CN111303420A - Alkali-developable positive polyimide photosensitive resin and preparation method thereof - Google Patents
Alkali-developable positive polyimide photosensitive resin and preparation method thereof Download PDFInfo
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- CN111303420A CN111303420A CN201911123409.1A CN201911123409A CN111303420A CN 111303420 A CN111303420 A CN 111303420A CN 201911123409 A CN201911123409 A CN 201911123409A CN 111303420 A CN111303420 A CN 111303420A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
Abstract
The invention discloses a novel positive photosensitive polyimide resin and a preparation method thereof, wherein the chemical structural general formula of the novel positive photosensitive polyimide resin is shown in figure 1. Ar (Ar)1Is an intermediate structure of a dianhydride monomer, Ar2Is the intermediate structure of diamine monomer, x =0.1-0.9, and n = 5-200. The photosensitive polyimide resin has simple preparation process, mild reaction condition and easy amplification production. The resin is imidized in the preparation process, so that high-temperature imidization treatment is not needed during pattern photoetching, the photosensitive resin is not needed to be stored at low temperature, and carboxyl in the photosensitive resin structure enables the photosensitive resin to be developed in an alkaline aqueous solution, so that the photosensitive resin is environment-friendly. The photoresist prepared from the photosensitive polyimide resin has the advantages of high film retention rate and contrast, low curing temperature, pattern resolution, room-temperature storage and the like.
Description
Technical Field
The invention belongs to the field of polyimide photoresist, and discloses a positive polyimide photosensitive resin and a preparation method thereof.
Background
Polyimide (PI) is used as a special engineering plastic, has excellent heat resistance, mechanical property, electrical property and film forming property, has been spread in the application fields of aerospace, automobile industry and electronic and electrical appliances, and is widely used as a photoinduced etching agent in the PI microelectronic industry. Photosensitive Polyimide (PSPI) is a high molecular material with dual functions of light sensing and heat resistance, and can greatly simplify the complicated photolithography process when using non-Photosensitive Polyimide, and simultaneously meet the special requirements of a plurality of aspects such as an insulating interlayer, a surface passivation layer, an ion implantation mask, electron beam lithography and the like in a multilayer interconnection system of a large-scale integrated circuit and a very large-scale integrated circuit, thereby being increasingly attracted by people.
The PSPI is prepared into photoresist, and the photoresist has different patterns obtained by photoetching, and is divided into a positive system and a negative system. The positive PSPI uses photosensitizer which is generally photodegradable and the obtained photoetching pattern is the same as the mask, and the negative PSPI uses photosensitizer which is generally photocrosslinking and the obtained photoetching pattern is opposite to the mask. At present, the commercial positive photosensitive polyimide resin mainly adopts a polyamic acid (PAA) precursor, and has the advantages that: the monomer has wide sources, can be developed in alkaline solution (2.38 percent tetramethyl ammonium hydroxide aqueous solution), and is environment-friendly. However, the dissolution rate of the polyamic acid precursor in the alkaline developer is very fast, and the difference between the dissolution rates of the exposed area and the non-exposed area is small, so that the film retention rate and the contrast are low, and the development process is difficult to control accurately. In the post-baking process, the conversion from the precursor polyamide acid (PAA) to PI not only needs high temperature treatment, generally more than 320 ℃, but also in the process, PAA needs to remove water molecules, which easily causes film shrinkage, generates stress between the film and the substrate and affects the reliability of the product.
