Compounds for photosensitive resins, heat-resistant resins, photosensitive resin compositions, patterned films, and display devices

Abstract

This invention provides a photosensitive resin compound, a heat-resistant resin, a photosensitive resin composition, a patterned film, and a display device. The compound has any one of the following general formulas (I), (II), and (III), wherein in formulas (I), (II), and (III), R1 represents any one or more of hydrogen atoms and alkyl groups with ≥1 carbon atom; R2 represents any one or more of hydrogen atoms, alkyl groups with ≥1 carbon atom, alkoxy groups with ≥1 carbon atom, hydroxyl groups, carboxyl groups, and fluorine, chlorine, and bromine substituents; R3 represents any one or more of hydrogen atoms, alkyl groups with ≥1 carbon atom, alkoxy groups with ≥1 carbon atom, and fluorine, chlorine, and bromine substituents; p represents an integer from 0 to 3; q represents an integer from 0 to 1; S represents a linking group, wherein the linking group has at least 6 carbon atoms and contains at least one fused ring structure of an alicyclic ring and / or an aromatic ring. A photosensitive resin composition with high sensitivity and excellent thermal properties is obtained.

Description

Technical Field

[0001] This invention relates to the field of optoelectronic semiconductor technology, and more specifically, to photosensitive resin compounds, heat-resistant resins, photosensitive resin compositions, patterned films, and display devices. Background Technology

[0002] In recent years, with the miniaturization of display light-emitting elements and semiconductor components, there is a growing demand for μm-level or even lower resolution and high sensitivity in surface protective films, interlayer insulating films, and pixel definition layers. Simultaneously, due to the requirements of manufacturing processes, high demands are placed on the heat resistance, electrical insulation, and chemical resistance of photosensitive materials. Therefore, highly photosensitive resin compositions derived from polyimide, polybenzoxazole, phenolic resins, and other materials with inherently good heat resistance and electrical insulation have received widespread attention and application in this field, especially positive photosensitive resin compositions where the exposed portion dissolves in alkaline aqueous solutions after ultraviolet light exposure.

[0003] Currently, a common method is to add a photosensitizing, solubility-inhibiting compound—diazonaphthoquinone—to a heat-resistant resin or its precursor that has good solubility in alkaline solutions. This inhibits the dissolution of unexposed areas in the alkaline solution through hydrogen bonding, electrostatic interactions, and alkaline-catalytic coupling of the diazononaphthoquinone group. After exposure, the diazononaphthoquinone group decomposes, transforming into carboxyl groups, thus eliminating the solubility inhibition and increasing the solubility of the exposed area. Examples include resin compositions containing diazononaphthoquinone in polyamic acid and resin compositions containing diazononaphthoquinone in hydroxyl-containing polyimides. Furthermore, to improve the solubility contrast between the shaded and exposed areas and reduce exposure, phenolic compounds are often added to the resin system. However, the introduction of diazononaphthoquinone, hydroxyl groups, and phenolic compounds can easily lead to decreased heat resistance and chemical resistance of the cured film after heat treatment, and an difficulty in balancing film thinning and exposure during development. Summary of the Invention

[0004] The purpose of this invention is to solve the above-mentioned technical problems and to provide a photosensitive resin compound, a heat-resistant resin, a photosensitive resin composition, a patterned film, and the fifth aspect of this invention.

[0005] The first aspect of this invention provides a compound for photosensitive resins, said compound having any one of the following general formulas (I), (II), and (III).

[0006]

[0007] In the structural formulas (I), (II), and (III), R1 represents any one or more of hydrogen atoms and alkyl groups with ≥1 carbon atom; R2 represents any one or more of hydrogen atoms, alkyl groups with ≥1 carbon atom, alkoxy groups, hydroxyl groups, carboxyl groups, and fluorine, chlorine, and bromine substituents; R3 represents any one or more of hydrogen atoms, alkyl groups with ≥1 carbon atom, alkoxy groups with ≥1 carbon atom, and fluorine, chlorine, and bromine substituents; p represents an integer from 0 to 3; q represents an integer from 0 to 1; S represents a linking group, wherein the linking group contains not less than 6 carbon atoms and the linking group contains at least one fused ring structure of an alicyclic ring and / or an aromatic ring.

[0008] Preferably, the S group comprises a tetravalent linker group of sulfone, sulfoxide, thioether, siloxane bond, or hexafluoropropyl.

[0009] And / or, the fused ring structure of the alicyclic and / or aromatic ring includes any one or more of the following: a structure in which two or more alicyclic structures are fused, a structure in which at least one alicyclic ring is fused with at least one aromatic ring, and a structure in which two or more aromatic rings are fused.

[0010] In other preferred embodiments, the linking group contains a fused ring structure of two alicyclic and / or aromatic rings, and the two fused ring structures of the alicyclic and / or aromatic rings are connected by a divalent group.

[0011] Preferably, the compound is selected from any one or more of the following structures;

[0012]

[0013]

[0014] In the structural formula, R1 represents any one or more of hydrogen atoms and alkyl groups with ≥1 carbon atom; R2 represents any one or more of hydrogen atoms, alkyl groups with ≥1 carbon atom, alkoxy groups, hydroxyl groups, carboxyl groups, and fluorine, chlorine, and bromine substituents; p represents an integer from 0 to 3; R3 represents any one or more of hydrogen atoms, alkyl groups with ≥1 carbon atom, alkoxy groups with ≥1 carbon atom, and fluorine, chlorine, and bromine substituents; X and Y represent divalent linking groups, where X is selected from -O-, -S-, -CO-, -SO-, -C(CF3)2-, alkyl or substituted alkyl groups with 0-20 carbon atoms, aryl or substituted aryl groups with 0-20 carbon atoms; and Y is selected from -O-, -S-, -CO-, -SO-, -SO2-, alkyl or substituted alkyl groups with 0-20 carbon atoms, aryl or substituted aryl groups with 0-20 carbon atoms, or divalent linking groups containing Si with a molecular weight of less than 800.

[0015] Furthermore, the compound containing a divalent linker X or Y is selected from any one or more of the following structures:

[0016]

[0017]

[0018]

[0019] In the structural formula, R1 represents any one or more of hydrogen atoms and alkyl groups with ≥1 carbon atom; R2 represents any one or more of hydrogen atoms, alkyl groups with ≥1 carbon atom, alkoxy groups with ≥1 carbon atom, hydroxyl groups, carboxyl groups, and fluorine, chlorine, and bromine substituents; p represents an integer from 0 to 3; and R3 represents any one or more of hydrogen atoms, alkyl groups with ≥1 carbon atom, alkoxy groups with ≥1 carbon atom, and fluorine, chlorine, and bromine substituents.

[0020] A second aspect of the present invention provides a heat-resistant resin formed from a photosensitive resin compound provided in the first aspect of the present invention, wherein the heat-resistant resin comprises one or more repeating units represented by the following general formulas (Ⅳ), (Ⅴ) or (Ⅵ):

[0021]

[0022] In the structural formulas (Ⅳ), (Ⅴ) or (Ⅵ), Q represents an organic group with 2 to 30 carbon atoms, D represents an organic group with 2 to 50 carbon atoms, and R4 represents any one of a hydrogen atom or a hydrocarbon group having one or more carbon atoms. R4 is preferably methyl, ethyl, propyl, isopropyl, or a fluorinated alkyl group.

