Novel xanthene dye for blue photoresist color paste and synthesis method of novel xanthene dye

Abstract

The invention relates to the technical field of organic dyes, in particular to a novel xanthene dye for blue photoresist color paste and a synthesis method of the novel xanthene dye. The invention relates to a synthesis method of a novel xanthene dye for blue photoresist color paste, which comprises the following steps: 1) taking rigid cyclic amine as a nucleophilic reagent, and carrying out aromatic nucleophilic substitution reaction on a chlorinated xanthene compound to obtain a xanthene intermediate; 2) performing chlorination reaction on the xanthene intermediate by using a chlorination reagent to obtain a chlorinated xanthene intermediate; 3) mixing active amine and the chlorinated xanthene intermediate, and performing substitution reaction under the action of alkali to obtain the novel xanthene dye for the blue photoresist color paste.The novel xanthene dye for the blue photoresist color paste.The novel xanthene dye for the blue photoresist color paste.The novel xanthene dye for the blue photoresist color paste.The novel xanthene dye for the blue photoresist color paste has the advantages of being high in solubility, good in thermal stability and high in contrast ratio.

Description

Technical Field

[0001] This invention relates to the field of organic dye technology, and more specifically, to a novel zeolite-based dye for blue photoresist color paste and its synthesis method. Background Technology

[0002] In the field of flat panel display technology, TFT-LCD (Thin Film Transistor Liquid Crystal Display) occupies a mainstream market position due to its mature technology system. The quality of its color display performance hinges on the optical characteristics of its core component, the color filter (CF). While the pigment-based photoresist system widely used in the industry currently excels in weather resistance and initial color saturation, it suffers from insurmountable technical defects, becoming a bottleneck restricting the improvement of display performance. Specifically, in these systems, pigment molecules, due to their poor solubility, often form large clusters dispersed within the photoresist. These clusters significantly scatter the light emitted from the backlight, directly leading to a substantial decrease in the contrast of the color filter. Simultaneously, traditional pigments exhibit significant deficiencies in their spectral absorption characteristics, with broad absorption bands and full width at half maximum (FWHM) typically reaching 80-120 nm. These shortcomings make it difficult for existing color filters to meet the technical requirements of next-generation LCD devices for wide color gamut display and low power consumption, becoming a major obstacle to the upgrading of display technology. To overcome this technological bottleneck and achieve precise color control, the fabrication process of color filters must strictly adhere to the principle of spectral selective absorption. The core of this principle lies in the precise design of the molecular structure of organic pigments, enabling the material to achieve targeted absorption and transmission characteristics in the visible light band (380-780nm), thereby achieving the desired color display effect. In the three-primary-color display system, for the preparation of blue pigments, practice has shown that relying solely on blue pigment cannot achieve the desired brightness and contrast indicators; spectral compensation must be achieved by combining it with a specific proportion of red dye to optimize its optical performance. Among the many materials available for improving the performance of color photoresist pigments, xanthan dyes demonstrate significant application potential. These dyes possess a broad spectral coverage, spanning a wide range from yellow to blue-red. More importantly, xanthan dyes exhibit excellent photophysical properties, including a high molar extinction coefficient for efficient absorption of specific wavelengths of light; high fluorescence quantum yield, contributing to improved light utilization efficiency; and high stability, ensuring consistent performance over long-term use. Furthermore, their synthesis process is relatively simple, and their molecular structure is easily modified. These characteristics make them an ideal choice for improving the performance of color photoresist pigments and enhancing the quality of TFT-LCD displays, providing a new technological path to solve existing technical challenges. Summary of the Invention

[0003] In view of the shortcomings of the prior art described above, the purpose of this invention is to provide a novel zeolite-based dye for blue photoresist pigment paste and its synthesis method, in order to solve the problems of poor pigment molecule solubility, broad spectral absorption band of pigments, and unsatisfactory brightness and contrast of blue pigments in the prior art.

[0004] To achieve the above and other related objectives, the present invention is obtained through the following technical solution.

[0005] In a first aspect, the present invention provides a novel zeolite-based dye for blue photoresist pigments, having a structure as shown in Formula A: In formula A: R 1 R 2 R 3 and R 4 Each can be independently represented by H, heteroatom, alkyl substituent, or aryl substituent; X is a linking group.

