Fluorine-free alkali-soluble resin, composition comprising same, cured film and pattern processing method

Abstract

Provided in the present invention are a fluoride-free alkali-soluble resin and a positive photosensitive resin composition comprising same. The fluoride-free alkali-soluble resin in the present invention comprises one or more of polyimide, polyamide acid and polyesteramide structures. By adjusting the imidization rate and the proportion of a hydroxyl-containing structure to an aliphatic structure, the fluoride-free alkali-soluble resin has a good solubility and optical and mechanical properties, and a cured film, which is formed by the fluoride-free alkali-soluble resin, and has been subjected to alkaline development after exposure, has the advantages of a good exposure sensitivity and a high pattern resolution, thereby solving the problems of environmental pollution, harm to human health, a high raw material price, etc., caused by the traditional photosensitive polyimide containing fluorine.

Description

Fluorine-free alkali-soluble resins, compositions thereof, cured films, and patterning methods

[0001] Cross-references to related applications

[0002] This application claims priority to Chinese patent application No. 202411890224.4, filed on December 20, 2024, entitled "Fluorine-free alkali-soluble resin and composition thereof, cured film and patterning method thereof", the entire contents of which are hereby incorporated herein by reference. Technical Field

[0003] This invention relates to a fluorine-free alkali-soluble resin, a positive photosensitive resin composition comprising the same, a cured film, and a patterning method. More specifically, this invention relates to a positive photosensitive resin composition suitable for use as a surface protective film for semiconductor devices, an interlayer insulating film, an insulating layer for organic electroluminescent (EL) devices, an insulating layer for thin-film transistors (TFTs), and the like, and a cured film using the same. Background Technology

[0004] Polyimide (PI) is an ideal polymer material with excellent heat resistance, mechanical properties, electrical insulation properties, and chemical stability, and is commonly used in aerospace, semiconductor, optoelectronics, and microelectronics fields. Compared to ordinary polyimide, photosensitive polyimide (PSPI) can be patterned without the need for other photoresists, shortening the process route and making it an ideal insulating material in the electronics and microelectronics fields.

[0005] In recent years, with the miniaturization of semiconductor devices, the intermediate insulating film and passivation layer of semiconductor devices also require finer exposure and development sensitivity and image resolution. Based on this, the existing technology often uses photosensitive polyimide resin composition varnish on the surface of semiconductor devices, and after exposure, it is developed under alkaline conditions to obtain ideal patterns. However, this often requires high exposure sensitivity and development resolution of the photosensitive polyimide resin composition.

[0006] Introducing a certain amount of fluorine into PSPI resin not only improves the resin's solubility but also significantly enhances the film's light transmittance, dielectric properties, and thermal properties, thus making it widely used in the design of high-performance PSPI. However, these polyimides prepared from fluorinated monomers are not only expensive, but the long-term presence and contact with fluorine can also have adverse health effects on human bones, teeth, growth, and development, as well as long-term environmental pollution. In recent years, international requirements and regulations for PFAS (polyfluoroalkyl sulfonates) have become increasingly stringent, making the development of fluorine-free photosensitive polyimide materials a current trend. However, removing fluorine inevitably leads to a decrease in the solubility and light transmittance of PSPI resin. Therefore, designing a fluorine-free PSPI that can meet the current high requirements for exposure sensitivity and development resolution of photosensitive polyimide resin compositions has become a research hotspot. Summary of the Invention

[0007] The purpose of this invention is to provide a fluorine-free alkali-soluble resin, a positive photosensitive resin composition containing such a fluorine-free alkali-soluble resin, a cured film, and a patterning method thereof. The alkali-soluble resin does not contain fluorine, and the positive photosensitive resin composition containing it has good solubility and light transmittance. The cured film formed therefrom can achieve high exposure sensitivity and development resolution.

[0008] The first aspect of the present invention provides a fluorine-free alkali-soluble resin, wherein the main chain structure of the fluorine-free alkali-soluble resin includes structural units having structural formula (a1) and structural units having structural formula (a2).

[0009] In the above structural formulas (a1) and (a2), X and Y represent reactive residues of dianhydrides, and P and Q represent reactive residues of diamines;

[0010] Furthermore, at least one of the monomers corresponding to X, Y, P, and Q contains a phenolic hydroxyl group; R1 and R2 each independently represent H or an organic group with 1-20 carbon atoms;

[0011] Furthermore, the imidization rate d of the fluorine-free alkali-soluble resin and the molar ratio c of the monomer containing phenolic hydroxyl groups to the total monomers of the polymer satisfy 90% ≥ (1-d) / 2 + c ≥ 40%.

[0012] Furthermore, the imidization rate of the fluorine-free alkali-soluble resin is d = 25%-99%; and / or, the molar ratio of monomers containing phenolic hydroxyl groups to the total polymer monomers is c = 30%-60%.

[0013] Furthermore, at least one of the monomers corresponding to X, Y, P, and Q is a monomer containing an aliphatic structure, the aliphatic structure being present on the main chain of the fluorine-free alkali-soluble resin, and the monomer containing the aliphatic structure accounting for 5%-40% of the total monomers.

[0014] Furthermore, the structural unit of the structural formula (a1) represents a polyimide precursor, comprising polyamic acid and polyamic ester; the polyamic acid accounts for 1%-50% of the fluorine-free alkali-soluble resin; the polyamic ester accounts for 0-90% of the fluorine-free alkali-soluble resin;

[0015] Furthermore, the structural unit of the structural formula (a2) represents polyimide, and the fluorine-free alkali-soluble resin includes one or more of polyamic acid, polyamic acid ester, and polyimide structures, wherein the sum of the proportions of polyamic acid, polyamic acid ester, and polyimide is 100%.

[0016] Furthermore, the molecular weight of the fluorine-free alkali-soluble resin is 30,000-80,000.

[0017] Furthermore, X and Y are each independently selected from one or more of the following substituted or unsubstituted structures:

[0018] And / or, P and Q are each independently selected from one or more of the following substituted or unsubstituted structures:

[0019] In this configuration, R3 is independently H or methyl; R5, R6, and R7 are independently H or hydroxyl; A1 and A2 are independently selected from -CO-, -O-, -S-, -CO2-, -SO2-, -CH2-, -C(CH3)2-, or -CONH-; B1 and B3 are independently selected from bonds, One of them, B2 is selected from Or a C2-C6 alkane chain, j = 0, 1, 2 or 3, k = 0, 1, 2 or 3, * indicates the connection position.

[0020] Preferably, X and Y are each independently selected from one or more of the following structures:

[0021] And / or, P and Q are each independently selected from one or more of the following structures:

[0022] Wherein, R3 is independently H or methyl; A1 and A2 are independently selected from -CO-, -O-, -S-, -CO2-, -SO2-, -CH2-, -C(CH3)2- or -CONH-; j = 0, 1, 2 or 3; * indicates the connection position.

[0023] Furthermore, X and Y are derived from one or more combinations of the following dianhydride structures:

[0024] 1,2,3,4-Butanetetracarboxylic dianhydride (BDA), cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride (HPMDA), 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, dimethylcyclobutanetetracarboxylic anhydride (DMCBDA), 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]malonium (B PADA), 9,9-bis(3,4-dicarboxyphenyl)fluorenyl dianhydride (BPAF), norbornane-2-spiro-α-cyclopentanone-α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic dianhydride (CpODA), diethylene glycol (4-tricarboxylic anhydride) (TMEG), 4,4'-terephthalodioxydiphthalic anhydride (HQDPA), p-phenylene-bisphenyltrimethacrylate dianhydride (TA) HQ), 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (ODPA), 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride (α-ODPA), 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA), 2,2',3,3'-benzophenone tetracarboxylic dianhydride (α-BTDA), 3,3,4,4-diphenyl sulfone tetracarboxylic dianhydride (DSDA), (4-phthalic anhydride)formyloxy-4-phthalate (8CI), bis[(3,4-dianhydride)phenyl]terephthalate (PHAP), bis(4-aminophenyl)terephthalate (BAPT), 1,3-dihydro-1,3-dioxy-5,5'-[(1-methylethylidene)di-4,1-phenylene] ester, methylcyclohexene tetracarboxylic dianhydride (MCTC), and dianhydrides with the following structures:

[0025] And / or, the P and Q are derived from one or more combinations of the following diamine structures:

[0026] Ethylenediamine, 1,3-diaminopropane, 2-methyl-1,3-propanediamine, 1,4-diaminobutane, 1,5-diaminopentane, 2-methyl-1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis( Aminomethyl)cyclohexane, 4,4'-methylenebis(cyclohexylamine), 4,4'-methylenebis(2-methylcyclohexylamine), 1,2-bis(2-aminoethoxy)ethane, 2,2'-diamino-4,4'-(cyclohexyl-1,1-diyl)diol (CHPS), polyoxyethylene diamine, polyethylene glycol diamine, bis(3-amino-4-hydroxyphenyl)sulfone (BAHS), bis(3-amino-4-hydroxyphenyl)propane (BAP), bis(3-amino-4-hydroxyphenyl)methane, bis(3-amino-4-hydroxyphenyl) ether (OBAP), bis(3-amino-4-hydroxyphenyl) ether (OBAP), bis(3-amino-4-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)methane, bis(3-amino-4-hydroxyphenyl) ether (OBAP), bis(3-amino-4-hydroxyphenyl)propane, ... 4-Hydroxyphenyl)fluorene, bis(4-aminophenyl)fluorene (FDA), bis(3-chloro-4-aminophenyl)fluorene (CFDA), 1,4-bis(4-aminophenoxy)benzene, 3,4'-diaminodiphenyl ether (DAPE), 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane (MDA), 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone (4,4-DDS), 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene, 4,4'-di... Amino diphenyl ether (ODA), bis(4-aminophenoxyphenyl) sulfone, bis(3-aminophenoxyphenyl) sulfone, bis{4-(4-aminophenoxy)phenyl} ether, 3-carboxy-4,4'-diaminodiphenyl ether, N,N'-[(1-methylethylidene)bis(6-hydroxy-3,1-phenylene)]bis[3-aminobenzamide, 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, N-(5-amino-2-hydroxyphenyl)-4-[2-[4-[(4-aminophenyl)carbamoyl]phenyl]-ether-2-yl]benzamide, 4,4'-diaminodiphenylmethane (MDA), 1,3-bis(4-aminophenoxy)benzene (TPE-R), 1,4-bis(4-aminophenoxy)benzene (TPE-Q), 1,3-bis(3'-aminophenoxy)benzene (APB), 2,2-bis(4-(4-) (Aminophenoxy)phenyl)propane (BAPP), 4,4'-bis(3-aminophenoxy)diphenyl sulfone (BAPS-M), 4-aminobenzoic acid 4-aminophenyl ester (APAB), [4-(4-aminobenzoyl)oxyphenyl]4-aminobenzoate (ABHQ), bis(4-aminophenyl)terephthalate (BAPT), 5(6)-1-(4-aminophenyl)-1,3,3-trimethylindene (indenediamine), 6 6'-Diamino-3,3'-methylenedibenzoic acid (MBAA), 4,4'-methylene(2-amino-3,6-dimethylphenol), N1,N8-bis(4-aminophenyl)octadiamide, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(3-aminophenoxy)diphenyl sulfone (M-BAPS), 1,1,3,3-tetramethyl-1,3-bis(3-aminopropyl)disiloxane, and diamines with the following structures:

[0027] More preferably, X and Y are derived from one or more combinations of the following dianhydride structures:

[0028] 1,2,3,4-Butanetetracarboxylic dianhydride (BDA), cyclobutanetetracarboxylic dianhydride (CBDA), 1,2,4,5-cyclohexanetetracarboxylic dianhydride (HPMDA), dimethylcyclobutanetetracarboxylic dianhydride (DMCBDA), norbornane-2-spiro-α-cyclopentanone-α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic dianhydride (CpODA), 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]malonium dianhydride (BPADA), diethylene glycol (4-tricarboxylic anhydride) (TMEG), p-phenylene-bisphenyltrilate dianhydride (TAHQ), 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (ODPA), 3,3,4,4-diphenyl sulfone tetracarboxylic dianhydride (DSDA), methylcyclohexenetetracarboxylic dianhydride (MCTC), and dianhydrides with the following structures:

[0029] And / or, the P and Q are derived from one or more combinations of the following diamine structures:

[0030] 1,4-Cyclohexanediamine, 2,2'-diamino-4,4'-(cyclohexyl-1,1-diyl)diol (CHPS), polyoxyethylene diamine, polyethylene glycol diamine, bis(3-amino-4-hydroxyphenyl)sulfone (BAHS), bis(3-amino-4-hydroxyphenyl)propane (BAP), bis(3-amino-4-hydroxyphenyl) ether (OBAP), 4,4'-diaminodiphenyl ether (ODA), 1,1,3,3-tetramethyl-1,3-bis(3-aminopropyl)disiloxane (SiDA), and diamines with the following structures:

[0031] Furthermore, the end-capping groups of the main chain structure of the fluorine-free alkali-soluble resin have the structures shown in general formula (2) and / or (3), where A is derived from primary monoamine and B is derived from dianhydride.

[0032] In the general formula (2), A is derived from a primary monoamine with a capped group; the primary monoamine with a capped group is preferably aniline, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminophenol, 3-aminophenol, 4-aminophenol, 3-amino-4,6-dihydroxypyrimidine, 2-aminobenzylthiophenol, 3-aminobenzylthiophenol, 4-aminobenzylthiophenol, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, etc., which can be used alone or in combination of two or more.

[0033] Furthermore, the mono-primary amine, as the end-capped group, accounts for 0-50 mol% of the total amine composition, with a particularly preferred 5-30 mol%.

[0034] In the general formula (3), B is derived from the dianhydride of the end-capped group; the dianhydride used as the end-capped group is preferably phthalic anhydride, maleic anhydride, norbornene anhydride, cyclohexanedicarboxylic anhydride, etc., which can be used alone or in combination of two or more.

[0035] Furthermore, the dianhydride, as the end-capping group, accounts for 0-50 mol% of the total anhydride composition, with a particularly preferred 5-30 mol%.

[0036] A second aspect of the present invention provides a positive photosensitive resin composition comprising the above-mentioned fluorine-free alkali-soluble resin, containing the following components:

[0037] (a) 100 parts by weight of alkali-soluble resin, wherein the alkali-soluble resin is the above-mentioned fluorine-free alkali-soluble resin.

[0038] (b) Photoacid-generating agent, 10-40 parts by weight;

[0039] (c) Thermal crosslinking agent, 15-60 parts by weight;

[0040] (d) Organic solvents;

[0041] A third aspect of the present invention provides a cured film obtained by curing the above-described positive photosensitive resin composition.

[0042] A fourth aspect of the present invention provides a method for pattern processing of a cured film, comprising the following steps: coating the positive photosensitive resin composition onto a substrate and drying it at 40-120°C for 1-10 min to form a photosensitive resin composition film; exposing the film under a mask; removing the exposed portion of the film using an alkaline developer, developing and cleaning it; and curing and drying the developed film at 100-400°C to obtain a cured film containing the desired pattern.

[0043] The beneficial effects of this invention lie in providing a fluorine-free alkali-soluble resin, which not only solves the problem of fluorine hazards but also addresses the alkali solubility issue of fluorine-free polyimide alkali-soluble resins by controlling the imidization rate and phenolic hydroxyl content of the polyimide resin. Furthermore, by introducing a certain proportion of aliphatic structures into the resin structure to increase light transmittance and solubility in organic solvents, a fluorine-free photosensitive polyimide resin composition with high development resolution and exposure sensitivity is obtained. Detailed Implementation

[0044] Hereinafter, specific embodiments of the fluorine-free alkali-soluble resin, the positive photosensitive resin composition containing the above-mentioned fluorine-free alkali-soluble resin, the cured film, and the pattern processing method thereof, which are involved in this invention, will be described in detail. However, this invention is not limited to the embodiments included in the following examples, and various modifications can be made that can achieve the purpose of the invention and do not exceed the scope of the spirit of the invention.

[0045] <Fluorine-free alkali-soluble resin>

[0046] The fluorine-free alkali-soluble resin involved in this invention contains structural units having structural formula (a1) and structural units having structural formula (a2), and the fluorine-free alkali-soluble resin has a main chain structure as shown in general formula (1):

[0047] In general formula (1), X and Y represent dianhydride or tetracarboxylic acid reaction residues, and P and Q represent diamine reaction residues; in formula (1), m is an integer from 0 to 50000, and n is an integer from 10 to 50000; in the embodiments of the present invention, the molecular weight of the fluorine-free alkali-soluble resin is 30000-80000.

[0048] In this invention, the structural unit of structural formula (a1) represents a polyimide precursor, including polyamic acid and polyamic acid ester, wherein the polyamic acid accounts for 1%-50% of the fluorine-free alkali-soluble resin, and the polyamic acid ester accounts for 0-90% of the fluorine-free alkali-soluble resin.

[0049] In this invention, the structural unit of structural formula (a2) represents polyimide. The structural formulas (a1) and (a2) are obtained by reacting tetracarboxylic acid or dianhydride monomers with diamine monomers. The sum of the proportions of polyamic acid, polyamic acid ester, and polyimide in the fluorine-free alkali-soluble resin is 100%.

[0050] In this invention, at least one of the monomers corresponding to X, Y, P, and Q contains a phenolic hydroxyl group. The phenolic hydroxyl group can be present in the dianhydride monomer or on the diamine monomer. From the perspective of ease of synthesis, it is preferred that the phenolic hydroxyl group is present on the diamine monomer.

[0051] R1 and R2 each independently represent H or an organic group having 1-20 carbon atoms, which can be selected from substituted or unsubstituted alkyl groups, substituted or unsubstituted phenyl groups, etc. In this invention, they are residues resulting from the reaction of dimethylformamide dimethyl acetal with a carboxylic acid.