[0023] The repeating unit containing R4 accounts for 40–100 mol% of the total repeating unit of the polyimide resin precursor, and R4 is a hydrogen atom repeating unit, accounting for 30–100 mol% of the total repeating unit containing R4.

[0024] Furthermore, 10 to 100 mol% of D is a residue of any one or more compounds of general formulas (I), (II), and (III).

[0025] A third aspect of the present invention provides a photosensitive resin composition comprising the heat-resistant resin provided in the second aspect of the present invention, a photoacid-producing agent, and a compound containing phenolic hydroxyl groups.

[0026] Furthermore, the phenolic hydroxyl compounds in the photosensitive resin composition have the structure shown in general formula (VII):

[0027]

[0028] In the structural formula (VII), E is an aliphatic chain or an organic structure containing an alicyclic ring with 1 to 30 carbon atoms, R5 represents a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, R6 represents any one or more of hydrogen atoms, hydroxyl groups, carboxyl groups, ester groups, and alkyl groups with 1 to 5 carbon atoms, n is an integer greater than 0, and k, o, l, and q represent integers from 0 to 5, respectively.

[0029] A fourth aspect of the present invention provides a photosensitive resin composition comprising a heat-resistant resin provided in the second aspect of the present invention, a photopolymerization initiator, and a monomer having photopolymerizable unsaturated bonds.

[0030] Furthermore, the monomer having photopolymerizable unsaturated bonds includes acrylic acid monomers with a functionality of 1 to 8, preferably acrylic acid monomers with a functionality of 2 to 4.

[0031] The fifth aspect of the present invention provides a patterned film, which is obtained by curing a photosensitive resin composition provided in the third or fourth aspect of the present invention. The patterned film is used as an insulating layer, pixel definition layer, planarization layer of an organic electroluminescent element, or a surface protective film or insulating layer of a semiconductor element.

[0032] A sixth aspect of the present invention provides a display device comprising the patterned film provided in the fifth aspect of the present invention.

[0033] The present invention has the following beneficial effects: The present invention provides a novel compound containing alicyclic and / or aromatic rings in a fused ring structure. Using this compound, positive photosensitive resin compositions with high sensitivity, high resolution, excellent thermal properties and chemical resistance can be obtained. It can also be used in high-resolution negative photosensitive resin compositions to prepare cured films with low residual film rate and excellent water absorption properties, so as to meet the development needs of display light-emitting elements and semiconductor elements. Detailed Implementation

[0034] This invention provides compounds for photosensitive resins, heat-resistant resins, photosensitive resin compositions, patterned films, and a fifth aspect of the invention. The invention will be described below with reference to specific embodiments. It should be noted that the following embodiments are examples of the invention and are used only to illustrate the invention, not to limit it. Other combinations and various modifications within the scope of the invention can be made without departing from its spirit or scope.

[0035] <Compounds for photosensitive resins>

[0036] The first aspect of this invention provides a compound for photosensitive resins, said compound having any one of the following general formulas (I), (II), and (III).

[0037]

[0038] In the structural formulas (I), (II), and (III), R1 represents any one or more of hydrogen atoms and alkyl groups with ≥1 carbon atom; R2 represents any one or more of hydrogen atoms, alkyl groups with ≥1 carbon atom, alkoxy groups, hydroxyl groups, carboxyl groups, and fluorine, chlorine, and bromine substituents; R3 represents any one or more of hydrogen atoms, alkyl groups with ≥1 carbon atom, alkoxy groups with ≥1 carbon atom, and fluorine, chlorine, and bromine substituents; p represents an integer from 0 to 3; q represents an integer from 0 to 1; S represents a linking group, wherein the linking group contains not less than 6 carbon atoms, and the linking group contains at least one fused ring structure of an alicyclic ring and / or an aromatic ring.

[0039] Preferably, the S group comprises a tetravalent linker group of sulfone, sulfoxide, thioether, siloxane bond, or hexafluoropropyl.

[0040] And / or, the fused ring structure of the alicyclic and / or aromatic ring includes any one or more of the following: a structure in which two or more alicyclic structures are fused, a structure in which at least one alicyclic ring is fused with at least one aromatic ring, and a structure in which two or more aromatic rings are fused, such as a decahydronaphthalene group, naphthyl, etc.

[0041] In other preferred embodiments, the linking group contains a fused ring structure of two alicyclic and / or aromatic rings, and the two fused ring structures of the alicyclic and / or aromatic rings are connected by a divalent group.

[0042] In some embodiments of the present invention, the compound is selected from any one or more of the following structures;

[0043]

[0044]

[0045] In the structural formula, R1 represents any one or more of hydrogen atoms and alkyl groups with ≥1 carbon atom; R2 represents any one or more of hydrogen atoms, alkyl groups with ≥1 carbon atom, alkoxy groups with ≥1 carbon atom, hydroxyl groups, carboxyl groups, and fluorine, chlorine, and bromine substituents; p represents an integer from 0 to 3; R3 represents any one or more of hydrogen atoms, alkyl groups with ≥1 carbon atom, alkoxy groups with ≥1 carbon atom, and fluorine, chlorine, and bromine substituents; X and Y represent divalent linking groups, where X is selected from -O-, -S-, -CO-, and -SO-. -C(CF3)2-, alkyl or substituted alkyl with 0-20 carbon atoms, aryl or substituted aryl with 0-20 carbon atoms, such as -CH2-, -C(CH3)2-, aryl with 0-20 carbon atoms containing a diphenyl ether group; Y is selected from -O-, -S-, -CO-, -SO-, -SO2-, alkyl or substituted alkyl with 0-20 carbon atoms, aryl or substituted aryl with 0-20 carbon atoms, or a divalent linking group containing Si with a molecular weight of less than 800, such as dimethylsiloxane.

[0046] As an example, compounds containing divalent linking groups X or Y are selected from any one or more of the following structures:

[0047]

[0048]

[0049] In the structural formula, R1 represents any one or more of hydrogen atoms and alkyl groups with ≥1 carbon atom; R2 represents any one or more of hydrogen atoms, alkyl groups with ≥1 carbon atom, alkoxy groups with ≥1 carbon atom, hydroxyl groups, carboxyl groups, and fluorine, chlorine, and bromine substituents; p represents an integer from 0 to 3; and R3 represents any one or more of hydrogen atoms, alkyl groups with ≥1 carbon atom, alkoxy groups with ≥1 carbon atom, and fluorine, chlorine, and bromine substituents.

[0050] Compounds with fused ring structures containing alicyclic and / or aromatic rings are beneficial for improving the heat resistance and chemical resistance of photosensitive resins. In addition, the formation or opening of lactone groups can further improve the sensitivity of photosensitive resins to light. Furthermore, the introduction of functional groups such as sulfone, sulfoxide, thioether, siloxane bonds, and hexafluoropropyl groups into heat-resistant resins can also improve the light transmittance or adhesion of photosensitive resins.

