Pretreatment method of blue pigment for color photoresist

Abstract

The invention discloses a pretreatment method of a blue pigment for color photoresist, and relates to the technical field of photoresist pigment pretreatment, the pretreatment method of the blue pigment comprises the following steps: S1, activating the blue pigment to prepare an activated intermediate; s2, N, N-dimethylethanolamine is prepared into a quaternary ammonium salt bridging unit; s3, modifying the activated intermediate by using a quaternary ammonium salt bridging unit to prepare a copper phthalocyanine-quaternary ammonium salt derivative; s4, modifying the copper phthalocyanine-quaternary ammonium salt derivative to prepare a blue pigment; the pretreated blue pigment is subjected to quaternary ammonium salt bridging and phosphonate grafting modification, so that the dispersing capacity of the blue pigment in resin can be improved, the blue pigment can also have a synergistic effect with benzotriazole and benzophenone, the heat and humidity resistance of the blue pigment is improved, and the service life of a photoresist device is prolonged; and polypropylene glycol bis (2-aminopropyl ether) and propylene glycol methyl ether acetate are added, so that the compatibility of the blue pigment and a photoetching process reagent can be improved, and the pollution of a film layer is reduced.

Description

Technical Field

[0001] This invention relates to the field of photoresist pigment pretreatment technology, and in particular to a pretreatment method for blue pigments used in color photoresists. Background Technology

[0002] The blue pigment in color photoresist is a functional coloring material specifically used in the manufacture of color filters, primarily responsible for producing a pure, vibrant blue in each pixel of a display (such as LCD and OLED).

[0003] In practical applications, blue pigments in color photoresists mainly suffer from the following defects: Regarding resistance to humidity and heat, the molecular structure of blue pigments and their compatibility with resins can easily lead to color fading, discoloration, and decreased film adhesion under high temperature and humidity conditions, potentially causing pattern deformation; Regarding film contamination, the inherent tendency of pigment particles to aggregate can lead to unstable dispersion. In addition, improper coating processes and environmental control (such as insufficient cleanliness and temperature and humidity fluctuations) can jointly cause defects such as foreign matter on the coating surface, poor uniformity, and residues after development.

[0004] Therefore, a pretreatment method for blue pigment used in color photoresists is proposed to solve the above problems. Summary of the Invention

[0005] The main objective of this invention is to provide a method for preparing blue pigments for color photoresists with low impurities, strong adhesion, and high resistance to damp heat, which can be applied to the preparation of blue pigments for color photoresists.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows: This invention provides a pretreatment method for blue pigment used in color photoresist, the pretreatment method for blue pigment comprising the following steps: S1. Activate the blue pigment to obtain an activation intermediate; S2. Prepare N,N-dimethylethanolamine into a quaternary ammonium salt bridging unit; S3. The copper phthalocyanine-quaternary ammonium salt derivative was prepared by modifying the activated intermediate with a quaternary ammonium salt bridging unit. S4. Modify copper phthalocyanine-quaternary ammonium salt derivatives to obtain a blue pigment.

[0007] The blue pigment matrix is ​​tetrasodium copper phthalocyanine tetrasulfonate; Further, the preparation of the activated intermediate in S1 includes the following steps: adding anhydrous ethanol to a reaction vessel, adding tetrasodium copper phthalocyanine tetrasulfonate and stirring at 300-400 rpm for 15-20 minutes, adding concentrated sulfuric acid dropwise and stirring at a rate of 1-2 drops / second, controlling the temperature below 30°C during the addition of concentrated sulfuric acid, stirring at 200-250 rpm for 10-12 minutes, heating the reaction vessel to 60°C and refluxing for 3 hours, allowing the reaction vessel temperature to cool naturally to 18-25°C, adding water at 0-2°C and stirring at 100-150 rpm for 5 minutes, filtering the filtrate using a polytetrafluoroethylene filter membrane to obtain a filter cake, washing the filter cake three times with ethanol at 0-5°C, and drying the washed filter cake in a vacuum drying oven at a vacuum degree of 0.08-0.09 MPa for 4 hours to obtain the activated intermediate.

[0008] Furthermore, the mass ratio of the copper phthalocyanine tetrasulfonate tetrasodium salt to anhydrous ethanol is 1:15.8; The mass ratio of tetrasodium copper phthalocyanine tetrasulfonate to concentrated sulfuric acid is 1:0.092; The mass ratio of copper phthalocyanine tetrasulfonate tetrasodium salt to water at 0-2℃ is 1:5; The pore size of the polytetrafluoroethylene filter membrane is 0.45 μm.

[0009] Further, the preparation of the quaternary ammonium salt bridging unit in S2 includes the following steps: acetone is placed in a water bath reactor, nitrogen gas is introduced into the water bath reactor using a nitrogen generator, N,N-dimethylethanolamine is added and stirred at 200-250 rpm for 5-8 minutes, the water bath temperature is lowered to 0-5℃, and stirring is maintained at this temperature. During the cooling process, the temperature decrease rate is 1-2℃ / min, the stirring speed is 150-200 rpm, and stirring is maintained for 20-25 minutes. The temperature is maintained at 0-5℃, epichlorohydrin is added dropwise and stirred at 150-200 rpm for 1-2 hours, the water bath temperature is heated to 30℃ and stirred at 200-250 rpm for 4 hours, and rotary evaporation is performed using a rotary evaporator at 40℃ and a rotation speed of 60-80 rpm for 30-40 minutes to obtain the quaternary ammonium salt bridging unit.

[0010] Furthermore, the mass ratio of acetone to N,N-dimethylethanolamine is 4:1; The mass ratio of N,N-dimethylethanolamine to epichlorohydrin is 1:0.86.

[0011] Further, the preparation of the copper phthalocyanine-quaternary ammonium salt derivative in S3 includes the following steps: adding anhydrous dimethylformamide to a reaction vessel, heating the reaction vessel to 40°C, adding an activation intermediate and stirring at 250-300 rpm for 20-25 minutes, adding triethylamine and stirring at 200-250 rpm for 5 minutes, adding a quaternary ammonium salt solution dropwise while stirring, maintaining the reaction vessel temperature at 40°C during the dropwise addition process, stirring at 200-250 rpm for 15-20 minutes, and heating the reaction vessel to 80°C. The reaction solution was prepared by stirring at ℃ for 6 hours. Ethyl acetate was added to a new reactor, and the reaction solution was stirred. The temperature was controlled at 20-25℃, the speed was 100-150 rpm, and the stirring time was 20 minutes. The filtrate was filtered off using a nylon filter membrane to obtain an activated intermediate filter cake. The activated intermediate filter cake was washed with ethyl acetate three times. The washed activated intermediate filter cake was placed in a vacuum drying oven and dried at a vacuum degree of 0.08-0.09 MPa and a temperature of 60℃ for 6 hours to obtain the copper phthalocyanine-quaternary ammonium salt derivative.

