Polyimide precursor resin, photosensitive resin composition, photosensitive cured film and application thereof

Abstract

The present invention relates to the technical field of polymer materials, and in particular to a polyimide precursor resin, a photosensitive resin composition, a photosensitive cured film, and an application thereof. The polyimide precursor resin provided by the present invention has a cyclic crown ether structure. When the polyimide precursor resin is applied to a photosensitive resin composition to form a cured film, the cured film exhibits excellent dielectric properties, heat resistance, adhesion properties, and organic solvent solubility, and is suitable for use as a surface protective film, an interlayer insulating film or a passivation film in semiconductor devices, an insulating layer in organic electroluminescent elements, an insulating layer in thin-film transistors, and the like.

Description

A polyimide precursor resin, a photosensitive resin composition, a photocurable film, and their applications.

[0001] Cross-referencing

[0002] This application claims priority to Chinese Patent Application No. 202411886841.7, filed on December 20, 2024, entitled “A polyimide precursor resin, a photosensitive resin composition, a photosensitive curable film and its application thereto,” the entire disclosure of which is incorporated herein by reference. Technical Field

[0003] This invention relates to the field of polymer materials technology, and particularly to a polyimide precursor resin, a photosensitive resin composition, a photosensitive curable film, and their applications. Specifically, it relates to a polyimide precursor resin and its preparation method, a photosensitive resin composition, a photosensitive curable film, and their applications. Background Technology

[0004] Polyimide (PI) is an aromatic heterocyclic polymer compound containing amide groups in repeating units. The rigid imide structure endows polyimide with unique properties. Its excellent thermal stability, good mechanical properties, good dimensional stability and electrical insulation properties make it widely used in microelectronic packaging as a buffer layer, passivation layer, alpha particle shielding layer, dielectric insulating layer for multilayer circuits and multi-component devices.

[0005] Compared to ordinary polyimide, photosensitive polyimide (PSPI) can form patterns without the need for other photoresists, saving material costs and significantly shortening the process circuit and improving yield. It is an ideal insulating material for the electronics and microelectronics fields. Negative PSPI achieves cross-linking under light irradiation by introducing photosensitive groups onto the polymer chain. The earliest commercialized product came from the research of Rubner at Siemens: grafting photopolymerizable hydroxyethyl methacrylate (HEMA) onto the side chains of polyimide acid (PAA). However, most negative PSPIs have poor solubility, requiring the use of highly polar organic solvents as developers during photolithography to dissolve and remove the unexposed areas, forming the pattern on the substrate.

[0006] Furthermore, with the miniaturization, precision, and multifunctionality of microelectronic products, higher requirements are placed on the properties of materials themselves, such as dielectric, optical, and thermal properties. However, due to the unique aromatic ring conjugated structure and imide structure in its structure, polyimide has a high water absorption rate and poor dielectric properties. It also suffers from poor adhesion to substrates and poor transparency, which greatly limits the application of photosensitive polyimide materials in the semiconductor and display fields.

[0007] Therefore, it is of great significance to provide a new low-dielectric polyimide precursor resin with good solubility, a photosensitive composition containing the precursor resin, and a photosensitive curable film. Summary of the Invention

[0008] To address the aforementioned technical problems, this invention provides a polyimide precursor resin, a photosensitive resin composition, a photocurable film, and their applications. The polyimide precursor resin provided by this invention has a cyclic crown ether structure. When applied to a photosensitive resin composition to form a cured film, it exhibits excellent dielectric properties, heat resistance, adhesion properties, and organic solvent solubility. It is suitable for use as surface protective films, interlayer insulating films, passivation films, insulating layers in organic electroluminescent devices, and insulating layers in thin-film transistors, etc., in semiconductor devices.

[0009] In a first aspect, the present invention provides a polyimide precursor resin having a structure as shown in Formula I:

[0010] Wherein, Ar1 is a dianhydride residue, Ar2 is a diamine residue, m is any integer between 5 and 10000, and R1 and R2 are each independently a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, or a cycloalkyl group with 3 to 20 carbon atoms. Any one of them;

[0011] Wherein, R3 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, such as ethyl, propyl, butyl, etc.; R4 is an alkylene group having 1 to 10 carbon atoms, such as ethylene, propylene, butylene, etc.; R5 is an arylene group containing a cyclic crown ether structure; and -* represents the linking bond of the group.

[0012] In Formula I, R1 in each repeating unit may be the same or different, and R2 in each repeating unit may be the same or different. Furthermore, taking the total amount of substance of R1 and R2 as 100%, the groups in R1 and R2... The amount of substance is 1% to 80%, for example, it can be 1%, 5%, 10%, 20%, 40%, 60%, 80%, etc.

[0013] Where m is any integer between 5 and 10000, such as 5, 10, 50, 100, 500, 1000, 2000, 5000, 10000, etc.

[0014] The alkyl group having 1 to 20 carbon atoms, for example, having 1, 2, 5, 10, 15, 20 carbon atoms, etc., preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, 2-propyl, n-butyl, etc.

[0015] The cycloalkyl group having 3 to 20 carbon atoms, for example, having 3, 6, 12, 18, 20 carbon atoms, etc., preferably having 5 to 15 carbon atoms, more preferably having 6 to 12 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, etc.

[0016] The polyimide precursor resin provided by this invention has a cyclic crown ether structure. When applied to a photosensitive resin composition and cured into a film, it exhibits excellent dielectric properties, heat resistance, adhesion properties, and organic solvent solubility. It is suitable for surface protective films, interlayer insulating films, passivation films, insulating layers of organic electroluminescent devices, and insulating layers of thin-film transistors in semiconductor devices. Specifically:

[0017] The present invention introduces a polyimide precursor resin containing a cyclic crown ether structure as shown in Formula III. Utilizing its cyclic void structure and steric hindrance effect, this effectively reduces the packing degree of polymer chain segments, improves solvent permeability, and increases free volume. This reduces the dielectric properties of the polyimide precursor resin while maintaining its heat resistance, and simultaneously improves its solubility in solvents. Furthermore, the structures shown in Formulas II and III can be combined with photosensitive compounds that generate active free radicals upon light irradiation, and cross-linking reactions between molecular chains are carried out through free radical polymerization to prepare a photosensitive resin composition. The ether structure effectively enhances the adhesion between the cured film prepared from this precursor resin and the substrate, resulting in a cured film with excellent dielectric properties, heat resistance, adhesion, and organic solvent solubility. This solves the problems of poor dielectric properties, poor solubility, and poor adhesion to substrates in existing polyimide resin systems. It is suitable for surface protective films, interlayer insulating films, passivation films, insulating layers of organic electroluminescent devices, and insulating layers of thin-film transistors in semiconductor devices.