[0051] The preparation method of the photosensitive resin compound provided in the first aspect of the present invention is not limited, and examples can be given: In a high-boiling solvent such as thiobenzene, N-methylpyrrolidone, butyrolactone, a benzocyclobutene compound or other di(enephilic) structure compound exhibiting a Diels-Alder reaction is mixed with a nitro-substituted coumarin compound in a stoichiometric ratio of 1:2 to 1:4, and heated at 50 to 250°C for 24 to 72 hours to obtain a dinitro compound via a Diels-Alder reaction. Alternatively, in a high-boiling solvent such as toluene, xylene, N-methylpyrrolidone, butyrolactone, a silane or thiol is added to a double bond compound formed by a Diels-Alder addition reaction of a nitro-substituted coumarin compound and cyclopentadiene to obtain a dinitro compound. The dinitro compound is then reduced with hydrogen under palladium on carbon (Pd / C) or Raney nickel catalysis to obtain the corresponding diamine compound. The specific reaction conditions are as follows: using methanol, ethanol, acetone, N-methylformamide, N-methyldiamide, γ-butyrolactone, propylene glycol methyl ether, or N,N-dimethylpyrrolidone as solvents, the dinitro compound is dissolved in the solvent. 0.1%–1% of the dinitro compound is added to 5–10 wt% Pd / C with stirring. Hydrogen gas is introduced, and the pressure can be controlled within atmospheric pressure to 10 atmospheres. The reaction is carried out at 20–50°C for 5–48 hours. Pd / C is then removed by filtration, and the filtrate is concentrated by rotary evaporation to obtain a diamine compound with a lactone group, as shown in general formula (I). The diamine compound containing the lactone group is hydrolyzed under alkaline conditions to obtain diamine compounds with general formulas (II) and (III), wherein the alkaline reagent can be NaOH or sodium alkoxide solution, and the reaction is carried out for 5-48 hours; then the pH value is adjusted to weak acidity, and the filtrate is concentrated by rotary evaporation.

[0052] The corresponding process is shown in the following formula:

[0053]

[0054]

[0055] R1, R2, R3, X, and Y in the process are the same as described above. In the hydrolysis step of the process, the lactone group undergoes complete or partial hydrolysis and ring-opening, which can be achieved by controlling the hydrolysis time. In other words, the process formula only shows a portion of the hydrolysis products and is not intended to limit the scope of this invention.

[0056] Alternatively, the dinitro compound can be obtained by direct reduction of iron or zinc powder in an acidic system. The iron or zinc powder used is 5-50 molar equivalents. The acid can be hydrochloric acid, phosphoric acid, sulfuric acid, acetic acid, methanesulfonic acid, or trifluoroformic acid, preferably 10 wt% hydrochloric acid. The pH is adjusted to 1-5, and the reaction is carried out at 60-100°C for 8-24 hours. The pH is then adjusted to weakly acidic, and the filtrate is concentrated by rotary evaporation. During this process, the lactone group is simultaneously hydrolyzed to obtain a diamine compound with general formula (II) or general formula (III).

[0057] <Heat-resistant resin>

[0058] A second aspect of the present invention provides a heat-resistant resin formed from the photosensitive resin compound provided in the first aspect of the present invention. Considering heat resistance, practicality, and ease of synthesis, the heat-resistant resin is preferably a copolymer of polyimide and a polyimide precursor, namely polyamic acid, obtained by polymerization of tetracarboxylic dianhydride and diamine, and has a structural formula including one or more repeating units shown in general formulas (Ⅳ), (Ⅴ), or (Ⅵ):

[0059]

[0060] In the structural formulas (Ⅳ), (Ⅴ) or (Ⅵ), Q represents an organic group with 2 to 30 carbon atoms, D represents an organic group with 2 to 50 carbon atoms, and R4 represents any one of a hydrogen atom or a hydrocarbon group having one or more carbon atoms. R4 is preferably methyl, ethyl, propyl, isopropyl, or a fluorinated alkyl group.

[0061] Furthermore, the repeating unit containing R4 accounts for 40–100 mol% of the total repeating unit of the polyimide resin precursor. This value indicates the degree of imidization. If the degree of imidization is too high when used in a photosensitive resin composition, it will lead to poor film properties. The repeating unit containing R4 as a hydrogen atom accounts for 30–100 mol% of the total repeating unit containing R4. The higher the value, the higher the carboxyl group content on the resin, and the better the solubility in alkaline developer when used in a photosensitive resin composition.

[0062] Further, Q represents a residue of tetracarboxylic acid dianhydride, the structure of which is not limited in this invention. To obtain a polyimide resin precursor with excellent heat resistance, organic groups containing aromatic rings or aromatic heterocycles are preferred, and examples include residues with the following structures: pyromellitic acid, 2,2',3,3'-biphenyltetracarboxylic anhydride, 3,3',4,4'-biphenyltetracarboxylic anhydride, 2,3,3',4'-biphenyltetracarboxylic anhydride, 3,3',4,4'-benzophenone tetracarboxylic anhydride, 2,2',3,3'-benzophenone tetracarboxylic anhydride, 2,2-bis(3,4-dicarboxylic anhydride phenyl)hexafluoropropane, 2,2-bis(2,3-dicarboxylic anhydride phenyl)hexafluoropropane, bis(3, Aromatic tetracarboxylic anhydrides such as 4-dicarboxylic anhydride phenyl) sulfone, di(3,4-dicarboxylic anhydride phenyl) ether, di(3,4-dicarboxylic anhydride phenyl)methane, di(2,3-dicarboxylic anhydride phenyl)methane, 1,1-di(3,4-dicarboxylic anhydride phenyl)ethane, 1,1-di(2,3-dicarboxylic anhydride phenyl)ethane, 1,2,5,6-naphthalenetetracarboxylic anhydride, 2,3,6,7-naphthalenetetracarboxylic anhydride, 2,3,5,6-pyridinetetracarboxylic anhydride, 3,4,9,10-perylenetetracarboxylic anhydride, etc., and aliphatic tetracarboxylic anhydrides such as butanetetracarboxylic anhydride, 1,2,3,4-cyclopentanetetracarboxylic anhydride, etc.

[0063] Polyimides whose structural formula includes one or more repeating units shown in general formulas (Ⅳ), (Ⅴ), or (Ⅵ) below, and polyimide precursors can also be prepared by reacting a tetracarboxylic acid diester diacyl chloride compound with a diamine. Q in general formulas (Ⅳ), (Ⅴ), or (Ⅵ) represents a residue of the tetracarboxylic acid diester diacyl chloride, which can be prepared from the corresponding acid anhydride via two steps: esterification and acyl chloride. The reaction process is a conventional tetracarboxylic acid diester diacyl chloride preparation process: first, the tetracarboxylic acid anhydride reacts with an alcohol to obtain a diester dicarboxyl compound; second, the diester dicarboxyl compound is exchanged with sulfoxide or an acyl chloride compound to obtain the corresponding tetracarboxylic acid diester diacyl chloride compound.

[0064] Further, D represents a diamine residue, wherein 10–100 mol% of D is a residue of any one or more compounds of general formulas (I), (II), and (III), preferably 40–100 mol%, more preferably 60–100 mol%, and even more preferably 80–100 mol%, which is beneficial for improving the heat resistance, mechanical properties, thermal stability, and permeability of the resin. D also includes other diamine residues, with no structural limitations, examples of which include: p-phenylenediamine, m-phenylenediamine, 3-carboxy-m-phenylenediamine, 3-hydroxy-m-phenylenediamine benzidine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene, bis(4-aminophenoxyphenyl)sulfone, bis(3- The aromatic diamines selected from one or more combinations thereof, including aminophenoxyphenyl sulfone, 1,4-bis(4-aminophenoxy)benzene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2,3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, and cycloalkyl or halogen-substituted aromatic diamines.