[0006] In some embodiments of the present invention, the R 1 R 2 R 3 and R 4 Each group is independently selected from the following groups: halogen, C1-C 10 Straight-chain or branched alkyl groups, C3-C 10 cycloalkyl, C2-C 10 Straight-chain or branched alkynyl groups, C1-C 10 Straight-chain or branched alkoxy groups, C1-C 10 Straight-chain or branched alkylthio groups, C1-C 10 Straight-chain or branched hydroxy-substituted alkyl groups, C2-C 10 Straight-chain or branched hydroxyalkoxy-substituted alkyl groups, C6-C 10 aryl or aryloxy substituted C1-C 10 alkyl.

[0007] In some embodiments of the present invention, X is selected from the following groups: C1-C groups substituted with or unsubstituted with halogen. 10 Straight-chain or branched alkyl groups, C2-C chains interrupted by one or more -O-, -S-, -O-CO- or -CO-O-. 10 Straight-chain or branched alkyl or alkoxy groups, C3-C 10 cycloalkyl, substituted or unsubstituted C6-C 10 Aryl, C2-C containing N, O and / or S 10 Heterocyclic groups.

[0008] Secondly, the present invention provides a method for synthesizing a novel xanthan dye for blue photoresist pigments, comprising the following steps: 1) Mix the chloroxanthonium compound, a rigid cyclic amine, and a solvent thoroughly, heat to allow for an aromatic nucleophilic substitution reaction, and purify to obtain the xanthonium intermediate; the chloroxanthonium compound has the structure shown in IA: The zeta intermediate has the structure shown in IIA: 2) After mixing the xanthanate intermediate with the catalyst, a chlorinating agent is added, the temperature is adjusted, and a chlorination reaction is carried out. The mixture is then filtered and distilled to obtain the xanthanate chloride intermediate. The xanthanate chloride intermediate has the structure shown in section IIIA. 3) Mix the thallium chloride intermediate, active amine, and solvent evenly, then add alkali to carry out a substitution reaction to obtain a new type of thallium dye for blue photoresist color paste.

[0009] In some embodiments of the present invention, in step 1), the molar ratio of the chloroxanthine compound to the rigid cyclic amine is 1:(2-10); And / or, the rigid cyclic amine is indoline or an indoline derivative.

[0010] In some embodiments of the present invention, in step 1), solvent one is one or more of N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, chlorobenzene, and xylene; And / or, the temperature of the aromatic nucleophilic substitution reaction is 20℃-150℃.

[0011] In some embodiments of the present invention, in step 2), the molar ratio of the thallium intermediate to the chlorinating agent is 1:(1-30).

[0012] In some embodiments of the present invention, in step 2), the chlorinating agent is one or more of thionyl chloride, oxalyl chloride, phosphorus oxychloride, and phosphorus pentachloride; And / or, the chlorination reaction is carried out at a temperature of 0°C-150°C.

[0013] In some embodiments of the present invention, in step 3), the molar ratio of thallium chloride intermediate to active amine is 1:(1-2); And / or, the molar ratio of the thallium chloride intermediate to the base is 1:(1-2); And / or, the base is one or more of triethylamine, pyridine, piperidine, 4-dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and diisopropylethylamine.

[0014] In some embodiments of the present invention, in step 3), the molecular structure of the active amine is an active amino group at one end and an acrylate group or a methacrylate group at the other end.

[0015] In some embodiments of the present invention, in step 3), solvent 2 is one or more of toluene, tetrahydrofuran, dichloromethane, chloroform, and dichloroethane; And / or, the temperature of the substitution reaction is -20℃ to 80℃.

[0016] As described above, the novel xanthan dye for blue photoresist pigments of the present invention has the following beneficial effects: 1. The novel zeolite-based dye provided by this invention can be mixed with other colorants to form a dye-based blue photoresist paste, which is used to improve the brightness of the paste.

[0017] 2. The novel xanthan dyes provided by this invention have excellent solubility, and superior performance in terms of brightness, contrast, and weather resistance, which can greatly improve the effect of the color paste.

[0018] 3. The novel zeolite dyes provided by this invention have advantages such as high transparency, high contrast, good dispersibility, high hiding power, and high tinting strength, as well as good thermal and light stability.

