Polyimide precursor and photoresist composition prepared from polyimide precursor

Abstract

The invention discloses a polyimide precursor and a photoresist composition prepared from the polyimide precursor. The structure of the polyimide precursor is shown as a general formula (1): # imgabs0 #. The photoresist composition prepared from the polyimide precursor comprises the following raw materials in parts by weight: 4-50 parts of the polyimide precursor, 0.5-15 parts of a photosensitive compound, 0.001-15 parts of an additive and 40-95 parts of a solvent. In the photoresist composition provided by the invention, the polyimide precursor is used as film-forming resin to be mixed with the photosensitive compound, the additive and the solvent, the film-forming resin plays a role of a skeleton, and the interaction strength with the photosensitive compound determines the development rate and the film retention rate of the photoresist, and the contrast ratio and the resolution ratio before and after development and other properties of the photoresist. The phenolic hydroxyl group not only can provide alkali solubility in a developing solution, but also can improve the strong interaction between the film-forming resin and the photosensitive compound.

Description

Technical Field

[0001] The present invention relates to the technical field of functional polymer materials, and particularly to a 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 aspects such as 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 and plays an important role in the preparation of OLED.

[0003] Packaging technology is a technology for packing integrated circuits with insulating plastic or ceramic materials. In the preparation process of large-scale integrated circuits, packaging is the last process. Currently, advanced packaging technology has developed from the individual separate packaging of single integrated circuit blocks to the simultaneous packaging of the entire silicon wafer, that is, wafer-level packaging. Compared with the photoresist used in IC manufacturing, the photoresist layer used in most packaging technologies is much thicker. For example, in applications such as secondary wiring, wafer bumps for flip chips, TAB, COG, copper pillar technology for chip-substrate interconnection in some CSPs, and MCM-D multi-layer substrates, the feature sizes and thicknesses of the above two photoresist materials are usually between 5um and 100um.

[0004] Polyimide precursor photoresist is a key functional material required in the panel Array segment processing 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 thick, a large exposure energy and development time are required to complete the corresponding lithography requirements, which reduces the processing efficiency. Whether it is panel or IC manufacturing, the sensitivity and film retention rate of the photoresist sample have a crucial impact on controlling product costs. Seeking a suitable path to balance the sensitivity and film retention rate of the photoresist has become an important development direction for polyimide precursor photoresist. Summary of the Invention

[0005] In view of the above problems existing in the prior art, the present invention provides a polyimide precursor and a photoresist composition prepared therefrom. The polyimide precursor of the present invention contains polyphenolic hydroxyl groups, which is beneficial for the prepared photoresist composition to balance sensitivity, film retention rate, and has excellent thermal properties.

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

[0007] The first object of the present invention is to provide a polyimide precursor, and the structure of the 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, C 1-10 alkyl or aryl groups, and the structure shown in the general formula (2);

[0011]

[0012] In the general formula (2), Ar s 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 ≥5%.

[0013] In an embodiment of the present invention, the polyimide precursor satisfies: m / (m + n)≥50%.

[0014] In an embodiment of the present invention, Ar1 and Ar3 respectively represent dianhydride residues obtained by removing 2 anhydride groups from dianhydrides, and Ar1 and Ar3 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).

[0015] In an embodiment of the present invention, 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.

[0016] 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, N-(5-amino-2-hydroxyphenyl)-4-[2-[4-[(4-aminophenyl)carbamoyl]phenyl]hexafluoropropan-2-yl]benzamide;The hydroxyl group-free diamines are 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-aminobenzoic acid 4-aminophenyl ester (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).;

[0017] In one embodiment of the present invention, the structure represented by the general formula (2) is any one of the following structures:

[0018]

[0019] In one embodiment of the present invention, Ar5 represents a C1-10 alkylene or arylene group.

[0020] Preferably, the structure represented by Ar s 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.

[0021] In one embodiment of the present invention, R1 independently represents hydrogen, C 1-10 alkyl or aromatic group.

