Blue-green zinc phthalocyanine dye for display photoresist and synthesis method thereof

Abstract

The application discloses a blue-green zinc phthalocyanine dye for display photoresist and a synthesis method thereof. The halogen, sulfone group and liposoluble reaction group are introduced into the side chain of the metal phthalocyanine ring through nucleophilic substitution reaction, oxidation reaction and esterification reaction, so that the solubility, heat resistance and coloring power of the dye molecule are further improved. The phthalocyanine dye molecule can be mixed with a yellow pigment to prepare a green photoresist color paste, so as to improve the light transmittance and dispersibility of the color paste, and the color paste has excellent coloring power and heat resistance. Meanwhile, the synthesis method is simple, safe and reliable in operation, and is easy to realize 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.

[0007] The technical scheme adopted by the present application to solve the above technical problems is as follows:

[0008] A blue-green zinc phthalocyanine dye for photoresist, the zinc phthalocyanine dye has the structure shown in general formula I:

[0009] ;

[0010] In general formula I, X is a halogen atom; a+b+c=16, 1≤a≤16, 0≤b≤15, 0≤c≤15;

[0011] R 1 is a structure shown in general formula II:

[0012] ;

[0013] 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.

[0014] 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.

[0015] Preferably, said R 1 The application is selected from one of the following specific examples, but the application is not limited to these specific examples:

[0016] .

[0017] The synthesis method of the blue-green zinc phthalocyanine dye for displaying photoresist as described above, including but not limited to the following steps:

[0018] (1) Nucleophilic substitution reaction: using phenol derivatives to undergo nucleophilic substitution reaction with mercapto derivatives under the participation of catalyst and suitable temperature, and obtaining sulfide derivatives through reasonable purification means;

[0019] (2) Oxidation reaction: dissolving sulfide derivatives in suitable organic solvents, and performing oxidation reaction with peroxide at suitable temperature, and obtaining sulfone derivatives through reasonable purification means;

[0020] (3) Esterification reaction: reacting sulfone derivatives with methacrylic acid or methacrylic anhydride under the participation of catalyst and / or condensation reagent and suitable temperature, and obtaining methacrylic acid derivatives through reasonable purification means;

[0021] (4) Preparation of compound of general formula III: mixing o-phthalonitrile derivatives and methacrylic acid derivatives uniformly in organic solvents, and adding catalyst under inert gas protection to perform reaction, and obtaining compound of general formula III through reasonable purification means;

[0022] The general formula III is:

[0023] ;

[0024] (5) Phthalocyanine ring reaction: mixing compound of general formula III and divalent metal zinc salt uniformly in organic solvents, and adding or not adding catalyst under inert gas protection to perform reaction, and obtaining zinc phthalocyanine dye represented by general formula I through reasonable purification means;

[0025] To realize the structure represented by general formula I, the above reaction steps can be simply described as the following reaction scheme:

[0026] ;

[0027] Wherein X is a halogen atom, R 1 -R 7 and a, b, c are consistent with the above.

[0028] Wherein X is preferably fluorine, chlorine, bromine or iodine;

[0029] R 3 , R 4preferably selected from hydrogen, ether linkage having 1-18 carbons, carboxyalkyl having 1-18 carbons, ester group having 1-18 carbons, amino having 1-18 carbons;

[0030] R 7 preferably selected from ether linkage having 1-18 carbons, alkyl having 1-18 carbons, hydroxyalkyl having 1-18 carbons, amino having 1-18 carbons, aromatic group or aromatic heterocycle having 4-14 carbons, olefin having 2-18 carbons.

[0031] 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.

[0032] Preferably, in step (1), the phenol derivative is 4-bromo-2,6-dimethoxyphenol.

[0033] Preferably, in step (1), the catalyst is selected from any one or several of sodium carbonate, potassium carbonate, potassium phosphate, cesium carbonate, more preferably potassium carbonate or cesium carbonate.

[0034] Preferably, in step (1), the equivalent ratio of the phenol derivative to the thiol derivative is 1:1-1:2.

