Reactive display photoresist color paste phthalocyanine dye and its synthesis method

Abstract

The application belongs to the technical field of display photoresist color paste, and specifically provides a phthalocyanine dye for reactive display photoresist color paste and a synthesis method thereof, the synthesis method comprising the following steps: (1) carrying out a substitution reaction on a nucleophilic reagent and an electrophilic reagent containing an epoxy group, and obtaining an intermediate A through post-treatment; (2) carrying out a substitution reaction on o-phthalodinitrile and the intermediate A, and obtaining an intermediate B through post-treatment; (3) carrying out a cyclization reaction on a zinc compound and the intermediate B, and obtaining the phthalocyanine dye through post-treatment. The phthalocyanine dye contains a reactive epoxy group, is applied to preparation of display photoresist color paste, and compared with phthalocyanine dyes without a reactive group structure, after film formation, exhibits excellent weather resistance, solvent resistance, migration resistance, and higher solubility, light transmittance and contrast.

Description

Technical Field

[0001] This application belongs to the field of display photoresist color paste technology, and in particular relates to a phthalocyanine dye for reactive display photoresist color paste and its synthesis method. Background Technology

[0002] Photoresist pigments are one of the key source materials for manufacturing color filters. Their performance directly affects the performance of the color filters and ultimately determines the image quality of the panel display. With technological advancements and market demands for high-quality displays, photoresist pigments manufactured using traditional pigment dispersion methods are no longer sufficient to meet the needs of high-end displays. Novel dye-based photoresist pigments are being studied extensively as a next-generation high-end display technology. Because dye molecules can be completely dissolved in the medium and exist within the color filter, they exhibit lower light scattering and higher transmittance and contrast. Therefore, color filter materials prepared from dyes have advantages such as high transmittance and good color purity. However, dye-based pigments generally have poorer weather resistance and solvent resistance compared to pigment-based pigments. In practical applications, they also suffer from problems such as easy migration and aggregation, limiting the widespread application of dye-based pigments in color filter manufacturing.

[0003] This study successfully designed and synthesized novel reactive dyes containing epoxy-based phthalocyanine structures, exhibiting not only excellent photothermal stability but also superior solvent resistance and migration resistance. Through structural design optimization, the problem of dye molecules leaching from solvents after photolithography was successfully suppressed, and the migration and aggregation of dye molecules in color filters was also avoided. Furthermore, these dye molecules possess high solubility, allowing them to be directly dissolved in organic solvents to form dyes. These dyes were then spin-coated onto glass substrates and exposed to simulate the fabrication of photoresist dry film devices. Compared to phthalocyanine dye dry film materials without reactive groups, the simulated dry film exhibits better photothermal stability, solvent resistance, migration resistance, and higher transmittance, tinting strength, and contrast. Summary of the Invention

[0004] To address the aforementioned issues, this application provides a phthalocyanine dye for reactive display photoresist color paste and a method for synthesizing the same.

[0005] This application first provides a phthalocyanine dye for reactive display photoresist color paste, having the following chemical structure of general formula I: Ⅰ In Formula I, R1 represents one of the following: hydrogen atom, halogen atom, alkoxy group, aryloxy group, alkylamine group, arylamine group, alkylthiol group, and arylthiol group; In Formula I, R3 represents a substituent having the following general formula II: II In Formula II, X represents a heteroatom; Y represents one of alkoxy, alkimidyl, alkamino, aryloxy, arylmeryl, and arylamino; m and n represent integers from 0 to 20.

[0006] This application also provides a method for synthesizing phthalocyanine dyes for reactive display photoresist color pastes, comprising the following steps: (1) The nucleophile is subjected to a substitution reaction with an electrophile containing an epoxy group, and after post-treatment, intermediate A is obtained; the nucleophile is one or more of diols, diphenols, diacids, diamines and alkyd compounds; (2) The o-phthalonitrile was subjected to a substitution reaction with intermediate A, and after post-treatment, intermediate B was obtained; (3) The zinc compound is subjected to a cyclization reaction with intermediate B, and after post-treatment, the product is obtained.

[0007] Furthermore, in step (1), the diols include, but are not limited to, one or more of ethylene glycol, propylene glycol, butanediol, and ethylene glycol ether; the diphenols include, but are not limited to, one or more of hydroquinone, resorcinol, catechol, biphenyl, and naphthol; the dicarboxylic acids include, but are not limited to, one or more of terephthalic acid, isophthalic acid, phthalic acid, biphenyl, and naphtholic acid; the diamines include, but are not limited to, one or more of ethylenediamine, propylenediamine, and butanediamine; and the alcoholic acid compounds include, but are not limited to, one or more of glycolic acid, hydroxypropionic acid, and 2-hydroxypropionic acid.

[0008] Furthermore, in step (1), the electrophilic reagent containing an epoxy group includes, but is not limited to, one or more of epichlorohydrin, epibromopropane and 2-(2-bromoethyl)ethylene oxide.

