Dye compound, photoresist composition, optical film and display panel

Abstract

The invention discloses a dye compound, a photoresist composition, an optical film and a display panel, the dye compound has a structure shown in a formula (1), the formula (1) has good solubility and stability, when the dye compound is applied to a photoresist material, the dye compound has excellent thermal stability and solvent resistance, and the service life of the dye compound is prolonged. The color saturation and the optical performance of the optical film can be remarkably improved.

Description

Technical Field

[0001] This application relates to the field of display technology, specifically to a dye compound, a photoresist composition, an optical film, and a display panel. Background Technology

[0002] In the manufacturing process of Liquid Crystal Displays (LCDs), color filters (CFs), as one of the core components for achieving color display functionality, form an array of red, green, and blue sub-pixels on a transparent substrate. These sub-pixels work in conjunction with the liquid crystal layer and backlight module to achieve the desired color representation of the image. The photoresist material used to prepare the color filter directly affects key indicators of the display, such as transmittance, color performance, contrast ratio, and resolution. Currently, pigment-based photoresist systems are commonly used as the coloring material in color filter manufacturing. However, since pigments exist in solid particle form, they require dispersants and complex dispersion and grinding processes to form a relatively stable system in the photoresist, inevitably leading to insufficient dispersion uniformity. Furthermore, pigment particles easily induce light scattering effects in the optical path, resulting in decreased transmittance and limited color purity, making it difficult to meet the high brightness and wide color gamut requirements of high-end display applications.

[0003] Compared to pigment-based photoresist systems, dye-based photoresists, because the coloring materials can be uniformly dissolved in the resin system at the molecular scale, more easily form a smooth, dense coating film, effectively reducing light scattering loss. This significantly improves the transmittance and color saturation of color filters and helps enhance the overall brightness of displays. Furthermore, dye-based photoresists typically do not require complex dispersion and polishing processes during fabrication, offering advantages in process simplification and manufacturing cost control. However, in actual color filter manufacturing processes, dye-based photoresists still reveal several technical challenges that urgently need to be addressed. On the one hand, the solubility and thermal stability of existing dye materials in photoresist are still insufficient. Under high-temperature baking or photolithography curing conditions, dye molecules may undergo structural deterioration or performance degradation, which in turn affects the long-term reliability of the film. On the other hand, since the dye molecules and the resin matrix mostly rely on physical dissolution or weak interaction, under the action of solvents in the post-processing, dye molecules are prone to migration or dissolution, resulting in film swelling, blurred pattern boundaries, decreased color density, and even color crosstalk between adjacent pixels, which adversely affects the pattern accuracy and display consistency of the color filter.

[0004] Therefore, while fully leveraging the advantages of high transmittance and excellent color performance of dye-based photoresists, how to balance the thermal stability and solvent resistance of materials through dye molecular structure design and synergistic regulation of the photoresist system is an urgent problem to be solved. Summary of the Invention

[0005] This application provides a dye compound, a photoresist composition, an optical film, and a display panel, aiming to solve the problems of poor thermal stability and solvent resistance of existing dye molecules.

[0006] This application provides a dye compound having the structure shown in formula (1): (1); R1, R2, R3, R4, R5, R6, R7 and R8 are each independently selected from halogen atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted alkoxy groups, substituted or unsubstituted aryl groups, hydroxyl groups, carboxyl groups, ester groups, amino groups, amide groups, acyl groups, nitro groups, sulfonic acid groups, mercapto groups, cyano groups, phosphate groups or any combination of the above groups; R9, R 10 R 11 R 12 R 13 R 14 R 15 and R 16 Each atom is independently selected from either a hydrogen atom or a halogen atom; M is selected from divalent metals.

[0007] In some embodiments, R1, R2, R3, R4, R5, R6, R7 and R8 are each independently selected from substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted alkenyl, ether, carbonyl, ester, amino, amide, alkoxy or combinations thereof having 1 to 20 carbon atoms. And / or, R9, R 10 R 11 R 12 R 13 R 14 R 15 and R 16 Selected from F, Cl, Br or I.

[0008] In some embodiments, at least one of R1, R2, R3, R4, R5, R6, R7 and R8 includes a straight-chain alkyl group having 1 to 8 carbon atoms that is substituted or unsubstituted, a branched alkyl group having 1 to 8 carbon atoms that is substituted or unsubstituted, or a cycloalkyl group having 3 to 8 carbon atoms that is substituted or unsubstituted. And / or, at least one of R1, R2, R3, R4, R5, R6, R7 and R8 includes a carbon-carbon double bond.

[0009] In some embodiments, the dye compound has the structure shown in formula (1-1): (1-1).

[0010] In some embodiments, the dye compound is selected from at least one of compounds M-1 to M-18:

[0011]

[0012]

[0013]

[0014]

[0015]

[0016]

[0017]

[0018] .

[0019] In some embodiments, the ultraviolet-visible absorption spectrum of the dye compound includes a first absorption peak and a second absorption peak; wherein the wavelength of the first absorption peak is in the range of 380 nm to 500 nm, and the wavelength of the second absorption peak is in the range of 580 nm to 780 nm.