[0012] Furthermore, the mass ratio of the anhydrous dimethylformamide to the activated intermediate is 18.9:1; The mass ratio of the activated intermediate to triethylamine is 1:0.36; The mass ratio of the activation intermediate to the quaternary ammonium salt solution is 1:5.1; The mass ratio of the reaction solution and ethyl acetate added to the new reactor is 1:2.5; The nylon filter membrane has a pore size of 0.22 μm.

[0013] Further, the preparation of the quaternary ammonium salt solution includes the following steps: adding anhydrous dimethylformamide into a magnetic reactor, adding a quaternary ammonium salt bridging unit and stirring magnetically, with a temperature ≤25℃ and a rotation speed of 300-500 rpm for 30 minutes to obtain the quaternary ammonium salt solution; The mass ratio of the anhydrous dimethylformamide to the quaternary ammonium salt bridging unit is 2.78:1.

[0014] Further, the preparation of the pretreated blue pigment in S4 includes the following steps: adding anhydrous ethanol to the reaction vessel, adding copper phthalocyanine-quaternary ammonium salt derivative and stirring at 300-350 rpm for 30-35 minutes, adding bis(hydroxyethyl)aminophosphate and stirring at 250-300 rpm for 10 minutes, adding trifluoroacetic acid and stirring at 200-250 rpm for 2 minutes, heating the reaction vessel to 50°C and stirring at 200-250 rpm for 8 hours to obtain a reaction solution, dialyzing the reaction solution using a dialysis bag filled with propylene glycol methyl ether acetate solution for 48 hours, changing the propylene glycol methyl ether acetate solution every 12 hours, and then dialyzing the dialyzed reaction solution... A modified copper phthalocyanine tetrasodium sulfonate solution was prepared by rotary evaporation at 40℃, vacuum 0.09MPa, and rotation speed of 50-60rpm for 45-60 minutes. Polypropylene glycol bis(2-aminopropyl ether) and propylene glycol methyl ether acetate were added to an ultrasonic disperser and dispersed at 100-150W for 10 minutes. The modified copper phthalocyanine tetrasodium sulfonate solution was then added and stirred at 250-300rpm for 20 minutes. Benzotriazole and benzophenone were added sequentially and stirred at 300-350rpm for 15 minutes. Triethyl citrate and vitamin E acetate were added and stirred at 200-350rpm for 10 minutes. The mixture was allowed to stand for 1 hour to obtain a blue pigment. The molecular weight cutoff of the dialysis bag is 10,000 Da; The mass ratio of the copper phthalocyanine-quaternary ammonium salt derivative to anhydrous ethanol is 1:15.78; The mass ratio of the copper phthalocyanine-quaternary ammonium salt derivative to trifluoroacetic acid is 1:0.019; The mass ratio of the copper phthalocyanine-quaternary ammonium salt derivative to bis(hydroxyethyl)aminophosphate is 1:0.275; The mass ratio of the modified copper phthalocyanine tetrasulfonic acid tetrasodium salt solution to polypropylene glycol bis(2-aminopropyl ether) is 1:0.0025; The modified copper phthalocyanine tetrasodium salt solution and propylene glycol methyl ether acetate were added to the ultrasonically dispersed solution at a mass ratio of 1:0.002. The mass ratio of the modified copper phthalocyanine tetrasulfonic acid tetrasodium salt solution to benzotriazole is 1:0.0015; The mass ratio of the modified copper phthalocyanine tetrasulfonic acid tetrasodium salt solution to benzophenone is 1:0.0012; The mass ratio of the modified copper phthalocyanine tetrasodium sulfonate solution to triethyl citrate is 1:0.001; The mass ratio of the modified copper phthalocyanine tetrasulfonic acid tetrasodium salt solution to vitamin E acetate is 1:0.0008.

[0015] Further, the preparation of the bis(hydroxyethyl)aminophosphate includes the following steps: N,N-bis(2-hydroxyethyl)aminomethylphosphonic acid diethyl ester and concentrated hydrochloric acid are added to a reaction vessel and stirred at 200-250 rpm. Deionized water is added during stirring, and the mixture is stirred for 15-20 minutes. The reaction vessel is then heated to 105°C and refluxed for 12 hours. The reaction vessel is then naturally cooled to 20-30°C to obtain a mixture of N,N-bis(2-hydroxyethyl)aminomethylphosphonic acid diethyl ester. This mixture is then placed in a rotary evaporator for rotary evaporation at 60-70°C and a vacuum of 0.08-0.09 MPa. Rotate at 50-60 rpm for 2.5-4 hours to obtain a crude product. Add the crude product and anhydrous ethanol to a reaction vessel and stir at 300-350 rpm for 15-20 minutes. Add activated carbon and stir at 300-350 rpm for 30-40 minutes. Filter using a polytetrafluoroethylene (PTFE) membrane to remove the filtrate and obtain a crude product filter cake. Place the crude product filter cake in a freeze crystallizer for freezing crystallization at -20℃ for 6-24 hours. Filter the filtrate of the crystallized crude product using a PTFE membrane to obtain bis(hydroxyethyl)aminophosphate. The pore size of the polytetrafluoroethylene filter membrane is 0.22 μm; The concentration of the concentrated hydrochloric acid is 37%. The mass ratio of N,N-bis(2-hydroxyethyl)aminomethylphosphonic acid diethyl ester to concentrated hydrochloric acid is 1:2.04; The mass ratio of N,N-bis(2-hydroxyethyl)aminomethylphosphonic acid diethyl ester to deionized water is 1:0.78; The mass ratio of N,N-bis(2-hydroxyethyl)aminomethylphosphonic acid diethyl ester to anhydrous ethanol is 1:0.93; The mass ratio of N,N-bis(2-hydroxyethyl)aminomethylphosphonic acid diethyl ester to activated carbon is 1:0.02.

[0016] The present invention has the following beneficial effects: 1. In this invention, a modified tetrasodium copper phthalocyanine tetrasulfonate solution is added. Its copper phthalocyanine matrix structure can stably exhibit a bright and pure blue color with long-lasting color performance, which can meet the strict requirements of color accuracy for color photoresists. After modification by quaternary ammonium salt bridging and phosphonate grafting, the polar groups (sulfonic acid group, quaternary ammonium salt cation, phosphonate group) introduced into the molecule can form good interactions with commonly used solvents and resins in photoresists, greatly improving dispersibility, avoiding particle agglomeration, and laying the foundation for subsequent uniform film coating. At the same time, the modified molecular structure has strong compatibility with the photolithography process, can form a suitable transmittance in the ultraviolet exposure range, and balances color development effect and photolithography image resolution. Moreover, after dialysis purification, the impurity content is low, which can reduce the impact on the electrical performance of semiconductor devices.

