Polymer, method for producing the same, use thereof, and intrinsic low-temperature curing negative photoresist

Abstract

The application discloses a polymer, a preparation method and application thereof, and an intrinsic low-temperature curing negative photoresist, and the polymer is prepared by the following steps: reacting a dianhydride monomer and an esterification reagent to obtain a first intermediate, performing acyl chlorination on the first intermediate to obtain a second intermediate, and reacting the second intermediate with a first diamine monomer and a second diamine monomer. The polymer disclosed by the application can effectively reduce the curing temperature of polyimide, and meanwhile, the mechanical property, dielectric property and thermal property of the polymer are also improved.

Description

Technical Field

[0001] This application relates to the field of microelectronic packaging and display technology, specifically to a polymer, a method for preparing the polymer, the use of the polymer, and an intrinsically low-temperature curable negative photoresist. Background Technology

[0002] Due to their excellent thermal, mechanical, and electrical properties, as well as good chemical resistance, polyimide (PI) and polybenzoxazole (PBO) are widely used as insulating, stress-buffering, and overlay coatings for interlayer interconnects in chip redistribution lines (RDLs) to improve the reliability of semiconductor devices, provide uniform bump height and precise bump shape for wafer layout, while maintaining low deposition internal stress. Advanced packaging technologies, such as multilayer RDLs, 3D stacking, and heterogeneous integration (HI), enable various chips and chiplets with different functions, capabilities, sizes, and origins to work collaboratively in a system, connected on substrates ranging from silicon and fan-out to organic and glass. Polyimide (PI) and polybenzoxazole (PBO) are also used in advanced display technologies as structural platforming layers and pixel definition layers in thin-film transistors (TFTs). Besides structural platforming, the former also functions as a stress buffer, while the latter aims to separate the three primary colors of light emission—red, green, and blue—preventing crosstalk between colors.

[0003] Photosensitive polyimide (PSPI), due to its photosensitive properties, has achieved large-scale application as an insulating protective layer in the microelectronics packaging field through coating, exposure, development, and pattern formation. With the continuous development of advanced packaging technologies, some molded devices and materials cannot withstand high temperatures, making it impossible to use conventional high-temperature curing PSPI materials. Low-temperature curing PSPI can avoid damaging devices with low heat resistance and also reduce wafer and planar warpage issues. During high-temperature thermal imidization, wafer warpage may occur, and low-melting-point solder joints in molded circuits may experience cracking, detachment, and recrystallization, severely damaging the performance of molded devices. Therefore, PSPI must be able to cure faster at lower temperatures while maintaining its mechanical, dielectric, and thermal properties. Summary of the Invention

[0004] The purpose of this application is to provide a low-temperature curing photosensitive polyimide polymer that can effectively reduce the curing temperature of polyimide, while also improving its mechanical properties, dielectric properties, and thermal properties.

[0005] To achieve the above objectives, the present application provides a polymer with the following structural formula:

[0006]

[0007] Where the degree of polymerization m = 1-1000, n = 1-1000;

[0008] Ar1 is selected from any of the following structures:

[0009]

[0010] Ar2 is selected from residues of any of the following diamine monomers: m-phenylenediamine, 2,2'-di(trifluoromethyl)-(1,1'-diphenyl)-4,4'-diamine, 9,9-bis(3-fluoro-4-aminophenyl)fluorene, 9,9-bis(4-aminophenyl)fluorene, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 9,9-dimethylfluorene-2,7-diamine, p-phenylenediamine, 4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, etc. 1,4-Aminophenoxy)benzene, 4,4'-diamino-2,2'-dimethylbiphenyl, 2-(4-aminophenyl)-5-aminobenzoxazole, 2-(4-aminophenyl)-5-aminobenzimidazole, 1,4-bis(3-aminophenoxy)benzene, 1,3-bis(3-hydroxy-4-aminophenoxy)benzene, 2-(4-aminophenyl)-6-aminobenzoxazole, 2,2-p-phenyl-bis(5-aminobenzozazole), 2,2'-p-phenyl-bis(6-aminobenzozazole), 2,2-bis(4-hydroxy-3-aminophenyl)propane, 3,3'-dihydroxybenzidine and 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid;

[0011] Ar3 is selected from residues of any of the following dianhydride monomers: 4,4'-biphenyl ether dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, 2,2'-bis(3,4-dicarboxylic acid)hexafluoropropane dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic acid dianhydride, 3,3,4,4-diphenyl sulfone tetracarboxylic acid dianhydride, naphthalene-1,4,5,8-tetracarboxylic acid dianhydride, diphenyl sulfide dianhydride, bisphenol A type diether dianhydride, hexafluoro dianhydride, hydrogenated... Pyromellitic dianhydride, cyclobutanetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorenyl dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, (4-phthalic anhydride)formyloxy-4-phthalate, bis[(3,4-dianhydride)phenyl]terephthalate, 4,4'-terephthalodioxybis-o-dicarboxylic anhydride, diethylene glycol (4-tricarboxylic anhydride), pyromellitic dianhydride and 9,9-bis(trifluoromethyl)-2,3,6,7-oxanthracenetetracarboxylic dianhydride;

[0012] R is formed by reacting the dianhydride monomer with any of the following esterifying agents: hydroxyethyl methacrylate, o-nitrobenzyl alcohol, 2-hydroxyethyl acrylate, hydroxypropyl methacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, acrylic acid, β-(acryloyloxy)propionic acid, 4-hydroxybutyl acrylate, N-(2-hydroxypropyl)-2-methyl-2-propionamide, 2-hydroxypropylmethacrylamide, and hydroxypropyl methacrylate.

[0013] The technical solution of this application also provides a method for preparing the above-mentioned polymer, comprising the following steps: reacting a dianhydride monomer and an esterification reagent in a first solvent to obtain a first intermediate; reacting the first intermediate and an acyl chloride reagent in the first solvent to obtain a second intermediate; and reacting the second intermediate, a first diamine monomer, and a second diamine monomer in a second solvent to obtain the polymer.

[0014] In some embodiments of this application, the dianhydride monomer is selected from 4,4'-biphenyl ether dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, 2,2'-bis(3,4-dicarboxylic acid)hexafluoropropane dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic acid dianhydride, 3,3,4,4-diphenyl sulfone tetracarboxylic acid dianhydride, naphthalene-1,4,5,8-tetracarboxylic acid dianhydride, diphenyl sulfide dianhydride, bisphenol A type diether dianhydride, hexafluorodianhydride, and hydrogenated pyromellitic acid. At least one of the following: tetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorenyl dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, (4-phthalic anhydride)formyloxy-4-phthalate, bis[(3,4-dianhydride)phenyl]terephthalate, 4,4'-terephthalodioxybis-o-dicarboxylic anhydride, diethylene glycol (4-tricarboxylic anhydride), pyromellitic dianhydride, and 9,9-bis(trifluoromethyl)-2,3,6,7-oxanthracenetetracarboxylic dianhydride;

[0015] The esterification reagent is selected from at least one of hydroxyethyl methacrylate, o-nitrobenzyl alcohol, 2-hydroxyethyl acrylate, hydroxypropyl methacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, acrylic acid, β-(acryloyloxy)propionic acid, 4-hydroxybutyl acrylate, N-(2-hydroxypropyl)-2-methyl-2-propionamide, 2-hydroxypropylmethacrylamide, and hydroxypropyl methacrylate;

[0016] The first diamine monomer is selected from at least one of the following structures:

[0017]

[0018] The second diamine monomer is selected from m-phenylenediamine, 2,2'-di(trifluoromethyl)-(1,1'-diphenyl)-4,4'-diamine, 9,9-bis(3-fluoro-4-aminophenyl)fluorene, 9,9-bis(4-aminophenyl)fluorene, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 9,9-dimethylfluorene-2,7-diamine, p-phenylenediamine, 4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 1,3-bis(4-aminophenoxy)benzene, and 1,4-bis(4-aminophenoxy)benzene. At least one of the following: 4,4'-diamino-2,2'-dimethylbiphenyl, 2-(4-aminophenyl)-5-aminobenzoxazole, 2-(4-aminophenyl)-5-aminobenzimidazole, 1,4-bis(3-aminophenoxy)benzene, 1,3-bis(3-hydroxy-4-aminophenoxy)benzene, 2-(4-aminophenyl)-6-aminobenzoxazole, 2,2-p-phenyl-bis(5-aminobenzozazole), 2,2'-p-phenyl-bis(6-aminobenzozazole), 2,2-bis(4-hydroxy-3-aminophenyl)propane, 3,3'-dihydroxybenzidine, and 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid.