[0018] As a preferred embodiment of the present invention, the groups in R1 and R2 The content of the substance is 2-50%. When it is less than 2%, it is easy to cause the dielectric constant of the precursor resin to be too high, the adhesion to be insufficient, and the solubility to be poor. When it is greater than 50%, the dielectric constant and adhesion of the precursor resin are improved, but the heat resistance of the cured film decreases.

[0019] As a preferred technical solution of the present invention, the group Choose from any one or more of the following structures:

[0020] As a preferred technical solution of the present invention, the group Choose from any one or more of the following structures:

[0021] This invention does not specifically limit the dianhydride residues; any dianhydride residue commonly used in the art is acceptable. As a preferred embodiment of this invention, the dianhydride residues include any one or more residues selected from the following: pyromellitic dianhydride (PMDA), 3,3,3',4'-biphenyltetracarboxylic dianhydride (s-BPDA), 2,3,3',4'-biphenyltetracarboxylic dianhydride (α-BPDA), 4,4'-(hexafluoroisopropene)phthalic anhydride (6FDA), 4,4'-oxophthalic anhydride (ODPA), 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA), p-phenylene-bis(phenyltrilate) dianhydride (TAHQ), 3,3',4,4'-diphenylmethane sulfone tetracarboxylic dianhydride (BSDA), cyclobutanetetracarboxylic dianhydride (CBDA), cyclohexanetetracarboxylic dianhydride (HPMDA), and 3,3,4,4-diphenylsulfonetetracarboxylic dianhydride (DSDA).

[0022] This invention does not specifically limit the diamine residues; any diamine residue commonly used in the art is acceptable. As a preferred embodiment of this invention, the diamine residues include 2,2-bis(4-hydroxy-3-aminophenyl)propane (BAP), 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone (BAHS), N,N'-[(1-methylethylidene)bis(6-hydroxy-3,1-phenylene)]bis[3-aminobenzamide, 2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP), 4,4'-bis(3-aminophenoxy)diphenyl sulfone, 2,2-bis[3-(4-aminobenzamido)-4-hydroxyphenyl]propane, 2,2-bis[3-(4-aminobenzamido)-4-hydroxyphenyl]sulfone, 2,2-bis[3-(4-] [aminobenzamido]-4-hydroxyphenyl] ether, N-(2-hydroxy-5-amino)phenyl-3-aminobenzamide, N-(5-amino-2-hydroxyphenyl)-4-[2-[4-[(4-aminophenyl)carbamoyl]phenyl]-propane-2-yl]benzamide, N-(5-amino-2-hydroxyphenyl)-4-[2-[4-[(4-aminophenyl)carbamoyl]phenyl]-sulfonyl-2-yl]benzamide, 2,2-bis[3-(4-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane (p-6FDAP), N-(5-amino-2-hydroxyphenyl)-4-[2-[4-[(4-aminophenyl)carbamoyl]phenyl]-ether-2-yl] Benzamide, 1,4-p-phenylenediamine (PDA), N-(5-amino-2-hydroxyphenyl-4-[2-[4-[(4-aminophenyl)carbamoyl]phenyl]-hexafluoropropane-2-yl]benzamide, m-phenylenediamine (m-PDA), o-phenylenediamine (o-PDA), 4,4'-diaminodiphenyl ether (ODA), 4,4'-diamino-p-terphenyl (DATP), 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (6FODA), 4,4'-diaminodiphenylmethane (MDA), 2,2'-dimethyl-4,4'-diaminobiphenyl (m-TB), p-aminobenzoic acid p-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]hexafluoropropane (HFBAPP), N-[5-[3-[(1,3-dioxy-2-benzofuran-5-carbonyl)amino]-4-hydroxyphenyl]sulfonyl-2-hydroxyphenyl]-1,3-dioxy-2-benzofuran-5-carboxamide, N,N'-[[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis(6-hydroxy-3,1-phenylene)]bis[1,3-dioxy-1,[3-Dihydroisobenzofuran-5-carboxamide] and 2,2-bis(4-(4-aminophenoxy)phenyl)propane (BAPP) residues.

[0023] In a second aspect, the present invention provides a method for preparing the polyimide precursor resin described in the first aspect, the method comprising:

[0024] Diosmic anhydride and An esterification reaction is carried out under the action of an alkaline catalyst to obtain a diester derivative, followed by an acyl chloride reaction using a chloride or a dehydration condensation reaction using a dehydrating agent, and then a diamine is added to carry out the reaction to obtain the polyimide precursor resin.

[0025] As a preferred embodiment of the present invention, the preparation method is carried out under an inert gas atmosphere, wherein the inert gas can be nitrogen or argon.

[0026] As a preferred embodiment of the present invention, the alkaline catalyst comprises any one or more of pyridine, 4-dimethylaminopyridine, triethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene and 1,5-diazabicyclo[4.3.0]non-5-ene.

[0027] As a preferred embodiment of the present invention, the chloride includes any one or more of thionyl chloride, thioyl chloride, and dichlorooxalic acid.

[0028] As a preferred embodiment of the present invention, the dehydrating agent comprises dicyclohexylcarbodiimide (DCC).

[0029] As a preferred embodiment of the present invention, a basic compound is added for neutralization reaction before the addition of diamine for the reaction.

[0030] As a preferred embodiment of the present invention, the alkaline compound includes any one or more of pyridine, 4-dimethylaminopyridine, and triethylamine.

[0031] In a preferred embodiment of the present invention, the molar ratio of the alkaline compound to the chloride is 1 to 3:1. If the amount of alkaline compound is too small, the molecular weight of the polyimide precursor resin will be low, and the internal stress after curing may be relatively high. If the amount of alkaline compound is too large, the polyimide precursor resin may be discolored.

[0032] As a preferred embodiment of the present invention, the molar ratio of the alkaline compound to the chloride is 1.5 to 2.5:1.