[0017] 2. In this invention, polypropylene glycol bis(2-aminopropyl ether) and propylene glycol methyl ether acetate are added. The flexible polypropylene glycol segments of polypropylene glycol bis(2-aminopropyl ether) can match the hydrophobic structure of the photoresist resin, effectively reducing the interfacial tension between pigment particles and resin, and enhancing compatibility. At the same time, its two end amino groups can form strong interactions with the hydroxyl groups of the substrate and the polar groups of modified copper phthalocyanine, significantly improving the adhesion of the film layer. It can also alleviate the shrinkage stress of the film layer through the flexible segments, reducing the risk of cracking. Propylene glycol methyl ether acetate has both excellent dispersion carrier and solvent properties. It can efficiently dissolve polypropylene glycol bis(2-aminopropyl ether), helping it to mix evenly with the modified copper phthalocyanine solution. At the same time, it has good compatibility with photolithography reagents and will not cause film swelling or contamination.

[0018] 3. In this invention, benzotriazole and benzophenone are added as stabilizing and photolithography synergists. They work synergistically with the modified copper phthalocyanine tetrasodium salt solution. The ultraviolet absorption characteristics of benzophenone and the low ultraviolet transmittance of modified copper phthalocyanine complement each other, allowing for precise control of the light transmission area during exposure. Combined with the resin crosslinking effect assisted by diphenyl methyl ether, the development contrast is improved, meeting the photolithography requirements. At the same time, the chelation protection of copper ions by benzotriazole and the anti-photoaging effect of benzophenone form a "double protection", which can effectively resist harsh environments such as humidity and heat and ultraviolet radiation. This results in small color difference of pigments after 1000h aging test, no blistering or fading of the film layer, and a significant extension of the service life of color photoresist devices. Detailed Implementation

[0019] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. 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.

[0020] It should be noted that all raw materials used in the following experiments are commercially available.

[0021] Example 1: A pretreatment method for blue pigment used in color photoresist, the pretreatment method for blue pigment includes the following steps: S1. Activate the blue pigment to obtain an activation intermediate; S2. Prepare N,N-dimethylethanolamine into a quaternary ammonium salt bridging unit; S3. The copper phthalocyanine-quaternary ammonium salt derivative was prepared by modifying the activated intermediate with a quaternary ammonium salt bridging unit. S4. Modify copper phthalocyanine-quaternary ammonium salt derivatives to obtain a blue pigment.

[0022] The preparation of the activated intermediate in S1 includes the following steps: Anhydrous ethanol is added to a reaction vessel, and tetrasodium copper phthalocyanine tetrasulfonate is added and stirred at 350 rpm for 15-20 minutes. Concentrated sulfuric acid is added dropwise and stirred at a rate of 1-2 drops / second, with the temperature controlled below 30°C during the addition of concentrated sulfuric acid. The stirring speed is 200-250 rpm for 10-12 minutes. The reaction vessel is heated to 60°C and refluxed for 3 hours. The temperature of the reaction vessel is naturally cooled to 18-25°C. Water at 0-2°C is added and stirred at 100-150 rpm for 5 minutes. The filtrate is filtered off using a polytetrafluoroethylene filter membrane to obtain a filter cake. The filter cake is washed three times with ethanol at 0-5°C. The washed filter cake is then placed in a vacuum drying oven and dried at a vacuum degree of 0.08-0.09 MPa for 4 hours to obtain the activated intermediate.

[0023] The mass ratio of tetrasodium copper phthalocyanine tetrasulfonate to anhydrous ethanol is 1:15.8; The mass ratio of tetrasodium copper phthalocyanine tetrasulfonate to concentrated sulfuric acid is 1:0.092; The mass ratio of copper phthalocyanine tetrasulfonate tetrasodium salt to water at 0-2℃ is 1:5; The pore size of the polytetrafluoroethylene filter membrane is 0.45 μm.

[0024] The preparation of the quaternary ammonium salt bridging unit in S2 includes the following steps: Acetone is placed in a water bath reactor, nitrogen gas is introduced into the water bath reactor using a nitrogen generator, N,N-dimethylethanolamine is added and stirred at 200-250 rpm for 5-8 minutes, the water bath temperature is lowered to 0-5℃, and stirring is maintained at this temperature. During the cooling process, the temperature decrease rate is 1.5℃ / min, the stirring speed is 150-200 rpm, and stirring is maintained for 20-25 minutes. The temperature is maintained at 0-5℃, epichlorohydrin is added dropwise and stirred at 150-200 rpm for 1-2 hours, the water bath temperature is heated to 30℃ and stirred at 200-250 rpm for 4 hours, and rotary evaporation is performed using a rotary evaporator at 40℃ and a rotation speed of 60-80 rpm for 30-40 minutes to obtain the quaternary ammonium salt bridging unit.

[0025] The mass ratio of acetone to N,N-dimethylethanolamine is 4:1; The mass ratio of N,N-dimethylethanolamine to epichlorohydrin is 1:0.86.

[0026] The preparation of the copper phthalocyanine-quaternary ammonium salt derivative in S3 includes the following steps: Anhydrous dimethylformamide is added to a reaction vessel, which is heated to 40°C. An activation intermediate is added and stirred at 250-300 rpm for 20-25 minutes. Triethylamine is added and stirred at 200-250 rpm for 5 minutes. A quaternary ammonium salt solution is added dropwise while stirring, maintaining the reaction vessel temperature at 40°C and stirring at 200-250 rpm for 15-20 minutes. The reaction vessel is then heated to 80°C and stirred... After 6 hours, the reaction solution was prepared. Ethyl acetate was added to a new reactor, and the reaction solution was stirred. The temperature was controlled at 20-25℃, the stirring speed was 100-150 rpm, and the stirring time was 20 minutes. The filtrate was filtered off using a nylon filter membrane to obtain an activated intermediate filter cake. The activated intermediate filter cake was washed with ethyl acetate three times. The washed activated intermediate filter cake was placed in a vacuum drying oven and dried at a vacuum degree of 0.08-0.09 MPa and a temperature of 60℃ for 6 hours to obtain the copper phthalocyanine-quaternary ammonium salt derivative.

[0027] The mass ratio of anhydrous dimethylformamide to the activated intermediate was 18.9:1; The mass ratio of the activating intermediate to triethylamine is 1:0.36; The mass ratio of the activation intermediate to the quaternary ammonium salt solution was 1:5.1; The mass ratio of the reaction solution to ethyl acetate added to the new reactor is 1:2.5; The pore size of the nylon filter membrane is 0.22 μm.

[0028] The preparation of quaternary ammonium salt solution includes the following steps: anhydrous dimethylformamide is added to a magnetic reactor, a quaternary ammonium salt bridging unit is added and magnetically stirred, the temperature is ≤25℃, the speed is 300-500rpm, and the stirring time is 30 minutes to obtain quaternary ammonium salt solution; The mass ratio of anhydrous dimethylformamide to quaternary ammonium salt bridging unit is 2.78:1.

