A new anthraquinone dye for blue photoresist color paste and a synthesis method thereof

Abstract

The application belongs to the technical field of organic dyes, and specifically provides a novel anthraquinone dye for blue photoresist color paste and a synthesis method thereof. The synthesis method of the novel anthraquinone dye for blue photoresist color paste comprises the following steps: (1) mixing an anthraquinone derivative and a sulfuryl chloride reagent to perform a sulfuryl chloride reaction to obtain an intermediate; (2) uniformly mixing a compound with two nucleophilic reaction sites, an organic base and a solvent, and then adding the intermediate to perform a substitution reaction to obtain the novel anthraquinone dye for blue photoresist color paste. The novel anthraquinone dye has excellent color performance, and further improves the thermal stability, light stability and contrast. The novel anthraquinone dye is suitable for mixed or dye-based blue photoresist color paste, and can significantly improve the brightness, transparency, weather resistance and dispersibility of the color paste. In addition, the synthesis method of the novel anthraquinone dye is simple in process and low in cost, and is suitable for industrial production.

Description

Technical Field

[0001] This invention belongs to the field of organic dye technology, and in particular relates to a novel anthraquinone dye for blue photoresist color paste and its synthesis method. Background Technology

[0002] In the preparation of color photoresist pastes, the performance of the colorant plays a crucial role. Anthraquinone dyes, with their excellent color saturation, lightfastness, and chemical stability, have become one of the important colorants. With the rapid development of high-resolution display devices (such as OLED and LCD), and the continuous upgrading of display technology, higher requirements are placed on the color purity, transmittance, and process compatibility of photoresist pastes. Traditional pigment dispersion systems are prone to agglomeration due to their inherent characteristics. This problem directly affects the uniformity and patterning accuracy of the paste. Anthraquinone dyes, however, can achieve high solubility and dispersion stability through molecular structure design, thereby effectively improving the performance of the paste. Currently, azo or phthalocyanine dyes are commonly used in color photoresist pigments, but they have significant limitations. Azo dyes' light absorption characteristics in the short wavelength region may interfere with the development process, affecting the accuracy of development; phthalocyanine dyes have similar problems with short-wavelength light absorption. Furthermore, both types of dyes have insufficient heat resistance, making them unsuitable for some high-temperature processes. In contrast, anthraquinone dyes have significant advantages. Through the conjugated structure of the anthraquinone core, they can precisely control the absorption spectrum to match the exposure wavelength of the photoresist (such as g-lines and i-lines), reducing interference with the exposure process. Simultaneously, anthraquinone dyes possess higher thermal stability (>200℃), making them well-suited for high-temperature curing processes and ensuring the performance stability of the pigment after high-temperature treatment. Furthermore, the molecular structure design of anthraquinone dyes is flexible. By introducing polar groups such as sulfonic acid groups and amino groups, the compatibility between anthraquinone dyes and resin systems can be enhanced, reducing residues generated during development, ensuring development results, and thus improving the clarity of pattern edges, meeting the requirements of high-resolution display devices for fine patterns. These characteristics make the application value of anthraquinone dyes in the field of color photoresist pastes increasingly prominent, providing strong support for the development of high-resolution display technology.

[0003] The patent application with publication number CN104725891A discloses a method for preparing a dye. The dye prepared in this application has the structure shown in formula (1). The dye prepared in this application is not sticky or clumpy.

[0004] However, the application of anthraquinone dyes in photoresists still faces challenges, such as insufficient thermal stability. Therefore, developing novel anthraquinone derivatives and optimizing their molecular structure and pigment formulations are of great significance for promoting the development of high-precision color filters and micro / nano lithography technologies. Summary of the Invention

[0005] To address the aforementioned problems and further improve the stability of dye colorant molecules used in photoresists, this invention provides a novel anthraquinone dye for blue photoresist color paste and its synthesis method.

[0006] This invention first provides a novel anthraquinone dye for blue photoresist color paste, having a structure as shown in Formula A: In formula A: R 1 R 2 Each can be independently classified as H, halogen, alkyl, or aryl; X is a nucleophilic functional group; Y is a linking group.

[0007] Furthermore, X is selected from the following groups: N, O, S; and Y is selected from the following groups: alkyl, aryl.