[0019] In some embodiments of this application, the first solvent and the second solvent are respectively selected from N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, tetrahydrofuran, 1,3-dimethyl-2-imidazolinone, γ-butyrolactone, ethyl acetate, butyl acetate, n-propyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, toluene, xylene, mesitylene, diacetone alcohol, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, methyl propyl ketone, tetrahydropyran, dioxane, dioxane, and ethylene glycol. The acyl chloride is selected from at least one of monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monomethyl ether acetate; the acyl chloride reagent is selected from at least one of thionyl chloride, aluminum chloride, boron trifluoride, antimony pentachloride, ferric bromide, ferric chloride, tin tetrachloride, titanium chloride, zinc chloride, diphenyl ether dicarboxylate chloride, isophthaloyl chloride, terephthaloyl chloride, biphenyl dicarboxylate chloride, diphenyl sulfone dicarboxylate chloride, diphenylmethane dicarboxylate chloride and benzophenone dicarboxylate chloride, octyl dicarboxylate chloride, hexadecanoyl chloride, nonadicarboxylate chloride, dicarboxylate chloride, dodecane dicarboxylate chloride, 1,4-cyclohexane dicarboxylate chloride, and 1,3-cyclobutane dicarboxylate chloride.

[0020] In some embodiments of this application, the reaction conditions of the dianhydride monomer and the esterification reagent satisfy at least one of the following: a. the molar ratio of the dianhydride monomer to the esterification reagent is 1:(1-4); b. the reaction temperature is 20℃-60℃, and the reaction time is 8 hours-24 hours; the reaction conditions of the first intermediate and the acyl chloride reagent satisfy at least one of the following: A. the molar ratio of the acyl chloride reagent to the dianhydride monomer is (2-2.8):1; B. the acyl chloride reagent is added dropwise at a rate of 1-5 drops / second under the protection of an inert gas and in an ice-water bath at 0-10℃.

[0021] In some embodiments of this application, the conditions of the second intermediate, the first diamine monomer and the second diamine monomer satisfy at least one of the following: (1) the ratio of the total molar number of the first diamine monomer and the second diamine monomer to the molar number of the second intermediate is 1:(1~2); (2) the reaction temperature is 15℃~35℃ and the reaction time is 3 hours~8 hours.

[0022] The technical solution of this application also provides the use of the above-mentioned polymer in the preparation of intrinsic low-temperature curing negative photoresist.

[0023] The technical solution of this application also provides an intrinsic low-temperature curing negative photoresist, the raw materials of which, by weight, include: 100 parts of the above-mentioned polymer; 1-10 parts of photoinitiator; 1-30 parts of crosslinking agent; 1-10 parts of silane coupling agent; and 30-80 parts of third solvent.

[0024] In some embodiments of this application, the photoinitiator includes ethyl 2,4,6-trimethylbenzoylphosphonate, 2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone, ethyl 4-dimethylaminobenzoate, 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyl oxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl] ethyl ketone 1-(O-acetyl oxime), bis( One or more of the following: 1-(2,4-difluorophenyl)-3-pyrrolithium, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, α,α-diethoxyacetophenone, 2-hydroxy-2-methyl-phenylacetone, 1-hydroxy-cyclohexylbenzophenone, 2-hydroxy-2-methyl-p-hydroxyethyl ether phenylacetone, 2,4,6-trimethylbenzoyl-ethoxy-phenylphosphine oxide, Mistral ketone, methyl ethyl Mistral ketone, and isopropylthioanthracene.

[0025] In some embodiments of this application, the crosslinking agent includes one or more of pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, α,ω-dimethacrylate-based polyethylene glycol, triethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, diethylene glycol dimethacrylate (containing the stabilizer methoxyhydroquinone), ethylene glycol phenyl ether acrylate, tetraethylene glycol dimethacrylate, tri(2-acryloyloxyethyl) isocyanurate, trimethylolpropane trimethacrylate, and trimethylolpropane triacrylate; the silane coupling agent includes triethoxysilylpropylmaleic acid, G3-methacryloyloxypropyltriethoxysilane, 3-ureapropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-propyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptomethyltrimethoxysilane. The solvent comprises one or more of the following: alkylene, 3-mercaptomethyldimethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropylsilane, 3-thiopropyltributoxysilane, 2-(3,4-epoxycyclohexane)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexane)ethyltriethoxysilane, epoxybutyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, p-aminophenyltrimethoxysilane, aminophenyltrimethoxysilane, 3-(m-aminophenyl)trimethylsilane, 3-methacryloyloxypropyltrimethoxysilane, 3-propenoxypropyltrimethoxysilane, 3-ethoxypropyltrimethoxysilane, and vinyltrimethoxysilane; the third solvent comprises one or more of the following: N-methylpyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, tetrahydrofuran, and cyclohexanone.

[0026] Compared with the prior art, the polymer, its preparation method, its uses, and the intrinsically low-temperature curable negative photoresist of this application have the following advantages:

[0027] The polymer in this application has unique structural characteristics, which is beneficial to increasing intermolecular forces, thereby improving the imidization rate and giving it better mechanical properties, thermal properties, photolithography properties, and chemical resistance. When this polymer with a specific structure is used to prepare low-temperature curing negative photoresists, the curing temperature can be effectively reduced, and its mechanical properties, dielectric properties, and thermal properties are also improved.

[0028] The preparation method of this polymer uses readily available raw materials, and the preparation steps and process conditions are simple, making it easy to promote and apply industrially. Attached Figure Description

[0029] The following accompanying drawings describe in detail the exemplary embodiments disclosed in this application. The same reference numerals denote similar structures in several views of the drawings. Those skilled in the art will understand that these embodiments are non-limiting and exemplary, and the drawings are for illustrative purposes only and are not intended to limit the scope of this application. Other embodiments may similarly fulfill the inventive intent of this application. It should be understood that the drawings are not drawn to scale. Wherein:

[0030] Figure 1 This is a structural formula of a polymer according to an embodiment of this application;

[0031] Figure 2 This is another polymer structural formula according to an embodiment of this application;

[0032] Figure 3 This is the structural reaction formula for the preparation of the polymer in Example 1 of this application;

[0033] Figure 4 The FT-IR spectrum of the polymer prepared in Example 1 of this application;

[0034] Figure 5 This is a photolithographic performance test diagram of the intrinsic temperature-curing negative photoresist of Example 2 of this application;

[0035] Figure 6 This is a photolithographic performance test diagram of the intrinsic temperature-curing negative photoresist of Example 3 of this application;

[0036] Figure 7 This is a 3D image of the surface of the cured film of Example 16 of this application after being immersed in N-methylpyrrolidone. Detailed Implementation

[0037] The following description provides specific application scenarios and requirements for this application, intended to enable those skilled in the art to make and use the content of this application. Various partial modifications to the disclosed embodiments will be apparent to those skilled in the art, and the general principles defined herein can be applied to other embodiments and applications without departing from the spirit and scope of this application. Therefore, this application is not limited to the embodiments shown, but rather to the widest scope consistent with the claims.

[0038] Based on the need to lower the curing temperature of polyimide and improve its mechanical and dielectric properties, this application provides an intrinsically low-temperature curable photosensitive polyimide polymer, the structural formula of which is as follows: Figure 1 As shown.

[0039] In the structural formula of the polymer, the degree of polymerization m = 1-1000, n = 1-1000.

[0040] In the structural formula of the polymer, Ar1 is selected from any of the following structures:

[0041]

[0042] In the structural formula of the polymer, Ar2 is selected from residues of any of the following diamine monomers: m-phenylenediamine, 2,2'-bis(trifluoromethyl)-(1,1'-diphenyl)-4,4'-diamine, 9,9-bis(3-fluoro-4-aminophenyl)fluorene, 9,9-bis(4-aminophenyl)fluorene, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 9,9-dimethylfluorene-2,7-diamine, p-phenylenediamine, 4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 1,3-bis(4-aminophenoxy)benzene, 1 4-Bis(4-aminophenoxy)benzene, 4,4'-diamino-2,2'-dimethylbiphenyl, 2-(4-aminophenyl)-5-aminobenzoxazole, 2-(4-aminophenyl)-5-aminobenzimidazole, 1,4-bis(3-aminophenoxy)benzene, 1,3-bis(3-hydroxy-4-aminophenoxy)benzene, 2-(4-aminophenyl)-6-aminobenzoxazole, 2,2-p-phenyl-bis(5-aminobenzozazole), 2,2'-p-phenyl-bis(6-aminobenzozazole), 2,2-bis(4-hydroxy-3-aminophenyl)propane, 3,3'-dihydroxybenzidine, and 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid.