[0029] The preparation of the pretreated blue pigment in S4 includes the following steps: Anhydrous ethanol is added to the reaction vessel, followed by the addition of a copper phthalocyanine-quaternary ammonium salt derivative and stirring at 300-350 rpm for 30-35 minutes. Then, bis(hydroxyethyl)aminophosphate is added and stirred at 250-300 rpm for 10 minutes. Trifluoroacetic acid is added and stirred at 200-250 rpm for 2 minutes. The reaction vessel temperature is heated to 50℃ and stirred at 200-250 rpm for 8 hours to obtain the reaction solution. The reaction solution is then dialyzed using a dialysis bag filled with propylene glycol methyl ether acetate solution for 48 hours, with the propylene glycol methyl ether acetate solution replaced every 12 hours. The dialyzed reaction solution is then... The modified copper phthalocyanine tetrasodium sulfonate solution was prepared by rotary evaporation at 40℃, vacuum degree 0.09MPa, and rotation speed 50-60rpm for 45-60 minutes. Polypropylene glycol bis(2-aminopropyl ether) and propylene glycol methyl ether acetate were added to an ultrasonic disperser and dispersed at 120W for 10 minutes. The modified copper phthalocyanine tetrasodium sulfonate solution was added and stirred at 250-300rpm for 20 minutes. Benzotriazole and benzophenone were added sequentially and stirred at 300-350rpm for 15 minutes. Triethyl citrate and vitamin E acetate were added and stirred at 200-350rpm for 10 minutes. The mixture was allowed to stand for 1 hour to obtain a blue pigment. The molecular weight cutoff of the dialysis bag is 10,000 Da; The mass ratio of copper phthalocyanine-quaternary ammonium salt derivative to anhydrous ethanol was 1:15.78; The mass ratio of copper phthalocyanine-quaternary ammonium salt derivative to trifluoroacetic acid was 1:0.019; The mass ratio of copper phthalocyanine-quaternary ammonium salt derivative to bis(hydroxyethyl)aminophosphate is 1:0.275; The mass ratio of the modified copper phthalocyanine tetrasulfonic acid tetrasodium salt solution to polypropylene glycol bis(2-aminopropyl ether) was 1:0.0025. The modified copper phthalocyanine tetrasodium salt solution and propylene glycol methyl ether acetate were added to the ultrasonically dispersed solution at a mass ratio of 1:0.002. The mass ratio of the modified copper phthalocyanine tetrasulfonic acid tetrasodium salt solution to benzotriazole is 1:0.0015; The mass ratio of the modified copper phthalocyanine tetrasulfonic acid tetrasodium salt solution to benzophenone was 1:0.0012; The mass ratio of the modified copper phthalocyanine tetrasodium sulfonate solution to triethyl citrate was 1:0.001. The mass ratio of modified copper phthalocyanine tetrasulfonic acid tetrasodium salt solution to vitamin E acetate is 1:0.0008.

[0030] The preparation of bis(hydroxyethyl)aminophosphate includes the following steps: Diethyl N,N-bis(2-hydroxyethyl)aminomethylphosphonic acid and concentrated hydrochloric acid are added to a reaction vessel and stirred at 200-250 rpm. Deionized water is added during stirring, and the mixture is stirred for 15-20 minutes. The reaction vessel is then heated to 105°C and refluxed for 12 hours. The reaction vessel is then naturally cooled to 20-30°C to obtain a mixture of diethyl N,N-bis(2-hydroxyethyl)aminomethylphosphonic acid. This mixture is then placed in a rotary evaporator and evaporated at 60-70°C under a vacuum of 0.08- At 0.09 MPa and a rotation speed of 50-60 rpm, the crude product was obtained by rotary evaporation for 2.5-4 hours. The crude product and anhydrous ethanol were added to a reaction vessel and stirred at 300-350 rpm for 15-20 minutes. Activated carbon was added and stirred at 300-350 rpm for 30-40 minutes. The mixture was filtered through a polytetrafluoroethylene (PTFE) membrane to remove the filtrate and obtain a crude product filter cake. The crude product filter cake was then placed in a freeze crystallizer for freezing crystallization at -20°C for 12 hours. The filtrate of the crystallized crude product was removed using a PTFE membrane to obtain bis(hydroxyethyl)aminophosphate. The pore size of the polytetrafluoroethylene filter membrane is 0.22 μm; The concentration of concentrated hydrochloric acid is 37%; The mass ratio of diethyl N,N-bis(2-hydroxyethyl)aminomethylphosphonic acid to concentrated hydrochloric acid is 1:2.04; The mass ratio of diethyl N,N-bis(2-hydroxyethyl)aminomethylphosphonic acid to deionized water is 1:0.78; The mass ratio of diethyl N,N-bis(2-hydroxyethyl)aminomethylphosphonic acid to anhydrous ethanol is 1:0.93; The mass ratio of N,N-bis(2-hydroxyethyl)aminomethylphosphonic acid diethyl ester to activated carbon is 1:0.02.

[0031] Example 2: A pretreatment method for blue pigment used in color photoresist, the pretreatment method for blue pigment includes the following steps: S1. Activate the blue pigment to obtain an activation intermediate; S2. Prepare N,N-dimethylethanolamine into a quaternary ammonium salt bridging unit; S3. The copper phthalocyanine-quaternary ammonium salt derivative was prepared by modifying the activated intermediate with a quaternary ammonium salt bridging unit. S4. Modify copper phthalocyanine-quaternary ammonium salt derivatives to obtain a blue pigment.

[0032] The preparation of the activated intermediate in S1 includes the following steps: Anhydrous ethanol is added to a reaction vessel, and tetrasodium copper phthalocyanine tetrasulfonate is added and stirred at 400 rpm for 15-20 minutes. Concentrated sulfuric acid is added dropwise and stirred at a rate of 1-2 drops / second, with the temperature controlled below 30°C during the addition of concentrated sulfuric acid. The stirring speed is 200-250 rpm for 10-12 minutes. The reaction vessel is heated to 60°C and refluxed for 3 hours. The temperature of the reaction vessel is naturally cooled to 18-25°C. Water at 0-2°C is added and stirred at 100-150 rpm for 5 minutes. The filtrate is filtered off using a polytetrafluoroethylene filter membrane to obtain a filter cake. The filter cake is washed three times with ethanol at 0-5°C. The washed filter cake is then placed in a vacuum drying oven and dried at a vacuum degree of 0.08-0.09 MPa for 4 hours to obtain the activated intermediate.

[0033] The mass ratio of tetrasodium copper phthalocyanine tetrasulfonate to anhydrous ethanol is 1:15.8; The mass ratio of tetrasodium copper phthalocyanine tetrasulfonate to concentrated sulfuric acid is 1:0.092; The mass ratio of copper phthalocyanine tetrasulfonate tetrasodium salt to water at 0-2℃ is 1:5; The pore size of the polytetrafluoroethylene filter membrane is 0.45 μm.