[0020] This application also provides a photoresist composition comprising a resin, a crosslinking monomer, and a colorant, wherein the colorant comprises a dye compound as described above.

[0021] In some embodiments, the colorant further includes a yellow pigment.

[0022] This application also provides an optical film comprising the dye compound described above, or prepared from the photoresist composition described above.

[0023] This application also provides a display panel, which includes the optical film described above.

[0024] This application provides a dye compound, a photoresist composition, an optical film, and a display panel. The dye compound of this application has the structure shown in formula (1). The dye compound uses a metal phthalocyanine macrocyclic structure as the dye molecule parent structure. The highly conjugated and rigid molecular skeleton endows the dye with excellent structural stability and a wide spectral absorption range. At the same time, through the modification of the peripheral substituents, the solubility and optical properties of the dye molecule are optimized by combining factors such as electronic effects, molecular polarity, asymmetric structure, and steric hindrance. The dye compound of this application has good solubility and stability. When applied to photoresist materials, it has both excellent thermal stability and solvent resistance, which can significantly improve the color saturation and optical performance of the optical film and simplify the process. Attached Figure Description

[0025] To more clearly illustrate the technical solutions in the embodiments of this application, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0026] Figure 1 This is a schematic diagram of the structure of an optical film provided in an embodiment of this application; Figure 2 This is a schematic diagram of another optical film structure provided in an embodiment of this application; Figure 3 This is a process flow diagram of the manufacturing process of an optical film provided in an embodiment of this application; Figure 4 This is a schematic diagram of the structure of a display panel provided in an embodiment of this application.

[0027] Explanation of reference numerals in the attached figures: 10. Display panel; 100. Color filter substrate; 120. Substrate; 110. Optical film; 111. Green color resist; 112. Red color resist; 113. Blue color resist; 114. Black matrix; 200. Array substrate; 300. Liquid crystal layer; 400. First polarizer; 500. Second polarizer; 601. Substrate; 602. Photoresist; 603. Heating stage; 604. Photomask. Detailed Implementation

[0028] The technical solutions of the embodiments of this application will be clearly described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0029] In this application, "substituted or unsubstituted" means that the defined group may or may not be substituted. When the defined group is substituted, it should be understood that it may be substituted by a group acceptable in the art, including but not limited to: halogen atoms, alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, aryl groups having 6 to 20 carbon atoms, aryloxy groups having 6 to 20 carbon atoms, heteroaryl groups having 5 to 20 carbon atoms, hydroxyl groups, carboxyl groups, ester groups, amino groups, amide groups, acyl groups, nitro groups, sulfonic acid groups, mercapto groups, cyano groups, phosphate groups, or combinations of any of the above groups.

[0030] In this application, "alkyl" may mean a straight-chain alkyl, a branched alkyl, or a cycloalkyl. "alkyl" may be an alkyl having 1 to 20 carbon atoms, an alkyl having 1 to 10 carbon atoms, an alkyl having 1 to 8 carbon atoms, or an alkyl having 1 to 5 carbon atoms, but is not limited thereto.

[0031] In this application, "aryl" can be a monocyclic aryl, a fused-ring aryl, or a polycyclic aryl, and for polycyclic ring species, at least one is an aromatic ring system. "Aryl" can be an aryl having 6 to 30 carbon atoms, an aryl having 6 to 20 carbon atoms, or an aryl having 6 to 10 carbon atoms, but is not limited thereto.

[0032] In this application, the "*" connected to a single bond indicates a connection or fusion site.

[0033] This application provides a dye compound having the structure shown in formula (1): (1); R1, R2, R3, R4, R5, R6, R7 and R8 are each independently selected from halogen atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted alkoxy groups, substituted or unsubstituted aryl groups, hydroxyl groups, carboxyl groups, ester groups, amino groups, amide groups, acyl groups, nitro groups, sulfonic acid groups, mercapto groups, cyano groups, phosphate groups or any combination of the above groups; R9, R 10 R 11 R 12 R 13 R 14 R 15 and R 16 Each atom is independently selected from either a hydrogen atom or a halogen atom; M is selected from divalent metals.

[0034] Among them, R1, R2, R3, R4, R5, R6, R7, and R8 can be selected from the same or different groups; R9, R 10 R11 R 12 R 13 R 14 R 15 and R 16 They can be selected from the same or different groups.

[0035] It is understood that the above "arbitrary combination of groups" refers to the structure represented by R1, R2, R3, R4, R5, R6, R7 or R8 containing at least one of the following: a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a hydroxyl group, a carboxyl group, an ester group, an amino group, an amide group, an acyl group, a nitro group, a sulfonic acid group, a mercapto group, a cyano group and a phosphate group.

[0036] In some embodiments, R1, R2, R3, R4, R5, R6, R7, and R8 are each independently selected from substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted alkenyl groups having 1 to 20 carbon atoms, substituted or unsubstituted alkoxy groups, ester groups, acyl groups, amide groups, or any combination thereof having 1 to 20 carbon atoms. Selecting these groups for R1, R2, R3, R4, R5, R6, R7, and R8 is more conducive to improving the solubility and solvent resistance of the dye compound.

