Blue-light green zinc phthalocyanine dye for display photoresist and synthesis method of blue-light green zinc phthalocyanine dye

Abstract

The invention discloses a blue-light green zinc phthalocyanine dye for display photoresist and a synthesis method thereof. Halogen, sulfuryl and fat-soluble reactive groups are introduced into a side chain of a metal phthalocyanine ring through nucleophilic substitution reaction, oxidation reaction, esterification reaction and the like, so that the solubility, heat resistance and tinting strength of dye molecules are further improved; the phthalocyanine dye molecule can be mixed with a yellow pigment to prepare a green photoresist color paste, is used for improving the light transmittance and dispersity of the color paste, and has excellent tinting strength and heat resistance; meanwhile, the synthesis method provided by the invention is simple, safe and reliable to operate and easy for large-scale production.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of color photoresist, and particularly relates to a blue-green zinc phthalocyanine dye for display photoresist and a synthesis method thereof. BACKGROUND

[0002] Since the first black and white television was born in 1939, the display screen as the terminal equipment of the important interface of human-computer interaction has undergone many technical changes, and has been gradually widely applied to various fields of production and life such as industry, transportation, communication, education, aerospace, entertainment, medical treatment, and plays an important role in modern information transmission and interaction. At the same time, as the core of the display technology, it has gradually evolved from the first generation of display technology represented by CRT (Cathode Ray Tube) in the 19th century to the third generation of display technology represented by OLED (Organic Light Emitting Diode) in the 21st century. During this period, it also experienced the second generation of display technology represented by PDP (Plasma Display Panel) technology and LCD (Liquid Crystal Display) technology.

[0003] Compared with the high cost and low yield of the third generation display technology, LCD technology still occupies the mainstream position due to its huge market prospect, low production cost and mature manufacturing process. However, it also faces fierce impact and great challenge from new technologies such as OLED, QLED and Micro-LED. Thin film transistor display technology has gradually become the mainstream technology of flat panel display because of its relatively mature process route and product design, and relatively rapid development of technology and performance. In order to compete with new technologies in terms of high definition, high contrast and low power consumption, the innovation and development of TFT-LCD technology are urgent.

[0004] Color filter (CF) is an indispensable part of OLED, LCD, CMOS and other display devices. Its main function is to convert white backlight into red, green and blue three primary colors, mix the three primary colors to form different colors, and change the on-off and strength of light under the action of thin film transistor driving unit, so as to finally present different color pictures and light and dark contrast to people. Color photoresist is a key raw material for industrial production of color filter, and is the technical core to ensure the color accuracy, color gamut and color depth of display equipment. The color paste accounts for 25% of the composition of color photoresist, and accounts for more than 70% of the cost of photoresist.

[0005] At present, green color paste is mainly prepared by phthalocyanine pigments represented by pigment green 7, pigment green 36 and pigment green 58, and compounded with yellow pigments by unique refinement technology. Phthalocyanine pigments have excellent heat resistance and light resistance due to the 16-center 18π-electron macrocyclic structure in the molecule and the stacking effect between molecules, but on the contrary, the solubility and permeability are decreased, so it is increasingly difficult to meet the technical requirements of higher contrast, higher resolution and lower power consumption. SUMMARY

[0006] The present application provides a blue-green zinc phthalocyanine dye for photoresist and a synthesis method thereof, which overcomes the technical defects of low solubility and high production equipment cost of the nano-dispersion method, one of the current mainstream technologies, for producing nano-phthalocyanine pigments.

[0007] The technical scheme adopted by the present application to solve the above technical problems is as follows: A blue-green zinc phthalocyanine dye for photoresist, the zinc phthalocyanine dye has a structure shown in general formula I: ; In general formula I, X is a halogen atom; a+b+c=16, 1≤a≤16, 0≤b≤15, 0≤c≤15; R 1 is a structure shown in general formula II: ; In general formula II, R 3 , R 4 , R 5 , R 6 , R 7 may be the same or different, R 3 , R 4 , R 5 , R 6 , R 7 are each independently selected from hydrogen, an ether bond with 1-18 carbons, an alkyl group with 1-18 carbons, a carboxyalkyl group with 1-18 carbons, a hydroxyalkyl group with 1-18 carbons, an ester group with 1-18 carbons, an amino group with 1-18 carbons, an aldehyde group with 1-18 carbons, an aromatic group or aromatic heterocycle with 4-14 carbons, or an olefin with 2-18 carbons. R 2 is selected from hydrogen, an ether bond with 1-18 carbons, an alkyl group with 1-18 carbons, a carboxyalkyl group with 1-18 carbons, a hydroxyalkyl group with 1-18 carbons, an ester group with 1-18 carbons, an amino group with 1-18 carbons, an aldehyde group with 1-18 carbons, or an olefin with 2-18 carbons.