[0008] Furthermore, the Y is selected from the following groups: C1-C groups that are halogenated or unsubstituted. 20 Alkyl groups, halogenated or unsubstituted C6-C 20 The aryl group, interrupted by one or more -O-, -CO-, -O-CO-, or -CO-O- ions in C2-C 20 The alkyl group is a straight-chain or branched alkyl group; the aryl group is selected from monocyclic aromatic groups, polycyclic fused aromatic groups, and aromatic heterocyclic groups containing N, O and / or S heteroatoms.

[0009] Secondly, the present invention provides a method for synthesizing a novel anthraquinone dye for blue photoresist color paste, comprising the following steps: (1) Anthraquinone derivative and sulfonyl chloride reagent are mixed and subjected to sulfonyl chloride reaction to obtain an intermediate; the anthraquinone derivative has the structure shown in IA: The intermediate has the structure shown in IIA: (2) Mix the amphiphilic nucleophilic reaction site compound, organic base and solvent evenly, then add intermediate and carry out substitution reaction to obtain a novel anthraquinone dye for blue photoresist color paste.

[0010] Furthermore, in step (1), the sulfonyl chloride reagent is one or both of chlorosulfonic acid and thionyl chloride; And / or, the molar ratio of the anthraquinone derivative to the sulfonyl chloride reagent is 1:(10-50).

[0011] Furthermore, the molar ratio of the anthraquinone derivative to the sulfonyl chloride reagent is 1:(20-40).

[0012] Furthermore, in step (1), the temperature of the sulfonyl chlorination reaction is -20℃ to 50℃.

[0013] Furthermore, the sulfonyl chlorination reaction is carried out at a temperature of -5°C to 45°C.

[0014] Furthermore, in step (2), the nucleophilic group of the compound with the binucleophilic reaction site is one or more of amino, hydroxyl, and thiol groups; And / or, the linking group of the amphiphilic reactive site compound is alkyl or aryl; And / or, the linking group of the amphiphilic reactive site compound is C3-C. 20 Alkyl or C6-C 20 Aryl groups.

[0015] Furthermore, the nucleophilic group of the amphiphilic reaction site compound is one or both of amino and hydroxyl groups; And / or, the linking group of the amphiphilic reactive site compound is C5-C. 10 Alkyl or C5-C 10 Aryl groups.

[0016] Furthermore, in step (2), the molar ratio of the amphiphilic reaction site compound to the intermediate is (1-3):1; And / or, the molar ratio of the intermediate to the organic base is 1:(1-4).

[0017] Furthermore, the molar ratio of the intermediate to the organic base is 1:(2-4).

[0018] Furthermore, in step (2), the organic base is one or more of triethylamine, pyridine, piperidine, 4-dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and diisopropylethylamine.

[0019] Furthermore, the organic base is one or more of triethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and diisopropylethylamine.

[0020] Furthermore, in step (2), the solvent is one or more of toluene, tetrahydrofuran, dichloromethane, chloroform, and dichloroethane.

[0021] Furthermore, the solvent is one or both of tetrahydrofuran and dichloromethane.

[0022] Furthermore, in step (2), the temperature of the substitution reaction is 0℃-40℃.

[0023] Furthermore, the temperature of the substitution reaction is 25°C-30°C.

[0024] Compared with the prior art, the present invention has the following beneficial effects: 1. The novel anthraquinone dye for blue photoresist color paste of the present invention constructs an intramolecular cyclic structure by reacting with a compound with a biphilic nucleophilic reaction site, which greatly improves the weather resistance of the molecule, such as light and heat resistance. This results in the novel anthraquinone dye for blue photoresist color paste having higher thermal stability and light stability. In addition, the novel anthraquinone dye for blue photoresist color paste itself has more lipid-soluble groups, thus improving solubility and dispersibility.

[0025] 2. The novel anthraquinone dye for blue photoresist color paste provided by this invention can be mixed with other colorants to prepare mixed or dye-type photoresist color pastes, which can improve the various properties of the color paste, such as brightness, contrast and weather resistance, and has good compatibility.

[0026] 3. 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

[0027] Figure 1 The image shows the 1H-NMR spectrum of the novel anthraquinone dye for the blue photoresist color paste prepared in Example 1 of this invention. Figure 2 The image shows the 1H-NMR spectrum of the novel anthraquinone dye for the blue photoresist color paste prepared in Example 2 of this invention. Figure 3 The image shows the 1H-NMR spectrum of the novel anthraquinone dye for the blue photoresist color paste prepared in Example 3 of this invention. Figure 4 The image shows the 1H-NMR spectrum of the anthraquinone dye used in the blue photoresist color paste prepared in Comparative Example 1 of this invention. Detailed Implementation

[0028] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0029] 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.