[0022] 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, phenylmethyl, phenylethyl, phenylpropyl.

[0023] In one embodiment of the present invention, the weight-average molecular weight of the polyimide precursor is 1000 - 200000 g / mol; the dissolution rate (ADR) in a 2.38% aqueous solution of tetramethylammonium hydroxide is 5 - 10000 Å / second.

[0024] 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 100 - 3000 Å / second.

[0025] The second object of the present invention is to provide a photoresist composition prepared from the above polyimide precursor, and the raw materials and the weight parts of each raw material of the photoresist composition are:

[0026]

[0027] In one embodiment of the present invention, the photosensitive compound is a polyphenol compound or an esterified product of polyhydroxybenzophenone and diazonaphthoquinone sulfonyl chloride.

[0028] Preferably, the photosensitive compound is any one of the following structures:

[0029]

[0030] wherein, R independently represents H,

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

[0032] In one embodiment of the present invention, the sensitizer is a polyphenol compound; preferably, the sensitizer is any one of the following structures:

[0033]

[0034] In one embodiment of the present invention, the curing agent is a compound containing an ether group, a hydroxymethyl group, an epoxy group, or a vinyl group.

[0035] Preferably, the curing agent is any one of the following structures:

[0036]

[0037] In one embodiment of the present invention, the leveling agent is a commercial acrylic, silicone, or fluorocarbon compound.

[0038] Preferably, the leveling agent is 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.

[0039] In one embodiment of the present invention, the solvent is one or more of ketone solvents, ester solvents, ether solvents, and aromatic hydrocarbon solvents.

[0040] Preferably, the solvent is one or more of propylene glycol monomethyl ether acetate, propylene glycol monoacetate, ethylene glycol monomethyl ether acetate, diethylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, butyl acetate, neopentyl acetate, ethyl lactate, methyl ethyl ketone, methyl isobutyl ketone, γ-butyrolactone, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide.

[0041] 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.

[0042] The beneficial technical effects of the present invention are as follows:

[0043] The polyamide precursor of the present invention is used as a film-forming resin, reducing the proportion of carboxyl groups in the film-forming resin, and the unexposed area is not easily dissolved by the developer; it has a large number of phenolic hydroxyl groups, providing sufficient alkali solubility. Before exposure, due to the strong interaction between the film-forming resin and the photosensitive compound, a high film retention rate is ensured. After exposure, the photosensitive compound de-nitrogenates to form indene carboxylic acid, and the interaction with the phenolic hydroxyl groups of the resin is destroyed, and it is dissolved in the alkaline developer together with the film-forming resin containing polyphenolic hydroxyl groups, thereby realizing the alkaline dissolution contrast between the exposed area and the unexposed area.

[0044] The present invention reduces the curing temperature, can reduce manufacturing energy consumption, and reducing the curing time can improve manufacturing efficiency. The polyimide precursor modified with polyphenolic hydroxyl compounds facilitates the curing of the film layer. A large number of phenolic hydroxyl groups are beneficial for the cross-linking of the film-forming resin and the curing agent to form a film, which can reduce the curing time and temperature. Moreover, a large number of cross-linking sites enable sufficient curing and improve the thermal properties of the cured film.

[0045] In the photoresist composition of the present invention, the polyimide precursor is mixed with a photosensitive compound, additives and a solvent as a film-forming resin. The film-forming resin plays a skeletal role, and the strength of its interaction with the photosensitive compound determines the development rate, film retention rate, contrast before and after development, resolution and other properties of the photoresist. For traditional polyimide precursor film-forming resins, in order to improve sensitivity, a certain proportion of carboxyl groups is retained to ensure the rapid dissolution of the exposed area in the developer. However, since the carboxyl groups are evenly distributed in the film layer, this method also increases the development rate of the unexposed area (reserved area), sacrificing the contrast between the exposed and unexposed areas, thereby reducing the film retention rate of the reserved area. In the present invention, the phenolic hydroxyl group can not only provide alkali solubility in the developer, but also enhance the strong interaction (intermolecular hydrogen bond, azo coupling effect) between the film-forming resin and the photosensitive compound. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] Figure 1 1.5-μm lithography topography of the polyimide precursor photoresist composition in Application Example 1 of the present invention;

[0047] Figure 2 2-μm lithography topography of the photoresist composition in Comparative Application Example 1 of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0048] The present invention will be specifically described below with reference to the drawings and examples.

