JPS5950248B2 - Method for producing copolymer resinous material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a resinous material that has excellent heat resistance and is relatively color-free.

Resins with hydradiimide bonds are already well known.

The manufacturing method is dicarboxylic acid hydrazide and NH2-NHC.
O-R-CONH-NH2 tetracarboxylic dianhydride is reacted to produce polyhydrazide acid, which is further heated to undergo ring closure to obtain a polymer having hydradiimide bonds.

However, because dicarboxylic acid hydrazide is used,
The disadvantage is that the solubility of the polymer is low, and the polymer itself tends to precipitate into the varnish.

In addition, in terms of heat resistance, it starts to lose weight on heating at around 370°C, so it is a relatively poor polymer in terms of heat resistance. The present invention provides a copolymer with little coloring property, which improves precipitation in the polymer, improves film formability, and heat resistance up to around 400°C.

The present invention is characterized in that a dihydrazide compound, a diaminodialkoxycarbonylamino compound, and a tetracarboxylic dianhydride are reacted in a solvent to synthesize a polyhydrazidic acid-amic acid urethane, and then the reaction product is ring-closed. In short, it may be a hydrazide compound other than phthalic dihydrazide, such as the formula shown below.

In addition, the compound represented by the above general formula specifically includes 3,3'-diamino-4,4'-diethoxycarbonylaminodig (wherein Arl is a tetracarboxylic dianhydride residue, Ar2 is a diaminodialkoxycarbonylamino compound residue, Ar
3 represents a dihydrazide compound residue.

) is a method for producing a copolymer resinous material. A reaction example of the present invention is shown in the following general formula. The blending ratio of dihydrazide and diaminodialkoxycarbonylamino compound in the present invention is selected from the range of 95 to 50 moles of the former and 5 to 50 moles of the latter. The reason why this range is good is that polymer precipitation, heat resistance, and coloring resistance are taken into consideration. The dihydrazide compound used in the present invention is preferably isophthalic acid dihydrazide, terephthalic acid dihydrazide, etc., but is one in which aromatic rings are bonded to each other by -0-, -SO2-, etc.

These compounds can be used alone or in combination of two or more. In addition, examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, 3,3', 4,4'-diphenyltetracarboxylic dianhydride and the like are used. Further, as a solvent, for example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide,
N,N-diethylformamide, hexamethylphosphoramide, dimethyl sulfoxide, etc. are used. In the present invention, first, the phthalic dihydrazide compound, the diaminodialkoxycarbonylamino compound, and the tetracarboxylic dianhydride compound are reacted in the solvent with stirring.

The reaction proceeds rapidly, the viscosity of the reaction system gradually increases, and polyhydrazidic acid-amic acid urethane is produced. Next, this polyhydrazide-amide urethane is ring-closed by heat treatment to convert it into the desired polymer having a hydradiimide bond and an imidazopyrrolone ring.
The final product obtained by the present invention has excellent heat resistance, coloring resistance, film formability, etc.

Hereinafter, the present invention will be explained in more detail by showing examples.

Example 1 Isophthalic acid dihydrazide (0.095 mol), 3,3
'-Diamino-4,4'-diethoxycarbonylamino diphenyl ether (0.005 mol) is suspended in N-methyl-2-pyrrolidone solvent, the flask is cooled in an ice bath, and the contents are stirred well.

Pyromellitic dianhydride (0.1 mol) is gradually added to this mixture, and the temperature is maintained below 10°C. The reaction was continued for 3 hours after the addition was completed. A portion of the resulting polyhydrazidic acid-amic acid urethane solution is poured into methanol, and the resulting precipitate is thoroughly washed with water and dried. Reduced specific viscosity ηSp of this material
/c is 0.8d1/θ (solvent dimethyl sulfoxide,
The concentration was 0.19/100 CC solution, the temperature was 30° C., and the measurement conditions were the same below). Next, the polyhydrazidic acid-amic acid urethane solution was poured onto a glass plate and heated to 80°C to obtain a durable film. Further, this film was heat-treated at 280° C. to close the ring, thereby converting it into a film having the desired hydradiimide bond and imidazopyrrolone ring. This product did not lose weight in air up to 400°C. Further, a film was obtained in which there was no precipitate in the polyhydrazidic acid-amic acid urethane polymer, the film formation was very good, and the coloring property was less noticeable than the conventional polyimide film. Example 2 In a flask similar to Example 1, isophthalic acid dihydrazide (0.05 mol) and 1,4-diamino-2,5-diethoxycarbonylaminobenzene (0.05 mol) were added to N,N-dimethylacetamide solvent. Cool the flask in an ice bath and stir the contents well.