[0008] Preferably, the R 1 is selected from one of the following specific examples, but the present application is not limited to these specific examples: .

[0009] The synthesis method of the blue-green zinc phthalocyanine dye for displaying photoresist as described above includes but is not limited to the following steps: (1) Nucleophilic substitution reaction: using phenol derivatives to undergo nucleophilic substitution reaction with mercapto derivatives in the presence of catalyst and at suitable temperature, and obtaining sulfide derivatives through reasonable purification means; (2) Oxidation reaction: dissolving sulfide derivatives in suitable organic solvent, and performing oxidation reaction with peroxide at suitable temperature, and obtaining sulfone derivatives through reasonable purification means; (3) Esterification reaction: reacting sulfone derivatives with methacrylic acid or methacrylic anhydride in the presence of catalyst and / or condensation reagent and at suitable temperature, and obtaining methacrylic acid derivatives through reasonable purification means; (4) Preparation of compound of general formula III: mixing phthalonitrile derivatives and methacrylic acid derivatives uniformly in organic solvent, and adding catalyst to perform reaction under inert gas protection, and obtaining compound of general formula III through reasonable purification means; The general formula III is: ; (5) Phthalocyanine cyclization reaction: mixing compound of general formula III and divalent metal zinc salt uniformly in organic solvent, and performing reaction under inert gas protection with or without catalyst, and obtaining zinc phthalocyanine dye represented by general formula I through reasonable purification means; To realize the structure represented by general formula I, the above reaction steps can be simply described as the following reaction scheme: ; wherein X is halogen atom, R 1 -R 7 and a, b, c are consistent with the above.

[0010] wherein X is preferably fluorine, chlorine, bromine or iodine; R 3 , R 4 are preferably selected from hydrogen, ether bond with 1-18 carbons, carboxyalkyl with 1-18 carbons, ester group with 1-18 carbons, amino group with 1-18 carbons; R 7 are preferably selected from ether bond with 1-18 carbons, alkyl with 1-18 carbons, hydroxyalkyl with 1-18 carbons, amino group with 1-18 carbons, aromatic group or aromatic heterocycle with 4-14 carbons, olefin with 2-18 carbons.

[0011] Preferably, in step (1), the equivalent ratio of the phenol derivative to the catalyst is 1:1-1:8, more preferably 1:2-1:4.

[0012] Preferably, in step (1), the phenol derivative is 4-bromo-2,6-dimethoxyphenol.

[0013] Preferably, in step (1), the catalyst is selected from any one or more of sodium carbonate, potassium carbonate, potassium phosphate, cesium carbonate, more preferably potassium carbonate or cesium carbonate.

[0014] Preferably, in step (1), the equivalent ratio of the phenol derivative to the thiol derivative is 1:1 to 1:2.

[0015] Preferably, in step (1), the thiol derivative is any one of 2-mercaptoethoxyethanol, 4-hydroxythiophenol, 4-mercapto-cyclohexan-1-ol.

[0016] Preferably, in step (1), the suitable temperature is selected to be -20 to 100°C, more preferably 20 to 80°C.

[0017] Preferably, in step (1), the reaction time is 0.5 to 12 h, more preferably 1 to 4 h.

[0018] Preferably, in step (1), the purification means is to remove the reaction solvent from the reaction solution by distillation under reduced pressure, to slowly add ice water to the concentrate under stirring, to adjust the pH to 7 to 8 using 1M dilute hydrochloric acid, to filter, to wash the filter cake with sufficient water, and to dry the filter cake at 50°C under air blast to obtain the sulfide derivative.

[0019] Preferably, in step (2), the equivalent ratio of the sulfide derivative to the peroxide is 1:2 to 1:12, more preferably 1:2 to 1:6.

[0020] Preferably, in step (2), the organic solvent is selected from any one or more of dichloromethane, acetone, N,N-dimethylformamide, acetonitrile, 1,4-dioxane, dimethyl sulfoxide.