[0030] 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.

[0031] 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.

[0032] 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.

[0033] 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.

[0034] 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.

[0035] 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.

[0036] In this invention, "above" or "below" both include the number itself. For example, "below 1" includes 1.

[0037] In this invention, room temperature refers to 0-40°C, including but not limited to 10-40°C, or further to 20-30°C.

[0038] Based on extensive experimental research, the first aspect of this invention is to provide a novel anthraquinone dye for blue photoresist pigments, having a structure as shown in Formula A: In formula A: R 1 R 2 Each can be independently classified as H, halogen, alkyl, or aryl; X is a nucleophilic functional group; Y is a linking group.

[0039] In some embodiments of the present invention, X is selected from the following groups: N, O, S; and Y is selected from the following groups: alkyl, aryl.

[0040] In some embodiments of the present invention, the Y is selected from the following groups: C1-C groups that are halogenated or unsubstituted. 20 Alkyl groups, halogenated or unsubstituted C6-C 20 The aryl group, C2-C interrupted by one or more -O-, -CO-, -O-CO- or -CO-O-. 20 The alkyl group is a straight-chain or branched alkyl group; the aryl group is selected from monocyclic aromatic groups, polycyclic fused aromatic groups, and aromatic heterocyclic groups containing N, O and / or S heteroatoms.

[0041] Secondly, the present invention provides a method for synthesizing a novel anthraquinone dye for blue photoresist color paste, comprising the following steps: (1) Anthraquinone derivative and sulfonyl chloride reagent are mixed and subjected to sulfonyl chloride reaction to obtain an intermediate; the anthraquinone derivative has the structure shown in IA: The intermediate has the structure shown in IIA: (2) Mix the amphiphilic nucleophilic reaction site compound, organic base and solvent evenly, then add intermediate and carry out substitution reaction to obtain a novel anthraquinone dye for blue photoresist color paste.

[0042] In some embodiments of the present invention, in step (1), the sulfonyl chloride reagent is one or both of chlorosulfonic acid and thionyl chloride; And / or, the molar ratio of the anthraquinone derivative to the sulfonyl chloride reagent is 1:(10-50).

[0043] In some specific embodiments of the present invention, the molar ratio of anthraquinone derivative to sulfonyl chloride reagent can be 1:(10-20), 1:(20-30), 1:(30-40), or 1:(40-50); typically, but not limitingly, for example, it can be 1:38, 1:39, 1:40, or 1:41.

[0044] In some embodiments of the present invention, in step (1), the temperature of the sulfonyl chlorination reaction is -20°C to 50°C.

[0045] In some specific embodiments of the present invention, the temperature of the sulfonyl chlorination reaction can be -20℃-(-10)℃, -10℃-0℃, 0℃-10℃, 10℃-20℃, 20℃-30℃, 30℃-40℃, or 40℃-50℃; typically, but not limitingly, it can be 30℃ or 45℃.

[0046] In some embodiments of the present invention, in step (2), the nucleophilic group of the binucleophilic reaction site compound is one or more of amino, hydroxyl, and thiol groups; And / or, the linking group of the amphiphilic reactive site compound is alkyl or aryl; And / or, the linking group of the amphiphilic reactive site compound is C3-C. 20 Alkyl or C6-C 20 Aryl groups.

[0047] In some specific embodiments of the present invention, the compound with the amphiphilic reaction site can be hexamethylenediamine, 1,6-hexanediol, or 1,5-pentanediol.

[0048] In some embodiments of the present invention, in step (2), the molar ratio of the binucleophilic reaction site compound to the intermediate is (1-3):1; And / or, the molar ratio of the intermediate to the organic base is 1:(1.5-4).

[0049] In some specific embodiments of the present invention, the molar ratio of the amphiphilic reaction site compound to the intermediate can be (1-0.5):1, (0.5-1):1, (1-1.5):1, (1.5-2):1, (2-2.5):1, (2.5-3):1; typically, but not limitingly, it can be 1:3, for example.

[0050] In some specific embodiments of the present invention, the molar ratio of the intermediate to the organic base can be 1:(1.5-2), 1:(2-2.5), 1:(2.5-3), 1:(3-3.5), or 1:(3.5-4); typically, but not limitingly, for example, it can be 1:3.

[0051] In some embodiments of the present invention, in step (2), the organic base is one or more of triethylamine, pyridine, piperidine, 4-dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and diisopropylethylamine.

