Black matrix polymer, method for producing the same, and use

Abstract

This invention discloses a polymer for black matrices. The polymer is produced by reacting a dianhydride monomer with an esterifying agent to obtain an intermediate, and then reacting the intermediate with a diamine monomer and 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone. The polymer described in this invention has unique structural characteristics, a high OD value, good mechanical performance, thermal performance, and photolithography performance. When used in black matrices, the polymer can better meet current industry requirements for black matrix performance. Furthermore, this invention discloses a method for producing and using the polymer. The production method is simple and easy to implement for industrialization. The use of the polymer not only provides a new polymer option for black matrices but can also significantly improve the mechanical and thermal performance of the black matrix.

Description

Technical Field

[0001] The present invention relates to a polymer for a black matrix, and particularly to a polymer for a genuine resin-based black matrix having high OD value, good mechanical properties, thermal properties and photolithography performance, a method for producing the same, and its use.

Background Art

[0002] Liquid crystal panel (LCD) photoresist is a technology-intensive industry with high technical barriers. At present, only a few manufacturers in Japan, South Korea and Taiwan have the ability to mass-produce LCD photoresist, and the important technologies are mastered by several Japanese companies, which has become a major constraint on the development of Chinese LCD photoresist. LCD photoresist includes color photoresist and black photoresist.

[0003] In recent years, with the rapid development of liquid crystal display technology, people's requirements for the contrast of the device have been increasing. A black matrix is arranged between the color filter and the dot interval, and the black matrix plays a role of shielding light and constructing a frame for the red, green and blue primary color photoresists to be subsequently coated, and the quality of the black matrix directly affects the color development performance of the color filter.

[0004] To improve the contrast of liquid crystal displays, chromium is used in the black matrix, primarily by depositing chromium onto the surface of a glass substrate and then forming a pattern by etching. While this method results in a black matrix with high optical density and strong mechanical performance, it has drawbacks such as high cost, high reflectivity of chromium, and environmental pollution from chromium-containing wastewater. Researchers have proposed using pigments to produce photoresist compositions for black matrices, but because the photoresist is doped with pigment, it cannot dissolve in the developer, resulting in longer development times, poor development effectiveness, and the inability to obtain high-resolution patterns. The introduction of carbon materials and organic dyes significantly reduces the electrical insulation performance of the black matrix. Some researchers also produce black matrices using colored pigments other than carbon black, but because colored pigments have poor light shielding properties, it is necessary to increase the mixing ratio of the black matrix photoresist composition. This increases the viscosity of the composition and reduces the strength of the resulting film.

[0005] Therefore, in order to avoid the above-mentioned drawbacks and to theoretically and technically support and promote the realization of domestic production of black matrix photoresists, it is necessary to conduct extensive research to develop intrinsic resin-based black matrices. [Overview of the Initiative]

[0006] The present invention aims to overcome the drawbacks of the prior art described above and to provide a polymer for black matrices that has good mechanical, thermal, and photolithographic performance. Furthermore, the present invention provides a method for producing the polymer and a method for using the same.

[0007] To achieve the above objective, the present invention employs the following technical solutions. The polymer has the following structural formula: [ka] However, R is H, [ka] , It is at least one of the MeOH species.

[0008] The polymer described in this invention has unique structural characteristics, can form high-resolution patterns, exhibits excellent mechanical and thermal properties, can be used as a positive-type photoresist for alkaline water development, and when used in a black matrix, can improve the performance of the black matrix.

[0009] The present invention further provides a method for producing the polymer described above, which has simple process steps and is easily industrializable. To achieve this objective, the present invention employs the following technical solutions. The above-described method for producing the polymer is: (1) A step of reacting a dianhydride monomer, an esterifying agent, and an acid chloride agent in solvent 1 to obtain an intermediate, (2) The step of reacting the intermediate obtained in step (1) with a diamine monomer and 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone in solvent 2 to obtain the polymer.

[0010] In the polymer production method according to the present invention, a polymer having the unique structural characteristics described above can be produced quickly and efficiently by reacting a dianhydride monomer with an esterifying agent in solvent 1 to obtain an intermediate, and then reacting the obtained intermediate with a diamine monomer and 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone, and the production method has simple process steps.

[0011] In the polymer production method described in the present invention, the structural formula of 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone is as follows. [ka]

[0012] In the polymer production method described in the present invention, the 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone can be purchased directly or produced by general technical means of the art. The method for producing the 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone includes, but is not limited to, the following two types: (1) and (2).

[0013] (1) If concentrated sulfuric acid and concentrated nitric acid are present, 1,8-dihydroxy-9,10-anthraquinone is nitrated to 1,8-dihydroxy-2,4,5,7-tetranitro-9,10-anthraquinone, and then the nitro group is reduced to an amino group to obtain 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone.

[0014] (2) If concentrated sulfuric acid and concentrated nitric acid are present, 1,8-dihydroxy-4,5-dinitro-9,10-anthraquinone is nitrated to 1,8-dihydroxy-2,4,5,7-tetranitro-9,10-anthraquinone, and then the nitro group is reduced to an amino group to obtain 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone.

[0015] In a preferred embodiment of the polymer production method described in the present invention, in step (1), a dianhydride monomer and an esterifying agent are reacted in solvent 1 to obtain a reaction solution, an acid chloride agent is added dropwise to the reaction solution under a nitrogen atmosphere and ice bath conditions, and an intermediate is obtained after the addition is complete.

[0016] In a preferred embodiment of the polymer production method described in the present invention, in step (1), the molar ratio of the dianhydride monomer to the esterifying agent is 1:1 to 1:2. In a more preferred embodiment of the polymer production method described in the present invention, in step (1), the molar ratio of the dianhydride monomer to the esterifying agent is 1:2.

[0017] In a preferred embodiment of the polymer production method described in the present invention, in step (1), the reaction temperature of the dianhydride monomer and the esterifying agent in solvent 1 is 30 to 90°C. In a more preferred embodiment of the polymer production method described in the present invention, in step (1), the reaction temperature of the dianhydride monomer and the esterifying agent in solvent 1 is 60°C.