[0021] Preferably, in step (2), the peroxide is selected from any one or more of benzoyl peroxide, cumene hydroperoxide, hydrogen peroxide, tert-butyl hydroperoxide, methyl ethyl ketone peroxide, meta-chloroperoxybenzoic acid, more preferably any one of hydrogen peroxide, benzoyl peroxide, and meta-chloroperoxybenzoic acid.

[0022] Preferably, in step (2), the reaction temperature is selected to be 20 to 80°C.

[0023] Preferably, in step (2), the reaction time is 1 to 16 h.

[0024] Preferably, in step (2), the purification means is to distill the reaction solution under reduced pressure to obtain a crude product, to perform column chromatography on the crude product using a mixture of 25% ethyl acetate / dichloromethane as the mobile phase, to collect the fractions, and to distill and dry the fractions under reduced pressure to obtain the sulfone derivative.

[0025] Preferably, in step (3), the equivalent ratio of the sulfone derivative to the methacrylic acid or methacrylic anhydride is 1:1-1:2.

[0026] Preferably, in step (3), the equivalent ratio of the sulfone derivative to the catalyst is 1:1-1:3.

[0027] Preferably, in step (3), the catalyst is any one selected from the group consisting of triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N-dimethylaminopyridine, 1-hydroxybenzotriazole, and N-hydroxy-7-azabenzotriazole.

[0028] Preferably, in step (3), the condensation reagent is any one selected from the group consisting of N,N'-dicyclohexylcarbodiimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, N,N,N',N'-tetramethyl-O-(7-azabenzotriazol-1-yl)urea hexafluorophosphate, and benzotriazole-N,N,N',N'-tetramethyluronium hexafluorophosphate.

[0029] Preferably, in step (3), the reaction temperature is -20-80°C.

[0030] Preferably, in step (3), the reaction time is 1-16h.

[0031] Preferably, in step (3), the purification means is filtering the reaction solution, eluting the filter cake with an appropriate amount of dichloromethane in multiple times, and drying to obtain the methacrylic acid derivative.

[0032] Preferably, in step (4), the equivalent ratio of the phthalonitrile derivative to the methacrylic acid derivative is 1:1-1:5.

[0033] Preferably, in step (4), the phthalonitrile derivative is any one selected from the group consisting of 4,5-dichlorophthalonitrile, tetrachlorophthalonitrile, and tetrafluorophthalonitrile.

[0034] Preferably, in step (4), the equivalent ratio of the phthalonitrile derivative to the catalyst is 1:1-1:6.

[0035] Preferably, in step (4), the organic solvent is N,N-dimethylformamide.

[0036] Preferably, in step (4), the catalyst is potassium carbonate.

[0037] Preferably, in step (4), the reaction temperature is -20-100°C.

[0038] Preferably, in step (4), the reaction time is 1-12h.

[0039] Preferably, in step (4), the purification means is pouring the reaction solution into ice water, filtering and drying to obtain a crude product, and using ethyl acetate to beat the crude product to obtain the compound of general formula III.

[0040] Preferably, in step (4), the branched chain of the compound of general formula III has at least one R 1 , and the rest of the branched chain can be R 2 , hydrogen, fluorine, chlorine, bromine or iodine.

[0041] Preferably, in step (5), the equivalent ratio of the compound of general formula III to the divalent zinc salt is 4:1 to 2:1.

[0042] Preferably, in step (5), the divalent zinc salt is selected from any one of zinc acetate, zinc chloride, zinc iodide, zinc sulfate and zinc phosphate, and more preferably is zinc acetate or zinc iodide.

[0043] Preferably, in step (5), the organic solvent is selected from any one of aliphatic alcohols, alcohol ethers and alcohol amines, R 1 , which can undergo an ester exchange reaction, R 2 If there is an ester group, it can also undergo an ester exchange reaction, and more preferably is n-pentanol or benzonitrile.

[0044] Preferably, in step (5), the equivalent ratio of the compound of general formula III to the catalyst is 1:0.5 to 1:1.

[0045] Preferably, in step (5), the catalyst is selected from 1,8-diazabicyclo[5.4.0]undec-7-ene or cesium carbonate, and more preferably is 1,8-diazabicyclo[5.4.0]undec-7-ene.