[0052] In some specific embodiments of the present invention, the organic base may be one or more of triethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and diisopropylethylamine; typically, but not limitingly, it may be triethylamine, for example.

[0053] In some embodiments of the present invention, in step (2), the solvent is one or more of toluene, tetrahydrofuran, dichloromethane, chloroform, and dichloroethane.

[0054] In some specific embodiments of the present invention, the solvent may be tetrahydrofuran.

[0055] In some embodiments of the present invention, the temperature of the substitution reaction in step (2) is 0°C-40°C.

[0056] In some specific embodiments of the present invention, the temperature of the substitution reaction can be 0℃-10℃, 10℃-20℃, 20℃-30℃, or 30℃-40℃; typically, but not limitingly, it can be 20℃, 25℃, or 30℃.

[0057] The present invention will be further illustrated by the following examples, but these examples do not limit the scope of the invention.

[0058] 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.

[0059] Example 1 The synthesis method of the novel anthraquinone dye for the blue photoresist color paste in this embodiment is as follows: (1) Take a dry and clean 1000mL four-necked flask and place a stir bar of appropriate size; add Solvent Blue 97 (53g, 100mmol, 1.0eq.), then add chlorosulfonic acid (440g, 3.98mol, 40.0eq.), and stir at 45℃ to 30℃ for 15min. After the temperature is maintained, start adding thionyl chloride (30g, 252mmol, 2.5eq.) dropwise using a constant pressure dropping funnel, with a dropping time of more than 30min. After the dropping is completed, react at room temperature overnight. Take a 5L plastic beaker and add 3.5L of ice-water mixture, stir slowly with a mechanical stirrer, and slowly add the reaction solution to the ice water with a glass dropper to quench it, ensuring that the ice does not melt throughout the process. After the dropping is completed, stir at -5℃ for 30min, filter with a Buchner funnel, wash the filter cake 3 times with ice water, collect the filter cake, dry at 50℃ to obtain 49.5g of intermediate, with a yield of 68.1%.

[0060] The chemical structural formula of the intermediate in this embodiment is shown in C1 below: (2) Take a dry and clean 500mL three-necked flask and place a stir bar of appropriate size; dissolve hexamethylenediamine (9.5g, 82mmol, 3eq.) and triethylamine (8.3g, 82mmol, 3.0eq.) in 200mL tetrahydrofuran, and add intermediate (20g, 27mmol, 1.0eq.) multiple times over 30min under ice-water bath conditions (0-5℃), and react overnight at room temperature. After the reaction is complete, first dilute the reaction solution with dichloromethane, then filter it with diatomaceous earth through a sintered glass funnel, and finally evaporate it to dryness and pass it through a column to obtain 4.35g of a novel anthraquinone dye for blue photoresist pigment, with a yield of 20.9%.

[0061] The chemical structural formula of the novel anthraquinone dye used in the blue photoresist color paste of this embodiment is shown in A1 below: Example 2 The synthesis method of the novel anthraquinone dye for blue photoresist color paste in this embodiment is as follows: A dry and clean 500mL three-necked flask was placed with a stir bar of appropriate size. 1,6-hexanediol (9.7g, 82mmol, 3eq.) and triethylamine (8.3g, 82mmol, 3.0eq.) were dissolved in 200mL tetrahydrofuran. Under ice-water bath conditions (0-5℃), an intermediate (20g, 27mmol, 1.0eq.) was added multiple times over 30 minutes, and the reaction was allowed to proceed overnight at room temperature. After the reaction was complete, the reaction solution was first diluted with dichloromethane, then filtered through a sintered glass funnel with diatomaceous earth, and finally evaporated to dryness and passed through a column chromatography to obtain 5.1g of the novel anthraquinone dye for blue photoresist color paste, with a yield of 24.5%.

[0062] The chemical structural formula of the novel anthraquinone dye used in the blue photoresist pigment of this embodiment is shown in A2 below: The method for synthesizing the intermediate in this embodiment is the same as that in Embodiment 1.

