JPH0214367B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a polyamic acid that provides a polyimide with excellent heat resistance, moisture resistance, and solvent resistance, and a method for producing the polyimide. [Background of the Invention] Polyimide polymers have been used as surface stabilizing films on the exposed ends of PN junctions, interlayer insulating films in multilayer wiring, and for preventing soft errors in memory devices caused by natural radiation (particularly alpha rays). It is already well known that it is useful as a shielding film. However, ordinary polyimide has drawbacks such as high moisture absorption and moisture permeability, and significant deterioration of adhesive properties due to moisture absorption. That is, when such a film absorbs moisture, leakage current at the PN junction increases, and in the case of multilayer wiring or an α-ray shielding film, there is a problem that Al, which is the wiring and electrode material, corrodes. Also,
If the moisture absorption rate is high, there may be a problem in the manufacturing process that the polyimide film swells due to rapid heating. An object of the present invention is to provide a method for producing polyamic acid that eliminates the drawbacks of the prior art and provides a useful polyimide that has excellent solvent resistance, low hygroscopicity, and thermal stability. [Summary of the invention] The above objects are: (a) General formula and (b) general formula [In the formula (), R is a trivalent or tetravalent organic group, and X is an amino group, a carbamoyl group, or a sulfamoyl group, and is bonded to the ortho position to _-NH2 . n is 1 or 2. ]
This is achieved by a method for producing a polyamic acid, which is characterized by reacting the amine compound represented by the formula with a tetracarboxylic acid or a derivative thereof. Furthermore, (a) General formula () and (b) general formula [In the formula (), R is a trivalent or tetravalent organic group, and X is an amino group, a carbamoyl group, or a sulfamoyl group, and is bonded to the ortho position to _-NH2 . n is 1 or 2. ]
This is achieved by subjecting a polyamic acid obtained by reacting the amino compound represented by the above with a tetracarboxylic acid or a derivative thereof to a dehydration condensation reaction. The inventors synthesized polyimides with various chemical structures and measured various physical properties such as moisture absorption rate, thermal decomposition characteristics, and solvent resistance. As a result, we found that polyimide using diamine (abbreviated as DAPP) with the chemical structure shown below has a very low moisture absorption rate. However, the introduction of the methyl group caused a problem in that the heat resistance was significantly reduced. Therefore, a diamine (abbreviated as 6FDAPP) in which -CH ₃ group was changed to -CF ₃ group
It was found that the moisture absorption rate was lower and the heat resistance did not decrease at all. However, polyimide using 6FDAPP also had the problem of being easily soluble in solvents and having a low glass transition temperature. As a result of intensive study on how to solve these problems, the inventors found that these problems can be greatly improved by introducing a small amount of ladder structure such as pyrrolone structure or isoindoquinazolinedione structure into the polymer skeleton. I discovered that. General formula () giving the most important ladder structure to the present invention The amine compounds represented by are 1,2,3-triaminobenzene, 1,2,4-triaminobenzene, 1,2,4,5-tetraaminobenzene,
-aminobenzidine, 3,3'-diaminobenzidine, 3,4,4'-triamino diphenyl ether, 3,3',4,4'-tetraamino diphenyl ether, 3,4,4'-triamino Benzophenone, 3,3',4,4'-tetraaminobenzophenone, 3,4,4'-triaminodiphenylmethane,
3,3',4,4'-tetraminodiphenylmethane, 3,4,4'-triaminodiphenyl sulfide, 3,3',4,4'-tetraminodiphenyl sulfide, 3,4 , 4'-triaminodiphenylsulfone, 3,3',4,4'-tetraminodiphenylsulfone, 2,2-bis(3,4-diaminophenyl)propane, 4,4'-bis(3 ,4-
Diaminophenoxy)biphenyl, 2,2-bis{4-(3,4-diaminophenoxy)phenyl}
Tri- or tetraamines such as propane, 2,2-bis{4-(3,4-diaminophenoxy)phenyl}hexafluoropropane, 1,3-diamino-2-carbamoylbenzene, 1,3-diamino-4 -Carbamoylbenzene, 1,4-diamino-2-carbamoylbenzene, 1,4-diamino-2,5-dicarbamoylbenzene, 3-carbamoylbenzidine, 3,3'-dicarbamoylbenzidine, 3-carbamoyl-4,4 '-Diamino diphenyl ether, 3,3'-dicarbamoyl-4,4'-diaminodiphenyl ether, 3-carbamoyl-4,4'-diaminobenzophenone,
3,3'-Dicarbamoyl-4,4'-diaminobenzophenone, 3-carbamoyl-4,4'-diaminodiphenylmethane, 3,3'-dicarbamoyl-
4,4'-diaminodiphenylmethane, 3-carbamoyl-4,4'-diaminodiphenyl sulfide, 3,3'-dicarbamoyl-4,4'-diamino-diphenyl sulfide, 3-carbamoyl-
4,4'-diaminodiphenylsulfone, 3,3'-
dicarbamoyl-4,4'-diaminodiphenylsulfone, 2,2-bis(3-carbamoyl-4-
aminophenyl)propane, 2,2-bis(3-
Carbamoyl-4-aminophenyl)hexafluoropropane, 4,4'-bis(3-carbamoyl-
4-aminophenoxy)biphenyl, 2,2-bis{4-(3-carbamoyl-4-aminophenoxy)phenyl}propane, 2,2-bis{4-
(3-carbamoyl-4-phenoxy)phenyl}
1 carbamoyl group such as hexafluoropropane
There are aromatic diamines with one or two atoms. 1,3-diamino-2-sulfamoylbenzene, 1,3-diamino-4-sulfamoylbenzene, 1,4-diamino-2-sulfamoylbenzene, 1,4-diamino-2,5-dis Rufuamoylbenzene, 3-sulfamoylbenzidine, 3,3'-disulfamoylbenzidine, 3-
Sulfamoyl-4,4'-diaminodiphenyl ether, 3,3'-disulfamoyl-4,4'-diaminodiphenyl ether, 3-sulfamoyl-4,4'-diaminobenzophenone, 3,3'-disulfamoyl- 4,4'-diaminobenzophenone, 3-sulfamoyl-4,4'-diaminodiphenylmethane, 3,3'-disulfamoyl-4,
4'-Diaminodiphenylmethane, 3-sulfamoyl-4,4'-diaminodiphenyl sulfide, 3,3'-disulfamoyl-4,4'-diaminodiphenyl sulfide, 3-sulfamoyl-4,4'- Diaminodiphenylsulfone, 3,
3'-disulfamoyl-4,4'-diaminodiphenylsulfone, 2,2-bis(3-sulfamoyl-4-aminophenyl)propane, 2,2-bis(3-sulfamoyl-4-aminophenyl)
Hexafluoropropane, 4,4'-bis(3-sulfamoyl-4-aminophenoxy)biphenyl, 2,2-bis{4-(3-sulfamoyl-
4-aminophenoxy)phenyl}propane,
2,2-bis{4-(3-sulfamoyl-4-
There are aromatic diamines having one or two sulfamoyl groups, such as aminophenoxy)phenyl}hexafluoropropane. Tetracarboxylic acids or derivatives thereof that can be used in the present invention include pyromellitic acid, 3,3',4,
4'-tetracarboxyphenyl, 2,3,3',
4'-tetracarboxydiphenyl, 3,3',4,
4'-Tetracarboxydiphenyl ether, 2,
3,3',4'-tetracarboxydiphenyl ether, 3,3',4,4'-tetracarboxybenzophenone, 2,3,3',4'-tetracarboxybenzophenone, 2,3, 6,7-tetracarboxynaphthalene, 1,4,5,7-tetracarboxynaphthalene, 1,2,5,6-tetracarboxynaphthalene, 3,3',4,4'-tetracarboxydiphenylmethane, 2, 2-bis(3,4-dicarboxyphenyl)propane, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, 3,3',4,4'-tetracarboxydiphenyl sulfone, 1,2,7,8-tetracarboxyperylene, 2,2-bis{4-(3,4-
