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CN111303422A - Polyimide resin for positive photoresist and preparation method thereof - Google Patents

Polyimide resin for positive photoresist and preparation method thereof Download PDF

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Publication number
CN111303422A
CN111303422A CN201911146652.5A CN201911146652A CN111303422A CN 111303422 A CN111303422 A CN 111303422A CN 201911146652 A CN201911146652 A CN 201911146652A CN 111303422 A CN111303422 A CN 111303422A
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polyimide resin
hours
carboxyl
polyimide
room temperature
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不公告发明人
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Shanghai Jizi Technology Co Ltd
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Shanghai Jizi Technology Co Ltd
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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
    • 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
    • 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
    • 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
    • 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

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Abstract

The invention discloses a novel photosensitive polyimide resin for positive photoresist and a preparation method thereof, wherein the structural formula of the polyimide resin contains an acidic group-carboxyl, and the polyimide resin has certain solubility in an alkaline developing solution due to the existence of the carboxyl, and can be matched with diazonaphthoquinone sulfonate to prepare the alkali-developed positive polyimide photoresist. The photosensitive polyimide resin disclosed by the invention is simple in preparation process, mild in reaction condition and easy to amplify for production. Because the resin is fully imidized in the preparation process, high-temperature curing treatment is not needed during pattern photoetching, the photosensitive resin is not needed to be stored at low temperature, and development in alkaline aqueous solution is environment-friendly. The photoresist prepared from the polyimide resin has the advantages of high film retention rate and contrast, low curing temperature, good pattern resolution, room-temperature storage and the like. The infrared absorption spectrum of the polyimide resin is shown in the figure.