[0052] In this invention, the imidization rate d of the fluorine-free alkali-soluble resin is 25%-99%. The inventors found in their research that an imidization rate below 25% will cause the development speed to be too fast, making it impossible to properly retain the film in the non-exposed areas, resulting in a low film retention rate and affecting the normal use of the film. If the imidization rate is higher than 99%, it will cause the film in the exposed areas to dissolve too slowly during the development process, resulting in higher exposure, reduced sensitivity, and even film residue in the exposed areas, leading to incomplete development and affecting the development quality.

[0053] To increase the solubility of the fluorine-free alkali-soluble resin in organic solvents and developers, this invention introduces a relationship between the molar ratio c of phenolic hydroxyl-containing monomers and the imidization rate d: 90% ≥ (1-d) / 2 + c ≥ 40%. Both factors jointly regulate the solubility of the fluorine-free alkali-soluble resin and the quality of development. The molar ratio c of phenolic hydroxyl-containing monomers is preferably controlled between 30% and 60% of the total polymer monomers. Polymer monomers refer to all monomers participating in the polymerization reaction, including dianhydrides, diamines, monoanhydrides, and monoamines; among them, phenolic hydroxyl-containing monomers refer to all monomers containing phenolic hydroxyl groups in the polymer monomers.

[0054] To meet the optical and mechanical performance requirements of the film, at least one of the monomers corresponding to X, Y, P, and Q in this invention contains an aliphatic structure, which is beneficial for photoresist preparation and increasing solid content. Furthermore, the aliphatic structure-containing monomer accounts for 5%-40% of the total monomers in the polymer. When the aliphatic structure content is too low, or even completely absent, it will, on the one hand, reduce the light transmittance of the cured film, affecting the resolution and sensitivity of development; on the other hand, it will reduce the solubility of the resin in the organic phase, leading to difficulties in resin preparation, low solid content, or the need to use large amounts of high-boiling-point solvents (resulting in excessive solvent residue after baking or curing, causing various device defects or malfunctions). It will also easily cause precipitation and blockage of pipelines during cleaning, affecting normal production. Conversely, when the aliphatic structure content exceeds 40%, the tensile strength and other mechanical properties of the film deteriorate, failing to meet normal operating requirements.

[0055] The monomer containing an aliphatic structure can be either a dianhydride monomer or a diamine monomer. The aliphatic structure exists on the main chain of polyimide or polyamic acid (ester), and the part of the aliphatic structure constituting the main chain preferably contains a chain or cyclic structure with two or more carbon atoms. In addition to carbon and hydrogen, it may also contain elements such as oxygen, nitrogen, sulfur, silicon, and chlorine. Specifically, it may contain aliphatic structures such as chain alkanes, cycloalkanes, alkenes, and ethers. In order to achieve better optical performance, the dianhydrides containing X and Y do not contain biphenyl dianhydride and pyromellitic dianhydride structures, and the diamines containing P and Q do not contain o-phenylenediamine, p-phenylenediamine, m-phenylenediamine, or biphenylenediamine structures.

[0056] As monomers required as structural units for the synthesis of structural formulas (a1) and (a2), X and Y represent the reactive residues of the dianhydride. X and Y can be the same or different. Specifically, X and Y can be selected from one or more of the following substituted or unsubstituted structures:

[0057] In this configuration, R3 is independently H or an alkyl substituent such as methyl, ethyl, propyl, or isopropyl; R5, R6, and R7 are independently H or hydroxyl groups, and their number can be 1, 2, 3, or 4; A1 and A2 are independently selected from -CO-, -O-, -S-, -CO2-, -SO2-, -CH2-, -C(CH3)2-, or -CONH-, j = 0, 1, 2, or 3; B1 and B3 are independently selected from bonds, One of the following, k = 0, 1, 2 or 3, B2 is selected from alkanes, polyethylene glycol or siloxanes, preferably C1-C10 straight-chain alkanes or branched alkanes, polyethylene glycol chains having 1-5 -CH2CH2O- structures or siloxane chains having 1-3 -Si-O- structures; B2 is further preferably Or a C2-C6 alkane chain, * indicates the connection position;

[0058] The optional structures of X and Y can be either substituted or unsubstituted; the substituent groups can be selected from hydroxyl, carboxyl, sulfonic acid, C1-C6 alkyl, C1-C6 alkoxy, amino, chlorine, etc.

[0059] As monomers required for the structural units of synthetic formulas (a1) and (a2), P and Q represent diamine residues. P and Q can be the same or different in general formula (1). Specifically, P and Q can be independently selected from one or more of the following substituted or unsubstituted structures:

[0060] In this configuration, R3 is independently H or an alkyl substituent such as methyl, ethyl, propyl, or isopropyl; R5, R6, and R7 are independently H, hydroxyl, or methyl, and their number can be 1, 2, 3, or 4; A1 and A2 are independently selected from -CO-, -O-, -S-, -CO2-, -SO2-, -CH2-, -C(CH3)2-, or -CONH-, j = 0, 1, 2, or 3; B1 and B3 are independently selected from bonds, One of the following, k = 0, 1, 2 or 3, B2 is selected from alkanes, polyethylene glycol or siloxanes, preferably C1-C10 straight-chain alkanes or branched alkanes, polyethylene glycol chains having 1-5 -CH2CH2O- structures or siloxane chains having 1-3 -Si-O- structures; B2 is further preferably Or a C2-C6 alkane chain, * indicates the connection position;

[0061] The optional structures of P and Q can be substituted or unsubstituted; the substituent groups can be hydroxyl, carboxyl, sulfonic acid, or C1-C6 alkyl, C1-C6 alkoxy, amino, chlorine, etc.

[0062] Furthermore, X and Y are each independently selected from one or more of the following structures:

[0063] And / or, P and Q are each independently selected from one or more of the following structures:

[0064] Wherein, R3 is independently H or methyl; A1 and A2 are independently selected from -CO-, -O-, -S-, -CO2-, -SO2-, -CH2-, -C(CH3)2- or -CONH-; j = 0, 1, 2 or 3; * indicates the connection position.

[0065] Specifically, the range of dianhydrides containing X or Y can be exemplified by: 1,2,3,4-butanetetracarboxylic dianhydride (BDA), cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride (HPMDA), 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, dimethylcyclobutanetetracarboxylic anhydride (DMCBDA), 2,2-bis[4-(3,4- [Dicarboxyphenoxy]phenyl]malonic anhydride (BPADA), 9,9-bis(3,4-dicarboxyphenyl)fluorenic anhydride (BPAF), norbornane-2-spiro-α-cyclopentanone-α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic anhydride (CpODA), diethylene glycol (4-tricarboxylic anhydride) (TMEG), 4,4'-terephthalodioxydiphthalic anhydride (HQDPA), p-phenylene-bis(phenylene) Triglyceride dianhydride (TAHQ), 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (ODPA), 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride (α-ODPA), 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA), 2,2',3,3'-benzophenone tetracarboxylic dianhydride (α-BTDA), 3,3,4,4-diphenyl sulfone tetracarboxylic dianhydride (DSDA), (4-phthalic acid) 4-(3,4-dianhydride)formyloxy-4-phthalate (8CI), bis[(3,4-dianhydride)phenyl]terephthalate (PHAP), bis(4-aminophenyl)terephthalate (BAPT), 1,3-dihydro-1,3-dioxy-5,5'-[(1-methylethylidene)di-4,1-phenylene] ester (BPEDA), methylcyclohexenetetracarboxylic dianhydride (MCTC), and dianhydrides with the following structures:

[0066] In this invention, the dianhydrides containing X or Y are preferably 1,2,3,4-butanetetracarboxylic dianhydride (BDA), cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride (HPMDA), 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, dimethylcyclobutanetetracarboxylic anhydride (DMCBDA), 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]malonium dianhydride (BPADA), diethylene glycol (4-tricarboxylic anhydride) (TMEG), 4,4'-terephthalodioxydiphthalic anhydride (HQDPA), p-phenylene-bis(phenyltrilate) dianhydride (TAHQ), and 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (…). ODPA), 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride (α-ODPA), 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA), 2,2',3,3'-benzophenone tetracarboxylic dianhydride (α-BTDA), 3,3,4,4-diphenyl sulfone tetracarboxylic dianhydride (DSDA), (4-phthalic anhydride)formyloxy-4-phthalate (8CI), bis[(3,4-dianhydride)phenyl]terephthalate (PHAP), 1,3-dihydro-1,3-dioxy-5,5'-[(1-methylethylidene)di-4,1-phenylene] ester (BPEDA), methylcyclohexene tetracarboxylic dianhydride (MCTC), and dianhydrides with the following structures:

[0067] In this embodiment of the invention, the dianhydride containing X or Y is selected from 1,2,3,4-butanetetracarboxylic dianhydride (BDA), cyclobutanetetracarboxylic dianhydride (CBDA), 1,2,4,5-cyclohexanetetracarboxylic dianhydride (HPMDA), dimethylcyclobutanetetracarboxylic dianhydride (DMCBDA), norbornane-2-spiro-α-cyclopentanone-α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic dianhydride (CpODA), 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]malonium dianhydride (BPADA), diethylene glycol (4-tricarboxylic anhydride) (TMEG), p-phenylene-bisphenyltrilate dianhydride (TAHQ), 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (ODPA), 3,3,4,4-diphenyl sulfone tetracarboxylic dianhydride (DSDA), methylcyclohexenetetracarboxylic dianhydride (MCTC), and dianhydrides with the following structures:

[0068] Specifically, the range of diamines containing P or Q can be exemplified by: ethylenediamine, 1,3-diaminopropane, 2-methyl-1,3-propanediamine, 1,4-diaminobutane, 1,5-diaminopentane, 2-methyl-1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, etc. 1,4-Bis(aminomethyl)cyclohexane, 4,4'-methylenebis(cyclohexylamine), 4,4'-methylenebis(2-methylcyclohexylamine), 1,2-bis(2-aminoethoxy)ethane, 2,2'-diamino-4,4'-(cyclohexyl-1,1-diyl)diphenol (CHPS), 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, polyoxyethylene diamine, polyethylene glycol diamine, bis(3-amino-4-hydroxyphenyl)sulfone (BAHS), bis(3-amino-4-hydroxyphenyl)propane (BAP), bis(3-amino-4-hydroxyphenyl)methane, bis(3-amino-4-hydroxyphenyl)sulfone 4-Hydroxyphenyl) ether (OBAP), bis(3-amino-4-hydroxyphenyl)fluorene, bis(4-aminophenyl)fluorene (FDA), bis(3-chloro-4-aminophenyl)fluorene (CFDA), 1,4-bis(4-aminophenoxy)benzene, 3,4'-diaminodiphenyl ether (DAPE), 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane (MDA), 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone (4,4-DDS), 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 1,4-bis(4-aminophenyl) 4,4'-Diaminodiphenyl ether (ODA), bis(4-aminophenoxyphenyl) sulfone, bis(3-aminophenoxyphenyl) sulfone, bis{4-(4-aminophenoxy)phenyl} ether, 3-carboxy-4,4'-diaminodiphenyl ether, N,N'-[(1-methylethylidene)bis(6-hydroxy-3,1-phenylene)]bis[3-aminobenzamide, 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, N-(5-amino-2-hydroxyphenyl) )-4-[2-[4-[(4-aminophenyl)carbamoyl]phenyl]-ether-2-yl]benzamide, 4,4'-diaminodiphenylmethane (MDA), 1,3-bis(4-aminophenoxy)benzene (TPE-R), p-aminophenyl p-aminobenzoate (APAB), 1,4-bis(4-aminophenoxy)benzene (TPE-Q), 1,3-bis(3'-aminophenoxy)benzene (APB), 2,2-bis(4-(4-aminophenoxy)phenyl)propane (BAPP), 4,4 '-Bis(3-aminophenoxy)diphenyl sulfone (BAPS-M), 4-aminobenzoic acid 4-aminophenyl ester (APAB), [4-(4-aminobenzoyl)oxyphenyl]4-aminobenzoate (ABHQ), bis(4-aminophenyl)terephthalate (BAPT), 5(6)-1-(4-aminophenyl)-1,3,3-trimethylindane (indanediamine), 6,6'-diamino-3,3'-methylenedibenzoic acid (MBAA), 4,4'-methylene(2-amino-3-aminophenyl)-diphenyl ester (BAPT), 5(6)-1-(4-aminophenyl)-1,3,3-trimethylindane (indanediamine), 6,6'-diamino-3,3'-methylenedibenzoic acid (MBAA), 4,4'-methylene(2-amino-3-aminophenyl)-diphenyl ester (BAPT), 4,6'-diamino-3,3'-methylenedibenzoic acid (BAPT), 4,4'-methylenediphenyl ester (BAPT), 4,6'-diamino-3,3'-methylenedibenzoic acid ... 6-Dimethylphenol), 3,3'-diamino-4,4'-dihydroxydiphenylmethane, N1,N8-bis(4-aminophenyl)octanediamide, 1,4-bis(4-aminophenoxy)benzene, p-aminobenzoic acid p-phenyl ester (APAB), 4,4'-bis(3-aminophenoxy)diphenyl sulfone (M-BAPS), 4,4'-diaminobenzoyl aniline (DABA), 1,1,3,3-tetramethyl-1,3-bis(3-aminopropyl)disiloxane, and diamines with the following structures:

[0069] In embodiments of the present invention, the diamine containing P or Q is preferably 1,4-cyclohexanediamine, 2,2'-diamino-4,4'-(cyclohexyl-1,1-diyl)diol (CHPS), polyoxyethylene diamine, polyethylene glycol diamine, bis(3-amino-4-hydroxyphenyl) sulfone (BAHS), bis(3-amino-4-hydroxyphenyl)propane (BAP), bis(3-amino-4-hydroxyphenyl) ether (OBAP), 4,4'-diaminodiphenyl ether (ODA), 1,1,3,3-tetramethyl-1,3-bis(3-aminopropyl)disiloxane (SiDA), and diamines with the following structures:

[0070] Furthermore, in order to improve adhesion to the substrate, etc., the total diamine may contain 0-10 mol% aliphatic groups with a siloxane structure, without reducing heat resistance. Specifically, diamines such as 1,1,3,3-tetramethyl-1,3-bis(3-aminopropyl)disiloxane and bis(p-aminophenyl)octamethylpentasiloxane can be listed, with 1,1,3,3-tetramethyl-1,3-bis(3-aminopropyl)disiloxane being preferred.

[0071] End cap base

[0072] At the end of the main chain structure of (a) alkali-soluble resin as shown in general formula (1), there are end capping groups as shown in general formula (2) and / or general formula (3).

[0073] In general formula (2), A is derived from a primary monoamine with a capped group. Examples of primary monoamines with capped groups include 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminophenol, 3-aminophenol, 4-aminophenol, 3-amino-4,6-dihydroxypyrimidine, 2-aminobenzylthiophenol, 3-aminobenzylthiophenol, 4-aminobenzylthiophenol, 4-aminosalicylic acid, 5-aminosalicylic acid, and 6-aminosalicylic acid. These can be used alone or in combination of two or more. The primary monoamine with capped groups accounts for 0-50 mol% of the total amine composition, with a particularly preferred percentage being 5-30 mol%.

[0074] In general formula (3), B is derived from a dianhydride with a capped group. Examples of dianhydrides with capped groups include phthalic anhydride, maleic anhydride, norbornene anhydride, and cyclohexanedicarboxylic anhydride, which can be used alone or in combination of two or more. The dianhydride with capped groups accounts for 0-50 mol% of the total anhydride composition, with 5-30 mol% being particularly preferred.

[0075] <Positive-type photosensitive resin composition>

[0076] The positive photosensitive resin composition of the present invention comprises (a) an alkali-soluble resin, (b) a photoacid-generating agent, (c) a thermal crosslinking agent and (d) an organic solvent.

[0077] (a) Alkali-soluble resin

[0078] The alkali-soluble resin (a) is the above-mentioned fluorine-free alkali-soluble resin.

[0079] (b) Photoacid generator

[0080] The positive photosensitive resin composition of this invention also uses (b) a photoacid-generating agent, which can be listed as a quinone diazide compound (naphthoquinone diazidesulfonate compound), sulfonium salt, phosphonium salt, diazonium salt, iodonium salt, etc., which can be used alone or in combination of two or more. These quinone diazide compounds can be synthesized by esterification reaction of phenolic hydroxyl compounds with quinone diazidesulfonyl chloride. In this invention, the quinone diazide compounds are preferably compounds in which 5-naphthoquinone diazidesulfonyl or 4-naphthoquinone diazidesulfonyl groups are bonded to compounds having phenolic hydroxyl groups.

[0081] Specific examples of phenolic hydroxyl compounds are shown in the following diagram:

[0082] As a quinone diazide compound, the molecular structure preferably has one or more combinations of naphthoquinone diazide sulfonate structures. Specifically, the following commercially available photoacid generators PAC-1 to PAC-20 are examples, and these substances can be used in one or more combinations.

[0083] (b) The amount of photoacid generator added is 5-40 parts by weight, preferably 10-40 parts by weight, relative to 100 parts by weight of (a) alkali-soluble resin.

[0084] (c) Thermal crosslinking agent

[0085] The positive photosensitive resin composition of the present invention contains (c) a thermal crosslinking agent. The thermal crosslinking agent can improve the chemical resistance of the cured film by undergoing a crosslinking reaction with (a) an alkali-soluble resin through heating. Examples of (c) thermal crosslinking agents include (c1) epoxy compounds and (c2) alkoxy / hydroxymethyl compounds. (c1) Epoxy compounds are preferably compounds containing two or more epoxy groups in one molecule. Examples include bisphenol A type epoxy resin, bisphenol A type oxetane resin, bisphenol F type epoxy resin, bisphenol F type oxetane resin, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polymethyl (glycidyloxypropyl)siloxane, and other epoxy-containing organosilicones, but are not limited to these. Specific examples include Dai Nippon Ink Chemical Industry Co., Ltd.'s EPICLON, EXA series products, Yuka Shell Epoxy Co. Ltd.'s Epikote series of bisphenol A type epoxy compounds, and ADEKA's EP series, etc. (c2) The alkoxy / hydroxymethyl compound is preferably a compound containing two or more functional groups in a molecule, with a functional group number of 2-8. Examples include the trade names DML, TriML, DMOM, HMOM, TMOM, etc. from Honshu Chemical, and the MX and MW series from Sanwa Chemical. The positive photosensitive resin composition of the present invention may contain one or more of the above-mentioned thermal crosslinking agents.