[0018] In a preferred embodiment of the polymer production method described in the present invention, the reaction time of the dianhydride monomer and the esterifying agent in solvent 1 in step (1) is 6 to 24 hours. In a more preferred embodiment of the polymer production method described in the present invention, the reaction time of the dianhydride monomer and the esterifying agent in solvent 1 in step (1) is 10 hours.

[0019] In a preferred embodiment of the polymer manufacturing method described in the present invention, the temperature of the ice bath in step (1) is 5 to 10°C. In a more preferred embodiment of the polymer manufacturing method described in the present invention, the temperature of the ice bath in step (1) is 5°C.

[0020] In a preferred embodiment of the polymer production method described in the present invention, in step (1), the molar ratio of the acid chloride agent to the dianhydride monomer is 2:1 to 2.5:1. In a more preferred embodiment of the polymer production method described in the present invention, in step (1), the molar ratio of the acid chloride agent to the dianhydride monomer is 2.2:1.

[0021] In a preferred embodiment of the polymer production method described in the present invention, in step (1), the dropping rate of the acid chloride agent is 1 to 4 drops / second. In a more preferred embodiment of the polymer production method described in the present invention, in step (1), the dropping rate of the acid chloride agent is 1 drop / second.

[0022] As a preferred embodiment of the method for producing the polymer according to the present invention, in the step (1), the solvent 1 is at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and tetrahydrofuran. As a more preferred embodiment of the method for producing the polymer according to the present invention, in the step (1), the solvent 1 is N-methylpyrrolidone.

[0023] As a preferred embodiment of the method for producing the polymer according to the present invention, in the step (1), the acid chlorinating agent is at least one of SOCl2, AlCl3, BF3, SbCl5, FeBr3, FeCl3, SnCl4, TiCl4, and ZnCl2. As a more preferred embodiment of the method for producing the polymer according to the present invention, in the step (1), the acid chlorinating agent is SOCl2.

[0024] As a preferred embodiment of the method for producing the polymer according to the present invention, in the step (1), the esterifying agent is at least one of n-butanol, ethanol, isopropanol, n-propanol, t-butanol, and methanol. As a more preferred embodiment of the method for producing the polymer according to the present invention, in the step (1), the esterifying agent is n-butanol.

[0025] As a preferred embodiment of the polymer production method described in the present invention, the dianhydride monomer in step (1) is at least one of 3,3',4,4'-diphenyl ether tetracarboxylic acid dianhydride, 3,3',4,4'-biphenyl tetracarboxylic acid dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, 2,2'-bis(3,4-dicarboxylic acid)hexafluoropropane dianhydride, 2,3,3',4'-biphenyl tetracarboxylic acid dianhydride, 3,3,4,4-diphenyl sulfone tetracarboxylic acid dianhydride, naphthalene-1,4,5,8-tetracarboxylic acid dianhydride, diphenyl sulfide dianhydride, and bisphenol A type diether dianhydride. As a more preferred embodiment of the polymer production method described in the present invention, the dianhydride monomer in step (1) is 3,3',4,4'-diphenyl ether tetracarboxylic acid dianhydride.

[0026] In a preferred embodiment of the polymer production method described in the present invention, the intermediate has the following structural formula. [ka] However, R is H, [ka] , It is at least one of the MeOH species.

[0027] In a preferred embodiment of the polymer production method described in the present invention, in step (2), the molar ratio of the diamine monomer, 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone, and intermediate is diamine monomer:1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone:intermediate = 1:1:2 to 1:1:4. In a more preferred embodiment of the polymer production method described in the present invention, in step (2), the molar ratio of the diamine monomer, 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone, and intermediate is diamine monomer:1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone:intermediate = 1:1:2.

[0028] As a preferred embodiment of the polymer production method described in the present invention, the diamine monomer in step (2) is m-phenylenediamine, p-phenylenediamine, 4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-diamino-2,2'-dimethylbiphenyl, 2-(4-aminophenyl)-5-aminobenzoxazole The diamine monomer is at least one of the following: 2-(4-aminophenyl)-5-aminobenzimidazole, 1,4-bis(3-aminophenoxy)benzene, 1,3-bis(3-hydroxy-4-aminophenoxy)benzene, 2-(4-aminophenyl)-6-aminobenzoxazole, 2,2-p-phenyl-bis(5-aminobenzoxazole), 2,2'-p-phenyl-bis(6-aminobenzoxazole), 2,2-bis(4-hydroxy-3-aminophenyl)propane, 3,3'-dihydroxybenzidine, or 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid. In a more preferred embodiment of the polymer production method described in the present invention, the diamine monomer in step (2) is 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane.

[0029] In a preferred embodiment of the polymer production method described in the present invention, the dianhydride monomer in step (1) is 3,3',4,4'-diphenyl ether tetracarboxylic acid dianhydride, and the diamine monomer in step (2) is 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane.

[0030] In a preferred embodiment of the polymer production method described in the present invention, in step (2), solvent 2 is at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and tetrahydrofuran. In a more preferred embodiment of the polymer production method described in the present invention, in step (2), solvent 2 is N-methylpyrrolidone.

[0031] In a preferred embodiment of the polymer manufacturing method described in the present invention, the reaction temperature in step (2) is 15 to 35°C. In a more preferred embodiment of the polymer manufacturing method described in the present invention, the reaction temperature in step (2) is 25°C.

[0032] In a preferred embodiment of the polymer manufacturing method described in the present invention, the reaction time in step (2) is 3 to 8 hours. In a more preferred embodiment of the polymer manufacturing method described in the present invention, the reaction time in step (2) is 6 hours.

[0033] Finally, the present invention further provides the use of polymers having the above-described structural characteristics in the production of black matrix.