Aromatic tetracarboxylic acids such as dicarboxyphenoxy)phenyl}propane (DAPP), 2,2-bis{4-(3,4-dicarboxyphenynoxy)phenyl}hexafluoropropane, or
These acid dianhydrides, partially esterified products with lower alcohols, etc. can be used. Furthermore, when high heat resistance is not required, aliphatic tetracarboxylic acids such as butanetetracarboxylic acid and cyclopentanetetracarboxylic acid or derivatives thereof may be used. In addition, in the present invention, as the aromatic diamine, the general formula () 2,2-bis{4-(p-aminophenoxy)phenyl}hexafluoropropane, represented by
2,2-bis{4-(m-aminophenoxy)phenyl}hexafluoropropane, 2,2-bis{4-(o-aminophenoxy)phenyl}hexafluoropropane, 2-{4-(p-aminophenoxy)phenyl} -2-{4-(m-aminophenoxy)phenyl}hexafluoropropane, 2-{4
-(m-aminophenoxy)phenyl}-2-{4
-(o-aminophenoxy)phenyl}hexafluoropropane, 2-{4-(o-aminophenoxy)phenyl}-2-{4-(p-aminophenoxy)phenyl}hexafluoropropane, as well as moisture resistance and heat resistance. A commonly used aromatic diamine may be used in combination within a range that does not significantly reduce the amount. Examples of aromatic diamines include the following. That is, m-phenylenediamine,
p-phenylenediamine, benzidine, 4,4″-
Diaminoterphenyl, 4,4-diaminoquarterphenyl, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, diaminodiphenyl sulfone, 2,2-bis(p-
aminophenyl)propane, 2,2-bis(p-
aminophenyl) hexafluoropropane, 1,5
-diaminonaphthalene, 2,6-diaminonaphthalene, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 3,3'-dimethyl-4,
4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 1,
4-bis(p-aminophenoxy)benzene,
4,4'-bis(p-aminophenoxy)biphenyl, 2,2-bis{4-(p-aminophenoxy)
phenyl}propane, general formula diamine, 2,3,5,6-tetraamino-p
- phenylene diamine, etc. Here m is 1
~3. In addition, for the purpose of improving adhesion with glass, ceramics, and metals, (R ₂ and R ₄ are divalent organic groups, R ₁ and R ₃ are monovalent organic groups p and q are integers greater than 1) A silicone-containing diamine represented by the following may be used in combination. In the present invention, the general formula () such as 6FDAPP
Diamines, tetracarboxylic acid derivatives, and general formula () represented by When obtaining a polymer by reacting a compound (or other diamine), the mixing ratio is such that the sum of the diamine of the general formula () and the compound of the general formula () is 0.9 per mole of the tetracarboxylic acid derivative. ~
A range of 1.1 mol is preferable. In addition, when using other diamines in combination, the diamine of general formula () and the general formula ()
The sum of the compound and other diamines is preferably in the range of 0.9 to 1.1 mol. The reaction conditions may be such that each raw material is reacted in a molten state, but usually it is reacted in a solvent at a relatively low temperature to obtain a polyamic acid varnish (precursor), then processed such as coating, and then heated. It is desirable to obtain the final modified polyimide by drying and ring-closing. When obtaining polyamic acid, if the tetracarboxylic acid derivative is anhydride, the temperature is preferably around -20 to 50℃;
For free carboxylic acids and ester compounds, 40
A temperature range of ~200°C is preferred. 200-500℃ for the final polymer, including subsequent imide ring closure.
It is necessary to heat it to a high temperature. In addition, as a solvent when obtaining a polyamic acid varnish, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, N,N-diethylformamide,
Hexamethylphosphoramide, sulfolane, tetramethylene sulfone, cresol, phenol,
Xylenol etc. are used. When dianhydride is used as the tetracarboxylic acid derivative in the reaction of the present invention, the general formula is expressed as follows, for example. In the above general formula, R'' represents a tetravalent organic group, and R represents a trivalent organic group. In the above general formula, R'' represents a tetravalent organic group and R represents a trivalent organic group. Y represents -N=, -CO-N= or -SO ₂ -N=. [Example] Next The present invention will now be described in more detail with reference to Examples. However, the present invention is not limited to the following Examples. Examples 1 to 4. Comparative Example 1 Thermometer, stirrer, chloride In a 300 c.c. four-necked flask equipped with a calcium tube and a nitrogen gas inlet,
2,2-bis{4-(4-aminophenoxy)phenyl}hexafluoropropane, 3,3'-diaminobenzidine, and N-methyl-2-pyrrolidone as a reaction solvent were charged in the amounts shown in Table 1,
The mixture was stirred and mixed at room temperature to dissolve. Next, cool to approximately 5℃ in an ice water bath, collect benzophenonetetracarboxylic dianhydride (BTDA) in the amount shown in Table 1, and take care not to exceed 15℃ as the temperature will rise due to the reaction heat. was added little by little. After the acid anhydride was dissolved, the reaction temperature was returned to room temperature, and stirring was continued until the viscosity of the varnish increased to the extent that it was rolled up on a stirring bar to obtain a desired polyamic acid varnish. Next, polyamic acid varnish was applied onto the surface SiO ₂ film using a rotary coating machine so that the film thickness after curing would be about 20 μm. Curing conditions are in nitrogen
A polyimide film was obtained by heating and curing under the conditions of 200°C/30 minutes + 300°C/1 hour + 400°C/15 minutes. After coating on a glass plate to measure physical properties in film form.
After heat treatment at 200°C for 30 minutes, it was peeled off, fixed with a metal frame, and then heat-treated at 300°C and 400°C to create samples. As a guideline for saturated moisture absorption rate and heat resistance at 25℃/75%RH, the temperature at which it takes 100 minutes to lose 3% when thermally decomposed in air, i.e.
The remaining film thickness (coating film on Si wafer) was measured after immersion in trichlorobenzene at 120°C for 20 minutes. In addition, heat resistance was measured at 200℃/10
After drying for 1 minute, the temperature was raised to the pyrolysis temperature at a rate of 300°C/min, and pyrolysis was carried out isothermally. The thermal decomposition temperature was determined at at least four points, and the above-mentioned temperature, which is a measure of heat resistance, was determined from the Arrhenius plot. The glass transition temperature was determined from the relationship between dimensional change and temperature using a Thermo Mechanical Analyzer (manufactured by Shinku Riko Co., Ltd.) using a film (50 μm thick).