Pyromellitic dianhydride (0.1 mol) is gradually added to this mixture, and the temperature is maintained at 10°C or less. The reaction was allowed to proceed at this temperature for 7 hours. The reduced specific viscosity ηSp/c of the produced polyhydrazidic acid-amidic acid amide was 1.1 d1/9.
A film was made from the above polyhydrazide acid-amic acid urethane, and the film was ring-closed by heating at 300°C to convert it into the desired product. This product did not lose weight in air up to 430°C. Moreover, no precipitates were observed in this polymer, and the coloring resistance was also relatively good. Example 3 In a flask similar to Example 1, isophthalic dihydrazide (0.07 mol), 3,3'-diamino-4,4'-
Diethoxycarbonylaminodiphenyl ether (0
．． 03 mol) in N,N-dimethylformamide solution, cool the flask in an ice bath, and stir the contents well.

In this, pyromellitic dianhydride (0.08 mol),
3,3',4,4'-Benzophenonetetracarboxylic dianhydride (0.02 mol) was gradually added and the temperature was increased to 10
Keep below ℃. The reaction was allowed to proceed at this temperature for 4 hours. Reduced specific viscosity ηS of the produced polyhydrazidic acid-amic acid urethane
p/c is 1. It was Id1/g. A film was made from the above polyhydrazide acid-amic acid urethane, and this was
The product was ring-closed by heating at 50°C to convert it into the desired product. This product did not lose weight in air up to 410°C. Moreover, no precipitates were observed in this polymer, and the coloring resistance was also relatively good. Example 4 In a flask similar to Example 1, isophthalic acid dihydrazide (0.04 mol) and terephthalic acid dihydrazide (0.04 mol) were added.
．． 01 mol), 1,5-diamino-2,4-diethoxycarbonylaminobenzene (0.05 mol) was suspended in N-methyl-2-pyrrolidone solvent, the flask was cooled in an ice bath, and the contents were thoroughly mixed. Stir.

Pyromellitic dianhydride (0.1 mol) is gradually added to this mixture, and the temperature is maintained below 10°C. The reaction was allowed to proceed at this temperature for 10 hours. The reduced specific viscosity ηSp/c of the produced polyhydrazidic acid-amic acid urethane was 1.1 d1/9. A film was made from the above polyhydrazide acid-amic acid urethane, and the film was ring-closed by heating at 220°C to convert it into the desired product. This product did not lose weight in air up to 410°C. Moreover, no precipitates were observed in this polymer, and the coloring resistance was also relatively good. Example 5 In a flask similar to Example 1, isophthalic acid dihydrazide (0.08 mol) and 3,3'-diamino-4,4'-diethoxycarbonylamino diphenyl ether (0.0
2 mol) in dimethyl sulfoxide solvent, cool the flask in an ice bath, and stir the contents well.

Pyromellitic dianhydride (0.1 mol) is gradually added to this mixture, and the temperature is maintained below 10°C. The reaction was allowed to proceed at this temperature for 3 hours. The reduced specific viscosity ηSp/c of the produced polyhydrazidic acid-amidic acid amide was 1.0 d1/9.

A film was made from the above polyhydrazide acid-amic acid urethane, and the film was ring-closed by heating at 300°C to convert it into the desired product. This product did not lose weight in air up to 410°C. Moreover, no precipitates were observed in this polymer, and the coloring resistance was also relatively good. The final product obtained by the present invention has excellent heat resistance, coloring resistance, and film formability, and since the polymer itself does not precipitate, it is useful for liquid crystal alignment films, semiconductor passivations, insulating films, and the like.

Claims (1)

[Scope of Claims] 1 A dihydrazide compound, a diaminodialkoxycarbonylamino compound, and a tetracarboxylic dianhydride are reacted in a solvent to synthesize a polyhydrazidic acid-amic acid urethane, and then the reaction product is ring-closed. ▲There are formulas, chemical formulas, tables, etc. that are characterized by
r_2 represents a diaminodialkoxycarbonylamino compound residue, and Ar_3 represents a dihydrazide compound residue. ) A method for producing a copolymer resinous material.