[0034] The polymer according to the present invention, due to its unique structural characteristics, can form high-resolution patterns, exhibits excellent mechanical and thermal performance, can be used as a positive-type photoresist for alkaline water development, and, when used in a black matrix, can improve the performance of the black matrix.

[0035] The polymer manufacturing method described in the present invention uses readily available raw materials, has simple manufacturing steps and process conditions, and is easy to implement and use in industrial applications.

[0036] The use of the polymers described in this invention in the production of black matrix not only provides new polymer options for black matrix, but can also significantly improve the mechanical and thermal properties of the black matrix. [Brief explanation of the drawing]

[0037] [Figure 1] This is the structural formula of the polymer described in the present invention. [Figure 2] This is the structural reaction formula of one embodiment of the polymer manufacturing method described in the present invention. [Figure 3] This is a diagram of the elution curve obtained by gel permeation chromatography of the polymer described in Example 1 of the present invention. [Figure 4] This is a diagram showing the molecular weight statistics obtained by gel permeation chromatography of the polymer described in Example 1 of the present invention. [Figure 5] This is a diagram of the elution curve obtained by gel permeation chromatography of the polymer described in Example 2 of the present invention. [Figure 6] This is a diagram showing the molecular weight statistics obtained by gel permeation chromatography of the polymer described in Example 2 of the present invention. [Figure 7] This is a diagram of the elution curve obtained by gel permeation chromatography of the polymer described in Example 3 of the present invention. [Figure 8] This is a diagram showing the molecular weight statistics obtained by gel permeation chromatography of the polymer described in Example 3 of the present invention. [Figure 9] This is a diagram of the elution curve obtained by gel permeation chromatography of the polymer described in Example 4 of the present invention. [Figure 10] This is a diagram showing the molecular weight statistics obtained by gel permeation chromatography of the polymer described in Example 4 of the present invention. [Figure 11]This is a diagram of the elution curve obtained by gel permeation chromatography of the polymer described in Example 5 of the present invention. [Figure 12] This is a diagram showing the molecular weight statistics obtained by gel permeation chromatography of the polymer described in Example 5 of the present invention. [Figure 13] This is a diagram of the elution curve obtained by gel permeation chromatography of the polymer described in Example 6 of the present invention. [Figure 14] This is a diagram showing the molecular weight statistics obtained by gel permeation chromatography of the polymer described in Example 6 of the present invention. [Figure 15] This is a diagram of the elution curve obtained by gel permeation chromatography of the polymer described in Example 7 of the present invention. [Figure 16] This is a diagram showing the molecular weight statistics obtained by gel permeation chromatography of the polymer described in Example 7 of the present invention. [Figure 17] This is a diagram of the elution curve obtained by gel permeation chromatography of the polymer described in Example 8 of the present invention. [Figure 18] This is a diagram showing the molecular weight statistics obtained by gel permeation chromatography of the polymer described in Example 8 of the present invention. [Figure 19] This is a diagram of the elution curve obtained by gel permeation chromatography of the polymer described in Example 9 of the present invention. [Figure 20] This is a diagram showing the molecular weight statistics obtained by gel permeation chromatography of the polymer described in Example 9 of the present invention. [Figure 21] This is a diagram of the elution curve obtained by gel permeation chromatography of the polymer described in Example 10 of the present invention. [Figure 22] This is a diagram showing the molecular weight statistics obtained by gel permeation chromatography of the polymer described in Example 10 of the present invention. [Figure 23] This figure shows the results of a thermal performance test of the polymer described in Example 1 of the present invention. [Figure 24] This is a photolithography performance test diagram of the polymer described in Example 1 of the present invention. [Figure 25] This is another photolithography performance test diagram of the polymer described in Example 1 of the present invention. [Figure 26] This is yet another photolithography performance test diagram of the polymer described in Example 1 of the present invention. [Figure 27] This is yet another photolithography performance test diagram of the polymer described in Example 1 of the present invention. [Figure 28] This is the nuclear magnetic resonance spectrum of the polymer described in Example 8 of the present invention. [Modes for carrying out the invention]

[0038] To better illustrate the object, technical solution, and advantages of the present invention, the present invention will be further described below with reference to the drawings and specific embodiments.

[0039] The 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone described in the following examples has the following structural formula. [ka]

[0040] The aforementioned 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone is produced by one of the following two methods: (1) and (2). (1) If concentrated sulfuric acid and concentrated nitric acid are present, 1,8-dihydroxy-9,10-anthraquinone is nitrated to 1,8-dihydroxy-2,4,5,7-tetranitro-9,10-anthraquinone, and then the nitro group is reduced to an amino group to obtain 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone. (2) If concentrated sulfuric acid and concentrated nitric acid are present, 1,8-dihydroxy-4,5-dinitro-9,10-anthraquinone is nitrated to 1,8-dihydroxy-2,4,5,7-tetranitro-9,10-anthraquinone, and then the nitro group is reduced to an amino group to obtain 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone.

[0041] The 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone described in this application can be produced using either of the two methods described above, and specifically, refer to the contents disclosed in CN202110708909.2. Furthermore, the method for obtaining the 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone includes, but is not limited to, the two methods described above, and can be obtained by those skilled in the art using other common methods in the prior art or other common methods.

[0042] The structural formula of the black matrix polymer of the present invention is shown in Figure 1.

[0043] A synthesis scheme for one embodiment of the polymer described in the present invention is shown in Figure 2, and the method for producing the polymer specifically includes the following steps (1) and (2).

[0044] (1) The dianhydride monomer and the esterifying agent are reacted in solvent 1 to obtain a reaction solution, and the acid chloride agent is added dropwise to the reaction solution under a nitrogen atmosphere and ice bath conditions, and an intermediate is obtained after the addition is complete. The molar ratio of the dianhydride monomer to the esterifying agent is 1:1 to 1:2. The solvent 1 is at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and tetrahydrofuran.

[0045] The reaction temperature of the dianhydride monomer and the esterifying agent in solvent 1 is 30 to 90°C.