[0035] Preferably, in step (1), the thiol derivative is any one of 2-mercaptoethoxyethanol, 4-hydroxythiophenol, 4-mercaptocyclohexan-1-ol.

[0036] Preferably, in step (1), the suitable temperature is selected to be -20-100°C, more preferably 20-80°C.

[0037] Preferably, in step (1), the reaction time is 0.5-12h, more preferably 1-4h.

[0038] Preferably, in step (1), the purification means is to remove the reaction solvent from the reaction solution by distillation under reduced pressure, slowly add ice water to the concentrate under stirring, adjust the pH to 7-8 using 1M dilute hydrochloric acid, filter, wash the filter cake with sufficient water, and dry the filter cake at 50°C with air blowing to obtain the thioether derivative.

[0039] Preferably, in step (2), the equivalent ratio of the thioether derivative to the peroxide is 1:2-1:12, more preferably 1:2-1:6.

[0040] Preferably, in step (2), the organic solvent is selected from any one or several of dichloromethane, acetone, N,N-dimethylformamide, acetonitrile, 1,4-dioxane, dimethyl sulfoxide.

[0041] 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, m-chloroperbenzoic acid, more preferably any one of hydrogen peroxide, benzoyl peroxide, m-chloroperbenzoic acid.

[0042] Preferably, in step (2), the reaction temperature is selected to be 20-80℃.

[0043] Preferably, in step (2), the reaction time is 1-16h.

[0044] Preferably, in step (2), the purification means is distillation of the reaction solution under reduced pressure to obtain a crude product, column chromatography of the crude product using a mixture of 25% ethyl acetate / dichloromethane as the mobile phase, collection of the fractions and distillation under reduced pressure and drying to obtain the sulfone derivative.

[0045] Preferably, in step (3), the equivalent ratio of the sulfone derivative to the methacrylic acid or methacrylic anhydride is 1:1-1:2.

[0046] Preferably, in step (3), the equivalent ratio of the sulfone derivative to the catalyst is 1:1-1:3.

[0047] Preferably, in step (3), the catalyst is selected from any one of triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N-dimethylaminopyridine, 1-hydroxybenzotriazole, N-hydroxy-7-azabenzotriazole.

[0048] Preferably, in step (3), the condensation reagent is selected from any one of N,N'-dicyclohexylcarbodiimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, N,N,N',N'-tetramethyl-O-(7-azabenzotriazol-1-yl)urea hexafluorophosphate, benzotriazole-N,N,N',N'-tetramethyluronium hexafluorophosphate.

[0049] Preferably, in step (3), the reaction temperature is -20-80℃.

[0050] Preferably, in step (3), the reaction time is 1-16h.

[0051] Preferably, in step (3), the purification means is filtration of the reaction solution, elution of the filter cake with an appropriate amount of dichloromethane in multiple times, and drying to obtain the methacrylic acid derivative.

[0052] Preferably, in step (4), the equivalent ratio of the phthalonitrile derivative to the methacrylic acid derivative is 1:1-1:5.

[0053] Preferably, in step (4), the phthalonitrile derivative is any one of 4,5-dichlorophthalonitrile, tetrachlorophthalonitrile, tetrafluorophthalonitrile.

[0054] Preferably, in step (4), the equivalent ratio of the phthalonitrile derivative to the catalyst is 1:1-1:6.

[0055] Preferably, in step (4), the organic solvent is N,N-dimethylformamide.

[0056] Preferably, in step (4), the catalyst is potassium carbonate.

[0057] Preferably, in step (4), the reaction temperature is -20-100℃.

[0058] Preferably, in step (4), the reaction time is 1-12h.

[0059] Preferably, in step (4), the purification means is pouring the reaction solution into ice water, filtering and drying to obtain a crude product, and then using ethyl acetate to beat the crude product to obtain the compound of general formula III.

