A kind of phthalocyanine dye containing polymerizable group and its synthesis method and application

Abstract

The application provides a kind of phthalocyanine dye containing polymerizable group and a synthesis method and application thereof.The application relates to the field of functional organic dyes, and provides a kind of phthalocyanine dye containing polymerizable group and a synthesis method and application thereof, which introduces halogen atoms, long alkyl chains and polymerizable active groups into phthalocyanine as a parent structure.The active groups introduced can be crosslinked with resins or monomers in a color photoresist component, so that the stability of a thin film can be improved, and the transmittance loss can be reduced.The application overcomes the problem that the light resistance, heat resistance and migration resistance of dye molecules in the prior art are still much poorer than those of pigments.A kind of phthalocyanine dye containing polymerizable group has the structure shown in the following general formula I.

Description

Technical Field

[0001] This invention relates to the field of functional organic dyes, and more particularly to a class of phthalocyanine dyes containing polymerizable groups, their synthesis methods, and applications. Background Technology

[0002] Photoresist is a photosensitive material that undergoes a chemical reaction upon exposure to light or other radiation, forming photosensitive materials with varying solubility. Color photoresist is a crucial raw material for the fabrication of TFT-LCD displays. Color photoresist generally consists of resin, colorants, siloxane coupling agents, and other additives. Existing colorants are primarily pigment systems, but the particulate nature of pigments causes light scattering, requiring dispersion during use. To effectively overcome the difficulties in dispersing pigment particles and the problem of particle aggregation, expensive and time-consuming grinding equipment is needed. Improving color properties requires increasing the amount of pigment used, which in turn leads to an increase in the amount of dispersant. This excessive use of dispersant makes it difficult to increase the proportion of pigment in color filters, increasing production costs, thus reaching a bottleneck for pigment-based color photoresists. To meet the resolution, contrast, and colorimetric requirements of new display technologies, the colorants in color photoresists are shifting from pigment systems to dye systems.

[0003] Dyes and pigments are generally compounds that possess inherent color and can impart vivid and stable colors to other substances in either a molecular or dispersed state. Organic dyes, after structural modification, can meet solubility requirements. Without the need for dispersants, their dosage can be increased to achieve contrast, color saturation, and brightness levels unattainable by traditional pigment-based color photoresists. However, dyes exhibit significantly lower lightfastness and heat resistance compared to pigments. Furthermore, due to their smaller molecular size, dye molecules are prone to migration during the manufacturing process. Green photoresists, typically used as a base color, require higher stability and migration resistance. During UV exposure, color photoresists undergo a cross-linking reaction involving olefin double bonds. Designing the molecular structure based on the manufacturing process can improve migration resistance and thus enhance the application value of dyes in color photoresists. Summary of the Invention

[0004] This invention provides a class of phthalocyanine dyes containing polymerizable groups, their synthesis methods, and applications. Using phthalocyanine as the parent structure, by introducing halogen atoms, long alkyl chains, and polymerizable active groups, the spectral properties, solubility, and photothermal stability of phthalocyanine dyes are modified, thereby overcoming the problem that the lightfastness, heat resistance, and migration resistance of dye molecules in the prior art are still significantly inferior to those of pigments.

[0005] To achieve the above objectives, the present invention provides the following technical solution: a class of phthalocyanine dyes containing polymerizable groups, having the structure shown in general formula I:

[0006]

[0007] In general formula I, Y and R are both phthalocyanine parent substituents; M is a divalent, trivalent, or tetravalent metal, halide metal, or nonmetal; Y is selected from halogen atoms, where 4≤y+r≤16;

[0008]

[0009] Formula R has the structure of general formula II, where R1, R2, R3, R4, and R5 are substituent groups on the benzene ring; R1, R2, R4, and R5 are each independently selected from ester groups or alkyl chains with ether bonds of carbons 0-18; R3 has the structure shown in general formula III.