[0019] 4. The synthesis method provided by this invention has a simple route, widely available reagents, low cost, and is easy to scale up for production. Attached Figure Description

[0020] Figure 1 The image shown is of the xanthan intermediate prepared in Example 1 of this invention. 1 H-NMR spectrum; Figure 2 The image shows the xapronil chloride intermediate prepared in Example 1 of this invention. 1 H-NMR spectrum; Figure 3 The image shown is a novel xanthan dye for use in blue photoresist pigment prepared according to Example 1 of this invention. 1 H-NMR spectrum; Figure 4 The image shows the UV-vis absorption spectrum of the novel xanthan dye for blue photoresist pigment prepared in Example 1 of this invention in PGMEA; Figure 5 The image shown is a thermogravimetric diagram of a novel zeolite-based dye for use in the blue photoresist color paste prepared in Example 1 of this invention. Detailed Implementation

[0021] To make the inventive objectives, technical solutions, and beneficial effects of this invention clearer, the invention will be further described in detail below with reference to embodiments. Those skilled in the art can easily understand other advantages and effects of this invention from the content disclosed in this specification.

[0022] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the specification of this invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0023] When using “including,” “having,” and “contains” as described herein, the intention is to cover non-exclusive inclusion, unless an explicit qualifying term such as “only,” “consisting of,” etc., is used, in which case another component may be added.

[0024] In this invention, the terms "preferredly," "more preferably," "better," and "even better" refer to embodiments of the invention that provide certain beneficial effects under certain circumstances. However, other embodiments may also be preferred under the same or other circumstances. Furthermore, the description of one or more preferred embodiments does not imply that other embodiments are unavailable, nor is it intended to exclude other embodiments from the scope of the invention. That is, in this invention, "preferredly," "more preferably," "better," and "even better" are merely descriptions of more effective implementations or examples, but do not constitute a limitation on the scope of protection of the invention.

[0025] In this invention, terms such as "further," "even more," and "particularly" are used for descriptive purposes and indicate differences in content, but should not be construed as limiting the scope of protection of this invention.

[0026] In this invention, "at least one" means one or more, such as one, two, or more. "Multiple" or "several" means at least two, such as two, three, etc., and "multi-layered" means at least two layers, such as two layers, three layers, etc., unless otherwise explicitly specified. In the description of this invention, "several" means at least one, such as one, two, etc., unless otherwise explicitly specified.

[0027] When a numerical range is disclosed herein, the range is considered continuous and includes the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to integers, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe a feature or characteristic, the ranges may be combined. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are incorporated.

[0028] Unless otherwise specified, all steps of the present invention may be performed sequentially or randomly. For example, the method comprising steps (a) and (b) indicates that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, the mention that the method may also include step (c) indicates that step (c) may be added to the method in any order; for example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc. Unless otherwise stated, singular terms may include plural forms and should not be construed as having a quantity of one.

[0029] In this invention, "above" or "below" both include the number itself. For example, "below 1" includes 1.

[0030] In this invention, room temperature refers to 0-40°C, including but not limited to 10-40°C, or further to 20-30°C.

[0031] The first aspect of this invention is to provide a novel succinate-based dye for blue photoresist pigments, having a structure as shown in Formula A: In formula A: R 1 R 2 R 3 and R 4 Each can be independently represented by H, heteroatom, alkyl substituent, or aryl substituent; X is a linking group.

[0032] In some embodiments of the present invention, the R 1 R 2 R 3 and R 4 Each group is independently selected from the following groups: halogen, C1-C 20 Straight-chain or branched alkyl groups, C3-C 20 cycloalkyl, C2-C 20 Straight-chain or branched alkynyl groups, C1-C 20Straight-chain or branched alkoxy groups, C1-C 20 Straight-chain or branched alkylthio groups, C1-C 20 Straight-chain or branched hydroxy-substituted alkyl groups, C2-C 20 Straight-chain or branched hydroxyalkoxy-substituted alkyl groups, C6-C 10 aryl or aryloxy substituted C1-C 20 alkyl.

[0033] In some embodiments of the present invention, X is selected from the following groups: C1-C groups that are halogenated or unsubstituted. 20 A straight-chain or branched alkyl group, interrupted by one or more -O-, -S-, -O-CO-, or -CO-O- C2-C 20 Straight-chain or branched alkyl or alkoxy groups, C3-C 20 cycloalkyl, substituted or unsubstituted C6-C 10 Aryl, C2-C containing N, O and / or S 20 Heterocyclic groups.

