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

Abstract

The invention provides fluoride-free alkali-soluble resin and a positive photosensitive resin composition containing the fluoride-free alkali-soluble resin. The fluoride-free alkali-soluble resin comprises one or more of polyimide, polyamide acid and polyesteramide structures, by adjusting the imidization rate and the proportion of the hydroxyl-containing structure to the aliphatic structure, the fluoride-free alkali-soluble resin has good solubility and optical and mechanical properties, a cured film formed by the fluoride-free alkali-soluble resin can be developed through alkali after exposure, and the fluoride-free alkali-soluble resin has the advantages of good exposure sensitivity and high pattern resolution; the problems of environmental pollution, harm to human health, high raw material price and the like caused by fluorine element contained in traditional photosensitive polyimide are solved.

Description

Technical Field

[0001] The present invention relates to a fluorine-free alkali-soluble resin, a positive photosensitive resin composition containing the same, a cured film, and a pattern processing method. More specifically, the present invention relates to a positive photosensitive resin composition suitable for use as a surface protective film of a semiconductor element, an interlayer insulating film, an insulating layer of an organic electroluminescent (EL) element, an insulating layer of a thin film transistor (TFT), etc., and a cured film using the same. Background Art

[0002] Polyimide (PI) is an ideal polymer material with excellent heat resistance, mechanical properties, electrical insulation and chemical stability, and is often used in aerospace, semiconductor, optoelectronics and microelectronics. Compared with ordinary polyimide, photosensitive polyimide (PSPI) does not require other photoresists to achieve graphic processing, shortening the process route, and is an ideal insulating material in the electronics and microelectronics fields.

[0003] In recent years, with the miniaturization of semiconductor components, the intermediate insulating film, passivation layer, etc. of the semiconductor components also require finer exposure and development sensitivity and image resolution; based on this, in the prior art, a photosensitive polyimide resin composition varnish is often used on the surface of the semiconductor component, and developed under alkaline conditions after exposure, so as to obtain an ideal pattern; but this often places high requirements on the exposure sensitivity and development resolution of the photosensitive polyimide resin composition.

[0004] By introducing a certain amount of fluorine into the PSPI resin, not only can the solubility of the resin be improved, but also the light transmittance, dielectric properties and thermal properties of the film can be improved very well, so it is widely used in the design of high-performance PSPI. However, these polyimides prepared from fluorine-containing monomers are not only expensive, but the long-term presence and contact of fluorine will bring adverse health effects on human bones, teeth, growth and development, etc., as well as long-term pollution to the ecological environment. In recent years, the international community has increasingly higher requirements and controls on PFAS (polymerized perfluoroalkane sulfonates), so the development of fluorine-free photosensitive polyimide materials has become a current trend. However, removing the fluorine element will inevitably lead to a decrease in the solubility, light transmittance and other properties of the 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 current research hotspot. Summary of the invention

[0005] The object of the present invention is to provide a fluorine-free alkali-soluble resin and a positive photosensitive resin composition, a cured film and a pattern processing method thereof comprising the fluorine-free alkali-soluble resin. The alkali-soluble resin does not contain fluorine element, and the positive photosensitive resin composition comprising the fluorine-free alkali-soluble resin has good solubility and light transmittance, and the cured film formed by the resin can obtain higher exposure sensitivity and development resolution.

[0006] 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 comprises a structural unit having a structural formula (a1) and a structural unit having a structural formula (a2);

[0007]

[0008] In the above structural formula (a1) and structural formula (a2), X and Y represent the reaction residues of dianhydride, and P and Q represent the reaction residues of diamine;

[0009] Further, 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 having 1 to 20 carbon atoms;

[0010] 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%.

[0011] Furthermore, the imidization rate of the fluorine-free alkali-soluble resin is d=25%-99%; and / or the molar ratio of the monomer containing phenolic hydroxyl group to the total amount of polymer monomer is c=30%-60%;

[0012] Furthermore, 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.

[0013] Further, the structural unit of the structural formula (a1) represents a polyimide precursor, including polyamic acid and polyamic acid ester; the polyamic acid accounts for 1%-50% of the fluorine-free alkali-soluble resin; the polyamic acid ester accounts for 0-90% of the fluorine-free alkali-soluble resin;

[0014] Furthermore, the structural unit of the structural formula (a2) represents polyimide, the fluorine-free alkali-soluble resin includes one or more of polyamic acid, polyamic acid ester, and polyimide structures, and the sum of the proportions of the polyamic acid, polyamic acid ester, and polyimide is 100%.

[0015] Furthermore, the molecular weight of the fluorine-free alkali-soluble resin is 30,000-80,000;

[0016] Furthermore, X and Y are each independently selected from one or more of the following substituted or unsubstituted structures:

[0017]

[0018]

[0019] And / or, P and Q are each independently selected from one or more of the following substituted or unsubstituted structures:

[0020]

[0021] Wherein, R3 is each independently H or methyl; R5, R6, and R7 are each independently H or hydroxyl; A1 and A2 are each independently selected from -CO-, -O-, -S-, -CO2-, -SO2-, -CH2-, -C(CH3)2-, or -CONH-; B1 and B3 are each independently selected from a bond, One of the following, 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.

[0022] Preferably, X and Y are each independently selected from one or more of the following structures:

[0023]

[0024]

[0025] And / or, P and Q are each independently selected from one or more of the following structures:

[0026]

[0027]

[0028] Wherein, R3 is each independently H or methyl; A1 and A2 are each independently selected from -CO-, -O-, -S-, -CO2-, -SO2-, -CH2-, -C(CH3)2- or -CONH-; j=0, 1, 2 or 3; * indicates the connection position.

[0029] Further, the X and Y are derived from one or more combinations of the following dianhydride structures:

[0030] 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 dianhydride (DMCBDA), 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]malonic dianhydride (BDA), PADA), 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride (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'-terephthalic anhydride (HQDPA), p-phenylene-diphthalic anhydride (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), 5-isobenzofurancarboxylic acid 1,3-dihydro-1,3-dioxy-5,5'-[(1-methylethylidene)di-4,1-phenylene] ester, methylcyclohexene tetracarboxylic dianhydride (MCTC), and dianhydrides of the following structures:

[0031]

[0032] And / or, the P and Q are derived from one or more combinations of the following diamine structures:

[0033] 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( 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), 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)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 ... aminodiphenyl 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-aminobenzamide)-4-hydroxyphenyl]propane, 2,2-bis[3-(4-aminobenzamide)-4-hydroxyphenyl]sulfone, 2,2-bis[3-(4-aminobenzamide)-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]-sulfone-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- 4-aminophenyl)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'-bisamino-3,3'-methylenedibenzoic acid (MBAA), 4,4'-methylene (2-amino-3,6-dimethylphenol), N1,N8-bis(4-aminophenyl) suberamide, 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 of the following structures:,