[0010] In general formula III, R6 and R7 are each independently selected from alkyl groups of ester or ether bonds with 0-18 carbons; 1≤n+m≤18, preferably, 0≤n≤8, 0≤m≤8 and m and n are not simultaneously 0.

[0011] Furthermore, the ultraviolet absorption wavelength of the phthalocyanine dye containing polymerizable groups is 650-710 nm, and its solubility is greater than 10%.

[0012] A method for synthesizing a class of phthalocyanine dyes containing polymerizable groups includes the following steps:

[0013] S1: A phthalonitrile having the structure shown in general formula IV is combined with an R-containing... 1-5 The substituted benzene is added to a first organic solvent and mixed evenly. Then, under the protection of an inert gas, an inorganic salt catalyst is added, and the reaction is carried out at 0-80°C for 4-16 hours to obtain an intermediate. In general formula IV, X1, X2, X3, and X4 can be the same or different, and each is independently selected from halogens or hydrogen atoms. Preferably, the halogen is selected from any one of Cl, Br, and I.

[0014] S2: Mix the intermediate obtained in step S1 and MCl2 evenly in a second organic solvent, add an organic catalyst under inert gas protection, and react at 130-200℃ for 14-24h to obtain the target product.

[0015] The reaction process is as follows:

[0016]

[0017] Further, in step S1, the one containing X 1-4 Substituent phthalonitriles and those containing R 1-5 The molar ratio of substituted benzenes is 1:1-4;

[0018] In step S2, the molar ratio of the intermediate obtained in step S1 to MCl2 is 4:1-2.

[0019] Further, in step S1, the first organic solvent is selected from one or a mixture of several of acetonitrile, toluene, DMF, and DMSO;

[0020] The inorganic salt catalyst is selected from one or a mixture of potassium carbonate, sodium carbonate, and potassium acetate.

[0021] Further, in step S2, the second organic solvent is selected from alcohols with a boiling point greater than 130°C; the organic catalyst is selected from strong basic catalysts, preferably, the organic catalyst is selected from DBU or cesium carbonate.

[0022] Furthermore, the second organic solvent is selected from one or more of pentanol, hexanol, quinoline, and hexanediol.

[0023] Application of a class of phthalocyanine dyes containing polymerizable groups in color filters.

[0024] In summary, the present invention has the following beneficial effects:

[0025] 1. Phthalocyanines are planar macrocyclic conjugated systems composed of four isoindole units. Unsubstituted metallic phthalocyanines are almost insoluble in water and organic solvents, limiting their application value. Modified substituted phthalocyanines, however, possess unique photoelectric and electron transfer properties, leading to their wide application in semiconductor materials, catalysts, and solar cells. The lightfastness, heat stability, and migration resistance of dye molecules still lag significantly behind those of pigments, representing a pressing challenge for industrial applications. Dye molecules offer advantages such as diversity and structural modifiability. Through systematic research on the molecular structure-performance relationship, the heat stability, light stability, and migration resistance of dye-based color filters can be improved.

[0026] 2. Introducing long alkyl chains containing acid ester structures into phthalocyanine dye molecules can improve the solubility of dye molecules and meet their solubility requirements in industrial organic solvents.

[0027] 3. By introducing polymerizable unsaturated bonds into phthalocyanine molecules, dye molecules can react with resins, multifunctional monomers, and active groups of dye molecules in the color photoresist components, thereby forming a resin-dye crosslinking network that fixes the dye molecules, increases the compactness and crosslinking density of the dye film, hinders the thermal motion of molecular chains, and ultimately improves the overall stability of dye molecules. This series of dye molecules is expected to be applied to all-dye-based color filters. Attached Figure Description

[0028] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0029] Figure 1 These are the mass spectra of fragment molecules 1, 2, 3, 4, 5, and 6;

[0030] Figure 2 These are the mass spectra of compounds 1, 2, 3, 4, 5, and 6;

[0031] Figure 3 These are the proton NMR spectra of fragment molecules 1, 2, 3, 4, 5, and 6.