[0065] For the heat-resistant resin provided in the second aspect of the present invention, in order to ensure adequate solubility in alkaline developing solution and good heat resistance and elongation of the resin after heat treatment, the number of repetitions of the structural unit is preferably in the range of 10 to 1000, more preferably 20 to 500, and even more preferably 50 to 100. This can be achieved by adjusting the addition ratio of dianhydride and diamine, preferably a molar ratio of dianhydride to diamine of (0.98 to 1.02):(0.98 to 1.02); a capping agent can also be introduced during polymerization, wherein the proportion of the capping agent introduced is 0.005 to 0.5 of the total molar amount of all added diamine and dianhydride monomers, more preferably 0.01 to 0.4; in order to obtain a resin composition with adequate solution viscosity and excellent film properties within the above range, the capping agent is selected from monoamine compounds, monofunctional acid anhydride compounds, and monofunctional aromatic acids, as specifically exemplified below:

[0066] Monoamine compounds: 3-aminophenol, 2-aminophenol, 4-aminophenol, 3-aminobenzoic acid, 3-amino-o-methylbenzoic acid, 3-amino-m-methylbenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 1-amino-8-hydroxynaphthalene, 1-amino-7-hydroxynaphthalene, 1-amino-6-hydroxynaphthalene, 1-amino-5-hydroxynaphthalene, 1-amino-4-hydroxynaphthalene, 1-amino-3-hydroxynaphthalene, 1-amino-2-hydroxynaphthalene, 1-carboxy-8-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 1-carboxy-4-aminonaphthalene, 1-carboxy-3-aminonaphthalene, 1-carboxy-2-aminonaphthalene, 3-amino-4,6-dihydroxypyrimidine, 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline;

[0067] Monofunctional acid anhydrides include: maleic anhydride, phthalic anhydride, cyclohexanedicarboxylic anhydride, cyclohexanepentanedicarboxylic anhydride, etc.

[0068] Monofunctional aromatic acids: benzoic acid, o-methylbenzoic acid, m-methylbenzoic acid, p-methylbenzoic acid, 2-carboxyphenol, 3-carboxyphenol, 4-carboxyphenol, 2-carboxybenzylthiophenol, 3-carboxybenzylthiophenol, 4-carboxybenzylthiophenol, carboxynaphthalene, 2-hydroxy-naphthoic acid, 3-hydroxy-naphthoic acid, 4-hydroxy-naphthoic acid, 5-hydroxy-naphthoic acid, 6-hydroxy-naphthoic acid, 7-hydroxy-naphthoic acid, 8-hydroxy-naphthoic acid, 9-hydroxy-naphthoic acid.

[0069] In the heat-resistant resin provided in the second aspect of the present invention, by adjusting the ratio of the compounds shown in general formulas (I), (II) and (III), the dissolution rate of the heat-resistant resin in the alkaline developer can be adjusted. Preferably, the dissolution rate of the unexposed film in the alkaline developer is 50 nm / min to 30000 nm / min, and the dissolution rate of the exposed film in the alkaline developer is 200 nm / min to 50000 nm / min.

[0070] <Photosensitive Resin Composition>

[0071] A third aspect of the present invention provides a photosensitive resin composition comprising the heat-resistant resin provided in the second aspect of the present invention, a photoacid-generating agent, and a compound containing phenolic hydroxyl groups. The photoacid-generating agent is a compound that generates acid upon light irradiation, thereby imparting increased solubility of the irradiated portion in alkaline aqueous solutions, and forming a positive pattern of dissolution in the exposed portion during development.

[0072] The photoacid-generating agent in the photosensitive resin composition is preferably a diazonaquinone compound. The addition amount is 5%-40% of the mass of the heat-resistant resin, preferably 10%-30%. Examples include one or more of the following: diazonaquinone compounds (diazonaphthoquinone sulfonate compounds), sulfonium salts, phosphonium salts, diazonium salts, iodonium salts, etc.; these diazonaquinone compounds can be synthesized by esterification of a phenolic hydroxyl compound with a diazonaquinone sulfonyl chloride. In this invention, the diazonaquinone compound is preferably a compound obtained by bonding a 5-diazonaphthoquinone sulfonyl group or a 4-diazonaphthoquinone sulfonyl group to a phenolic hydroxyl compound. Examples of phenolic hydroxyl compounds used to prepare the diazonaquinone compound include:

[0073]

[0074]

[0075] As a diazonoquinone compound, the molecular structure preferably has one or more combinations of diazonoquinone 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.

[0076]

[0077]

[0078] For compounds containing phenolic hydroxyl groups in photosensitive resin compositions, it is preferable that they have the structure shown in general formula (Ⅶ):

[0079]

[0080] In the structural formula (VII), E is an aliphatic chain or an organic structure containing an alicyclic ring with 1 to 30 carbon atoms, R5 represents a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, R6 represents any one or more of hydrogen atoms, hydroxyl groups, carboxyl groups, ester groups, and alkyl groups with 1 to 5 carbon atoms, n is an integer greater than 0, and k, o, l, and q represent integers from 0 to 5, respectively.

[0081] The purpose of using the phenolic hydroxyl compound of formula (VII) in the aforementioned photosensitive resin composition is to improve the developing effect and obtain a high-resolution pattern. The amount of the phenolic hydroxyl compound added is 1-40% of the total mass of the heat-resistant resin, more preferably 5%-30%. One or more of the following examples are preferred:

[0082]

[0083] More preferably:

[0084]

[0085] A fourth aspect of the present invention provides another photosensitive resin composition comprising the heat-resistant resin provided in the second aspect of the present invention, a photopolymerization initiator, and a monomer having photopolymerizable unsaturated bonds. The photopolymerization initiator is a compound that generates free radicals to initiate polymerization through bond breaking and / or reaction upon exposure, thereby reducing the solubility of the resin composition film in the alkaline developing solution at the exposure site, thereby enabling the formation of a negative pattern.

[0086] For the photopolymerization initiator, the amount of photopolymerization initiator added is 0.1 to 50 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the heat-resistant resin. The type of photopolymerization initiator is not limited in this invention; α-aminoketone-based photopolymerization initiators, oxime ester-based photopolymerization initiators, and acylphosphine oxide-based photopolymerization initiators can be used. Specific examples include: 1,3-diphenylpropane-1,2,3-trione-2-(O-ethoxycarbonyl)oxime, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butane-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinylphenyl)-butane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropane-1-one, 3,6-di(2-methyl-2-morpholinylpropionyl)-9-octyl-9H-carbazole; 1-phenylpropane-1,2-dione-2-(O-ethoxycarbonyl)oxime, 1-phenylbutane-1,2-dione-2-(O-methoxycarbonyl)oxime, 1-[4-(phenylthio)phenyl]octane-1,2-dione-2- (O-benzoyl) oxime, 1-[4-[4-(carboxyphenyl)thio]phenyl]propane-1,2-dione-2-(O-acetyl) oxime, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]acetone-1-(O-acetyl) oxime, 1-[9-ethyl-6-[2-methyl-4-[1-(2,2-dimethyl-1,3-dioxolane-4-yl)methyloxy]benzoyl]-9H-carbazole-3-yl]acetone-1-(O-acetyl) oxime; 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, di(2,4,6-trimethylbenzoyl)-phenylphosphine oxide or di(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphine oxide, etc.