[0033] In a preferred embodiment of the present invention, the molar ratio of the chloride or dehydrating agent to the dianhydride is 1 to 3:1, for example, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, etc. When the amount of chloride or dehydrating agent is too small, the molecular weight of the resulting polyimide precursor resin is too low, resulting in poor mechanical properties after curing. When the amount of chloride or dehydrating agent is too large, a large amount of hydrochloride salts of the alkaline compound remains in the polyimide precursor resin, reducing its electrical insulation after curing and affecting its performance.

[0034] As a preferred embodiment of the present invention, the molar ratio of the chloride or dehydrating agent to the dianhydride is 1.5 to 2.5:1.

[0035] In a preferred embodiment of the present invention, the molar ratio of the dianhydride to the diamine is 0.7–1.3:1. When the molar ratio is less than 0.7 or greater than 1.3, the resulting polyimide precursor resin has a small molecular weight and poor mechanical properties, affecting its performance. To better control the molecular weight and terminal residues, the preferred molar ratio of the dianhydride to the diamine is 0.9–1.1:1.

[0036] As a preferred technical solution of the present invention, the aforementioned and The total amount of substance is calculated as 100%. The molar content of the substance is 1-80%.

[0037] As a preferred technical solution of the present invention, the Selected from Any one or more of the following.

[0038] As a preferred technical solution of the present invention, the Selected from Any one or more of the following.

[0039] In a preferred embodiment of the present invention, the preparation method is carried out in an organic solvent, preferably a polar solvent capable of completely dissolving the polyimide precursor resin. Preferably, the organic solvent includes any one or more of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, tetramethylurea, hexamethylphosphonic triamide, and γ-butyrolactone.

[0040] The present invention, after reacting with diamine, yields a polyimide precursor resin solution with a solid content of 10-50%. As a preferred embodiment of the present invention, the reaction with diamine is followed by purification. The purification method involves precipitating the crude product with a precipitating agent, followed by filtration, washing, and drying to obtain the polyimide precursor resin.

[0041] As a preferred embodiment of the present invention, the precipitant is a poor solvent for polyimide precursor resin, including any one or more of deionized water, methanol, ethanol, isopropanol and n-butanol, preferably deionized water.

[0042] Thirdly, the present invention provides a photosensitive resin composition comprising the polyimide precursor resin described in the first aspect or the polyimide precursor resin prepared by the preparation method described in the second aspect, a photosensitive compound, a crosslinking agent, a polymerization inhibitor, an organosilane compound, a solvent, and optionally a rust inhibitor.

[0043] The photosensitive compound of this invention is a compound that generates active free radicals upon irradiation with light. As a preferred embodiment of this invention, the photosensitive compound includes any one or more of the following: oxime esters, aromatic ketones, quinones formed by alkyl anthraquinones and aromatic ring condensation, benzoin compounds, benzoin ether compounds, and benzoyl derivatives.

[0044] The aromatic ketone can be benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Mischel ketone), N,N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-acetone-1, etc. The benzoin compound can be benzoin, alkylbenzoin, etc. The benzoin ether compound can be benzoin alkyl ether, etc. The benzoin derivative can be benzoin dimethyl ketal, etc.

[0045] As a preferred embodiment of the present invention, the photosensitive compound is selected from oxime ester compounds, which have better sensitivity and can obtain better photolithographic patterns.

[0046] As a preferred embodiment of the present invention, the oxime ester compound is selected from any one or more of IRGACURE OXE-01 (manufactured by BASF), IRGACURE OXE-02 (manufactured by BASF), DFI-091 (manufactured by Daito Chemix Co., Ltd.), and ADEKA OPTOMERN-1919 (manufactured by ADEKA Co., Ltd.).

[0047] The crosslinking agent described in this invention reacts with the carbon-carbon unsaturated double bonds in the polyimide precursor resin either through the active free radicals generated by light irradiation.

[0048] As a preferred embodiment of the present invention, the crosslinking agent comprises any one or more of the following: diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, 2-hydroxyethyl (meth)acrylate, 1,3-(meth)acryloyloxy-2-hydroxypropane, methylenebisacrylamide, N,N-dimethylacrylamide, and N-hydroxymethylacrylamide.

[0049] As a preferred embodiment of the present invention, the crosslinking agent is selected from any one or more of diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, and 1,6-hexanediol dimethacrylate, thereby enhancing the photocurability of the photosensitive resin composition.

[0050] As a preferred embodiment of the present invention, the polymerization inhibitor is a free radical polymerization inhibitor or a free radical polymerization suppressor, and the present invention does not impose any particular limitation. Preferably, the polymerization inhibitor includes any one or more of the following: p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, o-dinitrobenzene, p-dinitrobenzene, m-dinitrobenzene, phenanthrenequinone, N-phenyl-2-naphthylamine, copper-iron reagent, 2,5-toluenequinone, tannic acid, p-benzylaminophenol, and nitrosamine compounds.

[0051] As a preferred embodiment of the present invention, the organosilane compound includes γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-acryloyloxypropyltrimethoxysilane, 3-ureapropyltriethoxysilane, 3-ylpropyltrimethoxysilane, triethoxysilylpropylethylcarbamate, 3-(triethoxysilyl)propylsuccinic anhydride, phenyltriethoxysilane, phenyltrimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane. Alkane, 3-triethoxysilyl-N-(1,3-dimethylbutylene)propylamine, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 1-isocyanate-methyltrimethylsilane, 1-isocyanate-methyltriethylsilane, 1-isocyanate-methyltripropylsilane, 1-isocyanate-methyltributylsilane, 1-isocyanate-methyldimethoxymethylsilane, 1-isocyanate-methylmethoxydimethylsilane, 1-isocyanate-methyltriethoxysilane, 1-isocyanate-methyltripropoxysilane, 1-isocyanate-methyltributoxysilane, 1-isocyanate-methyldiethoxyethylsilane, 3-isocyanate-propyltrimethylsilane, 3-isocyanate-methyltrimethylsilane Cyanate-based propyltriethylsilane, 3-isocyanate-based propyltrimethoxysilane, 3-isocyanate-based propyldimethoxymethylsilane, 3-isocyanate-based propylmethoxydimethylsilane, 3-isocyanate-based propyltriethoxysilane, 3-isocyanate-based propyldiethoxyethylsilane, 3-isocyanate-based propylethoxydiethylsilane, 6-isocyanate-based hexyltrimethoxysilane, 6-isocyanate-based hexyldimethoxymethylsilane, 6-isocyanate-based hexylmethoxydimethylsilane, 6-isocyanate-based hexyltriethoxysilane, 6-isocyanate-based hexyldiethoxyethylsilane, 6-isocyanate-based hexylethoxydiethylalane, bis(2-hydroxyethyl)-3-amino Propyltriethoxysilane, N,N-bis(2-hydroxyethyl)-N,N-bis(trimethoxysilylpropyl)ethylenediamine, N-(hydroxymethyl)-N-methylaminopropyltrimethoxysilane, 7-triethoxysilylpropyl-5-hydroxyflavone, N-(3-triethoxysilylpropyl)-4-hydroxybutamide, 2-hydroxy-4-(3-methyldiethoxysilylpropoxy)benzophenone, 1,3-bis(4-hydroxybutyl)tetramethyldisiloxane, 3-(N-acetyl-4-hydroxypropoxy)propyltriethoxysilane, hydroxymethyltriethoxysilane, and (3-triethoxysilylpropyl)-tert-butylcarbamate.