[0032] Figure 4 These are the 1H NMR spectra of compounds 1, 2, 3, 4, 5, and 6.

[0033] Figure 5 These are the ultraviolet absorption spectra of compounds 1, 2, 3, 4, 5, and 6;

[0034] Figure 6 These are the thermal stability analysis diagrams for compounds 1, 2, 3, 4, 5, and 6;

[0035] Figure 7 This is a thermal stability diagram of the dye evaluation films made from compounds 1, 2, 3, 4, 5, and 6;

[0036] Figure 8 This is a photostability diagram of the dye evaluation films made from compounds 1, 2, 3, 4, 5, and 6;

[0037] Figure 9 This is the UV absorption diagram of the solvent-resistant compounds 1, 2, 3, 4, 5, and 6. Detailed Implementation

[0038] Unless otherwise stated, the terms used herein have the following meanings.

[0039] The term "halogen" as used in this article includes chlorine, bromine, and iodine.

[0040] The term "alkyl" as used in this invention includes straight-chain or branched alkyl groups and oxygen-containing alkyl groups.

[0041] The solvent used in this article may be any suitable solvent, including organic solvents selected from pentanol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, pentaethylene glycol monomethyl ether, and hexaethylene glycol monomethyl ether.

[0042] The instruments and equipment used in the embodiments are as follows:

[0043] In the column chromatography process of this invention, 200-300 mesh and 100-200 mesh silica gel for column chromatography purchased from Qingdao Meigao Group Co., Ltd., and 20-40 mesh analytical grade quartz sand purchased from Tianda Chemical Reagent Factory are used.

[0044] The ultraviolet absorption of the dyes was measured using a Cary 60 UV-Vis spectrophotometer (Agilent Technologies, USA); the proton nuclear magnetic resonance (NMR) spectrometers were used for the AVANCE II (400MHz) (Bruker, Germany) and AVANCE III (500) (Bruker, Germany); the mass spectrometer was used for the matrix-assisted laser desorption / ionization time-of-flight mass spectrometer (MALDIMALDI-TOF) (Bruker, Germany); the spectral and color properties were measured using a HACA-2000 high-precision color analyzer (Hangzhou Yuanfang Optoelectronics Co., Ltd., China); the thermogravimetric analysis was performed using a TGA / DSC3+ (Mettler, Switzerland); and the coating was performed using a KW-4T spin coater (Institute of Microelectronics, Chinese Academy of Sciences, China).

[0045] The following is in conjunction with the appendix Figure 1-9 The invention will be further described in detail with reference to the embodiments. However, it is not limited to the following embodiments.

[0046] The following describes a class of phthalocyanine dyes containing polymerizable groups, represented by general formula I, with reference to specific embodiments:

[0047]

[0048] In general formula I, Y and R are both phthalocyanine parent substituents; M is a divalent, trivalent, or tetravalent metal, halide metal, or nonmetal; Y is selected from halogen atoms, where 4≤y+r≤16;

[0049]

[0050] R has the structure of general formula II, where R1, R2, R3, R4, and R5 are substituents on the benzene ring; R1, R2, R4, and R5 are each independently selected from ester groups or alkyl chains with ether bonds of carbons 0-18; R3 has the structure shown in general formula III.

[0051] In general formula III, R6 and R7 are each independently selected from alkyl groups of ester or ether bonds with 0-18 carbons; 1≤n+m≤18, preferably, 0≤n≤8, 0≤m≤8 and m and n are not simultaneously 0.

[0052] The following are specific examples of compounds represented by general formula II, but the present invention is not limited to these specific examples.

[0053]

[0054] The following are specific examples of compounds represented by general formula I, but the present invention is not limited to these specific examples.

[0055]

[0056]

[0057] The present invention can be synthesized from compounds represented by general formula I by the methods described below.

