Highly soluble phthalocyanine dyes, method for their synthesis and color filters

Abstract

The application discloses a kind of high solubility phthalocyanine dyes and its synthesis method and color filter, belong to display technical field.High solubility phthalocyanine dye is selected branched structure is more special, increase its solubility for color photoresist from multiple directions.This kind of dye shows extraordinary solubility in propylene glycol monomethyl ether acetate (PGMEA) It can reach about 15-50wt.%, and suitable for a variety of metal phthalocyanine.In addition, this dye shows excellent spectral properties and thermal stability.Therefore this dye meets the application in color filter, and can further self-regulation color gamut of color filter.

Description

Technical Field

[0001] This invention relates to the field of display technology, and in particular to a class of highly soluble phthalocyanine dyes, their synthesis methods, and color filters. Background Technology

[0002] Currently, the mainstream flat panel display product is the LCD (Liquid Crystal Display). LCDs dominate the market due to their significant advantages, such as strong anti-interference capabilities, low power consumption, high cost-effectiveness, and minimal operating voltage. Furthermore, the application of LCDs in service industries, transportation, and education is continuously expanding, demonstrating enormous future growth potential. Currently, LCD mainly refers to Thin Film Transistor LCD, where color filters are a crucial source of image color. Color filters involve red, green, and blue pixels on a glass substrate. When light passes through these pixels, light is emitted in the three primary colors, and these colors are mixed to achieve the desired color display effect.

[0003] Color filters are composed of fine, strip-shaped filter segments of two or more different hues arranged parallel or interlaced on the surface of a transparent substrate such as glass, or by arranging these fine filter segments in a fixed longitudinal and transverse pattern. Currently, the coloring layer of color filters is mainly composed of pigments. Coloring methods for the coloring layer include pigment dispersion, inkjet printing, electrolytic deposition, and printing. A common method is pigment dispersion, where pigments (average particle size less than 0.1 μm) are uniformly dispersed in a transparent polymer and formed into red, green, and blue (RGB) patterns through various processes.

[0004] In the manufacture of green filters, various phthalocyanine compounds are generally used as colorants. Phthalocyanine (PC) is a large conjugated system compound with 18 electrons. Due to its structural diversity and strong intermolecular interactions, phthalocyanines possess rich photophysical / photochemical properties and remarkable stability. Phthalocyanines are multi-substituted and multi-metallic types, with a wide variety of molecules. Therefore, phthalocyanines have a wide range of applications in various fields. Phthalocyanine dyes generally have good thermal stability; however, the dyes used in color filters must be soluble in the solvents used, such as PGMEA. Traditionally, the industry requires dyes to have a solubility in PGMEA exceeding 5 wt.%. Due to intermolecular interactions caused by their structure, phthalocyanines exhibit relatively low solubility in some solvents. Summary of the Invention

[0005] To address the problem of poor solubility of phthalocyanine dyes in propylene glycol monomethyl ether acetate solvent in existing technologies, this invention provides a phthalocyanine dye with high solubility and high photothermal stability for use as a pigment replacement in color photoresists, and for application in color filters and self-regulating color gamut of color filters.

[0006] To achieve the above objectives, the technical solution of the present invention is: a highly soluble phthalocyanine dye, wherein the highly soluble phthalocyanine dye has the structure shown in general formula I:

[0007]

[0008] Where M is selected from divalent, trivalent or tetravalent metals, halide metals or nonmetals, and X is a halogen atom; a+b+c=16, 1≤a≤16, 0≤b≤15, 0≤c≤15;

[0009] R1 has the structure shown in Formula II;

[0010]

[0011] In Formula II, R3 is selected from n-alkyl, isoalkyl, tertiary alkyl, straight-chain alkyl or branched alkyl containing ether bonds, or olefin having 2 to 10 carbons.

[0012] R2 is selected from hydrogen, an alkyl group having 1-18 carbons, a carboxyl group having 1-18 carbons, an ether group having 1-18 carbons, an ester group having 1-18 carbons, a hydroxyalkyl group having 1-18 carbons, an amino group having 1-18 carbons, an olefin group having 2-18 carbons, an aldehyde group having 1-18 carbons, or a structure shown in Formula III.

