Intrinsic black polymers and their preparation methods, black photoresists and their applications

Abstract

This application discloses an intrinsic black polymer and its preparation method, a black photoresist and its application. The intrinsic black polymer is prepared by reacting a dianhydride monomer and an alcohol, followed by acylation to obtain an intermediate, and then reacting the intermediate with a first diamine monomer and a second diamine monomer. When the intrinsic black polymer of this application is used in a black photoresist, no external light-blocking agent is required, resulting in a black photoresist with excellent optical, mechanical, and electrical properties.

Description

Technical Field

[0001] This application relates to the field of polymer technology, specifically to an intrinsic black polymer and its preparation method, a black photoresist and its application. Background Technology

[0002] Black photoresist is widely used in the display industry as a pixel definition layer (PDL). It forms a black grid pattern through photolithography to separate the individual pixels in the display screen and prevent light leakage or crosstalk. With the continuous development of flexible displays towards low power consumption and the advancement of polarization-free technology (Pol-Less), On Cell Polarizers (OCP), and Color On Encapsulation (COE), black polyimide photoresist has become a key material for the development of flexible display technology. As a black matrix photoresist material, it must meet the following requirements: (1) a high optical density (OD) value, so that a thin resin layer can block light penetration; (2) good mechanical properties to prevent the black grid pattern from falling off or leaking light under stress or heat, thus reducing the screen resolution; (3) good electrical insulation to ensure insulation between light-emitting materials and ensure the accuracy of pixel display. Black photoresist is the optimal raw material for making a black matrix. The black matrix can be obtained by exposing and developing the coated black film.

[0003] Currently, common black photoresists are mainly obtained by doping resins with opacifiers such as carbon black and titanium black. For example, black photoresists can be formed by doping polyimide precursors with black fillers or by doping acrylic acid with black fillers. Although this method can produce photoresists with high OD values, it requires high doping levels, and the opacifiers are prone to agglomeration, which reduces the stability of the black photoresist and easily leads to particulate residues during photolithography and development, thus reducing pattern quality. Preventing opacifier agglomeration further complicates the manufacturing process. As the doping level of opacifier increases, the electrical and mechanical properties of the photoresist decrease significantly, and its adhesion to the substrate also weakens, resulting in a decline in the properties of the prepared black matrix. Summary of the Invention

[0004] The purpose of this application is to overcome the shortcomings of the prior art and provide an intrinsic black polymer that eliminates the need for external light-blocking agents when preparing black photoresist, resulting in black photoresist with excellent optical, mechanical, and electrical properties. This application also provides a method for preparing the intrinsic black polymer, a black photoresist, and its applications.

[0005] To achieve the above objectives, the technical solution adopted in this application is: an intrinsically black polymer, the structural formula of which is as follows:

[0006]

[0007] R1 to R6 are selected from one of hydrogen, hydroxyl, carboxyl, amino, methyl, methoxy, carbonyl, ester, phenyl and 4-aminophenylamino, respectively;

[0008] R7 is a residue formed after the reaction of hydrogen or alcohol;

[0009] R8 is selected from one of benzene ring, biphenyl, biphenyl ether, biphenyl ketone, biphenyl sulfide and 4,4-hexafluoroisopropylphthalene;

[0010] R9, R 11 ~R 17 Each group is selected from one of hydrogen, hydroxyl, carboxyl, methyl, methoxy, methyl, trifluoromethyl, carbonyl, ester, and phenyl.

[0011] R 10 It is selected from one of the following: single bond, ether group, amide group, mercapto group, methylene group, aliphatic group with 1 to 6 carbon atoms, hexafluoroisopropylidene group, or hexafluoroisopropyl group;

[0012] The value of m ranges from 3 to 10, and the value of n ranges from 4 to 12.

[0013] This application also provides a method for preparing the above-mentioned intrinsic black polymer, comprising: reacting a dianhydride monomer with an alcohol to obtain an ester; reacting the ester with an acyl chloride reagent to obtain an intermediate; and reacting the intermediate, a first diamine monomer, and a second diamine monomer to obtain the intrinsic black polymer.

[0014] In some embodiments of this application, the dianhydride monomer includes at least one of 4,4'-oxophthalic anhydride, pyromellitic dianhydride, hexafluorodianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, and 3,3',4,4'-benzophenone tetracarboxylic dianhydride; and / or, the alcohol includes n-butanol and / or ethanol.

[0015] In some embodiments of this application, the first diamine monomer comprises 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone; and / or, the second diamine monomer comprises at least one of 4,4'-diaminodiphenyl ether, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2'-bis(trifluoromethyl)-4,4'-diaminophenyl ether, 3,3'-dichlorobenzidine, and 4,4'-diaminobenzoylaniline.

[0016] In some embodiments of this application, the molar ratio of the dianhydride monomer to the alcohol is (0.55-0.63):1; and / or, the molar ratio of the intermediate, the first diamine monomer, and the second diamine monomer is 1.08:(0.4-0.5):(0.5-0.6).

[0017] In some embodiments of this application, the reaction temperature of the dianhydride monomer and the alcohol is 40°C to 80°C; and / or, the reaction temperature of the intermediate, the first diamine monomer and the second diamine monomer is 0°C to 10°C.

[0018] In some embodiments of this application, the dianhydride monomer and the alcohol react in a first solvent, the first solvent comprising at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, γ-butyrolactone, and dimethyl sulfoxide; and / or, the catalyst for the reaction of the dianhydride monomer and the alcohol comprises pyridine; and / or, the acyl chloride reagent comprises dichlorosulfoxide; and / or, when the intermediate, the first diamine monomer, and the second diamine monomer react, an organic base is also added to the reaction system.

[0019] This application also provides a black photoresist, comprising, by weight: 5 to 35 parts of the above-mentioned intrinsic black polymer; 0.5 to 5 parts of photoacid generator; 2 to 6 parts of solvent inhibitor; and 60 to 90 parts of second solvent.

[0020] In some embodiments of this application, the photoacid generator includes at least one of diazonium salt, phosphonium salt, sulfonium salt, monazine salt, imide sulfonate, oxime sulfonate, diazonium disulfone, disulfone, and o-nitrobenzyl sulfonate; and / or, the solvent inhibitor is a hydroxyl-containing compound with 2 to 4 tert-butyl carbonate protecting groups; and / or, the second solvent includes at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, γ-butyrolactone, dimethyl sulfoxide, ethyl acetate, and methanol.

[0021] This application also provides the application of the described black photoresist in a black matrix.

[0022] Compared with the prior art, the intrinsic black polymer and its preparation method, black photoresist and their applications in this application have the following beneficial effects:

[0023] The intrinsic black polymer of this application introduces black diamine monomer segments, which eliminates the need for doping with opacifiers when preparing black photoresists. This directly solves the problems of agglomeration and performance degradation that exist in the production of doped photoresists. It also avoids the phenomenon of particulate residues in doped photoresists during photolithography and development, thereby improving pattern quality. At the same time, it also avoids the problem of decreased adhesion between photoresist and substrate due to excessive addition of opacifiers.