[0058] Example

[0059] Example 1

[0060] Prepare compound 1 having the following structure:

[0061]

[0062] Its synthesis method is as follows:

[0063] S1: Synthesis of Fragment Molecule: 3-Nitrophthalonitrile (3.12 g, 18 mmol) and ethyl ferulic acid (4.0 g, 18 mmol) were added to a 150 mL double-necked round-bottom flask containing DMF (50 mL). Under nitrogen atmosphere, anhydrous potassium carbonate (2.49 g, 18 mmol) was added in portions over 2 h, and the mixture was stirred for 40 min. The temperature was gradually increased to 80 °C, and the reaction was stopped after 12 h. After the reaction solution cooled to room temperature, it was poured into 800 mL of ice water and filtered to obtain a yellow-brown solid as the crude product. The crude product was further dissolved in a small amount of dichloromethane, and then purified by silica gel column chromatography using petroleum ether / dichloromethane (1:10, v / v) as the developing solvent. After evaporating the solvent to dryness, a white powdery solid was obtained. After purification, fragment molecule 1 (C 20 H 16 4.15 g of N₂O₄ was obtained, with a yield of 66.19%. Fragment molecule 1 was analyzed by NMR and mass spectrometry; the results are shown below. Figure 1 and Figure 3 .

[0064] S2: Synthesis of the compound: Take fragment molecule 1 (C 20 H 16N₂O₄ (1.000 g, 2.87 mmol) and anhydrous zinc chloride (146.80 mg, 1.08 mmol) were added to a 100 mL double-necked round-bottom flask containing 35 mL of anhydrous n-pentanol. Under a nitrogen atmosphere, DBU (180.03 mg, 717.65 μmol) was then added. The reaction mixture was stirred and heated to 150 °C for 15–24 h. The reaction progress was assessed by thin-layer chromatography, and the reaction was terminated. After the reaction mixture cooled to room temperature, it was poured into a suitable amount of ice-cold methanol and filtered to obtain a yellow-green solid. The crude product was vacuum dried, dissolved in a small amount of dichloromethane, and then purified by silica gel column chromatography using dichloromethane / methanol (100:1, v / v) as the developing solvent. After evaporating the solvent, a blue-green powdery solid was obtained. After purification, compound 1 (C) was obtained. 92 H 88 N8O 16 Zn (0.331 g), yield 28.29%. Compound 1 was subjected to NMR and mass spectrometry analysis; the results are shown below. Figure 2 and Figure 4 .

[0065] Example 2

[0066] Prepare compound 2 having the following structure:

[0067]

[0068] The synthesis method is as follows: The difference from Example 1 is that in step S1, 4-nitrophthalonitrile (3.12 g, 18 mmol) is used instead of 3-nitrophthalonitrile (3.12 g, 18 mmol), and after purification, fragment molecule 2 (C) is obtained. 20 H 16 5.40 g of N2O4 was obtained, with a yield of 86.12%. Fragment molecule 2 was subjected to NMR and mass spectrometry analysis; the results are shown below. Figure 1 and Figure 3 ;

[0069] In step S2, fragment molecule 2 (C) is used. 20 H 16 N2O4) replaces fragment molecule 1 (C) 20 H 16 After the reaction solution cooled to room temperature, it was poured into an appropriate amount of ice-cold methanol and filtered to obtain a blue-green solid. The crude product was vacuum dried, dissolved in a small amount of dichloromethane, and then purified by silica gel column chromatography using dichloromethane / methanol (180:1, v / v) as the developing solvent. After evaporating the solvent to dryness, a blue-green powdery solid was obtained. After purification, compound 2 (C) was obtained. 92 H 88 N8O 16Zn (0.412 g), yield 35.21%. Compound 2 was subjected to NMR and mass spectrometry analysis; the results are shown in [reference needed]. Figure 2 and Figure 4 .