[0049] Example 1

[0050] A method for preparing a polyimide precursor includes the following steps:

[0051] 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), 20 mmol of 3,4,5-trihydroxy-1-benzamidylethanol, 222.5 mmol of pyridine, and 50 g of anhydrous N-methylpyrrolidone (NMP) are added. The mixture is heated to 90 °C and stirred at this temperature for 10 h. After cooling to room temperature, 65 g of NMP is added, and the reaction mixture is cooled to 0 °C with an ice bath. 100 mmol of phenylphosphonic dichloride is slowly added using an addition funnel, and the mixture is stirred at room temperature for 2 h and then cooled to 0 °C. Then, 52 mmol of 2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane is added, and the reaction mixture is stirred at 0 °C for 1 h and at 50 °C for 10 h. Subsequently, 100 mmol of N,N-dimethylformamide dimethyl acetal is dropped in, and the reaction continues for 2 h. The resulting viscous solution is precipitated in 1000 mL of a 1:1 (v / v) methanol / H2O mixture. The polymer is collected by filtration, washed three times with deionized water, and the polymer is vacuum dried at 60 °C for 24 h to obtain a solid powder, which is the polyimide precursor 1.

[0052] The obtained polyimide precursor 1 has Mw = 25482 (g / mol) and ADR = 2467 (A / s).

[0053] Example 2

[0054] A method for preparing a polyimide precursor comprises the following steps:

[0055] 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), 10 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, then cooled 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 2,2′-dimethyl-4,4′-diaminobiphenyl (m-TB) was added, and the reaction mixture was stirred at 0 °C for 1 h and at 80 °C for 10 h. Subsequently, 90 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 a solid powder, which is polyimide precursor 2.

[0056] The obtained polyimide precursor 2 has Mw = 167950 (g / mol) and ADR = 35 (A / s).

[0057] Example 3

[0058] A method for preparing a polyimide precursor comprises the following steps:

[0059] 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), 23 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 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 again. 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, 70 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, which was polyimide precursor 3.

[0060] The obtained polyimide precursor 3 had a Mw of 59786 (g / mol) and an ADR of 8726 (A / s).

[0061] Example 4

[0062] A method for preparing a polyimide precursor comprises the following steps:

[0063] In a 250 mL three-necked round-bottom flask equipped with a mechanical stirrer and a condenser, 50 mmol of 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA), 13 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. 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 again. 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, 100 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, which was polyimide precursor 4.

[0064] The obtained polyimide precursor 4 had a Mw of 73451 (g / mol) and an ADR of 321 (A / s).

[0065] Example 5

[0066] A method for preparing a polyimide precursor comprises the following steps:

[0067] 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), 18 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, then cooled 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, 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, 90 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 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, which was the polyimide precursor 5.

[0068] The obtained polyimide precursor 5 had a Mw of 5214 (g / mol) and an ADR of 1258 (A / s).

[0069] Example 6

[0070] A method for preparing a polyimide precursor comprises the following steps:

[0071] 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), 7 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, then cooled 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, and 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. Subsequently, 70 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 a solid powder, which was polyimide precursor 6.

[0072] The obtained polyimide precursor 6 had Mw = 3398 (g / mol) and ADR = 342 (A / s).

[0073] Example 7 ..

[0074] A method for preparing a polyimide precursor comprises the following steps:

[0075] In a 250 mL three-necked round-bottom flask equipped with a mechanical stirrer and a condenser, 50 mmol of cyclohexane tetracarboxylic dianhydride (HPMDA), 5 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, then cooled 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, 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 at 90 °C for 10 h. Subsequently, 100 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 a solid powder, which was polyimide precursor 7.