[0086] The amount of thermal crosslinking agent (c) added is 15-100 parts by weight relative to 100 parts by weight of alkali-soluble resin (a), preferably 15-60 parts by weight.

[0087] (d) Organic solvents

[0088] The positive photosensitive resin composition of the present invention contains (d) an organic solvent. Specific examples of usable organic solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, propyl acetate, butyl acetate, methyl lactate, ethyl lactate, butyl lactate, bis(2-methoxyethyl) ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, methyl ethyl ketone, cyclohexanone, cyclopentanone, butanol, isobutanol, pentanol, γ-butyrolactone, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, etc., but are not limited to these.

[0089] <Cured film>

[0090] The cured film involved in this invention is a film obtained by curing the positive photosensitive resin composition of this invention.

[0091] <Pattern Processing Methods>

[0092] The following is a detailed description of a pattern processing method for forming resin patterns using the positive photosensitive resin composition of the present invention.

[0093] Methods for coating positive photosensitive resin compositions include spin coating, spray coating, blade coating, screen coating, and slot coating. Coating is generally preferred to achieve a dried film thickness of 0.5–50 μm. Drying can be performed using an oven, heated plate, infrared oven, etc., at a temperature between 40°C and 120°C for 1–10 minutes, or by a staged temperature-programmed drying process to evaporate the organic solvent. The substrate can be, but is not limited to, silicon wafers, ceramics, gallium arsenide, organic circuit boards, inorganic circuit boards, and substrates on which circuitry is disposed.

[0094] After coating and drying, a positive photosensitive resin composition film is formed on the substrate. The film is then exposed to exposure light through a mask with the desired pattern. The exposure light source is preferably a mercury lamp emitting i (365 nm), h (405 nm), or g (436 nm) rays. The exposure apparatus can be a reduction projection type exposure apparatus, a mask aligner, a mirror projection type exposure apparatus, etc.

[0095] After exposure, the exposed portions on the film are removed using a developer. Preferably, the developer is an aqueous solution of an alkaline compound such as tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium triethylamine, diethylamine, dimethylamine, dimethylaminoethanol, cyclohexylamine, or ethylenediamine. Alternatively, one or a combination of organic solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, methanol, ethanol, isopropanol, ethyl lactate, cyclopentanone, cyclohexanone, or acetone can be added to these alkaline aqueous solutions.

[0096] Developing methods include spray development, immersion development, and ultrasonic immersion development. The development time, temperature, and steps should be adjusted to remove the exposed portions. After development, the film is preferably rinsed with water, but an aqueous solution of alcohols or esters such as ethanol, isopropanol, or ethyl lactate can also be used. If necessary, the film can be baked before development at a temperature of 60–150°C, preferably 60–120°C, for 5 seconds to 60 minutes. After rinsing, the film is dried at 60–200°C for 1 minute to 60 minutes.

[0097] The positive photosensitive resin composition of the present invention, after exposure, development, and rinsing, undergoes a staged programmed temperature rise / isothermal heat treatment within a range of 100–400°C to cure and form a cured film. Examples of the temperature rise / isothermal heat treatment methods include: starting from room temperature with a heating rate of 5°C / min, then isothermal heat treatment at 120°C and 180°C for 30 min respectively, followed by isothermal heat treatment at 250°C for 2 h. Alternatively, the temperature can be raised from room temperature to 250°C within 2 h, followed by isothermal heat treatment at 250°C for 2 h. The temperature rise / isothermal heat treatment can be carried out under normal pressure, nitrogen, or vacuum. The cured film, containing an ideal pattern, exhibits heat resistance.

[0098] The cured film with an ideal pattern formed by the positive photosensitive resin composition of the present invention can be used as a surface protective film for semiconductor devices, an interlayer insulating film, an insulating layer for organic electroluminescent (EL) devices, an insulating layer for thin film transistors (TFTs), etc., but is not limited to these.

[0099] Example

[0100] Hereinafter, examples and the like will be given to illustrate the present invention, but the present invention is not limited to these examples. First, the evaluation methods in each example and comparative example will be described. A resin composition (hereinafter referred to as varnish) that has been filtered beforehand using a 1 μm polytetrafluoroethylene filter was used in the evaluation.

[0101] <Imidification rate of alkali-soluble resins>

[0102] For (a) the imidization rate of the alkali-soluble resin, a solution of N-methylpyrrolidone (NMP) with a solid component concentration of 50% by mass of the alkali-soluble resin was coated onto a silicon wafer. Then, a pre-baked film with a thickness of 2 μm was prepared by baking for 3 minutes using a 120°C heating plate (SKW-636 manufactured by Dainippon Screen Co., Ltd.). This film was divided in half, and one half was placed in an inert gas oven (INH-21CD manufactured by Koyo Thermo Systems). After 30 minutes, the temperature was raised to a curing temperature of 350°C and heated at 350°C for 60 minutes. Then, it was slowly cooled until the temperature inside the oven dropped below 50°C to obtain a cured film. The infrared absorption spectra of the cured film (A) and the uncured film (B) were measured using a Fourier transform infrared spectrophotometer FT-720 (manufactured by Horiba Corporation). The 1377 cm⁻¹ of the CN stretching vibration originating from the imide ring was determined. -1 The peak intensity near the curing point is used as the imidization rate, with the value of "peak intensity of the uncured film (B) / peak intensity of the cured film (A)" being the imidization rate.

[0103] <Preparation of the developing film>

[0104] The positive photosensitive resin composition of the present invention (hereinafter referred to as varnish) was coated onto a silicon wafer, and the pre-baked film thickness was 2 μm. Then, it was pre-baked at 120°C for 4 minutes using a heating plate (SCW-636; Dai Nippon Screen Manufacturing Co., Ltd.) to obtain the pre-baked film. A small photolithography developing apparatus (AC3000) was used on the i, g, and h lines with an exposure dose of 0–1000 mJ / cm. 2 In the case of 10mJ / cm 2 The film was exposed at a certain step size; after exposure, the film was developed in a 2.38% by mass TMAH aqueous solution for 70 seconds, and then rinsed with water to obtain a developed film with an isolated pattern.

[0105] <Calculation of Residual Film Rate>

[0106] Residual film rate (%) = Film thickness after development ÷ Film thickness after pre-baking × 100%

[0107] <Sensitivity>

[0108] Using an ACT-8 coating and developing apparatus (manufactured by Tokyo Electron Limited), varnish was applied to a 6-inch silicon wafer using the slit coating method, followed by a 3-minute pre-baking at 120°C. Exposure was performed using an NSR-2005i9C i-line stepper (manufactured by Nikon). After exposure, development was performed using the ACT-8 developing apparatus with a 2.38 wt% tetramethylammonium aqueous solution (hereinafter referred to as TMAH, manufactured by Tama Chemical Industry). The wafer was then rinsed with pure water and spin-dried. The lowest exposure level at which the exposed portion completely dissolved was used as the sensitivity.

[0109] <resolution>

[0110] Using a double-sided aligned single-sided exposure apparatus (PEM-6M mask aligner; manufactured by Union Optical Co., Ltd.), the varnish-coated film was patterned and exposed through a grayscale mask for sensitivity measurement (MDRM MODEL 4000-5-FS; manufactured by OptoLine International Co., Ltd.) using the i-line (wavelength 365nm), h-line (wavelength 405nm), and g-line (wavelength 436nm) of an ultra-high pressure mercury lamp. Development was then performed using a small photolithography developing apparatus (AD-2000; manufactured by Takizawa Sangyo Co., Ltd.), followed by curing in a high-temperature inert oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.) to obtain a cured film. The resolved pattern of the cured film was observed using an FPD / LSI inspection microscope (OPTIPHOT-330; manufactured by Union Co., Ltd.). The smallest pattern size of the line and gap pattern obtained without residue was taken as the resolution.

[0111] <Evaluation of the pattern on the developing film>

[0112] For the photosensitive resin composition film formed by development, the surface is visually inspected for stickiness in the unexposed areas and residue in the exposed areas. A film with no pattern defects is considered good, while a film with stickiness in the unexposed areas or residue in the exposed areas is considered poor.

[0113] Tensile Strength

[0114] The test was conducted using a universal testing machine (Instron 3360), with a sample width of 10 mm, a fixture spacing of 50 mm, a test speed of 50 mm / min, and 10 sets of test samples.

[0115] <Thermogravimetric Analysis (TGA)>

[0116] Thermogravimetric analysis was performed using a thermogravimetric analyzer (Mettler TGA / SDTA851) under a nitrogen atmosphere at a heating rate of 10 °C / min.

[0117] The embodiments of the present invention will be described in detail below. First, the abbreviations corresponding to some of the monomers involved in the embodiments will be explained.