[0046] Preferably, in step (5), if the compound of general formula III contains a substituent group -X, wherein X represents a halogen atom, no catalyst can be added in the reaction; or, if the reaction solvent is N,N-dimethylethanolamine, which has a basic catalytic effect, no catalyst can also be added in the reaction.

[0047] Preferably, in step (5), the reaction temperature is 90-210°C.

[0048] Preferably, in step (5), the reaction time is 10-36h.

[0049] Preferably, in step (5), the reasonable purification means includes, but is not limited to, any one of reduced pressure distillation, column chromatography, beating, recrystallization and the like, and the mobile phase of column chromatography is selected from a mixture of dichloromethane and methanol, acetonitrile and methanol.

[0050] Compared with the prior art (the current commercial mixed phthalocyanine), the present application has the following beneficial effects: (1) The zinc phthalocyanine dye molecule provided by the application can be mixed with a small amount of commercially available yellow pigment to configure a green photoresist color paste, further improving the transmittance; (2) The zinc phthalocyanine dye molecule provided by the application has excellent solubility, transmittance, heat resistance and excellent coloring power and the like; (3) The synthetic method provided by the application has simple route, simple and safe operation, wide reagent source, low cost and easy scale production. BRIEF DESCRIPTION OF DRAWINGS

[0051] Figure 1 The H-NMR spectrum of the dye intermediate A-4 prepared by the application is as follows: 1 H-NMR spectrum; Figure 2 The H-NMR spectrum of the dye intermediate B-4 prepared by the application is as follows: 1 H-NMR spectrum; Figure 3 The H-NMR spectrum of the dye intermediate C-4 prepared by the application is as follows: 1 H-NMR spectrum; Figure 4 The H-NMR spectrum of the dye intermediate D prepared by the application is as follows: 1 H-NMR spectrum; Figure 5 The UV-vis absorption spectrum of the dye A prepared by Example 1 of the application is as follows: Figure 6 The UV-vis transmission spectrum of the dye A prepared by Example 1 of the application is as follows: Figure 7 The thermogravimetric diagram of the dye A prepared by Example 1 of the application is as follows. DETAILED DESCRIPTION

[0052] In order to better understand the content of the application, the following further describes the application in combination with specific examples and drawings. It should be understood that the examples are only used to further illustrate the application, and are not used to limit the scope of the application. In addition, it should be understood that after reading the content described in the application, the person skilled in the art makes some non-essential modifications or adjustments to the application, which still belongs to the protection scope of the application.

[0053] The compound shown in general formula II and the dye intermediates of Examples 1-3 and Comparative Example 1 can be prepared by the synthetic method described below.

[0054] I. Preparation method of the dye intermediate A-4 of Example 1, the steps are as follows: (1) Preparation of intermediate A-1:

[0055] In a dry and clean 250 mL three-necked flask, equipped with a stirring bar, a thermometer and a reflux condenser, 4-bromo-2,6-dimethoxyphenol (10.00 g, 42.91 mmol, 1.00 eq.) and 2-mercaptoethoxyethanol (6.29 g, 51.49 mmol, 1.20 eq.) were weighed and added to the flask, acetone (100 ml) was measured and added, the whole was stirred until all the reagents were dissolved, and anhydrous potassium carbonate (8.90 g, 64.36 mmol, 1.50 eq.) was added. Then, under a nitrogen atmosphere, the reaction was stirred using an oil bath at reflux for 6 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure, ice water (200 ml) was slowly added to the concentrate under stirring, 1M dilute hydrochloric acid was used to adjust the pH to 7-8, and finally filtered, washed the filter cake with enough water, and the filter cake was dried at 50°C with air blowing to obtain 11.20 g of intermediate A-1, with a yield of 95.1%.

[0056] (2) Preparation of compound A-2:

[0057] Using the intermediate A-1 (10.00 g, 36.45 mmol, 1.00 eq.) obtained in the previous step and m-chloroperbenzoic acid (12.58 g, 72.90 mmol, 2.00 eq.), the weighed reagents were dissolved in a single-necked flask containing acetonitrile (200 ml) and stirred overnight at room temperature. The next day, after the reaction was completed, the crude product was obtained by distillation under reduced pressure, and column chromatography was performed using a mixture of 25% ethyl acetate / dichloromethane as the mobile phase, the fractions were collected and distilled under reduced pressure and dried to obtain 11.00 g of intermediate A-2 with a yield of 98.5%.