[0024] The intrinsic black polymer of this application also incorporates diamine monomer segments that are soluble in aqueous organic alkali solutions. Therefore, when the black photoresist prepared using this intrinsic black polymer is used as a positive photoresist, it has good solubility in aqueous organic alkali solutions. Consequently, aqueous organic alkali solutions can be used instead of organic solvents as the developer for the black photoresist, thereby improving the environmental friendliness of the photoresist.

[0025] The preparation method of the intrinsic black polymer of this application uses readily available raw materials, and the preparation steps and process conditions are simple, making it easy to promote industrialization.

[0026] When using the intrinsic black polymer of this application to prepare black photoresist, no additional opacifier is required, which can effectively avoid a series of problems caused by the introduction of opacifier, and significantly improve the optical properties, mechanical properties, electrical properties, stability and adhesion to the substrate of black photoresist. Attached Figure Description

[0027] The following accompanying drawings describe in detail the exemplary embodiments disclosed in this application. The same reference numerals denote similar structures in several views of the drawings. Those skilled in the art will understand that these embodiments are non-limiting and exemplary, and the drawings are for illustrative purposes only and are not intended to limit the scope of this application. Other embodiments may similarly fulfill the inventive intent of this application. It should be understood that the drawings are not drawn to scale. Wherein:

[0028] Figure 1 The structural formula of the intrinsic black polymer in this application embodiment is shown below. Detailed Implementation

[0029] The following description provides specific application scenarios and requirements for this application, intended to enable those skilled in the art to make and use the content of this application. Various partial modifications to the disclosed embodiments will be apparent to those skilled in the art, and the general principles defined herein can be applied to other embodiments and applications without departing from the spirit and scope of this application. Therefore, this application is not limited to the embodiments shown, but rather to the widest scope consistent with the claims.

[0030] Currently, common black photoresists are mainly obtained by doping resin with opacifiers. In order to obtain a high OD value, a large amount of opacifier needs to be added, but this reduces other properties of the black photoresist, such as stability, electrical properties, mechanical properties, and adhesion to the substrate.

[0031] Based on this, the first aspect of this application provides an intrinsically black polymer, the structural formula of which is attached. Figure 1 As shown, R1 to R6 are selected from one of hydrogen, hydroxyl, carboxyl, amino, methyl, methoxy, carbonyl, ester, phenyl, and 4-aminophenylamino, respectively. R7 is selected from hydrogen or a residue after the reaction of an alcohol. R8 is selected from one of a benzene ring, biphenyl, biphenyl ether, biphenyl ketone, biphenyl sulfide, and 4,4-hexafluoroisopropylphthalene. R9, R 11 ~R 17 Each group is selected from one of the following: hydrogen, hydroxyl, carboxyl, methyl, methoxy, methyl, trifluoromethyl, carbonyl, ester, and phenyl. R 10 It is selected from one of the following: single bond, ether group, amide group, mercapto group, methylene group, aliphatic group with 1 to 6 carbon atoms, hexafluoroisopropylidene group, or hexafluoroisopropyl group. The value of m is 3 to 10, preferably 4 to 8, and the value of n is 4 to 12, preferably 5 to 10.

[0032] The intrinsic black polymer in the embodiments of this application includes both black diamine monomer segment I and diamine monomer segment II, which is soluble in aqueous organic base solutions:

[0033]

[0034] The introduction of the black diamine monomer segment I eliminates the need for doping with a light-blocking agent when using the intrinsic black polymer to prepare black photoresist, thus avoiding the various problems associated with adding a light-blocking agent. The introduction of the diamine monomer segment II, which is soluble in an organic alkali aqueous solution, improves the solubility of the intrinsic black polymer in organic alkali solutions. When using the intrinsic black polymer to prepare black photoresist, an organic alkali aqueous solution can be used instead of an organic solvent as the developer, thereby improving the environmental friendliness of the photoresist.

[0035] In a preferred embodiment of the intrinsically black polymer of this application, the structural formula of the intrinsically black polymer is:

[0036]

[0037] Where R is a residue resulting from the reaction of hydrogen or ethanol.

[0038] The second aspect of this application provides a method for preparing the above-mentioned intrinsic black polymer, which has simple process steps and is easy to apply industrially.

[0039] In some embodiments, the preparation method of the intrinsically black polymer includes the following steps:

[0040] S1: Reacts dianhydride monomers with alcohols to obtain esterified products;

[0041] S2: React the esterified product with an acyl chloride reagent to obtain an intermediate;

[0042] S3: React the intermediate, the first diamine monomer, and the second diamine monomer to obtain the intrinsic black polymer.

[0043] In a preferred embodiment of the preparation method of this application, in step S1, the dianhydride monomer includes at least one selected from 4,4'-oxydiphthalic anhydride (ODPA), pyromellitic dianhydride (PMDA), hexafluorodianhydride (6FDA), 2,3,3',4'-biphenyltetracarboxylic dianhydride (BPDA), and 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA). In a more preferred embodiment of the preparation method of this application, the dianhydride monomer is 4,4'-oxydiphthalic anhydride (BPDA).

[0044] In a preferred embodiment of the preparation method of this application, in step S1, the alcohol includes n-butanol and / or ethanol. In a more preferred embodiment of the preparation method of this application, the alcohol is ethanol.

[0045] In a preferred embodiment of the preparation method of this application, in step S1, the dianhydride monomer and the alcohol react in a first solvent, and the resulting ester is dissolved in the first solvent to form a first system, wherein the first solvent includes at least one selected from N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, γ-butyrolactone, and dimethyl sulfoxide. In a more preferred embodiment of the preparation method of this application, the first solvent is N-methylpyrrolidone.

[0046] In a preferred embodiment of the preparation method of this application, the catalyst for the reaction of the dianhydride monomer and the alcohol includes pyridine.

[0047] In a preferred embodiment of the preparation method of this application, in step S1, the molar ratio of the dianhydride monomer to the alcohol is (0.55–0.63):1. By controlling the molar ratio of the dianhydride monomer to the alcohol to keep the esterification rate within an appropriate range, the prepared intrinsic black polymer can have a suitable dissolution rate in an organic alkaline aqueous solution, thereby enabling the black photoresist prepared using this intrinsic black polymer to have better exposure and development performance.

[0048] In a preferred embodiment of the preparation method of this application, in step S1, the reaction temperature of the dianhydride monomer and the alcohol is 40°C to 80°C. More preferably, the reaction temperature of the dianhydride monomer and the alcohol is 55°C, and the reaction time is 8 hours.

[0049] In a preferred embodiment of the preparation method of this application, in step S2, the acyl chloride reagent is sulfoxide (SOCl2).