[0034]

[0035] Further preferably, X and Y are derived from one or more combinations of the following dianhydride structures:

[0036] 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]malonic dianhydride (BPADA), diethylene glycol (4-tricarboxylic anhydride) (TMEG), p-phenylene-diphthalic acid dianhydride (TAHQ), 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (ODPA), 3,3,4,4-diphenyl sulfone tetracarboxylic dianhydride (DSDA), methylcyclohexene tetracarboxylic dianhydride (MCTC), and dianhydrides of the following structures:

[0037] And / or, the P and Q are derived from one or more combinations of the following diamine structures:

[0038] 1,4-cyclohexanediamine, 2,2'-diamino-4,4'-(cyclohexyl-1,1-diyl)diphenol (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 of the following structures:

[0039]

[0040] Furthermore, the end-capping groups of the main chain structure of the fluorine-free alkali-soluble resin have structures represented by general formula (2) and / or (3), A is derived from a primary monoamine, and B is derived from a dianhydride.

[0041]

[0042] In the general formula (2), A is derived from a primary monoamine of a terminal group; as the primary monoamine of the terminal group, preferably aniline, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminophenol, 3-aminophenol, 4-aminophenol, 3-amino-4,6-dihydroxypyrimidine, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, 4-aminothiophenol, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, etc., which can be used alone or in combination of two or more;

[0043] Furthermore, the monoprimary amine as the end-capping group accounts for 0-50 mol% of the total amine components, and particularly preferably 5-30 mol%;

[0044] In the general formula (3), B is derived from the dianhydride of the end-capping group; the dianhydride of the end-capping group is preferably phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, etc., which can be used alone or in combination of two or more.

[0045] Furthermore, the dianhydride as the end-capping group accounts for 0-50 mol %, particularly preferably 5-30 mol %, of the total anhydride components.

[0046] The second aspect of the present invention provides a positive photosensitive resin composition comprising the above-mentioned fluorine-free alkali-soluble resin, comprising the following components:

[0047] (a) 100 parts by weight of an alkali-soluble resin, wherein the alkali-soluble resin is the fluorine-free alkali-soluble resin described above;

[0048] (b) a photoacid generator, 10-40 parts by weight;

[0049] (c) thermal crosslinking agent, 15-60 parts by weight;

[0050] (d) organic solvents;

[0051] A third aspect of the present invention provides a cured film obtained by curing the positive photosensitive resin composition.

[0052] The fourth aspect of the present invention provides a method for pattern processing of a cured film, which comprises the following steps: coating the positive photosensitive resin composition on a substrate, drying 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; curing and drying the developed film at 100-400°C to obtain a cured film containing a desired pattern.

[0053] The beneficial effect of the present invention is to provide a fluorine-free alkali-soluble resin, which not only solves the problem of harm caused by fluorine element, but also solves the alkali solubility problem of the fluorine-free polyimide alkali-soluble resin by regulating the imidization rate and phenolic hydroxyl content of the polyimide resin; and by introducing a certain proportion of aliphatic structure into the resin structure to increase the light transmittance and solubility in organic solvents, a fluorine-free photosensitive polyimide resin composition with higher development resolution and exposure sensitivity is obtained. DETAILED DESCRIPTION

[0054] Hereinafter, specific embodiments of the fluorine-free alkali-soluble resin and the positive photosensitive resin composition, cured film and pattern processing method thereof comprising the fluorine-free alkali-soluble resin according to the present invention are described in detail. However, the present invention is not limited to the embodiments including the following examples and can be modified in various ways within the scope of the gist of the invention so as to achieve the purpose of the invention.

[0055] <Fluorine-free alkali-soluble resin>

[0056] The fluorine-free alkali-soluble resin of the present invention contains a structural unit having a structural formula (a1) and a structural unit having a structural formula (a2). The fluorine-free alkali-soluble resin has a main chain structure as shown in the general formula (1):

[0057]

[0058]

[0059] In the general formula (1), X and Y represent the reaction residues of dianhydride or tetraacid, and P and Q represent the reaction residues of diamine; in the formula (1), m is an integer of 0-50000, and n is an integer of 10-50000; in the embodiment of the present invention, the molecular weight of the fluorine-free alkali-soluble resin is 30000-80000;

[0060] In the present 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;

[0061] In the present invention, the structural unit of structural formula (a2) represents polyimide, and the structural formulas (a1) and (a2) are obtained by reacting tetraacid or dianhydride monomers with diamine monomers, and the sum of the proportions of polyamic acid, polyamic acid ester and polyimide in the fluorine-free alkali-soluble resin is 100%.

[0062] In the present invention, at least one of the monomers corresponding to X, Y, P, and Q contains a phenolic hydroxyl group, and the phenolic hydroxyl group may be present in the dianhydride monomer or in the diamine monomer. From the perspective of ease of synthesis, the phenolic hydroxyl group is preferably present in the diamine monomer;

[0063] R1 and R2 each independently represent H or an organic group having 1 to 20 carbon atoms, and may be selected from substituted or unsubstituted alkyl, substituted or unsubstituted phenyl, etc. In the present invention, it is a residue after the reaction of dimethylformamide dimethyl acetal and carboxylic acid.

[0064] In the present invention, the imidization rate d of the fluorine-free alkali-soluble resin is 25%-99%. The inventors found in their research that if the imidization rate is lower than 25%, the development speed will be too fast, and the film in the non-exposed area cannot be normally retained, and the film retention rate is low, which affects the normal use of the film; if the imidization rate is higher than 99%, the film dissolution rate in the exposed area will be too slow during the development process, resulting in high exposure, reduced sensitivity, and even residual film in the exposed area, incomplete development, and affecting the development quality.

[0065] In order to increase the solubility of the fluorine-free alkali-soluble resin in organic solvents and developer, the molar ratio c of the monomer containing phenolic hydroxyl groups to the total amount of polymer monomers introduced in the present invention and the imidization rate d satisfy the relationship 90% ≥ (1-d) / 2 + c ≥ 40%; the two jointly regulate the solubility of the fluorine-free alkali-soluble resin and the quality of development; the molar ratio c of the monomer containing phenolic hydroxyl groups to the total amount of polymer monomers is preferably controlled at 30%-60%. Polymer monomers refer to all monomers participating in the polymerization reaction, including dianhydrides, diamines, monoanhydrides, and monoamines; among them, monomers containing phenolic hydroxyl groups refer to all monomers containing phenolic hydroxyl groups in polymer monomers.

