JPH059254A - Production of polyamideimidesiloxane polymer - Google Patents

Abstract

PURPOSE:To produce the title polymer excellent in moisture resistance, heat resistance, adhesive properties, etc., in a short time by polycondensing an arom. tricarboxylic acid, an arom. diisocyanate, and a diaminosiloxane. CONSTITUTION:The title polymer is prepd. by polycondensing an arom. tricarboxylic acid (e.g. trimellitic acid) or its reactive deriv. (e.g. trimellitic anhydride monochloride), an arom. diisocynate of formula I (wherein X is-O-,- CH2-, or-SO2) (e.g. 4,4'-diphenylmethane diisocyanate), and a diaminosiloxane (e.g. a compd. of formula II). The reaction is carried out in two steps: the first step comprises reacting the diisocyanate with the diaminosiloxane in an inert polar org. solvent, and the second step comprises adding the acid or its deriv. to the reaction system to effect a reaction. Thus, the polymer is produced in a short time at a relatively low temp.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyamideimide siloxane polymer used for an interlayer insulating film or a protective film of a semiconductor device.

[0002]

2. Description of the Related Art Conventionally, a polyimide resin or an imidosiloxane copolymer having excellent moisture resistance and heat resistance has been used as an interlayer insulating film of a semiconductor element. However, in recent years, since the raw material of the polyimide resin is expensive, a heat-resistant polymer of polyamideimide type, which is a cheap raw material, is gradually being put into practical use.

[0003]

However, the above-mentioned polyamide-imide polymer has poor adhesion to, for example, a substrate, and particularly poor adhesion to glass, silicon wafers, and the like. Although a coupling agent or the like is added and used, its effect is insufficient.

The present invention has been made in view of the above circumstances, and a polyamideimide siloxane polymer having excellent moisture resistance and heat resistance, and excellent adhesion to a glass plate, a silicon wafer, a metal, etc., can be obtained at a low temperature at a short time. Its purpose is to make it in time.

[0005]

In order to achieve the above object, the method for producing a polyamideimide siloxane polymer of the present invention comprises at least one of an aromatic tricarboxylic acid and a reactive acid derivative thereof and the following general formula (1): ) The aromatic diisocyanate represented by the formula (1) and diaminosiloxane are polycondensed.

[0006]

[Chemical 2]

[0007]

In other words, the present inventors have conducted a series of studies in order to obtain a polymer having not only moisture resistance and heat resistance but also excellent adhesion to glass, silicon wafer and the like. As a result, an aromatic tricarboxylic acid and / or a reactive acid derivative thereof, and a special aromatic diisocyanate,
The inventors have found that a polymer having the above properties can be obtained at low temperature and in a short time by polycondensation with diaminosiloxane, and reached the present invention.

Next, the present invention will be described in detail.

In the method for producing the polyamideimide siloxane polymer of the present invention, an aromatic tricarboxylic acid and / or a reactive acid derivative thereof, a special aromatic diisocyanate and diaminosiloxane are used.

The above-mentioned aromatic tricarboxylic acid has 3 in its aromatic nucleus.
4 of the above 3 carboxyl groups are bonded to adjacent carbons. Of course, this aromatic ring may have a hetero ring introduced, or the aromatic rings may be bonded to alkylene, oxygen, carbonyl group or the like. Further, a substituent that does not participate in the condensation reaction, such as alkoxy, allyloxy, or alkylaminohalogen, may be introduced into the aromatic ring. Specifically, trimellitic acid, 3,3
4'-benzophenone tricarboxylic acid, 2,3,6-pyridine tricarboxylic 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 and the like can be used alone or in combination. Examples of the reactive acid derivative of the aromatic tricarboxylic acid include acid anhydrides, halides, esters, amides and ammonium salts of the aromatic tricarboxylic acid. For example, 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-dicarboxy-5-carbamoylnaphthalene, the above aromatic tricarboxylic acids and ammonia, dimethylamine Examples thereof include ammonium salts such as triethylamine and the like. These are used alone together.
Among these, trimellitic acid anhydride and trimellitic acid anhydride monochloride are typical. The amount of the aromatic tricarboxylic acid and its reactive acid derivative used is preferably set to 60 to 120 mol% with respect to the aromatic diisocyanate described later, and particularly preferably 65 to 110 mol%. That is, when the amount is less than 60 mol%, the number of imide groups per molecule is small, and thus the heat resistance is extremely lowered. This is because the heat resistance tends to decrease.

The above-mentioned special aromatic diisocyanate is represented by the following general formula (1), and the use of this is the greatest feature of the present invention. That is, by using this aromatic diisocyanate, it becomes possible to react the aromatic diisocyanate and the diaminosiloxane quickly under low temperature conditions.