[0013]

[0014] In Formula III, R4, R5, R6, R7, and R8 may be different or the same, and each of R4, R5, R6, R7, and R8 is independently selected from hydrogen, alkyl groups having 1-18 carbons, carboxyl groups having 1-18 carbons, ether groups having 1-18 carbons, ester groups having 1-18 carbons, hydroxyalkyl groups having 1-18 carbons, amino groups having 1-18 carbons, aldehyde groups having 1-18 carbons, olefin groups having 2-18 carbons, and phenyl groups having 1-10 carbons.

[0015] Furthermore, X is a halogen atom, preferably bromine or chlorine;

[0016] M is a divalent metal; preferably, M is Zn. 2+ Cu 2+ Co 2+ Mg 2+ In 2+ Fe 2+ No 2+ Mn 2+ Cd 2+ or Sn 2+ ;

[0017] R3 is selected from n-alkyl, isoalkyl, tertiary alkyl, or olefin with 1-10 carbon atoms; R2 is selected from hydrogen or the structure shown in Formula III;

[0018] R4, R5, R7, and R8 are preferably derived from hydrogen, ether bonds having 1-18 carbons, olefins having 2-18 carbons, or ester groups having 1-18 carbons.

[0019] R6 is preferably derived from an alkyl group having 1-18 carbons, a carboxyl group having 1-18 carbons, an ether group having 1-18 carbons, an ester group having 1-18 carbons, an olefin group having 2-18 carbons, a hydroxyalkyl group having 1-18 carbons, an amino group having 1-18 carbons, or an aldehyde group having 1-18 carbons.

[0020] Furthermore, R1 is selected from one of the following structures:

[0021]

[0022] A method for synthesizing highly soluble phthalocyanine dyes includes mixing the compound shown in formula Y-1 or the compound shown in formula Y-2 with the chloride of metal M in an organic solvent, adding a catalyst under the protection of an inert gas, reacting at 120-200℃ for 12-36 h, and purifying to obtain the highly soluble phthalocyanine dye shown in I.

[0023] The formula Y-1 is: The formula Y-2 is:

[0024] Preferably, the branch of Y-1 or Y-2 should have at least one R1, and the remaining branches can be fluorine, chlorine, bromine, iodine or R2;

[0025] The purification method involves removing the reaction solvent and then separating and purifying the crude product by column chromatography. The developing solvent is selected from a mixture of dichloromethane and methanol or a mixture of dichloromethane and ethyl acetate.

[0026] Furthermore, the organic solvent is selected from fatty alcohols or alcohol ethers, preferably from n-pentanol, n-butanol, and n-hexanol. R1 can undergo transesterification, and R2 can also undergo transesterification if it has an ester group.

[0027] Furthermore, the catalyst is selected from 1,8-diazabicycloundec-7-ene or cesium carbonate, preferably 1,8-diazabicycloundec-7-ene (DBU).

[0028] Furthermore, the molar ratio of the compound represented by formula Y-1 or the compound represented by formula Y-2 to the chloride of metal M is 4:1-2.

[0029] Furthermore, the chloride of the metal M is selected from at least one of zinc chloride, copper chloride, cobalt chloride, magnesium chloride, or indium trichloride, and even further, the chloride of the metal M is zinc chloride or copper chloride.

[0030] A color filter includes a pigment, the pigment comprising a highly soluble phthalocyanine dye. A color photoresist containing the highly soluble phthalocyanine dye is applied to the color filter to control the color gamut of the color filter. The projection wavelength after the color filter is 450-550 nm. The color difference of the phthalocyanine dye in the photothermal stability test of the color filter is small.

[0031] In summary, the present invention has the following beneficial effects:

[0032] First, the structure of this application is diverse. By introducing different branches, the spectral properties, color properties, chemical and physical properties of the dye can be controlled. According to the test, the highest peak of ultraviolet absorption wavelength is 600-750nm, and the molar extinction coefficient is relatively high.

[0033] Secondly, the dye molecule of this application only needs to contain the main branch R1 to greatly increase the solubility of phthalocyanine dye molecules in propylene glycol methyl ether acetate. According to the test, its solubility can reach 15-50 wt.%, and the molecule also has good thermal stability.

[0034] Third, because the dye molecules in this application have extremely high solubility, the proportion of dye in the formulation can be controlled when preparing color photoresist, thereby controlling the color gamut of the color filter without adding other colorants.

[0035] Fourth, the dye molecules of this application exhibit good photothermal stability, minimal change in transmittance, and small color difference when used in color filters.