[0009] Furthermore, in step (1), the molar ratio of the nucleophile to the electrophile containing the epoxy group is 1:(0.8-1.2).

[0010] Furthermore, in step (1), the base used for the substitution reaction is one or more of the following: triethylamine, diisopropylethylamine, pyridine, N,N-dimethylpyridine, sodium tert-butoxide, potassium tert-butoxide, sodium hydroxide, lithium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, and cesium carbonate.

[0011] Furthermore, in step (1), the solvent used for the substitution reaction is one or more of dichloromethane, 1,2-dichloroethane, ethyl acetate, toluene, xylene, tetrahydrofuran, methyltetrahydrofuran, diethyl ether, methyl tert-butyl ether, methyl cyclopentyl ether, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and sulfolane.

[0012] Furthermore, in step (1), the reaction temperature of the substitution reaction is 20℃-120℃.

[0013] Furthermore, in step (2), the phthalonitrile is one of 3,4-dichlorophthalonitrile, tetrachlorophthalonitrile, and tetrafluorophthalonitrile.

[0014] Furthermore, in step (2), the molar ratio of phthalonitrile to intermediate A is 1:(0.5-2).

[0015] Furthermore, in step (2), the base used for the substitution reaction is one or more of sodium hydride, lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, sodium hydroxide, lithium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, and cesium carbonate.

[0016] Furthermore, in step (2), the solvent used for the substitution reaction is one or more of toluene, xylene, tetrahydrofuran, methyltetrahydrofuran, diethyl ether, methyl tert-butyl ether, methyl cyclopentyl ether, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and sulfolane.

[0017] Furthermore, in step (2), the reaction temperature of the substitution reaction is 20℃-80℃.

[0018] Furthermore, in step (3), the zinc compound is one or more of zinc chloride, zinc bromide, zinc iodide, zinc acetate, zinc trifluoroacetate, zinc carbonate, and zinc oxide.

[0019] Furthermore, in step (3), the molar ratio of zinc compound to intermediate B is 1:(2-10).

[0020] Furthermore, in step (3), the solvent used for the cyclization reaction is one or more of n-pentanol, benzonitrile, N,N-dimethylformamide, 1,2-dichlorobenzene and sulfolane.

[0021] Furthermore, in step (3), the cyclization reaction temperature is 130℃-190℃.

[0022] Compared with the prior art, this application has the following beneficial effects: 1. This application provides a method for synthesizing phthalocyanine dyes containing reactive epoxy groups. The display photoresist color pastes prepared using phthalocyanine dyes have advantages such as high weather resistance, high transmittance, high contrast, and high tinting strength.

[0023] 2. The phthalocyanine dye molecules with macrocyclic structures provided in this application have better solvent resistance than phthalocyanine dyes without macrocyclic structures. This may be because the epoxy groups in the dye molecules can be effectively bound to the cured resin chain, which restricts the dissolution of the dye molecules, thereby improving their solvent resistance and inhibiting their migration and aggregation after film formation.

[0024] 3. The synthesis method provided in this application is simple, the reagents are readily available, the cost is low, and it can be mass-produced. Attached Figure Description

[0025] Figure 1 This is an image showing the appearance of the phthalocyanine dye used in the reactive display photoresist color paste in Example 1 under natural light.

[0026] Figure 2 The image shows the 1H NMR spectrum of the phthalocyanine dye used in the reactive display photoresist color paste in Example 1.

[0027] Figure 3 The image shows the 1H NMR spectrum of the phthalocyanine dye used in the reactive display photoresist color paste in Example 2.

[0028] Figure 4 The image shows the 1H NMR spectrum of the phthalocyanine dye used in the reactive display photoresist color paste in Example 3. Detailed Implementation

[0029] To make the inventive objectives, technical solutions, and beneficial technical effects of this application clearer, the following detailed description is provided in conjunction with embodiments, clearly and completely describing the technical solutions in the embodiments of this application. Obviously, the described embodiments are merely some embodiments of this application, and not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of this application without creative effort are within the scope of protection of this application.

[0030] 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 application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0031] 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.

[0032] The terms "preferred," "more preferably," "better," and "even better" used in this application refer to embodiments of this application 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 this application. That is, in this application, "preferred," "more preferably," "better," and "even better" are merely descriptions of implementations or embodiments with better effects, but do not constitute a limitation on the scope of protection of this application.

[0033] In this application, 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 application.

[0034] In this application, "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 application, "several" means at least one, such as one, two, etc., unless otherwise explicitly specified.

[0035] 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.

[0036] Unless otherwise specified, all steps in this application 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.

[0037] In this application, "above" or "below" includes the number itself. For example, "below 1" includes 1.

[0038] In this application, room temperature refers to 0-40°C, including but not limited to 10-40°C, or further to 20-30°C.

