Chemically amplified polyimide precursor and photoresist composition prepared from same

Abstract

The invention discloses a chemical amplification type polyimide precursor and a photoresist composition prepared from the chemical amplification type polyimide precursor. The structure of the chemical amplification type polyimide precursor is shown as a general formula (1). The # imgabs0 # photoresist composition is prepared from the following raw materials in parts by weight: 8 to 50 parts of the chemical amplification type polyimide precursor, 0.025 to 2 parts of a photoacid generator, 0.01 to 5 parts of an additive and 40 to 91 parts of a solvent. According to the method, a chemical amplification technology is adopted, the dissolution contrast between the exposure area and the non-exposure area of the photoresist can be effectively improved, the contrast ratio is improved, so that the high resolution and the high film retention rate of the developing morphology are ensured, the chemical amplification adopts photoacid production, then acidolysis groups on the resin are catalyzed for deprotection, the efficiency is high, the precision is high, and the high sensitivity can be well considered.

Description

Technical Field

[0001] The present invention relates to the technical field of functional polymer materials, and particularly to a chemically amplified polyimide precursor and a photoresist composition prepared therefrom. Background Art

[0002] Due to its unique aromatic ring conjugation and imide ring structure, polyimide exhibits good heat resistance, high insulation, chemical resistance, and good mechanical properties. It is widely used in the surface passivation layer, stress buffer layer, and interlayer insulation layer of semiconductor devices; it also has important application values in signal line distribution, α-particle shielding layer, micro solder ball process, stress buffer layer of plastic encapsulated circuits, flexible packaging substrates, etc. in advanced semiconductor packaging (BGA, CSP, SiP, WLP, etc.); at the same time, in display devices such as organic EL display devices or liquid crystal display devices, photosensitive polyimide resins are widely used in the planarization layer and pixel definition layer of the display device to improve interlayer insulation and reduce display color difference, and the polyimide film layer has excellent force, thermal, and electrical properties, playing an important role in the preparation of OLED.

[0003] Polyimide precursor photoresist is a key functional material required in the panel Array process and IC packaging process. Since the panel process is a large-area operation with high requirements for the beat, and the IC packaging film is relatively thick, a large exposure energy and development time are required to meet the corresponding lithography requirements, which reduces the processing efficiency. Whether it is panel or IC manufacturing, the sensitivity of the photoresist sample has a crucial impact on improving work efficiency. Moreover, with industrial upgrading, there are higher constraints on product performance, and the process is becoming increasingly miniaturized. High-resolution topography can achieve better via wiring. Seeking a suitable path to balance the high sensitivity and high resolution of the photoresist has become an important development direction for polyimide precursor photoresists.

[0004] Currently, conventional polyimide precursor photoresists are prepared by mixing an alkali-soluble polyimide precursor with a photosensitizer, additives, and a solvent. The prepared photoresist samples usually sacrifice a part of the film retention rate and resolution performance when considering sensitivity. This is because the above-mentioned polyimide precursor photoresist is a non-chemically amplified photoresist. When increasing the sensitivity by increasing the alkali-soluble component, the dissolution contrast between the exposed and unexposed areas will be reduced. It is difficult to be applied under the process requirements of higher resolution. Summary of the Invention

[0005] In view of the above problems existing in the prior art, the present invention provides a chemically amplified polyimide precursor and a photoresist composition prepared therefrom. The chemically amplified polyimide precursor of the present invention is mixed with a photoacid generator, an additive, and a solvent to form a polyimide chemically amplified photoresist composition. Compared with the traditional polyimide precursor photoresist, this photoresist has higher sensitivity, higher resolution, and higher film retention rate.

[0006] The technical solution of the present invention is as follows:

[0007] The first object of the present invention is to provide a chemically amplified polyimide precursor, and the structure of the chemically amplified polyimide precursor is shown in the general formula (1):

[0008]

[0009] In the general formula (1), Ar1 represents a dianhydride residue; Ar2 represents a diamine residue; Ar3 represents a dianhydride residue; Ar4 represents a diamine residue; m is an integer from 5 to 3000; n is an integer from 1 to 2000;

[0010] In the general formula (1), R1 independently represents one or more of hydrogen, an alkyl or aromatic group of C 1-10 and the structure shown in the general formula (2);

[0011]

[0012] In the general formula (2), Ar5 represents an alkylene or arylene group of C 1-10 ; p is 2 or 3; in the structure represented by R1, the proportion of the structure shown in the general formula (2) is ≥20%;

[0013] R2 represents hydrogen or an acid-decomposable group, and the proportion of the number of acid-decomposable groups is 15-75%.

[0014] In an embodiment of the present invention, in the chemically amplified polyimide precursor, it satisfies: m / (m + n) ≥ 50%.

[0015] In an embodiment of the present invention, Ar1 and Ar3 respectively represent dianhydride residues obtained by removing 2 acid anhydride groups from dianhydrides, Ar l, Ar3s are the same or different; the dianhydride is any one of the following structures: pyromellitic dianhydride (PMDA), 3,3,3′,4′-biphenyltetracarboxylic dianhydride (s-BPDA), 2,3,3′,4′-biphenyltetracarboxylic dianhydride (α-BPDA), 4,4'-oxydiphthalic anhydride (ODPA), 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA), p-phenylene-bis(trimellitate) dianhydride (TAHQ), 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride (BSDA), cyclobutanetetracarboxylic dianhydride (CBDA), cyclohexanetetracarboxylic dianhydride (HPMDA).

[0016] In one embodiment of the present invention, Ar2 and Ar4 respectively represent the residues obtained by removing two amino groups from the diamine, and Ar2 and Ar4 are the same or different; the diamine is a hydroxyl-containing diamine or a non-hydroxyl-containing diamine.

[0017] In one embodiment of the present invention, the hydroxylamine diamine is one or more of 2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2'-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis[3-(4-aminobenzamido)-4-hydroxyphenyl]propane, 2,2-bis[3-(4-aminobenzamido)-4-hydroxyphenyl]sulfonyl, 2,2-bis[3-(4-aminobenzamido)-4-hydroxyphenyl]ether, 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane, 2,2-bis[3-(4-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane, N-(2-hydroxy-5-amino)phenyl-3-aminobenzamide, N-(5-amino-2-hydroxyphenyl)-4-[2-[4-[(4-aminophenyl)carbamoyl]phenyl]propan-2-yl]benzamide, N-(5-amino-2-hydroxyphenyl)-4-[2-[4-[(4-aminophenyl)carbamoyl]phenyl]sulfon-2-yl]benzamide, N-(5-amino-2-hydroxyphenyl)-4-[2-[4-[(4-aminophenyl)carbamoyl]phenyl]ether-2-yl]benzamide, and N-(5-amino-2-hydroxyphenyl)-4-[2-[4-[(4-aminophenyl)carbamoyl]phenyl]hexafluoropropan-2-yl]benzamide;The hydroxyl group-free diamine is one or more of 1,4-phenylenediamine (PDA), m-phenylenediamine (m-PDA), o-phenylenediamine (o-PDA), 4,4'-diaminodiphenyl ether (ODA), 4,4'-diamino-p-terphenyl (DATP), 4,4'-diaminodiphenylmethane (MDA), 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB), 4-aminophenyl 4-aminobenzoate (APAB), 1,4-bis(4'-aminophenoxy)benzene (1,4,4-APB), 1,3-bis(4'-aminophenoxy)benzene (1,3,4-APB), 1,3-bis(3'-aminophenoxy)benzene (1,3,3-APB), 2,2-bis(4-(4-aminophenoxy)phenyl)propane (BAPP), 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl ether (6FODA), 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (TFMB), 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (HFBAPP), 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane (SIDA), N,N'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis(6-hydroxy-3,1-phenylene)]bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxamide) (6FAP-ATA), N-[5-[3-[(1,3-dioxo-2-benzofuran-5-carbonyl)amino]-4-hydroxyphenyl]sulfonyl-2-hydroxyphenyl]-1,3-dioxo-2-benzofuran-5-carboxamide (6FAP-ASA).;

[0018] In one embodiment of the present invention, the structure represented by the general formula (2) is any one of the following structures:

[0019]

[0020] Wherein, R2 represents H or any one of the following structures:

[0021]

[0022] In one embodiment of the present invention, Ar5 represents a C1-10 alkylene or arylene group.