[0070] Example 3

[0071] Prepare compound 3 having the following structure:

[0072]

[0073] The synthesis method differs from that in Example 1 only in that, in step S1, 3-nitrophthalonitrile (3.12 g, 18 mmol) is replaced with 4,5-dichlorophthalonitrile (3.55 g, 18 mmol); after purification, fragment molecule 3 (C) is obtained. 20 H 15 3.76 g of ClN2O4 was obtained, with a yield of 54.57%. Fragment molecule 3 was subjected to NMR and mass spectrometry analysis; the results are shown below. Figure 1 and Figure 3 .

[0074] In step S2, fragment molecule 3 (1.000 g, 2.61 mmol) is used to replace fragment molecule 1 (C). 20 H 16 After the reaction solution cooled to room temperature, it was poured into an appropriate amount of ice-cold methanol and filtered to obtain a blue-green solid. The crude product was vacuum dried, dissolved in a small amount of dichloromethane, and then purified by silica gel column chromatography using dichloromethane / methanol (100:1, v / v) as the developing solvent. After evaporating the solvent to dryness, a blue-green powdery solid was obtained. The purified product was P3(C 92 H 84 Cl4N8O 16 Zn)(0.433 g), yield 37.39%. Compound 3 was subjected to NMR and mass spectrometry analysis; the results are shown in [reference needed]. Figure 2 and Figure 4 .

[0075] Example 4

[0076] Compound 4 with the following structure was prepared:

[0077]

[0078] The synthesis method differs from that of Example 1 only in that, in step S1, 3-nitrophthalonitrile (3.12 g, 18 mmol) is replaced with 3,4,5,6-tetrachlorophthalonitrile (4.79 g, 18 mmol), and after purification, fragment molecule 4 (C) is obtained. 20 H 134.93 g of fragment molecule (Cl3N2O4) was obtained, with a yield of 60.64%. NMR and mass spectrometry analyses were performed on fragment molecule 4; the results are shown below. Figure 1 and Figure 3 .

[0079] In step S2, fragment molecule 4 (1.000 g, 2.21 mmol) is used to replace fragment molecule 1 (C). 20 H 16 After the reaction solution cooled to room temperature, it was poured into an appropriate amount of n-hexane and filtered to obtain a green solid. The crude product was vacuum dried, dissolved in a small amount of dichloromethane, and then purified by silica gel column chromatography using petroleum ether / ethyl acetate (40:1, v / v) as the developing solvent. After evaporating the solvent to dryness, a blue-green powdery solid was obtained. The purified product was P4(C 92 H 76 Cl 12 N8O 16 Zn)(0.418 g), yield 36.67%. Compound 4 was subjected to NMR and mass spectrometry analysis; the results are shown in [reference needed]. Figure 3 and Figure 4 Compound 4 was subjected to NMR and mass spectrometry analysis; the results are shown in [link to results]. Figure 2 and Figure 4 .

[0080] Example 5

[0081] Compound 5 with the following structure was prepared:

[0082]

[0083] Its synthesis method is as follows:

[0084] S1: 4,5-Dichlorophthalonitrile (1.77 g, 9.0 mmol), methyl 5-allyl-3-methoxysalicylate (2.0 g, 9 mmol), and anhydrous potassium carbonate (1.24 g, 9 mmol) were added to a 150 mL double-necked round-bottom flask containing 50 mL of DMF under a nitrogen atmosphere. The reaction was stopped after 8-14 h. After the reaction solution cooled to room temperature, it was poured into 800 mL of ice water and filtered to obtain a pale yellow solid as the crude product. Column chromatography was performed, with petroleum ether / dichloromethane (1:5, v / v). After evaporating the solvent, a white powdery solid was obtained. After purification, fragment molecule 5 (C) was obtained. 20 H 15 2.73 g of ClN₂O₄ was obtained, with a yield of 79.60%. Fragment molecule 5 was subjected to NMR and mass spectrometry analysis; the results are shown below. Figure 1 and Figure 3 .