[0037] In some embodiments, when R1, R2, R3, R4, R5, R6, R7, or R8 comprises an alkyl group, the alkyl group may be a straight-chain alkyl group having 1 to 20 carbon atoms that is substituted or unsubstituted, a branched alkyl group having 1 to 20 carbon atoms that is substituted or unsubstituted, or a cycloalkyl group having 3 to 20 carbon atoms that is substituted or unsubstituted.

[0038] In some embodiments, at least one of R1, R2, R3, R4, R5, R6, R7, and R8 includes a straight-chain alkyl group having 1 to 8 carbon atoms that is substituted or unsubstituted, a branched alkyl group having 1 to 8 carbon atoms that is substituted or unsubstituted, or a cycloalkyl group having 3 to 8 carbon atoms that is substituted or unsubstituted.

[0039] In some embodiments, when the terminal groups of R1, R2, R3, R4, R5, R6, R7 and R8 are alkyl groups, the terminal alkyl group can be a straight-chain alkyl group with 1 to 8 carbon atoms that has been substituted or unsubstituted, a branched alkyl group with 1 to 8 carbon atoms that has been substituted or unsubstituted, or a cycloalkyl group with 3 to 8 carbon atoms that has been substituted or unsubstituted. The terminal alkyl chain length is moderate, which is beneficial to improving the solubility of the dye compound and to the synthesis of the process.

[0040] Preferably, when the terminal groups of R1, R2, R3, R4, R5, R6, R7 and R8 are alkyl groups, the terminal alkyl group can be a substituted or unsubstituted alkyl group having 2 to 5 carbon atoms; more preferably, the terminal alkyl group can be a substituted or unsubstituted alkyl group having 2 to 3 carbon atoms; in order to further increase the solubility of the dye compound, enhance the compatibility of the dye compound with the solvent and resin in the photoresist composition, and at the same time, suppress intermolecular aggregation and improve the dispersion uniformity of the dye compound during heating.

[0041] In some embodiments, when the terminal groups of R1, R2, R3, R4, R5, R6, R7 and R8 are alkyl groups, the number of branches of the terminal alkyl group is 0 to 4, preferably 0 to 1, in order to improve the compatibility of the dye compound with the resin system.

[0042] In some embodiments, at least one of R1, R2, R3, R4, R5, R6, R7, and R8 includes an unsaturated group, such as a carbon-carbon double bond, so that the dye compound can undergo a crosslinking reaction with the resin and crosslinking monomer in the photoresist system and be connected by chemical bonds, thereby enhancing the anchoring effect of the dye compound in the cured photoresist film layer and further improving the solvent resistance of the dye compound.

[0043] In some embodiments, R9, R 10 R 11 R 12 R 13 R 14 R 15 and R 16 Each halogen is independently selected from F, Cl, Br, or I. By introducing halogen substitution units into the phthalocyanine macrocyclic structure and utilizing the heavy atom effect to regulate the molecular energy level structure, the absorption characteristics of this dye compound can be finely tuned.

[0044] In some embodiments, R9, R 10 R 11 R 12 R 13 R 14 R 15 and R 16 At least one of them is F. Using F atoms has a better spectral modulation effect, which makes the spectrum red-shifted to meet the optical performance requirements of the dye compound in this application.

[0045] In some embodiments, the divalent metal M can be Zn, Cu, Fe, etc.; preferably, M is Zn, to meet the optical performance requirements of the dye compound of this application.

[0046] In some embodiments, the dye compound has the structure shown in formula (1-1): (1-1); Among them, R1, R2, R3, R4, R5, R6, R7 and R8 in the structure shown in equation (1-1) are the same as the structure shown in equation (1), and will not be repeated here.

[0047] In some embodiments, R1, R2, R3, R4, R5, R6, R7, or R8 includes at least one of an ester group, a hydroxyl group, an amino group, or an amide group.

[0048] In some embodiments, at least one of R1, R2, R3, R4, R5, R6, R7, and R8 is selected from the structure represented by equation (2): (2); Where n is selected from 0, 1, 2, 3, 4, 5; R 17 Selected from hydroxyl, amino, ester or amide groups.

[0049] In some embodiments, R 17 It is selected from either methacrylate group or methacrylamide group.

[0050] It is understandable that when two or more of R1, R2, R3, R4, R5, R6, R7 and R8 are selected from the structure represented by equation (2), the R1, R2, R3, R4, R5, R6, R7 and R8 17 It can be selected from the same or different groups.

[0051] In some embodiments, the dye compound is selected from at least one of compounds M-1 to M-18:

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059] .