[0087] For monomers having photopolymerizable unsaturated bonds, the addition amount is 10 to 300 parts by weight, more preferably 20 to 200 parts by weight, based on 100 parts by weight of the heat-resistant resin. Preferred acrylic monomers, further including acrylic monomers with a functionality of 1 to 8, more preferably acrylic monomers with a functionality of 2 to 4. Examples include: trimethylolpropane tri(meth)acrylate, bis(trimethylolpropane tri(meth)acrylate, bis(trimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, 2,2-bis[4-(3-(meth)acryloyloxy-2-hydroxypropoxy)phenyl]propane, 1, 3,5-tris((meth)acryloyloxyethyl)isocyanuric acid, 1,3-di((meth)acryloyloxyethyl)isocyanuric acid, 9,9-di[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, 9,9-di[4-(3-(meth)acryloyloxypropoxy)phenyl]fluorene or 9,9-di(4-(meth)acryloyloxyphenyl)fluorene, and compounds obtained by ring-opening addition of compounds having two or more epoxy-containing structures with (meth)acrylic acid compounds, followed by reaction with a polybasic acid (anhydride).

[0088] The negative photosensitive resin composition provided in the fourth aspect of the present invention can also include a compound containing phenolic hydroxyl groups with the structure shown in the aforementioned general formula (Ⅶ) to adjust the solubility of the heat-resistant resin. At the same time, after heat treatment, it reacts with hydroxyl, carboxyl and other groups on the resin backbone to form a cross-linked structure, thereby improving the thermal stability of the cured film and reducing its hygroscopicity.

[0089] The negative photosensitive resin composition provided in the fourth aspect of this invention may further include compounds containing two or more epoxy groups, with the aim of controlling the thermal reflow and crosslinking properties of the heat-resistant resin, and obtaining the desired positive conical pattern after the curing process. Compounds may be selected from glycidyl ether type, glycidyl amine type, and olefin oxidation type compounds, with specific examples as follows: bisphenol A type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, hydrogenated bisphenol F type epoxy compounds, brominated bisphenol A type epoxy compounds, biphenyl type epoxy compounds, naphthalene type epoxy compounds, fluorene type epoxy compounds, spirocyclic type epoxy compounds, bisphenol alkane type epoxy compounds, phenol Novolac type epoxy compounds, o-cresol Novolac type epoxy compounds, trihydroxymethane type epoxy compounds, tetraphenolyl ethane type epoxy compounds, alicyclic type epoxy compounds, alcohol type epoxy compounds, etc. The amount of compound containing two or more epoxy groups added is 1 to 60 parts by weight, preferably 5 to 40 parts by weight, based on 100 parts by weight of heat-resistant resin.

[0090] For the positive photosensitive resin composition provided in the third aspect of this invention and the negative photosensitive resin composition provided in the fourth aspect of this invention, additives can be introduced to improve the adhesion and film-forming properties of the resin film to the substrate. The additives include adhesion promoters and surfactants; wherein the adhesion promoter is preferably a silane coupling agent, including one or more combinations of methacryloyloxydimethoxymethylsilane, 3-aminopropyltrimethoxysilane, vinyltrimethoxysilane, and vinyltriacryloyloxysilane; the amount of adhesion promoter added is 0.003 to 0.200% of the mass of the heat-resistant resin. The selected surfactants are fluorinated surfactants, silicone surfactants, acrylate surfactants, esters, and ketones; in the embodiments of this invention, ethyl lactate, ethyl acetate, methyl ethyl ketone, and cyclohexanone are preferred; the amount of surfactant added is 0.0003 to 0.05% of the mass of the heat-resistant resin.

[0091] The solvents in the positive photosensitive resin compositions provided in the third aspect of this invention and the negative photosensitive resin compositions provided in the fourth aspect of this invention are selected from solvents with a boiling point below 230°C, preferably solvents with a boiling point of 100-230°C. If the solvent boiling point is too high, it is not conducive to subsequent drying into a wet film; if the solvent boiling point is too low, the solvent evaporates too quickly during the drying process after coating, easily leading to film-forming defects. Solvents include, but are not limited to, one or more combinations of N,N-dimethylacetamide, N,N-dimethylformamide, γ-butyrolactone, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol, n-butanol, cyclohexanone, ethyl lactate, and butyl lactate; the amount of solvent added is 1-50 times the mass of the heat-resistant resin, more preferably 3-30 times the mass of the heat-resistant resin.

[0092] Patterned film

[0093] The fifth aspect of the present invention provides a patterned film, which is obtained by curing the positive photosensitive resin composition provided in the third aspect of the present invention and the negative photosensitive resin composition provided in the fourth aspect of the present invention. Specifically, it can be obtained by coating, drying, exposure, development and curing, but is not limited thereto.

[0094] The coating step involves applying the photosensitive resin composition onto a substrate. Examples of coating methods include spin coating, spray coating, blade coating, screen coating, and slot coating. Depending on the coating method and the composition, viscosity, and solid content of the composition used, the thickness of the dried film is typically 0.1 to 50 micrometers, preferably 0.5 to 50 micrometers. Examples of substrates include silicon wafers, ceramics, gallium arsenide substrates, organic circuit boards, inorganic circuit boards, and substrates on which circuitry is disposed, but are not limited to these.

[0095] For the drying step, the drying temperature is 70–130℃, such as 70–100℃ or 100–130℃; the drying time is 1–5 minutes. Drying is carried out using ovens, heating plates, infrared ovens, etc., at a temperature range of 40℃ to 80℃ for 1 to 10 minutes or through a phased temperature-programmed drying process, the purpose of which is to evaporate the organic solvents.

[0096] For the exposure step, the dried substrate is irradiated with photochemical rays through a mask to photocur the exposed areas of the photosensitive layer. These photochemical rays include electromagnetic waves and particle beams, such as ultraviolet light, X-rays, electron beams, radiation, and ion beams. The light source is not particularly limited and can be, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, an ambient lamp, a carbon rod arc lamp, or a metal halide lamp. The exposure apparatus may include a reduction projection type exposure apparatus, a mask aligner, or a mirror projection type exposure apparatus.

[0097] In the development step, the exposed substrate is developed in a developing solution for patterning. For positive photosensitive resin compositions, the exposed portion dissolves due to the photoacid-generating agent; for negative photosensitive resin compositions, the unexposed portion dissolves. The developing solution can use polar organic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, γ-butyrolactone, etc., and solvents mixed with water, but from an environmental perspective, an alkaline aqueous solution is preferred. The selected alkaline aqueous solution developer includes, but is not limited to, aqueous solutions of tetramethylammonium hydroxide, triethylamine, diethanolamine, dimethylaminoethanol, ethylenediamine, cyclohexylamine, hexamethylenediamine, diethylaminoethanol, methylamine, dimethylamine, etc., with a further preferred option being a 2.38 wt% aqueous solution of tetramethylammonium hydroxide. Development can be performed by directly or by misting the developing solution onto the coated surface, or by immersion in the developing solution. The development time is controlled between 5 s and 600 s, preferably between 5 s and 300 s, depending on the film thickness. After development, when using an alkaline aqueous solution as the developer, it is preferable to use water as the rinsing agent to clean the patterned film and then perform fixing treatment.