[0058] (3) Preparation of intermediate A-3:

[0059] In a 250 ml three-necked flask equipped with a thermometer, intermediate A-2 (10.00 g, 32.64 g, 1.00 eq.) obtained in the previous step and triethylamine (6.61 g, 65.29 mmol, 2.00 eq.) were weighed and dichloromethane (100 ml) was added to dissolve the mixture, and the reaction system was cooled to 0°C with the help of an ice bath. Methyl methacrylate (15.10 g, 97.93 mmol, 1.50 eq.) in dichloromethane (50 ml) was slowly added to the above reaction system through a constant pressure dropping funnel, and then the reaction was stirred at room temperature for 16 hours. After the reaction was completed, it was filtered, the filter cake was washed with dichloromethane several times, and then dried to obtain 10.60 g of intermediate A-3 with a yield of 87.0%.

[0060] (4) Preparation of intermediate A-4:

[0061] First, 4, 5-dichlorophthalonitrile (2.00 g, 10.15 mmol, 1.00 eq.) and the intermediate A-3 in the previous step (7.98 g, 21.32 mmol, 2.1 eq.) were weighed, the weighed chemicals were dissolved in a single-mouth flask containing N, N-dimethylformamide (100 ml) and stirred to dissolve, and anhydrous potassium carbonate (4.21 g, 30.45 mmol, 3.00 eq.) was added, and the reaction was stirred using an 80°C oil bath under nitrogen protection for 10 hours. After the reaction was completed, the reaction solution was poured into ice water (1000 ml) under vigorous stirring, and finally the crude product was obtained by filtration and drying. The crude product was slurried and purified using ethyl acetate, and dried to obtain 5.36 g of intermediate A-4 (its 1 H-NMR spectrum is shown in Figure 1 , and the yield was 60.5%.

[0062] II. Preparation process of dye intermediate D of Comparative Example 1, the steps are as follows: Preparation of intermediate D:

[0063] First, 3-nitrophthalonitrile (10.00 g, 57.76 mmol, 1.00 eq.) and 2, 6-dimethoxyphenol (10.68 g, 69.31 mmol, 1.20 eq.) were weighed and added to a 500 ml single-mouth flask containing N, N-dimethylformamide (100 ml), and then anhydrous potassium carbonate (11.97 g, 86.64 mmol, 1.50 eq.) was weighed and added, and the reaction was stirred using an 80°C oil bath for 16 hours. After the reaction was completed, the reaction solution was cooled to room temperature and poured into ice water (1000 ml), and the generated solid was filtered and dried to obtain the crude product. The crude product was column chromatographed using 50% dichloromethane / petroleum ether as the mobile phase, the fractions were collected and dried under reduced pressure, and 12.60 g of intermediate D (its 1 H-NMR spectrum is shown in Figure 4 , and the yield was 77.8%.

[0064] Referring to the basic synthesis method of the above intermediate A-1 to A-4, the dye intermediate B-4 of Example 2 (its 1 H-NMR spectrum is shown in Figure 2 , the dye intermediate C-4 of Example 3 (its 1 H-NMR spectrum is shown in Figure 3 ) and the dye intermediate D of Comparative Example 1 (its

[0065]

[0066] The synthesis process of intermediate B-4 is similar to that of intermediate A-4, except that 2-mercaptoethoxyethanol is replaced by 4-hydroxythiophenol, and 4,5-dichloro-phthalonitrile is replaced by tetrachloro-phthalonitrile.

[0067]

[0068] The synthesis process of intermediate C-4 is similar to that of intermediate A-4, except that 2-mercaptoethoxyethanol is replaced by 4-mercaptocyclohexan-1-ol, and 4,5-dichloro-phthalonitrile is replaced by tetrafluoro-phthalonitrile.

[0069] The dye molecule represented by the general formula I in the present application can be prepared by the synthesis method described below.

[0070] Example 1 (Synthesis of dye A)

[0071] Intermediate A-4 (4.20 g, 4.81 mmol, 3.00 eq.), anhydrous zinc acetate (294 mg, 1.60 mmol, 1.00 eq.) were weighed into a single-necked flask containing n-pentanol (50 ml), 1,8-diazabicyclo[5.4.0]undec-7-ene (488 mg, 3.21 mmol, 2.00 eq.) was added, and the reaction was heated to 150°C under a nitrogen atmosphere for 10 hours. After the reaction was completed, the reaction system was cooled to room temperature and poured into methanol (500 ml). The precipitated solid was filtered, washed with an appropriate amount of methanol and water, and dried at 50°C to obtain 2.30 g of dye A, with a yield of 53.8%.