[0043] In the structural formula of the polymer, Ar3 is selected from residues of any of the following dianhydride monomers: 4,4'-biphenyl ether dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, 2,2'-bis(3,4-dicarboxylic acid)hexafluoropropane dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic acid dianhydride, 3,3,4,4-diphenyl sulfone tetracarboxylic acid dianhydride, naphthalene-1,4,5,8-tetracarboxylic acid dianhydride, diphenyl sulfide dianhydride, bisphenol A type diether dianhydride, hexafluoropropane dianhydride, etc. Fluorodianhydride, hydrogenated pyromellitic dianhydride, cyclobutanetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorenyl dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, (4-phthalic anhydride)formyloxy-4-phthalate, bis[(3,4-dianhydride)phenyl]terephthalate, 4,4'-terephthalodioxybis(o-dicarboxylic anhydride), diethylene glycol (4-tricarboxylic anhydride), pyromellitic dianhydride, and 9,9-bis(trifluoromethyl)-2,3,6,7-oxanthracenetetracarboxylic dianhydride.

[0044] It should be noted that the residues of a substance mentioned in this application refer to the portion remaining in the molecular structure of that substance after removing the reactive functional groups. For example, when Ar2 is a monomer of m-phenylenediamine. When the residues are removed, the Ar2 structure, which is the molecular structure of m-phenylenediamine, is the part remaining after removing two amino groups (-NH2). For example, when Ar3 is a 4,4'-biphenyl dianhydride monomer. When the residues are removed, the structure of Ar3, that is, the molecular structure of 4,4'-biphenyl dianhydride, is the part remaining after removing two anhydride groups.

[0045] In the structural formula of the polymer, R is formed by reacting the dianhydride monomer with any of the following esterifying agents: hydroxyethyl methacrylate, o-nitrobenzyl alcohol, 2-hydroxyethyl acrylate, hydroxypropyl methacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, acrylic acid, β-(acryloyloxy)propionic acid, 4-hydroxybutyl acrylate, N-(2-hydroxypropyl)-2-methyl-2-propionamide, 2-hydroxypropylmethacrylamide, and hydroxypropyl methacrylate.

[0046] The polymers provided in this application demonstrate a significant influence of the main chain molecular structure on the imidization temperature. Compared to flexible main chain structures, rigid main chain structures face greater challenges in spatial functional group reactions and cyclization, requiring higher curing temperatures to achieve imidization levels comparable to flexible main chain structures. Although rigid main chain structures generally exhibit superior mechanical properties, a balance needs to be struck within the PI main chain structure to ensure both flexibility and performance. This involves both lowering the imidization temperature and maintaining optimal mechanical properties. The embodiments in this application, through the ingenious design of rigid unit structures and the introduction of flexible unit structures to form a semi-rigid polymer backbone, can enhance molecular chain motion, reduce interchain interactions, thereby promoting the imidization reaction and effectively lowering the imidization temperature. Simultaneously, increasing electron density helps strengthen intermolecular interactions and improve the imidization rate. This comprehensive design optimizes the imidization level while maintaining good mechanical properties.

[0047] In a preferred embodiment of this application, the polymer has the following structural formula: Figure 2 As shown.

[0048] This application also provides a method for preparing the above-mentioned polymer, the preparation method comprising the following steps:

[0049] S1: React the dianhydride monomer and the esterifying agent in the first solvent to obtain the first intermediate;

[0050] S2: React the first intermediate and the acyl chloride reagent in the first solvent to obtain the second intermediate;

[0051] S3: React the second intermediate, the first diamine monomer, and the second diamine monomer in a second solvent to obtain the polymer.

[0052] In some preferred embodiments of this application, in step S1, the dianhydride monomer is selected from 4,4'-biphenyl ether dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, 2,2'-bis(3,4-dicarboxylic acid)hexafluoropropane dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic acid dianhydride, 3,3,4,4-diphenyl sulfone tetracarboxylic acid dianhydride, naphthalene-1,4,5,8-tetracarboxylic acid dianhydride, diphenyl sulfide dianhydride, bisphenol A type diether dianhydride, hexafluorodianhydride, The dianhydride is selected from at least one of hydrogenated pyromellitic dianhydride, cyclobutanetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorenyl dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, (4-phthalic anhydride)formyloxy-4-phthalate, bis[(3,4-dianhydride)phenyl]terephthalate, 4,4'-terephthalodioxybis(o-dicarboxylic anhydride), diethylene glycol (4-tricarboxylic anhydride), pyromellitic dianhydride, and 9,9-bis(trifluoromethyl)-2,3,6,7-oxanthracene tetracarboxylic dianhydride. In a preferred embodiment of this application, the dianhydride monomer is 4,4'-biphenyl ether dianhydride or 3,3',4,4'-biphenyltetracarboxylic dianhydride.

[0053] In some preferred embodiments of this application, in step S1, the esterification agent is selected from at least one of hydroxyethyl methacrylate, o-nitrobenzyl alcohol, 2-hydroxyethyl acrylate, hydroxypropyl methacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, acrylic acid, β-(acryloyloxy)propionic acid, 4-hydroxybutyl acrylate, N-(2-hydroxypropyl)-2-methyl-2-propionamide, 2-hydroxypropylmethacrylamide, and hydroxypropyl methacrylate. In a more preferred embodiment of this application, the esterification agent is hydroxyethyl methacrylate.

[0054] In some preferred embodiments of this application, in step S1, the first solvent is selected from at least one of N-methylpyrrolidone, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone, tetrahydrofuran, 1,3-dimethyl-2-imidazolinone (DMI), γ-butyrolactone, ethyl acetate, butyl acetate, n-propyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, toluene, xylene, mesitylene, diacetone alcohol, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, methyl propyl ketone, tetrahydropyran, dioxane, dioxane, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monomethyl ether acetate. In a preferred embodiment of this application, the first solvent is N-methylpyrrolidone or DMF.

[0055] In some preferred embodiments of this application, in step S1, the molar ratio of the dianhydride monomer to the esterifying agent is 1:(1-4). When the molar ratio of the dianhydride monomer to the esterifying agent is too large, the polymer solubility will be poor; when the molar ratio of the dianhydride monomer to the esterifying agent is too small, gelation will occur. In a more preferred embodiment of this application, the molar ratio of the dianhydride monomer to the esterifying agent is 1:2.

[0056] In some preferred embodiments of this application, in step S1, the reaction temperature of the dianhydride monomer and the esterification reagent is 20°C to 60°C, and the reaction time is 8 hours to 24 hours. In a more preferred embodiment of this application, the reaction temperature of the dianhydride monomer and the esterification reagent is 30°C, and the reaction time is 16 hours.

[0057] In some preferred embodiments of this application, in step S2, the acyl chloride reagent is selected from at least one of thionyl chloride (SOCl2), aluminum chloride (AlCl3), boron trifluoride (BF3), antimony pentachloride (SbCl5), ferric bromide (FeBr3), ferric chloride (FeCl3), tin tetrachloride (SnCl4), titanium chloride (TiCl4), zinc chloride (ZnCl2), diphenyl ether dicarboxylate chloride, isophthaloyl chloride, terephthaloyl chloride, biphenyl dicarboxylate chloride, diphenyl sulfone dicarboxylate chloride, diphenylmethane dicarboxylate chloride and benzophenone dicarboxylate chloride, octyl dicarboxylate chloride, hexadecoyl chloride, nonadicarboxylate chloride, dicarboxylate chloride, dodecane dicarboxylate chloride, 1,4-cyclohexane dicarboxylate chloride and 1,3-cyclobutane dicarboxylate chloride. In a more preferred embodiment of this application, the acyl chloride reagent is SOCl2.

[0058] In some preferred embodiments of this application, in step S2, the molar ratio of the acyl chloride reagent to the dianhydride monomer is (2-2.8):1. In a more preferred embodiment of this application, the molar ratio of the acyl chloride reagent to the dianhydride monomer is 2.1:1.

[0059] In some preferred embodiments of this application, in step S2, an acyl chloride reagent is added dropwise to the reaction solution under an inert gas atmosphere and ice bath conditions. After the addition is complete, the second intermediate is obtained. In a more preferred embodiment of this application, the inert gas is nitrogen, the temperature of the ice-water bath is 0-10°C, and the acyl chloride reagent is added dropwise at a rate of 1-5 drops / second. In a more preferred embodiment of this application, the temperature of the ice-water bath is 5°C, and the dropping rate of the acyl chloride reagent is 1-5 drops / second.

[0060] In some preferred embodiments of this application, the first diamine monomer is selected from at least one of the following structures:

[0061]

[0062] In a preferred embodiment of this application, the first diamine monomer is (1,1-bis(4'-aminophenyl)cyclohexane), (4,4'-(1-methyldecahydroquinoline-6,6-diyl)diphenylamine), (4,4'-(3,5-dimethylcyclohexane-1,1-diyl)diphenylamine), (4,4'-(3,5-bis(trifluoromethyl)cyclohexane-1,1-diyl)diphenylamine), (4,4'-(5,6,7,8-tetrahydroquinazolin-7,7-diyl)diphenylamine), One of (4,4'-(3-(4,5-dihydro-1H-imidazol-5-yl)cyclohexane-1,1-diyl)diphenylamine).