[0039] Based on extensive experimental research, this application provides a phthalocyanine dye for reactive display photoresist color paste, having the following chemical structure of general formula I: Ⅰ In some embodiments of this application, R1 in Formula I represents one of hydrogen atom, halogen atom, alkoxy group, aryloxy group, alkylamino group, arylamino group, alkylthiol group, and arylthiol group; R3 in Formula I represents a substituent having the following general formula II: II In Formula II, X represents a heteroatom; Y represents one of alkoxy, alkimidyl, alkamido, aryloxy, arylmeryl, and arylamine; m and n represent integers from 0 to 20, for example, they can be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20.

[0040] This application also provides a method for synthesizing phthalocyanine dyes for reactive display photoresist color pastes, comprising the following steps: (1) The nucleophile is subjected to a substitution reaction with an electrophile containing an epoxy group, and after post-treatment, intermediate A is obtained; the nucleophile is one or more of diols, diphenols, diacids, diamines and alkyd compounds; (2) The o-phthalonitrile was subjected to a substitution reaction with intermediate A, and after post-treatment, intermediate B was obtained; (3) The zinc compound is subjected to a cyclization reaction with intermediate B, and after post-treatment, the product is obtained.

[0041] In some embodiments of this application, the synthetic route for phthalocyanine dyes used in reactive display photoresist color pastes is as follows: The symbols in the formula represent the following meanings: R1 represents one of the following: hydrogen atom, halogen atom, alkoxy group, aryloxy group, alkylamino group, arylamino group, alkylthiol group, and arylthiol group; LG represents leaving functional groups synthesized from alcohols, such as Cl, Br, I, OTs, OMs, and ONs. R2 represents a departing functional group, such as F, Cl, NO2, SO2R; R3 substituents are represented by substituents containing the following chemical structural formula: X represents a heteroatom, such as an oxygen atom, a sulfur atom, or a nitrogen atom; Y represents one of alkoxy, alkimido, alkamino, aryloxy, arylmero, and arylamino; m and n represent the number of methines, which can be integers from 0 to 20. For example, they can be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20.

[0042] In some embodiments of this application, in step (1), the diols include, but are not limited to, one or more of ethylene glycol, propylene glycol, butanediol, and ethylene glycol ether; the diphenols include, but are not limited to, one or more of hydroquinone, resorcinol, catechol, biphenyl, and naphthol; the dicarboxylic acids include, but are not limited to, one or more of terephthalic acid, isophthalic acid, phthalic acid, biphenyl, and naphtholic acid; the diamines include, but are not limited to, one or more of ethylenediamine, propylenediamine, and butanediamine; and the alcoholic acid compounds include, but are not limited to, one or more of glycolic acid, hydroxypropionic acid, and 2-hydroxypropionic acid.

[0043] In some embodiments of this application, in step (1), the electrophilic reagent containing an epoxy group includes, but is not limited to, one or more of epichlorohydrin, epibromopropane and 2-(2-bromoethyl)epoxyethylene.

[0044] In some embodiments of this application, in step (1), the molar ratio of the nucleophile to the electrophile containing the epoxy group is 1:(0.8-1.2), for example, it can be 1:0.8, 1:0.9, 1:1, 1:1.1, or 1:1.2.

[0045] In some embodiments of this application, in step (1), the base used for the substitution reaction is one or more of triethylamine, diisopropylethylamine, pyridine, N,N-dimethylpyridine, sodium tert-butoxide, potassium tert-butoxide, sodium hydroxide, lithium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, and cesium carbonate.

[0046] In some embodiments of this application, in step (1), the solvent used for the substitution reaction is one or more of dichloromethane, 1,2-dichloroethane, ethyl acetate, toluene, xylene, tetrahydrofuran, methyltetrahydrofuran, diethyl ether, methyl tert-butyl ether, methyl cyclopentyl ether, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and sulfolane.

[0047] In some embodiments of this application, the reaction temperature of the substitution reaction in step (1) is 20℃-120℃. For example, it can be 20℃, 25℃, 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, 60℃, 65℃, 70℃, 75℃, 80℃, 85℃, 90℃, 95℃, 100℃, 105℃, 110℃, 115℃, or 120℃.

[0048] In some embodiments of this application, in step (2), the phthalonitrile is one of 3,4-dichlorophthalonitrile, tetrachlorophthalonitrile, and tetrafluorophthalonitrile.

[0049] In some embodiments of this application, in step (2), the molar ratio of phthalonitrile to intermediate A is 1:(0.5-2), for example, it can be 1:0.5, 1:0.8, 1:1, 1:1.2, 1:1.5, 1:1.8, or 1:2.

[0050] In some embodiments of this application, in step (2), the base used for the substitution reaction is one or more of sodium hydride, lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, sodium hydroxide, lithium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, and cesium carbonate.

[0051] In some embodiments of this application, the solvent used for the substitution reaction in step (2) is one or more of toluene, xylene, tetrahydrofuran, methyltetrahydrofuran, diethyl ether, methyl tert-butyl ether, methyl cyclopentyl ether, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and sulfolane.

[0052] In some embodiments of this application, in step (2), the reaction temperature of the substitution reaction is 20℃-80℃, for example, it can be 20℃, 25℃, 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, 60℃, 65℃, 70℃, 75℃, or 80℃.