Aiming at the defects of the prior art, the invention designs and synthesizes the polyimide resin with carboxyl, the imidization is completed in the synthesis process, the defects caused in the application process of a precursor PAA are avoided, meanwhile, the carboxyl in the structure ensures that the photosensitive polyimide resin is normally developed in an alkaline aqueous solution to form a high-quality pattern, and the overhigh post-baking temperature after exposure is also avoided.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention discloses a novel positive photosensitive polyimide resin and a preparation method thereof, and the novel positive photosensitive polyimide resin is characterized in that the structure of polyimide contains an acid group-carboxyl which can be developed by an alkaline aqueous solution, and the chemical structural formula of the positive photosensitive polyimide resin is as follows:
wherein R is any one of the following 4 structures:
1 is an intermediate structure of a dianhydride monomer, Ar2Is the intermediate structure of diamine monomer, x = 0.2-1, n = 5-200.
Ar above1The structures of (a) include, but are not limited to, the following 5:
in the formula, Ar1=
,
,
,
,
。
Ar above2The structures of (a) include, but are not limited to, the following 5:
Ar2=
，
，
，
，
。
the experimental procedure for carrying out the polymerization was as follows:
under the protection of nitrogen, diamine monomers with R as an intermediate structure, namely diamine monomers containing carboxyl, co-diamine monomers without carboxyl, dianhydride monomers and organic solvents are sequentially added into a dry three-necked bottle, stirred at room temperature for 2-12 hours, then a mixture of triethylamine and acetic anhydride is slowly dropped into a reaction bottle, and the reaction is continued at room temperature for 4-18 hours. After the reaction was completed, the resulting highly viscous polymer solution was slowly poured into a large amount of methanol, and the precipitated solid was sufficiently washed with methanol and dried in a vacuum oven for 5 hours.
Or sequentially adding diamine monomers with R as an intermediate structure, namely diamine monomers containing carboxyl, co-diamine monomers containing no carboxyl, dianhydride monomers and organic solvents into a dry three-necked bottle under the protection of nitrogen, stirring for 2-12 hours at room temperature, then continuously and slowly dripping toluene into the reaction bottle, heating to 160 ℃, keeping the temperature at 160 ℃ and continuously reacting for 4-8 hours to ensure that the toluene and water are removed by azeotropy. After the reaction was complete, the resulting highly viscous polymer solution was taken.
The polymerization equation is as follows:
wherein, the diamine monomer taking R as an intermediate structure is any one of the following 4 structures:
the chemical structural formula of the copolymerized diamine monomer is as follows:
the chemical structure of the dianhydride monomer is as follows:
the molar ratio of the diamine monomer taking R as an intermediate structure, namely the diamine monomer containing carboxyl to the copolymerized diamine monomer is as follows: 9:1-1:9. The organic solvent is: one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide and gamma-butyrolactone. The total concentration of dianhydride and diamine monomers is: 5-40 w/v%.
The invention has the following technical effects:
the photosensitive polyimide resin has simple preparation process, mild reaction condition and easy amplification production. Because the resin is completely imidized in the preparation process, the photoetching pattern does not need high-temperature curing treatment, the photosensitive resin does not need low-temperature storage, and the carboxyl in the photosensitive resin structure can be developed in an alkaline aqueous solution, so that the photosensitive resin is environment-friendly. The photoresist prepared from the photosensitive polyimide resin has the advantages of high film retention rate and contrast, low curing temperature, pattern resolution, room-temperature storage and the like.
The conception, the specific structure and the technical effects of the present invention will be further described with reference to the accompanying drawings to fully understand the objects, the features and the effects of the present invention.
Drawings
FIG. 1 is a general structural formula of a positive photosensitive polyimide resin disclosed in the present invention;
FIG. 2 is an infrared spectrum of a photosensitive polyimide resin in a preferred embodiment of the present invention;
FIG. 3 is an infrared spectrum of another photosensitive polyimide resin in a preferred embodiment of the present invention;
FIG. 4 is a photograph of a lithographic pattern made of a polyimide photoresist according to a preferred embodiment of the present invention;
FIG. 5 is a photograph of a lithographic pattern made from another polyimide photoresist in accordance with a preferred embodiment of the present invention.
Test method
1. Infrared Spectroscopy (FT-IR), Perkin-Elmer Paragon 1000 Fourier transform Infrared Spectrophotometer, either KBr pellet or thin film.