[0063] In step S3, the second diamine monomer is selected from m-phenylenediamine, 2,2'-di(trifluoromethyl)-(1,1'-diphenyl)-4,4'-diamine, 9,9-bis(3-fluoro-4-aminophenyl)fluorene, 9,9-bis(4-aminophenyl)fluorene, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 9,9-dimethylfluorene-2,7-diamine, p-phenylenediamine, 4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl) The diamine monomer is at least one of the following: 4,4'-diamino-2,2'-dimethylbiphenyl, 2-(4-aminophenyl)-5-aminobenzoxazole, 2-(4-aminophenyl)-5-aminobenzimidazole, 1,4-bis(3-aminophenoxy)benzene, 1,3-bis(3-hydroxy-4-aminophenoxy)benzene, 2-(4-aminophenyl)-6-aminobenzoxazole, 2,2-p-phenyl-bis(5-aminobenzozazole), 2,2'-p-phenyl-bis(6-aminobenzozazole), 2,2-bis(4-hydroxy-3-aminophenyl)propane, 3,3'-dihydroxybenzidine, and 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid. In a preferred embodiment of this application, the second diamine monomer is 4,4'-diaminodiphenyl ether or 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane.

[0064] In some preferred embodiments of this application, in step S3, the second solvent is selected from at least one of N-methylpyrrolidone, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone, tetrahydrofuran, 1,3-dimethyl-2-imidazolinone (DMI), γ-butyrolactone, ethyl acetate, butyl acetate, n-propyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, toluene, xylene, mesitylene, diacetone alcohol, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, methyl propyl ketone, tetrahydropyran, dioxane, dioxane, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monomethyl ether acetate. In a preferred embodiment of this application, the second solvent is NMP or DMAc.

[0065] In some preferred embodiments of this application, in step S3, the ratio of the total molar number of the first diamine monomer and the second diamine monomer to the molar number of the second intermediate is 1:(1-2). If this molar ratio is too large, the polymer molecular weight will be too low; if it is too small, the polymer molecular weight will be too large, or even gel. The first diamine monomer and the second diamine monomer can be in any molar ratio. In a more preferred embodiment of this application, the ratio of the total molar number of the diamine monomer to the molar number of the second intermediate is 1:1, and the molar ratio of the first diamine monomer to the second diamine monomer is 1:1.

[0066] In some preferred embodiments of this application, in step S3, the reaction temperature of the second intermediate, the first diamine monomer, and the second diamine monomer is 15°C to 35°C, and the reaction time is 3 hours to 8 hours. In a more preferred embodiment of this application, the reaction temperature is 25°C, and the reaction time is 4 hours.

[0067] The polymer preparation method of this application embodiment first reacts a dianhydride monomer and an esterification reagent in a first solvent to obtain a first intermediate, and then reacts the first intermediate with the first diamine monomer and the second diamine monomer. This method can quickly and efficiently prepare the polymer with the above-mentioned unique structural characteristics. The raw materials of this preparation method are readily available, the steps and process conditions are simple, and it is easy to promote and apply industrially.

[0068] This application also provides the use of the above-described polymer in the preparation of intrinsically low-temperature curable negative photoresists. The polymer described in this application can effectively reduce the curing temperature of polyimide, while simultaneously improving its thermal, mechanical, and dielectric properties. This intrinsically low-temperature curable negative photoresist can be fully cured at a low temperature (200°C).

[0069] In some preferred embodiments of this application, the raw materials of the intrinsically low-temperature curable negative photoresist, by weight, include: 100 parts of the aforementioned polymer; 1-10 parts of photoinitiator; 1-30 parts of crosslinking agent; 1-10 parts of silane coupling agent; and 30-80 parts of a third solvent. In a more preferred embodiment of this application, the raw materials include: 1 part of photoinitiator; 15 parts of crosslinking agent; 5 parts of silane coupling agent; and 50 parts of a third solvent.

[0070] In some embodiments of this application, the photoinitiator includes ethyl 2,4,6-trimethylbenzoylphosphonate, 2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone, ethyl 4-dimethylaminobenzoate, 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyl oxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl] ethyl ketone 1-(O-acetyl oxime), bis( One or more of the following: 1-(2,4-difluorophenyl)-3-pyrrolithodiphenoxyacetone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, α,α-diethoxyacetophenone, 2-hydroxy-2-methyl-phenylacetone, 1-hydroxy-cyclohexylbenzophenone, 2-hydroxy-2-methyl-p-hydroxyethyl ether phenylacetone, 2,4,6-trimethylbenzoyl-ethoxy-phenylphosphine oxide, Mistral ketone, methyl ethyl Mistral ketone, and isopropylthioxanthracene. In a preferred embodiment of this application, the photoinitiator is 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyl oxime) or 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]acetophenone 1-(O-acetyl oxime).

[0071] In some embodiments of this application, the crosslinking agent includes one or more of pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, α,ω-dimethacrylate-based polyethylene glycol, triethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, diethylene glycol dimethacrylate (containing the stabilizer methoxyhydroquinone), ethylene glycol phenyl ether acrylate, tetraethylene glycol dimethacrylate, tri(2-acryloyloxyethyl) isocyanurate, trimethylolpropane trimethacrylate, and trimethylolpropane triacrylate. In a more preferred embodiment of this application, the crosslinking agent is tetraethylene glycol dimethacrylate.

[0072] In some embodiments of this application, the silane coupling agent includes triethoxysilylpropylmaleic acid, G3-methacryloyloxypropyltriethoxysilane, 3-ureapropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-propyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptomethyltrimethoxysilane, 3-mercaptomethyldimethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropylsilane, 3-thiopropyltributoxysilane, 2-(3, The silane coupling agent is one or more selected from the following: 4-epoxycyclohexane)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexane)ethyltriethoxysilane, epoxybutyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, p-aminophenyltrimethoxysilane, aminophenyltrimethoxysilane, 3-(m-aminophenyl)trimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-propenyloxypropyltrimethoxysilane, 3-ethoxypropyltrimethoxysilane, and vinyltrimethoxysilane. In a preferred embodiment of this application, the silane coupling agent is 3-methacryloyloxypropyltrimethoxysilane.

[0073] In some embodiments of this application, the third solvent includes one or more of N-methylpyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, tetrahydrofuran, and cyclohexanone. In a more preferred embodiment of this application, the third solvent is N-methylpyrrolidone.

[0074] The technical solution of this application will be clearly and completely described below with reference to the embodiments of this application. Unless otherwise specified, the reagents and raw materials used can be purchased commercially. Experimental methods in the following embodiments that do not specify specific conditions are performed according to conventional methods and conditions, or according to the product instructions.

[0075] Example 1

[0076] The polymer preparation method of this embodiment includes the following steps:

[0077] (1) Take 4,4'-biphenyl ether dianhydride and hydroxyethyl methacrylate in a molar ratio of 1:2 and add them to N-methylpyrrolidone. React in an oil bath at 30°C for 8 hours under a nitrogen atmosphere to obtain a reaction solution containing the first intermediate.

[0078] (2) Under a nitrogen atmosphere and an ice bath at 5°C, thionyl chloride was added dropwise to the reaction solution at a rate of 1 drop / second, and the molar ratio of thionyl chloride to 4,4'-biphenyl dianhydride was 2.1:1. After the addition was completed, the second intermediate was obtained.

[0079] (3) Take 4,4'-diaminodiphenyl ether, 1,1-bis(4'-aminophenyl)cyclohexane and the second intermediate in a molar ratio of 1:1:4 and add them to N-methyl-2-pyrrolidone. React at 25°C for 4 hours to obtain the reaction product. The obtained reaction product is uniformly introduced into deionized water, allowed to stand and separate into layers, the upper layer is removed, the resin is broken up, and the deionized water is replaced for soaking, washing and filtering. This process is repeated several times and the polymer is dried.

[0080] (4) Take 5g of the polymer, 0.05g of Miescherichia coli, 0.9g of pentaerythritol tetraacrylate, 0.15g of triethoxysilylpropylmaleic acid and 10g of N-methylpyrrolidone, stir and mix evenly to obtain intrinsic low-temperature curing negative photoresist.

[0081] The structural formula of the polymer in this embodiment can be referred to... Figure 2 Its structural reaction formula is as follows Figure 3 As shown.

[0082] The polymer prepared in Example 1 was subjected to Fourier transform infrared spectroscopy (FT-IR) testing: a Thermo Fisher Scientific Nicolet iS5 Fourier transform infrared spectrometer was used to test the sample, with a test range covering 4000-500 cm⁻¹. -1 The number of tests was set to 32. During the test, the sample was placed directly on the ATR component to obtain results as shown below. Figure 4 The FT-IR plot shown.