[0034] A second aspect of this invention is to provide a method for synthesizing a novel zeolite-based dye for blue photoresist pigments, comprising the following steps: 1) Mix the chloroxanthonium compound, a rigid cyclic amine, and a solvent thoroughly, heat to allow for an aromatic nucleophilic substitution reaction, and purify to obtain the xanthonium intermediate; the chloroxanthonium compound has the structure shown in IA: The zeta intermediate has the structure shown in IIA: 2) After mixing the xanthanate intermediate with the catalyst, a chlorinating agent is added, the temperature is adjusted, and a chlorination reaction is carried out. The mixture is then filtered and distilled to obtain the xanthanate chloride intermediate. The xanthanate chloride intermediate has the structure shown in section IIIA. 3) Mix the thallium chloride intermediate, active amine, and solvent evenly, then add alkali to carry out a substitution reaction to obtain a new type of thallium dye for blue photoresist color paste.

[0035] In some embodiments of the present invention, in step 1), the molar ratio of the chloroxanthine compound to the rigid cyclic amine is 1:(2-10); And / or, the rigid cyclic amine is indoline or an indoline derivative.

[0036] In some specific embodiments of the present invention, the molar ratio of the chloroxanthine compound to the rigid cyclic amine can be 1:(2-4), 1:(4-6), 1:(6-8), or 1:(8-10); typically, but not limitingly, for example, it can be 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, or 1:5.

[0037] In some embodiments of the present invention, in step 1), solvent one is one or more of N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, chlorobenzene, and xylene; And / or, the temperature of the aromatic nucleophilic substitution reaction is 20℃-150℃.

[0038] In some specific embodiments of the present invention, solvent one can be N-methylpyrrolidone or N,N-dimethylformamide.

[0039] In some specific embodiments of the present invention, the temperature of the aromatic nucleophilic substitution reaction can be 20°C-85°C or 85°C-150°C; typically, but not limitingly, it can be 50°C, 75°C, 100°C, or 125°C.

[0040] In some embodiments of the present invention, in step 2), the molar ratio of the thiamethoxam intermediate to the chlorinating agent is 1:(1-30).

[0041] In some specific embodiments of the present invention, the molar ratio of the thallium intermediate to the chlorinating agent can be 1:(1-10), 1:(10-20), or 1:(20-30); typically, but not limitingly, for example, it can be 1:5, 1:10, 1:20, or 1:30.

[0042] In some embodiments of the present invention, in step 2), the chlorinating agent is one or more of thionyl chloride, oxalyl chloride, phosphorus oxychloride, and phosphorus pentachloride; And / or, the chlorination reaction is carried out at a temperature of 0°C-150°C.

[0043] In some specific embodiments of the present invention, the chlorinating agent may be phosphorus oxychloride or thionyl chloride.

[0044] In some specific embodiments of the present invention, the temperature of the chlorination reaction can be 0℃-30℃, 30℃-60℃, 60℃-90℃, 90℃-120℃ or 120℃-150℃; typically, but not limitingly, for example, it can be 25℃, 30℃, 35℃ or 40℃.

[0045] In some embodiments of the present invention, in step 3), the molar ratio of thallium chloride intermediate to active amine is 1:(1-2); And / or, the molar ratio of the thallium chloride intermediate to the base is 1:(1-2); And / or, the base is one or more of triethylamine, pyridine, piperidine, 4-dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and diisopropylethylamine.

[0046] In some specific embodiments of the present invention, the molar ratio of xaton chloride intermediate to active amine can be 1:(1-1.2), 1:(1.2-1.4), 1:(1.4-1.6), 1:(1.6-1.8), or 1:(1.8-2); typically, but not limitingly, it can be 1:1, 1:1.5, or 1:2.

[0047] In some specific embodiments of the present invention, the molar ratio of xaton chloride intermediate to base can be 1:(1-1.5) or 1:(1.5-2); typically, but not limitingly, it can be 1:1.3, 1:1.5, or 1:2.

[0048] In some specific embodiments of the present invention, the base may be triethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene or diisopropylethylamine.

[0049] In some embodiments of the present invention, in step 3), the molecular structure of the active amine is an active amino group at one end and an acrylate group or a methacrylate group at the other end.

[0050] In some specific embodiments of the present invention, the molecular structure of the active amine has an active amino group at one end and a methacrylate group at the other end.

[0051] In some embodiments of the present invention, in step 3), solvent 2 is one or more of toluene, tetrahydrofuran, dichloromethane, chloroform, and dichloroethane; And / or, the temperature of the substitution reaction is -20℃ to 80℃.