[0118] CBDA: Cyclobutanetetracarboxylic dianhydride

[0119] DMCBDA: Dimethylcyclobutanetetracarboxylic anhydride

[0120] BDA: 1,2,3,4-Butanetetracarboxylic dianhydride

[0121] HPMDA: 1,2,4,5-cyclohexanetetracarboxylic dianhydride

[0122] TMEG: Diethylene glycol (4-tricarboxylic anhydride)

[0123] MCTC: Methylcyclohexenetetracarboxylic dianhydride

[0124] CpODA: norbornane-2-spiro-α-cyclopentanone-α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic dianhydride

[0125] ODPA: 3,3',4,4'-Diphenyl ether tetracarboxylic dianhydride

[0126] BPADA: 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]malonium

[0127] DSDA: 3,3,4,4-Diphenylsulfone tetracarboxylic anhydride

[0128] TAHQ: p-Phenylidene-bis(phenyltriester) dianhydride

[0129] PMDA: Pyromellitic dianhydride

[0130] M1:

[0131] Y1:

[0132] Y2:

[0133] ODA: 4,4'-Diaminodiphenyl ether

[0134] SiDA: 1,1,3,3-Tetramethyl-1,3-bis(3-aminopropyl)disiloxane

[0135] BAP: Bis(3-amino-4-hydroxyphenyl)propane

[0136] OBAP: Bis(3-amino-4-hydroxyphenyl) ether

[0137] CHPS: 2,2'-Diamino-4,4'-(cyclohexyl-1,1-diyl)diol

[0138] BAHS: Bis(3-amino-4-hydroxyphenyl)sulfone

[0139] p-HAB: 3,3'-Dihydroxybenzidine

[0140] NMP: N-methylpyrrolidone

[0141] Synthesis example 1

[0142] Synthesis of fluorine-free alkali-soluble resin A1

[0143] Under a dry nitrogen stream, CBDA (0.022 mol) and ODPA (0.030 mol) were dissolved in NMP (100 g), followed by the addition of 1,4-cyclohexanediamine (0.016 mol), SiDA (0.002 mol), BAHS (0.030 mol), and NMP (40 g). The reaction was carried out at 25 °C for 2 h. Then, 4-aminosalicylic acid (0.008 mol) was added, and the temperature was raised to 60 °C for 1 h. Toluene was added, and water was removed from the system by azeotropic reaction of toluene and water. The temperature was raised to 160 °C for 6 h. A white precipitate was obtained by precipitating in 2 L of ethanol:water = 2:1 (volume ratio). The precipitate was filtered, and the filter cake was washed several times with ethanol:water = 2:1 (volume ratio). The filter cake was vacuum dried at 50 °C for 72 h to obtain a fluorine-free alkali-soluble resin A1 powder. The infrared absorption spectrum was measured, and the imidization rate was 75%.

[0144] Synthesis example 2

[0145] Synthesis of fluorine-free alkali-soluble resin A2

[0146] Under a dry nitrogen stream, 0.033 mol of CBDA and 0.007 mol of ODPA were dissolved in 100 g of NMP. Then, 0.050 mol of BAHS and 40 g of NMP were added, and the mixture was reacted at 25 °C for 2 h. Next, 0.02 mol of phthalic anhydride was added, and the mixture was reacted at 60 °C for 1 h. Toluene was then added, and water was removed from the system using an azeotropic reaction of toluene and water. The mixture was then heated to 180 °C and reacted for 6 h. A white precipitate was obtained in 2 L of a solvent containing 1:3 volume ratio of ethanol and water. The precipitate was filtered, and the filter cake was washed several times with 1:3 volume ratio of ethanol and water. The filter cake was then vacuum-dried at 50 °C for 72 h to obtain a powder of fluorine-free alkali-soluble resin A2. The infrared absorption spectrum was measured, and the imidization rate was 84%.

[0147] Synthesis example 3

[0148] Synthesis of fluorine-free alkali-soluble resin A3

[0149] Under a dry nitrogen stream, BDA (0.013 mol) and BPADA (0.0355 mol) were dissolved in NMP (100 g). Then, SiDA (0.002 mol), BAP (0.045 mol), and NMP (40 g) were added, and the mixture was reacted at 25 °C for 2 h. Next, 4-aminosalicylic acid (0.003 mol) was added, and the mixture was reacted at 25 °C for 48 h. Dimethylformamide dimethyl acetal (0.085 mol) was added dropwise, and the mixture was then heated to 60 °C and reacted for 4 h. The precipitate was then collected in 2 L of ethanol:water (1:3 volume ratio) to form a white precipitate. The precipitate was filtered, and the filter cake was washed several times with ethanol:water (1:3 volume ratio). The filter cake was then vacuum-dried at 50 °C for 72 h to obtain a fluorine-free alkali-soluble resin A3 powder. Infrared absorption spectroscopy showed an imidization rate of 39%.

[0150] Synthesis example 4

[0151] Synthesis of fluorine-free alkali-soluble resin A4

[0152] Under a dry nitrogen stream, TMEG (0.005 mol) and BPADA (0.047 mol) were dissolved in NMP (100 g), followed by the addition of polyoxyethylene diamine (0.010 mol), SiDA (0.003 mol), CHPS (0.036 mol), and NMP (40 g), and then 4-aminosalicylic acid (0.006 mol). The reaction was carried out at 25 °C for 2 h, followed by the dropwise addition of dimethylformamide dimethyl acetal (0.080 mol), and the reaction was carried out at 120 °C for 6 h. The precipitate was then precipitated in 2 L of ethanol:water = 1:3 (volume ratio), and a white precipitate was obtained. The precipitate was filtered, and the filter cake was washed several times with ethanol:water = 1:3 (volume ratio). The filter cake was then vacuum dried at 50 °C for 72 h to obtain a fluorine-free alkali-soluble resin A4 powder. The infrared absorption spectrum was measured, and the imidization rate was 62%.

[0153] Synthesis example 5

[0154] Synthesis of fluorine-free alkali-soluble resin A5

[0155] Under a dry nitrogen stream, 0.030 mol of OBAP, 0.0175 mol of BAP, and 0.003 mol of SiDA were dissolved in 100 g of NMP. Then, 0.0175 mol of BDA, 0.037 mol of ODPA, and 40 g of NMP were added, followed by 0.008 mol of 4-aminosalicylic acid. The reaction was carried out at 25 °C for 2 h, and then 0.085 mol of dimethylformamide dimethyl acetal was added dropwise. The temperature was raised to 90 °C and the reaction was carried out for 5 h. A white precipitate was obtained by precipitating the precipitate in 2 L of a solvent with an ethanol:water ratio of 1:3 (v / v). The precipitate was filtered, and the filter cake was washed several times with an ethanol:water ratio of 1:3 (v / v). The filter cake was then vacuum-dried at 50 °C for 72 h to obtain a fluorine-free alkali-soluble resin A5 powder. The infrared absorption spectrum was measured, and the imidization rate was 42%.

[0156] Synthesis example 6

[0157] Synthesis of fluorine-free alkali-soluble resin A6

[0158] Under a dry nitrogen stream, SiDA (0.002 mol), Y1 (0.005 mol), ODA (0.012 mol), and CHPS (0.027 mol) were dissolved in NMP (100 g). Then, TAHQ (0.033 mol), TMEG (0.018 mol), and 40 g of NMP were added, and the mixture was reacted at 25 °C for 2 h. Next, 3-aminosalicylic acid (0.01 mol) was added, and the reaction was continued at 25 °C for 48 h. Finally, dimethylformamide dimethyl acetal (0.105 mol) was added dropwise, and the mixture was heated to 60 °C and reacted for 6 h. The precipitate precipitated in 2 L of ethanol:water (1:3 volume ratio), yielding a white precipitate. The precipitate was filtered, and the filter cake was washed several times with ethanol:water (1:3 volume ratio). The filter cake was then vacuum-dried at 50 °C for 72 h to obtain a fluorine-free alkali-soluble resin A6 powder. Infrared absorption spectroscopy revealed an imidization rate of 28%.

[0159] Synthesis Example 7

[0160] Synthesis of fluorine-free alkali-soluble resin A7

[0161] Under a dry nitrogen stream, BAP (0.055 mol) was dissolved in NMP (100 g). Then, DMCBDA (0.02 mol), BDTA (0.03 mol), CpODA (0.006 mol), and NMP (40 g) were added, and the reaction was carried out at 25 °C for 2 h. Next, aniline (0.002 mol) was added, and the reaction was carried out at 25 °C for 48 h. Dimethylformamide dimethyl acetal (0.085 mol) was added dropwise, and the reaction was then carried out at 45 °C for 6 h. A white precipitate was obtained by precipitating the precipitate in 2 L of ethanol:water (1:3 volume ratio). The precipitate was filtered, and the filter cake was washed several times with ethanol:water (1:3 volume ratio). The filter cake was vacuum dried at 50 °C for 72 h to obtain a fluorine-free alkali-soluble resin A7 powder. Infrared absorption spectroscopy showed an imidization rate of 25%.

