WO2023202454A1 - 一种用于黑色矩阵的聚合物、其制备方法及应用 - Google Patents

一种用于黑色矩阵的聚合物、其制备方法及应用 Download PDF

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WO2023202454A1
WO2023202454A1 PCT/CN2023/088004 CN2023088004W WO2023202454A1 WO 2023202454 A1 WO2023202454 A1 WO 2023202454A1 CN 2023088004 W CN2023088004 W CN 2023088004W WO 2023202454 A1 WO2023202454 A1 WO 2023202454A1
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polymer
preparation
dianhydride
bis
black matrix
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PCT/CN2023/088004
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English (en)
French (fr)
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路庆华
张配荧
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上海交通大学
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Publication of WO2023202454A1 publication Critical patent/WO2023202454A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/28—Preparatory processes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer

Definitions

  • the present invention relates to a polymer for black matrix, in particular to an intrinsic resin-based black matrix polymer, its preparation method and use.
  • Black Matrix is a negative photoresist with black dispersed pigments.
  • black matrix containing carbon black has been widely used in flat panel displays. It is usually set in the gaps between stripes and dots of color filters.
  • Black The main functions of the matrix are: 1.
  • the black matrix resist must have high optical density to prevent light leakage; 2. Separate each color pixel to prevent mutual interference between color pixels and improve image contrast; 3. Prevent light leakage current; 4. Prevent background light writing from causing low contrast.
  • the black matrix plays the role of blocking light and building a framework for the subsequently coated red, green, and blue primary color photoresists, so it has higher requirements for its performance.
  • Chromium-based black matrix has many disadvantages, such as high cost, complex manufacturing process, poor adhesion, high reflectivity, complex manufacturing process and potential environmental issues.
  • the black matrix has shifted from the chromium system to the resin system doped with black dye.
  • Films made of resin-based black matrices are used in color filters for liquid crystal displays. They have lower reflectivity than chromium oxide and less environmental pressure from process developers.
  • the introduction of carbon materials and organic dyes significantly reduces the Electrical insulation properties, and due to uneven distribution will inevitably damage its mechanical properties, organic dyes have poor heat resistance and will significantly reduce the heat resistance of the black matrix.
  • the object of the present invention is to overcome the above-mentioned shortcomings of the prior art and provide a polymer with better mechanical and thermal properties and photolithography properties for black matrix. At the same time, the present invention also provides a preparation method and application of the polymer.
  • the technical solution adopted by the present invention is: a polymer, the polymer obtains an intermediate by reacting a dianhydride monomer and hydroxyethyl methacrylate, and then combines the intermediate, an organic base, and a diamine. It is prepared by reacting the monomer and 1,8 dihydroxy-2,4,5,7 tetraamino-9,10-anthraquinone under the action of a catalyst.
  • the polymer of the present invention first uses dianhydride monomer and hydroxyethyl methacrylate to react in a solvent to obtain an intermediate, and then combines the obtained intermediate with diamine monomer and 1,8 dihydroxy-2,4, 5,7 Tetraamino-9,10-anthraquinone is prepared by reaction under the action of catalyst.
  • dianhydride monomer and hydroxyethyl methacrylate to react in a solvent to obtain an intermediate
  • diamine monomer 1,8 dihydroxy-2,4, 5,7 Tetraamino-9,10-anthraquinone is prepared by reaction under the action of catalyst.
  • the dianhydride monomer is 3,3,4,4'-diphenyl ether tetracarboxylic dianhydride, 4,4'-biphenyl tetracarboxylic dianhydride, 3 ,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2'-bis(3,4-dicarboxylic acid) hexafluoropropane dianhydride, 2,3,3',4'-biphenyl At least one of tetracarboxylic dianhydride, 3,3′,4,4′-diphenylsulfone tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, and diphenyl sulfide dianhydride .
  • the dianhydride monomer is 3,3,4,4'-diphenyl ether tetracarboxylic dianhydride, 4,4'-biphen
  • the structural formula of the intermediate is:
  • the organic base is at least one of triethylamine, methylamine, ethylamine, dimethylamine, and diethylamine.
  • the organic base is triethylamine.
  • the diamine monomer 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-aminobenzene Oxy)benzene, 4,4'-diamino-2,2'-dimethylbiphenyl, 2-(4-aminophenyl)-5-aminobenzoxazole, 2-(4-aminophenyl) )-5-aminobenzimidazole, 1,4-bis(3-aminophenoxy)benzene, 1,3-bis(3-hydroxy-4-aminophen
  • the catalyst is at least one of SOCl 2 , AlCl 3 , BF 3 , SbCl 5 , FeBr 3 , FeCl 3 , SnCl 4 , TiCl 4 and ZnCl 2 .
  • the catalyst is SOCl 2 .
  • the dianhydride monomer is 3,3,4,4'-diphenyl ether tetracarboxylic dianhydride
  • the diamine monomer is m-phenylenediamine
  • the structural formula of the polymer is:
  • n is an integer from 10 to 50.
  • n is an integer of 20 to 40.
  • Another object of the present invention is to provide a method for preparing the above-mentioned polymer with simple process steps and easy industrial application.
  • the technical solution adopted by the present invention is: a polymer
  • the preparation method of compound, described method includes the following steps:
  • step (1) Add the diamine monomer, organic base 1,8 dihydroxy-2,4,5,7 tetraamino-9,10-anthraquinone and the intermediate obtained in step (1) into solvent 2, and then add the catalyst reaction to obtain the polymer.
  • step (1) the molar ratio of dianhydride monomer to hydroxyethyl methacrylate is 1:2, and the reaction temperature is 40 to 80°C.
  • the reaction temperature in step (1) is 70°C.
  • the reaction conditions in step (1) are: 70°C oil bath under nitrogen atmosphere.
  • the dianhydride monomer in step (1) is 3,3,4,4'-diphenyl ether tetracarboxylic dianhydride, 4,4'- Biphenyl tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2'-bis(3,4-dicarboxylic acid) hexafluoropropane dianhydride, 2,3 ,3',4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, diphenyl At least one of thioether dianhydrides.