[0036] Fifth, the dye molecules of this application not only have high solubility and good thermal stability, but the phthalocyanine molecules of this application have different branches, including phthalocyanine dyes from blue to green. According to the test, the projection wavelength for color filters is 450-550nm. Attached Figure Description

[0037] 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.

[0038] Figure 1 These are the UV absorption spectra of compounds 1-6 in propylene glycol methyl ether acetate;

[0039] Figure 2 These are the ultraviolet absorption spectra of compound 1 in different solvents;

[0040] Figure 3 These are thermal stability test graphs for compounds 1-6;

[0041] Figure 4 This is a transmission diagram of compounds 1-3 using filters;

[0042] Figure 5 This is a graph showing the photothermal stability of compound 1;

[0043] Figure 6 This is the color coordinate diagram of the evaluation film for dyes of compounds 1-3. Detailed Implementation

[0044] The present invention will be further described below with reference to the embodiments, but it should be understood that the scope of protection of the present invention is not limited to the embodiments.

[0045] In this invention, unless otherwise explicitly stated, percentages and contents are all by mass. Unless otherwise specified, the experimental methods used are conventional methods, and the materials and reagents used are commercially available.

[0046] The terms used in this article have the following meanings.

[0047] The term "alkyl" as used in this invention includes straight-chain alkyl and branched-chain alkyl.

[0048] The instruments and equipment used in the embodiments are as follows:

[0049] Avance II (400MHz) nuclear magnetic resonance spectrometer (Bruker, Germany); MALDI-TOF matrix-assisted laser desorption / ionization time-of-flight mass spectrometer (Bruker, Germany); Cary 60 UV-Vis spectrophotometer (Agilent Technologies, USA); TGA / DSC 3+ (Mettler, Switzerland); KW-4T gel homogenizer (Institute of Microelectronics, Chinese Academy of Sciences, China); CKX53 optical microscope (Olympius, Japan); organic elemental analyzer (Bruker, Germany); multichannel spectrophotometer (Otsuka Electronics, Japan).

[0050] The highly soluble phthalocyanine dyes represented by general formula I are described in detail below with reference to examples.

[0051]

[0052] Among them, R1 has the structure shown in Formula II;

[0053]

[0054] In Formula II, R3 is selected from n-alkyl, isoalkyl, tertiary alkyl, straight-chain alkyl or branched alkyl containing ether bonds, or olefin having 2 to 10 carbons.

[0055] The following are specific examples of substituents represented by general formula II, but the present invention is not limited to these specific examples.

[0056]

[0057] The present invention can be synthesized from the compound represented by general formula II by the method described below.

[0058] Preparation of compound 1.1

[0059]

[0060] First, weigh 1 g (5.78 mmol, 1.00 eq) of 4-nitrophthalonitrile and ethyl 2-(4-hydroxyphenoxy)propionate (1.21 g, 5.78 mmol, 1.00 eq). Then, dissolve the weighed starting materials in a flask containing anhydrous N,N-dimethylformamide (30 mL) and add anhydrous potassium carbonate (1.24 g, 9.00 mmol, 1.55 eq). Under nitrogen protection, stir the mixture in an oil bath at 80 °C for 10 h. After the reaction is complete, pour the solution into ice water (100 mL) with vigorous stirring. Finally, discard the solution, leaving a gel-like substance. Using dichloromethane as the eluent, collect the pure product by silica gel column chromatography, 1.646 g, yield 84.82%.

[0061] Structural verification data: 1 H NMR (400MHz, DMSO-d6) δ8.07(dd,J=8.7,1.6Hz,1H),7.69(t,J=2.0Hz,1H),7.31(dt,J=8.8,2.0Hz,1H),7.19–7.09(m,2H),7.00(dd,J=9.0 ,1.6Hz,2H),4.98(qd,J=6.7,1.5Hz,1H),4.16(qtd,J=7.4,6.2,3.8,1.9Hz,2H),1.53(dd,J=6.8,1.6Hz,3H),1.19(td,J=7.1,1.5Hz,3H).

[0062] HRMS): m / z[M+H] + Calculated value: 336.11; Detected value: 359.03 ([M+Na]) + ).