[0085] S2: Synthesis of the compound: Fragment molecule 5 (2.000 g, 5.22 mmol), anhydrous zinc chloride (327.66 mg, 1.96 mmol), and DBU (327.66 mg, 1.31 mmol) were added to a 100 mL double-necked round-bottom flask containing 35 mL of anhydrous n-pentanol. The reaction was carried out at 150 °C for 15-24 h under a nitrogen atmosphere. The reaction progress was determined by thin-layer chromatography, and the reaction was terminated. After the reaction solution cooled to room temperature, it was poured into an appropriate amount of ice-cold methanol and filtered to obtain a blue-green solid. The crude product was vacuum dried, dissolved in a small amount of dichloromethane, and then purified by silica gel column chromatography using dichloromethane / methanol (50:1, v / v) as the developing solvent. After evaporating the solvent, a blue-green powdery solid was obtained. The purified product P3 (C 96 H 92 Cl4N8O 16 Zn (0.873 g), yield 36.68%. Compound 5 was subjected to NMR and mass spectrometry analysis; the results are shown below. Figure 2 and Figure 4 .

[0086] Example 6

[0087] Prepare compound 6 having the following structure:

[0088]

[0089] The synthesis method differs from that in Example 5 in that, in step S1, 3,4,5,6-tetrachlorophthalonitrile (2.39 g, 9.0 mmol) is used instead of 4,5-dichlorophthalonitrile (1.77 g, 9.0 mmol); after purification, fragment molecule 5 (C) is obtained. 20 H 13 3.45 g of Cl3N2O4 was obtained, with a yield of 77.58%. Fragment molecule 6 was analyzed by NMR and mass spectrometry; the results are shown below. Figure 1 and Figure 3 .

[0090] S2: Fragment molecule 6 (2.000 g, 4.43 mmol), anhydrous zinc chloride (226.29 mg, 1.66 mmol), and DBU (138.84 mg, 553.48 μmol) were added to a 100 mL double-necked round-bottom flask containing 35 mL of anhydrous n-pentanol. The reaction was carried out at 150 °C for 15–24 h under a nitrogen atmosphere. After the reaction solution cooled to room temperature, it was poured into an appropriate amount of n-hexane and filtered to obtain a green solid. The crude product was vacuum dried, dissolved in a small amount of dichloromethane, and then purified by silica gel column chromatography using dichloromethane / methanol (40:1, v / v) as the developing solvent. After evaporating the solvent, a green powdery solid was obtained. After purification, compound 6 (C) was obtained. 96 H84 Cl 12 N8O 16 Zn (0.968 g), yield 41.72%. Compound 6 was subjected to NMR and mass spectrometry analysis; the results are shown below. Figure 2 and Figure 4 .

[0091] Test case

[0092] Test Example 1: Ultraviolet Absorption

[0093] The compounds synthesized in Examples 1-6 were accurately weighed to yield 0.0065 g, 0.0065 g, 0.0070 g, 0.0081 g, 0.0073 g, and 0.0084 g, respectively, and 2 mL solutions with a concentration of 5 mmol / L were prepared using PGMEA as the solvent. These solutions were then diluted to obtain 4 μmol / L solutions for absorption spectroscopy analysis. The test results are shown below. Figure 5 All tests were conducted at 25°C.

[0094] from Figure 5 As can be seen, the six dyes exhibit two typical strongest absorption peaks: the Q band (600-750 nm) and the B band (320-400 nm). Compounds 1, 2, 3, and 5 show maximum absorption wavelengths in the Q band region at 680 nm, exhibiting a blue-green color, while compounds 4 and 6 show absorption at around 700 nm, exhibiting a green color. Furthermore, all six dyes show no absorption in the 450–550 nm range and exhibit uniform transmission, meeting the requirements of color filters for green photoresist.