[0053] In some embodiments of this application, in step (3), the zinc compound is one or more of zinc chloride, zinc bromide, zinc iodide, zinc acetate, zinc trifluoroacetate, zinc carbonate, and zinc oxide.

[0054] In some embodiments of this application, in step (3), the molar ratio of zinc compound to intermediate B is 1:(2-10), for example, it can be 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9, 1:9.5, or 1:10.

[0055] In some embodiments of this application, the solvent used in step (3) for the cyclization reaction is one or more of n-pentanol, benzonitrile, N,N-dimethylformamide, 1,2-dichlorobenzene and sulfolane.

[0056] In some embodiments of this application, the cyclization reaction temperature in step (3) is 130℃-190℃, for example, it can be 130℃, 135℃, 140℃, 145℃, 150℃, 155℃, 160℃, 165℃, 170℃, 075℃, 180℃, 185℃, or 190℃.

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

[0058] When numerical ranges are given in the embodiments, it should be understood that, unless otherwise stated in this application, 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 application 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 in this application, any prior art methods, equipment, and materials similar to or equivalent to those described, used, or made by the methods, equipment, and materials in the embodiments of this application may be used to implement this application.

[0059] Example 1 The method for synthesizing phthalocyanine dyes for reactive display photoresist color pastes in this embodiment includes the following steps: (1) Take a dry and clean 250 mL three-necked flask, put in a stir bar of appropriate size, add 100 mmol of hydroquinone and 110 mL of dichloromethane solvent, then add 110 mmol of triethylamine, and then slowly add 100 mmol of epichlorohydrin. Stir continuously at room temperature for 10 hours. After the reaction is completed, filter and distill under reduced pressure to obtain crude product. The crude product is subjected to column chromatography to obtain intermediate A 13.6 g, with a yield of 82.1%. (2) Take a dry and clean 250 mL three-necked flask, add a stir bar of appropriate size, add 60 mmol of intermediate A and 60 mL of N,N-dimethylformamide solvent, then add 60 mmol of sodium bicarbonate, and then add 30 mmol of tetrafluorophthalonitrile. Stir continuously at room temperature for 12 hours. After the reaction is completed, filter, extract, and distill under reduced pressure to obtain crude product. The crude product is subjected to column chromatography to obtain 10.4 g of intermediate B, with a yield of 76.0%. (3) Take a clean 250 mL three-necked flask, put in a stir bar of appropriate size, add the above-obtained intermediate B2 2.8 mmol and zinc iodide 6.8 mmol, and add 100 mL of dry benzonitrile solvent. Slowly raise the reaction system to 160 °C and react overnight. After the reaction is completed, filter and then distill under reduced pressure to obtain crude product. The crude product is then subjected to column chromatography to obtain 4.6 g, with a yield of 43.1%.

[0060] The chemical structural formula of the phthalocyanine dye for the reactive display photoresist color paste prepared in this embodiment is as follows: The 1H NMR spectrum data of the phthalocyanine dye for the reactive display photoresist color paste prepared in this embodiment are as follows: 1 H NMR (400 MHz, DMSO) δ 6.97 – 6.90 (m, 16H), 6.90 – 6.84 (m, 16H), 4.19 (dd, J =11.8, 3.2 Hz, 3H), 4.06 (d, J = 3.1 Hz, 10H), 3.94 (dd, J = 11.8, 3.2 Hz, 3H), 3.44 (p, J = 3.0 Hz, 8H), 3.19 (dd, J = 7.7, 2.9 Hz, 8H), 2.94 (dd, J = 7.6, 2.9Hz, 8H); the corresponding spectrum is shown in [reference needed]. Figure 2 .

[0061] Example 2 The method for synthesizing phthalocyanine dyes for reactive display photoresist color pastes in this embodiment includes the following steps: (1) Take a dry and clean 250 mL three-necked flask, put in a stir bar of appropriate size, add 100 mmol of p-phenylenediamine and 110 mL of dichloromethane solvent, then add 110 mmol of triethylamine, and then slowly add 100 mmol of epichlorohydrin. Stir continuously at room temperature for 10 hours. After the reaction is completed, filter and distill under reduced pressure to obtain crude product. The crude product is subjected to column chromatography to obtain intermediate A 11.3 g, with a yield of 69.2%. (2) Take a dry and clean 250 mL three-necked flask, add a stir bar of appropriate size, add 60 mmol of intermediate A and 60 mL of N,N-dimethylformamide solvent, then add 60 mmol of sodium bicarbonate, and then add 30 mmol of tetrafluorophthalonitrile. Stir continuously at room temperature for 12 hours. After the reaction is completed, filter, extract, and distill under reduced pressure to obtain crude product. The crude product is subjected to column chromatography to obtain intermediate B 7.7 g, with a yield of 56.6%. (3) Take a clean 250 mL three-necked flask, put in a stir bar of appropriate size, add the above-obtained intermediate B1 6.9 mmol and zinc iodide 6.8 mmol, and add 100 mL of dry benzonitrile solvent. Slowly raise the reaction system to 160 °C and react overnight. After the reaction is completed, filter and then distill under reduced pressure to obtain crude product. The crude product is then subjected to column chromatography to obtain 4.3 g, with a yield of 54.7%.