[0046] The reaction time between the dianhydride monomer and the esterifying agent in solvent 1 is 6 to 24 hours.

[0047] The temperature of the ice bath conditions is 5-10°C.

[0048] The molar ratio of the acid chloride agent to the dianhydride monomer is 2:1 to 2.5:1.

[0049] The dropping rate of the acid chloride agent is 1 to 4 drops / second.

[0050] The acid chloride agent is at least one of SOCl2, AlCl3, BF3, SbCl5, FeBr3, FeCl3, SnCl4, TiCl4, and ZnCl2.

[0051] The dianhydride monomer is at least one of the following: 3,3',4,4'-diphenylethertetracarboxylic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 2,2'-bis(3,4-dicarboxylic acid)hexafluoropropane dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid dianhydride, 3,3,4,4-diphenylsulfonetetracarboxylic acid dianhydride, naphthalene-1,4,5,8-tetracarboxylic acid dianhydride, diphenyl sulfide dianhydride, and bisphenol A type diether dianhydride.

[0052] The esterifying agent is at least one of n-butanol, ethanol, isopropanol, n-propanol, t-butanol, and methanol.

[0053] (2) The intermediate obtained in step (1), the diamine monomer, and 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone are reacted in solvent 2 to obtain the polymer.

[0054] The molar ratio of the diamine monomer, 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone, and intermediate is diamine monomer:1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone:intermediate = 1:1:2 to 1:1:4.

[0055] The aforementioned diamine monomers are m-phenylenediamine, p-phenylenediamine, 4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-diamino-2,2'-dimethylbiphenyl, 2-(4-aminophenyl)-5-aminobenzoxazole, and 2-(4-aminophenyl)-5-aminobenzoxazole. It is at least one of the following: nobenzimidazole, 1,4-bis(3-aminophenoxy)benzene, 1,3-bis(3-hydroxy-4-aminophenoxy)benzene, 2-(4-aminophenyl)-6-aminobenzoxazole, 2,2-p-phenyl-bis(5-aminobenzoxazole), 2,2'-p-phenyl-bis(6-aminobenzoxazole), 2,2-bis(4-hydroxy-3-aminophenyl)propane, 3,3'-dihydroxybenzidine, or 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid.

[0056] The solvent 2 is at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and tetrahydrofuran.

[0057] The intermediate produced in step (1) described above has the following structural formula. [ka] However, R is H, [ka] , It is at least one of the MeOH species.

[0058] The reaction temperature in step (2) is 15 to 35°C.

[0059] The reaction time in step (2) is 3 to 8 hours.

[0060] (Examples) (Example 1) In one embodiment of the polymer of the present invention, the method for producing the polymer described in this embodiment includes the following steps (1) and (2).

[0061] (1) 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride and n-butanol in a molar ratio of 1:2 were added to N-methylpyrrolidone and reacted in an oil bath at 60°C for 6 hours under a nitrogen atmosphere to obtain a reaction solution. Under an ice bath at 5°C under a nitrogen atmosphere, thionyl chloride was added dropwise to the reaction solution at a rate of 1 drop / second to adjust the molar ratio of thionyl chloride to 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride to 2:1, and an intermediate was obtained after the addition was complete.

[0062] (2) 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone, and an intermediate in a molar ratio of 1:1:4 are added to N,N-dimethylformamide and reacted at 25°C for 6 hours to obtain a reaction product. The obtained reaction product is uniformly introduced into deionized water, allowed to stand to separate into layers, the upper layer is removed, the resin is pulverized, the deionized water is replaced and the resin is washed by immersion, filtered, and repeated several times, and dried to obtain a solid resin, i.e., the polymer described in this example.

[0063] The polymer obtained in this example has the following structural formula. [ka]

[0064] (Example 2) In one embodiment of the polymer of the present invention, the method for producing the polymer described in this embodiment includes the following steps (1) and (2).

[0065] (1) 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride and n-butanol in a molar ratio of 1:2 were added to N-methylpyrrolidone and reacted in an oil bath at 70°C for 6 hours under a nitrogen atmosphere to obtain a reaction solution. Under an ice bath at 6°C under a nitrogen atmosphere, thionyl chloride was added dropwise to the reaction solution at a rate of 1 drop / second to adjust the molar ratio of thionyl chloride to 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride to 2:1, and an intermediate was obtained after the addition was complete.

[0066] (2) Add 2,2-bis(4-hydroxy-3-aminophenyl)propane, 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone and an intermediate in a molar ratio of 1:1:2 to N-methylpyrrolidone and react at 25°C for 6 hours to obtain a reaction product. The obtained reaction product is uniformly introduced into deionized water, allowed to stand to separate into layers, the upper layer is removed, the resin is pulverized, the deionized water is replaced and the resin is immersed and washed, filtered, and repeated several times, and dried to obtain a solid resin, i.e., the polymer described in this example.

[0067] The polymer obtained in this example has the following structural formula. [ka]

[0068] (Example 3) In one embodiment of the polymer of the present invention, the method for producing the polymer described in this embodiment includes the following steps (1) and (2).

[0069] (1) 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride and n-butanol in a molar ratio of 1:1 were added to N,N-dimethylacetamide and reacted in an oil bath at 60°C for 8 hours under a nitrogen atmosphere to obtain a reaction solution. Under an ice bath at 5°C under a nitrogen atmosphere, SbCl5 was added dropwise to the reaction solution at a rate of 1 drop / second to adjust the molar ratio of SbCl5 to 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride to 2.1:1. After the addition was complete, an intermediate was obtained.

[0070] (2) 1,4-bis(4-aminophenoxy)benzene, 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone, and an intermediate in a molar ratio of 1:1:2 are added to N-methylpyrrolidone, and the mixture is reacted at 25°C for 6 hours to obtain a reaction product. The obtained reaction product is uniformly introduced into deionized water, allowed to stand to separate into layers, the upper layer is removed, the resin is pulverized, the deionized water is replaced and the resin is immersed and washed, filtered, and repeated several times, and then dried to obtain a solid resin, i.e., the polymer described in this example.