[0023] Preferably, the structure represented by Ar5 is: methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, isobutylene, isopentylene, neopentylene, 2-methylpentylene, 3-methylenepentane, 2,2-dimethylbutylene, tert-butylene, cyclohexylene, phenylene, phenylmethyl, phenylethyl, phenylpropyl.

[0024] In one embodiment of the present invention, R1 independently represents hydrogen, an alkyl group having 1 to 10 carbon atoms, or an aromatic group.

[0025] Preferably, the structure represented by R1 is: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isobutyl, isopentyl, neopentyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl, tert-butyl, cyclohexyl, phenyl, benzyl, phenethyl, phenylpropyl.

[0026] In one embodiment of the present invention, the weight-average molecular weight of the polyimide precursor is 1000 - 150000 g / mol; the dissolution rate (ADR) in a 2.38% aqueous solution of tetramethylammonium hydroxide is 0.1 - 50 Å / second.

[0027] Preferably, the weight-average molecular weight of the polyimide precursor is 10000 - 100000 g / mol; the dissolution rate (ADR) in a 2.38% aqueous solution of tetramethylammonium hydroxide is 0.1 - 10 Å / second.

[0028] The second object of the present invention is to provide a photoresist composition prepared from the above chemically amplified polyimide precursor. The raw materials of the photoresist composition and the weight parts of each raw material are: 8 - 50 parts of the chemically amplified polyimide precursor, 0.025 - 2 parts of a photoacid generator, 0.01 - 5 parts of an additive, and 40 - 91 parts of a solvent.

[0029] In one embodiment of the present invention, the photoacid generator is any one of the following structures:

[0030]

[0031] In one embodiment of the present invention, the additive is one or more of a leveling agent, a quencher, and a curing agent.

[0032] In one embodiment of the present invention, the leveling agent is a commercial acrylic, silicone, or fluorocarbon compound.

[0033] Preferably, the leveling agent can be selected from commercial products produced by BYK of Germany, DIC Corporation, and Shin-Etsu Chemical Co., Ltd., such as: BYK 310, BYK 315, BYK 320, BYK 325, BYK 331, BYK333, BYK 358N, BYK 3550, BYK 3560, F554, F563, R40, R41, KP341, etc.

[0034] In one embodiment of the present invention, the quencher is preferably one or more of ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, triethanolamine, tripropylamine, triethoxyethanolamine, trioctylamine, tributylamine, trimethoxyethoxymethylethylamine, tetramethylammonium hydroxide, polyquaternium base, diaminodiphenyl sulfone, diaminodiphenyl methane, m-phenylenediamine, dicyandiamide, imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole.

[0035] In one embodiment of the present invention, the curing agent can be any one of the following structural compounds:

[0036]

[0037] Wherein R independently represents H or -CH2OCH3; in each compound, at least 2 Rs are -CH2OCH3.

[0038] In one embodiment of the present invention, the solvent is one or more of ketone solvents, ester solvents, ether solvents, aromatic hydrocarbon solvents, and other solvents.

[0039] Preferably, the solvent is one or more of propylene glycol methyl ether acetate, propylene glycol monoacetate, ethylene glycol methyl ether acetate, diethylene glycol, propylene glycol methyl ether, propylene glycol monoethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, butyl acetate, neopentyl acetate, ethyl lactate, methyl ethyl ketone, methyl isobutyl ketone, γ-butyrolactone, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide.

[0040] The third object of the present invention is to provide a photosensitive cured film prepared from the above-mentioned photoresist composition, which is cured from the photoresist composition and is suitable for the surface protective film or interlayer insulating film of semiconductor elements, the insulating layer of organic light-emitting elements or the insulating layer of thin-film transistors.

[0041] The beneficial technical effects of the present invention are as follows:

[0042] The chemically amplified polyimide precursor of the present invention contains acid-decomposable groups, which can ensure that after the photoacid generator in the exposed area generates acid, it catalyzes the polymer to deprotect, so that a strong dissolution contrast is formed between the exposed area and the unexposed area. The photoacid generator is sensitive to light and has high precision, ensuring the resolution of the photoresist.

[0043] For the chemically amplified polyimide precursor of the present invention, the dissolution rate in the alkaline solution in the unexposed area is extremely low, ensuring the film retention rate.

[0044] The chemically amplified polyimide precursor of the present invention uses phenolic hydroxyl groups as the protecting entity instead of carboxyl groups. This is considered in terms of the edge roughness after development. The acidity of carboxyl groups is too high, and a small proportion of the group ratio can achieve dissolution, resulting in edge pits being easily formed after development. In contrast to carboxyl groups, in order to achieve the same acidity level, the group ratio required for phenolic hydroxyl groups will be several times or even dozens of times that of carboxyl groups, so as to be more evenly distributed on the entire polymer chain, and the development boundary region is more gentle, which is also an important factor in ensuring resolution.

[0045] A large number of side-chain phenolic hydroxyl groups adopted by the present invention, on the one hand, ensure sufficient reactive sites, and on the other hand, prevent the reactive sites from being easily embedded inside the polymer, improving the degree of acidolysis reaction in the exposed area, thereby obtaining high sensitivity.

[0046] The present invention adopts chemically amplified technology, which can effectively improve the dissolution contrast between the exposed and unexposed areas of the photoresist, enhance the contrast, thereby ensuring high resolution and high film retention rate of the developed morphology. And the chemically amplified technology uses photoacid generation and then catalyzes the deprotection of the acidolysis groups on the resin, with high efficiency and accuracy, and can well balance high sensitivity. Brief Description of the Drawings

[0047] Figure 1 It is the picture of the best resolution of the photoresist composition in Application Example 1 of the present invention;

[0048] Figure 2 It is the picture of the best resolution of the photoresist composition in Comparative Application Example 1 of the present invention. Detailed Embodiments

[0049] The present invention will be specifically described below in conjunction with the drawings and embodiments.