[0076] The obtained polyimide precursor 7 had Mw = 181420 (g / mol) and ADR = 7 (A / s).

[0077] Comparative Example 1

[0078] Same as Example 1, except that 20 mmol of 3,4,5-trihydroxy-1-benzamidylethanol was replaced with 20 mmol of ethanol, and the resulting solid powder was the comparative resin 1.

[0079] The obtained comparative resin 1 had Mw = 9482 (g / mol) and ADR = 367 (A / s).

[0080] Comparative Example 2

[0081] Same as Example 2, except that 10 mmol of 2,4,6-trihydroxy-1-benzamidylethanol was replaced with 10 mmol of ethanol, and the resulting solid powder was the comparative resin 2.

[0082] The obtained comparative resin 2 had Mw = 103950 (g / mol) and ADR = 10 (A / s).

[0083] Comparative Example 3

[0084] Same as Example 3, except that 23 mmol of 2,3,4-trihydroxy-1-benzamidylmethanol was replaced with 23 mmol of methanol, and the resulting solid powder was the comparative resin 3.

[0085] The obtained comparative resin 3 had Mw = 35268 (g / mol) and ADR = 3421 (A / s).

[0086] Comparative Example 4

[0087] Same as Example 4, except that 13 mmol of 3,4-dihydroxy-1-benzamidylcyclohexanol was replaced with 13 mmol of hexanol, and the resulting solid powder was the comparative resin 4.

[0088] The obtained comparative resin 4 had Mw = 55209 (g / mol) and ADR = 103 (A / s).

[0089] Comparative Example 5

[0090] Same as Example 5, except that 18 mmol of 2,6-dihydroxy-1-benzamidylethanol was replaced with 18 mmol of ethanol, and the resulting solid powder was the comparative resin 5.

[0091] The obtained comparative resin 5 had Mw = 5214 (g / mol) and ADR = 241 (A / s).

[0092] Comparative Example 6

[0093] Same as Example 6, except that 7 mmol of 3,5-dihydroxy-1-benzamidobenzyl alcohol was replaced with 7 mmol of methanol, and the resulting solid powder was the comparative resin 6.

[0094] The obtained comparative resin 6 had Mw = 3012 (g / mol) and ADR = 92 (A / s).

[0095] Comparative Example 7

[0096] Same as Example 7, except that 5 mmol of 3,5-dihydroxy-1-benzamidobenzyl alcohol was replaced with 5 mmol of methanol, and the resulting solid powder was the comparative resin 7.

[0097] The obtained comparative resin 7 had Mw = 163023 (g / mol) and ADR = 5 (A / s).

[0098] Application Example 1

[0099] A photoresist composition is composed of the polyimide precursor 1 prepared in Example 1, a photosensitive compound, an additive, and propylene glycol methyl ether; it is formulated by mass fraction, shaken on an oscillator for 24 h to dissolve each other sufficiently, and filtered twice through a 0.5-μm pore size filter to obtain the photoresist composition. The types of additives are shown in Table 1. The amounts of each raw material of the composition are shown in Table 2.

[0100] The structure of the photosensitive compound is:

[0101]

[0102] Application Example 2

[0103] A photoresist composition is composed of the polyimide precursor 2 prepared in Example 2, a photosensitive compound, an additive, and propylene glycol methyl ether; it is formulated by mass fraction, shaken on an oscillator for 24 h to dissolve each other sufficiently, and filtered twice through a 0.5-μm pore size filter to obtain the photoresist composition. The types of additives are shown in Table 1. The amounts of each raw material of the composition are shown in Table 2.

