CN113736082B - Polyimide resin for negative photoresist and negative photoresist comprising the same - Google Patents
Polyimide resin for negative photoresist and negative photoresist comprising the same Download PDFInfo
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- CN113736082B CN113736082B CN202110884547.2A CN202110884547A CN113736082B CN 113736082 B CN113736082 B CN 113736082B CN 202110884547 A CN202110884547 A CN 202110884547A CN 113736082 B CN113736082 B CN 113736082B
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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
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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
- C08G73/1067—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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- 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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0387—Polyamides or polyimides
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Abstract
The application provides a novel polyimide which is obtained by reacting an imidazole-containing diamine, a non-imidazole-containing diamine and dianhydride in the presence of a catalyst, a water scavenger and a solvent under the protection of inert gas. The application also provides negative photoresist prepared from the novel polyimide. The negative photoresist has good sensitivity and resolution.
Description
Technical Field
The application relates to the technical field of polymers, in particular to polyimide resin for negative photoresist and the negative photoresist containing the polyimide resin.
Background
Polyimide material is a functional material with extremely excellent performance, especially high temperature resistance, insulating property and dielectric property, so that the polyimide material is widely applied to the fields of military industry and aerospace; as a civil product, polyimide is widely used in the microelectronics field, wherein photosensitive polyimide (PSPI) is used as a buffer layer, a passivation layer, and an α -particle blocking layer of an integrated circuit. Polyimide for photoresist has become one of the three main uses of polyimide, in which polyimide film and polyimide liquid crystal aligning agent are juxtaposed.
Polyimide is used as a photoresist and is mainly classified into photodegradable (positive photoresist) and photocrosslinkable (negative photoresist), and currently commercially available photocrosslinkable polyimide is mainly classified into daily-series Hitachi-DuPont HD4000 series, toray Photonece and Fuji Durimide7000 series. The technical routes of the negative photoresist are that the side group of acrylic ester is connected on the precursor of polyamide acid, and after illumination, the double bond of acrylic ester is opened to crosslink under the action of an initiator, thereby forming a crosslinked structure which can not be dissolved and removed by a developing solution, and forming a pattern.
However, as described above, in the prior art, the main design concept of polyimide negative photoresist is mainly to introduce acrylate or allyl double bond and a sensitized benzophenone dianhydride system, and the formed crosslinking structure can cause the activity and the movement capability of the photoacid generator to be limited by a polymer main chain, so that the negative photoresist has low sensitivity and poor resolution, and the product quality is affected.
Therefore, it is highly desirable to provide a new polyimide negative photoresist to achieve higher sensitivity and resolution.
Disclosure of Invention
In order to solve the above problems, a first aspect of the present application provides a polyimide resin for a negative photoresist, wherein the polyimide resin has a chemical structure of the following formula I:
wherein x is 0.05-0.95, preferably 0.4-0.7; n is 5 to 200, preferably 8 to 60;
Ar 1 、Ar 2 each independently selected from the group consisting of:
R 1 selected from the group consisting of: R 3 selected from single bond, oxygen atom, sulfur atom, benzene ring, methylene, carbonyl, sulfonyl, isopropyl or trifluoroisopropyl,
R 2 Selected from the group consisting of:
preferably, the polyimide resin has a chemical structure of:
a second aspect of the present application provides a method of preparing a polyimide resin for a negative photoresist, comprising: reacting an imidazole-containing diamine, a non-imidazole-containing diamine and dianhydride in the presence of a catalyst, a water scavenger and a solvent under the protection of inert gas to obtain the polyimide resin;
wherein the catalyst is selected from triethylamine, pyridine or isoquinoline;
the water scavenger is toluene;
the solvent is selected from the group consisting of: n, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, propylene Glycol Methyl Ether Acetate (PGMEA), γ -butyrolactone;
the imidazolyl-containing diamine is selected from the group consisting of:
R 3 selected from single bond, oxygen atom, sulfur atom, benzene ring, methylene, carbonyl, sulfonyl, isopropyl or trifluoroisopropyl,
A third aspect of the present application provides a negative photoresist, wherein it comprises, in parts by weight:
100 parts by weight of a solvent;
10 to 30 parts by weight of the polyimide resin for negative photoresist as described in the first aspect;
1-10 parts by weight of a photoacid generator, preferably an acid generator capable of generating sulfonic acid; and
0.1-2 parts by weight of auxiliary agent.
