anhydride monochloride was added such that the temperature did not exceed 5°C. 3 at room temperature
After stirring for an hour, 200 g of acetic anhydride and 50 g of pyridine
was added, and stirring was continued at 60°C for one day and night. The resulting reaction solution was treated in the same manner as in Synthesis Example 1 to isolate and purify the polyamideimide silicone polymer.

Synthesis Example 5 2. Diamine was added under a nitrogen gas atmosphere into a four-bottle flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube.
2-bis(4-”(4-aminophenoxy)phenyl)
65.6 g of propane (I60ξ mol) and formula % (formula % formula %) (80 mol %/2-O mol % in molar ratio) were added and dissolved in 335 g of diethylene glycol dimethyl ether. The solution was cooled to -10°C, and at this temperature 42.1 g (200 mmol) of trimellitic anhydride monochloride was added such that the temperature did not exceed -15°C. Once the trimellitic anhydride monochloride has dissolved, 23.2 g of propylene oxide is added and 96.2 g of diethylene glycol dimethyl ether is added. was added and stirring was continued for 3 hours at room temperature, then 61 g of acetic anhydride and 30 g of pyridine were added, and 60 g of pyridine was added.
Stirring was continued for one day and night at "C".The resulting reaction solution was synthesized in Synthesis Example 1.
The polyamideimide silicone polymer was isolated and purified in the same manner as above.

Synthesis Example 6 A diamine was prepared under a nitrogen gas atmosphere in a four-bottle flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube.
174.3 g (425 mmol) of 2-bis(4-(4-aminophenoxy)phenyl)propane and 225 g (75 mmol) of cyanosiloxane of the formula (85 mol%, 715 mol% in molar ratio) were added, and diethylene glycol was added. Dissolved in 1177 g of dimethyl ether.This solution was cooled to -10°C, and at this temperature 105.3 g (500ξ mol) of trimellitic anhydride monochloride was added so that the temperature did not exceed -15°C.After the addition , propylene oxide 87. was added, stirring was continued for 3 hours at room temperature, and when the viscosity of the reaction solution increased and the liquid became transparent, 841 g of diethylene glycol dimethyl ether was added and stirring was continued for another 1 hour, followed by anhydrous Acetic acid 128
g and 64 g of pyridine were added thereto, and stirring was continued at 60° C. for one day and night. The resulting reaction solution was diluted with n-hexane/methanol-1
/1 (weight ratio) into a large amount of mixed solvent to isolate the polymer. After drying this, it was dissolved in N,N-dimethylformamide, poured into methanol to purify the polyamide silicone polymer, and dried under reduced pressure.

Synthesis Example 7 In Synthesis Example 1, 1,3-bis(aminopropyl)tetramethylenedisiloxane was removed, and 2,2-bis(4-(4-
100 mol% aminophenoxy)phenyl]propane
A polymer was produced in accordance with Synthesis Example 1 except for the following.

Example 1 100 parts by weight of the polymer obtained in Synthesis Example 1 was dissolved in 400 parts by weight of diethylene glycol dimethyl ether, and spherical silicon dioxide powder (manufactured by Denki Kagaku Co., Ltd., FB-74) with an average particle size of 31.5 μm was added. A paste composition was prepared by adding the following ingredients in different amounts and kneading them for 2 hours in a rice cooker.

Example 2 A paste composition was prepared according to Example 1 except that the polymer obtained in Synthesis Example 2 was used.

Example 3 A paste composition was prepared according to Example 1 except that the polymer obtained in Synthesis Example 3 was used.

Example 4 A paste composition was prepared according to Example 1 except that the polymer obtained in Synthesis Example 4 was used.

Example 5 A paste and a l1ltc product were prepared according to Example 1 except that the polymer obtained in Synthesis Example 5 was used.

Example 6 A paste composition was prepared according to Example 1 except that the polymer obtained in Synthesis Example 6 was used.

Comparative Example 1 A paste composition was prepared according to Example 1 except that the polymer obtained in Synthesis Example 7 was used.