[0012]

[Chemical 3]

Examples of the diaminosiloxane include compounds represented by the following general formula (2).

[0014]

[Chemical 4]

[In the above formula (2), R ₁ is a divalent hydrocarbon group, R ₂ is a monovalent hydrocarbon group, and R ₁ and R ₂ may be the same or different from each other. Also, m
Is an integer of 1 or more. ]

In the above general formula (2), R ₁ is preferably an alkylene group having 1 to 5 carbon atoms, a phenyl group or an alkyl-substituted phenylene group, and R ₂ is preferably an alkyl group having 1 to 5 carbon atoms. , An alkoxy group, a phenyl group or an alkyl-substituted phenyl group. Further, in the general formula (2), the number of repetitions m is particularly preferably 100 or less. That is, when the repeating number m is too large, the ratio of amide bond and imide bond in the obtained polyamideimide siloxane polymer decreases, and heat resistance tends to deteriorate. Specifically, the following chemical formula (a) ~
Examples include those represented by (e).

[0017]

[Chemical 5]

However, in the above chemical formulas (a) to (e), the number of repetitions m'is 1 to 100. These diaminosiloxanes are used alone or in combination. The amount of the diaminosiloxane used is preferably set to 0.1 to 50 mol%, particularly preferably 0.1 to 30 mol% based on the aromatic diisocyanate. Further, from the viewpoints of adhesiveness, heat resistance, transparency and an appropriate molecular weight of the produced compound, it is most preferable to set it in the range of 0.2 to 20 mol%. That is, when the amount of diaminosiloxane used exceeds 50 mol%, the molecular weight and heat resistance of the resulting polyamideimide siloxane polymer decrease, and conversely, when it is less than 0.1 mol%, the effect of improving adhesiveness tends to be lost. Because it can be seen.

The method for producing the polyamideimide siloxane polymer of the present invention is carried out, for example, as follows. That is, first, the aromatic diisocyanate and diaminosiloxane are mixed at a temperature of 10 to 160 in a non-reactive polar organic solvent.
Sufficiently react at ℃, preferably 20-80 ℃. Then, at least one of the aromatic tricarboxylic acid and its reactive acid derivative is added to this and reacted with the residual aromatic diisocyanate at 100 to 300 ° C, preferably 120 to 160 ° C. A polyamideimide siloxane polymer is obtained by passing through such a two-step reaction process.

The non-reactive polar organic solvent is N-
Examples include methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, cresol, xylenol, chlorophenol, dimethylacetamide, dimethylformamide and nitrobenzene. Particularly, it is preferable to use N-methyl-2-pyrrolidone.

In the above-mentioned production method, in the reaction of the aromatic diisocyanate and the diaminosiloxane, which is the first reaction step, the reaction time can be shortened at a low temperature.

The polyamideimide siloxane polymer thus obtained preferably has a molecular weight (in terms of polystyrene) of Mw = 10 ^{4 to} 5 × 10 ⁵ . That is, when the molecular weight Mw is less than 10 ⁴ , heat resistance and mechanical strength are lowered, and when the molecular weight Mw exceeds 5 × 10 ⁵ , the solubility in the polar organic solvent is lowered and the solution viscosity is extremely increased to be handled. This is because it tends to be difficult.

The polyamideimide siloxane polymer obtained according to the present invention has the following general formulas (3) and (4):
It is considered that the repeating unit represented by is a structure in which the repeating units are combined. The bonding mode of the above two repeating units is block, alternating, or random.

[0024]

[Chemical 6]

The polyamideimide siloxane polymer thus obtained is excellent in heat resistance, solubility, and adhesiveness to substrates such as glass plates and silicon wafers, so that it can be used in various fields requiring the above properties. It is preferably used. For example, a material for forming an interlayer insulating layer of a semiconductor device, a material for forming a surface protective film, and the like can be given.

[0026]

As described above, the method for producing the polyamide-imide siloxane polymer of the present invention is based on at least one of an aromatic tricarboxylic acid and a reactive acid derivative thereof and an aromatic compound represented by the following general formula (1). Since it is produced by polycondensing diisocyanate and diaminosiloxane, it has excellent adhesion to, for example, glass plates, silicon wafers, metals, etc., and also has excellent heat resistance, moisture resistance, flexibility, and mechanical strength. Therefore, it is most suitable as an adhesive material or coating material for semiconductor elements. Moreover, the above production reaction
Since it is performed at low temperature and quickly, the cost of the product can be reduced.

Next, examples will be described together with comparative examples.