[0071] The polymer obtained in this example has the following structural formula. [ka]

[0072] (Example 4) In one embodiment of the polymer of the present invention, the method for producing the polymer described in this embodiment includes the following steps (1) and (2).

[0073] (1) 3,3',4,4'-benzophenonetetracarboxylic dianhydride and ethanol in a molar ratio of 1:2 were added to N-methylpyrrolidone and reacted in an oil bath at 80°C for 8 hours under a nitrogen atmosphere to obtain a reaction solution. Under an ice bath at 7°C under a nitrogen atmosphere, thionyl chloride was added dropwise to the reaction solution at a rate of 1 drop / second to adjust the molar ratio of thionyl chloride to 3,3',4,4'-benzophenonetetracarboxylic dianhydride to 2:1, and an intermediate was obtained after the addition was complete.

[0074] (2) 3,3'-dihydroxybenzidine, 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone, and an intermediate in a molar ratio of 1:1:3 are added to dimethyl sulfoxide and reacted at 25°C for 6 hours to obtain a reaction product. The obtained reaction product is uniformly introduced into deionized water, allowed to stand to separate into layers, the upper layer is removed, the resin is pulverized, the deionized water is replaced and the resin is washed by immersion, filtered, and repeated several times, and then dried to obtain a solid resin, i.e., the polymer described in this example.

[0075] The polymer obtained in this example has the following structural formula. [ka]

[0076] (Example 5) In one embodiment of the polymer of the present invention, the method for producing the polymer described in this embodiment includes the following steps (1) and (2).

[0077] (1) 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride and n-propanol in a molar ratio of 1:2 were added to N,N-dimethylformamide and reacted in an oil bath at 90°C for 10 hours under a nitrogen atmosphere to obtain a reaction solution. Under an ice bath at 5°C under a nitrogen atmosphere, thionyl chloride was added dropwise to the reaction solution at a rate of 1 drop / second to adjust the molar ratio of thionyl chloride to 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride to 2:1, and an intermediate was obtained after the addition was complete.

[0078] (2) 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid, 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone, and an intermediate in a molar ratio of 1:1:4 are added to N-methyl-2-pyrrolidone, and the reaction is carried out at 15°C for 6 hours to obtain a reaction product. The obtained reaction product is uniformly introduced into deionized water, allowed to stand to separate into layers, the upper layer is removed, the resin is pulverized, the deionized water is replaced and the resin is immersed and washed, filtered, and repeated several times, and dried to obtain a solid resin, i.e., the polymer described in this example.

[0079] The polymer obtained in this example has the following structural formula. [ka]

[0080] (Example 6) In one embodiment of the polymer of the present invention, the method for producing the polymer described in this embodiment includes the following steps (1) and (2).

[0081] (1) 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride and methanol in a molar ratio of 1:2 were added to N-methylpyrrolidone and reacted in an oil bath at 60°C for 12 hours under a nitrogen atmosphere to obtain a reaction solution. Under an ice bath at 10°C under a nitrogen atmosphere, thionyl chloride was added dropwise to the reaction solution at a rate of 4 drops / second to adjust the molar ratio of thionyl chloride to 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride to 2:1. After the addition was complete, an intermediate was obtained.

[0082] (2) 1,4-bis(3-aminophenoxy)benzene, 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone, and an intermediate in a molar ratio of 1:1:4 are added to N-methylpyrrolidone, and the mixture is reacted at 35°C for 6 hours to obtain a reaction product. The obtained reaction product is uniformly introduced into deionized water, allowed to stand to separate into layers, the upper layer is removed, the resin is pulverized, the deionized water is replaced and the resin is immersed and washed, filtered, and repeated several times, and then dried to obtain a solid resin, i.e., the polymer described in this example.

[0083] The polymer obtained in this example has the following structural formula. [ka]

[0084] (Example 7) In one embodiment of the polymer of the present invention, the method for producing the polymer described in this embodiment includes the following steps (1) and (2).

[0085] (1) 3,3,4,4-diphenylsulfonetetracarboxylic dianhydride and n-butanol in a molar ratio of 1:2 were added to N-methylpyrrolidone and reacted in an oil bath at 70°C for 24 hours under a nitrogen atmosphere to obtain a reaction solution. Under an ice bath at 5°C under a nitrogen atmosphere, thionyl chloride was added dropwise to the reaction solution at a rate of 1 drop / second to adjust the molar ratio of thionyl chloride to 3,3,4,4-diphenylsulfonetetracarboxylic dianhydride to 2.5:1. After the addition was complete, an intermediate was obtained.

[0086] (2) Add 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone and an intermediate in a molar ratio of 1:1:3 to N-ethyl-2-pyrrolidone and react at 25°C for 8 hours to obtain a reaction product. The obtained reaction product is uniformly introduced into deionized water, allowed to stand to separate into layers, the upper layer is removed, the resin is pulverized, the deionized water is replaced and the resin is immersed and washed, filtered, and repeated several times, and dried to obtain a solid resin, i.e., the polymer described in this example.

[0087] The polymer obtained in this example has the following structural formula. [ka]

[0088] (Example 8) In one embodiment of the polymer of the present invention, the method for producing the polymer described in this embodiment includes the following steps (1) and (2).

[0089] (1) 3,3,4,4-diphenylsulfonetetracarboxylic dianhydride and n-butanol in a molar ratio of 1:2 were added to N-methylpyrrolidone and reacted in an oil bath at 60°C for 12 hours under a nitrogen atmosphere to obtain a reaction solution. Under an ice bath at 6°C under a nitrogen atmosphere, thionyl chloride was added dropwise to the reaction solution at a rate of 3 drops / second to adjust the molar ratio of thionyl chloride to 3,3,4,4-diphenylsulfonetetracarboxylic dianhydride to 2:1, and an intermediate was obtained after the addition was complete.