[0104] The structure of the photosensitive compound is:

[0105]

[0106] Application Example 3

[0107] A photoresist composition is composed of the polyimide precursor 3 prepared in Example 3, a photosensitive compound, an additive, and propylene glycol methyl ether; it is formulated by mass fraction, shaken on an oscillator for 24 h to dissolve each other sufficiently, and filtered twice through a 0.5-μm pore size filter to obtain the photoresist composition. The types of additives are shown in Table 1. The amounts of each raw material of the composition are shown in Table 2.

[0108] The structure of the photosensitive compound is as follows:

[0109]

[0110] Application Example 4

[0111] A photoresist composition is composed of the polyimide precursor 4 obtained in Example 4, a photosensitive compound, an additive, and ethyl lactate; it is formulated according to mass parts, shaken on an oscillator for 24 h to dissolve them sufficiently with each other, and filtered twice through a filter with a pore size of 0.5 μm to obtain the photoresist composition. The types of additives are shown in Table 1. The amounts of each raw material of the composition are shown in Table 2.

[0112] The structure of the photosensitive compound is as follows:

[0113]

[0114] Application Example 5

[0115] A photoresist composition is composed of the polyimide precursor 5 obtained in Example 5, a photosensitive compound, an additive, and ethyl lactate; it is formulated according to mass parts, shaken on an oscillator for 24 h to dissolve them sufficiently with each other, and filtered twice through a filter with a pore size of 0.5 μm to obtain the photoresist composition. The types of additives are shown in Table 1. The amounts of each raw material of the composition are shown in Table 2.

[0116] The structure of the photosensitive compound is as follows:

[0117]

[0118] Application Example 6

[0119] A photoresist composition is composed of the polyimide precursor 6 obtained in Example 6, a photosensitive compound, an additive, and propylene glycol methyl ether; it is formulated according to mass parts, shaken on an oscillator for 24 h to dissolve them sufficiently with each other, and filtered twice through a filter with a pore size of 0.5 μm to obtain the photoresist composition. The types of additives are shown in Table 1. The amounts of each raw material of the composition are shown in Table 2.

[0120] The structure of the photosensitive compound is as follows:

[0121]

[0122] Application Example 7

[0123] A photoresist composition is composed of polyimide precursor 7 prepared in Example 7, a photosensitive compound, an additive, and N,N-dimethylformamide; it is formulated by mass fraction, shaken on an oscillator for 24 h to fully dissolve them with each other, and filtered twice through a 0.5-μm pore size filter to obtain the photoresist composition. The types of additives are shown in Table 1. The dosages of each raw material of the composition are shown in Table 2.

[0124] The structure of the photosensitive compound is:

[0125]

[0126] Application Comparative Example 1

[0127] Same as Application Example 1, except that polyimide precursor 1 is replaced with comparative resin 1 prepared in Comparative Example 1.

[0128] Application Comparative Example 2

[0129] Same as Application Example 2, except that polyimide precursor 2 is replaced with comparative resin 2 prepared in Comparative Example 2.

[0130] Application Comparative Example 3

[0131] Same as Application Example 3, except that polyimide precursor 3 is replaced with comparative resin 3 prepared in Comparative Example 3.

[0132] Application Comparative Example 4

[0133] Same as Application Example 4, except that polyimide precursor 4 is replaced with comparative resin 4 prepared in Comparative Example 4.

[0134] Application Comparative Example 5

[0135] Same as Application Example 5, except that polyimide precursor 5 is replaced with comparative resin 5 prepared in Comparative Example 5.

[0136] Application Comparative Example 6

[0137] Same as Application Example 6, except that polyimide precursor 6 is replaced with comparative resin 6 prepared in Comparative Example 6.

[0138] Application Comparative Example 7

[0139] Same as Application Example 7, except that polyimide precursor 7 is replaced with comparative resin 7 prepared in Comparative Example 7.