Preferably, the negative photoresist comprises, in parts by weight:
100 parts by weight of a solvent;
15-25 parts by weight of the polyimide resin for negative photoresist as described in the first aspect;
1-9 parts by weight of a photoacid generator, preferably an acid generator capable of generating sulfonic acid; and
0.1 to 1 part by weight of an auxiliary agent.
In one embodiment, the solvent is selected from one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, m-cresol, p-cresol, propylene Glycol Methyl Ether Acetate (PGMEA), and gamma-butyrolactone.
In one embodiment, the photoacid generator is selected from one or more of sulfonium salts, iodonium salts, triazines, sulfonate compounds, and p-toluenesulfonic acid derivatives.
In one embodiment, the auxiliary agent is selected from one or more of a sensitizer, a antisolvent, and an acid quencher.
In one embodiment, the adjuvant is selected from one or more of triethanolamine, tripentylamine, and tri-n-dodecylamine.
A fourth aspect of the present application provides use of the polyimide resin for negative photoresist according to the first aspect in the preparation of negative photoresist.
The beneficial technical effects of the application are as follows:
the novel polyimide resin and the photoacid generator are matched for use, so that the novel negative polyimide photoresist can be obtained. After spin-coating exposure, the photoacid generator generates protons, the imidazolyl is protonated, the solubility of polyimide resin in a solvent is greatly reduced, and a negative photoresist image is obtained during development. Unlike available polyimide resin with side chain grafted vinyl and main chain of benzophenone as negative photoresist system, the negative polyimide photoresist has high sensitivity and high resolution.
Drawings
Fig. 1 is an infrared spectrum of polyimide resins of examples one to eight of the present application.
FIG. 2 is a lithographic pattern of a negative tone photoresist according to a first embodiment of the present application.
FIG. 3 is a lithographic pattern of a negative tone photoresist according to a second embodiment of the present application.
FIG. 4 is a lithographic pattern of a negative tone photoresist of a third embodiment of the application.
FIG. 5 is a lithographic pattern of a negative tone photoresist of a fourth embodiment of the application.
FIG. 6 is a lithographic pattern of a negative tone photoresist of a fifth embodiment of the application.
FIG. 7 is a lithographic pattern of a negative tone photoresist of a sixth embodiment of the application.
FIG. 8 is a lithographic pattern of a negative tone photoresist of embodiment seven of the present application.
FIG. 9 is a lithographic pattern of a negative tone photoresist of embodiment eight of the present application.
Detailed Description
Embodiment one:
to a dry and clean glass bottle was added 50ml of NMP, protected by nitrogen, followed by 4.92g of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane (12 mmol) and 1.344g (6 mmol) of 2- (4-aminophenyl) -5-aminobenzimidazole, after all had been dissolved, 3.860g (17.7 mmol) of pyromellitic dianhydride was slowly added in portions, reacted at room temperature and kept stirring for 12 hours, toluene was slowly added dropwise and the temperature was raised to 160℃and stirring was continued for 10 hours. Precipitating the obtained polymer solution into methanol, stirring and washing, and drying in a vacuum oven for 6 hours to obtain polyimide resin containing imidazolyl;
2g of the dried polyimide resin is dissolved in 10ml of solvent gamma-butyrolactone, 0.2g of acid generator TME-triazine and 0.05g of triethanolamine are added, and the mixture is uniformly dissolved to prepare a sample No. 1 to be tested.