[0052] The organosilane compound provided by this invention can improve the adhesion of the cured film to the silicon substrate and the like.

[0053] As a preferred embodiment of the present invention, the solvent includes any one or more of ketone solvents, ester solvents, ether solvents, aromatic hydrocarbon solvents, or other solvents. Preferably, the solvent includes any one or more of N-methylpyrrolidone, tetrahydrofuran, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, tetramethylurea, hexamethylphosphoric triamine, propylene glycol methyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, γ-butyrolactone, δ-valerolactone, γ-valerolactone, cyclohexanone, cyclopentanone, 1,3-dimethyl-2-imidazolinone, propylene carbonate, methyl lactate, ethyl lactate, propyl lactate, and butyl lactate.

[0054] As a preferred embodiment of the present invention, the rust inhibitor includes any one or more of tetrazolium and its azole derivatives, benzotriazole and its derivatives. The rust inhibitor of the present invention is used on a copper substrate, and its addition can be selected based on actual conditions. Preferably, the rust inhibitor is selected from any one or more of 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, 5,5'-bis-1H-tetrazole, 1-methyl-5-ethyl-tetrazole, 1-methyl-5-mercapto-tetrazole, 1-carboxymethyl-5-mercapto-tetrazole, benzotriazole, and benzotriazole derivatives. The benzotriazole derivative can be 1H-benzotriazole-1-acetonitrile, benzotriazole-5-carboxylic acid, 1H-benzotriazole-1-methanol, carboxybenzotriazole, mercaptobenzoxazole, etc. Preferably, the rust inhibitor is selected from any one or more of 1H-tetrazole, 5-amino-1H-tetrazole, or benzotriazole.

[0055] As a preferred embodiment of the present invention, the content of each component in the photosensitive resin composition is as follows:

[0056] As a preferred embodiment of the present invention, the content of each component in the photosensitive resin composition is as follows:

[0057] As a preferred embodiment of the present invention, the content of each component in the photosensitive resin composition is as follows:

[0058] Fourthly, the present invention provides a photocurable film, which is formed by curing the photosensitive resin composition described in the third aspect.

[0059] It is understood that the curing of the photosensitive resin composition to form a cured film typically includes some pretreatment, such as coating, hot plate drying, exposure, development, and then curing. Each step employs conventional methods in the art. For example, coating is performed using a rotational viscometer, drying is done using a hot plate, and curing is performed under nitrogen atmosphere.

[0060] The photosensitive curable film provided by this invention has excellent dielectric properties, solubility, adhesion properties, and heat resistance. Preferably, the photosensitive curable film exhibits a peeling area of ​​<5% in the adhesion test (cross-cut adhesion test method), a dielectric constant DK ≤ 2.9, and a thermal weight loss temperature T5% ≥ 350℃.

[0061] Fifthly, the present invention provides the application of the photocurable film described in the fourth aspect as a protective film or insulating layer in semiconductor devices, organic electroluminescent devices, and thin-film transistors.

[0062] The technical solution provided by the embodiments of the present invention has the following advantages compared with the prior art:

[0063] The polyimide precursor resin provided by this invention has a cyclic crown ether structure. When applied to a photosensitive resin composition and cured, it exhibits excellent dielectric properties, heat resistance, adhesion properties, and organic solvent solubility. It is suitable for surface protective films, interlayer insulating films, passivation films, insulating layers of organic electroluminescent elements, and insulating layers of thin-film transistors in semiconductor devices. Detailed Implementation

[0064] To better understand the above-mentioned objectives, features, and advantages of the present invention, the solutions of the present invention will be further described below. It should be noted that, unless otherwise specified, the embodiments of the present invention and the features thereof can be combined with each other.

[0065] Many specific details are set forth in the following description in order to provide a full understanding of the invention, but the invention may also be practiced in other ways different from those described herein; obviously, the embodiments in the specification are only some embodiments of the invention, and not all embodiments.

[0066] Synthesis example 1

[0067] This synthetic example provides a method for synthesizing compound III-1, and the synthetic route is shown below:

[0068] The specific synthesis method includes the following steps:

[0069] (1) Weigh 2.48g of 4-methoxy-1,2-benzenediol, 2.86g of dichloroethyl ether, 4.5g of potassium hydroxide, and 0.01g of 2,6-di-tert-butyl-p-cresol, dissolve them in 100ml of dimethyl sulfoxide (DMSO), seal the solution, place it in an ultrasonic reaction vessel, heat it to 50-60℃, keep it at that temperature for 3h, add water and filter it while it is hot to remove the black viscous substance, wash it with water, wash the filter cake with alkali, let the filtrate stand and a grayish-white solid gradually precipitates out, filter it, recrystallize it with methanol to obtain 2.53g of product, with a yield of 56.0%.

[0070] (2) Dissolve 1 mol of the solid obtained in step (1) in dichloromethane, add 0.01 mol of boron tribromide (BBr3) catalyst, react at room temperature for 12 h, evaporate the solvent by rotary evaporation, continue washing with water, and allow the filtrate to stand until a grayish-white solid gradually precipitates out. Filter and recrystallize with methanol to obtain product Ⅲ-1-1 with a yield of 35.1%.