[0060] In some embodiments, the UV-Vis absorption spectrum of the dye compound of this application includes a first absorption peak and a second absorption peak; wherein the wavelength of the first absorption peak (B band) is located in the range of 380 nm to 500 nm, and the wavelength of the second absorption peak (Q band) is located in the range of 580 nm to 780 nm. The UV-Vis absorption spectrum of the dye compound of this application has a wide absorption range, covering the 380 nm to 500 nm band and the 580 nm to 780 nm band. The reason for this is that the dye compound uses a metal phthalocyanine macrocycle as its parent structure. The metal phthalocyanine macrocycle exhibits two characteristic absorption bands, the core of which originates from two specific electronic transitions of its 18π electron conjugated macrocycle, corresponding to the Q band and the B band (Soret band), respectively. The Q band (visible region) originates from the π→π* transition of the phthalocyanine macrocycle, and the B band (near UV region) is usually a mixture of π→π* and n→π* transitions. At the same time, the central metal and the aggregated state jointly regulate the peak position and intensity. In the prior art, the B-band wavelength range of metal phthalocyanines is typically 300 nm to 400 nm, and the Q-band wavelength range is typically 600 nm to 750 nm. This application modifies the substituents on the periphery of the metal phthalocyanine parent structure, utilizing phenoxy groups and R1~R... 16 The structure of the metal phthalocyanine matrix was modified to further adjust its optical properties, causing a red shift in the spectrum. This resulted in a wider absorption range (380 nm to 500 nm and 580 nm to 780 nm) for the dye compound, which could filter out more stray light and improve color purity. Therefore, the optical film using this dye compound had higher color purity and higher contrast.

[0061] It is understood that the dye compounds of this application have strong absorption in the 380 nm~500 nm and 580 nm~780 nm wavelength bands and high transmittance in the 500 nm~580 nm wavelength band. The dye compounds of this application can be used as green dyes and as colorants, such as colorants in photoresist compositions.

[0062] This application also provides methods for preparing the above-mentioned dye compounds, which are illustrated using compounds M-1 and M-9 as examples.

[0063] 1. Preparation of compound M-1 Synthetic route of intermediate 1:

[0064] Tetrafluorophthalonitrile (2.0 g, 10.0 mmol) and potassium carbonate (2.9 g, 20.99 mmol) were placed in a 100 mL three-necked flask, and acetone (5 mL) was added. The mixture was then cooled to 5 °C in an ice-water bath under nitrogen protection. A solution of 2-hydroxyethyl 4-hydroxybenzoate (1.82 g, 10 mmol) in acetone (8 mL) was slowly added dropwise over approximately 15 minutes. After the addition was complete, the mixture was stirred at 5 °C for 1 hour, then allowed to rise naturally to room temperature and stirred for 14 hours. Ethyl acetate (50 mL) was added, and the mixture was stirred at room temperature for 5 minutes. The mixture was then filtered, and the filter cake was washed with ethyl acetate (30 mL). The filtrate was evaporated to an oily state and allowed to stand for one day to obtain a crude solid. The crude solid was mixed with 20 mL of methanol and heated to 60 °C until clear. The mixture was then allowed to cool naturally to room temperature, resulting in the precipitation of a large amount of solid. The mixture was stirred for another 30 minutes while maintaining room temperature. The mixture was filtered, and the filter cake was washed with methanol (10 mL) to obtain a white solid compound, which was intermediate 1.

[0065] Synthetic route of compound M-1:

[0066] Intermediate 1 (2.62 g, 5.0 mmol) and zinc iodide (0.38 g, 1.25 mmol) were placed in a 100 mL single-necked flask, and benzonitrile (5 mL) was added. The mixture was then heated and stirred in an oil bath at 150 °C for 10 hours under a nitrogen atmosphere. The reaction solution initially turned yellow and then dark green. After cooling to room temperature, the solution was passed through a silica gel column to obtain a crude product. Recrystallization yielded a dark green solid, compound M-1.

[0067] 2. Preparation of compound M-9 Synthetic route of compound M-9:

[0068] Compound M-1 (21.6 g, 10.0 mmol) and triethylamine (2.0 g, 20.0 mmol) were dissolved in dry dichloromethane (200 mL), and the solution was cooled to 0–5 °C in an ice-water bath. A dichloromethane solution (20 mL) of methacryloyl chloride (8.9 g, 85 mmol) was slowly added dropwise. After the addition was complete, the solution was stirred at 5 °C for 1 hour, then allowed to warm naturally to room temperature and stirred for 24 hours. The crude product was washed sequentially with deionized water, saturated sodium bicarbonate, and saturated sodium chloride solutions. The organic layer was dried over anhydrous sodium sulfate, and after solvent removal, it was purified by column chromatography to obtain compound M-9.

[0069] The synthesis of other compounds and their intermediates can be carried out by referring to the synthesis methods of compounds M-1 and M-9 above, only the reaction raw materials need to be adjusted.

[0070] The compounds M-1 to M-18 prepared by the above method were verified by matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MODI-TOF), and the test results are shown in Table 1.

[0071] Table 1

[0072] In Table 1, “M measured” represents the actual measured molecular weight of the compound.

[0073] This application also provides a photoresist composition (i.e., a photosensitive coloring resin composition), the photoresist composition comprising a resin, a crosslinking monomer, and a colorant, the colorant comprising the dye compound described above.