[0066] In order to meet the requirements of optical and mechanical properties of the film, at least one of the monomers corresponding to X, Y, P, and Q in the present invention is a monomer containing an aliphatic structure, which is beneficial to the configuration of the photoresist and the increase of the solid content, and the molar ratio of the monomer containing the aliphatic structure to the total monomers of the polymer is 5%-40%; when the aliphatic structure content is too low, or even completely free of aliphatic structure, on the one hand, the light transmittance of the cured film will be deteriorated, affecting the resolution and sensitivity of the development, and on the other hand, the solubility of the resin in the organic phase will be deteriorated, resulting in difficulty in preparing the glue, or low solid content, or the need to use a large amount of high-boiling point solvent (resulting in excessive solvent residue at the end of baking during film coating, or excessive solvent residue after curing, causing various device defects or poor performance), resulting in precipitation and clogging of the pipeline during pipeline cleaning, affecting normal production; and when the aliphatic structure content exceeds 40%, the mechanical properties of the film, such as tensile strength, will deteriorate and cannot meet normal working requirements.

[0067] 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 of 2 carbon atoms or more. In addition to carbon and hydrogen elements, it can also contain elements such as oxygen, nitrogen, sulfur, silicon, and chlorine. Specifically, for example, the aliphatic structure contains structures such as chain alkanes, cycloalkanes, olefins, and ethers. In order to achieve better optical properties, the dianhydride containing X and Y does not contain biphenyl dianhydride and isophthalic anhydride structures, and the diamine containing P and Q does not contain o-phenylenediamine, p-phenylenediamine, m-phenylenediamine, and biphenylenediamine structures.

[0068] As monomers required for synthesizing the structural units of structural formulas (a1) and (a2), X and Y represent reaction residues of dianhydride, and X and Y may be the same or different; specifically, X and Y may be selected from one or more of the following substituted or unsubstituted structures:

[0069]

[0070] Wherein, R3 is each independently H or an alkyl substituent such as methyl, ethyl, propyl, isopropyl, etc.; R5, R6, R7 are each independently H or a hydroxyl group, and the number thereof can be 1, 2, 3 or 4; A1 and A2 are each independently selected from -CO-, -O-, -S-, -CO2-, -SO2-, -CH2-, -C(CH3)2- or -CONH-, and j=0, 1, 2 or 3; B1 and B3 are each independently selected from a bond, one of, k=0, 1, 2 or 3, B2 is selected from alkane or polyethylene glycol or siloxane, preferably C1-C10 straight-chain alkane or branched alkane, polyethylene glycol chain with 1-5 -CH2CH2O- structures or siloxane chain with 1-3 -Si-O- structures; B2 is further preferably or C2-C6 alkane chain, * indicates the connection position;

[0071] The optional structures of X and Y mentioned above may be substituted or unsubstituted; the substituent groups may be selected from hydroxyl, carboxyl, sulfonic acid, C1-C6 alkyl, C1-C6 alkoxy, amino, chlorine, etc.

[0072] As monomers required for synthesizing the structural units of the structural formulae (a1) and (a2), P and Q represent diamine residues. P and Q in the general formula (1) may be the same or different. Specifically, P and Q may be independently selected from one or more of the following substituted or unsubstituted structures:

[0073]

[0074] Wherein, R3 is each independently H or an alkyl substituent such as methyl, ethyl, propyl, isopropyl, etc.; R5, R6, R7 are each independently H, hydroxyl or methyl, and the number thereof can be 1, 2, 3 or 4; A1 and A2 are each independently selected from -CO-, -O-, -S-, -CO2-, -SO2-, -CH2-, -C(CH3)2- or -CONH-, j=0, 1, 2 or 3; B1 and B3 are each independently selected from a bond, one of, k=0, 1, 2 or 3, B2 is selected from alkane or polyethylene glycol or siloxane, preferably C1-C10 straight-chain alkane or branched alkane, polyethylene glycol chain with 1-5 -CH2CH2O- structures or siloxane chain with 1-3 -Si-O- structures; B2 is further preferably or C2-C6 alkane chain, * indicates the connection position;

[0075] The optional structures of P and Q mentioned above may be substituted or unsubstituted; the substituent groups may be hydroxyl, carboxyl, sulfonic acid or C1-C6 alkyl, C1-C6 alkoxy, amino, chlorine, etc.

[0076] Furthermore, X and Y are each independently selected from one or more of the following structures:

[0077]

[0078]

[0079] And / or, P and Q are each independently selected from one or more of the following structures:

[0080]

[0081] Wherein, R3 is each independently H or methyl; A1 and A2 are each independently selected from -CO-, -O-, -S-, -CO2-, -SO2-, -CH2-, -C(CH3)2- or -CONH-; j=0, 1, 2 or 3; * indicates the connection position.

[0082] Specifically, the dianhydride containing X or Y can be selected from: 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 dianhydride (DMCBDA), 2,2-bis[4-(3,4- dicarboxyphenoxy)phenyl]malonic anhydride (BPADA), 9,9-bis(3,4-dicarboxyphenyl)fluorene 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'-phenylenedioxydiphthalic anhydride (HQDPA), p-phenylene-bis(phenylenedioxy)phthalic anhydride (PPE) triester 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 bis(4-aminophenyl)terephthalate (BAPT), 1,3-dihydro-1,3-dioxy-5,5'-[(1-methylethylidene)di-4,1-phenylene]-5-isobenzofurancarboxylic acid 1,3-dihydro-1,3-dioxy-5,5'-[(1-methylethylidene)di-4,1-phenylene]ester (BPEDA), methylcyclohexenetetracarboxylic acid dianhydride (MCTC), and dianhydrides of the following structures:

[0083]

[0084] In the present invention, the dianhydride containing X or Y is 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 dianhydride (DMCBDA), 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]malonic dianhydride (BPADA), diethylene glycol (4-tricarboxylic anhydride) (TMEG), 4,4'-terephthalic anhydride (HQDPA), p-phenylene-diphthalic acid dianhydride (TAHQ), 3,3',4,4'-diphenylether 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), 5-isobenzofurancarboxylic acid 1,3-dihydro-1,3-dioxy-5,5'-[(1-methylethylidene)di-4,1-phenylene] ester (BPEDA), methylcyclohexene tetracarboxylic dianhydride (MCTC) and dianhydrides of the following structures:

[0085] In the embodiment of the present 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]malonic dianhydride (BPADA), diethylene glycol (4-tricarboxylic anhydride) (TMEG), p-phenylene-diphenyltrimethylol dianhydride (TAHQ), 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (ODPA), 3,3,4,4-diphenyl sulfone tetracarboxylic dianhydride (DSDA), methylcyclohexene tetracarboxylic dianhydride (MCTC) and dianhydrides of the following structures:

[0086] The diamine containing P or Q can be selected from 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, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,3 ... 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) 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-aminobenzamide)-4-hydroxyphenyl]propane, 2,2-bis[3-(4-aminobenzamide)-4-hydroxyphenyl]sulfone, 2,2-bis[3-(4-aminobenzamide)-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]-sulfone-2-yl]benzamide, N-(5-amino-2-hydroxyphenyl)-4-[2-[4-[(4-aminophenyl)carbamoyl]phenyl]-sulfone-2-yl]benzamide, )-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 para-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-trimethylindan (indanediamine), 6,6'-bisamino-3,3'-methylenedibenzoic acid (MBAA), 4,4'-methylene(2-amino-3 ,6-dimethylphenol), 3,3'-diamino-4,4'-dihydroxydiphenylmethane, N1,N8-bis(4-aminophenyl) suberamide, 1,4-bis(4-aminophenoxy)benzene, p-aminophenyl para-aminobenzoate (APAB), 4,4'-bis(3-aminophenoxy)diphenyl sulfone (M-BAPS), 4,4'-diaminobenzanilide (DABA), 1,1,3,3-tetramethyl-1,3-bis(3-aminopropyl)disiloxane and diamines of the following structures:,

[0087] In the embodiment of the present invention, the diamine containing P or Q is preferably 1,4-cyclohexanediamine, 2,2'-diamino-4,4'-(cyclohexyl-1,1-diyl)diphenol (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 of the following structures:

[0088]

[0089] Furthermore, in order to improve adhesion to the substrate, etc., 0-10 mol% of the total diamine may be an aliphatic group having a siloxane structure within a range that does not reduce heat resistance. Specifically, diamines such as 1,1,3,3-tetramethyl-1,3-bis(3-aminopropyl)disiloxane and bis(p-aminophenyl)octamethylpentasiloxane are listed, and 1,1,3,3-tetramethyl-1,3-bis(3-aminopropyl)disiloxane is preferred.

[0090] End-capping group

[0091] At the end of the main chain structure of the (a) alkali-soluble resin represented by the general formula (1), there is an end-capping group represented by the general formula (2) and / or the general formula (3).

[0092]

[0093] In the general formula (2), A is derived from a primary monoamine of an end-capping group. Examples of the primary monoamine of an end-capping group include 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminophenol, 3-aminophenol, 4-aminophenol, 3-amino-4,6-dihydroxypyrimidine, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, etc., which can be used alone or in combination of two or more. The primary monoamine of the end-capping group accounts for 0-50 mol %, and particularly preferably 5-30 mol %, of the total amine components.

[0094] In the general formula (3), B is derived from the dianhydride of the end-capping group. Examples of the dianhydride of the end-capping group include phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, etc., which can be used alone or in combination of two or more. The dianhydride of the end-capping group accounts for 0-50 mol %, and particularly preferably 5-30 mol % of the total anhydride components.

[0095] <Positive photosensitive resin composition>

[0096] The positive photosensitive resin composition of the present invention is composed of (a) an alkali-soluble resin, (b) a photoacid generator, (c) a thermal crosslinking agent and (d) an organic solvent.

[0097] (a) Alkali soluble resin

[0098] The (a) alkali-soluble resin is the above-mentioned fluorine-free alkali-soluble resin,

[0099] (b) Photoacid generator

[0100] The positive photosensitive resin composition of the present invention also uses (b) a photoacid generator, which can include quinonediazide compounds (naphthoquinonediazidesulfonate compounds), sulfonium salts, phosphonium salts, diazonium salts, iodonium salts, etc., which can be used alone or in combination of two or more. These quinonediazide compounds can be synthesized by esterification reaction of phenolic hydroxyl compounds with quinonediazidesulfonyl chloride. In the present invention, the quinonediazide compound preferably uses a compound in which 5-naphthoquinonediazidesulfonyl or 4-naphthoquinonediazidesulfonyl is bonded to a compound having a phenolic hydroxyl group.

[0101] Specific examples of phenolic hydroxy compounds are shown below:

[0102]

[0103]

[0104] As the quinonediazide compound, the molecular structure preferably has any one or more of the naphthoquinonediazidesulfonate structures. Specifically, the following commercial photoacid generators PAC-1 to PAC-20 can be used, and any one or more of the following substances can be used in combination.

[0105]

[0106]

[0107] The amount of the photoacid generator (b) added is 5 to 40 parts by weight, preferably 10 to 40 parts by weight, based on 100 parts by weight of the alkali-soluble resin (a).

[0108] (c) Thermal crosslinking agent

[0109] The positive photosensitive resin composition of the present invention contains (c) a thermal crosslinking agent. The thermal crosslinking agent can react with the alkali-soluble resin (a) by heating to crosslink, thereby improving the chemical resistance of the cured film. Examples of the thermal crosslinking agent (c) include (c1) epoxy compounds and (c2) alkoxy / hydroxymethyl compounds. The (c1) epoxy compound is preferably a compound containing two or more epoxy groups in one molecule, and examples thereof 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 silicones, but are not limited to these. Specifically, there are Dainippon Ink and Chemical Industry EPICLON, EXA and other series products, Yuka Shell Epoxy Co. Ltd.'s Epikote series of bisphenol A type epoxy compounds and ADEKA's EP series. (c2) Alkoxy / hydroxymethyl compounds preferably have two or more functional groups of 2 to 8 in one molecule, and examples thereof include the DML, TriML, DMOM, HMOM, TMOM series of Honshu Chemical and the MX and MW series of Sanwa Chemical. The positive photosensitive resin composition of the present invention may contain one or more of the above-mentioned thermal crosslinking agents.

[0110] The amount of the thermal crosslinking agent (c) added is 15 to 100 parts by weight, preferably 15 to 60 parts by weight, based on 100 parts by weight of the alkali-soluble resin (a).

[0111] (d) Organic solvents

[0112] 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, amyl alcohol, γ-butyrolactone, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, etc., but are not limited to these.

[0113] <Cured film>

[0114] The cured film involved in the present invention is a film obtained by curing the positive photosensitive resin composition of the present invention.

[0115] <Pattern processing method>

[0116] The following is a detailed description of a pattern processing method for forming a resin pattern using the positive photosensitive resin composition of the present invention.

[0117] The coating method of the positive photosensitive resin composition may include spin coating, spray coating, blade coating, screen coating, slit coating and the like. It is usually preferred to coat the composition in such a manner that the film thickness after drying becomes 0.5 to 50 μm. Drying may be performed using an oven, a hot plate, an infrared oven, etc., at 40°C to 120°C for 1 min to 10 min, or by step-programmed temperature drying to volatilize the organic solvent. The substrate may be a silicon wafer, a ceramic, a gallium arsenic, an organic circuit board, an inorganic circuit board, and a substrate having a circuit component material arranged thereon, but is not limited thereto.