[0071] (3) 100 ml toluene, 1 mol III-1-1, 0.02 mol p-toluenesulfonic acid catalyst, and 0.01 mol hydroquinone were placed in a 1 L glass flask connected to a cooling tube receiver (for moisture determination) and a reflux tube, and heated to 40 °C. 1 mol acrylic acid was added in portions over 10 minutes with simultaneous stirring. After the addition was complete, the mixture was stirred at the same temperature under reduced pressure of 10 mPa. After the reaction, the catalyst and auxiliary agent were separated by filtration to obtain III-1. The reaction time was approximately 6 hours, with a yield of 78%. The obtained light white compound was analyzed by GC-MS, and the m / z of the product was 443.4 (M+).

[0072] Synthesis example 2

[0073] This synthetic example provides a method for synthesizing compound III-2, which is the same as that for synthetic example 1, except that in this synthetic example, bis(dichloroethyl) ether is replaced with 1,2-bis(2-chloroethoxy)ethane to obtain compound III-2.

[0074] Synthesis example 3

[0075] This synthetic example provides a method for synthesizing compound III-3, and the synthetic route is shown below:

[0076] The specific synthesis method includes the following steps:

[0077] (1) Dissolve 0.1 mol of dibenzo-15-crown ether-5 in a mixed solution of 100 ml chloroform and 80 ml glacial acetic acid. At 0 °C, add 4.5 ml nitric acid and 15 ml acetic anhydride dropwise to this mixed solution. Heat the solution to 60 °C and react for 5 h. After filtration, recrystallization and vacuum drying, dinitrobenzo-15-crown ether-5 is obtained. The prepared dinitrobenzo-15-crown ether-5 is further dissolved in ethylene glycol methyl ether (concentration 0.02 mmol / ml). Add 2 wt% Pd / C catalyst. Purge the reaction vessel with H2 to 0.4 MPa and heat to 70-80 °C. After reacting for 3 h, filter to obtain the filtrate. Distill the filtrate under reduced pressure at 60-80 °C to obtain a red solid. After drying, recrystallization and vacuum drying, diaminodibenzo-15-crown ether-5 is obtained. Add 95% sulfuric acid to a reaction flask and stir in an ice-water bath at approximately 5°C. Slowly add finely ground sodium nitrite solid and maintain the temperature at 5-10°C for 30 minutes. Then, slowly raise the temperature to 70°C to obtain a light yellow, transparent nitrosylsulfuric acid liquid. Cool the temperature to 55°C and slowly add diaminodibenzo-15-crown ether-5. React for 30 minutes, and add a small amount of distilled water to adjust the acid concentration to obtain a diazonium solution. Separately, prepare a three-necked flask with a 75% sulfuric acid solution and a small amount of metallic Fe catalyst. Heat the solution to 170°C, add the above diazonium solution dropwise, and react for 30 minutes to obtain a hydrolysate.

[0078] (2) Post-treatment of hydrolysate: Add a mixture of toluene and water (180 / 80 ml) to a four-necked flask, control the temperature at 80℃, add the above hydrolysate while stirring vigorously, let stand for 20 min, add the separated organic phase to a 7% sodium hydroxide solution, stir vigorously and let stand for 30 min, separate the alkaline phase, add concentrated sulfuric acid to adjust the pH to about 6.5, separate the organic phase, and obtain a white solid (Ⅲ-3-1) by distillation, recrystallization and drying.

[0079] (3) 100 ml toluene, 1 mol III-3-1, 0.02 mol p-toluenesulfonic acid catalyst, and 0.01 mol hydroquinone were placed in a 1 L glass flask connected to a cooling tube receiver (for moisture determination) and a reflux tube, and heated to 40 °C. 1 mol acrylic acid was added in portions over 10 minutes with simultaneous stirring. After the addition was complete, the mixture was stirred at the same temperature under reduced pressure of 10 mPa. After the reaction, the catalyst and auxiliaries were separated by filtration to obtain III-3. The reaction time was approximately 6 hours, with a yield of 70%. The obtained light white compound was analyzed by GC-MS, and the m / z of the product was 443.4 (M+).

[0080] Synthesis example 4

[0081] This synthetic example provides a method for synthesizing compound III-4, which is the same as that for synthetic example 3, except that in this synthetic example, dibenzo-15-crown ether-5 is replaced with dibenzo-21-crown ether-7 to obtain compound III-4.

[0082] Preparation Example 1

[0083] This preparation example provides a polyimide precursor resin and a method for preparing the same, the preparation method comprising the following steps:

[0084] The reaction vessel was purged with nitrogen beforehand. After 30 minutes, 40 g of N-methylpyrrolidone (NMP, dehydrated with molecular sieves 24 hours prior) was added, followed by 6.20 g (0.02 mol) of diphenyl ether tetracarboxylic dianhydride (ODPA), 4.099 g (0.0315 mol) of hydroxyethyl methacrylate (HEMA, compound II-1), 5.991 g (0.012 mol) of compound III-1, and 3.3 g (0.042 mol) of pyridine (Py). The mixture was stirred at 25 °C for 24 hours. Then, 4.76 g (0.04 mmol) of thionyl chloride was added dropwise at 0 °C, and the mixture was stirred at room temperature for 4 hours. Finally, diaminodiphenyl ether (ODA) was added. 3.604 g (0.018 mol) was polymerized at room temperature for 4 h to end the reaction and obtain a polyimide resin solution. The resin solution was added to 1 L of deionized water, and the mixture was precipitated, filtered, and washed three times. The mixture was then vacuum dried at 50 °C for 48 h to obtain a polyimide precursor resin powder, which was named A-1.

[0085] Preparation Example 2

[0086] This preparation example provides a polyimide precursor resin and a method for preparing the same, the preparation method comprising the following steps:

[0087] The reaction vessel was purged with nitrogen beforehand. After 30 minutes, 40 g of N-methylpyrrolidone (NMP, dehydrated with molecular sieves 24 hours prior) was added, followed by 6.20 g (0.02 mol) of ODPA, 4.099 g (0.0315 mol) of HEMA (compound II-1), 5.991 g (0.012 mol) of compound III-1, and 3.3 g (0.042 mol) of pyridine (Py). The mixture was stirred at 25 °C for 24 hours. Then, 8.25 g (0.04 mmol) of DCC was added dropwise at 0 °C, and the mixture was stirred at room temperature for 2 hours. Finally, ODA was added. 3.604 g (0.018 mol) was polymerized at room temperature for 4 h to stop the reaction and obtain a polyimide resin suspension. The solid byproduct dicyclohexylurea (DCU) was filtered off to obtain a clear resin filtrate, which was then added to 1 L of anhydrous ethanol for precipitation, filtration, and washing three times. The filtrate was then dried under vacuum at 50 °C for 48 h to obtain a polyimide precursor resin powder, named A-2.