[0034] The preparation of the quaternary ammonium salt bridging unit in S2 includes the following steps: Acetone is placed in a water bath reactor, nitrogen gas is introduced into the water bath reactor using a nitrogen generator, N,N-dimethylethanolamine is added and stirred at 200-250 rpm for 5-8 minutes, the water bath temperature is lowered to 0-5℃, and stirring is maintained at this temperature. During the cooling process, the temperature decrease rate is 1-2℃ / min, the stirring speed is 150-200 rpm, and stirring is carried out for 20-25 minutes. The temperature is maintained at 0-5℃, epichlorohydrin is added dropwise and stirred at 150-200 rpm for 1-2 hours, the water bath temperature is heated to 30℃ and stirred at 200-250 rpm for 4 hours, and rotary evaporation is carried out at 40℃ and a rotation speed of 60-80 rpm for 30-40 minutes to obtain the quaternary ammonium salt bridging unit.

[0035] The mass ratio of acetone to N,N-dimethylethanolamine is 4:1; The mass ratio of N,N-dimethylethanolamine to epichlorohydrin is 1:0.86.

[0036] The preparation of the copper phthalocyanine-quaternary ammonium salt derivative in S3 includes the following steps: Anhydrous dimethylformamide is added to a reaction vessel, which is heated to 40°C. An activation intermediate is added and stirred at 250-300 rpm for 20-25 minutes. Triethylamine is added and stirred at 200-250 rpm for 5 minutes. A quaternary ammonium salt solution is added dropwise while stirring, maintaining the reaction vessel temperature at 40°C and stirring at 200-250 rpm for 15-20 minutes. The reaction vessel is then heated to 80°C and stirred... After 6 hours, the reaction solution was prepared. Ethyl acetate was added to a new reactor, and the reaction solution was stirred. The temperature was controlled at 20-25℃, the stirring speed was 100-150 rpm, and the stirring time was 20 minutes. The filtrate was filtered off using a nylon filter membrane to obtain an activated intermediate filter cake. The activated intermediate filter cake was washed with ethyl acetate three times. The washed activated intermediate filter cake was placed in a vacuum drying oven and dried at a vacuum degree of 0.08-0.09 MPa and a temperature of 60℃ for 6 hours to obtain the copper phthalocyanine-quaternary ammonium salt derivative.

[0037] The mass ratio of anhydrous dimethylformamide to the activated intermediate was 18.9:1; The mass ratio of the activated intermediate to triethylamine is 1:0.36; The mass ratio of the activation intermediate to the quaternary ammonium salt solution is 1:5.1; The mass ratio of the reaction solution and ethyl acetate added to the new reactor is 1:2.5; The nylon filter membrane has a pore size of 0.22 μm.

[0038] The preparation of quaternary ammonium salt solution includes the following steps: anhydrous dimethylformamide is added to a magnetic reactor, a quaternary ammonium salt bridging unit is added and magnetically stirred, the temperature is ≤25℃, the speed is 300-500rpm, and the stirring time is 30 minutes to obtain quaternary ammonium salt solution; The mass ratio of anhydrous dimethylformamide to quaternary ammonium salt bridging unit is 2.78:1.

[0039] Further, the preparation of the pretreated blue pigment in S4 includes the following steps: adding anhydrous ethanol to a reaction vessel, adding copper phthalocyanine-quaternary ammonium salt derivative and stirring at 300-350 rpm for 30-35 minutes, adding bis(hydroxyethyl)aminophosphate and stirring at 250-300 rpm for 10 minutes, adding trifluoroacetic acid and stirring at 200-250 rpm for 2 minutes, heating the reaction vessel to 50°C and stirring at 200-250 rpm for 8 hours to obtain a reaction solution, dialyzing the reaction solution using a dialysis bag filled with propylene glycol methyl ether acetate solution, dialyzing for 48 hours, replacing the propylene glycol methyl ether acetate solution every 12 hours, and then dialyzing the solution. The solution was evaporated using a rotary evaporator at 40℃, 0.09MPa, and 50-60rpm for 45-60 minutes to obtain a modified copper phthalocyanine tetrasodium sulfonate solution. Polypropylene glycol bis(2-aminopropyl ether) and propylene glycol methyl ether acetate were added to an ultrasonic disperser and dispersed at 150W for 10 minutes. The modified copper phthalocyanine tetrasodium sulfonate solution was then added and stirred at 250-300rpm for 20 minutes. Benzotriazole and benzophenone were added sequentially and stirred at 300-350rpm for 15 minutes. Triethyl citrate and vitamin E acetate were added and stirred at 200-350rpm for 10 minutes. The mixture was allowed to stand for 1 hour to obtain a blue pigment. The molecular weight cutoff of the dialysis bag is 10,000 Da; The mass ratio of copper phthalocyanine-quaternary ammonium salt derivative to anhydrous ethanol was 1:15.78; The mass ratio of copper phthalocyanine-quaternary ammonium salt derivative to trifluoroacetic acid was 1:0.019; The mass ratio of copper phthalocyanine-quaternary ammonium salt derivative to bis(hydroxyethyl)aminophosphate is 1:0.275; The mass ratio of the modified copper phthalocyanine tetrasulfonic acid tetrasodium salt solution to polypropylene glycol bis(2-aminopropyl ether) was 1:0.0025. The modified copper phthalocyanine tetrasodium salt solution and propylene glycol methyl ether acetate were added to the ultrasonically dispersed solution at a mass ratio of 1:0.002. The mass ratio of the modified copper phthalocyanine tetrasulfonic acid tetrasodium salt solution to benzotriazole is 1:0.0015; The mass ratio of the modified copper phthalocyanine tetrasulfonic acid tetrasodium salt solution to benzophenone was 1:0.0012; The mass ratio of the modified copper phthalocyanine tetrasodium sulfonate solution to triethyl citrate was 1:0.001. The mass ratio of modified copper phthalocyanine tetrasulfonic acid tetrasodium salt solution to vitamin E acetate is 1:0.0008.

[0040] The preparation of bis(hydroxyethyl)aminophosphate includes the following steps: Diethyl N,N-bis(2-hydroxyethyl)aminomethylphosphonic acid and concentrated hydrochloric acid are added to a reaction vessel and stirred at 200-250 rpm. Deionized water is added during stirring, and the mixture is stirred for 15-20 minutes. The reaction vessel is then heated to 105°C and refluxed for 12 hours. The reaction vessel is then naturally cooled to 20-30°C to obtain a mixture of diethyl N,N-bis(2-hydroxyethyl)aminomethylphosphonic acid. This mixture is then placed in a rotary evaporator and evaporated at 60-70°C under a vacuum of 0.08-0. At a pressure of 0.09 MPa and a rotation speed of 50-60 rpm, rotary evaporation was carried out for 2.5-4 hours to obtain a crude product. The crude product and anhydrous ethanol were added to a reaction vessel and stirred at a speed of 300-350 rpm for 15-20 minutes. Activated carbon was added and stirred at a speed of 300-350 rpm for 30-40 minutes. The mixture was filtered through a polytetrafluoroethylene (PTFE) membrane to remove the filtrate and obtain a crude product filter cake. The crude product filter cake was placed in a freeze crystallizer for freezing crystallization at a temperature of -20℃ for 6-24 hours. The filtrate of the crystallized crude product was removed through a PTFE membrane to obtain bis(hydroxyethyl)aminophosphate. The pore size of the polytetrafluoroethylene filter membrane is 0.22 μm; The concentration of concentrated hydrochloric acid is 37%; The mass ratio of diethyl N,N-bis(2-hydroxyethyl)aminomethylphosphonic acid to concentrated hydrochloric acid is 1:2.04; The mass ratio of diethyl N,N-bis(2-hydroxyethyl)aminomethylphosphonic acid to deionized water is 1:0.78; The mass ratio of diethyl N,N-bis(2-hydroxyethyl)aminomethylphosphonic acid to anhydrous ethanol is 1:0.93; The mass ratio of N,N-bis(2-hydroxyethyl)aminomethylphosphonic acid diethyl ester to activated carbon is 1:0.02.