[0060] Preferably, in step (4), the branched chain of the compound of general formula III has at least one R 1 , and the remaining branched chains can be R 2 , hydrogen, fluorine, chlorine, bromine or iodine.

[0061] Preferably, in step (5), the equivalent ratio of the compound of general formula III to the divalent metal zinc salt is 4:1-2:1.

[0062] Preferably, in step (5), the divalent metal zinc salt is selected from any one of zinc acetate, zinc chloride, zinc iodide, zinc sulfate, zinc phosphate, and more preferably is zinc acetate or zinc iodide.

[0063] Preferably, in step (5), the organic solvent is selected from any one of aliphatic alcohols, alcohol ethers, alcohol amines, R 1 , which can undergo ester exchange reaction, R 2 If there is an ester group, it can also undergo ester exchange reaction, and more preferably is n-pentanol or benzonitrile.

[0064] Preferably, in step (5), the equivalent ratio of the compound of general formula III to the catalyst is 1:0.5-1:1.

[0065] 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.

[0066] Preferably, in step (5), if the compound of general formula III contains a substituent -X, where X represents a halogen atom, then no catalyst needs to be added in the reaction; or, if the reaction solvent is N,N-dimethylethanolamine, since it has its own basic catalytic effect, then no catalyst needs to be added in the reaction.

[0067] Preferably, in step (5), the reaction temperature is 90~210℃.

[0068] Preferably, in step (5), the reaction time is 10~36h.

[0069] Preferably, in step (5), the appropriate purification method includes, but is not limited to, any one of vacuum distillation, column chromatography, pulping, recrystallization, etc., and the column chromatography mobile phase is selected from a mixture of dichloromethane and methanol, or acetonitrile and methanol.

[0070] Compared with existing technologies (currently commercially available hybrid phthalocyanines), the advantages of this invention are:

[0071] (1) The zinc phthalocyanine dye molecules provided by the present invention can be mixed with a small amount of commercially available yellow pigment to form a green photoresist paste, which further improves the transmittance;

[0072] (2) The zinc phthalocyanine dye molecules provided by the present invention have advantages such as excellent solubility, transmittance, heat resistance and excellent coloring power;

[0073] (3) The synthesis method provided by the present invention has a simple route, is easy and safe to operate, has a wide range of reagent sources, is low in cost, and is easy to scale up. Attached Figure Description

[0074] Figure 1 The dye intermediate A-4 prepared in this invention 1 H-NMR spectrum;

[0075] Figure 2 The dye intermediate B-4 prepared in this invention 1 H-NMR spectrum;

[0076] Figure 3 The dye intermediate C-4 prepared in this invention 1 H-NMR spectrum;

[0077] Figure 4 The dye intermediate D prepared in this invention 1 H-NMR spectrum;

[0078] Figure 5 The UV-vis absorption spectrum of dye A prepared in Example 1 of this invention is shown.

[0079] Figure 6 UV-vis transmission spectrum of dye A prepared in Example 1 of the present application;

[0080] Figure 7 Thermogravimetric diagram of dye A prepared in Example 1 of the present application. DETAILED DESCRIPTION

[0081] For better understanding of the present application, further description will be made in combination with specific examples and drawings. It should be understood that these examples are only used to further illustrate the present application, and are not used to limit the scope of the present application. In addition, it should be understood that after reading the content described in the present application, the skilled in the art can make some non-essential modifications or adjustments to the present application, which still falls within the protection scope of the present application.

[0082] The compound of the general formula II and the dye intermediates of Examples 1-3 and Comparative Example 1 can be prepared by the synthetic method described below.

[0083] I. Preparation method of dye intermediate A-4 of Example 1, the steps are as follows:

[0084] (1) Preparation of intermediate A-1:

[0085]

[0086] A suitable size stirring bar was equipped on a dry and clean 250 mL three-necked flask, and a thermometer and a reflux condenser were installed. 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 into the flask, acetone (100 ml) was measured and added, and stirring was performed to dissolve all the chemicals. Anhydrous potassium carbonate (8.90 g, 64.36 mmol, 1.50 eq.) was added. Then, under the protection of nitrogen atmosphere, the reaction was stirred using an oil bath reflux for 6 hours. After the reaction was completed, the reaction solvent was removed by reduced pressure distillation, ice water (200 ml) was slowly added to the concentrate under stirring, 1M dilute hydrochloric acid was used to adjust pH=7~8, and finally filtration was performed, and the filter cake was washed with sufficient 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%.