  • the dianhydride monomer 4,4'- Biphenyl tetracarboxylic dianhydride, 3,3',4,4'-benzophenone t
  • step (2) diamine monomer, 1,8 dihydroxy-2,4,5,7 tetraamino-9,10-anthraquinone and The molar ratio of the intermediate is 1:1:1, and the reaction temperature is 0 to 5°C.
  • 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, 2-(4-aminophenyl)-5-aminobenzimidazole, 1,4-bis(3-aminophenoxy)benzene, 1,3-bis(3- Hydroxy-4-
  • the dianhydride monomer in the step (1) is 3,3,4,4'-diphenyl ether tetracarboxylic dianhydride; the step (2) ), the diamine monomer is p-phenylenediamine.
  • the polymer obtained in step (1) is:
  • the 1,8 dihydroxy-2,4,5,7 tetraamino-9,10-anthraquinone in step (2) is prepared by the following method Formed: In the presence of concentrated sulfuric acid and concentrated nitric acid, 1,8 dihydroxy-9,10-anthraquinone is nitrated into 1,8 dihydroxy-2,4,5,7 tetranitro-9,10-anthracene Quinone, and then the nitro group is reduced to the amino group to obtain 1,8 dihydroxy-2,4,5,7 tetraamino-9,10-anthraquinone.
  • the 1,8 dihydroxy-2,4,5,7 tetraamino-9,10-anthraquinone in step (2) is prepared by the following method Formed: In the presence of concentrated sulfuric acid and concentrated nitric acid, 1,8 dihydroxy-4,5 dinitro-9,10-anthraquinone is nitrated into 1,8 dihydroxy-2,4,5,7 tetranitrate base-9,10-anthraquinone, and then reduce the nitro group to the amino group to obtain 1,8 dihydroxy-2,4,5,7tetraamino-9,10-anthraquinone.
  • the solvent 1 and solvent 2 are each independently selected from N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylethyl At least one of amide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and tetrahydrofuran;
  • the organic base in step (2) is triethylamine, methylamine , at least one of ethylamine, dimethylamine, and diethylamine;
  • the catalyst in step (2) is SOCl 2 , AlCl 3 , BF 3 , SbCl 5 , FeBr 3 , FeCl 3 , SnCl 4 , TiCl 4 , at least one of ZnCl 2 .
  • both solvent 1 and solvent 2 are N-methylpyrrolidone.
  • the organic base in step (2) is triethylamine, and the catalyst is SOCl 2 .
  • the present invention also provides the use of the above-mentioned polymer in preparing a black matrix.
  • a black matrix from the polymer of the present invention When preparing a black matrix from the polymer of the present invention, first mix the polymer with substances including but not limited to photoinitiators, cross-linking agents, solvents, etc., and stir evenly to prepare a black photosensitive resin composition.
  • the photoinitiators in the black photosensitive resin composition include but are not limited to oxime ester photoinitiators such as oxe-01, oxe-02, pbg-304, pbg314, etc.
  • the cross-linking agent is preferably tetraethylene glycol dimethyl Acrylic acid system photosensitive cross-linking agent such as acrylic acid ester, etc.
  • the solvent is an organic solvent.
  • the amount of solvent added is 150 to 300 ml of solvent per 100 g of polymer.
  • At least one of surfactants, fillers, adhesion accelerators, bridging agents, antioxidants, anti-aggregation agents and other additives may be added to the black photosensitive resin composition.
  • the polymer of the present invention is mixed with other components contained in the black photosensitive resin composition, and then stirred, for example, in a planetary gravity mixer (Mianyang Shinuo Technology Co., Ltd. ), stir and mix evenly, and then the mixture becomes a solution, thereby obtaining the black photosensitive resin composition.
  • a planetary gravity mixer Moanyang Shinuo Technology Co., Ltd.
  • the polymer of the present invention is used to prepare a black matrix
  • the following method can be used: the above-mentioned black photosensitive resin composition is coated on a substrate, and then pre-baked, exposed on a photolithography equipment, developed, and then After post-baking, a black matrix is obtained.
  • the equipment used is, for example: spin coating on the substrate on an RC-150 glue spreader (Suzhou Meitu Semiconductor Technology Co., Ltd.), and a PHP-8 hot plate (Suzhou Meitu Semiconductor).
  • Technology Co., Ltd. exposed on URE-2000/35 lithography equipment (Institute of Optoelectronics Technology, Chinese Academy of Sciences), developed, and then on a PHP-8 hot plate (Suzhou Meitu Semiconductor Technology Co., Ltd.) Post-bake.
  • the above-mentioned pre-baking treatment is carried out at a temperature of 70°C to 110°C for 1 minute to 15 minutes. After pre-baking, place the above-mentioned coating film under the designated mask for exposure, and then immerse it in the developer at a temperature of 23 ⁇ 2°C for 1 second to 5 minutes to remove unnecessary parts and form a specific pattern. .
  • the light used for exposure is preferably ultraviolet light such as g-line, h-line or i-line, and the ultraviolet irradiation device can be an (ultra) high-pressure mercury lamp or a metal halide lamp.
  • the polymer described in the present invention has unique structural characteristics, good mechanical and thermal properties and photolithographic properties. When applied to a black matrix, it can better meet the current industry requirements for black matrix performance.
  • the raw materials are convenient and easy to obtain, the preparation steps and process conditions are simple, and it is convenient for industrial promotion.
  • the application of the polymer in the preparation of the black matrix not only provides a new polymer choice for the black matrix, but also can significantly improve the mechanical and thermal properties of the black matrix.
  • Figure 1 is the structural formula of an embodiment of the polymer according to the present invention.
  • Figure 2 is a structural reaction formula of an embodiment of the polymer preparation method of the present invention.
  • Figure 3 is a graph showing the thermal performance test results of an embodiment of the polymer according to the present invention.
  • Figure 4 is a photolithographic performance test chart of an embodiment of the polymer according to the present invention.
  • Figure 5 is a photolithography performance test chart of another embodiment of the polymer according to the present invention.