[0083] Example 2

[0084] The method for preparing the polymer in this embodiment includes the following steps:

[0085] (1) Take bisphenol A type diether dianhydride and hydroxyethyl methacrylate in a molar ratio of 1:2 and add them to N-methylpyrrolidone. React in an oil bath at 30°C for 8 hours under a nitrogen atmosphere to obtain a reaction solution including the first intermediate.

[0086] (2) Under a nitrogen atmosphere and an ice bath at 5°C, thionyl chloride was added to the reaction solution at a rate of 1 drop / second, and the molar ratio of thionyl chloride to bisphenol A diether dianhydride was 2.1:1. After the addition was completed, the second intermediate was obtained.

[0087] (3) Take 4,4'-diaminodiphenyl ether, 4,4'-(1-methyldecahydroquinoline-6,6-diyl)diphenylamine and the second intermediate in a molar ratio of 1:1:2 and add them to N-methyl-2-pyrrolidone. React at 25°C for 4 hours to obtain the reaction product. The obtained reaction product is uniformly introduced into deionized water, allowed to stand and separate into layers, the upper layer is removed, the resin is broken up, and the deionized water is replaced for soaking, washing and filtering. This process is repeated several times and the polymer is dried.

[0088] (4) Take 5g of the polymer, 0.05g of Miescherichia coli, 0.9g of pentaerythritol tetraacrylate, 0.15g of triethoxysilylpropylmaleic acid and 10g of N-methylpyrrolidone, stir and mix evenly to obtain intrinsic low-temperature curing negative photoresist.

[0089] Example 3

[0090] The method for preparing the polymer in this embodiment includes the following steps:

[0091] (1) Take 9,9-bis(3,4-dicarboxyphenyl)fluorene dihydric anhydride and hydroxyethyl methacrylate in a molar ratio of 1:2, add them to N-methylpyrrolidone, and react them in an oil bath at 30°C for 8 hours under a nitrogen atmosphere to obtain a reaction solution including the first intermediate.

[0092] (2) Under a nitrogen atmosphere and an ice bath at 5°C, thionyl chloride was added dropwise to the reaction solution at a rate of 1 drop / second, and the molar ratio of thionyl chloride to 9,9-bis(3,4-dicarboxyphenyl)fluorene dihydric anhydride was 2.1:1. After the addition was completed, the second intermediate was obtained.

[0093] (3) Take 1,4-bis(3-aminophenoxy)benzene, 4,4'-(3,5-dimethylcyclohexane-1,1-diyl)diphenylamine and the second intermediate in a molar ratio of 1:1:3 and add them to N-methyl-2-pyrrolidone. React at 25°C for 4 hours to obtain the reaction product. The obtained reaction product is uniformly introduced into deionized water, allowed to stand and separate into layers, the upper layer is removed, the resin is broken up, and the resin is soaked, washed and filtered in deionized water. This process is repeated several times and the polymer is dried to obtain the polymer.

[0094] (4) Take 5g of the polymer, 0.05g of 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyl oxime), 0.9g of diethylene glycol dimethacrylate (containing stabilizer methoxyhydroquinone), 0.15g of triethoxysilylpropyl maleic acid and 10g of N-methylpyrrolidone, stir and mix evenly to obtain intrinsic low-temperature curing negative photoresist.

[0095] Example 4

[0096] The method for preparing the polymer in this embodiment includes the following steps:

[0097] (1) Take 2,2'-bis(3,4-dicarboxylic acid) hexafluoropropane dianhydride and hydroxyethyl methacrylate in a molar ratio of 1:4, add them to N,N-dimethylformamide, and react them in an oil bath at 40°C for 8 hours under a nitrogen atmosphere to obtain a reaction solution including the first intermediate.

[0098] (2) Under a nitrogen atmosphere and an ice bath at 5°C, thionyl chloride was added dropwise to the reaction solution at a rate of 1 drop / second, and the molar ratio of thionyl chloride to 2,2'-bis(3,4-dicarboxylic acid)hexafluoropropane dianhydride was 2.2:1. After the addition was completed, the second intermediate was obtained.

[0099] (3) Take 1,4-bis(3-aminophenoxy)benzene, 1,1-bis(4'-aminophenyl)cyclohexane and the second intermediate in a molar ratio of 1:1:4 and add them to N-methyl-2-pyrrolidone. React at 25°C for 4 hours to obtain the reaction product. The obtained reaction product is uniformly introduced into deionized water, allowed to stand and separate into layers, the upper layer is removed, the resin is broken up, and the resin is soaked, washed and filtered in deionized water. This process is repeated several times and the polymer is dried.

[0100] (4) Take 5g of the polymer, 0.05g of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl] acetone 1-(O-acetyl oxime), 0.9g of 1,6-hexanediol dimethacrylate, 0.15g of 3-propyltriethoxysilane and 10g of N-methylpyrrolidone, stir and mix evenly to obtain the intrinsic low-temperature curing negative photoresist.

[0101] Example 5

[0102] The method for preparing the polymer in this embodiment includes the following steps:

[0103] (1) Take 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride and hydroxyethyl methacrylate in a molar ratio of 1:3, add them to N-methylpyrrolidone, and react them in an oil bath at 60°C for 10 hours under a nitrogen atmosphere to obtain a reaction solution including the first intermediate.

[0104] (2) Under a nitrogen atmosphere and an ice bath at 5°C, thionyl chloride was added to the reaction solution at a rate of 1 drop / second, and the molar ratio of thionyl chloride to 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride was 2.1:1. After the addition was completed, the second intermediate was obtained.

[0105] (3) Take 2,2-bis(4-hydroxy-3-aminophenyl)propane, 1,1-bis(4'-aminophenyl)cyclohexane and the second intermediate in a molar ratio of 1:1:4 and add them to N-methyl-2-pyrrolidone. React at 25°C for 4 hours to obtain the reaction product. The obtained reaction product is uniformly introduced into deionized water, allowed to stand and separate into layers, the upper layer is removed, the resin is broken up, and the resin is soaked, washed and filtered in deionized water. This process is repeated several times and the polymer is dried.

[0106] (4) Take 5g of the polymer, 0.1g of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl] acetone 1-(O-acetyl oxime), 0.10g of 1,6-hexanediol dimethacrylate, 0.25g of 3-propyltriethoxysilane and 10g of N-methylpyrrolidone, stir and mix evenly to obtain the intrinsic low-temperature curing negative photoresist.

[0107] Example 6

[0108] The method for preparing the polymer in this embodiment includes the following steps:

[0109] (1) Take 3,3',4,4'-biphenyltetracarboxylic acid dianhydride and hydroxyethyl methacrylate in a molar ratio of 1:2, add them to N-methylpyrrolidone, and react them in an oil bath at 30°C for 8 hours under a nitrogen atmosphere to obtain a reaction solution including the first intermediate.

[0110] (2) Under a nitrogen atmosphere and an ice bath at 5°C, thionyl chloride was added dropwise to the reaction solution at a rate of 1 drop / second, and the molar ratio of thionyl chloride to 3,3',4,4'-biphenyltetracarboxylic acid dianhydride was 2.1:1. After the addition was completed, the second intermediate was obtained.

[0111] (3) Take 9,9-dimethylfluorene-2,7-diamine, 4,4'-(3,5-bis(trifluoromethyl)cyclohexane-1,1-diyl)diphenylamine and the second intermediate in a molar ratio of 1:1:4 and add them to N-methyl-2-pyrrolidone. React at 25°C for 4 hours to obtain the reaction product. The obtained reaction product is uniformly introduced into deionized water, allowed to stand and separate into layers, the upper layer is removed, the resin is broken up, and the resin is soaked, washed and filtered in deionized water. This process is repeated several times and the polymer is dried.

[0112] (4) Take 5g of the polymer, 0.1g of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl] acetone 1-(O-acetyl oxime), 0.10g of 1,6-hexanediol dimethacrylate, 0.25g of 3-propyltriethoxysilane and 10g of N-methylpyrrolidone, stir and mix evenly to obtain the intrinsic low-temperature curing negative photoresist.

[0113] Example 7

[0114] The method for preparing the polymer in this embodiment includes the following steps:

[0115] (1) Take diphenyl sulfide dianhydride and hydroxyethyl methacrylate in a molar ratio of 1:2 and add them to N-methylpyrrolidone. React in an oil bath at 30°C for 6 hours under a nitrogen atmosphere to obtain a reaction solution including the first intermediate.

[0116] (2) Under nitrogen atmosphere and 5°C ice bath conditions, thionyl chloride was added to the reaction solution at a rate of 1 drop / second, and the molar ratio of thionyl chloride to diphenyl sulfide dianhydride was 2.1:1. After the addition was completed, the second intermediate was obtained.