[0062] The chemical structural formula of the phthalocyanine dye for the reactive display photoresist color paste prepared in this embodiment is as follows: The 1H NMR spectrum data of the phthalocyanine dye for the reactive display photoresist color paste prepared in this embodiment are as follows: 1 H NMR (400 MHz, DMSO) δ 9.26 (d, J = 2.9 Hz, 4H), 8.75 (d, J = 2.8 Hz, 4H), 6.95 – 6.89(m, 16H), 6.68 – 6.62 (m, 16H), 4.44 (t, J = 5.2 Hz, 8H), 3.64 (ddd, J = 13.2,5.3, 2.7 Hz, 3H), 3.51 (dd, J = 5.2, 2.6 Hz, 10H), 3.45 (p, J = 2.4 Hz, 8H), 3.39(ddd, J = 13.2, 5.2, 2.6 Hz, 3H), 3.05 (dd, J = 8.2, 2.2 Hz, 8H), 2.80 (dd, J =8.2, 2.2 Hz, 8H); the corresponding spectrum is shown in [reference needed]. Figure 3 .

[0063] Example 3 The method for synthesizing phthalocyanine dyes for reactive display photoresist color pastes in this embodiment includes the following steps: (1) Take a dry and clean 250 mL three-necked flask, put in a stir bar of appropriate size, add 100 mmol of glycolic acid and 110 mL of dichloromethane solvent, then add 110 mmol of triethylamine, and then slowly add 100 mmol of epichlorohydrin. Stir continuously at room temperature for 10 hours. After the reaction is completed, filter and distill under reduced pressure to obtain crude product. The crude product is subjected to column chromatography to obtain intermediate A 10.0 g, with a yield of 75.4%. (2) Take a dry and clean 250 mL three-necked flask, add a stir bar of appropriate size, add 60 mmol of intermediate A and 60 mL of N,N-dimethylformamide solvent, then add 60 mmol of sodium bicarbonate, and then add 30 mmol of tetrafluorophthalonitrile. Stir continuously at room temperature for 12 hours. After the reaction is completed, filter, extract, and distill under reduced pressure to obtain crude product. The crude product is subjected to column chromatography to obtain 9.7 g of intermediate B, with a yield of 83.1%. (3) Take a clean 250 mL three-necked flask, put in a stir bar of appropriate size, add the intermediate B1 6.9 mmol and zinc iodide 6.8 mmol obtained above, and add 100 mL of dry benzonitrile solvent. Slowly raise the reaction system to 160 °C and react overnight. After the reaction is completed, filter and then distill under reduced pressure to obtain crude product. The crude product is then subjected to column chromatography to obtain 6.5 g, with a yield of 64.3%.

[0064] The chemical structural formula of the phthalocyanine dye for the reactive display photoresist color paste prepared in this embodiment is as follows: The 1H NMR spectrum data of the phthalocyanine dye for the reactive display photoresist color paste prepared in this embodiment are as follows: 1 H NMR (400 MHz, DMSO) δ 4.84 (s, 16H), 4.39 (dd, J = 11.5, 3.4 Hz, 8H), 4.13 (dd, J =11.5, 3.4 Hz, 8H), 3.58 (p, J = 3.2 Hz, 8H), 3.19 (dd, J = 7.7, 3.1 Hz, 8H), 2.94(dd, J = 7.7, 3.1 Hz, 8H); the corresponding spectrum is shown in [reference needed]. Figure 4 .

[0065] Comparative Example 1 The method for synthesizing phthalocyanine dyes for photoresist color pastes in this comparative example includes the following steps: (1) Take a dry and clean 250 mL three-necked flask, put in a stir bar of appropriate size, add 100 mmol of hydroquinone and 110 mL of dichloromethane solvent, then add 110 mmol of triethylamine, and then slowly add 100 mmol of 2-chloroethyl methyl ether. Stir continuously at room temperature for 10 hours. After the reaction is completed, filter and distill under reduced pressure to obtain crude product. The crude product is subjected to column chromatography to obtain intermediate A 14.7 g, with a yield of 83.7%. (2) Take a dry and clean 250 mL three-necked flask, add a stir bar of appropriate size, add 60 mmol of intermediate A and 60 mL of N,N-dimethylformamide solvent, then add 60 mmol of sodium bicarbonate, and then add 30 mmol of tetrafluorophthalonitrile. Stir continuously at room temperature for 12 hours. After the reaction is completed, filter, extract, and distill under reduced pressure to obtain crude product. The crude product is subjected to column chromatography to obtain 12.7 g of intermediate B, with a yield of 91.8%. (3) Take a clean 250 mL three-necked flask, put in a stir bar of appropriate size, add the above-obtained intermediate B2 7.5 mmol and zinc iodide 6.8 mmol, and add 100 mL of dry benzonitrile solvent. Slowly raise the reaction system to 160 °C and react overnight. After the reaction is completed, filter and then distill under reduced pressure to obtain crude product. The crude product is then subjected to column chromatography to obtain 8.9 g, with a yield of 67.8%.