[0088] Preparation Example 3

[0089] This preparation example provides a polyimide precursor resin and its preparation method. The preparation method is the same as that in Preparation Example 1. The difference is that in this preparation example, compound III-1 is replaced with compound III-2 (0.012 mol) 7.163 g to obtain polyimide precursor resin powder, named A-3.

[0090] Preparation Example 4

[0091] This preparation example provides a polyimide precursor resin and its preparation method. The preparation method is the same as that in Preparation Example 1. The difference is that in this preparation example, the amount of HEMA (compound II-1) is 0.036 mol and the amount of compound III-1 is 0.009 mol, and a polyimide precursor resin powder is obtained, named A-4.

[0092] Preparation Example 5

[0093] This preparation example provides a polyimide precursor resin and its preparation method. The preparation method is the same as that in Preparation Example 1, except that in this preparation example, diaminodiphenyl ether ODA is replaced with 7.389 g (0.018 mol) of 2,2'-bis[4-(4-aminophenoxyphenyl)]propane BAPP to obtain polyimide precursor resin powder, named A-5.

[0094] Preparation Example 6

[0095] This preparation example provides a polyimide precursor resin and its preparation method. The preparation method is the same as that in Preparation Example 1. The difference is that in this preparation example, diaminodiphenyl ether ODA is replaced with 3.821 g (0.018 mol) of 2,2'-dimethyl-4,4'-diaminobiphenyl m-TB to obtain polyimide precursor resin powder, named A-6.

[0096] Preparation Example 7

[0097] This preparation example provides a polyimide precursor resin and its preparation method. The preparation method is the same as that in Preparation Example 1. The difference is that in this preparation example, the amount of HEMA (compound II-1) is 0.0441 mol and the amount of compound III-1 is 0.0009 mol, and a polyimide precursor resin powder is obtained, named A-7.

[0098] Preparation Example 8

[0099] This preparation example provides a polyimide precursor resin and its preparation method. The preparation method is the same as that in Preparation Example 1. The difference is that in this preparation example, the amount of HEMA (compound II-1) is 0.02 mol and the amount of compound III-1 is 0.02 mol, and a polyimide precursor resin powder is obtained, named A-8.

[0100] Preparation Example 9

[0101] This preparation example provides a polyimide precursor resin and its preparation method. The preparation method is the same as that in Preparation Example 1. The difference is that in this preparation example, the amount of HEMA (compound II-1) is 0.008 mol and the amount of compound III-1 is 0.032 mol, and a polyimide precursor resin powder is obtained, named A-9.

[0102] Preparation Example 10

[0103] This preparation example provides a polyimide precursor resin and its preparation method. The preparation method is the same as that in Preparation Example 1. The difference between Preparation Example 1 and Preparation Example 1 is that in this preparation example, the amount of HEMA (compound II-1) is 0.0396 mol and the amount of compound III-1 is 0.0004 mol, and a polyimide precursor resin powder is obtained, named A-10.

[0104] Comparative Preparation Example 1

[0105] This comparative preparation example provides a polyimide precursor resin and its preparation method. The preparation method is the same as that of Preparation Example 1. The difference from Preparation Example 1 is that in this comparative preparation example, compound III-1 is not added, and the polyimide precursor resin powder is obtained and named A-11.

[0106] Performance Test 1

[0107] The polyimide precursor resin prepared above was subjected to an organic solvent solubility test.

[0108] Weigh 1g of resin and dissolve it in 9g of solvent, stir for 12h and observe its solubility. The strong polar organic solvents are: N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and γ-butyrolactone; the low polar organic solvents include tetrahydrofuran, 1,2-dichloroethane, propylene glycol methyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, methyl lactate, ethyl lactate, propyl lactate and butyl lactate.

[0109] The solubility test results of some organic solvents are shown in Table 1:

[0110] Table 1

[0111] It can be observed that the polyimide precursor resin provided by the present invention has good organic solvent solubility in strong polar solvents such as N-methylpyrrolidone and γ-butyrolactone, and low polar solvents such as tetrahydrofuran, propylene glycol methyl ether, and ethylene glycol monomethyl ether acetate.

[0112] Example 1

[0113] This embodiment provides a photosensitive resin composition and its preparation method. The content of each component in the photosensitive resin composition is shown in Table 2.

[0114] Table 2

[0115] The preparation method includes: dissolving each component in the above-mentioned formulation in a solvent, and mixing them thoroughly to obtain the photosensitive resin composition.

[0116] Examples 2-10

[0117] This embodiment provides a photosensitive resin composition and its preparation method. The content of each component in the photosensitive resin composition is the same as in Example 1, and the preparation method is the same as in Example 1. The difference from Example 1 is that in this embodiment, the polyimide precursor resin A-1 is replaced with A-2 (Example 2), A-3 (Example 3), A-4 (Example 4), A-5 (Example 5), A-6 (Example 6), A-7 (Example 7), A-8 (Example 8), A-9 (Example 9), and A-10 (Example 10), respectively.

[0118] Examples 11-12

[0119] This embodiment provides a photosensitive resin composition and its preparation method. The content of each component in the photosensitive resin composition is shown in Table 3.

[0120] Table 3

[0121] The preparation method is the same as in Example 1.

[0122] Comparative Example 1

[0123] This comparative example provides a photosensitive resin composition and its preparation method. The content of each component in the photosensitive resin composition is the same as that in Example 1, and the preparation method is the same as that in Example 1. The difference from Example 1 is that the polyimide precursor resin A-1 is replaced with A-11 in this comparative example.

[0124] Application examples

[0125] The photosensitive resin compositions obtained in the examples and comparative examples were used to prepare photosensitive curable films. The preparation method is as follows:

[0126] The photosensitive resin compositions prepared in the examples and comparative examples were wet-coated using a rotational viscometer (Mikasa: MS-B150+DA-60S), pre-dried on a hot plate, and then exposed and developed before being transferred to nitrogen for further curing. The curing temperature was 150-250°C for 30-180 min, and the films were removed at room temperature to obtain photosensitive cured films.