[0162] Synthesis example 8

[0163] Synthesis of fluorine-free alkali-soluble resin A8

[0164] Under a dry nitrogen stream, 0.045 mol of OBAP and 0.003 mol of SiDA were dissolved in 100 g of NMP. Then, 0.015 mol of MCTC, 0.017 mol of BPADA, 0.020 mol of M1, and 40 g of NMP were added, followed by 0.008 mol of aniline. The reaction was carried out at 25 °C for 2 h, and then 0.080 mol of dimethylformamide dimethyl acetal was added dropwise. The temperature was raised to 120 °C and the reaction was carried out for 5 h. A white precipitate was obtained by precipitating the precipitate in 2 L of a solvent with an ethanol:water ratio of 1:3 (v / v). The precipitate was filtered, and the filter cake was washed several times with an ethanol:water ratio of 1:3 (v / v). The filter cake was then vacuum-dried at 50 °C for 72 h to obtain a fluorine-free alkali-soluble resin A8 powder. The infrared absorption spectrum was measured, and the imidization rate was 53%.

[0165] Synthesis example 9

[0166] Synthesis of fluorine-free alkali-soluble resin A9

[0167] Under a dry nitrogen stream, ODA (0.020 mol), Y2 (0.025 mol), and SiDA (0.003 mol) were dissolved in NMP (100 g). HPMDA (0.022 mol), TAHQ (0.023 mol), and NMP (40 g) were then added, followed by phthalic anhydride (0.006 mol). The reaction was carried out at 25 °C for 2 h. Toluene was added, and water was removed from the system using an azeotropic reaction of toluene and water. The temperature was then raised to 160 °C and reacted for 6 h. A white precipitate was obtained by precipitating the precipitate in 2 L of a solvent with an ethanol:water ratio of 1:3 (volume ratio). The precipitate was filtered, and the filter cake was washed several times with an ethanol:water ratio of 1:3 (volume ratio). The filter cake was then vacuum-dried at 50 °C for 72 h to obtain a fluorine-free alkali-soluble resin A9 powder. The infrared absorption spectrum was measured, and the imidization rate was 70%.

[0168] Synthesis example 10

[0169] Synthesis of fluorine-free alkali-soluble resin A10

[0170] Under a dry nitrogen stream, ODPA (0.025 mol) and DSDA (0.026 mol) were dissolved in NMP (100 g); then polyethylene glycol diamine (0.005 mol), BAHS (0.040 mol), ODA (0.008 mol), and NMP (40 g) were added, and the mixture was reacted at 25 °C for 2 h; phthalic anhydride (0.004 mol) was then added, and the mixture was reacted at 60 °C for 2 h; toluene was added, and water was removed from the system by azeotropic reaction of toluene and water; the mixture was then heated to 180 °C and reacted for 8 h; a white precipitate was obtained by precipitating in 2 L of ethanol:water = 1:3 (volume ratio); the precipitate was filtered, and the filter cake was washed several times with ethanol:water = 1:3 (volume ratio); the filter cake was then vacuum dried at 50 °C for 72 h to obtain fluorine-free alkali-soluble resin A10 powder; the infrared absorption spectrum was measured, and the imidization rate was 99%.

[0171] Synthesis example 11

[0172] Synthesis of fluorine-free alkali-soluble resin A11

[0173] Under a dry nitrogen stream, BAP (0.043 mol) and SiDA (0.005 mol) were dissolved in NMP (100 g). Then, CBDA (0.025 mol), M1 (0.027 mol), and NMP (40 g) were added, followed by 4-aminophenol (0.008 mol). The reaction was carried out at 40 °C for 2 h, and then dimethylformamide dimethyl acetal (0.080 mol) was added dropwise. The temperature was then raised to 90 °C and the reaction was carried out for 5 h. A white precipitate was obtained in 2 L of ethanol:water (1:3 volume ratio). The precipitate was filtered, and the filter cake was washed several times with ethanol:water (1:3 volume ratio). The filter cake was vacuum dried at 50 °C for 72 h to obtain a fluorine-free alkali-soluble resin A11 powder. The infrared absorption spectrum was measured, and the imidization rate was 46%.

[0174] Synthesis example 12

[0175] Synthesis of fluorine-free alkali-soluble resin A12

[0176] Under a dry nitrogen stream, ODA (0.046 mol) and 1,4-diaminocyclohexane (0.005 mol) were dissolved in NMP (100 g). Then, ODPA (0.041 mol), CBDA (0.008 mol), and NMP (40 g) were added, and the mixture was reacted at 25 °C for 2 h. Phthalic anhydride (0.004 mol) was then added, and the reaction was continued at 25 °C for 48 h. Dimethylformamide dimethyl acetal (0.085 mol) was added dropwise, and the mixture was then heated to 60 °C and reacted for 4 h. The precipitate precipitated in 2 L of water, yielding a white precipitate. The precipitate was filtered, and the filter cake was washed several times with water. The filter cake was then vacuum-dried at 50 °C for 72 h to obtain a fluorine-free alkali-soluble resin A12 powder. Infrared absorption spectroscopy revealed an imidization rate of 34%.

[0177] Synthesis example 13

[0178] Synthesis of fluorine-free alkali-soluble resin A13

[0179] Under a dry nitrogen stream, BAHS (0.035 mol), SiDA (0.003 mol), and polyoxyethylene diamine (0.012 mol) were dissolved in NMP (100 g). Then, ODPA (0.040 mol), DSDA (0.015 mol), and NMP (40 g) were added, followed by aniline (0.005 mol) and 4-aminosalicylic acid (0.005 mol). The reaction was carried out at 25 °C for 2 h. Toluene was added, and water was removed from the system using an azeotropic reaction of toluene and water. The temperature was then raised to 180 °C and reacted for 6 h. The temperature was then raised to 140 °C and reacted for 4 h. A white precipitate was obtained by precipitating the precipitate in 2 L of a solvent with an ethanol:water ratio of 1:3 (volume ratio). The precipitate was filtered, and the filter cake was washed several times with an ethanol:water ratio of 1:3 (volume ratio). The filter cake was then vacuum-dried at 50 °C for 72 h to obtain a fluorine-free alkali-soluble resin A13 powder. The infrared absorption spectrum was measured, and the imidization rate was 86%.

[0180] Synthesis example 14

[0181] Synthesis of fluorine-free alkali-soluble resin A14

[0182] Under a dry nitrogen stream, BAP (0.04 mol) and ODA (0.007 mol) were dissolved in NMP (100 g). Then, TAHQ (0.043 mol), DSDA (0.008 mol), and NMP (40 g) were added, and the mixture was reacted at 25 °C for 2 h. Next, 4-aminosalicylic acid (0.008 mol) was added, and the mixture was reacted at 25 °C for 48 h. Dimethylformamide dimethyl acetal (0.085 mol) was added dropwise, and the mixture was then heated to 50 °C and reacted for 6 h. The precipitate was then collected in 2 L of ethanol:water (1:3 volume ratio) to form a white precipitate. The precipitate was filtered, and the filter cake was washed several times with ethanol:water (1:3 volume ratio). The filter cake was then vacuum-dried at 50 °C for 72 h to obtain a fluorine-free alkali-soluble resin A14 powder. The infrared absorption spectrum was measured, and the imidization rate was 33%.

[0183] Synthesis Example 15

[0184] Synthesis of fluorine-free alkali-soluble resin A15

[0185] Under a dry nitrogen stream, 0.030 mol of OBAP, 0.005 mol of SiDA, and 0.02 mol of polyoxyethylene diamine were dissolved in 100 g of NMP. Then, 0.025 mol of CBDA, 0.02 mol of BPADA, and 40 g of NMP were added, and the mixture was reacted at 25 °C for 2 h. Phthalic anhydride (0.02 mol) was then added, and the reaction was continued at 25 °C for 2 h. Finally, 0.090 mol of dimethylformamide dimethyl acetal was added dropwise, and the mixture was heated to 90 °C and reacted for 6 h. The precipitate was then collected in 2 L of a solvent containing 1:3 volume ratio of ethanol and water, resulting in a white precipitate. The precipitate was filtered, and the filter cake was washed several times with a 1:3 volume ratio of ethanol and water. The filter cake was then vacuum-dried at 50 °C for 72 h to obtain a fluorine-free alkali-soluble resin A15 powder. Infrared absorption spectroscopy revealed an imidization rate of 57%.

[0186] Synthesis Example 16

[0187] Synthesis of fluorine-free alkali-soluble resin A16

[0188] Under a dry nitrogen stream, CBDA (0.033 mol) and PMDA (0.007 mol) were dissolved in NMP (100 g). Then, p-HAB (0.050 mol) and 40 g of NMP were added, and the reaction was carried out at 25 °C for 2 h. Phthalic anhydride (0.02 mol) was then added, and the reaction was carried out at 40 °C for 2 h. Toluene was added, and water was removed from the system using an azeotropic reaction of toluene and water. The temperature was then raised to 180 °C and the reaction was carried out for 6 h. A white precipitate was obtained in 2 L of a solvent with an ethanol:water ratio of 1:3 (volume ratio). The precipitate was filtered, and the filter cake was washed several times with an ethanol:water ratio of 1:3 (volume ratio). The filter cake was then vacuum-dried at 50 °C for 72 h to obtain a fluorine-free alkali-soluble resin A16 powder. The infrared absorption spectrum was measured, and the imidization rate was 84%.