[0090] (2) Add 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone and an intermediate in a molar ratio of 1:1:2 to N-methylpyrrolidone and react at 15°C for 8 hours to obtain a reaction product. The obtained reaction product is uniformly introduced into deionized water, allowed to stand to separate into layers, the upper layer is removed, the resin is pulverized, the deionized water is replaced and the resin is washed by immersion, filtered, and repeated several times, and dried to obtain a solid resin, i.e., the polymer described in this example.

[0091] The polymer obtained in this example has the following structural formula. [ka]

[0092] (Example 9) In one embodiment of the polymer of the present invention, the method for producing the polymer described in this embodiment includes the following steps (1) and (2).

[0093] (1) 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride and isopropanol in a molar ratio of 1:2 were added to N-methylpyrrolidone and reacted in an oil bath at 30°C for 6 hours under a nitrogen atmosphere to obtain a reaction solution. Under an ice bath at 10°C under a nitrogen atmosphere, thionyl chloride was added dropwise to the reaction solution at a rate of 1 drop / second to adjust the molar ratio of thionyl chloride to 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride to 2:1, and an intermediate was obtained after the addition was complete.

[0094] (2) Add 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone and an intermediate in a molar ratio of 1:1:2 to N,N-dimethylformamide and react at 25°C for 3 hours to obtain a reaction product. The obtained reaction product is uniformly introduced into deionized water, allowed to stand to separate into layers, the upper layer is removed, the resin is pulverized, the deionized water is replaced and the resin is immersed and washed, filtered, and repeated several times, and dried to obtain a solid resin, i.e., the polymer described in this example.

[0095] The polymer obtained in this example has the following structural formula. [ka]

[0096] (Example 10) In one embodiment of the polymer of the present invention, the method for producing the polymer described in this embodiment includes the following steps (1) and (2).

[0097] (1) Diphenyl sulfide dianhydride and n-butanol in a molar ratio of 1:1 were added to N-methylpyrrolidone and reacted in an oil bath at 80°C for 6 hours under a nitrogen atmosphere to obtain a reaction solution. Under an ice bath at 8°C under a nitrogen atmosphere, thionyl chloride was added dropwise to the reaction solution at a rate of 1 drop / second to make the molar ratio of thionyl chloride to diphenyl sulfide dianhydride 2:1, and an intermediate was obtained after the addition was complete.

[0098] (2) Add 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone and an intermediate in a molar ratio of 1:1:4 to N-methylpyrrolidone and react at 25°C for 6 hours to obtain a reaction product. The obtained reaction product is uniformly introduced into deionized water, allowed to stand to separate into layers, the upper layer is removed, the resin is pulverized, the deionized water is replaced and the resin is immersed and washed, filtered, and repeated several times, and dried to obtain a solid resin, i.e., the polymer described in this example.

[0099] The polymer obtained in this example has the following structural formula. [ka]

[0100] (Example 11) Gel permeation chromatography (GPC) test of the polymer described in the present invention

[0101] The polymers described in Examples 1 to 10 were each used as test subjects, and the gel permeation chromatography (GPC) data obtained for each group of polymers was tested. The test method was as follows: When performing the test, the chromatography column was filled with a solvent of the sample to be tested so as to occupy all gaps between carrier particles and cavities inside the particles. Then, a sample solution prepared with the same solvent was added from the column head, rinsed with the same solvent, and the eluate was collected at the microend of the chromatography column. The volume and concentration of the eluate were calculated, and the total volume of the recovered eluate was called the elution volume. Regarding the elution volume and molecular weight of the solute, the larger the molecular weight, the smaller the elution volume. If the sample is polydispersible, a series of fractions can be collected in which the molecular weight decreases in the order of elution.

[0102] The elution curve of the polymer described in Example 1 is shown in Figure 3, and the statistical results of the molecular weight of the polymer are shown in Figure 4.

[0103] The elution curve of the polymer described in Example 2 is shown in Figure 5, and the statistical results of the molecular weight of the polymer are shown in Figure 6.

[0104] The elution curve of the polymer described in Example 3 is shown in Figure 7, and the statistical results of the molecular weight of the polymer are shown in Figure 8.

[0105] The elution curve of the polymer described in Example 4 is shown in Figure 9, and the statistical results of the molecular weight of the polymer are shown in Figure 10.

[0106] The elution curve of the polymer described in Example 5 is shown in Figure 11, and the statistical results of the molecular weight of the polymer are shown in Figure 12.

[0107] The elution curve of the polymer described in Example 6 is shown in Figure 13, and the statistical results of the molecular weight of the polymer are shown in Figure 14.

[0108] The elution curve of the polymer described in Example 7 is shown in Figure 15, and the statistical results of the molecular weight of the polymer are shown in Figure 16.

[0109] The elution curve of the polymer described in Example 8 is shown in Figure 17, and the statistical results of the molecular weight of the polymer are shown in Figure 18.

[0110] The elution curve of the polymer described in Example 9 is shown in Figure 19, and the statistical results of the molecular weight of the polymer are shown in Figure 20.

[0111] The elution curve of the polymer described in Example 10 is shown in Figure 21, and the statistical results of the molecular weight of the polymer are shown in Figure 22.

[0112] Table 1 below shows the weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight distribution index (PDI) of the polymers described in Examples 1 to 10.

[0113] Table 1: Detection results of Mw, Mn, and PDI of polymers obtained in Examples 1-10 [Table 1]

[0114] (Example 12) Mechanical performance tests and thermal performance tests of polymers according to the present invention

[0115] 1. Mechanical performance of the polymer described in the present invention The polymers described in Examples 1 to 10 and the polymers described in Comparative Examples 1 to 4 were used as test subjects, and the mechanical performance of the polymers obtained in each group was tested. The polymers described in Comparative Examples 1 to 4 are as follows:

[0116] The polymer production method described in Comparative Example 1 includes the following steps (1) and (2).