[0098] For the curing step, the developed film is heat-treated in a curing oven to completely transform the composition into a heat-resistant film. The heat treatment temperature is preferably 100°C to 400°C; more preferably 150°C to 300°C; particularly preferably 150°C to 250°C. The heat treatment time is controlled from 10 minutes to several hours, more preferably 30 minutes or more and 300 minutes or less; particularly preferably 30 minutes or more and 200 minutes or less. Simultaneously, multi-stage heat treatment can be performed, such as heat curing at 150°C for 30 minutes, followed by heat curing at 250°C for 30 minutes.

[0099] <Applications of Patterned Films>

[0100] A sixth aspect of the present invention provides an application of a patterned film, wherein the patterned film is used as an insulating layer, pixel definition layer, planarization layer, or surface protective film and insulating layer of an organic electroluminescent element, or a semiconductor element, but is not limited to these. The organic electroluminescent element includes, but is not limited to, flexible displays such as OLEDs and TFT-LCDs.

[0101] Example

[0102] The above and other advantages of the present invention can be better understood through the following embodiments, but the following embodiments are not intended to limit the scope of the present invention.

[0103] Code explanation:

[0104] Initiator B2:

[0105] Phenolic hydroxyl compound C1a:

[0106] Phenolic hydroxyl compound C1b:

[0107] Phenolic hydroxyl compound C1c:

[0108] Photopolymerizable unsaturated monomer C2: dipentaerythritol hexaacrylate

[0109] Compound D1 containing two or more epoxy groups:

[0110] Compound D2 containing two or more epoxy groups:

[0111] ODA: 4,4'-Diaminodiphenyl ether

[0112] 6FAP: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane

[0113] SiDA: 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane

[0114] 6FODA: 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl ether

[0115] 6FDA: 2,2'-bis(3,4-dicarboxylic acid phenyl)hexafluoropropane dianhydride

[0116] ODPA: 3,3',4,4'-Diphenyl ether tetracarboxylic dianhydride

[0117] BTDA: 3,3',4,4'-benzophenone tetracarboxylic dianhydride

[0118] CBDA: Cyclobutanetetracarboxylic dianhydride

[0119] Preparation Example 1

[0120] Benzocyclobutene undergoes cycloaddition with coumarin to derive a diamine (compound 1).

[0121]

[0122] In a high-pressure sealed container, 10 mmol of tricyclo[6.2.0.03,6]dec-1,3(6),7-triene (CAS 1610-51-1), 20 mmol of 7-nitrocoumarin, and 10 mL of N,N'-dimethylformamide were added. After reacting at 220 °C for 36 h, the mixture was poured into water, extracted with ethyl acetate, and concentrated to obtain a dinitro compound. This compound was then dissolved in 50 mL of ethanol, and 0.1 g of 10 wt% Pd / C was added. Hydrogen gas was introduced, and the mixture was reacted at 50 °C for 12 h. After filtering off the Pd / C, the mixture was concentrated and recrystallized to obtain compound 1.

[0123] Hydrolysis product of compound 1 (compound 1')

[0124]

[0125] Under nitrogen protection, compound 1 (30 mmol) was dissolved in 100 mL of ethanol, and 10 mL of 0.01 mol / mL NaOH aqueous solution was added dropwise. The temperature was raised to 60 °C and the reaction was carried out for 6 h. The pH was adjusted to 5-6 with dilute hydrochloric acid, extracted with ethyl acetate, and concentrated to obtain compound 1'.

[0126] The alcoholysis product of compound 1 (compound 1”)

[0127]

[0128] Under nitrogen protection, compound 1 (30 mmol) was dissolved in 100 mL of methanol, sodium methoxide (100 mmol) was added, the temperature was raised to 60 °C, and the reaction was carried out for 8 h. The pH was adjusted to 5-6 with dilute hydrochloric acid, extracted with ethyl acetate, and concentrated to obtain compound 1.

[0129] Preparation Example 2

[0130] The diamine derived from the cycloaddition of bisbenzocyclobutene aryl ether and coumarin (compound 2)

[0131]

[0132] Under nitrogen protection, 20 mmol of 4-bromobenzocyclobutene was dissolved in 100 mL of N,N'-dimethylformamide, and 60 mmol of sodium methoxide, 2 mL of pyridine, and 40 mmol of CuCl were added. The mixture was heated to 80 °C and reacted for 12 h. The solution was then poured into water, extracted with ethyl acetate, concentrated, and purified to obtain bisbenzocyclobutene aryl ether.

[0133] The obtained dibenzocyclobutene aryl ether (10 mmol), 7-nitrocoumarin (20 mmol), and N,N'-dimethylformamide (10 mL) were reacted at 210 °C for 40 h. The mixture was then poured into water, extracted with ethyl acetate, and concentrated to obtain a dinitro compound. This compound was then dissolved in 50 mL of ethanol, and 0.1 g of 10 wt% Pd / C was added. Hydrogen gas was bubbled through the solution, and the mixture was reacted at 50 °C for 12 h. The Pd / C was then filtered off, the mixture was concentrated, and recrystallized to obtain compound 2.

[0134] Hydrolysis product of compound 2 (compound 2')

[0135]

[0136] Under nitrogen protection, compound 2 (30 mmol) was dissolved in 100 mL of ethanol, and 10 mL of 0.01 mol / mL NaOH aqueous solution was added dropwise. The temperature was raised to 60 °C and the reaction was carried out for 6 h. The pH was adjusted to 5-6 with dilute hydrochloric acid, extracted with ethyl acetate, and concentrated to obtain compound 2'.

[0137] The alcoholysis product of compound 2 (compound 2”)

[0138]

[0139] Under nitrogen protection, compound 2 (30 mmol) was dissolved in 100 mL of methanol, sodium methoxide (100 mmol) was added dropwise, the temperature was raised to 60 °C, and the reaction was carried out for 6 h. The pH was adjusted to 5-6 with dilute hydrochloric acid, extracted with ethyl acetate, and concentrated to obtain compound 2.

[0140] Preparation Example 3

[0141] The diamine (compound 3) is derived from the cycloaddition of a siloxane bis(enzymophilic compound) with coumarin.

[0142]

[0143] Under nitrogen protection, 10 mmol of a siloxane-containing bis(eneophile) compound, 20 mmol of 7-nitrocoumarin, and 10 mL of N,N'-dimethylformamide were added. The reaction was carried out at 30 °C for 36 h, then poured into water, extracted with ethyl acetate, and concentrated to obtain a dinitro compound. This compound was then dissolved in 50 mL of ethanol, and 0.1 g of 10 wt% Pd / C was added. Hydrogen gas was introduced, and the mixture was pressurized to 10 MPa and reacted at 80 °C for 48 h. The Pd / C was filtered off, the mixture was concentrated, and recrystallized to obtain compound 3.

[0144] Hydrolysis product of compound 3 (compound 3')

[0145]

[0146] Under nitrogen protection, compound 3 (30 mmol) was dissolved in 100 mL of ethanol, 10 mL of 0.01 mol / mL NaOH aqueous solution was added dropwise, the temperature was raised to 50 °C, and the reaction was carried out for 8 h. The pH was adjusted to 6 with dilute hydrochloric acid, extracted with ethyl acetate, and concentrated to obtain compound 3'.