[0072] The UV-vis absorption spectrum of dye A is shown in Figure 5 , the UV-vis transmission spectrum of dye A is shown in Figure 6 , and the thermogravimetric diagram of dye A is shown in Figure 7 .

[0073] Example 2 (Synthesis of dye B)

[0074] Intermediate B-4 (3.00 g, 3.16 mmol, 1.00 eq.), zinc iodide (333 mg, 1.04 mmol, 0.33 eq.) were weighed into a single-necked flask, benzyl cyanide (50 ml) was added, and the reaction was heated to 160°C under a nitrogen atmosphere for 18 hours. After the reaction was completed, the reaction system was cooled to room temperature and poured into petroleum ether. The precipitated solid was filtered, washed with an appropriate amount of methanol and water, and dried at 50°C to obtain 2.27 g of dye B, with a yield of 74.4%.

[0075] Example 3 (Synthesis of dye C)

[0076] The intermediate C-4 (5.00 g, 5.38 mmol, 1.00 eq.), zinc iodide (567 mg, 1.78 mmol, 0.33 eq.) were weighed into a single-necked flask, and benzyl cyanide (80 ml) was added. The reaction was heated to 170°C under a nitrogen atmosphere for 16 hours. After the reaction was completed, the reaction system was cooled to room temperature and poured into petroleum ether. The precipitated solid was filtered, washed with an appropriate amount of ethanol and water, and dried at 50°C to obtain 3.15 dye B, with a yield of 62.0%.

[0077] Comparative Example 1 (Synthesis of dye D)

[0078] The intermediate D (5.00 g, 17.84 mmol, 3.00 eq.), anhydrous zinc acetate (1.09 g, 5.95 mmol, 1.00 eq.) were weighed into a single-necked flask containing N,N-dimethyl ethanolamine (50 ml), and heated to 140°C under a nitrogen atmosphere for 12 hours. After the reaction was completed, the reaction system was cooled to room temperature and poured into water. The precipitated solid was filtered and dried at 50°C to obtain a crude product. The crude product was subjected to column chromatography using a 3% methanol / dichloromethane mixture, the green band was collected, and the product was dried by vacuum distillation to obtain 3.10 g of dye D, with a yield of 59.0%.

[0079] Effect Experimental Example I. Test of the UV-Vis spectrum of the phthalocyanine dye molecule The test solvent was propylene glycol methyl ether acetate (PGMEA).

[0080] A one-hundredth scale balance was used to accurately weigh the phthalocyanine dyes prepared in Examples 1-3 and Comparative Example 1, which were in the form of solid powders, and dissolved in a solvent to prepare a 5.0 mmol / L stock solution, which was stored in a sample tube.

[0081] 6.0 μL of the above stock solution was removed using a micropipette gun and diluted in a quartz cuvette containing 3 ml of the same solvent, mixed well, and finally prepared into a dye solution with a concentration of 10 μmol / L, which was tested in a UV-Vis spectrophotometer at room temperature. The molar extinction coefficient of the dye was calculated by the following formula: A = εcl In the formula, A is the absorbance; ε is the molar extinction coefficient, L / (mol•cm); c is the concentration, mol / L; and l is the thickness of the absorption layer, cm.

[0082] The transmittance of the dye is calculated by the following formula: A = -lgT In the formula, A is the light absorption intensity; and T is the transmittance, %.

[0083] The test results of the UV-Vis spectrum of the phthalocyanine dye molecules prepared in Examples 1-3 and Comparative Example 1 are shown in Table 1.

[0084] Table 1 Test results of the UV-Vis spectrum of the phthalocyanine dye molecules prepared in Examples 1-3 and Comparative Example 1 Dye max / nm ​ ε / 10 4 L / (mol-cm) 500~550 nm transmittance / % Example 1 674.5 26.00 >91 Example 2 691.0 23.77 >93 Example 3 688.5 24.93 >93 Comparative Example 1 697.0 18.89 >97 As shown in Table 1, the maximum absorption wavelength of the phthalocyanine dye molecules prepared in Examples 1-3 is between 660-700 nm, and Examples 1-3 have a certain degree of blue shift compared with Comparative Example 1. The maximum absorption wavelength of Examples 2-3 has a significant red shift compared with Example 1, and the phthalocyanine dye molecule prepared in Example 1 has the highest molar absorption coefficient.