2. And (3) testing the photosensitive sensitivity: and coating the silicon wafer with the coating in a rotating manner to obtain a film with the thickness of 5-7 microns. The method is characterized in that i-line 365 nanometer exposure is adopted, the exposure intensity is 500mJ/cm2, 5% -60% gray-scale plates are adopted, and the sensitivity and the resolution are observed through a metallographic microscope.
Detailed Description
The technical contents of the preferred embodiments of the present invention will be more clearly and easily understood by referring to the drawings attached to the specification. The present invention may be embodied in many different forms of embodiments and the scope of the invention is not limited to the embodiments set forth herein.
Example 1
Under nitrogen protection, 1.71g (4.5 mmol) of 2, 5-bis (4-aminophenoxy) -1, 4-terephthalic acid, 0.146g (0.5 mmol) of 1, 3-bis (4-aminophenoxy) benzene and 25mL of N, N-dimethylacetamide were sequentially added to a dry 100 mL three-necked flask, magnetically stirred at room temperature, and after the monomers were completely dissolved, 2.22g (5 mmol) of 4, 4' - (hexafluoroisopropyl) diphthalic anhydride was added to the reaction flask and reacted at room temperature for 8 hours to form a highly viscous polyamic acid precursor. Then, a mixed solution of 3mL of triethylamine and 2.7mL of acetic anhydride was slowly added dropwise to the reaction flask, and the reaction was continued at room temperature for 24 hours. The resulting highly viscous polyimide solution was slowly poured into 150mL of methanol, filtered, collected as a filamentous solid, washed three times with methanol, dried under vacuum at 60 ℃ for 10 hours, and used as resin No. 1 to be tested for future use.
Example 2
Under nitrogen protection, 0.19 g (0.5 mmol) of 2, 5-bis (4-aminophenoxy) -1, 4-terephthalic acid, 1.44g (4.5 mmol) of 2,2 ' -bistrifluoromethyl-4, 4 ' -benzidine and 20mL of N-methylpyrrolidone were added in this order to a dry 100 mL three-necked flask, magnetically stirred at room temperature, and after the monomers were completely dissolved, 1.55g (5 mmol) of 4,4 ' -oxydiphthalic anhydride was added to the reaction flask and reacted at room temperature for 10 hours to form a highly viscous polyamic acid precursor. And then slowly dripping toluene into the reaction bottle, heating to 160-180 ℃, and keeping the temperature to continuously react for 6 hours. The resulting highly viscous polyimide solution was slowly poured into 150mL of methanol, filtered under suction, and the filamentous solid was collected, washed three times with methanol, and dried under vacuum at 80 ℃ for 10 hours. The resin No. 2 is to be tested for future use.
Example 3
0.504 g (1.5 mmol) of 2, 5-bis (4-aminophenoxy) -benzoic acid, 0.7g (3.5 mmol) of 4,4 '-diaminodiphenyl ether and 20mL of N-methylpyrrolidone were added in this order to a dry 100 mL three-necked flask under nitrogen protection, and after the monomers were completely dissolved, 2.22g (5 mmol) of 4, 4' - (hexafluoroisopropyl) diphthalic anhydride was added to the reaction flask and reacted at room temperature for 8 hours to form a highly viscous polyamic acid precursor. And then slowly dripping toluene into the reaction bottle, heating to 160-180 ℃, and keeping the temperature to continuously react for 7 hours. The resulting highly viscous polyimide solution was slowly poured into 150mL of methanol, filtered under suction, and the filamentous solid was collected, washed three times with methanol, and dried under vacuum at 80 ℃ for 4 hours. The resin is to be tested as resin No. 3 for standby.