  • Figure 6 is a photolithography performance test chart of another embodiment of the polymer according to the present invention.
  • the 1,8 dihydroxy-2,4,5,7 tetraamino-9,10-anthraquinone is prepared by the following method: in the presence of concentrated sulfuric acid and concentrated nitric acid, 1,8 dihydroxy-9 , 10-anthraquinone is nitrated to 1,8-dihydroxy-2,4,5,7tetranitro-9,10-anthraquinone, and then the nitro group is reduced to an amino group to obtain 1,8-dihydroxy-2,4, 5,7tetraamino-9,10-anthraquinone; or prepared by the following method: in the presence of concentrated sulfuric acid and concentrated nitric acid, 1,8dihydroxy-4,5dinitro-9,10- Anthraquinone is nitrated to 1,8 dihydroxy-2,4,5,7tetranitro-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-anthraquino
  • step (2) Add p-phenylenediamine, triethylamine and 1,8dihydroxy-2,4,5,7tetraamino-9,10-anthraquinone to the intermediate described in step (1), and then add SOCl 2 React at 0°C to obtain the polymer described in this example; the moles of the intermediate, p-phenylenediamine and 1,8dihydroxy-2,4,5,7tetraamino-9,10-anthraquinone The ratio is 1:1:1.
  • An embodiment of the polymer of the present invention includes the following steps:
  • step (2) Add m-phenylenediamine, triethylamine and 1,8dihydroxy-2,4,5,7tetraamino-9,10-anthraquinone to the intermediate described in step (1), and then add SOCl 2 React at 1°C to obtain the polymer described in this example; the moles of the intermediate, m-phenylenediamine and 1,8dihydroxy-2,4,5,7tetraamino-9,10-anthraquinone The ratio is 1:1:1.
  • An embodiment of the polymer of the present invention includes the following steps:
  • step (2) Add 4,4'-diaminobiphenyl, triethylamine and 1,8dihydroxy-2,4,5,7tetraamino-9,10-anthraquinone to the intermediate described in step (1) , then add SOCl 2 and react at 0°C to obtain the polymer described in this example; the intermediate, 4,4'-diaminobiphenyl and 1,8 dihydroxy-2,4,5,7 tetrahydrofuran The molar ratio of amino-9,10-anthraquinone is 1:1:1.
  • An embodiment of the polymer of the present invention includes the following steps:
  • An embodiment of the polymer of the present invention includes the following steps:
  • An embodiment of the polymer of the present invention includes the following steps:
  • An embodiment of the polymer of the present invention includes the following steps:
  • An embodiment of the polymer of the present invention includes the following steps:
  • step (2) Add p-phenylenediamine, triethylamine and 1,8dihydroxy-2,4,5,7tetraamino-9,10-anthraquinone to the intermediate described in step (1), and then add SOCl 2 React at 3°C to obtain the polymer described in this example; the moles of the intermediate, p-phenylenediamine and 1,8dihydroxy-2,4,5,7tetraamino-9,10-anthraquinone The ratio is 1:1:1.
  • the black photosensitive resin composition described in this embodiment includes the following weight components: 100 g of the polymer of Example 1, 3 to 5 g of photoinitiator, 5 to 10 g of crosslinking agent, and 150 to 300 ml of solvent.
  • the photoinitiator is an oxime ester photoinitiator, such as oxe-01, oxe-02, pbg-304, pbg314, etc.
  • the cross-linking agent is an acrylic system photosensitive cross-linking agent, such as tetraethyl Diol dimethacrylate
  • the solvent is an organic solvent.
  • the polymer is mixed with other ingredients, and then stirred, for example, in a planetary gravity mixer (Mianyang Shinuo Technology Co., Ltd.), until the mixture is evenly mixed and in a solution state. , the black photosensitive resin composition is obtained.
  • a planetary gravity mixer Mianyang Shinuo Technology Co., Ltd.
  • At least one of surfactants, fillers, adhesion accelerators, bridging agents, antioxidants, anti-aggregation agents and other additives can be added to the black photosensitive resin composition.
  • surfactants fillers, adhesion accelerators, bridging agents, antioxidants, anti-aggregation agents and other additives
  • the black photosensitive resin composition described in Example 9 was spin-coated on the substrate on an RC-150 glue spreader (Suzhou Meitu Semiconductor Technology Co., Ltd.), and on a PHP-8 hot plate (Suzhou Meitu Semiconductor Technology Co., Ltd. ), perform pre-baking on URE-2000/35 lithography equipment (Institute of Optoelectronics Technology, Chinese Academy of Sciences), develop, and then perform post-baking on PHP-8 hot plate (Suzhou Meitu Semiconductor Technology Co., Ltd.) , that is, the black matrix of this embodiment is obtained.
  • the pre-baking treatment is performed at a temperature of 70°C to 110°C for 1 minute to 15 minutes. After pre-baking, place the above-mentioned coating film under the designated mask for exposure, and then immerse it in the developer at a temperature of 23 ⁇ 2°C for 1 second to 5 minutes to remove unnecessary parts and form a specific pattern. . exposed
  • the light used is preferably ultraviolet light such as g-line, h-line or i-line, and the ultraviolet irradiation device can be an (ultra) high-pressure mercury lamp or a metal halide lamp.
  • the polymers described in Examples 1 to 8 were respectively used to prepare black matrices according to the method of Example 9 as test groups 1 to 8. During the preparation process of the black matrices of test groups 1 to 8, except for the polymers, the other component contents and preparation The process and so on are the same.
  • the black matrices prepared in test groups 1 to 8 were used as test objects to test the mechanical properties of the black matrices obtained in each group.
  • the specific test method is: use a DMA tester (model: TA Q800) to test, and test the sample film from Tensile starts at 0N, and the elongation at break ( ⁇ ) and tensile strength ( ⁇ ) are obtained through the test.
  • the black matrix (Example 9) prepared from the polymer described in Example 1 was used as the test object to test its thermal properties.