[0117] (1) 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride and n-butanol in a molar ratio of 1:2 were added to N-methylpyrrolidone and reacted in an oil bath at 60°C for 6 hours under a nitrogen atmosphere to obtain a reaction solution. Under an ice bath at 5°C under a nitrogen atmosphere, thionyl chloride was added dropwise to the reaction solution at a rate of 1 drop / second to adjust the molar ratio of thionyl chloride to 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride to 2:1, and an intermediate was obtained after the addition was complete.

[0118] (2) Add 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 4,4'-diaminodiphenyl ether, and the intermediate obtained in step (1) in a molar ratio of 1:1:4 to N,N-dimethylformamide and react at 25°C for 6 hours to obtain a reaction product. The obtained reaction product is uniformly introduced into deionized water, allowed to stand to separate into layers, the upper layer is removed, the resin is pulverized, the deionized water is replaced and the resin is washed by immersion, filtered, and repeated several times, and dried to obtain a solid resin, i.e., the polymer described in this comparative example.

[0119] The polymer described in Comparative Example 1 has the following structural formula. [ka]

[0120] The polymer production method described in Comparative Example 2 includes the following steps (1) and (2).

[0121] (1) 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride and n-butanol in a molar ratio of 1:2 were added to N-methylpyrrolidone and reacted in an oil bath at 60°C for 6 hours under a nitrogen atmosphere to obtain a reaction solution. Under an ice bath at 5°C under a nitrogen atmosphere, thionyl chloride was added dropwise to the reaction solution at a rate of 1 drop / second to adjust the molar ratio of thionyl chloride to 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride to 2:1, and an intermediate was obtained after the addition was complete.

[0122] (2) Add 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 4,4'-diaminodiphenyl ether, and the intermediate obtained in step (1) in a molar ratio of 1:1:4 to N,N-dimethylformamide and react at 25°C for 6 hours to obtain a reaction product. The obtained reaction product is uniformly introduced into deionized water, allowed to stand to separate into layers, the upper layer is removed, the resin is pulverized, the deionized water is replaced and the resin is washed by immersion, filtered, and repeated several times, and dried to obtain a solid resin, i.e., the polymer described in this comparative example.

[0123] The polymer described in Comparative Example 2 has the following structural formula. [ka]

[0124] The polymer production method described in Comparative Example 3 includes the following steps (1) and (2).

[0125] (1) 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride and n-butanol in a molar ratio of 1:1.2 were added to N-methylpyrrolidone and reacted in an oil bath at 60°C for 6 hours under a nitrogen atmosphere to obtain a reaction solution. Under an ice bath at 5°C under a nitrogen atmosphere, thionyl chloride was added dropwise to the reaction solution at a rate of 1 drop / second to adjust the molar ratio of thionyl chloride to 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride to 2:1, and an intermediate was obtained after the addition was complete.

[0126] (2) Add 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone, and the intermediate obtained in step (1) in a molar ratio of 1:1:4 to N,N-dimethylformamide and react at 25°C for 6 hours to obtain a reaction product. The obtained reaction product is uniformly introduced into deionized water, allowed to stand to separate into layers, the upper layer is removed, the resin is pulverized, the deionized water is replaced and the resin is washed by immersion, filtered, and repeated several times, and dried to obtain a solid resin, i.e., the polymer described in this comparative example.

[0127] The polymer described in Comparative Example 3 has the following structural formula. [ka]

[0128] The polymer production method described in Comparative Example 4 includes the following steps (1) and (2).

[0129] (1) 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride and n-butanol in a molar ratio of 1:1.5 were added to N-methylpyrrolidone and reacted in an oil bath at 60°C for 6 hours under a nitrogen atmosphere to obtain a reaction solution. Under an ice bath at 5°C under a nitrogen atmosphere, thionyl chloride was added dropwise to the reaction solution at a rate of 1 drop / second to adjust the molar ratio of thionyl chloride to 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride to 2:1, and an intermediate was obtained after the addition was complete.

[0130] (2) Add 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone, and the intermediate obtained in step (1) in a molar ratio of 1:1:4 to N,N-dimethylformamide and react at 25°C for 6 hours to obtain a reaction product. The obtained reaction product is uniformly introduced into deionized water, allowed to stand to separate into layers, the upper layer is removed, the resin is pulverized, the deionized water is replaced and the resin is washed by immersion, filtered, and repeated several times, and dried to obtain a solid resin, i.e., the polymer described in this comparative example.

[0131] The polymer described in Comparative Example 4 has the following structural formula. [ka]

[0132] The polymers of Examples 1-10 and Comparative Examples 1-4 were mixed with carbon black particles while stirring to obtain photoresist solutions. The mechanical performance of each group was then tested. The specific test methods are as follows.

[0133] OD value test: A black sample piece was placed in an optical densitometer, adjusted to zero, and the OD value was measured. The position of the photoresist coating layer was moved, and measurements were taken four times, and the average value was calculated.

[0134] Tensile performance test: [Table 2]

[0135] CTE Test: [Table 3]

[0136] DMA test: [Table 4]

[0137] The test results are shown in Table 2.

[0138] Table 2 Mechanical performance test results of polymers described in Examples 1-10 [Table 5]

[0139] As can be seen from the results in Table 2, the polymers described in Examples 1 to 10 of the present invention all have high OD values ​​and good mechanical performance compared to Comparative Examples 1 to 4.

[0140] 2. Thermal performance of the polymer described in the present invention

[0141] The thermal performance of the polymer described in Example 1 was tested, and the specific test method is as follows.

[0142] Td test: [Table 6]

[0143] The test results are shown in Figure 23.

[0144] As can be seen from Figure 23, the polymer described in the present invention has good thermal performance.

[0145] The polymers of Examples 2-10 have similar thermal properties, and their description is omitted here.

[0146] (Example 12) Photolithography performance of the polymer described in the present invention

[0147] The polymer described in Example 1 was used as the test subject to test the photolithography performance of the polymer described in the present invention, and the specific test method is as follows.