[0085] II. Solubility test of the phthalocyanine dye molecules The solubility of the phthalocyanine dye molecules prepared in Examples 1-3 and Comparative Example 1 in propylene glycol methyl ether acetate (PGMEA) and N,N-dimethylformamide (DMF) was tested.

[0086] A certain amount of dye and organic solvent were weighed, ultrasonically dispersed for 20 minutes and placed in a 20°C water bath for 24 hours, filtered three times using a filter membrane, and the filtrate was dried to calculate the solubility S of the dye: S = 100*M S / M L In the formula, M S is the mass of the dried dye, g; and M L is the mass of the solution, g.

[0087] The test results of the solubility of the phthalocyanine dye molecules prepared in Examples 1-3 and Comparative Example 1 are shown in Table 2.

[0088] Table 2 Test results of the solubility of the phthalocyanine dye molecules prepared in Examples 1-3 and Comparative Example 1 Dye [SA PGMEA ]] [SA DMF ]] Example 1 >10 >10 Example 2 8.2 >10 Example 3 7.9 >10 Comparative Example 1 0.37 7.8 As shown in Table 2, the phthalocyanine dye molecules prepared in Examples 1-3 have good solubility in PGMEA and DMF, while the dye molecules of Comparative Example 1 have decreased solubility due to the J aggregation of O→Zn 2+ between molecules; and the phthalocyanine dye molecule prepared in Example 1 has the best solubility in PGMEA and DMF.

[0089] III. Thermal stability test of phthalocyanine dye molecules In the process of industrial production of color filters, multiple baking processes at about 230℃ are required, so the dye molecules are required to have good thermal stability at this temperature. Under nitrogen protection, using a thermal gravimetric analyzer, the thermal decomposition temperature T of the dye molecules is determined by heating from room temperature to 500℃ at a heating rate of 10℃ / min. d The thermal stability of the synthetic dye is evaluated in this way.

[0090] The thermal stability test results of the phthalocyanine dye molecules prepared in Examples 1-3 and Comparative Example 1 are shown in Table 3.

[0091] Table 3 Thermal stability test results of the phthalocyanine dye molecules prepared in Examples 1-3 and Comparative Example 1 Dye T d (°C) Weight loss rate (230°C) / % Example 1 386.0 1.60 Example 2 428.2 0.43 Example 3 398.4 0.92 Comparative Example 1 321.0 2.1 As can be seen from Table 3, the T of the phthalocyanine dye molecules prepared in Examples 1-3 is 500℃, which is higher than that of the dye molecules prepared in Comparative Example 1. d The weight loss rate at 230℃ for 30 minutes is less than 5% in the range of 300-450℃, indicating that the dye molecules prepared by the present application have good thermal stability, which also reflects the advantages of introducing alkoxy and sulfonyl groups.

[0092] The present application introduces halogen, sulfonyl and liposoluble reactive groups into the side chain of metal phthalocyanine ring through nucleophilic substitution reaction, oxidation reaction and esterification reaction, thereby further improving the solubility, heat resistance and coloring power of the dye molecules; the present application provides a new type of blue-green zinc phthalocyanine dye molecule for display photoresist, which can be mixed with yellow pigment to prepare green photoresist color paste, for improving the light transmittance and dispersibility of the color paste, and has excellent coloring power and heat resistance; at the same time, the synthesis method provided by the present application is simple, safe and reliable to operate, and easy to scale up.

[0093] The above description is not a limitation of the present application, and the present application is not limited to the above examples. Changes, modifications, additions or substitutions made by those skilled in the art within the spirit and scope of the present application should also be within the protection scope of the present application.