[0063] Preparation of compound 1.2

[0064]

[0065] Ethyl 2-(4-hydroxyphenoxy)propionate (1.21 g, 5.78 mmol, 1.00 eq), 3-nitrophthalonitrile (1 g, 5.77 mmol, 1.00 eq), and anhydrous potassium carbonate (1.24 g, 9.00 mmol, 1.55 eq) were used. The weighed starting material was dissolved in a flask containing anhydrous N,N-dimethylformamide (30 mL). Under nitrogen protection, the flask was stirred in an oil bath at 80 °C for 10 h. After the reaction was complete, the solution was poured into ice water (100 mL) with vigorous stirring. Finally, the solution was discarded, leaving a gel-like substance. The pure product, 1.699 g (87.6%), was collected by silica gel column chromatography using dichloromethane as the eluent.

[0066] Structural verification data: 1 H NMR(400MHz,Chloroform-d)δ7.54(dd,J=8.7,7.7Hz,1H),7.43(dd,J=7.7,1.0Hz,1H),7.07–6.99(m,3H),6.99 –6.90(m,2H),4.74(q,J=6.8Hz,1H),4.25(qd,J=7.1,1.5Hz,2H),1.65(d,J=6.8Hz,3H),1.28(t,J=7.1Hz,3H).

[0067] HRMS): m / z[M+H] + Calculated value: 336.11; Detected value: 359.02 ([M+Na]) + ).

[0068] Preparation of compound 1.3

[0069]

[0070] Ethyl 2-(4-hydroxyphenoxy)propionate (0.79 g, 3.76 mmol, 1.00 eq), 3,4,5,6-tetrachlorobenzene-1,2-dicarboxynitrile (1 g, 3.76 mmol, 1.00 eq), and anhydrous potassium carbonate (0.78 g, 5.64 mmol, 1.55 eq) were used. The weighed reagents were dissolved in a flask containing N,N-dimethylformamide (30 mL). Under nitrogen protection, the flask was stirred in an oil bath at 80 °C for 10 h. After the reaction was complete, the solution was poured into ice water (100 mL) with vigorous stirring. Finally, the solution was discarded, leaving a gel-like substance. Column chromatography was performed using a 2.5:1 mixture of dichloromethane / petroleum ether eluent, and 0.927 g of the product was collected, with a yield of 56.2%.

[0071] Structural verification data: 1H NMR(400MHz,Chloroform-d)δ6.89–6.81(m,2H),6.78–6.67(m,2H),4.74–4.60(m,1H) ,4.22(qt,J=7.1,1.7Hz,2H),1.61(dd,J=6.8,1.4Hz,3H),1.25(td,J=7.1,1.4Hz,3H).

[0072] HRMS): m / z[M+H] + Calculated value: 437.99; Detected value: 460.94 ([M+Na]) + ).

[0073] Preparation of compound 1.4

[0074]

[0075] First, weigh 1 g (5.78 mmol, 1.00 eq) of 4-nitrophthalonitrile and 0.71 g (5.78 mmol, 1.00 eq) of p-ethylphenol. Then, dissolve the weighed reagents in a flask containing anhydrous N,N-dimethylformamide (30 mL) and add anhydrous potassium carbonate (1.24 g, 9.00 mmol, 1.55 eq). Under nitrogen protection, stir the flask in an oil bath at 80 °C for 10 h. After the reaction is complete, pour the solution into ice water (100 mL) with vigorous stirring. Finally, discard the solution, leaving a gel-like substance. Collect the pure product by silica gel column chromatography using dichloromethane as the eluent. 1.225 g of product was collected, with a yield of 85.10%.

[0076] Structural verification data: 1 H NMR (400MHz, DMSO-d6) δ8.07(dd,J=8.7,1.6Hz,1H),7.69(t,J=2.0Hz,1H),7.31(dt,J=8.8,2.0Hz,1H),7.19–7.09(m,2H),7.00(dd,J=9.0 ,1.6Hz,2H),4.98(qd,J=6.7,1.5Hz,1H),4.16(qtd,J=7.4,6.2,3.8,1.9Hz,2H),1.53(dd,J=6.8,1.6Hz,3H),1.19(td,J=7.1,1.5Hz,3H).

[0077] HRMS): m / z[M+H] + Calculated value: 336.11; Detected value: 359.03 ([M+Na]) + ).

[0078] The highly soluble phthalocyanine dye represented by general formula I can be synthesized by the method described below.