  • the specific test method is: use a TMA tester (model: TA Q400) to measure Test, heat the sample film from 25°C to 400°C, and take the CTE in the range of 50 to 150°C; take the temperature corresponding to the inflection point on the curve as Tg*.
  • TMA tester model: TA Q400
  • Example 1 The polymer described in Example 1 was used as the test object to test the photolithography performance of the polymer described in the present invention.
  • the specific test steps are as described in Example 10.
  • Figures 4-6 show the developed image of the black matrix in the present invention. It can be seen from Figures 4-6 that the black matrix can exhibit good graphics performance in the range of 15nm-25nm.

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Abstract

本发明公开一种用于黑色矩阵的聚合物，所述聚合物通过将二酐单体和甲基丙烯酸羟乙酯反应得到中间体，然后将中间体、二胺单体、三乙胺和1,8二羟基-2,4,5,7四氨基-9,10-蒽醌在催化剂的作用下反应制备得到。本发明所述聚合物，具有独特的结构特点，具备较好的力学热学性能和光刻性能，将其应用于黑色矩阵时，能够更好满足目前业界对于黑色矩阵性能的要求。同时，本发明还公开了一种所述聚合物的制备方法和应用，所述制备方法工艺简单、便于工业化推广和应用。所述聚合物的应用，不仅为黑色矩阵提供了新的聚合物选择，而且能够显著提高黑色矩阵的力学和热学性能。

Description

一种用于黑色矩阵的聚合物、其制备方法及应用 技术领域
本发明涉及一种用于黑色矩阵的聚合物，尤其是一种本征性树脂系黑色矩阵用聚合物、其制备方法及用途。
背景技术
黑色矩阵(Black Matrix)是一种黑色分散颜料的负性光刻胶，目前含有炭黑的黑色矩阵已经广泛应用于平板显示器当中，通常会在彩色滤光片的条纹和点的间隙设置，黑色矩阵主要作用是：1、黑色矩阵抗蚀剂必须具有高的光密度(Optical Density)，以防止光泄漏；2、将各个色像素分离，防止彩色像素之间相互干扰，提高图像对比度；3、防止光漏电流产生；4、防止背景光的写入造成对比度低下。
随着LCD行业的快速发展，人们对黑色矩阵的要求也越来越高。在彩色滤光片中，黑色矩阵起着遮蔽光线以及为后续涂布的红绿蓝三原色光阻构建框架的作用，因此对于其性能具有更高的要求。
早期的黑色矩阵以无机铬(Cr)为主，使用铬基黑矩阵的好处是拥有更高的光学密度和更强的材料稳定性。铬基黑色矩阵具有许多缺点，例如成本高，制造过程复杂，附着力差，反射率高以及制造工艺复杂和潜在的环境问题。为了解决由铬引起的这些问题，黑色矩阵从铬系转向掺杂黑色染料的树脂系。树脂基黑色矩阵制成的薄膜应用于液晶显示器的彩色滤光片中，具有比氧化铬反射率低和工艺显影剂环境压力小的特点，但碳材料和有机染料的引入显著降低了黑色矩阵的电绝缘性能，并由于分布不均匀会不可避免地损害其机械性能，有机染料耐热性差，会显著降低黑色矩阵的耐热性。
因此，开发一种本征性树脂系黑色矩阵来规避上述缺点，并且达到目前业界对于黑色矩阵的要求，为本领域技术人员亟需实现的目标。
发明内容
本发明的目的在于克服上述现有技术的不足之处而提供一种具有较好力学热学性能和光刻性能、用于黑色矩阵的聚合物。同时，本发明还提供了所述聚合物的制备方法及其应用。
为实现上述目的，本发明采取的技术方案为：一种聚合物，所述聚合物通过将二酐单体和甲基丙烯酸羟乙酯反应得到中间体，然后将中间体、有机碱、二胺单体和1,8二羟基-2,4,5,7四氨基-9,10-蒽醌在催化剂的作用下反应制备得到。
本发明所述聚合物，先采用二酐单体和甲基丙烯酸羟乙酯在溶剂中反应得到中间体，然后将得到的中间体与二胺单体和1,8二羟基-2,4,5,7四氨基-9,10-蒽醌在催化剂的作用下反应制备得到，所得结构的聚合物用于黑色矩阵时，具有较好的力学热学性能和光刻性能，能够更好满足目前业界对于黑色矩阵的性能要求。
作为本发明所述聚合物的优选实施方式，所述二酐单体为3,3,4,4'-二苯醚四甲酸二酐、4,4’-联苯四羧酸二酐、3,3',4,4'-二苯酮四酸二酐、2,2'-双(3,4-二羧酸)六氟丙烷二酐、2,3,3',4'-联苯四甲酸二酐、3,3′,4,4′-二苯砜四羧酸二酐、萘-1,4,5,8-四甲酸二酐、二苯硫醚二酐中的至少一种。作为本发明所述聚合物的更优选实施方式，所述二酐单体为3,3,4,4'-二苯醚四甲酸二酐。