[0118] After the coating and drying process, a positive photosensitive resin composition film is formed on the substrate. The film is exposed by irradiating exposure light through a mask having a desired pattern. The exposure light source preferably uses i (365nm), h (405nm), and g (436nm) rays of a mercury lamp. The exposure device can use a reduced projection exposure device, a mask aligner, a mirror projection exposure device, etc.

[0119] After exposure, the exposed part of the film is removed using a developer. As the developer, aqueous solutions of alkaline compounds such as tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, dimethylamine, dimethylaminoethanol, cyclohexylamine, and ethylenediamine are preferred. In addition, 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, and acetone can be added to these alkaline aqueous solutions.

[0120] The developing method can be spray developing, immersion developing, ultrasonic immersion developing and other methods. The developing time, developing temperature, developing steps and other conditions are the conditions for removing the exposed part. After development, the film is preferably rinsed with water, or it can be rinsed with an aqueous solution of alcohols and esters such as ethanol, isopropanol, ethyl lactate, etc. If necessary, the film can be baked before development, the baking temperature is 60-150°C, preferably 60-120°C, and the baking time is 5s-60min. After rinsing, the film is heated and dried in the range of 60-200°C, and the drying time is controlled in 1min-60min.

[0121] After exposure, development and rinsing, the positive photosensitive resin composition of the present invention is subjected to a staged program temperature rise / constant temperature heat treatment in the range of 100 to 400°C to cure and form a cured film. The temperature rise / constant temperature heat treatment method can be listed as, for example, starting from room temperature at a heating rate of 5°C / min, and then performing constant temperature heat treatment at 120°C and 180°C for 30 minutes, respectively, and then heating to 250°C for constant temperature heat treatment for 2 hours. Alternatively, the temperature is raised from room temperature to 250°C within 2 hours, and then the temperature is kept constant for 2 hours at 250°C. The temperature rise / constant temperature heat treatment can be carried out under normal pressure, nitrogen or vacuum. Curing obtains a cured film containing an ideal pattern with heat resistance.

[0122] The cured film having a desired pattern formed by the positive photosensitive resin composition of the present invention can be used as a surface protection film of a semiconductor element, an interlayer insulating film, an insulating layer of an organic electroluminescent (EL) element, an insulating layer of a thin film transistor (TFT), etc., but is not limited to these.

[0123] Example

[0124] The present invention is described below with reference to examples, but the present invention is not limited to these examples. First, the evaluation method in each example and comparative example is described. The evaluation used a resin composition (hereinafter referred to as varnish) that was previously filtered using a 1 μm polytetrafluoroethylene filter.

[0125] <Alkali Solubility Imidization rate of resin >

[0126] For the imidization rate of (a) alkali-soluble resin, a solution of N-methylpyrrolidone (hereinafter referred to as NMP) with a solid content concentration of 50% by mass of alkali-soluble resin is applied on a silicon wafer, and then baked for 3 minutes using a 120°C hot plate (SKW-636 manufactured by Dainippon Screen Manufacturing Co., Ltd.) to prepare a pre-baked film with a thickness of 2 μm. The film was divided into two halves, one half of which was placed in an inert gas oven (INH-21CD manufactured by Koyo Thermo Systems), and the curing temperature was raised to 350°C over 30 minutes, and heated at 350°C for 60 minutes. Then, it was slowly cooled to below 50°C in the oven to obtain a cured film. The infrared absorption spectra of the obtained cured film (A) and the film before curing (B) were measured using a Fourier transform infrared spectrophotometer FT-720 (manufactured by Horiba, Ltd.). The 1377cm-1 wavelength derived from the CN stretching vibration of the imide ring was determined. -1 The peak intensity near the imidization ratio was determined as "peak intensity of the film before curing (B) / peak intensity of the cured film (A)".

[0127] <Production of Developed Film>

[0128] The positive photosensitive resin composition of the present invention (hereinafter referred to as varnish) was coated on a silicon wafer to a film thickness of 2 μm after prebaking, and then prebaked at 120°C for 4 minutes using a hot plate (SCW-636; Dainippon Screen Manufacturing Co., Ltd.) to obtain a prebaked film. A small photolithography developer (AC3000) was used at i, g, and h lines with an exposure of 0 to 1000 mJ / cm 2 In the case of 10mJ / cm 2 After exposure, the film was developed in a 2.38 mass % TMAH aqueous solution for 70 seconds and then rinsed with water to obtain a developed film having an isolated pattern.

[0129] <Calculation of residual film rate>

[0130] Residual film rate (%) = film thickness after development ÷ film thickness after pre-baking × 100%

[0131] <Sensitivity>

[0132] The varnish was applied to a 6-inch silicon wafer by a slit coating method using a coating and developing device ACT-8 (manufactured by Tokyo Electron Limited), and pre-baked at 120°C for 3 minutes. Exposure was performed using an i-line stepper exposure machine NSR-2005i9C (manufactured by Nikon). After exposure, development was performed using a 2.38 wt% tetramethylammonium aqueous solution (hereinafter referred to as TMAH, manufactured by Tama Chemical Industry) using a developing device of ACT-8, and then washed with pure water and dried, and the minimum exposure amount when the exposed part was completely dissolved was taken as the sensitivity.

[0133] <Resolution>

[0134] The film obtained by coating the varnish was patterned exposed using the i-line (wavelength 365nm), h-line (wavelength 405nm) and g-line (wavelength 436nm) of an ultra-high pressure mercury lamp using a double-sided alignment single-sided exposure device (mask aligner PEM-6M; manufactured by Union Optical Co., Ltd.) through a grayscale mask for sensitivity measurement (MDRM MODEL 4000-5-FS; manufactured by OptoLine International), and then developed using a small developer for photolithography (AD-2000; manufactured by Takizawa Sangyo Co., Ltd.), and then cured using a high-temperature inert oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.) to obtain a cured film. The resolution pattern of the cured film was observed using an FPD / LSI inspection microscope (OPTIPHOT-330; manufactured by Union Co., Ltd.). The minimum pattern size of the line and space pattern obtained without residue was taken as the resolution.

[0135] <Pattern Evaluation of Developed Film>

[0136] The photosensitive resin composition film formed by development was visually observed for tackiness in the unexposed portion and residue in the exposed portion. The developed film was judged as good if there was no problem with the pattern, and judged as poor if tackiness occurred in the unexposed portion or residue occurred in the exposed portion.

[0137] <Tensile Strength>

[0138] The test was carried out using a universal material testing machine (Instron 3360), with a test sample width of 10 mm, a fixture interval of 50 mm, a test speed of 50 mm / min, and 10 test samples.

[0139] <Thermal Gravimetric Analysis>

[0140] Thermogravimetric analysis was performed using a thermogravimetric analyzer (Mettler TGA / SDTA851) in a nitrogen atmosphere with a heating rate of 10°C / min.