[0050] Example 1

[0051] A preparation method of a chemically amplified polyimide precursor includes the following steps:

[0052] In a 250 mL three-necked round-bottom flask equipped with a mechanical stirrer and a condenser, 50 mmol of 4,4'-oxydiphthalic anhydride (ODPA), 70 mmol of 3,4,5-trihydroxy-1-benzoylaminoethanol, 222.5 mmol of pyridine, and 50 g of anhydrous N-methylpyrrolidone (NMP) were added. The mixture was heated to 90 °C and stirred at this temperature for 10 h. After cooling to room temperature, 65 g of NMP was added. The reaction mixture was cooled to 0 °C using an ice bath, and 100 mmol of phenylphosphonic dichloride was slowly added using an addition funnel. The mixture was stirred at room temperature for 2 h and then cooled to 0 °C. Then, 50 mmol of 2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was added, and the reaction mixture was stirred at 0 °C for 1 h and at 50 °C for 10 h. Subsequently, 33 mmol of N,N-dimethylformamide dimethyl acetal was dropped in, and the reaction continued for 2 h. The resulting viscous solution was precipitated in a 1000 mL 1:1 (v / v) methanol / H2O mixture. The polymer was collected by filtration, washed three times with deionized water, and vacuum dried at 60 °C for 24 h to obtain a solid powder polymer A.

[0053] 20 g of polymer A was dissolved in 80 g of NMP and placed in a 250 mL three-necked round-bottom flask equipped with a mechanical stirrer. 0.0573 mol of di-tert-butyl dicarbonate (DBDC) (corresponding to 45% of the molar amount of hydroxyl groups in polymer A) and 0.00254 mol of DMAP were added, and the mixture was stirred at room temperature for 8 h. The reaction solution was dispersed in 5 L of deionized water, the solid was precipitated, filtered, and vacuum dried to obtain a primary polyimide precursor resin. It was dissolved in tetrahydrofuran to form a homogeneous solution, and residual metal or non-metal ions were removed by adsorption with anion and cation resins. Then, it was dispersed in 5 L of deionized water, the solid was precipitated, filtered, and vacuum dried to obtain a chemically amplified polyimide precursor 1.

[0054] 1 1H-NMR showed that a chemically amplified polyimide precursor 1 with 43% of phenolic hydroxyl groups protected by tert-butoxycarbonyl was obtained. Its Mw = 8472 g / mol and ADR = 1.9 A / s.

[0055] Example 2

[0056] A method for preparing a chemically amplified polyimide precursor, comprising the following steps:

[0057] In a 250 mL three-necked round-bottom flask equipped with a mechanical stirrer and a condenser, 50 mmol of 4,4′-(hexafluoroisopropylidene) diphthalic anhydride (6FDA), 65 mmol of 2,4,6-trihydroxy-1-benzamidylethanol, 222.5 mmol of pyridine and 50 g of anhydrous N-methylpyrrolidone (NMP) were added. The mixture was heated to 90 °C and stirred at this temperature for 10 h. After cooling to room temperature, 65 g of NMP was added. The reaction mixture was cooled to 0 °C with an ice bath. 100 mmol of phenylphosphonic dichloride was slowly added using an addition funnel. The mixture was stirred at room temperature for 2 h and then cooled to 0 °C. Then 50 mmol of 2,2'-dimethyl-4,4′-diaminobiphenyl (m-TB) was added. The reaction mixture was stirred at 0 °C for 1 h and then at 80 °C for 10 h. Subsequently, 37 mmol of N,N-dimethylformamide dimethyl acetal was added dropwise and the reaction continued for 2 h. The resulting viscous solution was precipitated in 1000 mL of a 1:1 (v / v) methanol / H2O mixture. The polymer was collected by filtration, washed three times with deionized water, and dried in vacuo at 60 °C for 24 h to obtain a solid powder polymer B.

[0058] 20 g of polymer B was dissolved in 80 g of NMP and placed in a 250 mL three-necked round-bottom flask equipped with a mechanical stirrer. 0.0480 mol of di-tert-butyl dicarbonate (DBDC) (corresponding to 38% of the molar amount of hydroxyl groups in polymer B) and 0.00254 mol of DMAP were added. The mixture was stirred at room temperature for 8 h. The reaction solution was dispersed in 5 L of deionized water, and the solid was precipitated, filtered, and dried in vacuo to obtain a primary polyimide precursor resin. It was dissolved in tetrahydrofuran to form a homogeneous solution, and residual metal or non-metal ions were removed by adsorption with anion and cation resins. Then it was dispersed in 5 L of deionized water, the solid was precipitated, filtered, and dried in vacuo to obtain a chemically amplified polyimide precursor 2.

[0059] 1 1H-NMR showed that a chemically amplified polyimide precursor 2 with 35% of the phenolic hydroxyl groups protected by tert-butoxycarbonyl was obtained. Its Mw = 72539 g / mol and ADR = 0.5 A / s.

[0060] Example 3

[0061] A preparation method of a chemically amplified polyimide precursor, comprising the following steps:

[0062] In a 250 mL three-necked round-bottom flask equipped with a mechanical stirrer and a condenser, 50 mmol of 4,4'-oxydiphthalic anhydride (ODPA), 78 mmol of 2,3,4-trihydroxy-1-benzamidomethyl alcohol, 222.5 mmol of pyridine, and 50 g of anhydrous N-methylpyrrolidone (NMP) were added. The mixture was heated to 90 °C and stirred at this temperature for 10 h. After cooling to room temperature, 65 g of NMP was added. The reaction mixture was cooled to 0 °C in an ice bath, and 100 mmol of phenylphosphonic dichloride was slowly added using an addition funnel. The mixture was stirred at room temperature for 2 h and then cooled to 0 °C. Then, 53 mmol of 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane was added, and the reaction mixture was stirred at 0 °C for 1 h and at 60 °C for 10 h. Subsequently, 25 mmol of N,N-dimethylformamide diethyl acetal was dropped in, and the reaction continued for 2 h. The resulting viscous solution was precipitated in a 1000 mL methanol / H2O mixture (1:1, v / v). The polymer was collected by filtration, washed three times with deionized water, and dried in vacuo at 60 °C for 24 h to obtain a solid powder polymer C.

[0063] 20 g of polymer C was dissolved in 80 g of NMP and placed in a 250 mL three-necked round-bottom flask equipped with a mechanical stirrer. 0.00109 mmol of pyridinium p-toluenesulfonate and 0.0435 mmol of ethyl vinyl ether (corresponding to 40% of the molar amount of hydroxyl groups in polymer C) were weighed and added to the reaction flask. The temperature was maintained at 25 °C, and the reaction time was 10 h. The polymer solution was dispersed in a 5 L aqueous solution containing 0.0013 mmol of triethylamine, and the solid was precipitated, filtered, and dried in vacuo to obtain a primary polyimide precursor resin. It was dissolved in tetrahydrofuran to form a homogeneous solution, and residual metal or non-metal ions were removed by adsorption with anion and cation resins. Then, it was dispersed in 5 L of deionized water, and the solid was precipitated, filtered, and dried in vacuo to obtain a chemically amplified polyimide 3.

[0064] 1 1H-NMR showed that a chemically amplified polyimide precursor 3 with 39% of phenolic hydroxyl groups protected by ethyl vinyl was obtained. Its Mw = 29829 g / mol and ADR = 1.3 A / s.