[0052] In some specific embodiments of the present invention, solvent two can be tetrahydrofuran or dichloromethane.

[0053] In some specific embodiments of the present invention, the temperature of the substitution reaction can be -20°C to 0°C, 0°C to 40°C, or 40°C to 80°C; typically, but not limitingly, it can be -20°C, 30°C, or 80°C.

[0054] The present invention will be further illustrated by the following examples, but these examples do not limit the scope of the invention.

[0055] When numerical ranges are given in the embodiments, it should be understood that, unless otherwise stated in the present invention, both endpoints of each numerical range and any value between the two endpoints may be selected. Unless otherwise defined, all technical and scientific terms used in this invention have the same meaning as commonly understood by one of ordinary skill in the art. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. All reagents or instruments whose manufacturers are not specified are conventional products that can be purchased commercially. In addition to the specific methods, equipment, and materials used in the embodiments, based on the knowledge of the prior art possessed by one of ordinary skill in the art and the description of this invention, any prior art methods, equipment, and materials similar to or equivalent to those described, used, and materials in the embodiments of this invention may be used to implement this invention.

[0056] Example 1 The synthesis method of the novel xanthan dye for the blue photoresist pigment in this embodiment is as follows: 1) Take a dry and clean 500mL two-necked flask and place a stir bar of appropriate size; add dichlorosulfonylfluorescein (3',6'-dichlorospiro[benzo[C][1,2]oxathiazole-3,9'-xanthium]1,1-dioxide) (5g, 12mmol, 1.0eq.), indoline (7.34g, 60mmol, 5.0eq.) and dry NMP solvent (50mL), then heat to 125℃ and react overnight. The next day, move the reaction to room temperature and quench the reaction dropwise with 1N hydrochloric acid aqueous solution, then filter and wash the solid product repeatedly with deionized water, dry in an oven, and then purify by column chromatography with a DCM / MeOH ratio of 50:1-40:1 to obtain 5.11g of blue xanthium intermediate, with a yield of 73%; The structure and purity of the xanthonium intermediate C1 were determined by NMR, and the NMR values ​​are as follows: 1H NMR (500 MHz, DMSO-d)δ 7.98 (dd, J=8.4, 1.6 Hz, 1H), 7.73 (ddt, J=7.3, 1.8, 1.0 Hz, 1H), 7.63 (dd,J=7.3, 1.4 Hz, 1H), 7.57-7.46 (m, 3H), 7.42 (td, J=7.2, 1.5 Hz, 1H), 7.38 (d,J=8.8 Hz, 1H), 7.35-7.27 (m, 2H), 7.20-7.12 (m, 2H), 7.05-6.96 (m, 2H), 6.92(dd, J=7.2, 1.3 Hz, 1H), 6.86-6.82 (m, 2H), 6.75 (d, J=2.2 Hz, 1H), 4.50(ddd, J=14.5, 6.6, 4.7 Hz, 2H), 4.13 (ddd, J=6.4, 4.6, 3.7 Hz, 2H), 3.33(dddd, J=21.6, 6.6, 4.7, 0.9 Hz, 2H), 3.14 (dddd, J=4.6, 3.7, 1.7, 0.9 Hz, 2H); The chemical structural formula of the xanthan intermediate in this embodiment is shown in C1 below: 2) Take a dry and clean 500mL two-necked flask and place a stir bar of appropriate size; add xanthan intermediate (10g, 17.5mmol, 1.0eq.) and dry DCM solvent (100mL) and DMF (1.0mL), and stir in an ice-water bath for 15 minutes; then, under a nitrogen atmosphere and in an ice-water bath, add oxalyl chloride (22.2g, 175mmol, 10eq.) dropwise; after the oxalyl chloride is added, slowly raise the above reaction system to room temperature and react at room temperature for 24 hours; after the reaction is completed, filter, and then distill under reduced pressure to obtain 9.32g of xanthan chloride intermediate, with a yield of 90.2%; The chemical structural formula of the xanthan chloride intermediate in this embodiment is shown in D1 below: 3) Take a clean 250mL three-necked flask and place a stir bar of appropriate size; add xanthan chloride intermediate (9.32g, 15.8mmol, 1.0eq.), 2-aminoethyl methacrylate (3.063g, 23.7mmol, 1.5eq.), DMAP (7.72mg, 0.06mmol, 0.004eq.), and add dry DCM solvent (100mL). Stir in an ice-water bath for 15 minutes; then, under a nitrogen atmosphere and in an ice-water bath, add triethylamine (2.39g, 23.7mmol, 1.5eq.) dropwise; after the triethylamine is added, slowly raise the above reaction system to room temperature and let it react overnight at room temperature; the next day, after the reaction is complete, filter, then distill under reduced pressure, and recrystallize using a mixed solvent such as dichloromethane to obtain 9.71g of a novel xanthan dye for blue photoresist pigment, with a yield of 90%.