Claims

1. A blue-green zinc phthalocyanine dye for display photoresist, characterized by The zinc phthalocyanine dye has a structure shown in general formula I: ； In general formula I, X is a halogen atom; a+b+c=16, 1≤a≤16, 0≤b≤15, 0≤c≤15; R 1 is of the structure shown in Formula II: ； In General Formula II, R 3 , R 4 , R 5 , R 6 , R 7 may be the same or different, R 3 , R 4 , R 5 , R 6 , R 7 are each independently selected from hydrogen, an ether linkage having 1 to 18 carbons, an alkyl group having 1 to 18 carbons, a carboxyalkyl group having 1 to 18 carbons, a hydroxyalkyl group having 1 to 18 carbons, an ester group having 1 to 18 carbons, an amino group having 1 to 18 carbons, an aldehyde group having 1 to 18 carbons, an aromatic group or aromatic heterocycle having 4 to 14 carbons, or an alkene having 2 to 18 carbons; R 2 selected from the group consisting of hydrogen, ether linkage having 1-18 carbons, alkyl having 1-18 carbons, carboxyalkyl having 1-18 carbons, hydroxyalkyl having 1-18 carbons, ester having 1-18 carbons, amino having 1-18 carbons, aldehyde having 1-18 carbons, olefin having 2-18 carbons.

2. The method for synthesizing a blue-green zinc phthalocyanine dye for display photoresist according to claim 1, wherein: The method comprises the following steps: (1) nucleophilic substitution reaction: using phenol derivatives to react with mercapto derivatives under the participation of a catalyst and at a suitable temperature, and then purifying to obtain sulfide derivatives; (2) oxidation reaction: dissolving the sulfide derivatives in a suitable organic solvent, and then performing oxidation reaction on the sulfide derivatives by using a peroxide at a suitable temperature, and then purifying to obtain sulfone derivatives; (3) esterification reaction: reacting the sulfone derivatives with methacrylic acid or methacrylic anhydride under the participation of a catalyst and / or a condensation reagent and at a suitable temperature, and then purifying to obtain methacrylic acid derivatives; (4) preparation of the compound of general formula III: uniformly mixing the phthalonitrile derivatives and the methacrylic acid derivatives in an organic solvent, and then adding a catalyst to perform reaction under the protection of an inert gas, and then purifying to obtain the compound of general formula III; The general formula III is as follows: ； (5) phthalocyanine ring formation reaction: uniformly mixing the compound of general formula III and a divalent metal zinc salt in an organic solvent, and then performing reaction under the protection of an inert gas, and then purifying to obtain the zinc phthalocyanine dye shown in general formula I.

3. The method for synthesizing a blue-green zinc phthalocyanine dye for display photoresist according to claim 2, wherein: In step (1), the equivalent ratio of the phenol derivatives to the catalyst is 1:1-1:8; and the equivalent ratio of the phenol derivatives to the mercapto derivatives is 1:1-1:

2.

4. The method for synthesizing a blue-green zinc phthalocyanine dye for display photoresist according to claim 2, wherein: In step (1), the catalyst is any one or more of sodium carbonate, potassium carbonate, potassium phosphate and cesium carbonate.

5. The method for synthesizing the blue-green zinc phthalocyanine dye for displaying photoresists according to claim 2, in step (2), the equivalent ratio of the sulfide derivatives to the peroxide is 1:2-1:

12.

6. The method for synthesizing a blue-green zinc phthalocyanine dye for display photoresist according to claim 2, wherein: In step (2), the peroxide is any one or more of benzoyl peroxide, cumene peroxide, hydrogen peroxide, tert-butyl hydroperoxide, methyl ethyl ketone peroxide and meta-chloro-peroxybenzoic acid.

7. The method for synthesizing a blue-green zinc phthalocyanine dye for display photoresist according to claim 2, wherein: In step (3), the equivalent ratio of the sulfone derivatives to the methacrylic acid or the methacrylic anhydride is 1:1-1:2; and the equivalent ratio of the sulfone derivatives to the catalyst is 1:1-1:

3.

8. The method for synthesizing a blue-green zinc phthalocyanine dye for display photoresist according to claim 2, wherein: In step (3), the catalyst is any one of triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N-dimethylaminopyridine, 1-hydroxybenzotriazole and N-hydroxy-7-azabenzotriazole.

9. The method for synthesizing a blue-green zinc phthalocyanine dye for display photoresist according to claim 2, wherein: In step (4), the equivalent ratio of the phthalonitrile derivatives to the methacrylic acid derivatives is 1:1-1:5; and the equivalent ratio of the phthalonitrile derivatives to the catalyst is 1:1-1:

6.

10. The method for synthesizing a blue-green zinc phthalocyanine dye for display photoresist according to claim 2, wherein: In step (5), the equivalent ratio of the compound of general formula III to the divalent metal zinc salt is 4:1-2:1.

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