[0065] Example 4

[0066] A method for preparing a chemically amplified polyimide precursor, comprising the following steps:

[0067] In a 250 mL three-necked round-bottom flask equipped with a mechanical stirrer and a condenser, 50 mmol of 3,3′,4,4′-benzophenone tetracarboxylic dianhydride (BTDA), 85 mmol of 3,4-dihydroxy-1-benzamidocyclohexanol, 222.5 mmol of pyridine, and 50 g of anhydrous N-methylpyrrolidone (NMP) were added. The mixture was heated to 90 °C and stirred at this temperature for 10 h. After cooling to room temperature, 65 g of NMP was added, and the reaction mixture was cooled to 0 °C in an ice bath. 100 mmol of phenylphosphonic dichloride was slowly added using an addition funnel, and the mixture was stirred at room temperature for 2 h and then cooled to 0 °C. Then, 53 mmol of N-(5-amino-2-hydroxyphenyl)-4-[2-[4-[(4-aminophenyl)carbamoyl]phenyl]-hexafluoropropan-2-yl]benzamide was added. The reaction mixture was stirred at 0 °C for 1 h and then at 60 °C for 10 h. Subsequently, 17 mmol of N,N-dimethylformamide dimethyl acetal was dropped in, and the reaction continued for 2 h. The resulting viscous solution was precipitated in a 1000 mL methanol / H2O mixture (1:1, v / v). The polymer was collected by filtration, washed three times with deionized water, and dried in vacuo at 60 °C for 24 h to obtain a solid powder polymer D.

[0068] 20 g of polymer D was dissolved in 80 g of NMP and placed in a 250 mL three-necked round-bottom flask equipped with a mechanical stirrer. 0.00074 mmol of pyridinium p-toluenesulfonate and 0.02825 mmol of cyclohexyl vinyl ether (corresponding to 38% of the molar amount of hydroxyl groups in polymer D) were weighed and added to the reaction flask. The temperature was maintained at 25 °C, and the reaction time was 10 h. The polymer solution was dispersed in a 5 L aqueous solution containing 0.00089 mmol of triethylamine, and the solid was precipitated, filtered, and dried in vacuo to obtain a primary polyimide precursor resin. It was dissolved in tetrahydrofuran to form a homogeneous solution, and residual metal or non-metal ions were removed by adsorption with anion and cation resins. Then, it was dispersed in 5 L of deionized water, and the solid was precipitated, filtered, and dried in vacuo to obtain a polyimide chemically amplified polyimide precursor 4.

[0069] 1 1H-NMR showed that a chemically amplified polyimide precursor 4 with 37% of phenolic hydroxyl groups protected by cyclohexyl vinyl was obtained. Its Mw = 55980 g / mol and ADR = 0.2 A / s.

[0070] Example 5

[0071] A preparation method of a chemically amplified polyimide precursor, comprising the following steps:

[0072] In a 250 mL three-necked round-bottom flask equipped with a mechanical stirrer and a condenser, 50 mmol of 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), 70 mmol of 2,6-dihydroxy-1-benzamidylethanol, 222.5 mmol of pyridine, and 50 g of anhydrous N-methylpyrrolidone (NMP) were added. The mixture was heated to 90 °C and stirred at this temperature for 10 h. After cooling to room temperature, 65 g of NMP was added, and the reaction mixture was cooled to 0 °C in an ice bath. 100 mmol of phenylphosphonic dichloride was slowly added using an addition funnel. The mixture was stirred at room temperature for 2 h and then cooled to 0 °C. Then, 60 mmol of N,N′-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis(6-hydroxy-3,1-phenylene)]bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxamide) (6FAP-ATA) was added. The reaction mixture was stirred at 0 °C for 1 h and at room temperature for 10 h. Subsequently, 33 mmol of N,N-dimethylformamide diethyl acetal was dropped in, and the reaction continued for 2 h. The resulting viscous solution was precipitated in 1000 mL of a 1:1 (v / v) methanol / H2O mixture; the polymer was collected by filtration, washed three times with deionized water, and vacuum-dried at 60 °C for 24 h to obtain a solid powder polymer E.

[0073] 20 g of polymer E was dissolved in 80 g of NMP and placed in a 250 mL three-necked round-bottom flask equipped with a mechanical stirrer. 0.00093 mmol of pyridinium p-toluenesulfonate and 0.0328 mmol of ethyl vinyl ether (corresponding to 35% of the molar amount of hydroxyl groups in polymer E) were weighed and added to the reaction kettle. The temperature was maintained at 25 °C, and the reaction time was 10 h. The polymer solution was dispersed in 5 L of an aqueous solution containing 0.0011 mmol of triethylamine, and the solid was precipitated, filtered, and vacuum-dried to obtain a primary polyimide precursor resin; it was dissolved in tetrahydrofuran to form a homogeneous solution, and residual metal or non-metal ions were removed by adsorption with anion and cation resins. Then, it was dispersed in 5 L of deionized water, and the solid was precipitated, filtered, and vacuum-dried to obtain a chemically amplified polyimide precursor 5.

[0074] 1 1H-NMR showed that a chemically amplified polyimide precursor 5 with 33% of phenolic hydroxyl groups protected by ethyl vinyl was obtained. Its Mw = 3412 g / mol and ADR = 27 A / s.

[0075] Example 6

[0076] A preparation method of a chemically amplified polyimide precursor includes the following steps:

[0077] In a 250 mL three-necked round-bottom flask equipped with a mechanical stirrer and a condenser, 50 mmol of 3,3′,4,4′-benzophenone tetracarboxylic dianhydride (BTDA), 85 mmol of 3,5-dihydroxy-1-benzamidobenzyl alcohol, 222.5 mmol of pyridine, and 50 g of anhydrous N-methylpyrrolidone (NMP) were added. The mixture was heated to 90 °C and stirred at this temperature for 10 h. After cooling to room temperature, 65 g of NMP was added. The reaction mixture was cooled to 0 °C in an ice bath, and 100 mmol of phenylphosphonic dichloride was slowly added using an addition funnel. The mixture was stirred at room temperature for 2 h and then cooled to 0 °C. Then, 60 mmol of 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl (TFMB) was added. The reaction mixture was stirred at 0 °C for 10 h, and then 17 mmol of N,N-dimethylformamide dimethyl acetal was added dropwise. The reaction continued for 2 h. The resulting viscous solution was precipitated in a 1000 mL methanol / H2O mixture (1:1, v / v). The polymer was collected by filtration, washed three times with deionized water, and dried in vacuo at 60 °C for 24 h to obtain a solid powder polymer F.

[0078] 20 g of polymer F was dissolved in 80 g of NMP and placed in a 250 mL three-necked round-bottom flask equipped with a mechanical stirrer. 0.3 mL of a saturated THF solution of HCl and 0.0255 mmol of 3,4-dihydropyran (corresponding to 40% of the molar amount of hydroxyl groups in polymer F) were weighed and added to the reaction flask. The temperature was maintained at 25 °C, and the reaction time was 48 h. The polymer solution was dispersed in an aqueous solution, and the solid was precipitated, filtered, and dried in vacuo to obtain a primary polyimide precursor resin. It was dissolved in tetrahydrofuran to form a homogeneous solution, and residual metal or non-metal ions were removed by adsorption with anion and cation resins. Then, it was dispersed in 5 L of deionized water, and the solid was precipitated, filtered, and dried in vacuo to obtain a chemically amplified polyimide precursor 6.