[0148] The obtained polymer, dissolution inhibitor, crosslinking agent, coupling agent, and solvent were mixed while stirring. The completely dissolved mixed solution was filtered under pressure to remove insoluble matter, and degassed under vacuum to obtain a photoresist solution. Subsequently, it was exposed using a contact lithography apparatus (Shenzhen Lanxingyu Electronic Technology Co., Ltd., URE-2000 / 35) and developed with alkaline water.

[0149] The test results are shown in Figures 24-27.

[0150] As can be seen from Figures 24-27, the polymer described in the present invention can form high-resolution patterns (5 μm).

[0151] The polymers of Examples 2-10 have similar photolithography properties, and their details are omitted here.

[0152] (Example 13) Nuclear magnetic resonance spectrum of the polymer described in the present invention

[0153] The polymer described in Example 8 was used as the test subject, and the nuclear magnetic resonance spectrum of the polymer described in the present invention was tested. The specific test method is as follows: The nuclear magnetic resonance tube was cleaned, the sample and the nuclear magnetic resonance tube were dried, the sample was transferred to the nuclear magnetic resonance tube (in the case of solution nuclear magnetic resonance, it is necessary to dissolve it before transferring), and the sample was placed in the instrument for testing.

[0154] The test results are shown in Figure 28.

[0155] As can be seen from Figure 28, we succeeded in synthesizing the polymer.

[0156] The polymers of Examples 2-10 have similar nuclear magnetic resonance spectra, and their description is omitted here.

[0157] The above embodiments are merely illustrative of the technical solutions of the present invention and do not limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims

1. The structural formula is as follows: 【Chemistry 1】 However, R is H, 【Chemistry 2】 、 It is at least one of MeOH, and n is an integer between 8 and 40. A polymer characterized by the following features.

2. A method for producing a polymer according to claim 1, (1) A step of reacting a dianhydride monomer, an esterifying agent, and an acid chloride agent in solvent 1 to obtain an intermediate, (2) The step of reacting the intermediate obtained in step (1) with a diamine monomer and 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone in solvent 2 to obtain the polymer, A manufacturing method characterized by the following features.

3. In step (1) above, the dianhydride monomer and the esterifying agent are reacted in the solvent 1 to obtain a reaction solution, the acid chloride agent is added dropwise to the reaction solution under a nitrogen atmosphere and ice bath conditions, and the intermediate is obtained after the dropwise addition is complete. A method for producing a polymer according to claim 2.

4. Step (1) above is, (1a) The condition that the molar ratio of the dianhydride monomer to the esterifying agent is 1:1 to 1:2, (1b) The condition that the reaction temperature of the dianhydride monomer and the esterifying agent in the solvent 1 is 30 to 90°C, (1c) The condition that the reaction time of the dianhydride monomer and the esterifying agent in the solvent 1 is 6 to 24 hours, (1d) The condition that the temperature of the ice bath is 5 to 10°C, (1e) The condition that the molar ratio of the acid chloride agent to the dianhydride monomer is 2:1 to 2.5:1, (1f) The condition that the dropping rate of the acid chloride agent is 1 to 4 drops / second, (1 g) The condition that the solvent 1 is at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and tetrahydrofuran, (1h) the acid chlorinating agent is SOCl ２ , AlCl ３ , BF ３ , SbCl ５ , FeBr ３ , FeCl ３ , SnCl ４ , TiCl ４ , ZnCl ２ and the condition that it is at least one of them, (1i) The method for producing a polymer according to claim 3, characterized in that at least one of the following conditions is met: (1i) The esterifying agent is at least one of n-butanol, ethanol, isopropanol, n-propanol, t-butanol, and methanol.

5. The dianhydride monomer is at least one of the following: 3,3',4,4'-diphenylethertetracarboxylic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 2,2'-bis(3,4-dicarboxylic acid)hexafluoropropane dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid dianhydride, 3,3,4,4-diphenylsulfonetetracarboxylic acid dianhydride, naphthalene-1,4,5,8-tetracarboxylic acid dianhydride, diphenyl sulfide dianhydride, and bisphenol A type diether dianhydride. A method for producing a polymer according to claim 2 or 3, characterized by the above.

6. The structural formula of the aforementioned intermediate is as follows: 【Transformation 3】 However, R is H, 【Chemistry 4】 、 It is at least one of the MeOH species. A method for producing a polymer according to claim 2 or 3, characterized by the above.

7. In step (2) above, the molar ratio of the diamine monomer, 1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone, and intermediate is diamine monomer:1,8-dihydroxy-2,4,5,7-tetraamino-9,10-anthraquinone:intermediate = 1:1:2 to 1:1:

4. A method for producing a polymer according to claim 2.

8. The diamine monomers in step (2) are m-phenylenediamine, p-phenylenediamine, 4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-diamino-2,2'-dimethylbiphenyl, 2-(4-aminophenyl)-5-aminobenzoxazole, and 2-(4-aminophenyl). At least one of the following: -5-aminobenzimidazole, 1,4-bis(3-aminophenoxy)benzene, 1,3-bis(3-hydroxy-4-aminophenoxy)benzene, 2-(4-aminophenyl)-6-aminobenzoxazole, 2,2-p-phenyl-bis(5-aminobenzoxazole), 2,2'-p-phenyl-bis(6-aminobenzoxazole), 2,2-bis(4-hydroxy-3-aminophenyl)propane, 3,3'-dihydroxybenzidine, 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid. A method for producing a polymer according to claim 2 or 7.

9. Step (2) above is, (2a) The condition that the solvent 2 is at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and tetrahydrofuran, (2b) The condition that the reaction temperature in step (2) is 15 to 35°C, (2c) The condition that the reaction time in step (2) is 3 to 8 hours, and that at least one of the following conditions is met. A method for producing a polymer according to claim 2.

10. Use of the polymer according to claim 1 in the production of a black matrix.

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