[0057] The chemical structural formula of the novel xanthan dye used in the blue photoresist pigment of this embodiment is shown in A1 below: Example 2 The synthesis method of the novel xanthan dye for the blue photoresist pigment in this embodiment is as follows: Take a clean 250 mL three-necked flask and place a stir bar of appropriate size inside; add xanthan chloride intermediate (9.32 g, 15.8 mmol, 1.0 eq.), 2-(2-(2-aminoethoxy)ethoxy)ethyl methacrylate (5.15 g, 23.7 mmol, 1.5 eq.), DMAP (7.72 mg, 0.06 mmol, 0.004 eq.), and add 100 mL of dry DCM solvent. In an ice water bath... The mixture was stirred in the bath for 15 minutes. Then, under a nitrogen atmosphere and in an ice-water bath, triethylamine (2.39 g, 23.7 mmol, 1.5 eq.) was added dropwise. After the addition of triethylamine was complete, the reaction system was slowly raised to room temperature and allowed to react overnight at room temperature. The next day, after the reaction was completed, the mixture was filtered, then distilled under reduced pressure, and recrystallized using a mixed solvent such as dichloromethane to obtain 9.90 g of a novel xanthan dye for blue photoresist pigment, with a yield of 85.3%.

[0058] The chemical structural formula of the novel xanthan dye used in the blue photoresist pigment of this embodiment is shown in A2 below: The synthesis method of the xatonium chloride intermediate in this embodiment is the same as that in Example 1.

[0059] Example 3 The synthesis method of the novel xanthan dye for the blue photoresist pigment in this embodiment is as follows: Take a clean 250 mL three-necked flask and place a stir bar of appropriate size; add xanthan chloride intermediate (9.32 g, 15.8 mmol, 1.0 eq.), 4-aminophenyl methacrylate (4.2 g, 23.7 mmol, 1.5 eq.), DMAP (7.72 mg, 0.06 mmol, 0.004 eq.), and dry DCM solvent (100 mL), and stir in an ice-water bath for 15 minutes; then, under a nitrogen atmosphere and in an ice-water bath, add triethylamine (2.39 g, 23.7 mmol, 1.5 eq.) dropwise; after the triethylamine is added, slowly raise the above reaction system to room temperature and let it react overnight at room temperature; the next day, after the reaction is complete, filter, then distill under reduced pressure, and recrystallize using a mixed solvent such as dichloromethane to obtain 10.45 g of a novel xanthan dye for blue photoresist pigment, with a yield of 95.3%.

[0060] The chemical structural formula of the novel xanthan dye used in the blue photoresist pigment of this embodiment is shown in A3 below: The synthesis method of the xatonium chloride intermediate in this embodiment is the same as that in Example 1.

[0061] Comparative Example 1 The synthesis method of the blue photoresist pigment in this comparative example using red xanthan dye is as follows: 1) Take a dry and clean 500mL two-necked flask and place a stir bar of appropriate size; add Acid Red 52 (17.8g, 30.6mmol, 1.0eq.) and dry DCM solvent (250mL) and DMF (2.0mL), and stir in an ice-water bath for 15 minutes; then, under a nitrogen atmosphere and in an ice-water bath, add phosphorus oxychloride (23.5g, 153.2mmol, 5.0eq.) dropwise; after the phosphorus oxychloride is added, slowly raise the above reaction system to room temperature and react at room temperature for 24 hours; after the reaction is completed, filter, and then distill under reduced pressure to obtain 7.35g of sulfonyl chloride intermediate, with a yield of 41.7%; 2) Take a clean 500mL three-necked flask and place a stir bar of appropriate size; add sulfonyl chloride intermediate (5.8g, 10mmol, 1.0eq.), N-(3-hydroxypropyl)methacrylamide (1.6g, 11mmol, 1.1eq.), DMAP (5mg, 0.04mmol, 0.004eq.), and add dry DCM solvent (75mL), and stir in an ice-water bath for 15 minutes; then, under a nitrogen atmosphere and in an ice-water bath, add triethylamine (1.1g, 11mmol, 1.1eq.) dropwise; after the triethylamine is added, slowly raise the above reaction system to room temperature and let it react overnight at room temperature; the next day, after the reaction is completed, filter, then distill under reduced pressure, and recrystallize using a mixed solvent such as dichloromethane to obtain 5.8g of purple-red xanthan dye, with a yield of 85%.