[0079] 1 1H-NMR showed that a chemically amplified polyimide precursor 6 with 38% of phenolic hydroxyl groups protected by pyranyl groups was obtained. Its Mw = 2448 g / mol and ADR = 6.7 A / s.

[0080] Example 7

[0081] A method for preparing a chemically amplified polyimide precursor, comprising the following steps:

[0082] In a 250 mL three-necked round-bottom flask equipped with a mechanical stirrer and a condenser, 50 mmol of cyclohexane tetracarboxylic dianhydride (HPMDA), 90 mmol of 3,5-dihydroxy-1-benzamidobenzyl alcohol, 222.5 mmol of pyridine, and 50 g of anhydrous N-methylpyrrolidone (NMP) were added. The mixture was heated to 90 °C and stirred at this temperature for 10 h. After cooling to room temperature, 65 g of NMP was added. The reaction mixture was cooled to 0 °C in an ice bath, and 100 mmol of phenylphosphonic dichloride was slowly added using an addition funnel. The mixture was stirred at room temperature for 2 h and then cooled to 0 °C. Then, 50 mmol of 4,4'-diaminodiphenyl ether (ODA) was added, and the reaction mixture was stirred at 0 °C for 1 h and at 90 °C for 10 h. Subsequently, 12 mmol of N,N-dimethylformamide dimethyl acetal was dropped in, and the reaction continued for 2 h. The resulting viscous solution was precipitated in a 1000 mL 1:1 (v / v) methanol / H2O mixture. The polymer was collected by filtration, washed three times with deionized water, and vacuum-dried at 60 °C for 24 h to obtain a solid powder polymer G.

[0083] 20 g of polymer G was dissolved in 80 g of NMP and placed in a 250 mL three-necked round-bottom flask equipped with a mechanical stirrer. 0.0255 mmol of trimethylchlorosilane (corresponding to 40% of the molar amount of hydroxyl groups in polymer F) was added to the reaction kettle, and the temperature was maintained at 25 °C for 24 h. The polymer solution was dispersed in an aqueous solution, and the solid was precipitated, filtered, and vacuum-dried to obtain a primary polyimide precursor resin. It was dissolved in tetrahydrofuran to form a homogeneous solution, and residual metal or non-metal ions were removed by adsorption with anion and cation resins. Then, it was dispersed in 5 L of deionized water, and the solid was precipitated, filtered, and vacuum-dried to obtain polyimide precursor 7.

[0084] 1 1H-NMR showed that a chemically amplified polyimide precursor 7 with 33% of phenolic hydroxyl groups protected by methylsilyl groups was obtained. Its Mw = 92790 g / mol and ADR = 1.7 A / s.

[0085] Comparative Example 1

[0086] In a 250 mL three-necked round-bottom flask equipped with a mechanical stirrer and a condenser, 50 mmol of 4,4'-oxydiphthalic anhydride (ODPA), 70 mmol of ethanol, 222.5 mmol of pyridine, and 50 g of anhydrous N-methylpyrrolidone (NMP) were added. The mixture was heated to 90 °C and stirred at this temperature for 10 h. After cooling to room temperature, 65 g of NMP was added, and the reaction mixture was cooled to 0 °C in an ice bath. 100 mmol of phenylphosphonic dichloride was slowly added using an addition funnel, and the mixture was stirred at room temperature for 2 h and then cooled to 0 °C. Then, 50 mmol of 2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was added, and the reaction mixture was stirred at 0 °C for 1 h and then at 50 °C for 10 h. Subsequently, 33 mmol of N,N-dimethylformamide dimethyl acetal was dropped in, and the reaction continued for 2 h. The resulting viscous solution was precipitated in 1000 mL of a 1:1 (v / v) methanol / H2O mixture. The polymer was collected by filtration, washed three times with deionized water, and dried in vacuo at 60 °C for 24 h to obtain the solid powder of Comparative Polymer A.

[0087] 20 g of Comparative Polymer A was dissolved in 80 g of NMP and placed in a 250 mL three-necked round-bottom flask equipped with a mechanical stirrer. 0.0229 mol of di-tert-butyl dicarbonate (DBDC) and 0.001016 mol of DMAP were added, and the mixture was stirred at room temperature for 8 h. The reaction solution was dispersed in 5 L of deionized water, and the solid was precipitated, filtered, and dried in vacuo to obtain the primary polyimide precursor resin. It was dissolved in tetrahydrofuran to form a homogeneous solution, and residual metal or non-metal ions were removed by adsorption with anion and cation resins. Then, it was dispersed in 5 L of deionized water, the solid was precipitated, filtered, and dried in vacuo to obtain the chemically amplified Comparative Polyimide Precursor 1.

[0088] 1 1H-NMR showed that the chemically amplified Comparative Polyimide Precursor 1 with 41% of the phenolic hydroxyl groups protected by tert-butoxycarbonyl was obtained. Its Mw = 7698 g / mol and ADR = 6 A / s.

[0089] Comparative Example 2

[0090] In a 250 mL three-necked round-bottom flask equipped with a mechanical stirrer and a condenser, 50 mmol of 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), 65 mmol of ethanol, 222.5 mmol of pyridine, and 50 g of anhydrous N-methylpyrrolidone (NMP) were added. The mixture was heated to 90 °C and stirred at this temperature for 10 h. After cooling to room temperature, 65 g of NMP was added. The reaction mixture was cooled to 0 °C using an ice bath, and 100 mmol of phenylphosphonic dichloride was slowly added using an addition funnel. The mixture was stirred at room temperature for 2 h and then cooled to 0 °C. Then, 50 mmol of 2,2'-dimethyl-4,4′-diaminobiphenyl (m-TB) was added. The reaction mixture was stirred at 0 °C for 1 h and then at 80 °C for 10 h. Subsequently, 37 mmol of N,N-dimethylformamide dimethyl acetal was added dropwise, and the reaction continued for 2 h. The resulting viscous solution was precipitated in 1000 mL of a 1:1 (v / v) methanol / H2O mixture. The polymer was collected by filtration, washed three times with deionized water, and dried in vacuo at 60 °C for 24 h to obtain a solid powder of Comparative Polymer B. Mw = 101256 g / mol, ADR = 44 A / s

[0091] Comparative Example 3

[0092] In a 250 mL three-necked round-bottom flask equipped with a mechanical stirrer and a condenser, 50 mmol of 4,4’-oxybisphthalic anhydride (ODPA), 78 mmol of methanol, 222.5 mmol of pyridine, and 50 g of anhydrous N-methylpyrrolidone (NMP) were added. The mixture was heated to 90 °C and stirred at this temperature for 10 h. After cooling to room temperature, 65 g of NMP was added. The reaction mixture was cooled to 0 °C using an ice bath, and 100 mmol of phenylphosphonic dichloride was slowly added using an addition funnel. The mixture was stirred at room temperature for 2 h and then cooled to 0 °C. Then, 53 mmol of 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane was added. The reaction mixture was stirred at 0 °C for 1 h and then at 60 °C for 10 h. Subsequently, 25 mmol of N,N-dimethylformamide diethyl acetal was added dropwise, and the reaction continued for 2 h. The resulting viscous solution was precipitated in 1000 mL of a 1:1 (v / v) methanol / H2O mixture. The polymer was collected by filtration, washed three times with deionized water, and dried in vacuo at 60 °C for 24 h to obtain a solid powder of Comparative Polymer C.