[0117] (3) Take 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 1,1-bis(4'-aminophenyl)cyclohexane and the second intermediate in a molar ratio of 1:1:4 and add them to N-methyl-2-pyrrolidone. React at 35°C for 4 hours to obtain the reaction product. The obtained reaction product is uniformly introduced into deionized water, allowed to stand and separate into layers, the upper layer is removed, the resin is broken up, and the resin is soaked, washed and filtered in deionized water. This process is repeated several times and the polymer is dried.

[0118] (4) Take 5g of the polymer, 0.1g of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl] acetone 1-(O-acetyl oxime), 0.10g of α,ω-dimethacrylate-based polyethylene glycol, 0.25g of 3-propyltriethoxysilane and 10g of N-methylpyrrolidone, stir and mix evenly to obtain an intrinsic low-temperature curing negative photoresist.

[0119] Example 8

[0120] The method for preparing the polymer in this embodiment includes the following steps:

[0121] (1) Take 3,3,4,4-diphenylsulfone tetracarboxylic acid dianhydride and hydroxyethyl methacrylate in a molar ratio of 1:2, add them to N-methylpyrrolidone, and react them in an oil bath at 30°C for 6 hours under a nitrogen atmosphere to obtain a reaction solution including the first intermediate.

[0122] (2) Under a nitrogen atmosphere and an ice bath at 5°C, thionyl chloride was added dropwise to the reaction solution at a rate of 1 drop / second, and the molar ratio of thionyl chloride to 3,3,4,4-diphenylsulfone tetracarboxylic acid dianhydride was 2.1:1. After the addition was completed, the second intermediate was obtained.

[0123] (3) Take 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 4,4'-(5,6,7,8-tetrahydroquinazoline-7,7-diyl)diphenylamine and the second intermediate in a molar ratio of 1:1:4 and add them to N,N-dimethylformamide. React at 35°C for 4 hours to obtain the reaction product. The obtained reaction product is uniformly introduced into deionized water, allowed to stand and separate into layers, the upper layer is removed, the resin is broken up, and the resin is soaked, washed and filtered in deionized water. This process is repeated several times and the polymer is dried.

[0124] (4) Take 5g of the polymer, 0.1g of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl] acetone 1-(O-acetyl oxime), 0.10g of α,ω-dimethacrylate-based polyethylene glycol, 0.25g of 3-propyltriethoxysilane and 10g of N-methylpyrrolidone, stir and mix evenly to obtain an intrinsic low-temperature curing negative photoresist.

[0125] Example 9

[0126] The method for preparing the polymer in this embodiment includes the following steps:

[0127] (1) Take 3,3',4,4'-benzophenone tetracarboxylic dianhydride and hydroxyethyl methacrylate in a molar ratio of 1:2, add them to N-methylpyrrolidone, and react them in an oil bath at 30°C for 8 hours under a nitrogen atmosphere to obtain a reaction solution including the first intermediate.

[0128] (2) Under a nitrogen atmosphere and an ice bath at 5°C, thionyl chloride was added dropwise to the reaction solution at a rate of 1 drop / second, and the molar ratio of thionyl chloride to 3,3',4,4'-benzophenone tetracarboxylic dianhydride was 2.1:1. After the addition was completed, the second intermediate was obtained.

[0129] (3) Take m-phenylenediamine, 4,4'-(3-(4,5-dihydro-1H-imidazol-5-yl)cyclohexane-1,1-diyl)diphenylamine and the second intermediate in a molar ratio of 1:1:4 and add them to N,N-dimethylformamide. React at 25°C for 4 hours to obtain the reaction product. The obtained reaction product is uniformly introduced into deionized water, allowed to stand and separate into layers, the upper layer is removed, the resin is broken up, and the resin is soaked, washed and filtered in deionized water. This process is repeated several times and the polymer is dried.

[0130] (4) Take 5g of the polymer, 0.1g of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl] acetone 1-(O-acetyl oxime), 0.10g of trimethylolpropane trimethacrylate, 0.25g of 3-propyltriethoxysilane and 10g of N-methylpyrrolidone, stir and mix evenly to obtain the intrinsic low-temperature curing negative photoresist.

[0131] Example 10

[0132] The method for preparing the polymer in this embodiment includes the following steps:

[0133] (1) Take hexafluorodianhydride and hydroxyethyl methacrylate in a molar ratio of 1:2 and add them to N-methylpyrrolidone. React in an oil bath at 30°C for 8 hours under a nitrogen atmosphere to obtain a reaction solution containing the first intermediate.

[0134] (2) Under a nitrogen atmosphere and an ice bath at 5°C, thionyl chloride was added dropwise to the reaction solution at a rate of 1 drop / second, and the molar ratio of thionyl chloride to hexafluorodianhydride was 2.1:1. After the addition was completed, the second intermediate was obtained.

[0135] (3) Take 4,4'-diamino-2,2'-dimethylbiphenyl, 1,1-bis(4'-aminophenyl)cyclohexane and the second intermediate in a molar ratio of 1:1:4 and add them to N,N-dimethylformamide. React at 25°C for 4 hours to obtain the reaction product. The obtained reaction product is uniformly introduced into deionized water, allowed to stand and separate into layers, the upper layer is removed, the resin is broken up, and the deionized water is replaced for soaking, washing and filtering. This process is repeated several times and the polymer is dried.

[0136] (4) Take 5g of the polymer, 0.1g of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl] acetone 1-(O-acetyl oxime), 0.10g of trimethylolpropane trimethacrylate, 0.25g of 3-ureapropyltriethoxysilane and 10g of N-methylpyrrolidone, stir and mix evenly to obtain the intrinsic low-temperature curing negative photoresist.

[0137] Gel permeation chromatography (GPC) test

[0138] The polymers prepared in Examples 1-10 were subjected to gel permeation chromatography (GPC) tests. The test method was as follows: the column was filled with a solvent containing the sample to be tested, filling all the voids between the carrier particles and the cavities inside the particles. Then, a sample solution prepared with the same solvent was added from the column head, and the column was eluted with the same solvent. The eluent was collected at the micro-end of the column, and the volume and concentration of the eluent were calculated. The total volume of the collected eluent was called the elution volume. The elution volume of the solute is related to its molecular weight; the larger the molecular weight, the smaller the elution volume. If the sample is polydisperse, a series of fractions with decreasing molecular weights can be collected according to the order of elution. The weight-average molecular weight (Mw) and molecular weight distribution index (PDI) of the polymers in Examples 1-10 were obtained, as shown in Table 1.

[0139] Table 1. Test results of Mw and PDI of polymers in Examples 1-10

[0140]

[0141]

[0142] Photolithography performance testing

[0143] The intrinsic low-temperature curing negative photoresists of Examples 2 and 3 were spin-coated onto the corresponding silicon wafer substrates and pre-baked on a 100°C hot plate for 120 seconds to evaporate most of the solvent and obtain a dry film.

[0144] (2) The dry film was exposed using a stepper lithography machine (SSB320) at an exposure dose of 100 mJ / cm, then developed with cyclopentanone at a development time of 40 s * 2 times, and finally cleaned with fixer to obtain a negative pattern. The pattern was observed under a microscope.

[0145] The patterns after exposure and development using the intrinsic low-temperature curing negative photoresist of Examples 2 and 3 are as follows: Figure 5 and Figure 6 As shown in the figure, the intrinsic low-temperature curing negative photoresist prepared in Examples 2 and 3 has good photolithographic performance, no residual photoresist in the holes, and the hole size is completely consistent with the set size.

[0146] Example 11

[0147] The polymer prepared in Example 1 was made into dumbbell-shaped specimens and cured in an oxygen-free environment at 200°C with an oxygen content of less than 100 ppm for 1 hour to obtain cured PSPI specimens.

[0148] Example 12

[0149] The polymer prepared in Example 1 was made into dumbbell-shaped specimens and cured in an oxygen-free environment at 220°C with an oxygen content of less than 100 ppm for 1 hour to obtain cured PSPI specimens.

[0150] Example 13

[0151] The polymer prepared in Example 1 was made into dumbbell-shaped specimens and cured in an oxygen-free environment at 250°C with an oxygen content of less than 100 ppm for 1 hour to obtain cured PSPI specimens.

[0152] Example 14

[0153] The polymer prepared in Example 1 was made into dumbbell-shaped specimens and cured in an oxygen-free environment at 260°C with an oxygen content of less than 100 ppm for 1 hour to obtain cured PSPI specimens.

[0154] Example 15

[0155] The polymer prepared in Example 1 was made into dumbbell-shaped specimens and cured in an oxygen-free environment at 300°C with an oxygen content of less than 100 ppm for 1 hour to obtain cured PSPI specimens.

[0156] Comparative Example 1

[0157] The polymer prepared in Example 1 was made into dumbbell-shaped specimens and cured in an oxygen-free environment at 350°C with an oxygen content of less than 100 ppm for 1 hour. The performance of the PSPI specimens was then tested.