作为本发明所述聚合物的优选实施方式，所述中间体的结构式为：
作为本发明所述聚合物的优选实施方式，所述有机碱为三乙胺、甲胺、乙胺、二甲胺、二乙胺中的至少一种。作为本发明所述聚合物的更优选实施方式，所述有机碱为三乙胺。
作为本发明所述聚合物的优选实施方式，所述二胺单体为间苯二胺、对苯二胺、4,4’-二氨基联苯、4,4’-二氨基二苯醚、3,4’-二氨基二苯醚、4,4’-二氨基二苯甲酮、4,4'-二氨基二苯甲烷、1,3-双(4-氨基苯氧基)苯、1,4-双(4-氨基苯 氧基)苯、4,4'-二氨基-2,2'-二甲基联苯、2-(4-氨基苯基)-5-氨基苯并噁唑、2-(4-氨基苯基)-5-氨基苯并咪唑、1,4-双(3-氨基苯氧基)苯、1,3-双(3-羟基-4--氨基苯氧基)苯、2-(4-氨基苯基)-6-氨基苯并噁唑、2,2-对苯基-双(5-氨基苯并唑)、2,2'-对苯基-双(6-氨基苯并唑)中的至少一种。作为本发明所述聚合物的更优选实施方式，所述二胺单体为间苯二胺。
作为本发明所述聚合物的优选实施方式，所述催化剂为SOCl2、AlCl3、BF3、SbCl5、FeBr3、FeCl3、SnCl4、TiCl4、ZnCl2中的至少一种。作为本法民所述聚合物的更优选实施方式，所述催化剂为SOCl2。
作为本发明所述聚合物的优选实施方式，所述二酐单体为3,3,4,4'-二苯醚四甲酸二酐，所述二胺单体为间苯二胺。
上述所述1,8二羟基-2,4,5,7四氨基-9,10-蒽醌的结构式为：
作为本发明所述聚合物的优选实施方式，所述聚合物的结构式为：
其中，n为10～50的整数。
作为本发明所述聚合物的更优选实施方式，所述聚合物的结构式中，n为20～40的整数。
同时，本发明另一目的在于提供一种工艺步骤简单、便于工业化应用的如上所述聚合物的制备方法，为实现此目的，本发明采取的技术方案为：一种聚 合物的制备方法，所述方法包括如下步骤：
(1)取二酐单体和甲基丙烯酸羟乙酯在溶剂1中反应，得到中间体；
(2)取二胺单体、有机碱1,8二羟基-2,4,5,7四氨基-9,10-蒽醌和步骤(1)得到的中间体加入溶剂2中，然后加入催化剂反应，即得所述聚合物。
作为本发明所述聚合物的制备方法的优选实施方式，所述步骤(1)中二酐单体与甲基丙烯酸羟乙酯的摩尔比为1:2，反应温度为40～80℃。
作为本发明所述聚合物的制备方法的优选实施方式，所述步骤(1)中的反应温度为70℃。
作为本发明所述聚合物的制备方法的优选实施方式，所述步骤(1)中的反应条件为：氮气气氛下70℃油浴。
作为本发明所述聚合物的制备方法的优选实施方式，所述步骤(1)中的二酐单体为3,3,4,4'-二苯醚四甲酸二酐、4,4’-联苯四羧酸二酐、3,3',4,4'-二苯酮四酸二酐、2,2'-双(3,4-二羧酸)六氟丙烷二酐、2,3,3',4'-联苯四甲酸二酐、3,3′,4,4′-二苯砜四羧酸二酐、萘-1,4,5,8-四甲酸二酐、二苯硫醚二酐中的至少一种。作为本法民所述聚合物的制备方法的更优选实施方式，所述步骤(1)中的二酐单体为3,3,4,4'-二苯醚四甲酸二酐。
作为本发明所述聚合物的制备方法的优选实施方式，所述步骤(2)中二胺单体、1,8二羟基-2,4,5,7四氨基-9,10-蒽醌和中间体的摩尔比为1:1:1，反应温度为0～5℃。
作为本发明所述聚合物的制备方法的优选实施方式，所述步骤(2)中的二胺单体为间苯二胺、对苯二胺、4,4’-二氨基联苯、4,4’-二氨基二苯醚、3,4’-二氨基二苯醚、4,4’-二氨基二苯甲酮、4,4'-二氨基二苯甲烷、1,3-双(4-氨基苯氧基)苯、1,4-双(4-氨基苯氧基)苯、4,4'-二氨基-2,2'-二甲基联苯、2-(4-氨基苯基)-5-氨基苯并噁唑、2-(4-氨基苯基)-5-氨基苯并咪唑、1,4-双(3-氨基苯氧基)苯、1,3-双(3-羟基-4--氨基苯氧基)苯、2-(4-氨基苯基)-6-氨基苯并噁唑、2,2-对苯基-双(5-氨基苯并唑)、2,2'-对苯基-双(6-氨基苯并唑)中的至少一种。作为本发明所述聚合物的制备方法的更优选实施方式，所述步骤(2)中的二胺单体为间苯二胺。
作为本发明所述聚合物的制备方法的优选实施方式，所述步骤(1)中的二酐单体为3,3,4,4'-二苯醚四甲酸二酐；所述步骤(2)中的二胺单体为对苯二胺。
作为本发明所述聚合物的制备方法的优选实施方式，所述步骤(1)所得中 间体的结构式为：
作为本发明所述聚合物的制备方法的优选实施方式，所述步骤(2)中的1,8二羟基-2,4,5,7四氨基-9,10-蒽醌采用如下方法制备而成：在存在浓硫酸和浓硝酸的情况下，使1,8二羟基-9,10-蒽醌硝化成1,8二羟基-2,4,5,7四硝基-9,10-蒽醌，然后将硝基还原成氨基，得到1,8二羟基-2,4,5,7四氨基-9,10-蒽醌。
作为本发明所述聚合物的制备方法的优选实施方式，所述步骤(2)中的1,8二羟基-2,4,5,7四氨基-9,10-蒽醌采用如下方法制备而成：在存在浓硫酸和浓硝酸的情况下，使1,8二羟基-4,5二硝基-9,10-蒽醌硝化成1,8二羟基-2,4,5,7四硝基-9,10-蒽醌，然后将硝基还原成氨基，得到1,8二羟基-2,4,5,7四氨基-9,10-蒽醌。