[0093] 20 g of comparative polymer C was dissolved in 80 g of NMP and placed in a 250 mL three-necked round-bottom flask equipped with a mechanical stirrer. 0.00042 mmol of pyridinium p-toluenesulfonate and 0.0174 mmol of ethyl vinyl ether were weighed and added to the reaction kettle. The temperature was maintained at 25 °C and the reaction time was 10 h. The polymer solution was dispersed in 5 L of an aqueous solution containing 0.0013 mmol of triethylamine, and the solid was precipitated, filtered, and vacuum dried to obtain a primary polyimide precursor resin; it was dissolved in tetrahydrofuran to form a homogeneous solution, and residual metal or non-metal ions were removed by adsorption with anion and cation resins, and then dispersed in 5 L of deionized water, and the solid was precipitated, filtered, and vacuum dried to obtain a chemically amplified comparative polyimide precursor 3.

[0094] 1 1H-NMR showed that the chemically amplified comparative polyimide precursor 3 with 36% of phenolic hydroxyl groups protected by ethyl vinyl was obtained. Its Mw = 37867 g / mol and ADR = 4.6 A / s.

[0095] Comparative Example 4

[0096] In a 250 mL three-necked round-bottom flask equipped with a mechanical stirrer and a condenser, 50 mmol of 3,3′,4,4′-benzophenone tetracarboxylic dianhydride (BTDA), 85 mmol of hexanol, 222.5 mmol of pyridine, and 50 g of anhydrous N-methylpyrrolidone (NMP) were added. The mixture was heated to 90 °C and stirred at this temperature for 10 h, cooled to room temperature, 65 g of NMP was added, the reaction mixture was cooled to 0 °C with an ice bath, and 100 mmol of phenylphosphonic dichloride was slowly added dropwise with an addition funnel. The mixture was stirred at room temperature for 2 h and then cooled to 0 °C; then 53 mmol of N-(5-amino-2-hydroxyphenyl)-4-[2-[4-[(4-aminophenyl)carbamoyl]phenyl]-hexafluoropropan-2-yl]benzamide was added, and the reaction mixture was stirred at 0 °C for 1 h and at 60 °C for 10 h. Subsequently, 17 mmol of N,N-dimethylformamide dimethyl acetal was dropped in and the reaction was continued for 2 h. The resulting viscous solution was precipitated in 1000 mL of a 1:1 (v / v) methanol / H2O mixture; the polymer was collected by filtration and washed three times with deionized water. The polymer was vacuum dried at 60 °C for 24 h to obtain a solid powder of comparative polymer D.

[0097] 20 g of comparative polymer D was dissolved in 80 g of NMP and placed in a 250 mL three-necked round-bottom flask equipped with a mechanical stirrer. 0.00037 mmol of pyridinium p-toluenesulfonate and 0.01412 mmol of cyclohexyl vinyl ether were weighed and added to the reaction kettle. The temperature was maintained at 25 °C and the reaction time was 10 h. The polymer solution was dispersed in 5 L of an aqueous solution containing 0.00089 mmol of triethylamine, and the solid was precipitated, filtered, and vacuum dried to obtain the primary polyimide precursor resin. It was dissolved in tetrahydrofuran to form a homogeneous solution, and the residual metal or non-metal ions were removed by adsorption with anion and cation resins. Then it was dispersed in 5 L of deionized water, and the solid was precipitated, filtered, and vacuum dried to obtain the chemically amplified comparative polyimide precursor 4 of polyimide.

[0098] 1 1H-NMR showed that the chemically amplified comparative polyimide precursor 4 with 35% of phenolic hydroxyl groups protected by cyclohexyl vinyl was obtained. Its Mw = 53980 g / mol and ADR = 2.3 A / s.

[0099] Comparative Example 5

[0100] In a 250 mL three-necked round-bottom flask equipped with a mechanical stirrer and a condenser, 50 mmol of 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), 70 mmol of ethanol, 222.5 mmol of pyridine, and 50 g of anhydrous N-methylpyrrolidone (NMP) were added. The mixture was heated to 90 °C and stirred at this temperature for 10 h. After cooling to room temperature, 65 g of NMP was added, and the reaction mixture was cooled to 0 °C with an ice bath. 100 mmol of phenylphosphonic dichloride was slowly added using an addition funnel. The mixture was stirred at room temperature for 2 h and then cooled to 0 °C. Then 60 mmol of N,N′-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis(6-hydroxy-3,1-phenylene)]bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxamide) (6FAP-ATA) was added, and the reaction mixture was stirred at 0 °C for 1 h and at room temperature for 10 h. Subsequently, 33 mmol of N,N-dimethylformamide diethyl acetal was dropped in and the reaction continued for 2 h. The resulting viscous solution was precipitated in 1000 mL of a 1:1 (v / v) methanol / H2O mixture; the polymer was collected by filtration, washed three times with deionized water, and the polymer was vacuum dried at 60 °C for 24 h to obtain the solid powder comparative polymer E.

[0101] 20 g of comparative polymer E was dissolved in 80 g of NMP and placed in a 250 mL three-necked round-bottom flask equipped with a mechanical stirrer. 0.00047 mmol of pyridinium p-toluenesulfonate and 0.0164 mmol of ethyl vinyl ether were weighed and added to the reaction kettle. The temperature was maintained at 25 °C and the reaction time was 10 h. The polymer solution was dispersed in 5 L of an aqueous solution containing 0.0011 mmol of triethylamine, and the solid was precipitated, filtered, and dried in vacuo to obtain a primary polyimide precursor resin; it was dissolved in tetrahydrofuran to form a homogeneous solution, and the residual metal or non-metal ions were removed by adsorption with anion and cation resins, and then dispersed in 5 L of deionized water, and the solid was precipitated, filtered, and dried in vacuo to obtain a chemically amplified comparative polyimide precursor 5.

[0102] 1 H-NMR showed that the chemically amplified comparative polyimide precursor 5 with 30% of the phenolic hydroxyl groups protected by ethyl vinyl was obtained. Its Mw = 4379 g / mol and ADR = 38 A / s.

[0103] Comparative Example 6

[0104] In a 250 mL three-necked round-bottom flask equipped with a mechanical stirrer and a condenser, 50 mmol of 3,3′,4,4′-benzophenone tetracarboxylic dianhydride (BTDA), 85 mmol of methanol, 222.5 mmol of pyridine, and 50 g of anhydrous N-methylpyrrolidone (NMP) were added. The mixture was heated to 90 °C and stirred at this temperature for 10 h, cooled to room temperature, 65 g of NMP was added, the reaction mixture was cooled to 0 °C with an ice bath, and 100 mmol of phenylphosphonic dichloride was slowly added dropwise with a dropping funnel. The mixture was stirred at room temperature for 2 h and then cooled to 0 °C; then 60 mmol of 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl (TFMB) was added, and the reaction mixture was stirred at 0 °C for 10 h, and then 17 mmol of N,N-dimethylformamide dimethyl acetal was added dropwise and the reaction continued for 2 h. The viscous solution obtained was precipitated in 1000 mL of a 1:1 (v / v) methanol / H2O mixture; the polymer was collected by filtration and washed three times with deionized water, and the polymer was dried in vacuo at 60 °C for 24 h to obtain a solid powder comparative polymer F. Its Mw = 2042 g / mol and ADR = 8.9 A / s.