[0141] The following is a detailed description of the embodiments of the present invention. First, the abbreviations corresponding to some monomers involved in the embodiments are described.

[0142] CBDA: Cyclobutanetetracarboxylic dianhydride

[0143] DMCBDA: dimethylcyclobutanetetracarboxylic anhydride

[0144] BDA: 1,2,3,4-Butanetetracarboxylic dianhydride

[0145] HPMDA: 1,2,4,5-cyclohexanetetracarboxylic dianhydride

[0146] TMEG: diethylene glycol (4-tricarboxylic anhydride)

[0147] MCTC: Methylcyclohexene tetracarboxylic dianhydride

[0148] CpODA: Norbornane-2-spiro-α-cyclopentanone-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic dianhydride

[0149] ODPA: 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride

[0150] BPADA: 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]malonic anhydride

[0151] DSDA:3,3,4,4-Diphenylsulfone tetracarboxylic dianhydride

[0152] TAHQ: p-phenylene-trimethylene dianhydride

[0153] PMDA: pyromellitic dianhydride

[0154] M1:

[0155] Y1:

[0156] Y2:

[0157] ODA: 4,4'-diaminodiphenyl ether

[0158] SiDA: 1,1,3,3-Tetramethyl-1,3-bis(3-aminopropyl)disiloxane

[0159] BAP: Bis(3-amino-4-hydroxyphenyl)propane

[0160] OBAP:Bis(3-amino-4-hydroxyphenyl)ether

[0161] CHPS: 2,2'-diamino-4,4'-(cyclohexyl-1,1-diyl)diphenol

[0162] BAHS:Bis(3-amino-4-hydroxyphenyl)sulfone

[0163] p-HAB: 3,3'-dihydroxybenzidine

[0164] NMP: N-methylpyrrolidone

[0165] Synthesis example 1

[0166] Synthesis of fluorine-free alkali-soluble resin A1

[0167] Under a dry nitrogen flow, CBDA (0.022 mol) and ODPA (0.030 mol) were dissolved in NMP (100 g), and then 1,4-cyclohexanediamine (0.016 mol), SiDA (0.002 mol), BAHS (0.030 mol), and NMP (40 g) were added thereto, and the mixture was reacted at 25°C for 2 h. Then 4-aminosalicylic acid (0.008 mol) was added, and the mixture was heated to 60°C for 1 h. Toluene was added, and the water in the system was removed by azeotropy with toluene and water, and the mixture was heated to 160°C for 6 h. The mixture was precipitated in a solvent of 2L ethanol: water = 2:1 (volume ratio), and a white precipitate was obtained. 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 powder of fluorine-free alkali-soluble resin A1. The infrared absorption spectrum was measured, and the imidization rate was 75%.

[0168] Synthesis example 2

[0169] Synthesis of fluorine-free alkali-soluble resin A2

[0170] Under a dry nitrogen flow, CBDA (0.033 mol) and ODPA (0.007 mol) were dissolved in NMP (100 g). BAHS (0.050 mol) and 40 g NMP were then added thereto, and the mixture was reacted at 25 °C for 2 h. Phthalic anhydride (0.02 mol) was then added, and the mixture was reacted at 60 °C for 1 h. Toluene was added, and the water in the system was removed by azeotropy of toluene and water, and the mixture was heated to 180 °C for 6 h. The mixture was precipitated in a solvent of 2 L ethanol: water = 1: 3 (volume ratio) to obtain a white precipitate, which 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 powder of fluorine-free alkali-soluble resin A2. The infrared absorption spectrum was measured, and the imidization rate was 84%.

[0171] Synthesis example 3

[0172] Synthesis of Fluorine-free Alkali-soluble Resin A3

[0173] Under a dry nitrogen flow, BDA (0.013 mol) and BPADA (0.0355 mol) were dissolved in NMP (100 g). SiDA (0.002 mol), BAP (0.045 mol) and NMP (40 g) were then added thereto, and the mixture was reacted at 25°C for 2 h. 4-aminosalicylic acid (0.003 mol) was then 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 heated to 60°C for 4 h. The mixture was precipitated in a solvent of 2L ethanol: water = 1:3 (volume ratio) to obtain a white precipitate, which 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 powder of fluorine-free alkali-soluble resin A3. The infrared absorption spectrum was measured, and the imidization rate was 39%.

[0174] Synthesis example 4

[0175] Synthesis of Fluorine-free Alkali-soluble Resin A4

[0176] Under a dry nitrogen flow, TMEG (0.005 mol) and BPADA (0.047 mol) were dissolved in NMP (100 g), and then polyoxyethylene diamine (0.010 mol), SiDA (0.003 mol), CHPS (0.036 mol), and NMP (40 g) were added thereto, and then 4-aminosalicylic acid (0.006 mol) was added, and the mixture was reacted at 25°C for 2 h. Dimethylformamide dimethyl acetal (0.080 mol) was added dropwise, and the mixture was heated to 120°C for reaction for 6 hours; the mixture was precipitated in a solvent of 2L ethanol: water = 1:3 (volume ratio) to obtain a white precipitate, which 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 powder of fluorine-free alkali-soluble resin A4. The infrared absorption spectrum was measured, and the imidization rate was 62%.

[0177] Synthesis example 5

[0178] Synthesis of Fluorine-free Alkali-soluble Resin A5

[0179] Under a dry nitrogen flow, OBAP (0.030 mol), BAP (0.0175 mol), and SiDA (0.003 mol) were dissolved in NMP (100 g). Subsequently, BDA (0.0175 mol), ODPA (0.037 mol), and NMP (40 g) were added thereto, and then 4-aminosalicylic acid (0.008 mol) was added, and the mixture was reacted at 25°C for 2 h. Dimethylformamide dimethyl acetal (0.085 mol) was added dropwise, and the mixture was heated to 90°C for 5 h. The mixture was precipitated in a solvent of 2L ethanol: water = 1:3 (volume ratio) to obtain a white precipitate, which 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 powder of fluorine-free alkali-soluble resin A5. The infrared absorption spectrum was measured, and the imidization rate was 42%.

[0180] Synthesis example 6

[0181] Synthesis of Fluorine-free Alkali-soluble Resin A6

[0182] Under a dry nitrogen flow, SiDA (0.002 mol), Y1 (0.005 mol), ODA (0.012 mol), and CHPS (0.027 mol) were dissolved in NMP (100 g); TAHQ (0.033 mol), TMEG (0.018 mol), and 40 g NMP were then added thereto, and the mixture was reacted at 25°C for 2 h, and 3-aminosalicylic acid (0.01 mol) was added, and the mixture was reacted at 25°C for 48 h, and dimethylformamide dimethyl acetal (0.105 mol) was added dropwise, and the mixture was heated to 60°C for 6 h. The mixture was precipitated in a solvent of 2L ethanol: water = 1:3 (volume ratio) to obtain a white precipitate, which 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 powder of fluorine-free alkali-soluble resin A6, and the infrared absorption spectrum was measured, and the imidization rate was 28%.