The chemical structure of the polyimide resin is as follows:
embodiment two:
70ml of NMP, protected by nitrogen, were placed in a dry and clean glass bottle, followed by 0.82g of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane (2 mmol) and 6.656g (16 mmol) of 2,2' -bis (4-aminophenyl) -5,5' -bisbenzimidazole, after all had been dissolved, 7.734g (17.4 mmol) of 4,4' - (hexafluoroisopropyl) diphthalic anhydride were slowly added in portions, reacted at room temperature and kept stirring for 12 hours, toluene was slowly added dropwise and the temperature was raised to 160℃and stirring continued for 10 hours. Precipitating the obtained polymer solution into methanol, stirring and washing, and drying in a vacuum oven for 8 hours to obtain polyimide resin containing imidazolyl;
2g of the dried polyimide resin was dissolved in 10ml of NMP, and 0.4g of PIW-501 (Heraeus) as an acid generator and 0.1g of tripentylamine were added to prepare sample No. 2.
The chemical structure of the polyimide resin is as follows:
embodiment III:
in a dry and clean glass bottle, 60ml of NMP as solvent was added, nitrogen was introduced for protection, then 1.44g of 2,2' -bistrifluoromethyl-4, 4' -benzidine (5.4 mmol) was added to the flask, after all of which 2.353g (5.3 mmol) of 4,4' - (hexafluoroisopropyl) diphthalic anhydride was slowly added in portions and stirred at room temperature for 2 hours; then, 2.75g (6.6 mmol) of 2,2 '-bis (3-aminophenyl) -5,5' -bisbenzimidazole and 1.973g (6.1 mmol) of 3,3', 4' -benzophenone tetracarboxylic dianhydride were added thereto, the reaction was continued at room temperature with stirring for 12 hours, toluene was slowly added dropwise and the temperature was raised to 160℃with stirring for 10 hours. Precipitating the obtained polymer solution into methanol, stirring and washing, and drying in a vacuum oven for 8 hours to obtain polyimide resin containing imidazolyl;
2g of the dried polyimide resin was dissolved in 10ml of NMP solvent, followed by addition of 0.5g of the acid generator trifluoromethyl sulfonic triphenylsulfonium salt and 0.1g of tripentylamine, and the resulting mixture was uniformly dissolved to prepare sample No. 3.
The chemical structure of the polyimide resin is as follows:
embodiment four:
to a dry and clean glass bottle was added 50ml of solvent gamma-butyrolactone, protected by nitrogen, followed by 1.4g (7.0 mmol) of 4,4' -diaminodiphenyl ether and 2.912g (7.0 mmol) of 2,2' -bisbenzimidazole benzidine, after all had been dissolved 5.639g (12.7 mmol) of 4,4' - (hexafluoroisopropyl) diphthalic anhydride, was slowly added in portions, reacted at room temperature and kept stirring for 12 hours, toluene was slowly added dropwise and stirring was continued at 160℃for 10 hours. Precipitating the obtained polymer solution into methanol, stirring and washing, and drying in a vacuum oven for 8 hours to obtain polyimide resin containing imidazolyl;
2g of the dried polyimide resin was dissolved in 10ml of NMP, followed by addition of 0.8g of an acid generator, trifluoromethyl sulfonic triphenylsulfonium salt, and 0.1g of tri-n-dodecylamine, and the resulting mixture was uniformly dissolved to prepare sample No. 4.