[0105] Comparative Example 7

[0106] In a 250 mL three-necked round-bottom flask equipped with a mechanical stirrer and a condenser, 50 mmol of cyclohexane tetracarboxylic dianhydride (HPMDA), 90 mmol of methanol, 222.5 mmol of pyridine, and 50 g of anhydrous N-methylpyrrolidone (NMP) were added. The mixture was heated to 90 °C and stirred at this temperature for 10 h. After cooling to room temperature, 65 g of NMP was added, and the reaction mixture was cooled to 0 °C using an ice bath. 100 mmol of phenylphosphonic dichloride was slowly added using an addition funnel, and the mixture was stirred at room temperature for 2 h and then cooled to 0 °C. Then, 50 mmol of 4,4'-diaminodiphenyl ether (ODA) was added, and the reaction mixture was stirred at 0 °C for 1 h and then at 90 °C for 10 h. Subsequently, 12 mmol of N,N-dimethylformamide dimethyl acetal was dropped in, and the reaction continued for 2 h. The resulting viscous solution was precipitated in 1000 mL of a 1:1 (v / v) methanol / H2O mixture. The polymer was collected by filtration, washed three times with deionized water, and vacuum dried at 60 °C for 24 h to obtain a solid powder of comparative polymer G. Its Mw = 102696 g / mol and ADR = 5 A / s.

[0107] Application Example 1

[0108] A photoresist composition is composed of the chemically amplified polyimide precursor 1 prepared in Example 1, a photoacid generator, additives, and propylene glycol methyl ether. It is formulated by mass fraction, shaken on an oscillator for 24 h to ensure sufficient mutual dissolution, filtered once through a 0.5 μm pore size filter, and then filtered once through a 0.2 μm pore size filter to obtain the photoresist composition. The types of photoacid generator and additives are shown in Table 1. The usage amounts of each raw material of the composition are shown in Table 2.

[0109] Application Example 2

[0110] A photoresist composition is composed of the chemically amplified polyimide precursor 2 prepared in Example 2, a photoacid generator, additives, and propylene glycol methyl ether. It is formulated by mass fraction, shaken on an oscillator for 24 h to ensure sufficient mutual dissolution, filtered once through a 0.5 μm pore size filter, and then filtered once through a 0.2 μm pore size filter to obtain the photoresist composition. The types of photoacid generator and additives are shown in Table 1. The usage amounts of each raw material of the composition are shown in Table 2.

[0111] Application Example 3

[0112] A photoresist composition is prepared from the chemically amplified polyimide precursor 3 prepared in Example 3, a photoacid generator, additives, and ethyl lactate. The mixture is prepared in parts by mass, shaken on an oscillator for 24 hours to allow for complete dissolution, and filtered once through a 0.5 μm pore size filter and then again through a 0.2 μm pore size filter to obtain the photoresist composition. The types of photoacid generators and additives are listed in Table 1. The amounts of the various raw materials used in the composition are listed in Table 2.

[0113] Application Example 4

[0114] A photoresist composition is prepared from the chemically amplified polyimide precursor 4 prepared in Example 4, a photoacid generator, additives, and ethyl lactate. The composition is prepared in parts by mass, shaken on an oscillator for 24 hours to allow for complete dissolution, and filtered once through a 0.5 μm pore size filter and then again through a 0.2 μm pore size filter to obtain the photoresist composition. The types of photoacid generators and additives are listed in Table 1. The amounts of the various raw materials used in the composition are listed in Table 2.

[0115] Application Example 5

[0116] A photoresist composition is prepared from the chemically amplified polyimide precursor 5 prepared in Example 5, a photoacid generator, additives, and methyl ethyl ketone. The mixture is prepared in parts by mass, shaken on an oscillator for 24 hours to allow for complete dissolution, and filtered once through a 0.5 μm pore size filter and then again through a 0.2 μm pore size filter to obtain the photoresist composition. The types of photoacid generators and additives are listed in Table 1. The amounts of the various raw materials used in the composition are listed in Table 2.

[0117] Application Example 6

[0118] A photoresist composition is prepared from the chemically amplified polyimide precursor 6 prepared in Example 6, a photoacid generator, additives, and propylene glycol methyl ether. The composition is prepared in parts by mass, shaken on an oscillator for 24 hours to allow for complete dissolution, and filtered once through a 0.5 μm pore size filter and then again through a 0.2 μm pore size filter to obtain the photoresist composition. The types of photoacid generators and additives are listed in Table 1. The amounts of the various raw materials used in the composition are listed in Table 2.

[0119] Application Example 7

[0120] A photoresist composition is prepared from the chemically amplified polyimide precursor 7 prepared in Example 7, a photoacid generator, additives, and γ-butyrolactone. The components are mixed according to mass fractions, shaken on an oscillator for 24 hours to allow for complete dissolution, and filtered once through a 0.5 μm pore size filter and then again through a 0.2 μm pore size filter to obtain the photoresist composition. The types of photoacid generators and additives are listed in Table 1. The amounts of the various raw materials used in the composition are listed in Table 2.

[0121] Application Comparative Example 1

[0122] Same as Application Example 1, except that polyimide precursor 1 was replaced with comparative polyimide precursor 1 prepared in Comparative Example 1.

[0123] Application Comparative Example 2

[0124] Same as Application Example 2, except that polyimide precursor 2 was replaced with comparative polymer B prepared in Comparative Example 2.

[0125] Application Comparative Example 3

[0126] Same as Application Example 3, except that polyimide precursor 3 was replaced with comparative polyimide precursor 3 prepared in Comparative Example 3.

[0127] Application Comparative Example 4

[0128] Same as Application Example 4, except that polyimide precursor 4 was replaced with comparative polyimide precursor 4 prepared in Comparative Example 4.

[0129] Application Comparative Example 5

[0130] Same as Application Example 5, except that polyimide precursor 5 was replaced with comparative polyimide precursor 5 prepared in Comparative Example 5.

[0131] Application Comparative Example 6

[0132] Same as Application Example 6, except that polyimide precursor 6 was replaced with comparative polymer F prepared in Comparative Example 6.

[0133] Application Comparative Example 7

[0134] Same as Application Example 7, except that polyimide precursor 7 was replaced with comparative polymer G prepared in Comparative Example 7.

[0135] Table 1

[0136]

[0137]

[0138] Table 2

[0139]

[0140] The performance of the above-prepared photoresist composition was tested, and the test results are shown in Table 3 below:

[0141] Table 3

[0142]

[0143] Applied Comparative Example 1 56 2 ++++ ++++ Applied Comparative Example 2 >200 No Image +++++ +++++ Applied Comparative Example 3 74 3 ++++ ++++ Applied Comparative Example 4 82 2 ++++ ++++ Applied Comparative Example 5 102 3 +++ +++ Applied Comparative Example 6 >200 No Image +++++ +++++ Applied Comparative Example 7 >200 No Image +++++ +++++

[0144] Sensitivity test: On a 6-inch silicon wafer, increase the adhesion with 110°C CHMDS for 60 seconds. Spin-coat the above-prepared photoresist composition on the silicon wafer at a speed of 300 - 5000 revolutions per minute to form a film, bake it on a hot plate at 120°C for 120 seconds to obtain a 2-μm-thick film layer, then expose it with a Nikon I9 exposure machine, and the exposure intensity is 20 - 200 mj / cm 2 , and finally develop it in a 2.38% TMAH developer solution.