[Table] The infrared absorption spectra of the polyamic acid and polyimide of Example 4 were measured. As a result, polyamic acid has amide absorption at 1660 cm ^-1 and amide absorption at 1710 cm -1
Absorption of carboxylic acid appeared at cm ^-1 . In heat-cured polyimide, absorption due to the imide ring appears at 1780 cm ^-1 and absorption due to -C=N- of the pyrolone ring appears at 1620 cm ^-1 , while absorption due to amic acid at 1660 cm ^-1 appears. But it disappeared. From these results, it was confirmed that the desired polymer was obtained. However, polyamic acid varnish is applied in the form of a film, immersed in water, and washed in an ultrasonic cleaner for 30 minutes.
After washing with distilled water for 6 minutes each time, a sample was prepared by vacuum drying. Further, the film was converted into polyimide in the same manner as in Example 1. Infrared absorption spectra were measured using the KBr tablet method. Examples 5 to 7. Comparative Example 2 Under the same conditions as Examples 1 to 4, N-methyl-2
-6FDAPP, 4,4'-diamino-3-carbamoyl diphenyl ether (DDEC), pyromellitic dianhydride (PMDA) in pyrrolidone
was reacted with BTDA to obtain a polyamic acid varnish. Furthermore, polyimide coatings or polyimide films were prepared on Si wafers and their physical properties were measured. Table 2 shows the blending ratio and various physical properties.