[0079] Example 1

[0080] Preparation of compound 1:

[0081]

[0082] Compound 1.1 (1.68 g, 5.00 mmol, 3.03 eq), anhydrous zinc chloride (0.22 g, 1.65 mmol, 1.00 eq), and DBU (0.50 g, 3.30 mmol, 2.00 eq) were added to 1-pentanol (50 mL), and the mixture was heated to 150 °C and stirred for 12 hours under a nitrogen atmosphere. The crude product was precipitated by pouring the reaction solution into methanol (100 mL). After filtering the mixture, the collected solid was dried under vacuum. The solid was loaded onto a silica gel column with a 20:1 eluent of dichloromethane / methanol. When the crude product eluted from the column, the green band was collected and dried to give a green solid in 48.2% yield, which was named compound 1.

[0083] Structural verification data: 1 H NMR(400MHz,DMSO-d6)δ8.80–8.51(m,4H),8.32–8.09(m,4H),7.66–7.36(m,12H),7.26–7.09(m,8H),5.1 7–5.03(m,4H),4.29–4.08(m,8H),1.73–1.52(m,20H),1.28(dd,J=8.2,4.6Hz,16H),0.89–0.79(m,12H).

[0084] MALDI-TOF MS: Calculated m / z value: 1576.56; Detected value: 1577.6 ([M+H]) + ).

[0085] Example 2

[0086] Preparation of compound 2

[0087]

[0088] The only difference from Example 1 is that compound 1.1 was replaced with compound 1.2 (1.68 g, 5.00 mmol, 3.03 eq).

[0089] When the crude product was eluted from the column, the green band was collected and dried to give a green solid with a yield of 22.4%, which was designated as compound 2.

[0090] Structural verification data:1 H NMR(400MHz,DMSO-d6)δ8.81–6.70(m,28H),5.14–4.83(m,4H),4.32–3.97(m ,8H),1.58(dt,J=52.3,6.6Hz,20H),1.34–1.18(m,16H),0.90–0.76(m,12H).

[0091] MALDI-TOF MS: Calculated m / z value: 1576.56; Detected value: 1577.6 ([M+H]) + ).

[0092] Example 3

[0093] Synthesis of compound 3:

[0094]

[0095] The only difference from Example 1 is that compound 1.1 was replaced with compound 1.3 (2.2 g, 5.00 mmol, 3.03 eq).

[0096] When the crude product was eluted from the column, the green band was collected and dried to give a green solid with a yield of 67.4%, which was designated as compound 3.

[0097] Structural verification data: 1 H NMR(400MHz,DMSO-d6)δ6.95(d,J=56.7Hz,16H),4.90(d,J=13.8Hz,4H),4.05(s, 7H), 1.62–1.35 (m, 20H), 1.20 (d, J=19.2Hz, 16H), 0.78 (dd, J=15.5, 8.5Hz, 12H).

[0098] MALDI-TOF MS: m / z calculated value: 1990.08; detected value: 1990.1.

[0099] Example 4

[0100] Synthesis of Compound 4

[0101]

[0102] The only difference from Example 1 is that anhydrous copper chloride (0.22 g, 1.65 mmol, 1.00 eq) was used instead of anhydrous zinc chloride.

[0103] The solid was loaded onto a silica gel column using a 60:1 mixture of dichloromethane / MeOH eluent. As the crude product eluted from the column, the greenish-blue band was collected and dried to give a blue solid in 44.3% yield, which was named compound 4.

[0104] Structural confirmation data: MALDI-TOF MS: calculated m / z value: 1990.08; detected value: 1990.1.

[0105] Elemental analysis: Calculated values: C, 67.01; H, 5.62; N, 7.10; O, 16.23%. Detected values: C, 67.41; H, 5.64; N, 7.11; O, 16.34%.

[0106] Example 5

[0107] Synthesis of Compound 5

[0108]

[0109] The only difference from Example 2 is that anhydrous copper chloride (0.22 g, 1.65 mmol, 1.00 eq) was used instead of anhydrous zinc chloride.

[0110] The solid was loaded onto a silica gel column using a 60:1 mixture of dichloromethane / MeOH eluent. As the crude product eluted from the column, the greenish-blue band was collected and dried to give a blue solid in 62.4% yield. This product was named compound 5.

[0111] Structural confirmation data: MALDI-TOF MS: calculated m / z value: 1575.56; detected value: 1575.6.

[0112] Elemental analysis: Calculated values: C, 67.01; H, 5.62; N, 7.10; O, 16.23%. Detected values: C, 67.07; H, 5.42; N, 7.10; O, 16.60%.