[0158] The PSPI samples of Examples 11-15 and Comparative Example 1 were tested using a Nicolet iS5 Fourier transform infrared spectrometer from ThermoFisher Technology Co., Ltd., in attenuated total reflectance mode to verify the degree of imidization of the films. The imidization rates are shown in Table 2. The imidization rate results show that, at a low curing temperature of 200°C, the imidization degree of the embodiments in this application is close to complete curing. Mechanical property testing

[0159] The tensile properties, coefficient of thermal expansion, and dynamic thermomechanical properties (DMA) of the PSPI spline of Examples 11-15 and Comparative Example 1 were tested, and the test results are shown in Table 2.

[0160] Tensile property testing: The tensile strength, Young's modulus, and elongation at break of the specimens were characterized using a CMT-1104 universal tensile testing machine from Zhuhai Sansitaijie Electrical Equipment Co., Ltd. The tests were conducted according to the "Standard Test Method for Tensile Properties of Plastics" (ASTM-D638), with a tensile speed of 5 mm / min until the specimen broke. The final data was the average of five measurements.

[0161] TMA testing: The coefficient of thermal expansion (CTE) of the specimens was characterized using a TA Instruments Q400 static thermomechanical analyzer to determine their dimensional stability within the normal operating temperature range. In tensile mode, the specimens were heated to 300°C in a nitrogen atmosphere at a heating rate of 30°C / min and held for 5 min to eliminate residual thermodynamic potential. They were then cooled to room temperature at the same rate, followed by a second heating to 390°C at a heating rate of 5°C / min. The static force was set to 0.05 N, and the final CTE values ​​were taken from the range of 50–150°C.

[0162] DMA testing: The glass transition temperature (Tg) of the specimens was characterized using a TA Instruments Q800 dynamic thermomechanical analyzer to determine their upper limit of normal operating temperature. In dynamic stretching mode, the temperature was increased to 500℃ in a nitrogen atmosphere at a heating rate of 5℃ / min, with the test frequency set to 1Hz.

[0163] Table 2 shows the mechanical property test results of the polymer prepared in Example 1 at different curing temperatures. The results indicate that the polymer of this application embodiment exhibits better overall mechanical properties when cured at low temperatures (200℃~300℃) than when cured at high temperatures (350℃), demonstrating that the polymer of this application embodiment can cure faster at low temperatures while maintaining excellent performance. The Tg of the polymer of this application embodiment increases with increasing curing temperature, and all values ​​exceed 200℃, meeting the application requirements.

[0164] Table 2 shows the mechanical property test results of Examples 11-15 and Comparative Example 1.

[0165]

[0166] Thermal performance testing

[0167] The thermal properties of the PSPI specimens from Examples 11-15 and Comparative Example 1 were tested using the following specific testing methods:

[0168] The stability of the material was characterized using a Discovery TGA55 thermogravimetric analyzer from TA Instruments, USA. 10-15 mg of sample was weighed and carefully placed in an alumina high-temperature crucible. Under a nitrogen atmosphere, the temperature was increased to 120 °C at a rate of 20 °C / min and held for 10 min to remove trace amounts of moisture. The temperature was then lowered to room temperature, followed by a second heating at a rate of 10 °C / min to 800 °C, with the nitrogen pressure not exceeding 0.1 MPa. The test results are shown in Table 3.

[0169] Table 3 shows the thermal performance test results of the polymer prepared in Example 1 at different curing temperatures. The Td of the polymer increases with increasing curing temperature, and all exceed 250°C. Therefore, the polymer of this application embodiment has excellent thermal properties and meets the application requirements.

[0170] Table 3. Thermal performance test results of Examples 11-15 and Comparative Example 1

[0171]

[0172] Chemical resistance test

[0173] Example 16

[0174] The low-temperature curing negative photoresist of Example 1 was spin-coated onto a silicon wafer and pre-baked on a 100°C hot plate for 120 seconds to evaporate most of the solvent and obtain a dry film. The dry film was exposed using a stepper lithography machine (SSB320) at an exposure dose of 100 mJ / cm. Then, it was developed with cyclopentanone for 40 seconds twice. Finally, it was cleaned with a fixer to obtain a negative pattern.

[0175] A silicon wafer with a negative pattern is placed in a nitrogen-protected oven (oxygen concentration below 100 ppm) and cured at 120°C for 30 minutes, then heated to 200°C and cured for 1 hour to obtain a cured film.

[0176] Example 17

[0177] The silicon wafer with the negative pattern of Example 16 was placed in a nitrogen-protected forced-air oven (oxygen concentration below 100 ppm) and cured at 120°C for 30 min, then the temperature was raised to 220°C and cured for 1 h to obtain a cured film.

[0178] Example 18

[0179] The silicon wafer with the negative pattern of Example 16 was placed in a nitrogen-protected forced-air oven (oxygen concentration below 100 ppm) and cured at 120°C for 30 min, then the temperature was raised to 250°C and cured for 1 h to obtain a cured film.

[0180] Example 19

[0181] The silicon wafer with the negative pattern of Example 16 was placed in a nitrogen-protected forced-air oven (oxygen concentration below 100 ppm) and cured at 120°C for 30 min, then the temperature was raised to 260°C and cured for 1 h to obtain a cured film.

[0182] Example 20

[0183] The silicon wafer with the negative pattern of Example 16 was placed in a nitrogen-protected forced-air oven (oxygen concentration below 100 ppm) and cured at 120°C for 30 min, then heated to 300°C and cured for 1 h to obtain a cured film.

[0184] The silicon wafers with cured films obtained in Examples 16-20 and the PSPI sample of Comparative Example 1 were immersed in organic reagents acetone (25°C, 60s), ammonia (25°C, 60s), HCl (25°C, 60s), a mixture of H2SO4 and H2O2 (25°C, 180s), and N-methylpyrrolidone (80°C, 30min), respectively. After washing with water and drying with a forced air, the change in film thickness of the silicon wafers with cured films before and after immersion was measured with a film thickness gauge. The patterns were observed with an optical microscope to evaluate their chemical resistance.

[0185] Chemical resistance is rated A for films with thickness changes within ±5% before and after immersion, B for films with thickness changes beyond ±5%, and C for films with surface cracks, edge cracks, chemical penetration into the edges of the pattern, or peeling of the cured film from the substrate. The test results are shown in Table 4.

[0186] Table 4. Results of chemical resistance tests for Examples 16-20 and Comparative Example 1

[0187]

[0188] As shown in Table 4, the polymer prepared in the embodiments of this application has good chemical resistance.

[0189] Figure 7 A 3D image of the cured film of Example 16 after immersion in N-methylpyrrolidone is shown. Figure 7 As can be seen, the film surface is smooth and there are no cracks, which proves that the cured film has excellent chemical resistance.

[0190] Dielectric performance testing

[0191] The dielectric constant ε' and dielectric loss ε" of the PSPI splines in Examples 11-15 and Comparative Example 1 were characterized at 60 GHz using a Keysight Technologies PNA N5227B vector network analyzer. The PSPI splines were pre-cut into small pieces of approximately 3 × 3 cm, and the measured thicknesses were entered into the testing software. The pieces were then clamped onto specialized fixtures for the corresponding frequencies for testing. The test results are shown in Table 5.

[0192] Table 5 shows the dielectric performance test results of Examples 11-15 and Comparative Example 1.

[0193] Example 11 200℃ 0.017 2.92 0.046 Example 12 220℃ 0.017 2.92 0.044 Example 13 250℃ 0.015 2.91 0.045 Example 14 260℃ 0.015 2.90 0.044 Example 15 300℃ 0.015 2.91 0.045 Comparative Example 1 350℃ 0.015 4.50 0.113

[0194] Compared with Comparative Example 1, the materials prepared in Examples 11-15 of this application have a lower dielectric constant, thus significantly improving dielectric properties.

[0195] The above description of the embodiments is intended to enable those skilled in the art to understand and apply this application. It will be apparent to those skilled in the art that various modifications can be easily made to these embodiments, and the general principles described herein can be applied to other embodiments without creative effort. Therefore, this application is not limited to the embodiments described herein, and any improvements and modifications made by those skilled in the art based on the disclosure of this application without departing from the scope and spirit of this application are within the scope of this application.