[0074] In some embodiments, the resin used in this application is an alkali-soluble resin, such as an acrylic resin. This application uses an acrylic alkali-soluble resin with adjustable acid value as the matrix material to support dyes and other functional components, and to impart good development properties to the composition. Acrylic resins possess high transparency and contain a certain proportion of acidic functional groups, enabling them to achieve good solubility in alkaline developing solutions. As a film-forming and bonding matrix in photoresists, acrylic resins not only improve the light transmittance of the film layer but also exhibit excellent coating appearance quality, including high gloss and good leveling properties. Furthermore, acrylic resins have comprehensive advantages in weather resistance, photoaging resistance, and color retention, effectively ensuring the stability of optical films under long-term use and high-temperature processing conditions.

[0075] In some embodiments, the resin of this application has the structure shown in formula (3): (3); Where m is an integer greater than 0; R0 is selected from substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms. In formula (3), R0 at different linkage sites can be selected from the same or different groups. A is selected from at least one of substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 10 carbon atoms, etc. B is selected from at least one of silyl, epoxy, hydroxy, carboxyl, and amino groups; C is selected from substituted or unsubstituted unsaturated groups having 1 to 20 carbon atoms.

[0076] In some embodiments, the mass percentage of resin in the photoresist composition of this application ranges from 5% to 20%. For example, the mass percentage of resin may be 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, etc., but is not limited thereto.

[0077] In some embodiments, the crosslinking monomer of this application contains polymerizable functional groups, such as carbon-carbon double bonds. The crosslinking monomer can undergo a polymerization reaction, during which its double bonds are converted into single bonds and form a crosslinked network structure, so that a dense film layer is formed in the exposed area, thereby being retained during the development process to obtain the desired patterned optical film structure.

[0078] In some embodiments, the crosslinking monomer is an acrylate compound containing hydroxyl groups, such as a polyol acrylate compound. This type of crosslinking monomer exhibits good compatibility with the resin (acrylic resin) in the photoresist composition; furthermore, it is colorless and does not cause color change before or after photocuring, nor does it react with dye compounds (colorants). It also possesses high photoreactivity, enabling it to rapidly participate in the crosslinking reaction under the action of a photoinitiator, forming a stable and dense crosslinked network structure.

[0079] In some embodiments, the mass percentage of the crosslinking monomer in the photoresist composition of this application ranges from 5% to 20%. For example, the mass percentage of the crosslinking monomer can be 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, etc., but is not limited thereto.

[0080] In some embodiments, the crosslinking monomer may be M404 adhesive, dicyclopentenyl acrylate (DPCA-12 or DPCA-60), dipentaerythritol hexaacrylate (DPHA), etc., but is not limited thereto. Using the above-mentioned crosslinking monomers helps to improve the mechanical strength, solvent resistance, and pattern retention of the film layer in the exposed area.

[0081] Specifically, the crosslinking monomer can be selected from the following structures:

[0082] Among them, R' is selected from H or CH3; Z1 is selected from (CH2CH2) k Or (CH2CH2O) k k is an integer greater than 0.

[0083] In some embodiments, the mass percentage of the colorant in the photoresist composition of this application ranges from 7% to 25%. For example, the mass percentage of the colorant may be 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, etc., but is not limited thereto.

[0084] In some embodiments, the colorant further includes a pigment, which serves as an auxiliary coloring material for spectral compensation to meet the requirements of high color gamut displays for comprehensive color performance. Furthermore, the pigment is a yellow pigment, while the dye compound in this application is a green dye. Using a yellow pigment can adjust the chromaticity of the green dye to enhance the color saturation of the optical film.

[0085] In some embodiments, the pigment content in the photoresist composition of this application ranges from 2% to 10% by mass. For example, the pigment content may be 2%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc., but is not limited thereto.

[0086] In some embodiments, the pigment may be selected from CI pigments Y128, Y129, Y133, Y134, Y136, Y137, Y138, Y139, Y142, Y147, Y148, Y150, Y151, Y153, Y154, Y155, Y157, Y158, Y159, Y160, Y161, Y162, Y163, Y164, Y165, Y166, Y167, Y168, Y169, Y170, Y172, Y173, Y174, Y175, Y176, Y180, Y181, Y182, Y183, Y184, Y185, Y188, Y189, Y190, Y191, etc., but is not limited thereto.

[0087] In some embodiments, the mass percentage of the dye compound in the photoresist composition of this application ranges from 5% to 15%. For example, the mass percentage of the dye compound may be 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, etc., but is not limited thereto.

[0088] In some embodiments, the photoresist composition of this application further includes a photoinitiator, which can rapidly generate free radicals or ionic active intermediates under specific wavelength light irradiation conditions, thereby initiating a photocrosslinking reaction of the resin system.

[0089] In some embodiments, the photoinitiator in the photoresist composition of this application has a mass percentage content ranging from 0.5% to 3%. For example, the mass percentage content of the photoinitiator may be 0.5%, 0.8%, 1%, 2%, 3%, etc., but is not limited thereto.