[0087] (2) Preparation of compound A-2:

[0088]

[0089] Using the intermediate A-1 (10.00 g, 36.45 mmol, 1.00 eq.) and m-chloroperbenzoic acid (12.58 g, 72.90 mmol, 2.00 eq.) obtained in the previous step, the weighed chemicals were dissolved in a single-neck flask containing acetonitrile (200 ml) and stirred at room temperature overnight. The next day, after the reaction was completed, the crude product was distilled 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%.

[0090] (3) Preparation of intermediate A-3:

[0091]

[0092] In a 250-ml three-neck flask equipped with a thermometer, intermediate A-2 (10.00 g, 32.64 g, 1.00 eq.) and triethylamine (6.61 g, 65.29 mmol, 2.00 eq.) obtained in the previous step were weighed and dissolved in dichloromethane (100 ml) and stirred to dissolve. The reaction system was cooled to 0°C with an ice bath. A solution of 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, the filtrate was washed with dichloromethane, and the filter cake was dried to obtain 10.60 g of intermediate A-3, with a yield of 87.0%.

[0093] (4) Preparation of intermediate A-4:

[0094]

[0095] First, 4,5-dichlorophthalonitrile (2.00 g, 10.15 mmol, 1.00 eq.) and intermediate A-3 (7.98 g, 21.32 mmol, 2.1 eq.) obtained in the previous step were weighed and dissolved in a single-neck flask containing N,N-dimethylformamide (100 ml) and stirred to dissolve. Anhydrous potassium carbonate (4.21 g, 30.45 mmol, 3.00 eq.) was added, and the reaction was stirred at 80°C using an 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 then filtered and dried to obtain the crude product. The crude product was purified by slurry with ethyl acetate and dried to obtain 5.36 g of intermediate A-4 (its 1 H-NMR spectrum is shown in Figure 1 ), with a yield of 60.5%.

[0096] II. Preparation of dye intermediate D of Comparative Example 1, the procedure is as follows:

[0097] Preparation of intermediate D:

[0098]

[0099] First, 3-nitrophthalonitrile (10.00 g, 57.76 mmol, 1.00 eq.), 2,6-dimethoxyphenol (10.68 g, 69.31 mmol, 1.20 eq.) were weighed into a 500 ml single-necked flask containing N,N-dimethylformamide (100 ml), then anhydrous potassium carbonate (11.97 g, 86.64 mmol, 1.50 eq.) was weighed and added, and the reaction was stirred in an oil bath at 80°C for 16 hours. After the reaction was completed, the temperature was lowered to room temperature, and the reaction solution was poured into ice water (1000 ml), and the generated solid was filtered and dried to obtain a crude product. Column chromatography was performed on the crude product using 50% dichloromethane / petroleum ether as the mobile phase, the fractions were collected and dried by distillation under reduced pressure to obtain 12.60 g of intermediate D (its 1 The H-NMR spectrum is shown in Figure 4 , and the yield was 77.8%.

[0100] Referring to the basic synthesis method of the above intermediate A-1~A-4, the following dye intermediate B-4 of Example 2 (its 1 The H-NMR spectrum is shown in Figure 2 , and the dye intermediate C-4 of Example 3 (its 1 The H-NMR spectrum is shown in Figure 3 ).

[0101]

[0102] 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-dichlorophthalonitrile is replaced by tetrachlorophthalonitrile.

[0103]

[0104] 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-dichlorophthalonitrile is replaced by tetrachlorophthalonitrile.

[0105] The dye molecules represented by the general formula I in the present application can be prepared by the synthesis method described below.