[0113] Example 6

[0114] Synthesis of Compound 6

[0115]

[0116] The only difference from Example 3 is that anhydrous copper chloride (0.22 g, 1.65 mmol, 1.00 eq) was used instead of anhydrous zinc chloride.

[0117] The solid was loaded onto a silica gel column using a 60:1 mixture of dichloromethane / MeOH eluent. As the crude product eluted from the column, the greenish-blue band was collected and dried to give a blue solid with a yield of 62.4%. This product was named compound 6.

[0118] Structural confirmation data: MALDI-TOF MS: calculated m / z value: 1989.08, detected value: 1989.4.

[0119] Elemental analysis: Calculated values: C, 53.10; H, 3.85; N, 5.63; O, 12.86%. Detected values: C, 53.91; H, 3.81; N, 5.80; O, 13.56%.

[0120] Example 7

[0121] Synthesis of Compound 7

[0122]

[0123] Compound 1.4 (1.24 g, 5.00 mmol, 3.03 eq), anhydrous zinc chloride (0.22 g, 1.65 mmol, 1.00 eq), and DBU (0.50 g, 3.30 mmol, 2.00 eq) were added to 1-pentanol (50 mL), and the mixture was heated to 150 °C and stirred for 12 hours under a nitrogen atmosphere. The crude product was precipitated by pouring the reaction solution into methanol (100 mL). After filtering the mixture, the collected solid was dried under vacuum. The solid was loaded onto a silica gel column with a 20:1 eluent mixture of dichloromethane and methanol. When the crude product eluted from the column, the green band was collected and dried to give compound 7 as a green solid. Yield: 48.2%.

[0124] Performance testing of compounds 1-7

[0125] 1. Ultraviolet-Visible Absorption Spectroscopy Measurement

[0126] The dyes of compounds 1-6, in their solid powder state, were accurately weighed using a 0.01 g / L balance and dissolved in PGMEA to prepare a 5.0 mmol / L PGMEA dye stock solution in a brown sample bottle, which was then stored at 4°C for later use. The dyes synthesized in Examples 1-6 were then subjected to UV-Vis absorption spectroscopy measurements.

[0127] Test method: 6.0 μL of the dye stock solution was measured using a micropipette and dissolved in a quartz cuvette containing 3 mL of the test solvent. The mixture was thoroughly mixed to obtain a final dye concentration of 10.0 μmol / L, which was then used for absorption spectroscopy testing. The test results are shown in the figure below. Figure 1 All tests were performed at room temperature.

[0128] Furthermore, the UV absorption spectra of compounds 1-6 in other solvents were tested using the above-described test method. Solutions in various solvents, including N,N-dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), 3-methoxybutyl ester (3MBA), cyclohexanone (CYC), and PGMEA, were at a concentration of 10 μmol / L. The test results are as follows: Figure 2 All tests were performed at room temperature.

[0129] Depend on Figure 1 As can be seen, the Q band (600-700 nm) and B band (300-400 nm) represent typical spectral regions for examining phthalocyanine absorption. The observed absorption peaks are caused by π-electronic transitions within the PC structure. Specifically, the Q-band absorption peak is generated by transitions from the highest occupied molecular orbital (HOMO) level to the lowest unoccupied molecular orbital (LUMO) level, while the B-band absorption peak is a result of transitions from deeper π levels to the LUMO level. Each prepared dye exhibits maximum absorption between 600-750 nm.

[0130] Substituent effects significantly influence the maximum absorption wavelength of the dyes. Furthermore, the molar extinction coefficients of all six dyes exceed 45000 L·mol⁻¹. -1 ·cm -1 This indicates that the synthesized series of dyes possess significant light absorption capabilities. The maximum absorption peaks of compounds 1-6 in PGMEA are located at 678, 692, 694, 678, 696, and 642 nm, respectively. The phthalocyanine containing Cl exhibits a red shift compared to other substituted metal phthalocyanines without Cl at the same position. Since the α-position substitution shows a red shift compared to the β-position, compounds 1, 2, 3, and 5 show greater potential for application in color filters based on color observation.

[0131] Depend on Figure 2 It can be seen that the dye exhibits different spectra in different solvents, but the position of the main absorption peak hardly changes, which shows the potential of compound 1 for use in color filters.