[0090] In some embodiments, the photoinitiator includes, but is not limited to, photoinitiators such as acetophenones, diimidazoles, benzoin (benzoin-based), and benzophenones. The photoinitiators used in this application have UV absorption characteristics that match the spectrum of the exposure equipment well, can efficiently generate free radicals, have excellent reactivity, and are compatible with the resin, crosslinking monomers, and solvents in the photoresist composition, and will not cause yellowing during photopolymerization.

[0091] In some embodiments, the photoinitiator may be selected from the following structures: ; Wherein, R'' and R''' are each independently selected from H, substituted or unsubstituted alkyl groups; Ar1, Ar2, and Ar3 are each independently selected from substituted or unsubstituted aryl groups.

[0092] In some embodiments, the photoinitiator may be PBG-345, IGM-369, etc., but is not limited thereto.

[0093] In some embodiments, the photoresist composition of this application further includes a solvent, which is used to adjust the viscosity and rheological properties of the photoresist system to suit the requirements of the film formation process.

[0094] In some embodiments, the solvent includes, but is not limited to, at least one of benzene, toluene, xylene, methanol, ethanol, acetone, chloroform, dichloromethane, ethyl acetate, diethyl ether, propylene glycol methyl ether acetate (PGMEA), ethylene glycol methyl ether acetate (EGMEA), butyl 3-methoxyacetate (MBA), ethyl 3-ethoxypropionate (EEP), N-ethylpyrrolidone (NEP), and 1-methoxy-2-propionate. Preferably, the solvent may be at least one of PGMEA and NEP.

[0095] In some embodiments, the mass percentage of the solvent in the photoresist composition of this application ranges from 65% to 85%. For example, the mass percentage of the solvent may be 65%, 70%, 75%, 80%, 85%, etc., but is not limited thereto.

[0096] In some embodiments, the photoresist composition of this application further includes additives such as dispersants, antioxidants, and leveling agents, but is not limited thereto. The dispersants, antioxidants, and leveling agents described above can be materials commonly used in the art, and this application does not impose any restrictions.

[0097] In some embodiments, the mass percentage of the additives in the photoresist composition of this application ranges from 0% to 2%. For example, the mass percentage of the additives may be 0%, 0.2%, 0.6%, 1%, 1.5%, 2%, etc., but is not limited thereto.

[0098] It is understood that the total mass percentage of each component in the photoresist composition of this application is 100%.

[0099] This application also provides an optical film 110, please refer to... Figures 1-2 The optical film 110 of this application includes the dye compound as described above, or is prepared from the photoresist composition as described above.

[0100] In some embodiments, please refer to Figure 1 The optical film 110 of this application can be used as a filter film, allowing green light to pass through while filtering out other colors of light.

[0101] In some embodiments, please refer to Figure 2 The optical film 110 of this application may be a color filter. The optical film 110 includes a green color resist 111, a red color resist 112 and a blue color resist 113. The green color resist 111 includes the dye compound described above, or is prepared from the photoresist composition described above.

[0102] In some embodiments, a black matrix 114 (BM) is also included between adjacent color resists to separate adjacent color resists and avoid color mixing.

[0103] This application also provides a method for preparing an optical film 110, comprising: A photoresist composition is obtained by mixing resin, crosslinking monomer, colorant, photoinitiator, solvent and additives in a certain proportion. A substrate is provided, a photoresist composition is coated onto the surface of the substrate, and steps such as baking, exposure, and development are performed to form a patterned optical film.

[0104] Specifically, the step of "mixing resin, crosslinking monomer, colorant, photoinitiator, solvent, and additives in a certain proportion to obtain a photoresist composition" includes: S1. Preparation of transparent substrate: Weigh the photoinitiator, resin, crosslinking monomer and solvent according to the mass ratio in Table 2, place them in the first reaction vessel and perform primary stirring treatment. The stirring time is controlled in the range of 25-35 minutes. Then weigh a certain amount of additives and add them to the first reaction vessel. Continue stirring for 30 minutes until they are mixed evenly to obtain the transparent substrate.

[0105] S2. Color paste preparation: Add the dye compound and pigment to the second reactor in the mass ratio of Table 3, add a solvent containing a certain amount of dispersant, and stir for 30 minutes to obtain a uniform color paste.

[0106] S3. Photoresist preparation: Take an appropriate amount of the color paste obtained in step S2 and add it to the transparent substrate obtained in step S1 according to the mass ratio in Table 4. Continue stirring for 1 h to obtain a photoresist dispersion. Filter the photoresist dispersion using a 0.5 μm PP filter membrane to obtain the prepared photoresist.