[0041] Example 3: A pretreatment method for blue pigment used in color photoresist, the pretreatment method for blue pigment includes the following steps: S1. Activate the blue pigment to obtain an activation intermediate; S2. Prepare N,N-dimethylethanolamine into a quaternary ammonium salt bridging unit; S3. The copper phthalocyanine-quaternary ammonium salt derivative was prepared by modifying the activated intermediate with a quaternary ammonium salt bridging unit. S4. Modify copper phthalocyanine-quaternary ammonium salt derivatives to obtain a blue pigment.

[0042] The preparation of the activated intermediate in S1 includes the following steps: Anhydrous ethanol is added to a reaction vessel, and tetrasodium copper phthalocyanine tetrasulfonate is added and stirred at 300-400 rpm for 15-20 minutes. Concentrated sulfuric acid is added dropwise and stirred at a rate of 1-2 drops / second, with the temperature controlled below 30°C during the addition of concentrated sulfuric acid. The stirring speed is 200-250 rpm for 10-12 minutes. The reaction vessel is heated to 60°C and refluxed for 3 hours. The temperature of the reaction vessel is naturally cooled to 18-25°C. Water at 0-2°C is added and stirred at 100-150 rpm for 5 minutes. The filtrate is filtered off using a polytetrafluoroethylene filter membrane to obtain a filter cake. The filter cake is washed three times with ethanol at 0-5°C. The washed filter cake is then placed in a vacuum drying oven and dried at a vacuum degree of 0.08-0.09 MPa for 4 hours to obtain the activated intermediate.

[0043] The mass ratio of tetrasodium copper phthalocyanine tetrasulfonate to anhydrous ethanol is 1:15.8; The mass ratio of tetrasodium copper phthalocyanine tetrasulfonate to concentrated sulfuric acid is 1:0.092; The mass ratio of copper phthalocyanine tetrasulfonate tetrasodium salt to water at 0-2℃ is 1:5; The pore size of the polytetrafluoroethylene filter membrane is 0.45 μm.

[0044] The preparation of the quaternary ammonium salt bridging unit in S2 includes the following steps: Acetone is placed in a water bath reactor, nitrogen gas is introduced into the water bath reactor using a nitrogen generator, N,N-dimethylethanolamine is added and stirred at 200-250 rpm for 5-8 minutes, the water bath temperature is lowered to 0-5℃, and stirring is maintained at this temperature. During the cooling process, the temperature decrease rate is 2℃ / min, the stirring speed is 150-200 rpm, and stirring is carried out for 20-25 minutes. The temperature is maintained at 0-5℃, epichlorohydrin is added dropwise and stirred at 150-200 rpm for 1-2 hours, the water bath temperature is heated to 30℃ and stirred at 200-250 rpm for 4 hours, and rotary evaporation is carried out using a rotary evaporator at 40℃ and a rotation speed of 60-80 rpm for 30-40 minutes to obtain the quaternary ammonium salt bridging unit.

[0045] The mass ratio of acetone to N,N-dimethylethanolamine is 4:1; The mass ratio of N,N-dimethylethanolamine to epichlorohydrin is 1:0.86.

[0046] The preparation of the copper phthalocyanine-quaternary ammonium salt derivative in S3 includes the following steps: Anhydrous dimethylformamide is added to a reaction vessel, which is heated to 40°C. An activation intermediate is added and stirred at 250-300 rpm for 20-25 minutes. Triethylamine is added and stirred at 200-250 rpm for 5 minutes. A quaternary ammonium salt solution is added dropwise while stirring, maintaining the reaction vessel temperature at 40°C and stirring at 200-250 rpm for 15-20 minutes. The reaction vessel is then heated to 80°C and stirred... After 6 hours, the reaction solution was prepared. Ethyl acetate was added to a new reactor, and the reaction solution was stirred. The temperature was controlled at 20-25℃, the stirring speed was 100-150 rpm, and the stirring time was 20 minutes. The filtrate was filtered off using a nylon filter membrane to obtain an activated intermediate filter cake. The activated intermediate filter cake was washed with ethyl acetate three times. The washed activated intermediate filter cake was placed in a vacuum drying oven and dried at a vacuum degree of 0.08-0.09 MPa and a temperature of 60℃ for 6 hours to obtain the copper phthalocyanine-quaternary ammonium salt derivative.

[0047] The mass ratio of anhydrous dimethylformamide to the activated intermediate was 18.9:1; The mass ratio of the activating intermediate to triethylamine is 1:0.36; The mass ratio of the activation intermediate to the quaternary ammonium salt solution was 1:5.1; The mass ratio of the reaction solution to ethyl acetate added to the new reactor is 1:2.5; The pore size of the nylon filter membrane is 0.22 μm.

[0048] The preparation of quaternary ammonium salt solution includes the following steps: anhydrous dimethylformamide is added to a magnetic reactor, a quaternary ammonium salt bridging unit is added and magnetically stirred, the temperature is ≤25℃, the speed is 300-500rpm, and the stirring time is 30 minutes to obtain quaternary ammonium salt solution; The mass ratio of anhydrous dimethylformamide to quaternary ammonium salt bridging unit is 2.78:1.