[0106] Example 1 (synthesis of dye A)

[0107]

[0108] Take intermediate A-4 (4.20 g, 4.81 mmol, 3.00 eq.), zinc acetate (294 mg, 1.60 mmol, 1.00 eq.) into a single-necked flask containing n-pentanol (50 ml), add 1,8-diazabicyclo[5.4.0]undec-7-ene (488 mg, 3.21 mmol, 2.00 eq.), heat to 150°C under nitrogen atmosphere for 10 hours. After the reaction is completed, the reaction system is cooled to room temperature and poured into methanol (500 ml). The precipitated solid is filtered, washed with 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%.

[0109] 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 The thermogravimetric diagram of dye A is shown in Figure 7 .

[0110] Example 2 (synthesis of dye B)

[0111]

[0112] Take intermediate B-4 (3.00 g, 3.16 mmol, 1.00 eq.), zinc iodide (333 mg, 1.04 mmol, 0.33 eq.) into a single-necked flask, add benzyl cyanide (50 ml), heat to 160°C under nitrogen atmosphere for 18 hours. After the reaction is completed, the reaction system is cooled to room temperature and poured into petroleum ether. The precipitated solid is filtered, washed with 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%.

[0113] Example 3 (synthesis of dye C)

[0114]

[0115] Take intermediate C-4 (5.00 g, 5.38 mmol, 1.00 eq.), zinc iodide (567 mg, 1.78 mmol, 0.33 eq.) into a single-necked flask, add benzyl cyanide (80 ml), heat to 170°C under nitrogen atmosphere for 16 hours. After the reaction is completed, the reaction system is cooled to room temperature and poured into petroleum ether. The precipitated solid is filtered, washed with appropriate amount of ethanol and water, and dried at 50°C to obtain 3.15 dye C, with a yield of 62.0%.

[0116] Comparative Example 1 (synthesis of dye D)

[0117]

[0118] 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-dimethylethanolamine (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 dried by distillation under reduced pressure to obtain 3.10 g of dye D, with a yield of 59.0%.

[0119] Effect experiment example

[0120] I. UV-Vis spectrum test of phthalocyanine dye molecules

[0121] The test solvent was propylene glycol methyl ether acetate (PGMEA).

[0122] A micro-precision balance was used to accurately weigh the phthalocyanine dyes prepared in Examples 1-3 and Comparative Example 1 in the form of solid powder, and dissolved in a solvent to prepare a 5.0 mmol / L stock solution, which was stored in a sample tube.

[0123] 6.0 μL of the above stock solution was removed with a micro-pipette gun and diluted in a quartz cuvette containing 3 ml of the same solvent, mixed uniformly to prepare 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:

[0124] A = εcl

[0125] 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.

[0126] The transmittance of the dye was calculated by the following formula:

[0127] A = -lgT

[0128] In the formula, A is the absorbance; and T is the transmittance, %.

[0129] The results of the UV-Vis spectrum test of the phthalocyanine dye molecules prepared in Examples 1-3 and Comparative Example 1 are shown in Table 1.

[0130] Table 1. Results of the UV-Vis spectrum test of the phthalocyanine dye molecules prepared in Examples 1-3 and Comparative Example 1

[0131] 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

[0132] 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 to Comparative Example 1. The maximum absorption wavelength of Examples 2-3 has a significant red shift compared to Example 1, and the phthalocyanine dye molecule prepared in Example 1 has the highest molar absorption coefficient.

[0133] II. Solubility test of phthalocyanine dye molecules

[0134] 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.

[0135] A certain amount of dye and organic solvent was weighed, ultrasonically dispersed for 20 minutes and placed in a 20℃ water bath for 24 hours. The filtrate was filtered three times using a filter membrane, and the filter cake was dried to calculate the solubility S of the dye:

[0136] S = 100*M S / M L

[0137] In the formula, M S is the mass of the dried dye, g; and M L is the mass of the solution, g.