The chemical structure of the polyimide resin is as follows:
fifth embodiment:
in a dry and clean glass bottle, 40ml of solvent PGMEA was added, nitrogen was purged, followed by 0.16g of 2,2' -bistrifluoromethyl-4, 4' -benzidine (0.5 mmol) and 3.952g (9.5 mmol) of 2,2' -bis (4-aminophenyl) -5,5' -bisbenzimidazole, after all had been dissolved, 4.396g (9.9 mmol) of 4,4' - (hexafluoroisopropyl) diphthalic anhydride were slowly added in portions, reacted at room temperature and kept stirring for 8 hours, toluene was slowly added dropwise and stirring was continued at 160℃for 12 hours. Precipitating the obtained polymer solution into methanol, stirring and washing, and drying in a vacuum oven for 8 hours to obtain polyimide resin containing imidazolyl;
2g of the dried polyimide resin is dissolved in 10ml of solvent NMP, 0.8g of acid generator TME-triazine and 0.05g of tri-n-dodecylamine are added to prepare sample No. 5.
The chemical structure of the polyimide resin is as follows:
example six:
into a dry and clean glass bottle, 50ml of NMP as a solvent was added, nitrogen was introduced for protection, then 5.166g of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane (12.6 mmol) and 2.747g (12.6 mmol) of phthalic anhydride were added, after stirring at room temperature for 2 hours, 2.246g (5.4 mmol) of 2,2 '-bisbenzimidazole benzidine was added, and after all of the solution had been dissolved, 1.674g (5.4 mmol) of 4,4' -oxydiphthalic anhydride was slowly added in portions, reacted at room temperature and kept stirring for 12 hours, toluene was slowly added dropwise and stirring was continued at 160℃for 12 hours. Precipitating the obtained polymer solution into methanol, stirring and washing, and drying in a vacuum oven for 6 hours to obtain polyimide resin containing imidazolyl;
3g of the dried polyimide resin was dissolved in 15ml of solvent gamma-butyrolactone, and 0.5g of acid generator PIW-501 (Heraeus) and 0.05g of tri-n-dodecylamine were added to prepare sample No. 6.
The chemical structure of the polyimide resin is as follows:
embodiment seven:
to a dry and clean glass bottle was added 30ml of NMP as a solvent, and the mixture was protected by nitrogen, followed by 1.813g (3.5 mmol) of 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane and 2.21g (6.5 mmol) of 1, 4-bis (5-aminobenzimidazolyl) benzene, and after all of them were dissolved, 3.157g (9.8 mmol) of 3,3'4,4' -benzophenone tetracarboxylic dianhydride was added slowly in portions, and the mixture was reacted at room temperature and kept under stirring for 12 hours, toluene was slowly added dropwise and the temperature was raised to 160℃and stirring was continued for 12 hours. Precipitating the obtained polymer solution into methanol, stirring and washing, and drying in a vacuum oven for 6 hours to obtain polyimide resin containing imidazolyl;
2g of the dried polyimide resin is dissolved in 10ml of solvent gamma-butyrolactone, 0.2g of acid generator N-hydroxyphthalimide p-methylbenzenesulfonate and 0.01g of tri-N-dodecylamine are added, and the mixture is uniformly dissolved to prepare a sample No. 7 to be detected.
The chemical structure of the polyimide resin is as follows:
example eight:
to a dry and clean glass bottle was added 60ml of solvent GBL, protected by nitrogen, followed by 2.92g of 1, 3-bis (4-aminophenoxy) benzene (10 mmol) and 4.32g (10 mmol) of 4,4 '-bis (5-aminobenzimidazolyl) diphenyl ether, after all had been dissolved, 8.821g (19.87 mmol) of 4,4' - (hexafluoroisopropyl) diphthalic anhydride was slowly added in portions, reacted at room temperature and kept stirring for 12 hours, toluene was slowly added dropwise and stirring was continued at 160℃for 12 hours. Precipitating the obtained polymer solution into methanol, stirring and washing, and drying in a vacuum oven for 6 hours to obtain polyimide resin containing imidazolyl;
2g of the dried polyimide resin is dissolved in 10ml of solvent gamma-butyrolactone, 0.2g of acid generator N-hydroxyphthalimide p-methylbenzenesulfonate and 0.02g of tri-N-dodecylamine are added, and the mixture is uniformly dissolved to prepare a sample No. 8 to be detected.