作为本发明所述聚合物的制备方法的优选实施方式，所述溶剂1和溶剂2各自独立选自N-甲基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜、N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、四氢呋喃中的至少一种；所述步骤(2)中的有机碱为三乙胺、甲胺、乙胺、二甲胺、二乙胺中的至少一种；所述步骤(2)中的催化剂为SOCl2、AlCl3、BF3、SbCl5、FeBr3、FeCl3、SnCl4、TiCl4、ZnCl2中的至少一种。
作为本发明所述聚合物的制备方法的优选实施方式，所述溶剂1和溶剂2均为N-甲基吡咯烷酮。
作为本发明所述聚合物的制备方法的优选实施方式，所述步骤(2)中的有机碱为三乙胺，催化剂为SOCl2。
最后，本发明还提供了如上所述聚合物在制备黑色矩阵中的应用。
本发明所述聚合物在制备黑色矩阵时，首先将所述聚合物与包括但不限于光引发剂、交联剂和溶剂等物质混合，搅拌均匀后，制得黑色感光性树脂组成物。所述黑色感光性树脂组成物中的光引发剂包括但不限于oxe-01、oxe-02、pbg-304、pbg314等肟酯类光引发剂，所述交联剂优选四乙二醇二甲基丙烯酸酯等丙烯酸体系光敏交联剂，所述溶剂为有机溶剂。所述黑色感光性树脂组成物 中，聚合物、光引发剂和交联剂的质量比优先为：聚合物：光引发剂：交联剂＝100:(3～5)：(5～10)。所述黑色感光性树脂组成物中，溶剂的添加量为每100g聚合物加入150～300ml溶剂。
所述黑色感光性树脂组成物中必要时还可添加界面活性剂、填充剂、密着促进剂、架桥剂、抗氧化剂、防凝集剂等添加剂中的至少一种。
所述黑色感光性树脂组成物制备时，将本发明所述聚合物与所述黑色感光性树脂组成物中包含的其他成分混合，然后搅拌，例如在行星式重力搅拌机(绵阳世诺科技有限公司)中搅拌，搅拌混合均匀后呈溶液状态，即得所述黑色感光性树脂组成物。
本发明所述聚合物在制备黑色矩阵时，例如可采用如下方法：将上述所述黑色感光性树脂组成物涂布在基板上，然后进行前烘，在光刻设备上曝光，历经显影，再进行后烘，即得黑色矩阵。
所述黑色矩阵的制备过程中，使用的设备例如为：在RC-150匀胶机(苏州美图半导体技术有限公司)上旋转涂布在基板上，在PHP-8热板(苏州美图半导体技术有限公司)上进行前烘，在URE-2000/35光刻设备(中国科学院光电技术研究所)上进行曝光，历经显影，再在PHP-8热板(苏州美图半导体技术有限公司)上进行后烘。
上述所述前烘处理是在70℃至110℃温度下进行1分钟至15分钟。前烘后，将上述涂膜放置于指定的掩模版下曝光，然后在23±2℃的温度下浸渍于显影剂中，历时1秒至5分钟，以将不要的部分除去而形成特定的图案。曝光所使用的光线，以g线、h线或i线等的紫外线为佳，而紫外线照射装置可为(超)高压水银灯及金属卤素灯。
本发明所述的聚合物，具有独特的结构特点，具备较好的力学热学性能和光刻性能，将其应用于黑色矩阵时，能够更好满足目前业界对于黑色矩阵性能的要求。
本发明所述聚合物的制备方法中，原料方便易得，制备步骤和工艺条件简单，便于工业化推广。
本发明所述聚合物在制备黑色矩阵中的应用，不仅为黑色矩阵提供了新的聚合物选择，而且能够显著提高黑色矩阵的力学和热学性能。
附图说明
图1为本发明所述聚合物的一种实施例的结构式；
图2为本发明所述聚合物制备方法的一种实施例的结构反应式；
图3为本发明所述聚合物一种实施例的热学性能测试结果图；
图4为本发明所述聚合物一种实施例的光刻性能测试图；
图5为本发明所述聚合物另一实施例的光刻性能测试图；
图6为本发明所述聚合物再一实施例的光刻性能测试图。
具体实施方式
为更好的说明本发明的目的、技术方案和优点，下面将结合附图和具体实施例对本发明作进一步说明。
以下实施例中所述1,8二羟基-2,4,5,7四氨基-9,10-蒽醌的结构式为：
所述1,8二羟基-2,4,5,7四氨基-9,10-蒽醌采用如下方法制备而成：在存在浓硫酸和浓硝酸的情况下，使1,8二羟基-9,10-蒽醌硝化成1,8二羟基-2,4,5,7四硝基-9,10-蒽醌，然后将硝基还原成氨基，得到1,8二羟基-2,4,5,7四氨基-9,10-蒽醌；或者采用如下方法制备而成：在存在浓硫酸和浓硝酸的情况下，使1,8二羟基-4,5二硝基-9,10-蒽醌硝化成1,8二羟基-2,4,5,7四硝基-9,10-蒽醌，然后将硝基还原成氨基，得到1,8二羟基-2,4,5,7四氨基-9,10-蒽醌。
实施例1
本发明聚合物的一种实施例，本实施例所述聚合物的结构式如附图1所示，本实施例所述聚合物的制备方法包括以下步骤：
(1)取摩尔比为1：2的3,3,4,4'-二苯醚四甲酸二酐和甲基丙烯酸羟乙酯，加入到N-甲基吡咯烷酮中，在氮气气氛下70℃油浴反应，得到中间体；
(2)在步骤(1)所述中间体中加入对苯二胺、三乙胺和1,8二羟基-2,4,5,7四氨基-9,10-蒽醌，然后加入SOCl2在0℃下反应，即得本实施例所述聚合物；所述中间体、对苯二胺和1,8二羟基-2,4,5,7四氨基-9,10-蒽醌的摩尔比为1:1:1。
本实施例所述聚合物的结构反应式如附图2所示。
实施例2
本发明聚合物的一种实施例，本实施例所述聚合物的制备方法包括以下步骤：
(1)取摩尔比为1：2的4,4’-联苯四羧酸二酐和甲基丙烯酸羟乙酯，加入到N,N-二甲基甲酰胺中，在氮气气氛下60℃油浴反应，得到中间体；
(2)在步骤(1)所述中间体中加入间苯二胺、三乙胺和1,8二羟基-2,4,5,7四氨基-9,10-蒽醌，然后加入SOCl2在1℃下反应，即得本实施例所述聚合物；所述中间体、间苯二胺和1,8二羟基-2,4,5,7四氨基-9,10-蒽醌的摩尔比为1:1:1。