[0066] The chemical structural formula of the phthalocyanine dye used in the photoresist color paste prepared in this comparative example is as follows: Comparative Example 2 The method for synthesizing phthalocyanine dyes for photoresist color pastes in this comparative example includes the following steps: (1) Take a dry and clean 250 mL three-necked flask, put in a stir bar of appropriate size, add 100 mmol of p-phenylenediamine and 110 mL of dichloromethane solvent, then add 110 mmol of triethylamine, and then slowly add 100 mmol of 2-chloroethyl methyl ether. Stir continuously at room temperature for 10 hours. After the reaction is completed, filter and distill under reduced pressure to obtain crude product. The crude product is subjected to column chromatography to obtain intermediate A 12.2 g, with a yield of 73.5%. (2) Take a dry and clean 250 mL three-necked flask, add a stir bar of appropriate size, add 60 mmol of intermediate A and 60 mL of N,N-dimethylformamide solvent, then add 60 mmol of sodium bicarbonate, and then add 30 mmol of tetrafluorophthalonitrile. Stir continuously at room temperature for 12 hours. After the reaction is completed, filter, extract, and distill under reduced pressure to obtain crude product. The crude product is subjected to column chromatography to obtain 8.8 g of intermediate B, with a yield of 64.6%. (3) Take a clean 250 mL three-necked flask, put in a stir bar of appropriate size, add the above-obtained intermediate B1 9.3 mmol and zinc iodide 6.8 mmol, and add 100 mL of dry benzonitrile solvent. Slowly raise the reaction system to 160 °C and react overnight. After the reaction is completed, filter and then distill under reduced pressure to obtain crude product. The crude product is 4.4 g by column chromatography, with a yield of 47.9%.

[0067] The chemical structural formula of the phthalocyanine dye used in the photoresist color paste prepared in this comparative example is as follows: Comparative Example 3 The method for synthesizing phthalocyanine dyes for photoresist color pastes in this comparative example includes the following steps: (1) Take a dry and clean 250 mL three-necked flask, put in a stir bar of appropriate size, add 100 mmol of glycolic acid and 110 mL of dichloromethane solvent, then add 110 mmol of triethylamine, and then slowly add 100 mmol of 2-chloroethyl methyl ether. Stir continuously at room temperature for 10 hours. After the reaction is completed, filter and distill under reduced pressure to obtain crude product. The crude product is subjected to column chromatography to obtain intermediate A 9.2 g, with a yield of 68.5%. (2) Take a dry and clean 250 mL three-necked flask, add a stir bar of appropriate size, add 60 mmol of intermediate A and 60 mL of N,N-dimethylformamide solvent, then add 60 mmol of sodium bicarbonate, and then add 30 mmol of tetrafluorophthalonitrile. Stir continuously at room temperature for 12 hours. After the reaction is completed, filter, extract, and distill under reduced pressure to obtain crude product. The crude product is subjected to column chromatography to obtain 8.1 g of intermediate B, with a yield of 68.9%. (3) Take a clean 250 mL three-necked flask, put in a stir bar of appropriate size, add the above-obtained intermediate B2 0.7 mmol and zinc iodide 6.8 mmol, and add 100 mL of dry benzonitrile solvent. Slowly raise the reaction system to 160 °C and react overnight. After the reaction is completed, filter and then distill under reduced pressure to obtain crude product. The crude product is then subjected to column chromatography to obtain 3.5 g, with a yield of 41.9%.

[0068] The chemical structural formula of the phthalocyanine dye used in the photoresist color paste prepared in this comparative example is as follows: Performance testing 1. Solubility test The phthalocyanine dyes prepared in Examples 1-3 and Comparative Examples 1-3 were weighed and reacted with propylene glycol methyl ether acetate (PGMEA) and N,N-dimethylformamide (DMF) organic solvents, respectively. After stirring at room temperature for 10 min, the mixtures were allowed to stand for 24 h. The mixtures were then filtered three times using a filter membrane. The filtrates were dried, and the solubility of the dyes in PGMEA and DMF was calculated using the following formula: S = 100M. S / M L , In the formula, M S It is the mass of the dye after drying, in grams (g); in milliliters (M). L It is the mass of the solution, in grams. The solubility test results are shown in Table 1.

[0069] Table 1. Solubility test results of phthalocyanine dyes in Examples 1-3 and Comparative Examples 1-3 As shown in Table 1, the phthalocyanine dyes for reactive display photoresist color pastes prepared in Examples 1-3 all have good solubility in PGMEA and DMF.