[0183] Synthesis Example 7

[0184] Synthesis of Fluorine-free Alkali-soluble Resin A7

[0185] Under a dry nitrogen stream, BAP (0.055 mol) was dissolved in NMP (100 g). DMCBDA (0.02 mol), BDTA (0.03 mol), CpODA (0.006 mol), and NMP (40 g) were then added thereto, and the mixture was reacted at 25°C for 2 h. Aniline (0.002 mol) was then 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 heated to 45°C for 6 h. The mixture was precipitated in a solvent of 2L ethanol: water = 1:3 (volume ratio) to obtain a white precipitate, which 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 powder of fluorine-free alkali-soluble resin A7. The infrared absorption spectrum was measured, and the imidization rate was 25%.

[0186] Synthesis example 8

[0187] Synthesis of Fluorine-free Alkali-soluble Resin A8

[0188] Under a dry nitrogen stream, OBAP (0.045 mol) and SiDA (0.003 mol) were dissolved in NMP (100 g). MCTC (0.015 mol), BPADA (0.017 mol), M1 (0.020 mol), NMP (40 g) were then added, and aniline (0.008 mol) was added, and the mixture was reacted at 25°C for 2 h. Dimethylformamide dimethyl acetal (0.080 mol) was added dropwise, and the mixture was heated to 120°C for 5 h. The mixture was precipitated in a solvent of 2L ethanol: water = 1:3 (volume ratio) to obtain a white precipitate, which 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 powder of fluorine-free alkali-soluble resin A8. The infrared absorption spectrum was measured, and the imidization rate was 53%.

[0189] Synthesis example 9

[0190] Synthesis of Fluorine-free Alkali-soluble Resin A9

[0191] Under a dry nitrogen flow, 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), and the mixture was reacted at 25 °C for 2 h; toluene was added, and the water in the system was removed by azeotropy with toluene and water, and the mixture was heated to 160 °C for 6 h. The mixture was precipitated in a solvent of 2L ethanol: water = 1:3 (volume ratio) to obtain a white precipitate, which 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 powder of fluorine-free alkali-soluble resin A9, and the infrared absorption spectrum was measured, and the imidization rate was 70%.

[0192] Synthesis example 10

[0193] Synthesis of fluorine-free alkali-soluble resin A10

[0194] Under a dry nitrogen flow, ODPA (0.025 mol) and DSDA (0.026 mol) were dissolved in NMP (100 g); polyethylene glycol diamine (0.005 mol), BAHS (0.040 mol), ODA (0.008 mol), and NMP (40 g) were then added thereto, 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 in the system was removed by azeotropy with toluene and water, and the mixture was heated to 180° C. and reacted for 8 hours; the mixture was precipitated in a solvent of 2 L ethanol: water = 1:3 (volume ratio) to obtain a white precipitate, which was filtered, and the filter cake was washed several times with ethanol: water = 1:3 (volume ratio), and the filter cake was vacuum dried at 50° C. for 72 h to obtain a powder of fluorine-free alkali-soluble resin A10, and the infrared absorption spectrum was measured, and the imidization rate was 99%.

[0195] Synthesis example 11

[0196] Synthesis of fluorine-free alkali-soluble resin A11

[0197] Under a dry nitrogen flow, BAP (0.043 mol) and SiDA (0.005 mol) were dissolved in NMP (100 g). Subsequently, CBDA (0.025 mol), M1 (0.027 mol), NMP (40 g) were added, and then 4-aminophenol (0.008 mol) was added, and the mixture was reacted at 40°C for 2 h. Dimethylformamide dimethyl acetal (0.080 mol) was added dropwise, and then the mixture was heated to 90°C for 5 h. The mixture was precipitated in a solvent of 2L ethanol: water = 1:3 (volume ratio) to obtain a white precipitate, which 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 powder of fluorine-free alkali-soluble resin A11. The infrared absorption spectrum was measured, and the imidization rate was 46%.

[0198] Synthesis example 12

[0199] Synthesis of fluorine-free alkali-soluble resin A12

[0200] Under a dry nitrogen flow, ODA (0.046 mol) and 1,4-diaminocyclohexane (0.005 mol) were dissolved in NMP (100 g). ODPA (0.041 mol), CBDA (0.008 mol), and NMP (40 g) were then added thereto, 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 25°C for 48 h. Dimethylformamide dimethyl acetal (0.085 mol) was added dropwise, and the mixture was heated to 60°C for 4 h. The mixture was precipitated in 2 L of water to obtain a white precipitate, which was filtered and the filter cake was washed with water several times. The filter cake was vacuum dried at 50°C for 72 h to obtain a powder of fluorine-free alkali-soluble resin A12. The infrared absorption spectrum was measured, and the imidization rate was 34%.

[0201] Synthesis example 13

[0202] Synthesis of fluorine-free alkali-soluble resin A13

[0203] Under a dry nitrogen flow, BAHS (0.035 mol), SiDA (0.003 mol), and polyoxyethylene diamine (0.012 mol) were dissolved in NMP (100 g). ODPA (0.040 mol), DSDA (0.015 mol), and NMP (40 g) were then added thereto, followed by aniline (0.005 mol) and 4-aminosalicylic acid (0.005 mol), and the mixture was reacted at 25°C for 2 h, toluene was added, and the water in the system was removed by azeotropy with toluene and water, and the mixture was heated to 180°C for 6 h. The mixture was then heated to 140°C for 4 h. The mixture was precipitated in a solvent of 2L ethanol: water = 1:3 (volume ratio) to obtain a white precipitate, which 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 powder of fluorine-free alkali-soluble resin A13, and the infrared absorption spectrum was measured, and the imidization rate was 86%.

[0204] Synthesis example 14

[0205] Synthesis of fluorine-free alkali-soluble resin A14

[0206] Under a dry nitrogen flow, BAP (0.04 mol) and ODA (0.007 mol) were dissolved in NMP (100 g). TAHQ (0.043 mol), DSDA (0.008 mol), and NMP (40 g) were then added thereto, and the mixture was reacted at 25°C for 2 h. 4-aminosalicylic acid (0.008 mol) was then 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 heated to 50°C for 6 h. The mixture was precipitated in a solvent of 2L ethanol: water = 1:3 (volume ratio) to obtain a white precipitate, which 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 powder of fluorine-free alkali-soluble resin A14. The infrared absorption spectrum was measured, and the imidization rate was 33%.