实施例3
本发明聚合物的一种实施例，本实施例所述聚合物的制备方法包括以下步骤：
(1)取摩尔比为1：2的萘-1,4,5,8-四甲酸二酐和甲基丙烯酸羟乙酯，加入到N,N-二甲基乙酰胺中，在氮气气氛下80℃油浴反应，得到中间体；
(2)在步骤(1)所述中间体中加入4,4’-二氨基联苯、三乙胺和1,8二羟基-2,4,5,7四氨基-9,10-蒽醌，然后加入SOCl2在0℃下反应，即得本实施例所述聚合物；所述中间体、4,4’-二氨基联苯和1,8二羟基-2,4,5,7四氨基-9,10-蒽醌的摩尔比为1:1:1。
实施例4
本发明聚合物的一种实施例，本实施例所述聚合物的制备方法包括以下步骤：
(1)取摩尔比为1：2的二苯硫醚二酐和甲基丙烯酸羟乙酯，加入到二甲基亚砜中，在氮气气氛下50℃油浴反应，得到中间体；
(2)在步骤(1)所述中间体中加入1,4-双(4-氨基苯氧基)苯、三乙胺和1,8二羟基-2,4,5,7四氨基-9,10-蒽醌，然后加入SOCl2在2℃下反应，即得本实施例所述聚合物；所述中间体、1,4-双(4-氨基苯氧基)苯和1,8二羟基-2,4,5,7四氨基-9,10-蒽醌的摩尔比为1:1:1。
实施例5
本发明聚合物的一种实施例，本实施例所述聚合物的制备方法包括以下步骤：
(1)取摩尔比为1：2的2,3,3',4'-联苯四甲酸二酐和甲基丙烯酸羟乙酯，加入到N-乙基-2-吡咯烷酮中，在氮气气氛下55℃油浴反应，得到中间体；
(2)在步骤(1)所述中间体中加入2,2-对苯基-双(5-氨基苯并唑)、三乙胺和1,8二羟基-2,4,5,7四氨基-9,10-蒽醌，然后加入SOCl2在0℃下反应，即得本实施例所述聚合物；所述中间体、2,2-对苯基-双(5-氨基苯并唑)和1,8二羟基-2,4,5,7四氨基-9,10-蒽醌的摩尔比为1:1:1。
实施例6
本发明聚合物的一种实施例，本实施例所述聚合物的制备方法包括以下步骤：
(1)取摩尔比为1：2的2,2'-双(3,4-二羧酸)六氟丙烷二酐和甲基丙烯酸羟乙酯，加入到四氢呋喃中，在氮气气氛下75℃油浴反应，得到中间体；
(2)在步骤(1)所述中间体中加入4,4’-二氨基二苯醚、三乙胺和1,8二羟基-2,4,5,7四氨基-9,10-蒽醌，然后加入SOCl2在4℃下反应，即得本实施例所述聚合物；所述中间体、4,4’-二氨基二苯醚和1,8二羟基-2,4,5,7四氨基-9,10-蒽醌的摩尔比为1:1:1。
实施例7
本发明聚合物的一种实施例，本实施例所述聚合物的制备方法包括以下步骤：
(1)取摩尔比为1：2的3,3,4,4'-二苯醚四甲酸二酐和甲基丙烯酸羟乙酯，加入到N-甲基-2-吡咯烷酮中，在氮气气氛下60℃油浴反应，得到中间体；
(2)在步骤(1)所述中间体中加入1,4-双(3-氨基苯氧基)苯、三乙胺和1,8二羟基-2,4,5,7四氨基-9,10-蒽醌，然后加入SOCl2在5℃下反应，即得本实施例所述聚合物；所述中间体、1,4-双(3-氨基苯氧基)苯和1,8二羟基-2,4,5,7四氨基-9,10-蒽醌的摩尔比为1:1:1。
实施例8
本发明聚合物的一种实施例，本实施例所述聚合物的制备方法包括以下步骤：
(1)取摩尔比为1：2的3,3',4,4'-二苯酮四酸二酐和甲基丙烯酸羟乙酯，加入到N-甲基吡咯烷酮中，在氮气气氛下70℃油浴反应，得到中间体；
(2)在步骤(1)所述中间体中加入对苯二胺、三乙胺和1,8二羟基-2,4,5,7四氨基-9,10-蒽醌，然后加入SOCl2在3℃下反应，即得本实施例所述聚合物；所述中间体、对苯二胺和1,8二羟基-2,4,5,7四氨基-9,10-蒽醌的摩尔比为1:1:1。
实施例9
采用本发明所述聚合物制备黑色矩阵的一种实施例
1、制备黑色感光性树脂组成物
本实施例所述黑色感光性树脂组成物包含以下重量的成分：实施例1的聚合物100g、光引发剂3～5g、交联剂5～10g、溶剂150～300ml。
本实施例中，所述光引发剂为肟酯类光引发剂，例如oxe-01、oxe-02、pbg-304、pbg314等，所述交联剂为丙烯酸体系光敏交联剂，例如四乙二醇二甲基丙烯酸酯，所述溶剂为有机溶剂。
本实施例所述黑色感光性树脂组成物在制备时，将聚合物与其他成分混合，然后搅拌，例如在行星式重力搅拌机(绵阳世诺科技有限公司)中搅拌，搅拌混合均匀后呈溶液状态，即得所述黑色感光性树脂组成物。
所述黑色感光性树脂组成物中在必要时还可添加界面活性剂、填充剂、密着促进剂、架桥剂、抗氧化剂、防凝集剂等添加剂中的至少一种，本领域技术人员可根据实际需要进行选择。
2、制备黑色矩阵
本实施例黑色矩阵采用如下方法制备而成：
在RC-150匀胶机(苏州美图半导体技术有限公司)上将实施例9所述黑色感光性树脂组成物旋转涂布在基板上，在PHP-8热板(苏州美图半导体技术有限公司)上进行前烘，在URE-2000/35光刻设备(中国科学院光电技术研究所)上进行曝光，历经显影，再在PHP-8热板(苏州美图半导体技术有限公司)上进行后烘，即得本实施例黑色矩阵。
本实施例中，所述前烘处理是在70℃至110℃温度下进行1分钟至15分钟。前烘后，将上述涂膜放置于指定的掩模版下曝光，然后在23±2℃的温度下浸渍于显影剂中，历时1秒至5分钟，以将不要的部分除去而形成特定的图案。曝 光所使用的光线，以g线、h线或i线等的紫外线为佳，而紫外线照射装置可为(超)高压水银灯及金属卤素灯。