[0063] Example 3 The synthesis method of the novel anthraquinone dye for blue photoresist color paste in this embodiment is as follows: A dry and clean 500mL three-necked flask was placed with a stir bar of appropriate size. 1,5-Pentanediol (4.3g, 41mmol, 3eq.) and triethylamine (4.2g, 41mmol, 3.0eq.) were dissolved in 200mL tetrahydrofuran. Under ice-water bath conditions (0-5℃), an intermediate (10g, 14mmol, 1.0eq.) was added multiple times over 30 minutes, and the reaction was allowed to proceed overnight at room temperature. After the reaction was complete, the reaction solution was first diluted with dichloromethane, then filtered through a sintered glass funnel with diatomaceous earth, and finally evaporated to dryness and passed through a column chromatography to obtain 2.7g of the novel anthraquinone dye for blue photoresist color paste, with a yield of 25.4%.

[0064] The chemical structural formula of the novel anthraquinone dye used in the blue photoresist pigment of this embodiment is shown in A3 below: The method for synthesizing the intermediate in this embodiment is the same as that in Embodiment 1.

[0065] Comparative Example 1 The synthesis method of the anthraquinone dye for the blue photoresist pigment in this comparative example is as follows: (1) Take a dry and clean 1000mL four-necked flask and place a stir bar of appropriate size; add Solvent Blue 104 (50g, 100mmol, 1.0eq.), then add chlorosulfonic acid (440g, 3.78mol, 38eq.), and stir at 45℃ to 30℃ for 15min. After the temperature is maintained, start adding thionyl chloride (30g, 252mmol, 2.5eq.) dropwise using a constant pressure dropping funnel, with a dropping time of more than 30min. After the dropping is completed, react at room temperature overnight. Take a 5L plastic beaker and add 3.5L of ice-water mixture, stir slowly with a mechanical stirrer, and slowly add the reaction solution to the ice water with a glass dropper to quench it, ensuring that the ice does not melt throughout the process. After the dropping is completed, stir at -5℃ for 30min, filter with a Buchner funnel, wash the filter cake 3 times with ice water, collect the filter cake, dry at 50℃ to obtain 38g of blue intermediate C2, with a yield of 56.6%.

[0066] The chemical structural formula of the intermediate in this comparative example is shown in C2 below: (2) Take a dry and clean 500mL three-necked flask and place a stir bar of appropriate size; dissolve cyclohexylamine (8.1g, 82mmol, 3eq.) and triethylamine (8.3g, 82mmol, 3.0eq.) in 200mL tetrahydrofuran, and add intermediate (20g, 27mmol, 1.0eq.) in multiple batches over 30min under ice-water bath conditions (0-5℃), and react overnight at room temperature. After the reaction is complete, first dilute the reaction solution with dichloromethane, then filter it with diatomaceous earth through a sintered glass funnel, and finally evaporate it to dryness and pass it through a column to obtain 3.8g of anthraquinone dye for blue photoresist pigment paste, with a yield of 17.7%.

[0067] The chemical structural formula of the anthraquinone dye used in the blue photoresist pigment of this comparative example is shown in A4 below: Performance testing 1. Nuclear magnetic resonance hydrogen spectrum test The 1H-NMR spectra of the anthraquinone dyes prepared in Examples 1-3 and Comparative Example 1 are shown below. Figure 1-3 and Figure 4 As shown.

[0068] 2. Determination of UV-Vis absorption spectra of anthraquinone dyes The anthraquinone dyes prepared in Examples 1-3 and Comparative Example 1 were formulated into 10 μmol / L solutions using N,N-dimethylformamide (DMF) 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 absorption 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.

[0069] The UV-Vis absorption spectra of the anthraquinone dyes prepared in Examples 1-3 and Comparative Example 1 are shown in Table 1.

[0070] Table 1. UV-Vis absorption spectra of anthraquinone dyes prepared in Examples 1-3 and Comparative Example 1 As shown in Table 1, the anthraquinone dyes prepared in Example 2 showed a slight blue shift compared to those in Example 1, and the anthraquinone dyes prepared in Example 2 had the highest molar absorptivity. The anthraquinone dyes prepared in Example 3 showed a red shift compared to those in Example 1, and also had a higher molar absorptivity.

[0071] 3. Solubility test of anthraquinone dyes The solubility of anthraquinone dyes prepared in Examples 1-3 and Comparative Example 1 in propylene glycol methyl ether acetate (PGMEA) and N,N-dimethylformamide (DMF) was tested. 10 mg of anthraquinone dye and 100 mg of organic solvent were weighed out, stirred at room temperature for 10 min, and allowed to stand for 24 h. The mixture was filtered three times using a filter membrane, and the filtrate was dried. The solubility S of the anthraquinone dye was calculated. S=100M S / M L In the formula, M S This refers to the mass of anthraquinone dyes after drying, in grams (g); M L This is the mass of the solution, in grams (g).