[0207] Synthesis Example 15

[0208] Synthesis of fluorine-free alkali-soluble resin A15

[0209] Under a dry nitrogen flow, OBAP (0.030 mol), SiDA (0.005 mol), and polyoxyethylene diamine (0.02 mol) were dissolved in NMP (100 g); CBDA (0.025 mol), BPADA (0.02 mol), and NMP (40 g) were then added thereto, and the mixture was reacted at 25°C for 2 h, and then phthalic anhydride (0.02 mol) was added, and the mixture was reacted at 25°C for 2 h; dimethylformamide dimethyl acetal (0.090 mol) was added dropwise, and the mixture was heated to 90°C for 6 h. The mixture was precipitated in a solvent of 2L ethanol: water = 1:3 (volume ratio) to obtain a white precipitate, which 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 powder of fluorine-free alkali-soluble resin A15, and the infrared absorption spectrum was measured, and the imidization rate was 57%.

[0210] Synthesis example 16

[0211] Synthesis of fluorine-free alkali-soluble resin A16

[0212] Under a dry nitrogen flow, CBDA (0.033 mol mol) and PMDA (0.007 mol) were dissolved in NMP (100 g). Then p-HAB (0.050 mol) and 40 g NMP were added thereto, and the mixture was reacted at 25 °C for 2 h. Phthalic anhydride (0.02 mol) was added, and the mixture was reacted at 40 °C for 2 h. Toluene was added, and the water in the system was removed by azeotropy of toluene and water, and the mixture was heated to 180 °C for 6 h. The mixture was precipitated in a solvent of 2 L ethanol: water = 1: 3 (volume ratio) to obtain a white precipitate, which 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 powder of fluorine-free alkali-soluble resin A16. The infrared absorption spectrum was measured, and the imidization rate was 84%.

[0213] Synthesis Example 17

[0214] Synthesis of fluorine-free alkali-soluble resin A17

[0215] 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); TAHQ (0.040 mol), MCTC (0.011 mol), 40 g NMP were then added thereto, and then aniline (0.003 mol) and 4-aminosalicylic acid (0.005 mol) were added, and the mixture was reacted at 25° C. for 2 h, and dimethylformamide dimethyl acetal (0.090 mol) was added dropwise, and the mixture was reacted at 25° C. for 12 h. The mixture was precipitated in a solvent of 2L ethanol: water = 1:3 (volume ratio) to obtain a white precipitate, which 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 powder of fluorine-free alkali-soluble resin A17, and the infrared absorption spectrum was measured, and the imidization rate was 5%.

[0216] Example 1

[0217] The present embodiment provides a positive photosensitive resin composition, and the preparation method thereof is as follows: 10 g of a fluorine-free alkali-soluble resin A1 is taken, and thereto are added photoacid generators: 0.6 g of PAC-1 and 0.6 g of PAC-7, thermal crosslinking agents: 1.5 g of HMOM-TPHAP (manufactured by Honshu Chemical Industry Co., Ltd.) and 2.5 g of EXA-4880 (manufactured by Dainippon Ink & Chemicals Co., Ltd.), and a solvent: 10 g of γ-butyrolactone to prepare a varnish.

[0218] The varnish was applied on a silicon substrate and dried at 120°C for 2 minutes to form a film, which was then exposed using a small-scale developer for photolithography (AC3000; manufactured by Takizawa Industries 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 about 2 μm. The thermal curing conditions were thermal curing at 250°C for 60 minutes in a nitrogen atmosphere. The positive photosensitive resin composition of the present invention was then evaluated.

[0219] Embodiment 2-10

[0220] Examples 2-10 respectively provide a positive photosensitive resin composition, and the preparation method thereof is substantially 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 sequence, and other conditions remain unchanged.

[0221] Comparative Examples 1-7

[0222] Comparative Examples 1-7 respectively provide a positive photosensitive resin composition, and the preparation method thereof is substantially the same as that in Example 1, except that the fluorine-free alkali-soluble resin A1 in Example 1 is replaced by fluorine-free alkali-soluble resins A11-A17 respectively, and other conditions remain unchanged.

[0223] The evaluation results of the above examples and comparative examples are shown in Table 1.

[0224] Table 1 - Performance evaluation results of Examples 1-10 and Comparative Examples 1-7

[0225]

[0226]

[0227] According to the present invention, a film can be developed with an alkaline aqueous solution, has excellent sensitivity and resolution, a clear pattern, and a high residual film rate in the unexposed portion, and is suitable for use as a semiconductor element protective film, a planarization layer, an interlayer insulating film, an insulating film for a display, an insulating layer from an organic field to a light-emitting element, an insulating layer for a thin film transistor TFT, etc.

Claims

1. A fluorine-free alkali-soluble resin, characterized in that: The main chain structure of the fluorine-free alkali-soluble resin comprises a structural unit having a structural formula (a1) and a structural unit having a structural formula (a2); In the above structural formula (a1) and structural formula (a2), X and Y represent reaction residues of dianhydride, and P and Q represent reaction residues of diamine; 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 having 1 to 20 carbon atoms; and 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%.

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

3. The fluorine-free alkali-soluble resin according to claim 1 or 2, characterized in that: 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 to 3, characterized in that: The X and Y are 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 each independently H or methyl; R5, R6, and R7 are each independently H or hydroxyl; A1 and A2 are each independently selected from -CO-, -O-, -S-, -CO2-, -SO2-, -CH2-, -C(CH3)2-, or -CONH-; B1 and B3 are each independently selected from a bond, One of the following, 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, characterized in that: The 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 each independently H or methyl; A1 and A2 are each 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, characterized in that: 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]malonic dianhydride (BPADA), diethylene glycol (4-tricarboxylic anhydride) (TMEG), p-phenylene-diphthalic acid dianhydride (TAHQ), 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (ODPA), 3,3,4,4-diphenyl sulfone tetracarboxylic dianhydride (DSDA), methylcyclohexene tetracarboxylic dianhydride (MCTC), and dianhydrides of 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)diphenol (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 of the following structures:

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

8. A positive photosensitive resin composition, characterized in that: Contains the following ingredients: (a) 100 parts by weight of an alkali-soluble resin, wherein the alkali-soluble resin is the fluorine-free alkali-soluble resin according to any one of claims 1 to 7; (b) a photoacid generator, 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 according to claim 8.

10. A method for patterning a cured film, comprising the following steps: i) coating the positive photosensitive resin composition according to claim 8 on a substrate, and drying at 40-120° C. for 1-10 min to form a positive photosensitive resin composition film; ii) exposing the film under a mask; iii) removing the exposed portion of the film using an alkaline developer, developing and washing; iiii) The developed film is cured and dried at 100-400° C. to obtain a cured film having a desired pattern.

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