实施例11
本发明所述聚合物的性能试验。
一、本发明所述聚合物制备得到的黑色矩阵的力学热学性能
1、本发明所述聚合物制得得到的黑色矩阵的力学性能
分别采用实施例1～8所述聚合物按照实施例9的方法制备黑色矩阵作为试验组1～8，试验组1～8的黑色矩阵制备过程中，除了聚合物不同外，其余成分含量及制备工艺等均相同。将试验组1～8制备所得黑色矩阵作为试验对象，测试各组所得黑色矩阵的力学性能，具体测试方法为：使用DMA测试仪(型号：TA Q800)进行测试，将样品薄膜在25℃下从0N开始拉伸，测试获得断裂伸长率(ε)和拉伸强度(σ)。
测试结果如表1所示。
表1试验组1～8所述黑色矩阵的力学测试结果
由表1结果可知，由本发明实施例1～8所述聚合物制备所得黑色矩阵均具有良好的力学性能。
2、本发明所述聚合物制备所得黑色矩阵的热学性能
以实施例1所述聚合物制备得到的黑色矩阵(实施例9)作为试验对象，测试其热学性能，具体测试方法为：使用TMA测试仪(型号：TA Q400)进行测 试，将样品薄膜从25℃加热至400℃，取50～150℃区间内的CTE；取曲线上拐点对应的温度为Tg*。测试结果如附图3所示。
由附图3可知，本发明所述聚合物制备得到的黑色矩阵具有良好的热学性能。
二、本发明所述聚合物的光刻性能
以实施例1所述聚合物为试验对象，测试本发明所述聚合物的光刻性能。具体测试步骤如实施例10所述。
测试结果如附图4～6所示。
图4-6展示了本发明中黑色矩阵的显影后图像，由附图4～6可知本黑色矩阵在15nm-25nm区间能展现出良好的图形性能。
最后所应当说明的是，以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制，尽管参照较佳实施例对本发明作了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的实质和范围。

Claims (10)

  1. 一种聚合物，其特征在于，所述聚合物通过将二酐单体和甲基丙烯酸羟乙酯反应得到中间体，然后将中间体、有机碱、二胺单体和1,8二羟基-2,4,5,7四氨基-9,10-蒽醌在催化剂的作用下反应制备得到。
  2. 如权利要求1所述的聚合物，其特征在于，所述聚合物的结构式为：
    其中，n为10～50的整数。
  3. 一种如权利要求1～2任一项所述聚合物的制备方法，其特征在于，所述方法包括如下步骤：
    (1)取二酐单体和甲基丙烯酸羟乙酯在溶剂1中反应，得到中间体；
    (2)取二胺单体、有机碱、1,8二羟基-2,4,5,7四氨基-9,10-蒽醌和步骤(1)得到的中间体加入溶剂2中，然后加入催化剂反应，即得所述聚合物。
  4. 如权利要求3所述聚合物的制备方法，其特征在于，所述步骤(1)中二酐单体与甲基丙烯酸羟乙酯的摩尔比为1:2，反应温度为40～80℃。
  5. 如权利要求3或4所述聚合物的制备方法，其特征在于，所述步骤(1)中的二酐单体为3,3,4,4'-二苯醚四甲酸二酐、4,4’-联苯四羧酸二酐、3,3',4,4'-二苯酮四酸二酐、2,2'-双(3,4-二羧酸)六氟丙烷二酐、2,3,3',4'-联苯四甲酸二酐、3,3′,4,4′-二苯砜四羧酸二酐、萘-1,4,5,8-四甲酸二酐、二苯硫醚二酐中的至少一种。
  6. 如权利要求3所述聚合物的制备方法，其特征在于，所述步骤(2)中二胺单体、1,8二羟基-2,4,5,7四氨基-9,10-蒽醌和中间体的摩尔比为1:1:1，反应温度为0～5℃。
  7. 如权利要求3所述聚合物的制备方法，其特征在于，所述步骤(2)中的二胺单体为间苯二胺、对苯二胺、4,4’-二氨基联苯、4,4’-二氨基二苯醚、3,4’-二氨基二苯醚、4,4’-二氨基二苯甲酮、4,4'-二氨基二苯甲烷、1,3-双(4-氨基苯氧基)苯、1,4-双(4-氨基苯氧基)苯、4,4'-二氨基-2,2'-二甲基联苯、2-(4-氨基苯基)-5-氨基苯并噁唑、2-(4-氨基苯基)-5-氨基苯并咪唑、1,4-双(3-氨基苯氧基)苯、1,3-双(3-羟基-4--氨基苯氧基)苯、2-(4-氨基苯基)-6-氨基苯并噁唑、2,2-对苯基-双(5-氨基苯并唑)、2,2'-对苯基-双(6-氨基苯并唑)中的至少一种。
  8. 如权利要求3所述聚合物的制备方法，其特征在于，所述步骤(1)所得中间体的结构式为：
  9. 如权利要求3所述聚合物的制备方法，其特征在于，所述溶剂1和溶剂2各自独立选自N-甲基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜、N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、四氢呋喃中的至少一种；所述步骤(2)中的有机碱为三乙胺、甲胺、乙胺、二甲胺、二乙胺中的至少一种；所述步骤(2)中的催化剂为SOCl2、AlCl3、BF3、SbCl5、FeBr3、FeCl3、SnCl4、TiCl4、ZnCl2中的至少一种。
  10. 如权利要求1或2所述聚合物在制备黑色矩阵中的应用。
PCT/CN2023/088004 2022-04-19 2023-04-13 一种用于黑色矩阵的聚合物、其制备方法及应用 WO2023202454A1 (zh)

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