[0145] Optimal resolution test: Place the developed wafer under a TEL - CDSEM for observation, and observe the highest-resolution image that can be fully developed at the optimal exposure energy. The optimal resolution picture of the photoresist composition in Application Example 1 is as Figure 1 shown. It can be seen from the figure that the optimal resolution is 0.8 umL / S; the optimal resolution picture of the photoresist composition in Comparative Application Example 1 is as Figure 2 shown. It can be seen from the figure that the optimal resolution is 2 umL / S.

[0146] Developed film retention rate ability test: In the evaluation of the film retention rate, under the set process conditions, 100% ≥ developed film retention rate > 95% is +++++; 95% ≥ developed film retention rate > 90% is ++++; 90% ≥ developed film retention rate > 85% is +++; 85% ≥ developed film retention rate > 80% is ++, and the film retention rate ≤ 80% is +.

[0147] Fabrication of the photosensitive cured film: Use a rotational viscometer (Mikasa: MS - B150 + DA - 60S) for wet film coating, pre-dry it on a hot plate, then transfer it to nitrogen drying for further curing after exposure and development, cure it at 230°C for 60 minutes, and take it out after cooling to room temperature.

[0148] Cured film retention rate ability test: In the evaluation of the film retention rate, under the set process conditions, the developed film retention rate > 85% is +++++; 85% ≥ developed film retention rate > 80% is ++++; 80% ≥ developed film retention rate > 75% is +++; 75% ≥ developed film retention rate > 70% is ++, and the film retention rate ≤ 70% is +.

[0149] After testing, it can be seen from Table 3 that by introducing the structural unit of the general formula (2) into the polyimide, the corresponding polyimide precursor photoresist can achieve a cured film layer of the photoresist sample that takes into account high sensitivity, high resolution, and high film retention rate. In summary, the photoresist composition of the present invention is suitable for applications in panels and packaging fields with high requirements for sensitivity, film retention rate, and resolution.

[0150] The embodiments provided above are not intended to limit the scope covered by the present invention, nor are the described steps intended to limit the order of their execution. Obvious improvements made by those skilled in the art in combination with the existing well-known general knowledge also fall within the protection scope defined by the claims of the present invention.

Claims

1. A chemically amplified polyimide precursor, characterized in that, The structure of the chemically amplified polyimide precursor is shown in the general formula (1): In the general formula (1), Ar1 represents a dianhydride residue; Ar2 represents a diamine residue; Ar3 represents a dianhydride residue; Ar4 represents a diamine residue; m is an integer from 5 to 3000; n is an integer from 1 to 2000; In general formula (1), R1 independently represents hydrogen, an alkyl group or an aromatic group of C 1-10 or one or more of the structures represented by general formula (2); In general formula (2), Ar5 represents an alkylene or arylene group of C 1-10 ; p is 2 or 3; in the structure represented by R1, the proportion of the structure shown in general formula (2) is ≥20%; R2 represents hydrogen or an acid-decomposable group, and the proportion of the number of acid-decomposable groups is 15-75%.

2. The chemically amplified polyimide precursor according to claim 1, wherein m / (m + n) ≥ 50%.

3. The chemically amplified polyimide precursor according to claim 1, wherein Ar1 and Ar3 respectively represent dianhydride residues obtained by removing two anhydride groups from dianhydrides, and Ar1 and Ar3 are the same or different; the dianhydride is any one of the following structures: pyromellitic dianhydride, 3,3,3′,4′-biphenyltetracarboxylic dianhydride, 2,3,3′,4′-biphenyltetracarboxylic dianhydride, 4,4′-oxydiphthalic anhydride, 4,4′-(hexafluoroisopropylidene)diphthalic anhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, p-phenylene-bis(trimellitate) dianhydride, 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride.

4. The chemically amplified polyimide precursor according to claim 1, wherein Ar2 and Ar4 respectively represent residues obtained by removing two amino groups from diamines, and Ar2 and Ar4 are the same or different; the diamine is a hydroxyl-containing diamine or a non-hydroxyl-containing diamine.

5. The chemically amplified polyimide precursor according to claim 4, characterized in that, The hydroxylamine-containing diamine is one or more of 2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2'-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis[3-(4-aminobenzamido)-4-hydroxyphenyl]propane, 2,2-bis[3-(4-aminobenzamido)-4-hydroxyphenyl]sulfonyl, 2,2-bis[3-(4-aminobenzamido)-4-hydroxyphenyl]ether, 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane, 2,2-bis[3-(4-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane, N-(2-hydroxy-5-amino)phenyl-3-aminobenzamide, N-(5-amino-2-hydroxyphenyl)-4-[2-[4-[(4-aminophenyl)carbamoyl]phenyl]propan-2-yl]benzamide, N-(5-amino-2-hydroxyphenyl)-4-[2-[4-[(4-aminophenyl)carbamoyl]phenyl]sulfonyl-2-yl]benzamide, N-(5-amino-2-hydroxyphenyl)-4-[2-[4-[(4-aminophenyl)carbamoyl]phenyl]ether-2-yl]benzamide, N-(5-amino-2-hydroxyphenyl)-4-[2-[4-[(4-aminophenyl)carbamoyl]phenyl]hexafluoropropane-2-yl]benzamide; the hydroxylamine-free diamine is one or more of 1,4-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diamino-p-terphenyl, 4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4-aminophenyl 4-aminobenzoate, 1,4-bis(4'-aminophenoxy)benzene, 1,3-bis(4'-aminophenoxy)benzene, 1,3-bis(3'-aminophenoxy)benzene, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl ether, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane, N,N'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis(6-hydroxy-3,1-phenylene)]bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxamide), N-[5-[3-[(1,3-dioxo-2-benzofuran-5-carbonyl)amino]-4-hydroxyphenyl]sulfonyl-2-hydroxyphenyl]-1,3-dioxo-2-benzofuran-5-carboxamide.

6. The chemically amplified polyimide precursor according to claim 1, wherein The structure represented by the general formula (2) is any one of the following structures: Among them, R2 represents H or any one of the following structures:

7. The chemically amplified polyimide precursor according to claim 1, wherein The weight-average molecular weight of the polyimide precursor is 1000-150000 g / mol; the dissolution rate in 2.38% aqueous solution of tetramethylammonium hydroxide is 0.1-50 Å / second.

8. A photoresist composition prepared from the chemically amplified polyimide precursor according to claim 1, characterized in that, The raw materials of the photoresist composition and the weight parts of each raw material are as follows:

9. The photoresist composition according to claim 8, wherein The photoacid generator is any one of the following structures: -C3F7, -C8H 17 or -C3F7, -C4H9 or -CF3, -C6F5 or For The additive is one or more of a leveling agent, a quenching agent, and a curing agent; The solvent is one or more of a ketone solvent, an ester solvent, an ether solvent, and an aromatic hydrocarbon solvent.

10. A photosensitive cured film prepared from the photoresist composition according to claim 8, characterized in that, It is cured from the photoresist composition and is applicable to the surface protective film or interlayer insulating film of semiconductor elements, the insulating layer of organic light-emitting elements, or the insulating layer of thin-film transistors.

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