[0050] In a preferred embodiment of the preparation method of this application, in step S2, the reaction temperature of the esterified product and the acyl chloride reagent is 0°C to 10°C.

[0051] In a preferred embodiment of the preparation method of this application, in step S2, the intermediate has the following structural formula:

[0052]

[0053] Wherein, R1' is hydrogen or a residue after the reaction of the alcohol, and R8' is selected from one of benzene ring, biphenyl, biphenyl ether, biphenyl ketone, biphenyl sulfide and 4,4-hexafluoroisopropylphthalene.

[0054] In a preferred embodiment of the preparation method of this application, in step S2, the first system obtained in step S1 is placed in an ice-water bath and cooled to the temperature of the acyl chloride reaction. Then, the acyl chloride reagent is slowly added dropwise to the first system. After the addition is completed, the system is restored to room temperature and reacted for a certain time, preferably 4 hours, to obtain a reaction system containing an intermediate.

[0055] In a preferred embodiment of the preparation method of this application, in step S3, the first diamine monomer is a black diamine monomer, and the black diamine monomer is 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone, the structural formula of which is as follows:

[0056]

[0057] The 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone can be prepared by the following method: nitrating 1,8-dihydroxy-9,10-anthraquinone to 1,8-dihydroxy-2,4,5,7-tetranitro-9,10-anthraquinone in the presence of concentrated sulfuric acid and concentrated nitric acid, and then reducing the nitro group to an amino group to obtain 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone; or by the following method: nitrating 1,8-dihydroxy-4,5-dinitro-9,10-anthraquinone to 1,8-dihydroxy-2,4,5,7-tetranitro-9,10-anthraquinone in the presence of concentrated sulfuric acid and concentrated nitric acid, and then reducing the nitro group to an amino group to obtain 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone.

[0058] In a preferred embodiment of the preparation method of this application, in step S3, the second diamine monomer is a diamine monomer soluble in an aqueous organic base solution, and the second diamine monomer includes at least one selected from 4,4'-diaminodiphenyl ether (ODA), 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (TFMB), 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP), 2,2'-bis(trifluoromethyl)-4,4'-diaminophenyl ether (6FODA), 3,3'-dichlorobenzidine (DCB), and 4,4'-diaminobenzoylaniline (DABA). More preferably, the second diamine monomer is 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 2,2'-bis(trifluoromethyl)-4,4'-diaminophenyl ether.

[0059] In a preferred embodiment of the preparation method of this application, in step S3, the molar ratio of the intermediate, the first diamine monomer, and the second diamine monomer is 1.08:(0.4-0.5):(0.5-0.6).

[0060] In a preferred embodiment of the preparation method of this application, in step S3, the reaction temperature of the intermediate, the first diamine monomer, and the second diamine monomer is 0°C to 10°C, preferably 0°C. The reaction time is preferably 4 hours.

[0061] In a preferred embodiment of the preparation method of this application, in step S3, when the intermediate, the first diamine monomer, and the second diamine monomer react, an organic base is also added to the reaction system. The organic base is preferably triethylamine. The organic base can neutralize the hydrogen chloride produced by the reaction of the intermediate with the first and second diamine monomers, thus promoting the reaction in the forward direction.

[0062] In a preferred embodiment of the preparation method of this application, step S3 includes the following steps:

[0063] S31: Dissolve the first diamine monomer, the second diamine monomer, and the organic base in a third solvent to obtain a third system;

[0064] S32: Lower the temperature of the third system to the reaction temperature, slowly add the second system with intermediates obtained in step S2 to the third system and react to obtain the fourth system with the intrinsic black polymer.

[0065] In a preferred embodiment of the preparation method of this application, in step S31, the third solvent is preferably N-methylpyrrolidone.

[0066] In a preferred embodiment of the preparation method of this application, after step S32, step S33 is further included: the fourth system is dropped into deionized water to precipitate the precipitate, and after being repeatedly washed with deionized water several times, it is freeze-dried to obtain the intrinsic black polymer.

[0067] In the preparation method of this application, the polymer has intrinsic black properties by introducing a black diamine monomer. By introducing a second diamine monomer that is soluble in an aqueous organic base solution and controlling an appropriate esterification rate, the polymer can be well dissolved in an aqueous organic base solution.

[0068] A third aspect of this application provides a black photoresist, comprising, by weight: 5 to 35 parts of the aforementioned intrinsic black polymer; 0.5 to 5 parts of a photoacid generator; 2 to 6 parts of an inhibitor; and 60 to 90 parts of a second solvent.

[0069] The photoacid generator described in this application refers to a compound that generates acid upon irradiation by active light or radiation. In a preferred embodiment of the black photoresist of this application, the photoacid generator includes at least one selected from diazoonium salts, phosphonium salts, sulfonium salts, monazine salts, imide sulfonates, oxime sulfonates, disulfones, disulfones, and o-nitrobenzyl sulfonates. More preferably, the photoacid generator includes (Z,E)-2-(4-methoxyphenyl)([((4-methylphenyl)sulfonyl)oxy]imino)acetonitrile.

[0070] In a preferred embodiment of the black photoresist of this application, the solvent inhibitor is a hydroxyl-containing compound with 2 to 4 tert-butyl carbonate protecting groups. This hydroxyl-containing compound with 2 to 4 tert-butyl carbonate protecting groups is insoluble in alkaline water, but can be decomposed by acid catalysis generated by a photoacid generator to produce a substance soluble in an organic alkaline aqueous solution. More preferably, the solvent inhibitor is selected from compounds with the following structural formulas:

[0071]

[0072] More preferably, the solvent is 9,9-bis[4-(tert-butoxycarbonyloxy)phenyl]fluorene.

[0073] The 9,9-bis[4-(tert-butoxycarbonyloxy)phenyl]fluorene can be prepared by the following method: Di-tert-butyl dicarbonate is added to a system comprising 9,9'-bis(4-hydroxyphenyl)fluorene, tetrahydrofuran, and 4-(N,N-dimethylamino)pyridine to initiate a reaction. The resulting system is then added dropwise to a solvent comprising methanol and water (volume ratio, for example, 4:1), the crude product is recovered, and the crude product is recrystallized, filtered, and dried to obtain the 9,9-bis[4-(tert-butoxycarbonyloxy)phenyl]fluorene. Recrystallization can be performed using a mixed solvent of hexane and tetrahydrofuran in a volume ratio of 5:1.

[0074] In a preferred embodiment of the black photoresist of this application, the second solvent includes at least one selected from N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, γ-butyrolactone, dimethyl sulfoxide, ethyl acetate, and methanol. More preferably, the second solvent is N-methylpyrrolidone.

[0075] In preparing the black photoresist, the intrinsic black polymer, the photoacid generator, the solvent inhibitor, and the second solvent of this application are mixed evenly, for example, in a planetary gravity mixer (Mianyang Shinuo Technology Co., Ltd.). After being mixed evenly, the mixture is in a solution state, thus obtaining the black photoresist.