Example 4
Under the protection of nitrogen, 0.95 g (2.5 mmol) of 2, 5-bis (3-aminophenoxy) -1, 4-terephthalic acid, 1.295g (2.5 mmol) of 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane and 20mL of gamma butyrolactone are sequentially added into a dry 100 mL three-necked flask, magnetic stirring is carried out at room temperature, after the monomers are completely dissolved, 1.61g (5 mmol) of 3,3 ', 4, 4' -benzophenone tetracarboxylic dianhydride is added into the reaction flask, and reaction is carried out for 8 hours at room temperature, so as to form a highly viscous polyamic acid precursor. Then, a mixed solution of 3mL of triethylamine and 2.7mL of acetic anhydride was slowly added dropwise to the reaction flask, and the reaction was continued at room temperature for 24 hours. The resulting highly viscous polyimide solution was slowly poured into 150mL of methanol, filtered, collected as a filamentous solid, washed three times with methanol, and dried under vacuum at 80 ℃ for 6 hours. The resin No. 4 is to be tested for future use.
Example 5
0.84 g (2.5 mmol) of 2, 5-bis (3-aminophenoxy) -benzoic acid, 1.025g (2.5 mmol) of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane and 20mL of N-methylpyrrolidone were added in this order to a dry 100 mL three-necked flask under nitrogen protection, magnetically stirred at room temperature, and after the monomers were completely dissolved, 2.22g (5 mmol) of 4, 4' - (hexafluoroisopropyl) diphthalic anhydride was added to the reaction flask and reacted at room temperature for 10 hours to form a highly viscous polyamic acid precursor. And then slowly dripping toluene into the reaction bottle, heating to 160-180 ℃, and keeping the temperature to continuously react for 6 hours. The resulting highly viscous polyimide solution was slowly poured into 150mL of methanol, filtered under suction, and the filamentous solid was collected, washed three times with methanol, and dried under vacuum at 80 ℃ for 5 hours. The resin No. 5 is to be tested for future use.
Example 6
Under nitrogen protection, 1.176 g (3.5 mmol) of 2, 5-bis (3-aminophenoxy) -benzoic acid, 0.615g (1.5 mmol) of 2, 2-bis [4- (4-aminophenoxy) phenyl ] and 20mL of N-methylpyrrolidone were added in this order to a dry 100 mL three-necked flask, and magnetically stirred at room temperature, after the monomers were completely dissolved, 1.55g (5 mmol) of 4, 4' -oxydiphthalic anhydride was added to the reaction flask and reacted at room temperature for 10 hours to form a highly viscous polyamic acid precursor. Then, a mixed solution of 3mL of triethylamine and 2.7mL of acetic anhydride was slowly added dropwise to the reaction flask, and the reaction was continued at room temperature for 24 hours. The resulting highly viscous polyimide solution was slowly poured into 150mL of methanol, filtered under suction, and the filamentous solid was collected, washed three times with methanol, and dried under vacuum at 80 ℃ for 7 hours. The resin No. 6 is to be tested for future use.
Example 7
Under the protection of nitrogen, 0.19 g (0.5 mmol) of 2, 5-bis (3-aminophenoxy) -1, 4-terephthalic acid, 1.44g (4.5 mmol) of 2,2 ' -difluoromethyl-4, 4 ' -benzidine and 20mL of N-methylpyrrolidone are sequentially added into a dry 100 mL three-necked flask, magnetic stirring is carried out at room temperature, after the monomers are completely dissolved, 1.55g (5 mmol) of 4,4 ' -oxydiphthalic anhydride is added into the reaction flask, and reaction is carried out for 10 hours at room temperature, so as to form a highly viscous polyamic acid precursor. And then slowly dripping toluene into the reaction bottle, heating to 160-180 ℃, and keeping the temperature to continuously react for 6 hours. The resulting highly viscous polyimide solution was slowly poured into 150mL of methanol, filtered under suction, and the filamentous solid was collected, washed three times with methanol, and dried under vacuum at 80 ℃ for 10 hours. The resin No. 7 is to be tested for future use.