[0138] The solubility test results of the phthalocyanine dye molecules prepared in Examples 1-3 and Comparative Example 1 are shown in Table 2.

[0139] Table 2 Solubility test results of the phthalocyanine dye molecules prepared in Examples 1-3 and Comparative Example 1

[0140] 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

[0141] 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 in 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.

[0142] III. Thermal stability test of phthalocyanine dye molecules

[0143] In the industrial production of color filter process to undergo 230 ℃ or so multiple baking process, therefore requires that the dye molecules can have good thermal stability at this temperature. In nitrogen protection, using thermal gravimetric analyzer, using from room temperature to 10 ℃ / min heating rate to 500 ℃ test method, determine its thermal decomposition temperature T d , in order to evaluate the thermal stability of synthetic dyes.

[0144] The thermal stability test results of the phthalocyanine dye molecules prepared in examples 1~3 and comparative example 1 are shown in table 3.

[0145] Table 3 thermal stability test results of the phthalocyanine dye molecules prepared in examples 1~3 and comparative example 1

[0146] 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

[0147] As can be seen from table 3, the T d In the range of 300~450 ℃, the weight loss rate at 230 ℃ for 30 min is less than 5%, indicating that the dye molecules prepared by the present application have good thermal stability, also from the side of the introduction of alkoxy and sulfonyl group advantages.

[0148] The present application introduces halogen, sulfonyl and liposoluble reaction groups in the side chain of metal phthalocyanine ring through nucleophilic substitution reaction, oxidation reaction and esterification reaction, thereby further improving the solubility, heat resistance and color strength 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 color strength 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.

[0149] 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 ordinary skilled in the art within the 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 in that, The zinc phthalocyanine dye has one of the following structures: ； ； 。 2. The method for synthesizing a blue-green zinc phthalocyanine dye for display photoresist as described in claim 1, characterized in that, 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, to obtain sulfide derivatives through purification; The phenol derivative has the following structure: ; wherein said X is a halogen atom; said thiol derivative is any one of 2-mercaptoethoxyethanol, 4-hydroxythiophenol, 4-mercaptocyclohexan-1-ol; (2) oxidation reaction: dissolving the sulfide derivatives in a suitable organic solvent, and performing oxidation reaction with peroxide at a suitable temperature, to obtain sulfone derivatives through purification; (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, to obtain methacrylic acid derivatives through purification; (4) preparation of the compound of general formula III: uniformly mixing phthalonitrile derivatives with methacrylic acid derivatives in an organic solvent, and adding a catalyst to perform reaction under the protection of inert gas, to obtain the compound of general formula III through purification; the phthalonitrile derivatives are any one of 4,5-dichlorophthalonitrile, tetrachlorophthalonitrile and tetrafluorophthalonitrile; The general formula III is: ; The specific structure of the compound of general formula III is one of the following structures: ； and ; (5) phthalocyanine ring reaction: uniformly mixing the compound of general formula III with a divalent metal zinc salt in an organic solvent, and performing reaction under the protection of inert gas, to obtain the zinc phthalocyanine dye shown in claim 1 through purification.

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

2.

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

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

12.

6. The method for synthesizing a blue-green zinc phthalocyanine dye for display photoresist as described in claim 2, characterized in that, 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 as described in claim 2, characterized in that, In step (3), the equivalent ratio of the sulfone derivative to the methacrylic acid or the methacrylic anhydride is 1:1-1:2; and the equivalent ratio of the sulfone derivative to the catalyst is 1:1-1:

3.

8. The method for synthesizing a blue-green zinc phthalocyanine dye for display photoresist as described in claim 2, characterized in that, 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 as described in claim 2, characterized in that, In step (4), the equivalent ratio of the phthalonitrile derivative to the methacrylic acid derivative is 1:1-1:5; and the equivalent ratio of the phthalonitrile derivative to the catalyst is 1:1-1:

6.

10. The method for synthesizing a blue-green zinc phthalocyanine dye for display photoresist as described in claim 2, characterized in that, 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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