[0076] The fourth aspect of this application also provides the application of the aforementioned black photoresist in a black matrix.

[0077] When preparing a black matrix using the black photoresist described in this application, the following method can be used, for example: the black photoresist is uniformly coated onto a substrate (e.g., a wafer), then pre-baked, exposed on a photolithography device, and then developed with a developer (e.g., using a 2.38% tetramethylammonium hydroxide aqueous solution). The developer is then removed by rinsing with deionized water and post-baked to obtain the black matrix. Post-baking can be performed in a high-temperature nitrogen-filled oven for curing.

[0078] Example

[0079] The technical solution of this application will be clearly and completely described below with reference to the embodiments of this application. Unless otherwise specified, the reagents and raw materials used can be purchased commercially. Experimental methods in the following embodiments that do not specify specific conditions are performed according to conventional methods and conditions, or according to the product instructions.

[0080] Example 1

[0081] Preparation of intrinsic black polymers:

[0082] (1) Add 30.1534g of ODPA, 72.8924g of N-methylpyrrolidone, 8.0604g of ethanol and 0.5782g of pyridine to a 250mL three-necked flask, heat to 55℃ and react for 8 hours to obtain the first system;

[0083] (2) Cool the first system in an ice-water bath, slowly add 22.8388 g of thionyl chloride dropwise to the first system, and after the addition is completed, restore the reaction to room temperature for 4 hours to obtain the second system;

[0084] (3) Add 10.8097g of 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone, 16.4817g of 6FAP, 3.0261g of 6FODA, 21.6064g of triethylamine and 170.0822g of N-methylpyrrolidone to a 500mL three-necked flask, and after complete dissolution, obtain the third system;

[0085] (4) Cool the third system to 0°C, slowly add the second system dropwise to the third system, and react for 4 hours to obtain the fourth system;

[0086] (5) The fourth system was dropped into deionized water to precipitate the precipitate. After repeated washing with deionized water, the precipitate was freeze-dried to obtain the intrinsic black polymer.

[0087] Preparation of black photoresist:

[0088] 24 parts of the intrinsic black polymer prepared in this embodiment, 1 part of (Z,E)-2-(4-methoxyphenyl)([((4-methylphenyl)sulfonyl)oxy]imino)acetonitrile, 4 parts of 9,9-bis[4-(tert-butoxycarbonyl)phenyl]fluorene and 71 parts of N-methylpyrrolidone were mixed evenly to obtain a black photoresist.

[0089] Preparation of the black matrix:

[0090] The black photoresist of this embodiment is uniformly coated on a quartz wafer, then baked at 120°C for 3 minutes, exposed on a photolithography device, and then developed with a 2.38% tetramethylammonium hydroxide aqueous solution. The developer is removed by rinsing with deionized water, and then cured in a high-temperature nitrogen-filled oven under nitrogen atmosphere by increasing the temperature from room temperature to 200°C at a rate of 20°C / min and holding for 60 minutes, and then increasing the temperature to 350°C at a rate of 10°C / min and holding for 60 minutes.

[0091] Example 2

[0092] Preparation of intrinsic black polymers:

[0093] (1) Add 0.1534 g of ODPA, 72.2607 g of N-methylpyrrolidone, 8.0604 g of ethanol and 0.5782 g of pyridine to a 250 mL three-necked flask, heat to 55 °C and react for 8 hours to obtain the first system;

[0094] (2) Cool the first system in an ice-water bath, slowly add 22.8388 g of thionyl chloride dropwise to the first system, and after the addition is completed, restore the reaction to room temperature for 4 hours to obtain the second system;

[0095] (3) Add 13.5122 g of 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone, 13.1854 g of 6FAP, 3.0261 g of 6FODA, 19.4458 g of triethylamine and 168.6082 g of N-methylpyrrolidone to a 500 mL three-necked flask, and after complete dissolution, obtain the third system;

[0096] (4) Cool the third system to 0°C, slowly add the second system dropwise to the third system, and react for 4 hours to obtain the fourth system;

[0097] (5) The fourth system was dropped into deionized water to precipitate the precipitate. After repeated washing with deionized water, the precipitate was freeze-dried to obtain the intrinsic black polymer.

[0098] Preparation of black photoresist:

[0099] 24 parts of the intrinsic black polymer prepared in this embodiment, 1 part of (Z,E)-2-(4-methoxyphenyl)([((4-methylphenyl)sulfonyl)oxy]imino)acetonitrile, 4 parts of 9,9-bis[4-(tert-butoxycarbonyl)phenyl]fluorene and 71 parts of N-methylpyrrolidone were mixed evenly to obtain a black photoresist.

[0100] Preparation of the black matrix:

[0101] The black photoresist of this embodiment is uniformly coated on a quartz wafer, then baked at 120°C for 3 minutes, exposed on a photolithography device, and then developed with a 2.38% tetramethylammonium hydroxide aqueous solution. The developer is removed by rinsing with deionized water, and then cured in a high-temperature nitrogen-filled oven under nitrogen atmosphere by increasing the temperature from room temperature to 200°C at a rate of 20°C / min and holding for 60 minutes, and then increasing the temperature to 350°C at a rate of 10°C / min and holding for 60 minutes.

[0102] Example 3

[0103] Preparation of intrinsic black polymers:

[0104] (1) Add 30.1534g of ODPA, 71.9398g of N-methylpyrrolidone, 7.1648g of ethanol and 0.5782g of pyridine to a 250mL three-necked flask, heat to 55℃ and react for 8 hours to obtain the first system;

[0105] (2) Cool the first system in an ice-water bath, slowly add 20.3011 g of thionyl chloride dropwise to the first system, and after the addition is complete, restore the reaction to room temperature for 4 hours to obtain the second system;

[0106] (3) Add 10.8097g of 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone, 16.4817g of 6FAP, 3.0261g of 6FODA, 17.2851g of triethylamine and 167.8595g of N-methylpyrrolidone to a 500mL three-necked flask, and dissolve completely to obtain the third system;

[0107] (4) Cool the third system to 0°C, slowly add the second system dropwise to the third system, and react for 4 hours to obtain the fourth system;

[0108] (5) The fourth system was dropped into deionized water to precipitate the precipitate. After repeated washing with deionized water, the precipitate was freeze-dried to obtain the intrinsic black polymer.

[0109] Preparation of black photoresist:

[0110] 24 parts of the intrinsic black polymer prepared in this embodiment, 1 part of (Z,E)-2-(4-methoxyphenyl)([((4-methylphenyl)sulfonyl)oxy]imino)acetonitrile, 4 parts of 9,9-bis[4-(tert-butoxycarbonyl)phenyl]fluorene and 71 parts of N-methylpyrrolidone were mixed evenly to obtain a black photoresist.