[0107] For details, please refer to Figure 3 The steps of "providing a substrate, coating a photoresist composition onto the substrate surface, and performing baking, exposure, and development steps to form a patterned optical film" include: Q1. Using a TFT-LCD glass substrate (10 cm × 10 cm, 0.5 mm thick) manufactured by AGC Corporation of Japan as substrate 301, the substrate surface was cleaned using a SUS720 EUV equipment from Ushio Corporation of Tokyo, Japan. Q2. The photoresist 602 obtained in step S3 is uniformly coated onto the substrate surface using a MIKASA desktop spin coater in Tokyo, Japan, to form a coating with a dry film thickness of approximately 2.3 μm. Q3. After standing for 5 minutes, use the hot plate of AS ONE Corporation in Osaka, Japan as the heating stage 603, and pre-bake at 90°C for 88 seconds to fully remove the solvent in the photoresist. Q4. The photoresist is photochemically reacted using an exposure machine (including a 604 photomask) manufactured by KEYI Technology Co., Ltd. in Taiwan, to generate an insoluble structure. The soluble part is then selectively removed using a developer containing 0.042% potassium hydroxide (KOH) by the company's developer to complete the patterning process. Q5. The pattern is cured in a dust-free high-temperature oven to achieve the final formation of the patterned optical film.

[0108] The manufacturing process of the above optical films can be referred to Figure 3 In this context, (a) represents cleaning, (b) represents coating, (c) represents pre-baking, (d) represents exposure, (e) represents development, (f) represents post-baking, 601 represents substrate, 602 represents photoresist, 603 represents heating stage, and 604 represents photomask.

[0109] Table 2 Transparent Substrate Formulation

[0110] Table 3 Color paste ratio

[0111] Table 4. Photoresist composition ratio

[0112] The optical film of this application will be further described below through specific embodiments: The proportions of the photoresist compositions in Examples 1 to 3 and the comparative examples are shown in Table 5. Optical films C1 to C4 were prepared using the above-described optical film preparation method. The film thickness, color and color gamut, and color stability of each optical film were tested.

[0113] 1. Film thickness measurement (α-Step method): The dry film thickness after photoresist deposition was measured using an ET4000A α-Step step meter from Kosaka Corporation, Japan. The measurement accuracy was ±0.01 μm. The film thickness of the optical films in Examples 1 to 3 and the comparative examples was controlled at 2.4 μm.

[0114] 2. Colorimetric and gamut analysis (MCPD method): Transmission spectral data in the wavelength range of 380-780 nm were collected using a Lambda Vision microspectrophotometer from Japan. The chromaticity coordinates (Gx, Gy) and luminance (GY) were calculated using the CIE 1931 colorimetric system. The calculation results are shown in Table 9.

[0115] 3. Color stability assessment (ΔE*ab): Immerse each optical film in NMP solution at 25℃ for 5 min, then place the optical film on a hot plate at 240℃ for 15 min, and then perform colorimetric tests. Calculate ΔE*ab by comparing the changes in color points. The calculation results are shown in Table 10.

[0116] Table 5. Formulation of photoresist compositions in Examples 1 to 3 and comparative examples.

[0117] It should be noted that in the above embodiments, I-1 represents acetophenone photoinitiator, I-2 represents diimidazole photoinitiator, P1 represents methacrylic resin, P2 represents acrylic resin, M1 represents M404, M2 represents DPCA-12, and M3 represents DPHA. The performance parameters of I-1, I-2, P1, P2, M1, M2, and M3 are shown in Tables 6, 7, and 8.

[0118] Table 6 Resin Performance Parameters

[0119] Table 7 Crosslinking monomer performance parameters

[0120] Table 8 Performance parameters of photoinitiators

[0121] Table 9 Chromaticity coordinates and luminance data

[0122] Table 10 Color stability data

[0123] As shown in Tables 9 and 10, the optical films C1 to C3 prepared from the dye compounds of this application have better chromaticity, brightness, and color stability than the optical film C4 of the comparative example. Compared with the pigment-type photoresist system of the comparative example, the photoresist system using the dye compounds of this application has higher transmittance, better solubility and solvent resistance, better thermal stability, and does not generate foreign matter.

[0124] Furthermore, as shown in Table 10, the ΔE*ab values ​​of Examples 2 and 3 are significantly lower than those of the comparative examples. This is because the dye compounds M-9 and M-18 of this application contain more double bonds, which can have a stronger crosslinking effect with the resin and crosslinking monomers in the photoresist composition, significantly enhancing the solvent resistance of the dye compounds. Therefore, the ΔE*ab value of the optical film is smaller and the stability is higher.

[0125] In this application, the components of the photoresist composition are formulated according to the proportions specified in this application. The resulting dye-based photoresist composition exhibits excellent thermal stability and solvent resistance while maintaining excellent solubility. After immersion in the organic solvent NMP, its color change value ΔE*ab is as low as 0.42, demonstrating excellent solvent resistance. Furthermore, the dye-based photoresist composition of this application effectively suppresses the color drift problem caused by the thermal degradation of dye compounds during the high-temperature manufacturing process of optical films (color filters), and significantly outperforms traditional pigment-based photoresist systems in terms of light transmittance, thereby reducing light energy loss and improving the overall light efficiency of the display panel.

[0126] This application also provides a display panel 10, please refer to... Figure 4 The display panel 10 of this application includes the optical film 110 as described above.