[0095] Test Example 2: Dye Solubility

[0096] Excess dye was weighed and added to the solvent PGMEA. The solution was then sonicated for 10 minutes using an ultrasonic cleaner. After standing at 20°C for 24 hours, the solution was filtered three times to obtain a saturated solution, which was then weighed. Finally, the solution was baked at 180°C for 30 minutes to evaporate the solvent. The resulting solid was the weight of the dissolved solid in the volatile solvent. The solvent weight and solute weight were then obtained, and the solubility was calculated. The results are shown in Table 1.

[0097] Table 1 Solubility

[0098] compound Solubility (gper100g) 1 21.01 2 17.28 3 13.90 4 23.06 5 12.40 6 12.67

[0099] Since phthalocyanines are planar macrocyclic conjugated systems composed of four isoindole units, unsubstituted metal phthalocyanines are almost insoluble in water and organic solvents, and the phthalocyanine matrix itself has very poor solubility. This application introduces ester and ether-containing side chains onto the phthalocyanine matrix, improving its solubility. It exhibits good solubility in the commonly used solvent PGMEA. Table 1 shows that the dyes have solubility greater than 5 wt% in industrial solvents. The phenoxy derivatives containing ester groups increase the steric hindrance between dye molecules, weakening intermolecular aggregation and resulting in better solubility of these dyes.

[0100] Test Example 3: Thermal stability of dyes

[0101] In the process of manufacturing color filters, multiple post-baking processes are required. Therefore, it is necessary to ensure that the dye can withstand the temperature of the manufacturing process (230°C) without decomposition, and that the mass loss is less than 5 wt% when maintained at 230°C for 30 minutes.

[0102] To test the thermal stability of the dyes in Examples 1-6, thermogravimetric analysis was performed after incubation at 230°C for 30 min. The results are as follows: Figure 6 As shown.

[0103] from Figure 6 It can be seen that the mass loss of all six dyes after being held at 230℃ for 30 min was less than 5 wt%. The weight loss rates of compounds 1, 2, 3, 4, 5, and 6 after baking at 230℃ for 30 min were 2%, 2%, 3%, 1%, 2%, and 1%, respectively, meeting industrial requirements (weight loss rate < 5%). These results indicate that the dyes possess good thermal stability, and the introduction of substituents does not significantly reduce their heat resistance. Generally, dyes with strong intermolecular forces exhibit good thermal stability. Further molecular structure modification can adjust the dispersion of dye molecules in photoresist and their compatibility with the resin matrix, demonstrating potential application prospects.

[0104] Based on the data from test examples 1-3 above, it can be seen that compound 4 has high solubility in PGMEA, good thermal stability, and its UV-Vis absorption spectrum meets the requirement of uniform transmission in the 450–550 nm range. Therefore, this dye molecule was selected to prepare a dye evaluation film, and the following tests were conducted.

[0105] Test Example 4: Dye Evaluation of the Thermal Stability of the Film

[0106] Accurately weigh 0.06 g of the dye synthesized in Example 4, 0.1 g of photoinitiator, 1.0 g of resin, and 0.03 g of leveling agent. Dissolve them completely in 1.8 g of PGMEA, filter through a 0.2 μm filter membrane, and then coat the film. Adjust the temperature to 200℃ and bake for 30 min. Use a high-precision color analyzer to test the transmission spectrum of the dye film before and after baking, and calculate the color difference of the film before and after baking. The calculation results are shown in Table 2.

[0107] Table 2 Color difference of thin film

[0108]

[0109] The smoothness of the film surface was observed using an optical microscope; the test results are shown in [reference needed]. Figure 7 .

[0110] Combine Table 2 and Figure 7 As can be seen from the spectrometer, no large particles aggregated on the surface of the prepared evaluation film, indicating that the surface is relatively uniform. Table 2 shows that the color difference is less than 3, with minimal change; the transmission spectrum before and after baking showed no significant change, indicating that the dye evaluation film is uniform and has good thermal stability.