[0070] 2. Thermal stability test Thermogravimetric analysis (TGA) was used to evaluate the thermal stability of the synthesized dyes. The phthalocyanine dyes prepared in Examples 1-3 and Comparative Examples 1-3 were heated from room temperature to 500°C at a heating rate of 10°C / min under nitrogen protection to determine their thermal decomposition temperature T. d The weight loss rate at 230℃ is shown in Table 2.

[0071] Table 2. Thermal stability test results of phthalocyanine dyes in Examples 1-3 and Comparative Examples 1-3 The fabrication of color filters involves a post-baking process at 200°C or higher. Industrial requirements dictate that dye molecules must exhibit good thermal stability at this temperature. As shown in Table 2, the phthalocyanine dyes for reactive display photoresist color pastes prepared in Examples 1-3 exhibit T... d Within the temperature range of 321-335℃, the weight loss rate at 230℃ was less than 5%, indicating that the phthalocyanine dyes for reactive display photoresist pigments prepared in Examples 1-3 have good thermal stability.

[0072] 3. Light stability test The phthalocyanine dyes (3%) prepared in Examples 1-3 and Comparative Examples 1-3 were mixed with resin (Lisennoco Polymer Materials (Shanghai) Co., Ltd., SP-DW-TH3001, 20%), monomer (dipentaerythritol hexaacrylate DPHA, 5%), photoinitiator (diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide TPO, 5%), and solvent (propylene glycol methyl ether acetate PMA, 67%) to prepare a photoresist. The photoresist was then coated onto a 0.4 mm thick glass substrate using a spin coater (800 rpm, 15 s), followed by heating and drying on a 150 °C hot plate for 2 min, irradiation with 365 nm ultraviolet light for 1 min, and post-baking in a 230 °C cleanroom oven for 30 min to obtain a photoresist colored film. The properties of the obtained colored film were measured. ∆E (L0, a0, b0) values, then place the sample at 51 W / m 2 After irradiation at 65 °C for 24 hours under a xenon lamp, the properties of the obtained colored film were measured again. ∆E (L1, a1, b1) values. Based on the color difference calculation formula. ΔE ab ={(L1-L0)} 2 +(a1-a0) 2 +(b1-b0) 2} 1 / 2 Calculate color difference, if ΔE ab If the value is less than 3, the photostability is excellent. The measurement results are shown in Table 3.

[0073] Table 3. Results of photostability tests on phthalocyanine dyes in Examples 1-3 and Comparative Examples 1-3 As shown in Table 3, the ΔE of the phthalocyanine dyes for reactive display photoresist pigments prepared in Examples 1-3 is... ab The values ​​are all less than 3, indicating that the phthalocyanine dye has good photostability.

[0074] 4. Solvent resistance test The phthalocyanine dyes (3%) prepared in Examples 1-3 and Comparative Examples 1-3 were mixed with resin (Lisennoco Polymer Materials (Shanghai) Co., Ltd., SP-DW-TH3001, 20%), monomer (dipentaerythritol hexaacrylate DPHA, 5%), photoinitiator (diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide TPO, 5%), and solvent (one of N-methylpyrrolidone NMP, ethanol EtOH, and propylene glycol methyl ether acetate PGMEA, 67%) to prepare a photoresist. The photoresist was then coated onto a 0.4 mm thick glass substrate using a spin coater (800 rpm, 15 s), followed by heating and drying on a 150 °C hot plate for 2 min, irradiation with 365 nm ultraviolet light for 1 min, and post-baking in a 230 °C cleanroom oven for 30 min to obtain a photoresist colored film. The properties of the obtained colored film were measured. ∆E (L0, a0, b0) values, then place the sample at 51 W / m 2 After irradiation at 65 °C for 24 hours under a xenon lamp, the properties of the obtained colored film were measured again. ∆E (L1, a1, b1) values. Based on the color difference calculation formula. ΔE ab ={(L1-L0)} 2 +(a1-a0) 2 +(b1-b0) 2} 1 / 2 Calculate color difference, if ΔE ab If the value is less than 3, the solvent resistance is excellent. The test results are shown in Table 4.

[0075] Table 4 Solvent resistance test results of phthalocyanine dyes in Examples 1-3 and Comparative Examples 1-3 As shown in Table 4, the reactive display photoresist color pastes prepared in Examples 1-3 contain phthalocyanine dyes. ΔE ab The values ​​are all less than 3, indicating that the phthalocyanine dye has good solvent resistance.

[0076] Although this application 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 this application should be included within the protection scope of this application.

Claims

1. A phthalocyanine dye for reactive display photoresist color paste, characterized in that: It has the following chemical structure of general formula I: Ⅰ In Formula I, R1 represents one of the following: hydrogen atom, halogen atom, alkoxy group, aryloxy group, alkylamine group, arylamine group, alkylthiol group, and arylthiol group; In Formula I, R3 represents a substituent having the following general formula II: Ⅱ In Formula II, X represents a heteroatom; Y represents one of alkoxy, alkimidyl, alkamino, aryloxy, arylmeryl, and arylamino; m and n represent integers from 0 to 20.