[0111] Preparation of the black matrix:

[0112] The black photoresist of this embodiment is uniformly coated on a quartz wafer, then baked at 120°C for 3 minutes, exposed on a photolithography device, and then developed with a 2.38% tetramethylammonium hydroxide aqueous solution. The developer is removed by rinsing with deionized water, and then cured in a high-temperature nitrogen-filled oven under nitrogen atmosphere by increasing the temperature from room temperature to 200°C at a rate of 20°C / min and holding for 60 minutes, and then increasing the temperature to 350°C at a rate of 10°C / min and holding for 60 minutes.

[0113] Example 4

[0114] Preparation of intrinsic black polymers:

[0115] (1) Add 30.1534g of ODPA, 71.3081g of N-methylpyrrolidone, 7.1648g of ethanol and 0.5782g of pyridine to a 250mL three-necked flask, heat to 55℃ and react for 8 hours to obtain the first system;

[0116] (2) Cool the first system in an ice-water bath, slowly add 20.3011 g of thionyl chloride dropwise to the first system, and after the addition is complete, restore the reaction to room temperature for 4 hours to obtain the second system;

[0117] (3) Add 13.5122 g of 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone, 13.1854 g of 6FAP, 3.0261 g of 6FODA, 17.2851 g of triethylamine and 166.3855 g of N-methylpyrrolidone to a 500 mL three-necked flask, and dissolve completely to obtain the third system;

[0118] (4) Cool the third system to 0°C, slowly add the second system dropwise to the third system, and react for 4 hours to obtain the fourth system;

[0119] (5) The fourth system was dropped into deionized water to precipitate the precipitate. After repeated washing with deionized water, the precipitate was freeze-dried to obtain the intrinsic black polymer.

[0120] Preparation of black photoresist:

[0121] 24 parts of the intrinsic black polymer prepared in this embodiment, 1 part of (Z,E)-2-(4-methoxyphenyl)([((4-methylphenyl)sulfonyl)oxy]imino)acetonitrile, 4 parts of 9,9-bis[4-(tert-butoxycarbonyl)phenyl]fluorene and 71 parts of N-methylpyrrolidone were mixed evenly to obtain a black photoresist.

[0122] Preparation of the black matrix:

[0123] The black photoresist of this embodiment is uniformly coated on a quartz wafer, then baked at 120°C for 3 minutes, exposed on a photolithography device, and then developed with a 2.38% tetramethylammonium hydroxide aqueous solution. The developer is removed by rinsing with deionized water, and then cured in a high-temperature nitrogen-filled oven under nitrogen atmosphere by increasing the temperature from room temperature to 200°C at a rate of 20°C / min and holding for 60 minutes, and then increasing the temperature to 350°C at a rate of 10°C / min and holding for 60 minutes.

[0124] Example 5

[0125] Five parts of the intrinsic black polymer prepared in Example 2, 0.5 parts of (Z,E)-2-(4-methoxyphenyl)([((4-methylphenyl)sulfonyl)oxy]imino)acetonitrile, 2 parts of 9,9-bis[4-(tert-butoxycarbonyl)phenyl]fluorene, and 60 parts of N-methylpyrrolidone were mixed evenly to obtain a black photoresist.

[0126] Preparation of the black matrix:

[0127] The black photoresist of this embodiment is uniformly coated on a quartz wafer, then baked at 120°C for 3 minutes, exposed on a photolithography device, and then developed with a 2.38% tetramethylammonium hydroxide aqueous solution. The developer is removed by rinsing with deionized water, and then cured in a high-temperature nitrogen-filled oven under nitrogen atmosphere by increasing the temperature from room temperature to 200°C at a rate of 20°C / min and holding for 60 minutes, and then increasing the temperature to 350°C at a rate of 10°C / min and holding for 60 minutes.

[0128] Example 6

[0129] The intrinsic black polymer prepared in Example 2, 5 parts of (Z,E)-2-(4-methoxyphenyl)([((4-methylphenyl)sulfonyl)oxy]imino)acetonitrile, 6 parts of 9,9-bis[4-(tert-butoxycarbonyl)phenyl]fluorene and 90 parts of N-methylpyrrolidone were mixed evenly to obtain a black photoresist.

[0130] Preparation of the black matrix:

[0131] The black photoresist of this embodiment is uniformly coated on a quartz wafer, then baked at 120°C for 3 minutes, exposed on a photolithography device, and then developed with a 2.38% tetramethylammonium hydroxide aqueous solution. The developer is removed by rinsing with deionized water, and then cured in a high-temperature nitrogen-filled oven under nitrogen atmosphere by increasing the temperature from room temperature to 200°C at a rate of 20°C / min and holding for 60 minutes, and then increasing the temperature to 350°C at a rate of 10°C / min and holding for 60 minutes.

[0132] Comparative Example 1

[0133] Polymer preparation:

[0134] (1) Add 30.1534g of ODPA, 74.2606g of N-methylpyrrolidone, 9.3468g of isopropanol and 0.5782g of pyridine to a 250mL three-necked flask, heat to 90℃ and react for 8 hours to obtain the first system;

[0135] (2) Cool the first system in an ice-water bath, slowly add 20.3011 g of thionyl chloride dropwise to the first system, and after the addition is complete, restore the reaction to room temperature for 4 hours to obtain the second system;

[0136] (3) Add 10.8097g of 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone, 16.4817g of 6FAP, 3.0261g of 6FODA, 17.2851g of triethylamine and 173.2747g of N-methylpyrrolidone to a 500mL three-necked flask, and after complete dissolution, obtain the third system;

[0137] (4) Cool the third system to 0°C, slowly add the second system dropwise to the third system, and react for 4 hours to obtain the fourth system;

[0138] (5) The fourth system was dropped into deionized water to precipitate the precipitate. After repeated washing with deionized water, the precipitate was freeze-dried to obtain the polymer.

[0139] Preparation of black photoresist:

[0140] 24 parts of the polymer prepared in this comparative example, 1 part of (Z,E)-2-(4-methoxyphenyl)([((4-methylphenyl)sulfonyl)oxy]imino)acetonitrile, 4 parts of 9,9-bis[4-(tert-butoxycarbonyl)phenyl]fluorene and 71 parts of N-methylpyrrolidone were mixed evenly to obtain a black photoresist.

[0141] Preparation of the black matrix:

[0142] The black photoresist prepared in this comparative example was uniformly coated on a quartz wafer, then baked at 120°C for 3 minutes, exposed on a photolithography device, and then developed with a 2.38% tetramethylammonium hydroxide aqueous solution. The developer was removed by rinsing with deionized water, and then cured in a high-temperature nitrogen-filled oven under nitrogen atmosphere by increasing the temperature from room temperature to 200°C at a rate of 20°C / min and holding for 60 minutes, and then increasing the temperature to 350°C at a rate of 10°C / min and holding for 60 minutes.