Comparative Example 2 100 parts by weight of a mixture of an epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., Epicoat 825) as a binder and a curing agent (manufactured by Meiwa Kayi Co., Ltd., phenol novolac medium-1) was dissolved in 400 parts by weight of butyl cellosolve. A paste composition was prepared in the same manner as in Example 1, except that a paste composition was used.

The properties of the paste compositions obtained in the above Examples and Comparative Examples were measured and the results are shown in Table 1 below.

In addition, the characteristics were measured by the following method.

(a) Coating thickness The coating thickness is expressed when the wet spread is 10 cm in diameter.

(b) Dynamic elastic modulus Measured by dynamic viscoelasticity method (using a spectrometer manufactured by Harumoto Seisakusho in air, heating rate 2°C/min frequency 10H)
z).

(C) Glass transition temperature measured by dynamic viscoelasticity method (tan of the measured value in (b) above)
δ peak).

(b) Moisture resistant adhesion was determined (Pushable gauge, wire strength 5)
cg f /cj).

○: Not peeled off from the board at all (wire breakage).

(Peel strength: 5 kg f /d or more Δ: Partially peeled off from the substrate (wire broke midway).

(Peel strength: 5 kgr/d> ×: All peeled off from the substrate (wire did not break).

(Color peeling strength 0.5 kgf/cj or less) (e)
Heat cycle at room temperature for 30 seconds ← → solder bath at 260°C for 30 seconds and visually observe whether there is any peeling or cracking It has excellent adhesive properties, excellent moisture resistance, and is useful as a protective film material for semiconductor components against moisture absorption, contamination, external stress, thermal stress during work, etc. A semiconductor device using this material has high reliability with excellent moisture resistance, contamination resistance, resistance to external stress, and resistance to heat stress.

Claims (1)

[Claims] 1. (A) A polyamide silicone polymer or an aromatic tricarboxylic acid obtained by polycondensation reaction of an aromatic dicarboxylic acid or its reactive acid derivative and a diamine containing diaminosiloxane as an essential component. 100 parts by weight of a polyamideimide silicone polymer obtained by polycondensation reaction of a reactive acid derivative and a diamine containing diaminosiloxane as an essential component, (B) 200 to 3,500 parts by weight of an organic solvent, and (C) 100 to 100 parts by weight of silicon dioxide powder. A paste composition containing 3500 parts by weight. 2. Diaminosiloxane has the general formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, Y_1 is a divalent hydrocarbon group, Y_2 is a monovalent hydrocarbon group, The paste composition according to claim 1, wherein the number of Y_1 may be the same or different, the number of Y_2 may be the same or different from each other, and m is an integer of 1 or more. . 3. The diamine is (a) 0.1 to 40 mol% of diaminosiloxane, (b)
General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R_1, R_2, R_3 and R_4 each independently represent hydrogen, lower alkyl group, lower alkoxy group or halogen atom, and X is Chemical bond, -O-, -S-, ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼, -SO_2-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
Tables, etc. ▼ or ▲ Numerical formulas, chemical formulas, tables, etc. ▼, where R_5 and R_6 each independently represent hydrogen, lower alkyl group, trifluoromethyl group, trichloromethyl group, or phenyl group) Or general formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (In the formula, X' represents -O- or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, where R'_4 and R '_5 each independently represents hydrogen, lower alkyl group, trifluoromethyl group,
Indicates a trichloromethyl group or a phenyl group, R'_1,
R'_2 and R'_3 each independently represent a lower alkyl group, a lower alkoxy group or a halogen, and x, y and z each represent the number of substituents and are an integer of 0 to 4,
Two X' may be the same or different, R'_1,
When a plurality of R'_2 and R'_3 are bonded, each may be the same or different) 99.9 to 60 mol%, (c) the above (a) and aromatic diamines excluding (b) 39.9-0
and (d) 39.9 to 0 mol% of the diamine excluding the above (a), (b) and (c) so that the total amount is 100 mol%. Paste composition. 4. A semiconductor device comprising a protective film obtained by applying and drying the paste composition according to claim 1, 2 or 3 on the surface of a semiconductor component.