[0147] The alcoholysis product of compound 3 (compound 3”)

[0148]

[0149] Under nitrogen protection, compound 3 (30 mmol) was dissolved in 100 mL of methanol, sodium methoxide (100 mmol) was added, the temperature was raised to 50 °C, and the reaction was carried out for 8 h. The pH was adjusted to 6 with dilute hydrochloric acid, extracted with ethyl acetate, and concentrated to obtain compound 3.

[0150] Preparation Example 4

[0151] The diamine derived from the cycloaddition of sulfone-containing bi(enzymophilic) compound with coumarin (compound 4)

[0152]

[0153] Under nitrogen protection, a sulfone-containing bis(eneophile) compound (10 mmol), 7-nitrocoumarin (20 mmol), and N,N'-dimethylformamide (10 mL) were added. The reaction was carried out at 80 °C for 36 h, then poured into water, extracted with ethyl acetate, and concentrated to obtain a dinitro compound. This compound was then dissolved in 50 mL of ethanol, and 0.1 g of 10 wt% Pd / C was added. Hydrogen gas was introduced, and the mixture was pressurized to 3 MPa and reacted at 40 °C for 12 h. The Pd / C was filtered off, the mixture was concentrated, and recrystallized to obtain compound 4.

[0154] Hydrolysis product of compound 4 (compound 4')

[0155]

[0156] Under nitrogen protection, compound 4 (30 mmol) was dissolved in 100 mL of ethanol, 10 mL of 0.01 mol / mL NaOH aqueous solution was added dropwise, the temperature was raised to 50 °C, and the reaction was carried out for 8 h. The pH was adjusted to 6 with dilute hydrochloric acid, extracted with ethyl acetate, and concentrated to obtain compound 4'.

[0157] The alcoholysis product of compound 4 (compound 4”)

[0158]

[0159] Under nitrogen protection, compound 4 (30 mmol) was dissolved in 100 mL of methanol, sodium methoxide (100 mmol) was added, the temperature was raised to 50 °C, and the reaction was carried out for 8 h. The pH was adjusted to 6 with dilute hydrochloric acid, extracted with ethyl acetate, and concentrated to obtain compound 4.

[0160] Preparation Example 5

[0161] Synthesis of coumarin-like structure-derived amines (compound 5)

[0162]

[0163] The hydrochloride of 7-aminocoumarin (20 mmol) was suspended in 30 mL of n-hexane and irradiated with a 250-450 nm high-pressure mercury lamp for 48 h. After filtration, the [2+2] cyclized product of 7-aminocoumarin hydrochloride was obtained. The pH of this product was adjusted to neutral with a saturated aqueous solution of sodium bicarbonate to obtain the [2+2] cyclized product of 7-aminocoumarin, namely compound (5).

[0164] Hydrolysis product of compound 5 (compound 5')

[0165]

[0166] Under nitrogen protection, compound 5 (31 mmol) was dissolved in 100 mL of ethanol, 10 mL of 0.01 mol / mL NaOH aqueous solution was added dropwise, the temperature was raised to 60 °C, and the reaction was carried out for 6 h. The pH was adjusted to 5-6 with dilute hydrochloric acid, extracted with ethyl acetate, and concentrated to obtain compound 5'.

[0167] The alcoholysis product of compound 5 (compound 5”)

[0168]

[0169] Under nitrogen protection, compound 5 (31 mmol) was dissolved in 100 mL of methanol, sodium methoxide (100 mmol) was added, the temperature was raised to 60 °C, and the reaction was carried out for 8 h. The pH was adjusted to 5-6 with dilute hydrochloric acid, extracted with ethyl acetate, and concentrated to obtain compound 5.

[0170] Preparation Example 6

[0171] Synthesis of diazonoquinone compounds (B1a)

[0172] Under the protection of a dry nitrogen flow, phenol (100 mmol) and 2-diazo-1-naphthoquinone-5-sulfonyl chloride (350 mmol) were dissolved in 500 mL of dioxane. While the system temperature did not exceed 30 °C, a reagent mixture of 50 mL dioxane / 30 mL triethylamine was added dropwise. The reaction was carried out for 3 h. The triethylamine salt was filtered out, and the filtrate was added dropwise to water. The precipitate was filtered and dried to obtain the diazononaphthoquinone compound B1a represented by the following formula.

[0173]

[0174] Preparation Example 7

[0175] Synthesis of diazonoquinone compounds (B1b)

[0176] Under a dry nitrogen atmosphere, bisphenol AF (100 mmol) and 2-diazo-1-naphthoquinone-5-sulfonyl chloride (190 mmol) were dissolved in 400 mL of dioxane. While maintaining a system temperature not exceeding 30 °C, 15 g of triethylamine in 100 mL of THF was added dropwise. After complete addition, the reaction mixture was stirred for 2 hours. The triethylamine salt was filtered, and the filtrate was poured into water. The precipitate was then filtered, collected, and dried to obtain 55 g of the diazonoquinone compound (B1b) represented by the following formula.

[0177]

[0178] Synthesis example 1

[0179] Under a dry nitrogen atmosphere, diamine compound 1 (10 mmol), diamine compound 1 (80 mmol), and m-aminophenol (20 mmol) were dissolved in 200 g of N-methylpyrrolidone (NMP). The mixture was stirred at room temperature for 0.2 h, then 6 FDA (80 mmol) and CBDA (20 mmol) were added, and the mixture was stirred at room temperature for 8 h. The temperature was then raised to 90 °C and reacted for 6 h. The solution was then poured into 2 L of water, and the polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum drying oven at 60 °C for 24 h to obtain resin precursor A1.

[0180] Synthesis Examples 2, 4-6, 8-10, 12-16, 18, 19

[0181] According to the types and amounts of raw materials recorded in Table 1, resin precursors A2, A4-A6, A8-A10, A12-A16, A18, and A19 were prepared using the same preparation method as in Synthesis Example 1.

[0182] Synthesis example 3

[0183] Under a dry nitrogen atmosphere, diamine compound 1 (90 mmol) and m-aminophenol (20 mmol) were dissolved in 200 g of N-methylpyrrolidone (NMP) and stirred at room temperature for 0.2 h. Then, 6 FDA (80 mmol) and CBDA (20 mmol) were added and stirred at room temperature for 24 h. Next, 1.8 mmol of acetic anhydride and 1.8 mmol of pyridine were added, and the reaction was allowed to proceed for 6 h. The solution was then poured into 2 liters of water, and the polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum drying oven at 60 °C for 24 h, and used as polyimide resin precursor A3.

[0184] Synthesis Examples 7, 11, 17

[0185] Resin precursors A7, A11, and A17 were prepared using the same preparation method as in Synthesis Example 2, according to the types and amounts of raw materials listed in Table 1.

[0186] Table 1. Types of raw materials, amounts added, and preparation processes for synthetic examples 1-19

[0187]

[0188] Example 1

[0189] Resin precursor A1 (10.0 g), diazonoquinone compounds B1a (2.5 g), B1b (1.5 g), compound C1 (0.5 g) as additive C, compound D1 (2.0 g) as component D, silane coupling agent 3-aminophenylpropyltrimethoxysilane (0.1 g), surfactant BYK 320 (0.05 g) were dissolved in γ-butyrolactone 22.5 g and ethyl lactate 7.5 g. After stirring at room temperature for 3 h, the mixture was filtered through an organic filter membrane with a pore size of 0.45 μm to obtain the photosensitive resin composition slurry.