[0127] Performance Test 2

[0128] The photosensitive curable film prepared for the corresponding use case was tested:

[0129] (1) Dielectric constant (DK)

[0130] The test was conducted using a Keysight N5290A vector network analyzer (cavity resonator method) at a frequency of 1 kHz. The sample size was 6 × 6 cm. The results are shown in Table 4.

[0131] (2) Adhesion

[0132] Adhesion was evaluated using the cross-cut adhesion test, in which 10 rows and 10 columns of cross-cut adhesion were performed on the cured film surface at 1mm intervals using a cross-cut tester. The adhesion strength was 350–400 g / cm². 2 The 3M 600 adhesive tape was applied smoothly to the test grid. After 1 minute, the tape was quickly peeled off vertically (90°). The same test was performed twice at the same location. The adhesion between the cured film and the substrate was evaluated based on the adhesion state of the cured film. A small piece of cured film detached from the intersection of the scribe lines with a detachment area of ​​<5% was classified as A; a small piece of cured film detached from the intersection of the scribe lines with a detachment area of ​​5% to 15% was classified as B; and a large area of ​​cured film detached from the intersection of the scribe lines with a detachment area of ​​>15% was classified as C. The results are shown in Table 4.

[0133] (3) Thermal weight loss temperature

[0134] The thermal decomposition temperature was determined using a thermogravimetric analyzer (model TGA-55) with a heating rate of 10℃ / min and a sample size of 3–5 mg. The temperature range was RT–700℃. The results are shown in Table 4.

[0135] The test results are shown in Table 4:

[0136] Table 4

[0137] As can be seen from the table above, the photosensitive resin composition provided by the present invention, after being coated with a rotational viscometer, dried on a hot plate, exposed, developed, and thermally cured under nitrogen, produces a photosensitive cured film that exhibits excellent adhesion and dielectric properties, as well as good heat resistance. The preferred adhesion results are A, DK≤2.9 and 5% thermogravimetric temperature≥350℃. It is suitable for surface protective films and interlayer insulating films of semiconductor devices, insulating layers of organic electroluminescent devices, and insulating layers of thin-film transistors.

[0138] Meanwhile, it can be observed that when the arylene structures containing cyclic crown ether structures account for 2% to 50% of the total amount of groups in R1 and R2 in the polyimide precursor resin, the prepared polyimide precursor resin, in addition to having good organic solvent solubility, also exhibits good dielectric properties, adhesion properties, and heat resistance when applied to form a cured film in a photosensitive resin composition. When the amount of arylene structural units containing cyclic crown ether structures is <2%, the solubility of the precursor resin and the adhesion and dielectric properties of the cured film cannot be guaranteed; when the amount of arylene structural units containing cyclic crown ether structures is >50%, the heat resistance of the cured film decreases significantly.

[0139] It should be noted that, in this document, relational terms such as "first" and "second" are used merely to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitations, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0140] The above description is merely a specific embodiment of the present invention, enabling those skilled in the art to understand or implement the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the present invention is not to be limited to the embodiments described herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A polyimide precursor resin, characterized in that, The polyimide precursor resin has a structure as shown in Formula I: Wherein, Ar1 is a dianhydride residue, Ar2 is a diamine residue, m is any integer between 5 and 10000, and R1 and R2 are each independently a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, or a cycloalkyl group with 3 to 20 carbon atoms. Any one of them; Wherein, R3 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R4 is an alkylene group having 1 to 10 carbon atoms, R5 is an arylene group containing a cyclic crown ether structure, and -* represents the linking bond of the group; In Formula I, R1 in each repeating unit may be the same or different, and R2 in each repeating unit may be the same or different. Furthermore, taking the total amount of substance of R1 and R2 as 100%, the groups in R1 and R2... The molar content of the substance is 1-80%.

2. The polyimide precursor resin according to claim 1, characterized in that, Group Choose from any one or more of the following structures: and / or, groups Choose from any one or more of the following structures:

3. The polyimide precursor resin according to claim 1 or 2, characterized in that, The dianhydride residues include any one or more residues selected from pyromellitic dianhydride, 3,3,3',4'-biphenyltetracarboxylic acid dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid dianhydride, 4,4'-(hexafluoroisopropene) phthalic anhydride, 4,4'-oxobisphthalic anhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, p-phenylene-bisphenyltriester dianhydride, 3,3',4,4'-diphenylmethanesulfonate tetracarboxylic acid dianhydride, cyclobutanetetracarboxylic acid dianhydride, cyclohexanetetracarboxylic acid dianhydride, and 3,3,4,4-diphenylsulfonate tetracarboxylic acid dianhydride. And / or, the diamine residues include 2,2-bis(4-hydroxy-3-aminophenyl)propane, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, N,N'-[(1-methylethylidene)bis(6-hydroxy-3,1-phenylene)]bis[3-aminobenzamide, 2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 4,4'-bis(3-aminophenoxy)diphenyl sulfone, 2,2-bis[3-(4-aminobenzamido)-4-hydroxyphenyl]propane, 2,2-bis[3-(4-aminobenzamido)-4-hydroxyphenyl]sulfone, 2,2-bis[3-(4-aminobenzamido)-4-hydroxyphenyl]sulfone, and 2,2-bis[3-(4-aminobenzamido] -4-hydroxyphenyl] ether, N-(2-hydroxy-5-amino)phenyl-3-aminobenzamide, N-(5-amino-2-hydroxyphenyl)-4-[2-[4-[(4-aminophenyl)carbamoyl]phenyl]-propane-2-yl]benzamide, N-(5-amino-2-hydroxyphenyl)-4-[2-[4-[(4-aminophenyl)carbamoyl]phenyl]-sulfonyl-2-yl]benzamide, 2,2-bis[3-(4-aminobenzoamido)-4-hydroxyphenyl]hexafluoropropane, N-(5-amino-2-hydroxyphenyl)-4-[2-[4-[(4-aminophenyl)carbamoyl]phenyl]-ether- 2-yl]benzamide, 1,4-p-phenylenediamine, N-(5-amino-2-hydroxyphenyl-4-[2-[4-[(4-aminophenyl)carbamoyl]phenyl]-hexafluoropropane-2-yl]benzamide, m-phenylenediamine, o-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diamino-p-terphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminobiphenyl, p-aminobenzoic acid p-aminophenyl ester, 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]hexafluoropropane, N-[5-[3-[(1,3-dioxy-2-benzofuran-5-carbonyl)amino]-4-hydroxyphenyl]sulfonyl-2-hydroxyphenyl]-1,3-dioxy-2-benzofuran-5-carboxamide, N,N'-[[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis(6-hydroxy-3,1-phenylene)]bis[1,3-dioxy-1,3-dihydroisobenzofuran-5-carboxamide] and 2,2-bis(4-(4-aminophenoxy)phenyl)propane, or any one or more residues thereof.