2. The method for synthesizing phthalocyanine dyes for reactive display photoresist color pastes according to claim 1, characterized in that: Includes the following steps: (1) The nucleophile is subjected to a substitution reaction with an electrophile containing an epoxy group, and after post-treatment, intermediate A is obtained; the nucleophile is one or more of diols, diphenols, diacids, diamines and alkyd compounds; (2) The o-phthalonitrile was subjected to a substitution reaction with intermediate A, and after post-treatment, intermediate B was obtained; (3) The zinc compound is subjected to a cyclization reaction with intermediate B, and after post-treatment, the product is obtained.

3. The method for synthesizing phthalocyanine dyes for reactive display photoresist color pastes according to claim 2, characterized in that: In step (1), the diols include, but are not limited to, one or more of ethylene glycol, propylene glycol, butanediol and ethylene glycol ether; the diphenols include, but are not limited to, one or more of hydroquinone, resorcinol, catechol, biphenyl and naphthol; the dicarboxylic acids include, but are not limited to, one or more of terephthalic acid, isophthalic acid, phthalic acid, biphenyl and naphtholic acid; the diamines include, but are not limited to, one or more of ethylenediamine, propylenediamine and butanediamine; and the alcoholic acid compounds include, but are not limited to, one or more of glycolic acid, hydroxypropionic acid and 2-hydroxypropionic acid.

4. The method for synthesizing phthalocyanine dye for reactive display photoresist color paste according to claim 2, characterized in that: In step (1), the electrophilic reagent containing epoxy groups includes, but is not limited to, one or more of epichlorohydrin, epibromopropane and 2-(2-bromoethyl)epoxyethylene.

5. The method for synthesizing phthalocyanine dye for reactive display photoresist color paste according to claim 2, characterized in that: In step (1), the molar ratio of the nucleophile to the electrophile containing the epoxy group is 1:(0.8-1.2).

6. The method for synthesizing phthalocyanine dye for reactive display photoresist color paste according to claim 2, characterized in that: In step (1), the base used for the substitution reaction is one or more of the following: triethylamine, diisopropylethylamine, pyridine, N,N-dimethylpyridine, sodium tert-butoxide, potassium tert-butoxide, sodium hydroxide, lithium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, and cesium carbonate.

7. The method for synthesizing phthalocyanine dye for reactive display photoresist color paste according to claim 2, characterized in that: In step (1), the solvent used for the substitution reaction is one or more of dichloromethane, 1,2-dichloroethane, ethyl acetate, toluene, xylene, tetrahydrofuran, methyltetrahydrofuran, diethyl ether, methyl tert-butyl ether, methyl cyclopentyl ether, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and sulfolane.

8. The method for synthesizing phthalocyanine dye for reactive display photoresist color paste according to claim 2, characterized in that: In step (1), the reaction temperature of the substitution reaction is 20℃-120℃.

9. The method for synthesizing phthalocyanine dye for reactive display photoresist color paste according to claim 2, characterized in that: In step (2), the phthalonitrile is one of 3,4-dichlorophthalonitrile, tetrachlorophthalonitrile, and tetrafluorophthalonitrile.

10. The method for synthesizing phthalocyanine dye for reactive display photoresist color paste according to claim 2, characterized in that: In step (2), the molar ratio of o-phthalonitrile to intermediate A is 1:(0.5-2).

11. The method for synthesizing phthalocyanine dyes for reactive display photoresist color pastes according to claim 2, characterized in that: In step (2), the base used for the substitution reaction is one or more of sodium hydride, lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, sodium hydroxide, lithium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, and cesium carbonate.

12. The method for synthesizing phthalocyanine dye for reactive display photoresist color paste according to claim 2, characterized in that: In step (2), the solvent used for the substitution reaction is one or more of toluene, xylene, tetrahydrofuran, methyltetrahydrofuran, diethyl ether, methyl tert-butyl ether, methyl cyclopentyl ether, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and sulfolane.

13. The method for synthesizing phthalocyanine dye for reactive display photoresist color paste according to claim 2, characterized in that: In step (2), the reaction temperature of the substitution reaction is 20℃-80℃.

14. The method for synthesizing phthalocyanine dye for reactive display photoresist color paste according to claim 2, characterized in that: In step (3), the zinc compound is one or more of zinc chloride, zinc bromide, zinc iodide, zinc acetate, zinc trifluoroacetate, zinc carbonate, and zinc oxide.

15. The method for synthesizing phthalocyanine dye for reactive display photoresist color paste according to claim 2, characterized in that: In step (3), the molar ratio of zinc compound to intermediate B is 1:(2-10).

16. The method for synthesizing phthalocyanine dye for reactive display photoresist color paste according to claim 2, characterized in that: In step (3), the solvent used for the cyclization reaction is one or more of n-pentanol, benzonitrile, N,N-dimethylformamide, 1,2-dichlorobenzene and sulfolane.

17. The method for synthesizing phthalocyanine dye for reactive display photoresist color paste according to claim 2, characterized in that: In step (3), the cyclization reaction temperature is 130℃-190℃.

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