[0062] The chemical structural formula of the cyclohexane dye is shown in A4 below: Performance testing 1. Nuclear magnetic resonance hydrogen spectrum test 10 mg each of the xanthones intermediate, chloride intermediate, and novel xanthones dye for blue photoresist pigment prepared in Example 1 were weighed and dissolved in deuterated reagent (MDSO). The results were then analyzed by proton nuclear magnetic resonance spectroscopy. 1 H-NMR spectrum as shown Figure 1 , Figure 2 and Figure 3 As shown.

[0063] 2. Ultraviolet-Visible Absorption Spectroscopy Measurement The dyes prepared in Examples 1-3 and Comparative Example 1 were formulated into 10 μmol / L solutions using propylene glycol methyl ether acetate (PGMEA) as the solvent, and their absorption spectra were measured using a UV-Vis spectrophotometer. The molar extinction coefficient of the dyes was calculated using the following formula: Α = εcl In the formula, A is the absorbance intensity; ε is the molar extinction coefficient, L / (mol·cm); c is the concentration, mol / L; and l is the thickness of the absorption layer, cm. The UV-vis absorption spectrum of the xanthan intermediate in Example 1 was tested as follows: Figure 4 As shown.

[0064] The UV-Vis absorption spectra of the dyes prepared in Examples 1-3 and Comparative Example 1 are shown in Table 1.

[0065] Table 1. Results of UV-Vis absorption spectra of dyes prepared in Examples 1-3 and Comparative Example 1 As can be seen from Table 1, the dyes prepared in Examples 2 and 3 have a slight blue shift compared to that in Example 1, and have a higher molar absorptivity.

[0066] 3. Solubility test The solubility of the dyes prepared in Examples 1-3 and Comparative Example 1 in PGMEA and N,N-dimethylformamide (DMF) was tested. 100 mg of dye and 1 g of organic solvent were weighed, sonicated at room temperature for 10 min, and allowed to stand for 24 h. The mixture was then filtered three times using a filter membrane. The filtrate was dried, and the solubility S of the dye was calculated. S=100M S / M L In the formula, M S This refers to the mass of the dye after drying, in grams (g); in milliliters (M). L This is the mass of the solution, in grams (g).

[0067] The solubility test results of the dyes prepared in Examples 1-3 and Comparative Example 1 are shown in Table 2.

[0068] Table 2. Solubility test results of dyes prepared in Examples 1-3 and Comparative Example 1 As shown in Table 2, the dyes prepared in Examples 1-3 all have good solubility in PGMEA and DMF. Among them, the dye prepared in Example 3 has the best solubility in PGMEA and DMF, while Comparative Example 1 has poor solubility in PGMEA and DMF.

[0069] 4. Thermal stability test The fabrication of color filters involves a post-baking process at 200℃ or higher, as industrial applications require dye molecules to exhibit good thermal stability at this temperature. Thermogravimetric analysis (TGA) is used to evaluate the thermal stability of dyes. Under nitrogen protection, the dye is heated from room temperature to 500℃ at a rate of 10℃ / min to determine its thermal decomposition temperature T. d The blue photoresist pigment in Example 1 was tested using a novel xanthan dye, and the resulting thermogravimetric analysis is shown below. Figure 5 As shown.

[0070] The thermal stability test results of the dyes prepared in Examples 1-3 and Comparative Example 1 are shown in Table 3.

[0071] Table 3. Thermal stability test results of dyes prepared in Examples 1-3 and Comparative Example 1 As shown in Table 3, the T values ​​of the xanthan dye molecules prepared in Examples 1-3 are... dWithin the temperature range of 287℃ to 330℃, the weight loss rate at 230℃ is less than 5%, indicating that the above dyes have good thermal stability.