4. The method for preparing the polyimide precursor resin according to any one of claims 1 to 3, characterized in that, The preparation method includes: Diosmic anhydride and An esterification reaction is carried out under the action of an alkaline catalyst to obtain a diester derivative, followed by an acyl chloride reaction using a chloride or a dehydration condensation reaction using a dehydrating agent, and then a diamine is added to carry out the reaction to obtain the polyimide precursor resin.

5. The preparation method according to claim 4, characterized in that, The preparation method is carried out under an inert gas atmosphere; And / or, the alkaline catalyst comprises any one or more of pyridine, 4-dimethylaminopyridine, triethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene and 1,5-diazabicyclo[4.3.0]non-5-ene; And / or, the chloride includes any one or more of thionyl chloride, thioyl chloride, and dichlorooxalic acid; And / or, the dehydrating agent comprises dicyclohexylcarbodiimide; And / or, the molar ratio of the chloride or dehydrating agent to the dianhydride is 1 to 3:1, preferably 1.5 to 2.5:1; And / or, the molar ratio of the dianhydride to the diamine is 0.7 to 1.3:1, preferably 0.9 to 1.1:

1.

6. A photosensitive resin composition, characterized in that, The photosensitive resin composition comprises the polyimide precursor resin according to any one of claims 1 to 3 or the polyimide precursor resin prepared by the preparation method according to claim 4 or 5, a photosensitive compound, a crosslinking agent, a polymerization inhibitor, an organosilane compound, a solvent, and an optional rust inhibitor.

7. The photosensitive resin composition according to claim 6, characterized in that, The photosensitive compound includes any one or more of oxime ester compounds, aromatic ketones, quinone compounds formed by alkyl anthraquinones and aromatic ring condensation, benzoin compounds, benzoin ether compounds, and benzoyl derivatives, preferably oxime ester compounds; And / or, the crosslinking agent comprises any one or more of diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, 2-hydroxyethyl methacrylate, 1,3-(meth)acryloyloxy-2-hydroxypropane, methylenebisacrylamide, N,N-dimethylacrylamide, and N-hydroxymethylacrylamide; And / or, the polymerization inhibitor comprises any one or more of the following: p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, o-dinitrobenzene, p-dinitrobenzene, m-dinitrobenzene, phenanthrenequinone, N-phenyl-2-naphthylamine, copper-iron reagent, 2,5-toluenequinone, tannic acid, p-benzylaminophenol, and nitrosamine compounds; And / or, the organosilane compound includes γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-acryloyloxypropyltrimethoxysilane, 3-ureapropyltriethoxysilane, 3-ylpropyltrimethoxysilane, triethoxysilylpropylethylcarbamate, 3-(triethoxysilyl)propylsuccinic anhydride, phenyltriethoxysilane, phenyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-triethoxysilane Silyl-N-(1,3-dimethylbutylene)propylamine, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 1-isocyanate-methyltrimethylsilane, 1-isocyanate-methyltriethylsilane, 1-isocyanate-methyltripropylsilane, 1-isocyanate-methyltributylsilane, 1-isocyanate-methyldimethoxymethylsilane, 1-isocyanate-methylmethoxydimethylsilane, 1-isocyanate-methyltriethoxysilane, 1-isocyanate-methyltripropoxysilane, 1-isocyanate-methyltributoxysilane, 1-isocyanate-methyldiethoxyethylsilane, 3-isocyanate-propyltrimethylsilane, 3-isocyanate-propyl Triethylsilane, 3-isocyanopropyltrimethoxysilane, 3-isocyanopropyldimethoxymethylsilane, 3-isocyanopropylmethoxydimethylsilane, 3-isocyanopropyltriethoxysilane, 3-isocyanopropyldiethoxyethylsilane, 3-isocyanopropylethoxydiethylsilane, 6-isocyanopropylhexyltrimethoxysilane, 6-isocyanopropylhexyldimethoxymethylsilane, 6-isocyanopropylhexylmethoxydimethylsilane, 6-isocyanopropylhexyltriethoxysilane, 6-isocyanopropylhexyldiethoxyethylsilane, 6-isocyanopropylhexylethoxydiethylsilane, bis(2-hydroxyethyl)-3-aminopropyltrimethoxysilane The following are any one or more of the following: ethoxysilane, N,N-bis(2-hydroxyethyl)-N,N-bis(trimethoxysilylpropyl)ethylenediamine, N-(hydroxymethyl)-N-methylaminopropyltrimethoxysilane, 7-triethoxysilylpropyl-5-hydroxyflavone, N-(3-triethoxysilylpropyl)-4-hydroxybutyramide, 2-hydroxy-4-(3-methyldiethoxysilylpropoxy)benzophenone, 1,3-bis(4-hydroxybutyl)tetramethyldisiloxane, 3-(N-acetyl-4-hydroxypropoxy)propyltriethoxysilane, hydroxymethyltriethoxysilane, and (3-triethoxysilylpropyl)-tert-butylcarbamate; And / or, the solvent includes any one or more of ketone solvents, ester solvents, ether solvents, and aromatic hydrocarbon solvents; And / or, the rust inhibitor includes any one or more of tetrazolium and its azole derivatives, benzotriazole and its derivatives.

8. The photosensitive resin composition according to claim 6 or 7, characterized in that, The content of each component in the photosensitive resin composition is as follows:

9. A photosensitive curable film, characterized in that, The photosensitive curable film is formed by curing the photosensitive resin composition according to any one of claims 6 to 8.

10. The application of the photocurable film of claim 9 as a protective film or insulating layer in semiconductor devices, organic electroluminescent devices, and thin-film transistors.

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