[0143] Comparative Example 2

[0144] The polymer prepared using Comparative Example 1;

[0145] Preparation of black photoresist:

[0146] 24 parts of the polymer prepared in Comparative Example 1, 4 parts of phenylacetonitrile, 2-methyl-A-[2-[[(propylsulfonyl)oxy]imino]-3(2H)-thiophene, 4 parts of 9,9-bis[4-(tert-butoxycarbonyl)phenyl]fluorene and 70 parts of N-methylpyrrolidone were mixed evenly to obtain a black photoresist.

[0147] Preparation of the black matrix:

[0148] The black photoresist prepared in this comparative example was uniformly coated on a quartz wafer, then baked at 120°C for 3 minutes, exposed on a photolithography device, and then developed with a 2.38% tetramethylammonium hydroxide aqueous solution. The developer was removed by rinsing with deionized water, and then cured in a high-temperature nitrogen-filled oven under nitrogen atmosphere by increasing the temperature from room temperature to 200°C at a rate of 20°C / min and holding for 60 minutes, and then increasing the temperature to 350°C at a rate of 10°C / min and holding for 60 minutes.

[0149] Comparative Example 3

[0150] The polymer prepared using Comparative Example 1;

[0151] Preparation of black photoresist:

[0152] 24 parts of the polymer prepared in Comparative Example 1, 2 parts of a salt of bis[4-(1,1-dimethylethyl)phenyl]iodonium and trifluoromethanesulfonic acid (1:1), 4 parts of 9,9-bis[4-(tert-butoxycarbonyloxy)phenyl]fluorene and 70 parts of N-methylpyrrolidone were mixed evenly to obtain a black photoresist.

[0153] Preparation of the black matrix:

[0154] The black photoresist prepared in this comparative example was uniformly coated on a quartz wafer, then baked at 120°C for 3 minutes, exposed on a photolithography device, and then developed with a 2.38% tetramethylammonium hydroxide aqueous solution. The developer was removed by rinsing with deionized water, and then cured in a high-temperature nitrogen-filled oven under nitrogen atmosphere by increasing the temperature from room temperature to 200°C at a rate of 20°C / min and holding for 60 minutes, and then increasing the temperature to 350°C at a rate of 10°C / min and holding for 60 minutes.

[0155] Comparative Example 4

[0156] Polymer preparation:

[0157] (1) Add 27.9198g of ODPA, 89.7195g of N-methylpyrrolidone, 26.1144g of color alcohol and 0.5353g of pyridine to a 250mL three-necked flask, heat to 70℃ and react for 8 hours to obtain the first system;

[0158] (2) Cool the first system in an ice-water bath, slowly add 21.1470 g of thionyl chloride dropwise to the first system, and after the addition is complete, restore the reaction to room temperature for 4 hours to obtain the second system;

[0159] (3) Add 10.8097g of 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone, 16.4817g of 6FAP, 3.0261g of 6FODA, 18.0053g of triethylamine and 209.3456g of N-methylpyrrolidone to a 500mL three-necked flask, and dissolve completely to obtain the third system;

[0160] (4) Cool the third system to 0°C, slowly add the second system dropwise to the third system, and react for 4 hours to obtain the fourth system;

[0161] (5) The fourth system was dropped into deionized water to precipitate the precipitate. After repeated washing with deionized water, the precipitate was freeze-dried to obtain the polymer.

[0162] Preparation of black photoresist:

[0163] 24 parts of the polymer prepared in this comparative ratio, 1 part of (Z,E)-2-(4-methoxyphenyl)([((4-methylphenyl)sulfonyl)oxy]imino)acetonitrile, 4 parts of 9,9-bis[4-(tert-butoxycarbonyl)phenyl]fluorene and 71 parts of N-methylpyrrolidone were mixed evenly to obtain a black photoresist.

[0164] Preparation of the black matrix:

[0165] The black photoresist prepared in this comparative example was uniformly coated on a quartz wafer, then baked at 120°C for 3 minutes, exposed on a photolithography device, and then developed with a 2.38% tetramethylammonium hydroxide aqueous solution. The developer was removed by rinsing with deionized water, and then cured in a high-temperature nitrogen-filled oven under nitrogen atmosphere by increasing the temperature from room temperature to 200°C at a rate of 20°C / min and holding for 60 minutes, and then increasing the temperature to 350°C at a rate of 10°C / min and holding for 60 minutes.

[0166] Comparative Example 5

[0167] Polymer preparation:

[0168] (1) Add 30.1534g of ODPA, 73.8450g of N-methylpyrrolidone, 8.9560g of ethanol and 0.5782g of pyridine to a 250mL three-necked flask, heat to 55℃ and react for 8 hours to obtain the first system;

[0169] (2) Cool the first system in an ice-water bath, slowly add 25.3764 g of thionyl chloride to the first system, and after the addition is complete, restore the reaction to room temperature for 4 hours to obtain the second system;

[0170] (3) Add 10.8097g of 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone, 16.4817g of 6FAP, 3.0261g of 6FODA, 21.6064g of triethylamine and 172.3048g of N-methylpyrrolidone to a 500mL three-necked flask, and after complete dissolution, obtain the third system;

[0171] (4) Cool the third system to 0°C, slowly add the second system dropwise to the third system, and react for 4 hours to obtain the fourth system;

[0172] (5) The fourth system was dropped into deionized water to precipitate the precipitate. After repeated washing with deionized water, the precipitate was freeze-dried to obtain the polymer.

[0173] Preparation of black photoresist:

[0174] 24 parts of the polymer prepared in this comparative example, 1 part of (Z,E)-2-(4-methoxyphenyl)([((4-methylphenyl)sulfonyl)oxy]imino)acetonitrile, 4 parts of 9,9-bis[4-(tert-butoxycarbonyl)phenyl]fluorene and 71 parts of N-methylpyrrolidone were mixed evenly to obtain a black photoresist.

[0175] Preparation of the black matrix:

[0176] The black photoresist prepared in this comparative example was uniformly coated on a quartz wafer, then baked at 120°C for 3 minutes, exposed on a photolithography device, and then developed with a 2.38% tetramethylammonium hydroxide aqueous solution. The developer was removed by rinsing with deionized water, and then cured in a high-temperature nitrogen-filled oven under nitrogen atmosphere by increasing the temperature from room temperature to 200°C at a rate of 20°C / min and holding for 60 minutes, and then increasing the temperature to 350°C at a rate of 10°C / min and holding for 60 minutes.