Example 8
Under nitrogen protection, 1.71g (4.5 mmol) of 2, 5-bis (3-aminophenoxy) -1, 4-terephthalic acid, 0.146g (0.5 mmol) of 1, 3-bis (4-aminophenoxy) benzene and 25mL of N, N-dimethylacetamide were sequentially added to a dry 100 mL three-necked flask, magnetically stirred at room temperature, and after the monomers were completely dissolved, 2.22g (5 mmol) of 4, 4' - (hexafluoroisopropyl) diphthalic anhydride was added to the reaction flask and reacted at room temperature for 8 hours to form a highly viscous polyamic acid precursor. Then, a mixed solution of 3mL of triethylamine and 2.7mL of acetic anhydride was slowly added dropwise to the reaction flask, and the reaction was continued at room temperature for 24 hours. The highly viscous polyimide solution obtained was slowly poured into 150mL of methanol, filtered, collected as a filamentous solid, washed three times with methanol, dried under vacuum at 60 ℃ for 10 hours, and used as resin No. 8 to be tested for future use.
Example 9
Under nitrogen protection, 1.008g (3 mmol) of 2, 5-bis (3-aminophenoxy) -benzoic acid, 0.64g (2 mmol) of 2,2 ' -bis trifluoromethyl-4, 4 ' -benzidine and 20mL of gamma-butyrolactone were added in this order to a dry 100 mL three-necked flask, magnetically stirred at room temperature, and after the monomers were completely dissolved, 2.22g (5 mmol) of 4,4 ' - (hexafluoroisopropyl) diphthalic anhydride was added to the reaction flask and reacted at room temperature for 8 hours to form a highly viscous polyamic acid precursor. Then, a mixed solution of 3mL of triethylamine and 2.7mL of acetic anhydride was slowly added dropwise to the reaction flask, and the reaction was continued at room temperature for 24 hours. The resulting highly viscous polyimide solution was slowly poured into 150mL of methanol, filtered under suction, and the filamentous solid was collected, washed three times with methanol, and dried under vacuum at 80 ℃ for 7 hours. The resin No. 9 is to be tested for future use.
Example 10
0.672 g (2 mmol) of 2, 5-bis (4-aminophenoxy) -benzoic acid, 0.96g (3 mmol) of 2,2 ' -bistrifluoromethyl-4, 4 ' -benzidine and 20mL of N-methylpyrrolidone were added in this order to a dry 100 mL three-necked flask under nitrogen protection, stirred magnetically at room temperature, and after the monomers were completely dissolved, 1.55g (5 mmol) of 4,4 ' -oxydiphthalic anhydride was added to the reaction flask and reacted at room temperature for 6 hours to form a highly viscous polyamic acid precursor. Then, a mixed solution of 3mL of triethylamine and 2.7mL of acetic anhydride was slowly added dropwise to the reaction flask, and the reaction was continued at room temperature for 24 hours. The resulting highly viscous polyimide solution was slowly poured into 150mL of methanol, filtered under suction, and the filamentous solid was collected, washed three times with methanol, and dried under vacuum at 80 ℃ for 7 hours. The resin No. 10 is to be tested for future use.
Dissolving the 10 resins obtained in the embodiment in a solvent to prepare glue solutions with different solid contents, adding a commercial photo-acid generator diazonaphthoquinone sulfonate (DNQ) according to a certain proportion, filtering after all the resins are dissolved, standing and defoaming for more than 48 hours, carrying out spin coating exposure, and testing the sensitivity and the resolution. The formulations of the 10 resins for photoresist formulation are shown in table 1.