[0189] Synthesis Example 17

[0190] Synthesis of fluorine-free alkali-soluble resin A17

[0191] Under a dry nitrogen stream, BAHS (0.035 mol), SiDA (0.002 mol), and polyethylene glycol diamine (0.010 mol) were dissolved in NMP (100 g). Then, TAHQ (0.040 mol), MCTC (0.011 mol), and 40 g of NMP were added, followed by aniline (0.003 mol) and 4-aminosalicylic acid (0.005 mol). The reaction was carried out at 25 °C for 2 h, and then dimethylformamide dimethyl acetal (0.090 mol) was added dropwise, and the reaction was continued at 25 °C for 12 h. A white precipitate was obtained by precipitating the precipitate in 2 L of ethanol:water (1:3 volume ratio). The precipitate was filtered, and the filter cake was washed several times with ethanol:water (1:3 volume ratio). The filter cake was then vacuum-dried at 50 °C for 72 h to obtain a fluorine-free alkali-soluble resin A17 powder. The infrared absorption spectrum was measured, and the imidization rate was 5%.

[0192] Example 1

[0193] This embodiment provides a positive photosensitive resin composition, which is prepared by taking 10g of fluorine-free alkali-soluble resin A1, adding photoacid generators: 0.6g PAC-1 and 0.6g PAC-7, adding thermal crosslinking agents: 1.5g HMOM-TPHAP (manufactured by Honshu Chemical Industry Co., Ltd.) and 2.5g EXA-4880 (Dai Nippon Ink Chemical Industry Co., Ltd.), adding solvent: 10g γ-butyrolactone, and preparing a varnish.

[0194] A varnish was applied to a silicon substrate and dried at 120°C for 2 minutes to form a film. The film was then exposed using a small photolithography developing apparatus (AC3000; manufactured by Takizawa Sangyo Co., Ltd.). After exposure, the film was developed for 70 seconds using a 2.38% by mass tetramethylammonium hydroxide aqueous solution and rinsed with water for 30 seconds. After development and rinsing, the film was thermally cured at 250°C using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.) to produce a cured film with a thickness of approximately 2 μm. The thermal curing conditions were 250°C for 60 minutes under a nitrogen atmosphere. The positive photosensitive resin composition of the present invention was then evaluated.

[0195] Example 2-10

[0196] Examples 2-10 each provide a positive photosensitive resin composition, the preparation method of which is roughly the same as that in Example 1, except that the fluorine-free alkali-soluble resin A1 in Example 1 is replaced with fluorine-free alkali-soluble resins A2-A10 in turn, while other conditions remain unchanged.

[0197] Comparative Examples 1-7

[0198] Comparative Examples 1-7 each provide a positive photosensitive resin composition, the preparation method of which is roughly the same as that in Example 1, except that the fluorine-free alkali-soluble resin A1 in Example 1 is replaced with fluorine-free alkali-soluble resins A11-A17 respectively, while other conditions remain unchanged.

[0199] The evaluation results of the above embodiments and comparative examples are shown in Table 1.

[0200] Table 1 - Performance evaluation results of Examples 1-10 and Comparative Examples 1-7

[0201] According to the present invention, a film can be obtained that can be developed with alkaline aqueous solution, has excellent sensitivity and resolution, clear pattern, and high residual film rate in unexposed areas, and is suitable for use as a protective film for semiconductor devices, planarization layer, interlayer insulating film, insulating film for displays, insulating layer from organic field to light-emitting element, insulating layer for thin film transistors (TFTs), etc.

Claims

1. A fluorine-free alkali-soluble resin, wherein, The main chain structure of the fluorine-free alkali-soluble resin includes structural units with structural formula (a1) and structural units with structural formula (a2). In the above structural formulas (a1) and (a2), X and Y represent reactive residues of dianhydrides, and P and Q represent reactive residues of diamines; at least one of the monomers corresponding to X, Y, P, and Q contains a phenolic hydroxyl group; R1 and R2 each independently represent H or an organic group with 1-20 carbon atoms; the imidization rate d of the fluorine-free alkali-soluble resin and the molar ratio c of the monomer containing a phenolic hydroxyl group to the total monomers of the polymer satisfy 90% ≥ (1-d) / 2 + c ≥ 40%.

2. The fluorine-free alkali-soluble resin according to claim 1, wherein, The imidization rate of the fluorine-free alkali-soluble resin is d = 25%-99%; and / or, the molar ratio of monomers containing phenolic hydroxyl groups to the total polymer monomers is c = 30%-60%; and / or, the fluorine-free alkali-soluble resin comprises one or more of polyamic acid, polyamic acid ester, and polyimide structures, wherein the proportion of polyamic acid is 1%-50%, the proportion of polyamic acid ester is 0-90%, and the sum of the proportions of polyamic acid, polyamic acid ester, and polyimide is 100%.

3. The fluorine-free alkali-soluble resin according to claim 1 or 2, wherein, At least one of the monomers corresponding to X, Y, P, and Q is a monomer containing an aliphatic structure. The aliphatic structure exists on the main chain of the fluorine-free alkali-soluble resin, and the monomer containing the aliphatic structure accounts for 5%-40% of the total monomers.

4. The fluorine-free alkali-soluble resin according to any one of claims 1-3, wherein, X and Y are each independently selected from one or more of the following structures: And / or, P and Q are each independently selected from one or more of the following structures: In this configuration, R3 is independently H or methyl; R5, R6, and R7 are independently H or hydroxyl; A1 and A2 are independently selected from -CO-, -O-, -S-, -CO2-, -SO2-, -CH2-, -C(CH3)2-, or -CONH-; B1 and B3 are independently selected from bonds, One of them, B2 is selected from Or a C2-C6 alkane chain, j = 0, 1, 2 or 3, k = 0, 1, 2 or 3, * indicates the connection position.

5. The fluorine-free alkali-soluble resin according to claim 4, wherein, X and Y are each independently selected from one or more of the following structures: And / or, P and Q are each independently selected from one or more of the following structures: Wherein, R3 is independently H or methyl; A1 and A2 are independently selected from -CO-, -O-, -S-, -CO2-, -SO2-, -CH2-, -C(CH3)2- or -CONH-; j = 0, 1, 2 or 3; * indicates the connection position.

6. The fluorine-free alkali-soluble resin according to claim 4 or 5, wherein, The X and Y are derived from one or more combinations of the following dianhydride structures: 1,2,3,4-Butanetetracarboxylic dianhydride (BDA), cyclobutanetetracarboxylic dianhydride (CBDA), 1,2,4,5-cyclohexanetetracarboxylic dianhydride (HPMDA), dimethylcyclobutanetetracarboxylic dianhydride (DMCBDA), norbornane-2-spiro-α-cyclopentanone-α'-spiro-2”-norbornane-5,5”,6,6”-tetracarboxylic dianhydride (CpODA), 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]malonium dianhydride (BPADA), diethylene glycol (4-tricarboxylic anhydride) (TMEG), p-phenylene-bisphenyltrilate dianhydride (TAHQ), 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (ODPA), 3,3,4,4-diphenyl sulfone tetracarboxylic dianhydride (DSDA), methylcyclohexenetetracarboxylic dianhydride (MCTC), and dianhydrides with the following structures: And / or, the P and Q are derived from one or more combinations of the following diamine structures: 1,4-Cyclohexanediamine, 2,2'-diamino-4,4'-(cyclohexyl-1,1-diyl)diol (CHPS), polyoxyethylene diamine, polyethylene glycol diamine, bis(3-amino-4-hydroxyphenyl)sulfone (BAHS), bis(3-amino-4-hydroxyphenyl)propane (BAP), bis(3-amino-4-hydroxyphenyl) ether (OBAP), 4,4'-diaminodiphenyl ether (ODA), 1,1,3,3-tetramethyl-1,3-bis(3-aminopropyl)disiloxane (SiDA), and diamines with the following structures:

7. The fluorine-free alkali-soluble resin according to any one of claims 1-6, wherein, The end-capping groups of the main chain structure of the alkali-soluble resin (a) have the structures shown in general formula (2) and / or (3), where A is derived from primary monoamine and B is derived from dianhydride.

8. A positive photosensitive resin composition, wherein, It contains the following ingredients: (a) 100 parts by weight of alkali-soluble resin, wherein the alkali-soluble resin is any one of the fluorine-free alkali-soluble resins according to claims 1-7. (b) Photoacid-generating agent, 10-40 parts by weight; (c) Thermal crosslinking agent, 15-60 parts by weight; (d) Organic solvents.

9. A cured film, obtained by curing the positive photosensitive resin composition as described in claim 8.

10. A method for patterning a cured film, comprising the following steps: i) The positive photosensitive resin composition of claim 8 is coated on a substrate and dried at 40-120°C for 1-10 min to form a positive photosensitive resin composition film. ii) Expose the film under a mask; iii) Remove the exposed portions of the film using an alkaline developer, develop and clean it; iiii) The developed film is cured and dried at 100-400℃ to obtain a cured film containing the desired pattern.

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