[0177] Comparative Example 6

[0178] Polymer preparation:

[0179] (1) Add 30.1534g of ODPA, 73.2133g of N-methylpyrrolidone, 8.9560g of ethanol and 0.5782g of pyridine to a 250mL three-necked flask, heat to 55℃ and react for 8 hours to obtain the first system;

[0180] (2) Cool the first system in an ice-water bath, slowly add 25.3764 g of thionyl chloride to the first system, and after the addition is complete, restore the reaction to room temperature for 4 hours to obtain the second system;

[0181] (3) Add 13.5122 g of 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone, 13.1854 g of 6FAP, 3.0261 g of 6FODA, 21.6064 g of triethylamine and 170.8309 g of N-methylpyrrolidone to a 500 mL three-necked flask, and after complete dissolution, obtain the third system;

[0182] (4) Cool the third system to 0°C, slowly add the second system dropwise to the third system, and react for 4 hours to obtain the fourth system;

[0183] (5) The fourth system was dropped into deionized water to precipitate the precipitate. After repeated washing with deionized water, the precipitate was freeze-dried to obtain the polymer.

[0184] Preparation of black photoresist:

[0185] 24 parts of the polymer prepared in this comparative example, 1 part of (Z,E)-2-(4-methoxyphenyl)([((4-methylphenyl)sulfonyl)oxy]imino)acetonitrile, 4 parts of 9,9-bis[4-(tert-butoxycarbonyl)phenyl]fluorene and 71 parts of N-methylpyrrolidone were mixed evenly to obtain a black photoresist.

[0186] Preparation of the black matrix:

[0187] The black photoresist of this comparative example was uniformly coated on a quartz wafer, then baked at 120°C for 3 minutes, exposed on a photolithography device, and then developed with a 2.38% tetramethylammonium hydroxide aqueous solution. The developer was removed by rinsing with deionized water, and then cured in a high-temperature nitrogen-filled oven under nitrogen atmosphere by increasing the temperature from room temperature to 200°C at a rate of 20°C / min and holding for 60 minutes, and then increasing the temperature to 350°C at a rate of 10°C / min and holding for 60 minutes.

[0188] Comparative Example 7

[0189] Polymer preparation:

[0190] (1) Add 30.1534g of ODPA, 70.0346g of N-methylpyrrolidone, 5.3736g of ethanol and 0.5782g of pyridine to a 250mL three-necked flask, heat to 55℃ and react for 8 hours to obtain the first system;

[0191] (2) Cool the first system in an ice-water bath, slowly add 15.2258 g of thionyl chloride dropwise to the first system, and after the addition is complete, restore the reaction to room temperature for 4 hours to obtain the second system;

[0192] (3) Add 10.8097g of 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone, 16.4817g of 6FAP, 3.0261g of 6FODA, 12.9638g of triethylamine and 163.4140g of N-methylpyrrolidone to a 500mL three-necked flask, and after complete dissolution, obtain the third system;

[0193] (4) Cool the third system to 0°C, slowly add the second system dropwise to the third system, and react for 4 hours to obtain the fourth system;

[0194] (5) The fourth system was dropped into deionized water to precipitate the precipitate. After repeated washing with deionized water, the precipitate was freeze-dried to obtain the polymer.

[0195] Preparation of black photoresist:

[0196] 24 parts of the polymer prepared in this comparative example, 1 part of (Z,E)-2-(4-methoxyphenyl)([((4-methylphenyl)sulfonyl)oxy]imino)acetonitrile, 4 parts of 9,9-bis[4-(tert-butoxycarbonyl)phenyl]fluorene and 71 parts of N-methylpyrrolidone were mixed evenly to obtain a black photoresist.

[0197] Preparation of the black matrix:

[0198] The black photoresist of this comparative example was uniformly coated on a quartz wafer, then baked at 120°C for 3 minutes, exposed on a photolithography device, and then developed with a 2.38% tetramethylammonium hydroxide aqueous solution. The developer was removed by rinsing with deionized water, and then cured in a high-temperature nitrogen-filled oven under nitrogen atmosphere by increasing the temperature from room temperature to 200°C at a rate of 20°C / min and holding for 60 minutes, and then increasing the temperature to 350°C at a rate of 10°C / min and holding for 60 minutes.

[0199] Comparative Example 8

[0200] Polymer preparation:

[0201] (1) Add 30.1534g of ODPA, 68.1294g of N-methylpyrrolidone, 3.5824g of ethanol and 0.5782g of pyridine to a 250mL three-necked flask, heat to 55℃ and react for 8 hours to obtain the first system;

[0202] (2) Cool the first system in an ice-water bath, slowly add 10.1506 g of thionyl chloride dropwise to the first system, and after the addition is complete, restore the reaction to room temperature for 4 hours to obtain the second system;

[0203] (3) Add 10.8097g of 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone, 16.4817g of 6FAP, 3.0261g of 6FODA, 8.6426g of triethylamine and 158.9686g of N-methylpyrrolidone to a 500mL three-necked flask, and after complete dissolution, obtain the third system;

[0204] (4) Cool the third system to 0°C, slowly add the second system dropwise to the third system, and react for 4 hours to obtain the fourth system;

[0205] (5) The fourth system was dropped into deionized water to precipitate the precipitate. After repeated washing with deionized water, the precipitate was freeze-dried to obtain the polymer.

[0206] Preparation of black photoresist:

[0207] 24 parts of the polymer prepared in this comparative example, 1 part of (Z,E)-2-(4-methoxyphenyl)([((4-methylphenyl)sulfonyl)oxy]imino)acetonitrile, 4 parts of 9,9-bis[4-(tert-butoxycarbonyl)phenyl]fluorene and 71 parts of N-methylpyrrolidone were mixed evenly to obtain a black photoresist.

[0208] Preparation of the black matrix:

[0209] The black photoresist of this comparative example was uniformly coated on a quartz wafer, then baked at 120°C for 3 minutes, exposed on a photolithography device, and then developed with a 2.38% tetramethylammonium hydroxide aqueous solution. The developer was removed by rinsing with deionized water, and then cured in a high-temperature nitrogen-filled oven under nitrogen atmosphere by increasing the temperature from room temperature to 200°C at a rate of 20°C / min and holding for 60 minutes, and then increasing the temperature to 350°C at a rate of 10°C / min and holding for 60 minutes.

[0210] The weight-average molecular weight, pattern resolution after exposure and development, OD value of the black matrix, and mechanical properties of the polymers prepared in Examples 1-6 and Comparative Examples 1-8 were tested. The test results are shown in Table 1. The specific test methods are as follows:

[0211] (1) Weight average molecular weight: Shimadzu LC-20ADXR was used, with 20 mmol / L H3PO4 added to N-methylpyrrolidone (NMP) as the mobile phase, and the test was performed at 40 °C at a flow rate of 0.7 ml / min.

[0212] (2) Image resolution test: The black photoresist was exposed using an MDA-400M exposure machine, and coated, baked, and developed using a Jiangsu Leibo-SD200. Under the condition of a film thickness of 2μm, the exposure dose was 200-500mj / cm. 2The resolution is based on a CD with the smallest opening and no residual circular holes.

[0213] (3) OD value test: The absorbance of five black matrices with different film thicknesses at 550 nm was measured using Shimadzu UV-1900i, and the OD value at 1 μm was calculated by fitting. The higher the OD value, the better.