Claims

1. A polymer, characterized in that, The polymer has the following structural formula: ； Where the degree of polymerization m = 1-1000, n = 1-1000; Ar1 is selected from any of the following structures: 、 、 、 、 、 ； Ar2 is selected from residues of any of the following diamine monomers: m-phenylenediamine, 2,2'-di(trifluoromethyl)-(1,1'-diphenyl)-4,4'-diamine, 9,9-bis(3-fluoro-4-aminophenyl)fluorene, 9,9-bis(4-aminophenyl)fluorene, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 9,9-dimethylfluorene-2,7-diamine, p-phenylenediamine, 4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, etc. 1,4-Aminophenoxy)benzene, 4,4'-diamino-2,2'-dimethylbiphenyl, 2-(4-aminophenyl)-5-aminobenzoxazole, 2-(4-aminophenyl)-5-aminobenzimidazole, 1,4-bis(3-aminophenoxy)benzene, 1,3-bis(3-hydroxy-4-aminophenoxy)benzene, 2-(4-aminophenyl)-6-aminobenzoxazole, 2,2-p-phenyl-bis(5-aminobenzozazole), 2,2'-p-phenyl-bis(6-aminobenzozazole), 2,2-bis(4-hydroxy-3-aminophenyl)propane, 3,3'-dihydroxybenzidine and 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid; Ar3 is selected from residues of any of the following dianhydride monomers: 4,4'-biphenyl ether dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, 2,2'-bis(3,4-dicarboxylic acid)hexafluoropropane dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic acid dianhydride, 3,3,4,4-diphenyl sulfone tetracarboxylic acid dianhydride, naphthalene-1,4,5,8-tetracarboxylic acid dianhydride, diphenyl sulfide dianhydride, bisphenol A type diether dianhydride, hexafluoro dianhydride, hydrogenated... Pyromellitic dianhydride, cyclobutanetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorenyl dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, (4-phthalic anhydride)formyloxy-4-phthalate, bis[(3,4-dianhydride)phenyl]terephthalate, 4,4'-terephthalodioxybis-o-dicarboxylic anhydride, diethylene glycol (4-tricarboxylic anhydride), pyromellitic dianhydride and 9,9-bis(trifluoromethyl)-2,3,6,7-oxanthracenetetracarboxylic dianhydride; R is formed by reacting hydroxyethyl methacrylate with the dianhydride monomer.

2. A method for preparing the polymer according to claim 1, characterized in that, Includes the following steps: The dianhydride monomer and the esterifying agent are reacted in the first solvent to obtain the first intermediate; The first intermediate and the acyl chloride reagent are reacted in the first solvent to obtain the second intermediate; The second intermediate, the first diamine monomer, and the second diamine monomer are reacted in a second solvent to obtain the polymer. The dianhydride monomer is selected from 4,4'-biphenyl ether dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, 2,2'-bis(3,4-dicarboxylic acid)hexafluoropropane dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic acid dianhydride, 3,3,4,4-diphenyl sulfone tetracarboxylic acid dianhydride, naphthalene-1,4,5,8-tetracarboxylic acid dianhydride, diphenyl sulfide dianhydride, bisphenol A type diether dianhydride, hexafluorodianhydride, and hydrogenated pyromellitic tetracarboxylic acid dianhydride. At least one of the following: cyclobutanetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorenyl dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, (4-phthalic anhydride)formyloxy-4-phthalate, bis[(3,4-dianhydride)phenyl]terephthalate, 4,4'-terephthalodioxybis-o-dicarboxylic anhydride, diethylene glycol (4-tricarboxylic anhydride), pyromellitic dianhydride, and 9,9-bis(trifluoromethyl)-2,3,6,7-oxanthracene tetracarboxylic dianhydride; The esterification reagent is hydroxyethyl methacrylate; The first diamine monomer is selected from at least one of the following structures: 、 、 、 、 、 ； The second diamine monomer is selected from m-phenylenediamine, 2,2'-di(trifluoromethyl)-(1,1'-diphenyl)-4,4'-diamine, 9,9-bis(3-fluoro-4-aminophenyl)fluorene, 9,9-bis(4-aminophenyl)fluorene, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 9,9-dimethylfluorene-2,7-diamine, p-phenylenediamine, 4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 1,3-bis(4-aminophenoxy)benzene, and 1,4-bis(4-aminophenoxy)benzene. At least one of the following: 4,4'-diamino-2,2'-dimethylbiphenyl, 2-(4-aminophenyl)-5-aminobenzoxazole, 2-(4-aminophenyl)-5-aminobenzimidazole, 1,4-bis(3-aminophenoxy)benzene, 1,3-bis(3-hydroxy-4-aminophenoxy)benzene, 2-(4-aminophenyl)-6-aminobenzoxazole, 2,2-p-phenyl-bis(5-aminobenzozazole), 2,2'-p-phenyl-bis(6-aminobenzozazole), 2,2-bis(4-hydroxy-3-aminophenyl)propane, 3,3'-dihydroxybenzidine, and 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid.

3. The method for preparing the polymer according to claim 2, characterized in that, The first solvent and the second solvent are each selected from at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, tetrahydrofuran, 1,3-dimethyl-2-imidazolinone, γ-butyrolactone, ethyl acetate, butyl acetate, n-propyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, toluene, xylene, mesitylene, diacetone alcohol, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, methyl propyl ketone, tetrahydropyran, dioxane, dioxane, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monomethyl ether acetate. The acyl chloride reagent is selected from at least one of thionyl chloride, diphenyl ether dicarboxylate chloride, isophthaloyl chloride, terephthaloyl chloride, biphenyl dicarboxylate chloride, diphenyl sulfone dicarboxylate chloride, diphenylmethane dicarboxylate chloride and benzophenone dicarboxylate chloride, octyl dicarboxylate chloride, adipoxy dicarboxylate chloride, nonadicarboxylate chloride, dicarboxylate chloride, dodecane dicarboxylate chloride, 1,4-cyclohexane dicarboxylate chloride and 1,3-cyclobutane dicarboxylate chloride.

4. The method for preparing the polymer according to claim 2, characterized in that, The reaction conditions between the dianhydride monomer and the esterifying agent must satisfy at least one of the following: a. The molar ratio of the dianhydride monomer to the esterification reagent is 1:(1~4); b. The reaction temperature is 20℃~60℃, and the reaction time is 8 hours~24 hours; The reaction conditions between the first intermediate and the acyl chloride reagent satisfy at least one of the following: A. The molar ratio of the acyl chloride reagent to the dianhydride monomer is (2~2.8):1; B. Under the protection of an inert gas and in an ice-water bath at 0-10°C, the acyl chloride reagent is added dropwise at a rate of 1-5 drops / second.

5. The method for preparing the polymer according to claim 2, characterized in that, The reaction conditions of the second intermediate, the first diamine monomer, and the second diamine monomer satisfy at least one of the following: (1) The ratio of the total molar number of the first diamine monomer and the second diamine monomer to the molar number of the second intermediate is 1:(1~2); (2) The reaction temperature is 15℃~35℃ and the reaction time is 3 hours~8 hours.

6. Use of the polymer of claim 1 in the preparation of intrinsic low-temperature curing negative photoresist.

7. An intrinsically low-temperature curable negative photoresist, characterized in that, The raw materials, by weight, include: 100 parts of the polymer as described in claim 1; 1-10 parts of photoinitiator; 1-30 parts of crosslinking agent; 1-10 parts of silane coupling agent; and 30-80 parts of third solvent.

8. The negative photoresist according to claim 7, characterized in that, The photoinitiator includes ethyl 2,4,6-trimethylbenzoylphosphonate, 2-methyl-1-[4-methylthiophenyl]-2-morpholino-1-propanone, ethyl 4-dimethylaminobenzoate, 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzoyl oxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]acetophenone-1-(O-acetyl oxime), bis(1-(2,4-) One or more of the following: (difluorophenyl)-3-pyrrolithodicarbonate, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, α,α-diethoxyacetophenone, 2-hydroxy-2-methyl-phenylacetone, 1-hydroxycyclohexylbenzophenone, 2-hydroxy-2-methyl-p-hydroxyethyl ether phenylacetone, 2,4,6-trimethylbenzoyl-ethoxy-phenylphosphine oxide, Mistral ketone, methyl ethyl Mistral ketone, and isopropylthioanthracene.

9. The negative photoresist according to claim 7, characterized in that, The crosslinking agent includes one or more of the following: pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, α,ω-dimethacrylate-based polyethylene glycol, triethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, diethylene glycol dimethacrylate containing the stabilizer methoxyhydroquinone, ethylene glycol phenyl ether acrylate, tetraethylene glycol dimethacrylate, tri(2-acryloyloxyethyl) isocyanurate, trimethylolpropane trimethacrylate, and trimethylolpropane triacrylate; The silane coupling agent includes triethoxysilylpropylmaleic acid, 3-methacryloyloxypropyltriethoxysilane, 3-ureapropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptomethyltrimethoxysilane, 3-mercaptomethyldimethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropylsilane, 3-mercaptopropyltributoxysilane, 2-(3,4-epoxycyclohexyl) The following are one or more of the following: ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, epoxybutyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, p-aminophenyltrimethoxysilane, aminophenyltrimethoxysilane, 3-(m-aminophenyl)trimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-propenoxypropyltrimethoxysilane, 3-ethoxypropyltrimethoxysilane, and vinyltrimethoxysilane; The third solvent includes one or more of N-methylpyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, tetrahydrofuran, and cyclohexanone.

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