[Table] Infrared absorption spectra of the polyamic acid and polyimide of Example 7 were conducted in the same manner as in Example 4. As a result, polyamic acid has
Absorption due to amic acid appears at 1660cm ^-1 and 1710cm ^-1 , and absorption due to imide ring at 1780cm ^-1 and absorption due to isoindoquinazolinedione ring at 1620cm ^-1 appear in the polyimide after curing. appears,
Absorption due to amic acid disappeared. From these results, it was confirmed that the desired polymer was obtained. Examples 8 to 10. Comparative Example 3 In Examples 1 to 4, N-methyl-2
- in pyrrolidone, 2,2-bis{4-(m-aminophenoxy)phenyl}hexafluoropropane (abbreviated as 6FDMAPP), PMDA and 3,3'-
A polyamic acid varnish was obtained by reacting with diaminobenzidine. Next, a film was prepared or coated on a Si wafer to a thickness of 20 μm, and various physical properties were measured. The results are shown in Table 3.

[Table] Examples 11 to 13. Comparative Example 4 Under the same conditions as Examples 1 to 4, N-methyl-2
- 2,2-bis{4-(m-aminophenoxy)phenyl}hexafluoropropane (6FDMAPP) and 3-carbamoyl-4,
4'-diaminodiphenyl ether (DDEC) 2,
2-bis{4(3,4-dicarboxyphenoxy)
Phenyl}hexafluoropropane dianhydride (abbreviated as 6FTCPP) was reacted to obtain a polyamic acid varnish. Next, an imidized film (20 μm) was formed by coating on a film and a Si wafer, and the physical properties were measured. The results are shown in Table 4.

〔Effect of the invention〕

According to the present invention, it is possible to obtain a polyamic acid that provides a fluorine-containing polyimide having excellent water resistance and solvent resistance, and the polyimide.

Claims (1)

[Claims] 1 (a) General formula and (b) general formula [In the formula (), R is a trivalent or tetravalent organic group, and X is an amino group, a carbamoyl group, or a sulfamoyl group, and is bonded to the ortho position to _-NH2 . n is 1 or 2. ]
A method for producing a polyamic acid, which comprises reacting an amine compound represented by the formula with a tetracarboxylic acid or a derivative thereof. 2 (a) General formula and (b) general formula [In the formula (), R is a trivalent or tetravalent organic group, and X is an amino group, a carbamoyl group, or a sulfamoyl group, and is bonded to the ortho position to _-NH2 . n is 1 or 2. ]
A method for producing a polyimide, which comprises subjecting a polyamic acid obtained by reacting an amine compound represented by the above with a tetracarboxylic acid or a derivative thereof to undergo a dehydration condensation reaction.