[0214] (4) Mechanical property test: The test was conducted using an Instron 68SC-1 tensile testing machine. The black matrix sample film was stretched from 0 N at a speed of 10 mm / min at 25 °C. The modulus, elongation at break and tensile strength were obtained.

[0215] (5) Electrical performance test: The dielectric constant of the black matrix sample was determined using a DETECH E5080 vector network analyzer at 25℃ and 1GHz.

[0216] Table 1 Test Results

[0217]

[0218] As shown in Table 1, compared with Comparative Examples 1-8, the black photoresist prepared using the intrinsic black polymers prepared in Examples 1-6 of this application has excellent optical, mechanical and electrical properties.

[0219] In Comparative Example 1, isopropanol was replaced with ethanol in Example 1, resulting in a decrease in OD value and mechanical properties. Comparing Comparative Examples 1 to 3, only Comparative Example 1 displayed the graph normally. This is because Comparative Example 1 used the same photoacid generator as Examples 1-6, namely (Z,E)-2-(4-methoxyphenyl)([((4-methylphenyl)sulfonyl)oxy]imino)acetonitrile, while Comparative Examples 2 and 3 used phenylacetonitrile, 2-methyl-A-[2-[((propylsulfonyl)oxy]imino]-3(2H)-thiophene, and a salt (1:1) of bis[4-(1,1-dimethylethyl)phenyl]iodonium and trifluoromethanesulfonic acid as photoacid generators, respectively. Therefore, the black photoresist prepared using (Z,E)-2-(4-methoxyphenyl)([((4-methylphenyl)sulfonyl)oxy]imino)acetonitrile as the photoacid generator exhibits better exposure performance. Meanwhile, the resolution results of Comparative Example 3 show the presence of a substrate film, indicating that the photoacid generator in Comparative Example 3 has the worst effect.

[0220] Comparative Example 4 used an esterification reaction between aromatic chromols and ODPA, which resulted in poor solubility of the final polymer. Consequently, the black photoresist prepared using the polymer of Comparative Example 4 could only swell but not dissolve after exposure and development, resulting in no photolithographic pattern appearing.

[0221] Because the molar ratio of dianhydride monomer to alcohol was too small in Comparative Examples 5 and 6, the polymer had fewer carboxylic acid groups in the dianhydride residues and a higher molecular weight. As a result, the black photoresist prepared from this polymer had poor solubility in alkaline solution. Therefore, it could only swell during exposure and development and could not form a photolithographic pattern.

[0222] For Comparative Examples 7 and 8, the molar ratio of dianhydride monomer to alcohol was too high, resulting in an excessive number of carboxylic acid groups in the dianhydride residues of the black photoresist. This made the black photoresist too soluble in the alkaline solution, causing it to completely dissolve and fail to form a photolithographic pattern.

[0223] The above description of the embodiments is intended to enable those skilled in the art to understand and apply this application. It will be apparent to those skilled in the art that various modifications can be easily made to these embodiments, and the general principles described herein can be applied to other embodiments without creative effort. Therefore, this application is not limited to the embodiments described herein, and any improvements and modifications made by those skilled in the art based on the disclosure of this application without departing from the scope and spirit of this application are within the scope of this application.

Claims

1. A black photoresist, characterized in that, By weight, it includes: 5-35 parts of intrinsic black polymer; Photosensitive acid generator 0.5-5 parts; 2-6 parts of solvent inhibitor; 60-90 parts of the second solvent; The structural formula of the intrinsically black polymer is as follows: ； R1 to R6 are selected from one of hydrogen, hydroxyl, carboxyl, amino, methyl, methoxy, carbonyl, ester, phenyl and 4-aminophenylamino, respectively; R7 is selected from hydrogen or residues resulting from the reaction of alcohols; R8 is selected from one of benzene ring, biphenyl, biphenyl ether, biphenyl ketone, biphenyl sulfide and 4,4-hexafluoroisopropylphthalene; R9, R11~R17 are selected from one of hydrogen, hydroxyl, carboxyl, methyl, methoxy, trifluoromethyl, carbonyl, ester and phenyl groups, respectively; R10 is selected from one of the following: single bond, ether group, amide group, mercapto group, aliphatic group with 1 to 6 carbon atoms, hexafluoroisopropylidene group, or hexafluoroisopropyl group; The value of m is 3~10, and the value of n is 4~12; The intrinsic black polymer was prepared using the following method: The dianhydride monomer reacts with an alcohol to yield an esterified product; The esterified product is reacted with an acyl chloride reagent to obtain an intermediate; The intermediate, the first diamine monomer, and the second diamine monomer are reacted to obtain the intrinsic black polymer. The dianhydride monomer includes at least one of 4,4'-oxobisphthalic anhydride, pyromellitic dianhydride, hexafluorodianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, and 3,3',4,4'-benzophenone tetracarboxylic dianhydride. The alcohols include n-butanol and / or ethanol; The molar ratio of the dianhydride monomer to the alcohol is (0.55~0.63):1; The molar ratio of the intermediate, the first diamine monomer, and the second diamine monomer is 1.08:(0.4~0.5):(0.5~0.6). The first diamine monomer is 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone; The photoacid generator is (Z,E)-2-(4-methoxyphenyl)([(((4-methylphenyl)sulfonyl)oxy]imino)acetonitrile; The solvent is 9,9-bis[4-(tert-butoxycarbonyloxy)phenyl]fluorene.

2. The black photoresist according to claim 1, characterized in that, The second diamine monomer includes at least one of 4,4'-diaminodiphenyl ether, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2'-bis(trifluoromethyl)-4,4'-diaminophenyl ether, 3,3'-dichlorobenzidine, and 4,4'-diaminobenzoylaniline.

3. The black photoresist according to claim 1, characterized in that, In the preparation method of the intrinsic black polymer, the reaction temperature of the dianhydride monomer and the alcohol is 40℃~80℃.

4. The black photoresist according to claim 1, characterized in that, The reaction temperature of the intermediate, the first diamine monomer, and the second diamine monomer is 0℃~10℃.

5. The black photoresist according to claim 1, characterized in that, In the preparation method of the intrinsic black polymer, the dianhydride monomer and the alcohol react in a first solvent, wherein the first solvent includes at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, γ-butyrolactone, and dimethyl sulfoxide.

6. The black photoresist according to claim 1, characterized in that, The catalyst used in the reaction of the dianhydride monomer and the alcohol includes pyridine.

7. The black photoresist according to claim 1, characterized in that, The acyl chloride reagent includes sulfoxide.

8. The black photoresist according to claim 1, characterized in that, When the intermediate, the first diamine monomer, and the second diamine monomer react, an organic base is also added to the reaction system.

9. The black photoresist according to claim 1, characterized in that, The second solvent includes at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, γ-butyrolactone, dimethyl sulfoxide, ethyl acetate, and methanol.

10. The application of the black photoresist according to any one of claims 1-9 in a black matrix.

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