The chemical structure of the polyimide resin is as follows:
comparative example one
Imidazole polyimide homopolymer: to a dry and clean glass bottle was added 60ml of NMP, protected by nitrogen, followed by 4.32g (10 mmol) of 4,4 '-bis (5-aminobenzimidazolyl) diphenyl ether, after all had been dissolved, 4.18g (9.68 mmol) of 4,4' - (hexafluoroisopropyl) diphthalic anhydride was slowly added in portions, reacted at room temperature and kept stirring for 12 hours, toluene was slowly added dropwise and the temperature was raised to 160℃and stirring continued for 12 hours. Precipitating the obtained polymer solution into methanol, stirring and washing, and drying in a vacuum oven for 6 hours to obtain polyimide resin containing imidazolyl;
2g of the dried polyimide resin is dissolved in 20ml of solvent NMP, 0.3g of acid generator N-hydroxyphthalimide p-toluenesulfonate and 0.01g of tri-N-dodecylamine are added, and the mixture is uniformly dissolved to prepare a sample No. 9 to be tested.
The chemical structure of the polyimide resin is as follows:
comparative example two
Polyimide homopolymer containing no imidazolyl group: to a dry and clean glass bottle was added 50ml of solvent gamma-butyrolactone, protected by nitrogen, followed by 1.4g (7.0 mmol) of 4,4 '-diaminodiphenyl ether, after all dissolved, 3.092g (6.97 mmol) of 4,4' - (hexafluoroisopropyl) diphthalic anhydride was slowly added in portions, reacted at room temperature and kept stirring for 12 hours, toluene was slowly added dropwise and the temperature was raised to 160 ℃ for further stirring for 10 hours. The obtained polymer solution was precipitated into methanol, washed with stirring, and dried in a vacuum oven for 8 hours to obtain an imidazole group-containing polyimide resin, 2g of the dried resin was dissolved in 10ml of solvent NMP, followed by adding 0.8g of the acid generator trifluoromethylsulfonyl triphenylsulfonium salt and 0.05g of tri-n-dodecylamine, and after dissolving uniformly, a comparative sample No. 10 was prepared.
The chemical structure of the polyimide resin is as follows:
performance tests were performed on the above examples one to eight and comparative examples one and two, with the following results:
test method
1. The polymers were subjected to infrared spectroscopy (FT-IR) using a Perkin-Elmer Paragon 1000 Fourier transform infrared spectrophotometer to verify their chemical structure.
2. Thickness, photosensitivity and resolution test: and (3) spin coating the photoresist on a 4-inch silicon wafer at 800-1000 rpm, and baking at 110 ℃ for 300 seconds to obtain a film with the thickness of 5-10 microns. With i-line 365 nm exposure, the exposure intensity was 1500mJ/cm 2 Developing 5% -60% gray mask plate in cyclopentanone/NMP (1:1) mixed solution, and fixing in tetrahydrofuran to obtain photoetching pattern; the thickness, sensitivity and resolution were observed under an olympus metallographic microscope.
Test results
The test results are shown in Table one below
Comparison of thickness, sensitivity and resolution of samples after spin-on exposure of resist
As can be seen from the above table and the second to ninth drawings, compared with the first and second comparative examples, the photoresist of the present application has significantly better technical effects in terms of sensitivity and resolution, and significant technical progress is achieved.
Claims (14)
1. The negative photoresist is characterized by comprising the following components in parts by weight:
100 parts by weight of a solvent;
10-30 parts by weight of a polyimide resin for negative photoresist;
1-10 parts by weight of a photoacid generator; and
0.1-2 parts by weight of an auxiliary agent;
wherein the polyimide resin has the chemical structure of formula I:
wherein x is 0.05-0.95; n is 5-200;
Ar 1 、Ar 2 each independently selected from the group consisting of:
R 1 selected from the group consisting of:
R 3 selected from a single bond, an oxygen atom, a sulfur atom, a benzene ring, a methylene group, a carbonyl group, a sulfone group, an isopropyl group or a trifluoroisopropyl group;
R 2 selected from the group consisting of:
2. the negative photoresist according to claim 1, comprising, in parts by weight:
100 parts by weight of a solvent;
15-25 parts by weight of a polyimide resin for negative photoresist;
1-9 parts by weight of a photoacid generator; and
0.1 to 1 part by weight of an auxiliary agent.