[0190] The photosensitive resin composition slurry is coated onto a silicon wafer or glass substrate and baked at 120°C for 2 minutes to form a film. The film is then exposed using a contact / proximity miniature exposure machine, and then developed with a 2.38wt% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, followed by water washing for 30 seconds to obtain a patterned film. Finally, it is heat-treated at 260°C for 1 hour to obtain a cured film with a thickness of approximately 2 micrometers.

[0191] Examples 2-19, Comparative Examples 1-4

[0192] The synthesis methods of Examples 2-19 and Comparative Examples 1-4 are the same as those of Example 1, except that the types and amounts of raw material resin precursor A, photosensitive compound B, additive C, and additive D are different. The specific formulations are shown in Table 2.

[0193] Table 2. Types and amounts of raw materials added in Examples 1-19 and Comparative Examples 1-4

[0194]

[0195] The photosensitive resin compositions prepared in Examples 2-19 and Comparative Examples 1-4 were evaluated for their imaging ability, sensitivity, adhesion, transmittance, residual film rate, water absorption, heat resistance, and chemical resistance. The results are shown in Table 3.

[0196] Table 3 Evaluation indicators of the photosensitive resin compositions obtained in Examples 2-19 and Comparative Examples 1-4

[0197]

[0198] <Evaluation Methods for Photosensitive Resin Compositions>

[0199] (1) Imaging capability evaluation: After exposure, development and cleaning of the films obtained in each embodiment and comparative example, the state of etched lines or grooves was detected by SEM. The best result is that lines or grooves with a width of less than 5 μm can still be clearly etched without bending or defects; the good result is that lines or grooves with a width of 5 to 10 μm can be clearly etched without bending or defects; the poor result is that only lines or grooves with a width of more than 10 μm can be clearly etched without bending or defects.

[0200] (2) Sensitivity assessment

[0201] Using an ACT-8 coating and developing apparatus (manufactured by Tokyo Electron Limited), the photosensitive resin composition slurry was coated onto a 6-inch silicon wafer via spin coating and pre-baked at 120°C for 2 minutes. Exposure was performed using an i-line stepper. After exposure, development was performed using a 2.38 wt% tetramethylammonium (TMAH) aqueous solution for 60 seconds, followed by rinsing with pure water and spin drying. The lowest exposure value D at which the exposed portion completely dissolved was taken as the sensitivity.

[0202] (3) Adhesion evaluation: The patterned film that has been developed was observed with an optical microscope (OLS5000) to see if the lines were peeling off. Peeling off when the line width is ≤2μm was designated as A, peeling off when the line width is 2μm < line width ≤10μm was designated as B, peeling off when the line width is 10μm < line width ≤20μm was designated as C, and peeling off when the line width is >20μm was designated as D.

[0203] (4) Light transmittance (T%)

[0204] The cured films prepared in the aforementioned embodiments and comparative examples were tested using an Agilent UV-Vis spectrophotometer Cary 4000 in transmission mode.

[0205] (5)Residual film rate

[0206] The thickness of the film obtained in each embodiment and comparative example is d1, and the thickness of the corresponding film after development and heat treatment is d2. The residual film rate is calculated as: d2 / d1*100%. A residual film rate of more than 70% after heat treatment is preferred, a residual film rate of 50-70% after heat treatment is good, and a residual film rate of less than 50% after heat treatment is inferior.

[0207] (6) Water absorption

[0208] The cured films (mass greater than 0.5 g) prepared in each example and comparative example were placed in a sealed environment with a relative humidity of 60% for 72 h, and the weight change of the film samples before and after placement was measured. A = (W-W0) / W0×100%, where W A The value W represents the water absorption rate, W represents the weight after water absorption, and W0 represents the weight before water absorption. A <0.5% is considered excellent, 0.5% <W A <1.5% is considered good, W A >1.5% is considered poor.

[0209] (7) Heat resistance

[0210] The cured films prepared in each example and comparative example were analyzed using a thermogravimetric analyzer (TGA, NETZSCH STA2500 Regulus) to determine the residual weight ratio (R) of the samples at 400 degrees Celsius. 400 ). With R 400 >80% is considered excellent, 75% is considered good. <R 400 <80% is considered good, R 400 <75% is considered poor.

[0211] (8) Chemical resistance

[0212] The cured films (area greater than 5*5cm, thickness 2μm) prepared in each example and comparative example were placed in [a specific environment] for 72h, and the film thickness change of the film samples before and after immersion in N-methylpyrrolidone at 40℃ for 120s was measured. ΔTHK=(THK1-THK0) / THK0×100%, where ΔTHK represents the film thickness change rate, THK1 represents the film thickness after immersion, and THK represents the film thickness before immersion. [The text then abruptly shifts to a different topic:] Using W [a specific unit of measurement]... A <1% is considered excellent, 1% <W A <2% is considered good, W A >2% is considered poor.

Claims

1. A compound for use in photosensitive resins, characterized in that, The compound is selected from any one or more of the following structures; ， Where R1 represents any one or more of hydrogen atoms and alkyl groups with ≥1 carbon atom; R2 represents any one or more of hydrogen atoms, alkyl groups with ≥1 carbon atom, alkoxy groups with ≥1 carbon atom, hydroxyl groups, carboxyl groups, and fluorine, chlorine, and bromine substituents; R3 represents any one or more of hydrogen atoms, alkyl groups with ≥1 carbon atom, alkoxy groups with ≥1 carbon atom, and fluorine, chlorine, and bromine substituents; p represents an integer from 0 to 3; q represents an integer from 0 to 1.

2. A heat-resistant resin, formed from the photosensitive resin compound of claim 1, characterized in that, The heat-resistant resin comprises one or more repeating units of the following general formulas (Ⅳ), (Ⅴ) or (Ⅵ): In the structural formulas (Ⅳ), (Ⅴ) or (Ⅵ), Q represents an organic group with 2 to 30 carbon atoms, D represents an organic group with 2 to 50 carbon atoms, and R4 represents any one of a hydrogen atom or a hydrocarbon group having one or more carbon atoms. The repeating unit containing R4 accounts for 40-100 mol% of the total repeating unit of the polyimide resin precursor, and R4 is a hydrogen atom repeating unit, accounting for 30-100 mol% of the total repeating unit containing R4.

3. The heat-resistant resin according to claim 2, characterized in that, The 10-100 mol% of D refers to residues of the compound for photosensitive resins as described in claim 1.

4. A photosensitive resin composition, characterized in that, The photosensitive resin composition comprises the heat-resistant resin as described in claim 2 or 3, a photoacid-producing agent, and a compound containing phenolic hydroxyl groups.

5. A photosensitive resin composition, characterized in that, The photosensitive resin composition comprises the heat-resistant resin as described in claim 2 or 3, a photopolymerization initiator, and a monomer having photopolymerizable unsaturated bonds.

6. A patterned film, obtained by curing the photosensitive resin composition according to claim 4 or 5, characterized in that, The patterned film is used as an insulating layer, pixel definition layer, planarization layer for organic electroluminescent elements, or a surface protective film and insulating layer for semiconductor elements.

7. A display device, characterized in that, Includes the patterned film as described in claim 6.

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