Table 1 shows the photoresist formulations prepared from 10 photosensitive resins in the examples and the test results
Claims (6)
1. A positive photosensitive polyimide resin and its preparation method, characterized by that the structure of polyimide has acid group-carboxyl that can be developed by alkali aqueous solution, the chemical structural formula of the positive photosensitive polyimide resin is as follows:
wherein R is any one of the following 4 structures:
Ar1is an intermediate structure of a dianhydride monomer, Ar2Is the intermediate structure of diamine monomer, x =0.1-0.9, and n = 5-200.
Ar above1The structures of (a) include, but are not limited to, the following 5:
in the formula, Ar1=
,
,
,
,
。
Ar above2The structures of (a) include, but are not limited to, the following 5:
Ar2=
，
，
，
，
。
2. the polyimide according to claim 1, wherein the polyimide has a structure having a carboxyl group as an acidic group developable with an alkaline aqueous solution. Wherein the carboxyl-containing diamine monomer participating in the preparation of the polyimide structure is any one of the following structures:
3. the photosensitive polyimide resin as claimed in claim 1, which is prepared by a method comprising the steps of:
adding a diamine monomer containing carboxyl, other diamine monomers containing no carboxyl, a dianhydride monomer and an organic solvent into a dry three-necked bottle in sequence under the protection of nitrogen, stirring for 2-12 hours at room temperature, then slowly dropwise adding a mixture of triethylamine and acetic anhydride into the reaction bottle, and continuing to react for 4-18 hours at room temperature. After the reaction was completed, the resulting highly viscous polymer solution was slowly poured into a large amount of methanol, and the precipitated solid was sufficiently washed with methanol and dried in a vacuum oven for 5 hours.
Or sequentially adding a diamine monomer containing carboxyl, other diamine monomers containing no carboxyl, a dianhydride monomer and an organic solvent into a dry three-necked bottle under the protection of nitrogen, stirring for 2-12 hours at room temperature, then continuously and slowly dripping toluene into the reaction bottle, heating to 160 ℃, keeping the temperature at 160 ℃, and continuously reacting for 4-8 hours to ensure that the toluene and the water are removed by azeotropy. After the reaction was complete, the resulting highly viscous polymer solution was taken.
4. The process according to claim 3, wherein the molar ratio of the diamine monomer having a carboxyl group to the diamine monomer having no carboxyl group is: 1:9-9:1.
5. The process according to claim 3, wherein the organic solvent is: one or more mixed solvents of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, Propylene Glycol Methyl Ether Acetate (PGMEA) and gamma-butyrolactone.
6. The method of claim 5, wherein the total concentration of dianhydride and diamine monomers in the organic solvent is: 5-40 w/v%.
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| CN1468391A (en) * | 2000-10-04 | 2004-01-14 | �ղ���ѧ��ҵ��ʽ���� | Positive photosensitive polyimide resin composition |
| CN1599884A (en) * | 2001-10-30 | 2005-03-23 | 钟渊化学工业株式会社 | Photosensitive resin composition and photosensitive films and laminates made by using the same |
| CN101218539A (en) * | 2005-07-05 | 2008-07-09 | 日立化成工业株式会社 | Photosensitive adhesive composition, and obtained adhesive film, adhesive sheet, semiconductor wafer with adhesive layer, semiconductor device and electronic part using the same |
| CN101395234A (en) * | 2006-03-03 | 2009-03-25 | 株式会社Pi技术研究所 | Photosensitive ink composition for screen printing and method of forming positive relief pattern with use thereof |
| CN101675386A (en) * | 2007-08-20 | 2010-03-17 | Lg化学株式会社 | Alkali developable photosensitive resin composition and dry film manufactured by the same |
| CN102985876A (en) * | 2010-07-14 | 2013-03-20 | 株式会社Lg化学 | Positive-type photosensitive resin composition and black bank of an organic light-emitting device including same |
| CN106842819A (en) * | 2016-12-28 | 2017-06-13 | 杭州福斯特光伏材料股份有限公司 | One kind is containing alkynyl monomers end-blocking and developer solution selects flexible positive type photosensitive polyimide resin composition |
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