[0049] The preparation of the pretreated blue pigment in S4 includes the following steps: Anhydrous ethanol is added to a reaction vessel, followed by the addition of a copper phthalocyanine-quaternary ammonium salt derivative and stirring at 300-350 rpm for 30-35 minutes. Then, bis(hydroxyethyl)aminophosphate is added and stirred at 250-300 rpm for 10 minutes. Trifluoroacetic acid is added and stirred at 200-250 rpm for 2 minutes. The reaction vessel temperature is heated to 50°C and stirred at 200-250 rpm for 8 hours to obtain the reaction solution. The reaction solution is then dialyzed using a dialysis bag containing propylene glycol methyl ether acetate solution for 48 hours, with the propylene glycol methyl ether acetate solution replaced every 12 hours. The dialyzed reaction solution is then purified using a rotary osmotic pressure (ROP) system. A modified copper phthalocyanine tetrasodium sulfonate solution was prepared by rotary evaporation at 40℃, vacuum 0.09MPa, and rotation speed of 50-60rpm for 45-60 minutes. Polypropylene glycol bis(2-aminopropyl ether) and propylene glycol methyl ether acetate were then added to an ultrasonic disperser and dispersed at 100-150W for 10 minutes. The modified copper phthalocyanine tetrasodium sulfonate solution was then added and stirred at 250-300rpm for 20 minutes. Benzotriazole and benzophenone were then added sequentially and stirred at 300-350rpm for 15 minutes. Triethyl citrate and vitamin E acetate were then added and stirred at 200-350rpm for 10 minutes. The mixture was allowed to stand for 1 hour to obtain a blue pigment. The molecular weight cutoff of the dialysis bag is 10,000 Da; The mass ratio of copper phthalocyanine-quaternary ammonium salt derivative to anhydrous ethanol was 1:15.78; The mass ratio of copper phthalocyanine-quaternary ammonium salt derivative to trifluoroacetic acid was 1:0.019; The mass ratio of copper phthalocyanine-quaternary ammonium salt derivative to bis(hydroxyethyl)aminophosphate is 1:0.275; The mass ratio of the modified copper phthalocyanine tetrasulfonic acid tetrasodium salt solution to polypropylene glycol bis(2-aminopropyl ether) was 1:0.0025. The modified copper phthalocyanine tetrasodium salt solution and propylene glycol methyl ether acetate were added to the ultrasonically dispersed solution at a mass ratio of 1:0.002. The mass ratio of the modified copper phthalocyanine tetrasulfonic acid tetrasodium salt solution to benzotriazole is 1:0.0015; The mass ratio of the modified copper phthalocyanine tetrasulfonic acid tetrasodium salt solution to benzophenone was 1:0.0012; The mass ratio of the modified copper phthalocyanine tetrasodium sulfonate solution to triethyl citrate was 1:0.001. The mass ratio of modified copper phthalocyanine tetrasulfonic acid tetrasodium salt solution to vitamin E acetate is 1:0.0008.

[0050] The preparation of bis(hydroxyethyl)aminophosphate includes the following steps: Diethyl N,N-bis(2-hydroxyethyl)aminomethylphosphonic acid and concentrated hydrochloric acid are added to a reaction vessel and stirred at 200-250 rpm. Deionized water is added during stirring, and the mixture is stirred for 15-20 minutes. The reaction vessel is then heated to 105°C and refluxed for 12 hours. The reaction vessel is then naturally cooled to 20-30°C to obtain a mixture of diethyl N,N-bis(2-hydroxyethyl)aminomethylphosphonic acid. This mixture is then placed in a rotary evaporator and evaporated at 60-70°C under a vacuum of 0.08- At 0.09 MPa and a rotation speed of 50-60 rpm, the crude product was obtained by rotary evaporation for 2.5-4 hours. The crude product and anhydrous ethanol were added to a reaction vessel and stirred at 300-350 rpm for 15-20 minutes. Activated carbon was added and stirred at 300-350 rpm for 30-40 minutes. The mixture was filtered through a polytetrafluoroethylene (PTFE) membrane to remove the filtrate and obtain a crude product filter cake. The crude product filter cake was then placed in a freeze crystallizer for freezing crystallization at -20°C for 24 hours. The filtrate of the crystallized crude product was removed using a PTFE membrane to obtain bis(hydroxyethyl)aminophosphate. The pore size of the polytetrafluoroethylene filter membrane is 0.22 μm; The concentration of concentrated hydrochloric acid is 37%; The mass ratio of diethyl N,N-bis(2-hydroxyethyl)aminomethylphosphonic acid to concentrated hydrochloric acid is 1:2.04; The mass ratio of diethyl N,N-bis(2-hydroxyethyl)aminomethylphosphonic acid to deionized water is 1:0.78; The mass ratio of diethyl N,N-bis(2-hydroxyethyl)aminomethylphosphonic acid to anhydrous ethanol is 1:0.93; The mass ratio of N,N-bis(2-hydroxyethyl)aminomethylphosphonic acid diethyl ester to activated carbon is 1:0.02.

[0051] Comparative Example 1: The difference between this comparative example and Example 1 is that: The solution used in this comparative example is unmodified copper phthalocyanine tetrasulfonic acid tetrasodium salt solution.

[0052] Comparative Example 2: The difference between this comparative example and Example 1 is that: This comparative example does not contain polypropylene glycol bis(2-aminopropyl ether) and propylene glycol methyl ether acetate.

[0053] Comparative Example 3 differs from Example 1 in that: This comparative example does not contain benzotriazole or benzophenone.

[0054] Performance testing: The blue pigments prepared in Examples 1, 2, 3, 1, 2 and 3 were tested.

[0055] Performance testing: The relevant performance of the samples of the pretreatment method for blue pigment in color photoresist provided in Examples 1-3 and Comparative Examples 1-3 were tested respectively, and the test data are recorded in the table below: Among them, the impurity test results of the blue pigments prepared in Examples 1, 2, 3, Comparative Examples 1, 2, and 3 were as follows: the metal impurity (copper ion) was 9.4 ppm, 9.7 ppm, 9.6 ppm, 12.9 ppm, 10.7 ppm, and 10.6 ppm, respectively; the adhesion grades of the blue pigments prepared in Examples 1, 2, 3, Comparative Examples 1, 2, and 3 were 4.5B, 4.3B, 4.3B, 3.7B, 3.1B, and 3.3B, respectively; the damp heat resistance test results (optical performance change rate %) of the blue pigments prepared in Examples 1, 2, 3, Comparative Examples 1, 2, and 3 (after 1000 hours of exposure to 85℃ / 85%RH) were 4.5%, 4.6%, 4.9%, 5.2%, 5.1%, and 6.7%, respectively. It can be seen that the blue pigments prepared by the present invention not only have lower impurity levels and stronger adhesion, but also exhibit more stable damp heat resistance. This indicates that the pretreatment method for blue pigment in color photoresist provided by the present invention has a broader market prospect and is more suitable for promotion.

[0056] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0057] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to the specific implementations described. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A pretreatment method for blue pigment used in color photoresist, characterized in that, The pretreatment method for the blue pigment includes the following steps: S1. Activate the blue pigment to obtain an activation intermediate; S2. Prepare N,N-dimethylethanolamine into a quaternary ammonium salt bridging unit; S3. The copper phthalocyanine-quaternary ammonium salt derivative was prepared by modifying the activated intermediate with a quaternary ammonium salt bridging unit. S4. Modify copper phthalocyanine-quaternary ammonium salt derivatives to obtain a blue pigment.

2. The preparation method according to claim 1, characterized in that, The preparation of the activation intermediate in S1 includes the following steps: Anhydrous ethanol was added to the reaction vessel, followed by the addition of tetrasodium copper phthalocyanine tetrasulfonate and stirring. Concentrated sulfuric acid was then added dropwise and stirred. The reaction vessel was heated to 60°C and refluxed for 3 hours. The temperature of the reaction vessel was then allowed to cool naturally to 18-25°C. Water at 0-2°C was added and stirred. The filtrate was filtered off using a polytetrafluoroethylene filter membrane to obtain a filter cake. The filter cake was washed three times with ethanol at 0-5°C. The washed filter cake was then dried in a vacuum drying oven to obtain the activated intermediate.