[0132] 2. Solubility test

[0133] The solubility of the dyes was assessed by ultrasonic treatment of 0.6 g of each of compounds 1-6 with 1.00 g of PGMEA solvent for 5 minutes. The mixtures were allowed to stand at room temperature (25°C) for 24 hours and then filtered three times through a filter membrane. The filtrate was baked at 180°C for 30 minutes to evaporate the solvent, and the solubility of the dyes was determined by weighing. The solubility values ​​are shown in Table 1.

[0134] Table 1 Solubility

[0135] compound 1 2 3 4 5 6 7 Solubility (wt.%) 37.2 33.5 40.8 26.4 31.2 15.0 1.2

[0136] Table 1 shows that the solubilities of compounds 1-6 in PGMEA are 37.2, 33.5, 40.8, 26.4, 31.2, and 15.0 wt.%, respectively, significantly exceeding the industrial requirement of 5 wt.%. Compound 7, lacking the R1 branch, exhibits a solubility of only 1.2 wt.%. This indicates that the selection of the R1 branch is excellent; the branch structure is similar to that of PGMEA, thus improving solubility. Based on solubility data, compounds 1-5 show greater potential for application in color filters.

[0137] 3. Thermal stability test

[0138] Phthalocyanine molecules exhibit stacking in solids, which contributes to their excellent heat and light resistance. Nevertheless, the presence of certain substituents in phthalocyanine molecules increases their size and steric hindrance, thus hindering molecular accumulation. This translates to increased solubility, but may reduce durability.

[0139] To remove residual moisture and organic solvents, the synthesized dye was heated from room temperature to 100°C and held for 10 minutes under an argon atmosphere. The temperature was then increased to 230°C and held for 30 minutes, followed by a further increase at a rate of 20°C / min until a final temperature of 350°C was reached. Test results are available in [link to test results]. Figure 3 .

[0140] from Figure 3 It can be seen that the weight loss of all six compounds after holding at 230°C for 30 minutes was less than 5 wt.%. Specifically, the weight losses of compounds 1-6 were 0.96, 2.46, 2.68, 0.63, 0.5, and 0.53 wt.%, respectively, meeting the industrial requirement of less than 3% for color filters. This indicates that this type of structure maintains good thermal stability while improving solubility.

[0141] In another typical embodiment of this application, a color filter is provided, comprising a pigment including the aforementioned highly soluble phthalocyanine dye. Because the solubility of the highly soluble phthalocyanine dye in this application is improved, it can be uniformly dispersed in the PGMEA solvent during the preparation of the color filter, thereby achieving uniform dispersion in the resulting filter and improving the filtering effect.

[0142] The dyes synthesized in Examples 1-6 were then tested in relation to optical filters:

[0143] 1. Spectral properties and photothermal stability testing

[0144] Test method: 0.055 g of highly soluble phthalocyanine dye, 0.525 g of PGMEA, and 0.675 g of resin were accurately weighed and thoroughly mixed by ultrasonic treatment for 10 minutes to prepare a dye solution. The dye solution was then spin-coated onto a 5 × 5 cm glass substrate at 1000 rpm to prepare a dye evaluation film. The film thickness was measured using a step profiler. The film thickness of compounds 1-3 was approximately 2 μm.

[0145] The film was pre-baked at 120°C for 90 seconds and then post-baked at 230°C for 30 minutes. The transmittance and color characteristics of the film were measured using a multichannel photodetector (MCPD). The test results are shown below. Figure 4 .

[0146] from Figure 4 It can be seen that the maximum transmittance values ​​of compounds 1-3 are at 503, 525, and 525 nm, respectively, and the transmittance is greater than 90%. This indicates that compounds 1-3 have the potential to be used in color filters.

[0147] The thermal stability of the film was evaluated by placing the film of compound 1 in an oven at 230°C for 30 minutes and measuring its color characteristics after cooling. It was then baked again for an additional 30 minutes before another round of color characteristic measurements after cooling. The color difference (ΔE) was calculated from the color coordinate values ​​obtained before and after baking. -ab Using an LED light with a wavelength of 365nm at 20mW / cm² 2 The dye evaluation film was irradiated with light density for 5 minutes. Then, ΔE was measured before and after irradiation. -ab To evaluate the photostability of the film, the test results are shown in [link to test results]. Figure 5 And Table 2.