[0111] Test Example 5: Evaluation of the photostability of the film using dyes

[0112] According to the requirements of GB / T 31370.2-2015, an LED lamp with a wavelength of 365nm was selected, and the distance between the dye film and the LED lamp was adjusted so that the light density received by the dye film was 20mW / cm². 2 The irradiation time was 5 minutes, resulting in a light density of 20 mW / cm² on the dye film. 2 The irradiation time was 5 minutes, and no obvious color change was observed. The transmission spectra of the exposed and unexposed dye films before and after irradiation were measured using a high-precision color analyzer. The test results were submitted to [the relevant authority / initiative]. Figure 8 .

[0113] from Figure 8 It can be seen that its maximum transmittance has not changed much, remaining close to 90%, indicating that the dye evaluation film has good photostability.

[0114] Test Example 6: Evaluation of the solvent resistance of the film by dye

[0115] The prepared dye film was immersed in the commonly used solvent PGMEA for 15 minutes. The surface morphology changes were measured using an atomic force microscope; the test results are shown below. Figure 9 .

[0116] from Figure 9 As can be seen, the roughness before and after immersion is 0.501 nm and 0.614 nm, respectively, with no significant change. Measuring the UV absorption of the immersion solution, after immersion for 15 minutes, no obvious characteristic absorption peak of dye molecules was observed, proving that dye molecules did not precipitate. Therefore, this dye evaluation film exhibits good solvent resistance, and the introduction of polymerizable active groups improves its solvent resistance, potentially enabling the fabrication of all-dye-based color filters.

[0117] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A class of phthalocyanine dyes containing polymerizable groups, characterized in that, It has any of the following structures, 、 、 、 、 、 、 、 。 2. The type of phthalocyanine dye containing polymerizable groups according to claim 1, characterized in that, The phthalocyanine dye containing polymerizable groups has an ultraviolet absorption wavelength of 650-710 nm and a solubility greater than 10%.

3. The method for synthesizing a type of phthalocyanine dye containing polymerizable groups according to claim 1 or 2, characterized in that, Includes the following steps: S1: A phthalonitrile having the structure shown in general formula IV is combined with an R-containing... 1-5 The substituted phenol is added to the first organic solvent and mixed evenly. Then, under the protection of an inert gas, an inorganic salt catalyst is added, and the reaction is carried out at 0-80℃ for 4-16 hours to obtain the intermediate. S2: Mix the intermediate obtained in step S1 and MCl2 evenly in a second organic solvent, add an organic catalyst under inert gas protection, and react at 130-200℃ for 14-24 h to obtain the target product. The reaction process is as follows: The selection of X1, X2, X3, X4, R1, R2, R3, R4, R5, M, R, r, Y, and y is the same as the corresponding structure of the phthalocyanine dye in claim 1.

4. The synthesis method according to claim 3, characterized in that, In step S1, X is included. 1-4 Substituent phthalonitriles and those containing R 1-5 The molar ratio of substituted phenols is 1:1-4; In step S2, the molar ratio of the intermediate obtained in step S1 to MCl2 is 4:1-2.

5. The synthesis method according to claim 3, characterized in that, In step S1, the first organic solvent is selected from one or a mixture of several of acetonitrile, toluene, DMF, and DMSO; The inorganic salt catalyst is selected from one or a mixture of potassium carbonate, sodium carbonate, and potassium acetate.

6. The synthesis method according to claim 3, characterized in that, In step S2, the second organic solvent is selected from alcohols with a boiling point greater than 130°C; the organic catalyst is selected from strong basic catalysts.

7. The synthesis method according to claim 5, characterized in that, The second organic solvent is selected from one or more of pentanol, hexanol, quinoline, and hexanediol.

8. The application of a class of phthalocyanine dyes containing polymerizable groups according to claim 1 or 2, characterized in that, The application of the polymerizable phthalocyanine dyes mentioned above in color filters.

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