[0140] Table 1

[0141]

[0142]

[0143]

[0144] Table 2

[0145]

[0146] [[ID=V8]]The performance of the above-prepared photoresist composition was tested, and the test results are shown in Table 3 below:

[0147] Table 3

[0148]

[0149]

[0150] Sensitivity test: On a 6-inch silicon wafer, HMDS was used for adhesion enhancement at 110 °C for 60 seconds. The above-prepared photoresist composition was spin-coated on the silicon wafer at a speed of 300 - 5000 revolutions per minute, baked on a hot plate at 120 °C for 120 seconds to obtain a 2-μm thick photoresist layer, and then exposed with a Nikon I9 exposure machine at an exposure intensity of 20 - 200 mj / cm 2 , and finally developed in a 2.38% TMAH developer.

[0151] Optimal resolution test: The developed wafer was observed under a TEL-CDSEM, and the highest resolution image that could be completely developed at the optimal exposure energy was obtained.

[0152] Developed film retention rate test: In the evaluation of the film retention rate, under the set process conditions, when 100% ≥ developed film retention rate > 95%, it is rated as +++++; when 95% ≥ developed film retention rate > 90%, it is rated as ++++; when 90% ≥ developed film retention rate > 85%, it is rated as +++; when 85% ≥ developed film retention rate > 80%, it is rated as ++, and when the film retention rate ≤ 80%, it is rated as +.

[0153] Fabrication of the photosensitive cured film: A wet film was coated using a rotational viscometer (Mikasa: MS-B150 + DA-60S), pre-dried on a hot plate, then transferred to nitrogen drying for further curing after exposure and development, cured at 230 °C for 60 min, and taken out after cooling to room temperature.

[0154] Cured film retention rate test: In the evaluation of the film retention rate, under the set process conditions, when the developed film retention rate > 85%, it is rated as +++++; when 85% ≥ developed film retention rate > 80%, it is rated as ++++; when 80% ≥ developed film retention rate > 75%, it is rated as +++; when 75% ≥ developed film retention rate > 70%, it is rated as ++, and when the film retention rate ≤ 70%, it is rated as +.

[0155] Glass transition temperature (Tg): Measured using a thermomechanical analyzer (TA Instrument, model Q400). Atmosphere: Nitrogen atmosphere; Temperature: Heating rate of 10 °C / min.

[0156] Thermogravimetric temperature (T5%): The thermal decomposition temperature was measured using a thermogravimetric analyzer (model TGA-55) with a heating rate of 10 °C / min and a sample size of 3-5 mg; the temperature range was from R.T. to 500 °C.

[0157] After testing, as can be seen from Table 3, by introducing the structural unit of the general formula (2) into the polyimide, the corresponding polyimide precursor photoresist can achieve high sensitivity, high resolution, high film retention rate, and a cured film layer of the photoresist sample with good heat resistance. 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, resolution, and heat resistance.

[0158] 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 to the present invention in combination with the existing well-known common sense also fall within the protection scope defined by the claims of the present invention.

Claims

1. A polyimide precursor, characterized in that, The structure of the 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), Ar s represents an alkylene or arylene group having 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 ≥ 5%.

2. The polyimide precursor according to claim 1, characterized in that, m / (m + n) ≥ 50%.

3. The polyimide precursor according to claim 1, characterized in that, 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'-oxybisphthalic 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 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 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 non-hydroxylamine-containing 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, p-aminophenyl p-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 polyimide precursor according to claim 1, characterized in that, The structure represented by the general formula (2) is any one of the following structures:

7. The polyimide precursor according to claim 1, wherein The weight-average molecular weight of the polyimide precursor is 1000-200000 g / mol; the dissolution rate in 2.38% aqueous tetramethylammonium hydroxide solution is 5-10000 Å / second.

8. A photoresist composition for preparing the 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:

9. The photoresist composition according to claim 8, wherein, The photosensitive compound is a polyphenol compound or an esterified product of polyhydroxy benzophenone and diazonaphthoquinone sulfonyl chloride; the additive is one or more of a sensitizer, a curing agent, and a leveling agent; the solvent is one or more of a ketone solvent, an ester solvent, an ether solvent, an aromatic hydrocarbon solvent, and other solvents.

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 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.

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