[0148] Table 2 Stability data for Compound 1

[0149] L a b x y <![CDATA[ΔE -ab ]]> 1-Baking 81.257 -47.357 -9.185 0.22283 0.32554 1- Additional baking 82.143 -47.25 -9.5225 0.22314 0.3246 0.954123 1-Light 80.902 -47.006 -10.488 0.22079 0.3221 1.591165

[0150] For commercial viability, the ΔE of the color filter film... -ab It should be less than 3. From Figure 5 It can be seen that the color difference of compound 1 is less than 3, and the transmittance does not change much. Compound 1 meets the requirements for color filter applications.

[0151] 2. Color gamut control of color filters

[0152] Test Method: Filters were prepared using both the original formulation and a formulation with increased dye content. Preparation method for the original formulation filter: 0.055g dye, 0.525g PGMEA, and 0.675g resin (purchased from Jiangsu Boyan Electronic Technology Co., Ltd.) were accurately weighed and thoroughly mixed ultrasonically for 10 minutes to prepare a dye evaluation solution. The solution was then spin-coated onto a 5×5cm glass substrate at 1000rpm for 10 seconds to prepare a dye evaluation film. The film was pre-baked at 120℃ for 90 seconds and then post-baked at 230℃ for 30 minutes.

[0153] The method to increase the dye proportion is to keep the mass of the other substances unchanged and only increase the amount of dye used, such as weighing 0.18g of 1b, 0.16g of 2b, and 0.2g of 3b respectively. After preparation, the relevant color properties were tested using MCPD. The test results are shown in [reference needed]. Figure 6 .

[0154] Compound 1: 1b; Compound 2: 2b; Compound 3: 3b; Films 1b-1, 2b-1 and 3b-1 with the original formulation; Films 1b-2, 2b-2 and 3b-2 with increased dye content.

[0155] from Figure 6 It can be seen that increasing the amount of dye in the above formulation (1b: 0.18g; 2b: 0.16g; 3b: 0.2g) significantly expands the color gamut. Therefore, due to the high solubility of the dye, the filter can exhibit excellent color characteristics. When using pigments in the prior art, additional complementary pigments must be included to change the color characteristics in order to achieve the above-mentioned effects of this application. However, this application does not require the addition of additional complementary pigments to still have excellent color characteristics.

[0156] 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 therein. Such 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 highly soluble phthalocyanine dyes, characterized in that, The highly soluble phthalocyanine dye described herein has the structure shown in general formula I: Where M is Zn and X is a halogen atom; a+b+c=16, a=4, 0≤b≤15, c=12; R1 has the structure shown in Formula II; In Formula II, R3 is selected from n-alkyl, isoalkyl, tertiary alkyl, straight-chain alkyl or branched alkyl containing ether bonds, or olefin having 2 to 10 carbons. R2 is selected from hydrogen, alkyl groups having 1-18 carbons, carboxyl groups having 1-18 carbons, ether groups having 1-18 carbons, hydroxyalkyl groups having 1-18 carbons, amino groups having 1-18 carbons, and olefins having 2-18 carbons.

2. The highly soluble phthalocyanine dye according to claim 1, characterized in that, X is a halogen atom; R3 is selected from alkyl, isoalkyl, tertiary alkyl or olefin with 1-10 carbon atoms; R2 is selected from hydrogen.

3. The highly soluble phthalocyanine dye according to claim 1 or 2, characterized in that, R1 is selected from one of the following structures: 。 4. The method for synthesizing the highly soluble phthalocyanine dye according to any one of claims 1-3, characterized in that, The method involves mixing the compound shown in Formula Y-1 or the compound shown in Formula Y-2 with the chloride of metal M in an organic solvent, adding a catalyst under the protection of an inert gas, and reacting at 120-200℃ for 12-36 h to obtain the highly soluble phthalocyanine dye shown in I. The formula Y-1 is: The formula Y-2 is: .

5. The synthesis method according to claim 4, characterized in that, The organic solvent is selected from fatty alcohols or alcohol ethers.

6. The synthesis method according to claim 4, characterized in that, The catalyst is selected from 1,8-diazabicycloundec-7-ene or cesium carbonate.

7. The synthesis method according to claim 4, characterized in that, The molar ratio of the compound represented by formula Y-1 or the compound represented by formula Y-2 to the chloride of metal M is 4:1-2.

8. The synthesis method according to claim 4, characterized in that, The chloride of metal M is zinc chloride.

9. A color filter comprising pigment, characterized in that, The pigment includes the highly soluble phthalocyanine dye as described in any one of claims 1-3.

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