[0028]

Example 1 In a separable three-necked flask equipped with a thermometer, a stirrer, and a condenser, 77.64 g of 4,4'-diphenylmethane diisocyanate (MDI) and 1,3
-Bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane 2.61 g and N-methyl-2-
Pyrrolidone (215.61 g) was mixed and sufficiently reacted at 40 ° C. for 2 hours while dissolving with stirring. Then, 57.6 g of trimellitic anhydride (TMA) was added to this,
The temperature was raised to 140 ° C. in 30 minutes, and the reaction was continued for 6 hours in this state. Then 106.1 g of N-methyl-2
-Pyrrolidone was added and the temperature was lowered to 50 ° C to complete the reaction. The viscosity of the obtained polyamideimide siloxane polymer-containing solution was 30 poise at 30 ° C., and the molecular weight Mw of the polymer was 5 × 10 ⁴ in terms of polystyrene.

[0029]

Example 2 1,3-bis (3-aminopropyl)-
The amount of 1,1,3,3-tetramethyldisiloxane added was 19.38 g, and the amount of trimellitic anhydride added was 5
It was changed to 7.6 g. A polyamideimide siloxane polymer-containing solution was prepared in the same manner as in Example 1 except for the above.
The viscosity of the obtained polyamideimide siloxane polymer-containing solution was 12 poise at 30 ° C., and the molecular weight Mw of the polymer was 2.3 × 10 ⁴ in terms of polystyrene.

[0030]

Example 3 MDI was replaced with 4,4'-diphenyl ether diisocyanate, and 77.13 g of this was used. A polyamideimide siloxane polymer-containing solution was prepared in the same manner as in Example 1 except for the above. The viscosity of the obtained polyamideimide siloxane polymer-containing solution was 35 poise at 30 ° C., and the molecular weight Mw of the polymer was 4.5 × 10 ⁴ in terms of polystyrene.

[0031]

Example 4 MDI was replaced with 4,4'-diphenylsulfone diisocyanate, and 93.33 g of this was used. A polyamideimide siloxane polymer-containing solution was prepared in the same manner as in Example 1 except for the above. The viscosity of the obtained polyamideimide siloxane polymer-containing solution was 41 poise at 30 ° C., and the molecular weight Mw of the polymer was 6.3 × 10 ⁴ in terms of polystyrene.

[0032]

[Comparative Example] In a separable three-necked flask equipped with a thermometer, a stirrer and a condenser, 75.0 g of 4,4'-diphenylmethane diisocyanate and 5 parts of trimellitic anhydride were added.
7.6 g and N-methyl-2-pyrrolidone 215.61
g was added and reacted with stirring at 140 ° C. for 6 hours. Then 106.1 g of N-methyl-2
-Pyrrolidone was added and the temperature was lowered to 50 ° C to complete the reaction. The viscosity of the obtained solution was 22 poise at 30 ° C., and the molecular weight Mw of the polymer was 3.7 × 10 in terms of polystyrene.
^{It was 4} .

Adhesion to a silicon wafer was measured and evaluated using the solution containing the polyamideimide siloxane polymer as the example product and the solution as the comparative example product obtained as described above. The results are shown in Table 1 below.

The adhesion to the silicon wafer was measured and evaluated according to the following method. That is, each solution of the above-mentioned Example product and Comparative Example product was diluted with N-methyl-2-pyrrolidone to prepare a 20 wt% concentration solution. Apply this solution by flow coating on a silicon wafer,
It was dried and cured under the drying conditions of 0 ° C. × 15 minutes + 250 ° C. × 1 hour. Further, the solution was applied by flow coating in the opposite direction to the above application direction, and dried and cured under the same conditions. The test piece thus obtained was subjected to 2 atm × 121 ° C. × 100% RH
It was left for 100 hours in the Precure Kurtzker tester of conditions. The initial test piece before being left for 100 hours and the test piece after being left for 100 hours were respectively subjected to JIS D 02.
In accordance with No. 02 cross-cut test method (cured layer on silicon wafer was divided into 1 mm x 1 mm divided into 100), a peel test was performed using cellophane adhesive tape, and the number of parts remaining on the silicon wafer surface without peeling was measured and compared. evaluated.

[0035]

[Table 1]

From Table 1 above, all of the comparative products peeled off after 100 hours, but the products of Examples did not peel off at the beginning and after 100 hours, and adhered to the silicon wafer. From this, it can be seen that the products of Examples are excellent in heat resistance, moisture resistance and adhesiveness to a silicon wafer.

Claims (1)

Claim: What is claimed is: 1. At least one of an aromatic tricarboxylic acid and a reactive acid derivative thereof, and an aromatic diisocyanate represented by the following general formula (1) are polycondensed with diaminosiloxane. A process for producing a characteristic polyamideimide siloxane polymer. [Chemical 1]