3. The negative photoresist according to claim 1 or 2, wherein x is 0.4-0.7.
4. The negative photoresist according to claim 1 or 2, wherein n is 8-60.
5. The negative photoresist according to claim 1 or 2, wherein the polyimide resin has a chemical structure of:
6. the negative photoresist according to claim 1 or 2, wherein the solvent is selected from one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, m-cresol, p-cresol, propylene Glycol Methyl Ether Acetate (PGMEA) and γ -butyrolactone.
7. The negative photoresist according to claim 1 or 2, wherein the photoacid generator is an acid generator that generates sulfonic acid.
8. The negative photoresist according to claim 1 or 2, wherein the photoacid generator is selected from one or more of sulfonium salts, iodonium salts, triazines, sulfonate compounds, and p-toluenesulfonic acid derivatives.
9. The negative photoresist according to claim 1 or 2, wherein the auxiliary agent is selected from one or more of a sensitizer, a antisolvent, and an acid quencher.
10. The negative photoresist according to claim 1 or 2, wherein the auxiliary agent is selected from one or more of triethanolamine, tripentylamine, and tri-n-dodecylamine.
11. Use of a polyimide resin for a negative photoresist in the preparation of a negative photoresist, wherein the polyimide resin has the chemical structure of formula I:
wherein x is 0.05-0.95; n is 5-200;
Ar 1 、Ar 2 each independently selected from the group consisting of:
R 1 selected from the group consisting of:
R 3 selected from a single bond, an oxygen atom, a sulfur atom, a benzene ring, a methylene group, a carbonyl group, a sulfone group, an isopropyl group or a trifluoroisopropyl group;
R 2 selected from the group consisting of:
12. use according to claim 11, wherein x is 0.4-0.7.
13. Use according to claim 11, wherein n is 8-60.
14. The use according to claim 11, wherein the polyimide resin has the chemical structure:
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| CN105330860A (en) * | 2015-12-01 | 2016-02-17 | 常州市尚科特种高分子材料有限公司 | Thermoplastic polyimide resin powder and preparation method thereof |
| CN108727587A (en) * | 2018-06-26 | 2018-11-02 | 同济大学 | A kind of heat-proof polyimide of the ring structure containing imidazolyl aromatic and preparation method thereof |
| JP2020055930A (en) * | 2018-09-29 | 2020-04-09 | 日鉄ケミカル＆マテリアル株式会社 | Polyamic acid, polyimide, resin film, metal-clad laminate, and method of manufacturing the same |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004285129A (en) * | 2003-03-19 | 2004-10-14 | Nippon Zeon Co Ltd | Photosensitive polyimide precursor, photosensitive polyimide resin composition and method for manufacturing semiconductor element using the resin composition |
| CN101921483A (en) * | 2010-09-07 | 2010-12-22 | 东华大学 | Polybenzimidazole imide membrane and preparation method thereof |
| CN105330860A (en) * | 2015-12-01 | 2016-02-17 | 常州市尚科特种高分子材料有限公司 | Thermoplastic polyimide resin powder and preparation method thereof |
| CN108727587A (en) * | 2018-06-26 | 2018-11-02 | 同济大学 | A kind of heat-proof polyimide of the ring structure containing imidazolyl aromatic and preparation method thereof |
| JP2020055930A (en) * | 2018-09-29 | 2020-04-09 | 日鉄ケミカル＆マテリアル株式会社 | Polyamic acid, polyimide, resin film, metal-clad laminate, and method of manufacturing the same |
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