3. The preparation method according to claim 2, characterized in that, The mass ratio of the copper phthalocyanine tetrasulfonic acid tetrasodium salt to anhydrous ethanol is 1:15.8; The mass ratio of the copper phthalocyanine tetrasulfonic acid tetrasodium salt to concentrated sulfuric acid is 1:0.092; The mass ratio of the copper phthalocyanine tetrasulfonate tetrasodium salt to water at 0-2℃ is 1:

5.

4. The preparation method according to claim 1, characterized in that, The preparation of the quaternary ammonium salt bridging unit in S2 includes the following steps: Acetone was placed in a water bath reactor, nitrogen gas was introduced into the reactor using a nitrogen generator, N,N-dimethylethanolamine was added and stirred, epichlorohydrin was added dropwise and stirred, the water bath temperature was heated to 30°C and stirred, and the quaternary ammonium salt bridging unit was obtained by rotary evaporation.

5. The preparation method according to claim 4, characterized in that, The mass ratio of acetone to N,N-dimethylethanolamine is 4:1; The mass ratio of N,N-dimethylethanolamine to epichlorohydrin is 1:0.

86.

6. The preparation method according to claim 1, characterized in that, The preparation of the copper phthalocyanine-quaternary ammonium salt derivative in S3 includes the following steps: anhydrous dimethylformamide is added to a reaction vessel, the reaction vessel is heated to 40°C, an activation intermediate is added and stirred, triethylamine is added and stirred, a quaternary ammonium salt solution is added dropwise and stirred to obtain a reaction solution, ethyl acetate is added to a new reaction vessel, the reaction solution is added and stirred, the filtrate is filtered off using a nylon filter membrane to obtain an activation intermediate filter cake, the activation intermediate filter cake is washed with ethyl acetate three times, and the washed activation intermediate filter cake is placed in a vacuum drying oven to dry to obtain the copper phthalocyanine-quaternary ammonium salt derivative.

7. The preparation method according to claim 6, characterized in that, The mass ratio of the anhydrous dimethylformamide to the activated intermediate is 18.9:1; The mass ratio of the activated intermediate to triethylamine is 1:0.36; The mass ratio of the activation intermediate to the quaternary ammonium salt solution is 1:5.1; The mass ratio of the reaction solution and ethyl acetate added to the new reactor is 1:2.

5.

8. The preparation method according to claim 7, characterized in that, The preparation of the quaternary ammonium salt solution includes the following steps: adding anhydrous dimethylformamide into a magnetic reactor, adding a quaternary ammonium salt bridging unit and stirring magnetically to obtain the quaternary ammonium salt solution; The mass ratio of the anhydrous dimethylformamide to the quaternary ammonium salt bridging unit is 2.78:

1.

9. The preparation method according to claim 1, characterized in that, The preparation of the pretreated blue pigment in S4 includes the following steps: Anhydrous ethanol was added to a reaction vessel, followed by the addition of copper phthalocyanine-quaternary ammonium salt derivative and stirring. Then, bis(hydroxyethyl)aminophosphate was added and stirred, followed by the addition of trifluoroacetic acid and stirring. The reaction vessel was heated to 50°C and stirred to obtain a reaction solution. The reaction solution was then added to a dialysis bag for dialyzing. A propylene glycol methyl ether acetate solution was placed in the dialysis bag, and dialyzing was performed for 48 hours, with the propylene glycol methyl ether acetate solution being replaced every 12 hours. The dialyzed reaction solution was then evaporated using a rotary evaporator to obtain a modified copper phthalocyanine tetrasulfonate tetrasodium salt solution. Polypropylene glycol bis(2-aminopropyl ether) and propylene glycol methyl ether acetate were added to an ultrasonic disperser for dispersion. The modified copper phthalocyanine tetrasulfonate tetrasodium salt solution was added and stirred. Benzotriazole and benzophenone were added sequentially and stirred. Triethyl citrate and vitamin E acetate were added and stirred. The mixture was allowed to stand for 1 hour to obtain a blue pigment. The mass ratio of the copper phthalocyanine-quaternary ammonium salt derivative to anhydrous ethanol is 1:15.78; The mass ratio of the copper phthalocyanine-quaternary ammonium salt derivative to trifluoroacetic acid is 1:0.019; The mass ratio of the copper phthalocyanine-quaternary ammonium salt derivative to bis(hydroxyethyl)aminophosphate is 1:0.275; The mass ratio of the modified copper phthalocyanine tetrasulfonic acid tetrasodium salt solution to polypropylene glycol bis(2-aminopropyl ether) is 1:0.0025; The modified copper phthalocyanine tetrasodium salt solution and propylene glycol methyl ether acetate were added to the ultrasonically dispersed solution at a mass ratio of 1:0.

002. The mass ratio of the modified copper phthalocyanine tetrasulfonic acid tetrasodium salt solution to benzotriazole is 1:0.0015; The mass ratio of the modified copper phthalocyanine tetrasulfonic acid tetrasodium salt solution to benzophenone is 1:0.0012; The mass ratio of the modified copper phthalocyanine tetrasodium sulfonate solution to triethyl citrate is 1:0.001; The mass ratio of the modified copper phthalocyanine tetrasulfonic acid tetrasodium salt solution to vitamin E acetate is 1:0.0008.

10. The preparation method according to claim 9, characterized in that, The preparation of the bis(hydroxyethyl)aminophosphate includes the following steps: adding diethyl N,N-bis(2-hydroxyethyl)aminomethylphosphonic acid and concentrated hydrochloric acid to a reaction vessel and stirring, adding deionized water during stirring, heating the reaction vessel to 105°C and refluxing for 12 hours, and then naturally cooling the reaction vessel to 20-30°C to obtain a mixture of diethyl N,N-bis(2-hydroxyethyl)aminomethylphosphonic acid; placing the mixture of diethyl N,N-bis(2-hydroxyethyl)aminomethylphosphonic acid into a rotary evaporator for rotary evaporation to obtain a crude product; adding the crude product and anhydrous ethanol to a reaction vessel and stirring, adding activated carbon and stirring, filtering with a polytetrafluoroethylene filter membrane, removing the filtrate to obtain a crude product filter cake; placing the crude product filter cake into a freeze crystallizer for freeze crystallization to obtain bis(hydroxyethyl)aminophosphate; The concentration of the concentrated hydrochloric acid is 37%. The mass ratio of N,N-bis(2-hydroxyethyl)aminomethylphosphonic acid diethyl ester to concentrated hydrochloric acid is 1:2.04; The mass ratio of N,N-bis(2-hydroxyethyl)aminomethylphosphonic acid diethyl ester to deionized water is 1:0.78; The mass ratio of N,N-bis(2-hydroxyethyl)aminomethylphosphonic acid diethyl ester to anhydrous ethanol is 1:0.93; The mass ratio of N,N-bis(2-hydroxyethyl)aminomethylphosphonic acid diethyl ester to activated carbon is 1:0.02.

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