Description

Polyimide resin for positive photoresist and preparation method thereof
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 a polyimide structure has carboxyl and good alkali solubility, and the chemical structural formula of the positive photosensitive polyimide resin is as follows:
Figure 940623DEST_PATH_IMAGE001
wherein R is any one of the following structures:
(wherein Y is
Figure 417872DEST_PATH_IMAGE002
,
Figure 471279DEST_PATH_IMAGE003
,
Figure 842217DEST_PATH_IMAGE004
,
Figure 322877DEST_PATH_IMAGE005
,
Figure 21843DEST_PATH_IMAGE006
,
Figure 878941DEST_PATH_IMAGE007
Any one of them)
Figure 573227DEST_PATH_IMAGE008
，
Figure 755947DEST_PATH_IMAGE009
Figure 801263DEST_PATH_IMAGE010
，
Figure 602997DEST_PATH_IMAGE011
Figure 682949DEST_PATH_IMAGE012
，
Figure 770990DEST_PATH_IMAGE013
Figure 954802DEST_PATH_IMAGE014
，
Figure 153702DEST_PATH_IMAGE015
Figure 88160DEST_PATH_IMAGE016
，
Figure 347103DEST_PATH_IMAGE017
Figure 507957DEST_PATH_IMAGE018
，
Figure 244969DEST_PATH_IMAGE019
Ar1Is 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=
Figure 768354DEST_PATH_IMAGE020
,
Figure 729357DEST_PATH_IMAGE021
,
Figure 705403DEST_PATH_IMAGE022
,
Figure 652631DEST_PATH_IMAGE023
,
Figure 296102DEST_PATH_IMAGE024
。
Ar above2The structures of (a) include, but are not limited to, the following 5:
Ar2=
Figure 162427DEST_PATH_IMAGE025
，
Figure 891348DEST_PATH_IMAGE026
，
Figure 970163DEST_PATH_IMAGE027
，
Figure 874665DEST_PATH_IMAGE028
，
Figure 380732DEST_PATH_IMAGE029
。
the experimental procedure for carrying out the polymerization was as follows:
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:
Figure 128109DEST_PATH_IMAGE030
wherein the diamine monomer taking R as an intermediate structure is any one of the following structures:
(wherein Y is
Figure 10614DEST_PATH_IMAGE002
,
Figure 268158DEST_PATH_IMAGE003
,
Figure 210706DEST_PATH_IMAGE004
,
Figure 179799DEST_PATH_IMAGE005
,
Figure 600416DEST_PATH_IMAGE006
,
Figure 72986DEST_PATH_IMAGE007
Any one of them)
Figure 327381DEST_PATH_IMAGE031
，
Figure 252611DEST_PATH_IMAGE032
Figure 8078DEST_PATH_IMAGE033
，
Figure 335154DEST_PATH_IMAGE034
Figure 26029DEST_PATH_IMAGE035
，
Figure 438556DEST_PATH_IMAGE036
,
Figure 732134DEST_PATH_IMAGE037
Figure 913717DEST_PATH_IMAGE038
,
Figure 775494DEST_PATH_IMAGE039
Figure 675316DEST_PATH_IMAGE040
,
Figure 241427DEST_PATH_IMAGE041
，
Figure 808675DEST_PATH_IMAGE042
The chemical structural formula of the copolymerized diamine monomer is as follows:
Figure 434828DEST_PATH_IMAGE044
，
Figure 727007DEST_PATH_IMAGE045
，
Figure 831229DEST_PATH_IMAGE046
，
Figure 518562DEST_PATH_IMAGE047
，
Figure 315617DEST_PATH_IMAGE048
。
the chemical structure of the dianhydride monomer is as follows:
Figure 924453DEST_PATH_IMAGE049
，
Figure 504470DEST_PATH_IMAGE050
，
Figure 515151DEST_PATH_IMAGE051
，
Figure 14266DEST_PATH_IMAGE052
，
Figure 516922DEST_PATH_IMAGE053
。
the molar ratio of the carboxyl diamine monomer taking R as an intermediate structure to the copolyamine monomer is as follows: 1:1-1:0, and the molar ratio of the total diamine monomer to the dianhydride monomer is 0.9:1-1.1: 1. 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 an infrared spectrum of a photosensitive polyimide resin according to a preferred embodiment of the present invention;
FIG. 2 is a photograph of a lithographic pattern made of a polyimide photoresist according to a preferred embodiment of the present invention;
FIG. 3 is a photograph of a lithographic pattern made from another polyimide photoresist according to the 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
2.052g (4.5 mmol) of 4,4 '-bis (2-carboxy-4-aminophenoxy) biphenyl, 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 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 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 the protection of nitrogen, 0.228 g (0.5 mmol) of 4,4 '-bis (3-carboxy-4-aminophenoxy) biphenyl, 1.44g (4.5 mmol) of 2, 2' -bis trifluoromethyl-4, 4 '-benzidine and 20mL of N-methylpyrrolidone were added in sequence 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. 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
0.684 g (1.5 mmol) of 4,4 ' -bis (2-carboxy-5-aminophenoxy) biphenyl, 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 magnetically stirred at room temperature, 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, 1.14 g (2.5 mmol) of 4,4 ' -bis (3-carboxy-5-aminophenoxy) biphenyl, 1.295g (2.5 mmol) of 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane and 20mL of gamma butyrolactone were sequentially added to a dry 100 mL three-necked flask, magnetically stirred at room temperature, and after the monomers were completely dissolved, 1.61g (5 mmol) of 3,3 ', 4,4 ' -benzophenone tetracarboxylic dianhydride 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, and dried under vacuum at 80 ℃ for 6 hours. The resin No. 4 is to be tested for future use.
Example 5
Under nitrogen protection, 1.14 g (2.5 mmol) of 4,4 '-bis (3-amino-4-carboxyphenoxy) biphenyl, 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, 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 the protection of nitrogen, 1.596 g (3.5 mmol) of 4,4 '-bis (2-carboxy-3-aminophenoxy) biphenyl, 0.615g (1.5 mmol) of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane and 20mL of N-methylpyrrolidone were sequentially added 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
0.303 g (0.5 mmol) of 2, 2-bis [4- (2-carboxy 5-aminophenoxy) phenyl ] hexafluoropropane, 1.44g (4.5 mmol) of 2,2 ' -difluoromethyl-4, 4 ' -benzidine and 20mL of LN-methylpyrrolidone were sequentially added to a dry 100 mL three-necked flask under nitrogen atmosphere, 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. 7 is to be tested for future use.
Example 8
2.243g (4.5 mmol) of 2, 2-bis [4- (2-carboxy 5-aminophenoxy) phenyl ] propane, 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 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 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 the protection of nitrogen, 1.416g (3 mmol) of 4,4 '-bis (2-carboxy-4-aminophenoxy) diphenyl ether, 0.64g (2 mmol) of 2, 2' -bistrifluoromethyl-4, 4 '-benzidine and 20mL of gamma-butyrolactone 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 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
Under nitrogen protection, 0.944 g (2 mmol) of 4,4 '-bis (3-carboxy-4-aminophenoxy) diphenyl ether, 0.96g (3 mmol) of 2, 2' -bistrifluoromethyl-4, 4 '-benzidine and 20mL of N-methylpyrrolidone were sequentially added 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 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 formula of the photoresist prepared by 10 resins is shown in the table I.
Table A photoresist formulation prepared from 10 photosensitive resins in the examples and test results
Figure 962947DEST_PATH_IMAGE054

Claims (6)

1. A positive photosensitive polyimide resin and its preparation method, characterized by that the polyimide structure has carboxyl, have very good alkali solubility, the chemical structural formula of the positive photosensitive polyimide resin is as follows:
Figure RE-FDA0002317187440000011
wherein R is any one of the following structures:
(wherein Y is
Figure RE-FDA0002317187440000012
Any one of them)
Figure RE-FDA0002317187440000013
Figure RE-FDA0002317187440000021
Wherein Ar is1Is an intermediate structure of a dianhydride monomer, Ar2Is an intermediate structure of a diamine monomer, x is 0.1-0.9，n＝5-200。
Ar above1The structures of (a) include, but are not limited to, the following 5:
in the formula (I), the compound is shown in the specification,
Figure RE-FDA0002317187440000022
Figure RE-FDA0002317187440000023
ar above2The structures of (a) include, but are not limited to, the following 5:
Figure RE-FDA0002317187440000024
2. the polyimide according to claim 1, wherein the polyimide has a carboxyl group in its structure and has a good alkali solubility. Wherein the diamine monomer participating in the preparation of the polyimide structure is any one of the following structures:
(wherein Y is
Figure RE-FDA0002317187440000025
Any one of them)
Figure RE-FDA0002317187440000026
Figure RE-FDA0002317187440000031
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 5, 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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