[0127] In some embodiments, please refer to Figure 4 The display panel 10 includes a color filter substrate 100 and an array substrate 200 disposed opposite to each other. The color filter substrate 100 includes a substrate 120 and an optical film 110 disposed on the side of the substrate 120 near the array substrate 200. The optical film 110 may be a color filter.

[0128] Furthermore, the display panel 10 also includes a liquid crystal layer 300 disposed between the array substrate 200 and the color filter substrate 100, that is, the display panel 10 can be a liquid crystal display panel.

[0129] In some embodiments, the display panel 10 further includes a first polarizer 400 and a second polarizer 500, wherein the first polarizer 400 is located on the side of the color filter substrate 100 away from the array substrate 200, and the second polarizer 500 is located on the side of the array substrate 200 away from the color filter substrate 100.

[0130] The dye compounds and photoresist compositions of this application, when applied to liquid crystal display panels, can achieve higher pattern resolution and film formation consistency. Their concentrated spectral response and low stray absorption effectively improve the purity and saturation of displayed colors. Simultaneously, due to reduced light absorption loss, the light transmittance of the display panel 10 is improved. Furthermore, this photoresist system exhibits excellent dissolution behavior and storage stability, which is beneficial for widening the process window and optimizing process control, thus providing reliable material support for the fabrication of high-performance liquid crystal display panels.

[0131] This application provides a dye compound, a photoresist composition, an optical film, and a display panel. The dye compound of this application has the structure shown in formula (1). The dye compound uses a metal phthalocyanine macrocyclic structure as the dye molecule parent structure. The highly conjugated and rigid molecular skeleton endows the dye with excellent structural stability and a wide spectral absorption range. At the same time, through the modification of the peripheral substituents, the solubility and optical properties of the dye molecule are optimized by combining factors such as electronic effects, molecular polarity, asymmetric structure, and steric hindrance. The dye compound of this application has good solubility and stability. When applied to photoresist materials, it has both excellent thermal stability and solvent resistance, which can significantly improve the color saturation and optical performance of the optical film and simplify the process.

[0132] This document uses specific examples to illustrate the principles and implementation methods of this application. The descriptions of the above embodiments are only for the purpose of helping to understand the methods and core ideas of this application. At the same time, for those skilled in the art, there will be changes in the specific implementation methods and application scope based on the ideas of this application. Therefore, the content of this specification should not be construed as a limitation of this application.

Claims

1. A dye compound, characterized in that, The dye compound has the structure shown in formula (1): （1）； R1, R2, R3, R4, R5, R6, R7 and R8 are each independently selected from halogen atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted alkoxy groups, substituted or unsubstituted aryl groups, hydroxyl groups, carboxyl groups, ester groups, amino groups, amide groups, acyl groups, nitro groups, sulfonic acid groups, mercapto groups, cyano groups, phosphate groups or any combination of the above groups; R9, R 10 R 11 R 12 R 13 R 14 R 15 and R 16 Each atom is independently selected from either a hydrogen atom or a halogen atom; M is selected from divalent metals.

2. The dye compound according to claim 1, characterized in that, R1, R2, R3, R4, R5, R6, R7 and R8 are each independently selected from substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted alkenyl groups having 1 to 20 carbon atoms, substituted or unsubstituted alkoxy groups, ester groups, acyl groups, amide groups or any combination of the above groups having 1 to 20 carbon atoms. And / or, R9, R 10 R 11 R 12 R 13 R 14 R 15 and R 16 Each is independently selected from F, Cl, Br, or I.

3. The dye compound according to claim 1, characterized in that, At least one of R1, R2, R3, R4, R5, R6, R7 and R8 includes a straight-chain alkyl group having 1 to 8 carbon atoms that is substituted or unsubstituted, a branched alkyl group having 1 to 8 carbon atoms that is substituted or unsubstituted, or a cycloalkyl group having 3 to 8 carbon atoms that is substituted or unsubstituted. And / or, at least one of R1, R2, R3, R4, R5, R6, R7 and R8 includes a carbon-carbon double bond.

4. The dye compound according to claim 1, characterized in that, The dye compound has the structure shown in formula (1-1): （1-1）。 5. The dye compound according to claim 1, characterized in that, The dye compound is selected from at least one of compounds M-1 to M-18: 。 6. The dye compound according to any one of claims 1-5, characterized in that, The ultraviolet-visible absorption spectrum of the dye compound includes a first absorption peak and a second absorption peak; The wavelength of the first absorption peak is in the range of 380 nm to 500 nm, and the wavelength of the second absorption peak is in the range of 580 nm to 780 nm.

7. A photoresist composition, characterized in that, The photoresist composition includes a resin, a crosslinking monomer, and a colorant, wherein the colorant includes a dye compound as described in any one of claims 1-6.

8. The photoresist composition according to claim 7, characterized in that, The colorant also includes yellow pigment.

9. An optical film, characterized in that, The optical film comprises a dye compound as described in any one of claims 1-6, or is prepared from a photoresist composition as described in any one of claims 7-8.

10. A display panel, characterized in that, The display panel includes the optical film as described in claim 9.

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