[0072] The solubility test results of the anthraquinone dyes prepared in Examples 1-3 and Comparative Example 1 are shown in Table 2.

[0073] Table 2. Solubility test results of anthraquinone dyes prepared in Examples 1-3 and Comparative Example 1 As shown in Table 2, the anthraquinone dyes prepared in Examples 1-3 all have good solubility in PGMEA and DMF, with the anthraquinone dye molecules prepared in Example 2 having the best solubility in PGMEA.

[0074] 4. Thermal stability test of anthraquinone dyes 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) was used to evaluate the thermal stability of anthraquinone dyes. Anthraquinone dyes were heated from room temperature to 500℃ under nitrogen protection at a rate of 10℃ / min to determine their thermal decomposition temperature T. d .

[0075] The thermal stability test results of the anthraquinone dyes prepared in Examples 1-3 and Comparative Example 1 are shown in Table 3.

[0076] Table 3. Thermal stability test results of anthraquinone dyes prepared in Examples 1-3 and Comparative Example 1 As shown in Table 3, the T values ​​of the anthraquinone dyes prepared in Examples 1-3 are... d Within the temperature range of 289-342℃, the weight loss rate at 230℃ is less than 5%, indicating that the above-mentioned anthraquinone dye molecules have good thermal stability.

[0077] This invention provides a novel anthraquinone dye for blue photoresist color paste. The anthraquinone dye molecule can be mixed with other colorants to form a blue photoresist color paste to improve the brightness of the color paste. It also has advantages such as high transparency, high contrast, good dispersibility, high hiding power, and high tinting strength, as well as good thermal and light stability. At the same time, the synthesis method provided by this invention is simple, low in cost, and easy to scale up for production.

[0078] Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A novel anthraquinone dye for blue photoresist color paste, characterized in that: It has a structure as shown in Equation A: In formula A: R 1 R 2 Each can be independently H, halogen, or alkyl; X is selected from the following groups: N or O; Y is selected from C3-C 20 Alkyl groups.

2. The method for synthesizing a novel anthraquinone dye for blue photoresist color paste as described in claim 1, characterized in that: Includes the following steps: (1) Anthraquinone derivative and sulfonyl chloride reagent are mixed and subjected to sulfonyl chloride reaction to obtain an intermediate; the anthraquinone derivative has the structure shown in IA: The intermediate has the structure shown in IIA: (2) Mix the amphiphilic nucleophilic reaction site compound, organic base and solvent evenly, then add intermediate and carry out substitution reaction to obtain a novel anthraquinone dye for blue photoresist color paste.

3. The method for synthesizing a novel anthraquinone dye for blue photoresist pigment paste according to claim 2, characterized in that: In step (1), the sulfonyl chloride reagent is one or both of chlorosulfonic acid and thionyl chloride; And / or, the molar ratio of the anthraquinone derivative to the sulfonyl chloride reagent is 1:(10-50).

4. The method for synthesizing a novel anthraquinone dye for blue photoresist pigment paste according to claim 2, characterized in that: In step (1), the temperature of the sulfonyl chlorination reaction is -20℃ to 50℃.

5. The method for synthesizing a novel anthraquinone dye for blue photoresist pigment paste according to claim 2, characterized in that: In step (2), the nucleophilic group of the compound with the amphiphilic reaction site is one or more of amino, hydroxy, and thiol groups; And / or, the linking group of the amphiphilic reactive site compound is C3-C. 20 Alkyl groups.

6. The method for synthesizing a novel anthraquinone dye for blue photoresist pigment paste according to claim 2, characterized in that: In step (2), the molar ratio of the amphiphilic reaction site compound to the intermediate is (1-3):1; And / or, the molar ratio of the intermediate to the organic base is 1:(1-4).

7. The method for synthesizing a novel anthraquinone dye for blue photoresist pigment paste according to claim 2, characterized in that: In step (2), the organic base is one or more of triethylamine, pyridine, piperidine, 4-dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and diisopropylethylamine.

8. The method for synthesizing a novel anthraquinone dye for blue photoresist pigment paste according to claim 2, characterized in that: In step (2), the solvent is one or more of toluene, tetrahydrofuran, dichloromethane, chloroform, and dichloroethane.

9. The method for synthesizing a novel anthraquinone dye for blue photoresist pigment paste according to claim 2, characterized in that: In step (2), the temperature of the substitution reaction is 0℃-40℃.

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