[0072] This invention develops a novel class of xanthan dyes, particularly suitable as key coloring components in blue photoresist pigments. These dyes not only significantly enhance the brightness and saturation of the pigment, but also possess the following comprehensive advantages: excellent optical properties, outstanding dispersion stability, and strong hiding power and coloring intensity. Furthermore, these dyes exhibit excellent thermal stability. From an industrialization perspective, the synthesis process of this invention is simple and efficient, the raw materials are readily available, and the production cost is significantly advantageous, fully meeting the needs of large-scale industrial production.

[0073] The above embodiments are merely illustrative of the principles and effects of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by those skilled in the art without departing from the spirit and technical concept disclosed in the present invention should still be covered by the claims of the present invention.

Claims

1. A novel xanthene dye for a blue photoresist color paste, characterized by: having a structure as shown in Formula A: In Formula A: R 1 , R 2 , R 3 , and R 4 are each independently H, a heteroatom, an alkyl group, an aryl group; X is a linking group.

2. A novel xanthene dye for a blue photoresist color paste according to claim 1, characterized by: said X is selected from the group consisting of: C1-C 10 straight-chain or branched alkyl, C2-C 10 straight-chain or branched alkyl or alkoxy, C3-C 10 cycloalkyl, substituted or unsubstituted C6-C 10 aryl, C2-C 10 heterocyclic group containing N, O and / or S.

3. The method for synthesizing a novel zeolite-based dye for blue photoresist pigment as described in claim 1, characterized in that: comprising the following steps: 1) uniformly mixing a chlorinated xanthene compound, a rigid cyclic amine, a solvent, heating, and performing an aromatic nucleophilic substitution reaction, purifying to obtain a xanthene intermediate; the chlorinated xanthene compound has a structure as shown in IA: The xanthene intermediate has a structure as shown in IIA: 2) mixing the xanthene intermediate with a catalyst, then adding a chlorinating reagent, adjusting the temperature, and performing a chlorination reaction, filtering, and distilling to obtain a chlorinated xanthene intermediate; the chlorinated xanthene intermediate has a structure as shown in IIIA: 3) uniformly mixing the chlorinated xanthene intermediate, an active amine, a solvent, then adding a base, and performing a substitution reaction to obtain a novel xanthene dye for blue photoresist color paste.

4. A process for the synthesis of novel xanthene dyes for blue photoresist color paste according to claim 3, characterized by: In the step 1), the molar ratio of the chlorinated xanthene compound to the rigid cyclic amine is 1:(2-10); And / or, the rigid cyclic amine is indoline or an indoline derivative.

5. A novel xanthene dye synthesis method for a blue photoresist color paste according to claim 3, characterized by: In the step 1), the solvent one is one or more of N,N-dimethylformamide, dimethyl sulfoxide, N-methyl pyrrolidone, chlorobenzene, and xylene; And / or, the temperature of the aromatic nucleophilic substitution reaction is 20-150°C.

6. A novel xanthene dye synthesis method for a blue photoresist color paste according to claim 3, characterized by: In the step 2), the molar ratio of the xanthene intermediate to the chlorinating reagent is 1:(1-30).

7. A novel xanthene dye synthesis method for a blue photoresist color paste according to claim 3, characterized by: In the step 2), the chlorinating reagent is one or more of dichlorosulfoxide, oxalyl chloride, phosphorus oxychloride, and phosphorus pentachloride; And / or, the temperature of the chlorination reaction is 0-150°C.

8. A novel xanthene dye synthesis method for a blue photoresist color paste according to claim 3, characterized by: In the step 3), the molar ratio of the chlorinated xanthene intermediate to the active amine is 1:(1-2); And / or, the molar ratio of the chlorinated xanthene intermediate to the base is 1:(1-2); And / or, the base is one or more of triethylamine, pyridine, piperidine, 4-dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and diisopropylethylamine.

9. A novel xanthene dye synthesis method for a blue photoresist color paste according to claim 1, characterized by: In the step 3), the active amine has a reactive amino group at one end of the molecular structure and an acrylate group or a methacrylate group at the other end.

10. A novel xanthene dye synthesis method for a blue photoresist color paste according to claim 3, characterized by: In the step 3), the solvent two is one or more of toluene, tetrahydrofuran, dichloromethane, chloroform, and dichloroethane; And / or, the temperature of the substitution reaction is -20-80°C.

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