A naphthalimide derivative polymer dye, a yellow photosensitive resin composition, and applications thereof

Abstract

The present application relates to a kind of naphthalimide derivative polymer dyes, yellow photosensitive resin composition and its application, the structure general formula of dye is as follows: general formula (I);Wherein, n is the positive integer of 1-100, 0 < a ≤ 100, 0 ≤ b < 100, and a+b=100;X1-X4 each is independently selected from any one of hydrogen atom, alkyl, aryl or heteroaryl substituent, Y1-Y5 each is independently selected from any one of hydrogen atom, alkyl, aryl or heteroaryl substituent, Z is selected from any one of oxygen atom, nitrogen atom or sulfur atom;R1-R3 each is independently selected from any one of hydrogen atom, alkyl, alkenyl, ether group, substituted alkyl, aryl or heteroaryl substituent.Compared with prior art, the naphthalimide derivative polymer dyes have high solubility, excellent light resistance and heat resistance, and the yellow photosensitive resin composition prepared based on the dye has high color density.

Description

Technical Field

[0001] This invention relates to the field of dye preparation technology, and in particular to a naphthalimide derivative polymer dye, a yellow photosensitive resin composition, and their applications. Background Technology

[0002] Liquid crystal displays (LCDs) rapidly rose to prominence in the late 20th century due to their advantages such as low power consumption, low radiation, high image quality, and portability. They have now become the mainstream technology in the display field and continue to evolve towards higher resolution and larger sizes. The color reproduction of LCDs is highly dependent on the color filter (CF), whose quality directly determines the final effect of the displayed image. A conventional color filter mainly consists of a transparent glass substrate, a black body matrix, a color photoresist layer, an outer coating, and an ITO conductive film. The color photoresist layer contains the three basic colors of red, green, and blue (RGB). To achieve excellent color reproduction, the color filter needs to possess high color purity and high transmittance, while also meeting requirements for high contrast, low reflectivity, and excellent heat, light, and chemical stability. Among these, the formulation of the photoresist is the core step in the color filter manufacturing process.

[0003] The photoresist system comprises components such as color paste, photocurable resin, photoinitiator, and solvent. The quality of the finished color filter is largely determined by the physicochemical properties of the photoresist itself and the subsequent coating process, especially the photoresist dye, which plays a crucial role as a colorant. Compared to pigment particles, dye colorants typically exist in the photoresist system in the form of small molecules, avoiding the light scattering and refraction phenomena that occur in pigment systems. Dye molecules can achieve high color purity through chemical modification, which is beneficial for preparing high-purity color filters and thus improving the color gamut of the display. Although dyes can generally be used to manufacture color filters with high transmittance and high contrast, they have poor heat resistance and lightfastness, and are prone to color changes during the high-temperature heating process in the color filter manufacturing step. In addition, they should be highly soluble in industrial solvents and have sharp absorption peaks to obtain excellent optical performance. Specifically: (1) Traditional dyes exhibit low solubility in alkaline aqueous solutions or organic solvents, making it difficult to obtain colorable curable compositions with the desired spectrum.

[0004] (2) Dyes in a molecularly dispersed state are more likely to aggregate, thus causing changes in optical properties.

[0005] (3) Dyes in a molecularly dispersed state have poor light and heat resistance, and their optical properties are prone to change during the high-temperature baking process of subsequent device fabrication and long-term light exposure after service.

[0006] In recent years, the yellow colorant materials reported for color photoresists mainly include acid yellow pigments and BODIPY dyes (CN113980488A, CN121427333A, CN113913030A). Patent CN113980488A discloses an acid yellow compound and its preparation method, as well as a method for preparing a yellow filter. The molecule of the acid yellow compound is obtained by reacting acid yellow 23 with acryloylpropyltrimethylammonium chloride. However, the molecular structure of this patent has insufficient thermal stability, resulting in significant color differences in the filter during thermal stability testing, failing to meet the requirements for processing under high-temperature environments. Summary of the Invention

[0007] The purpose of this invention is to provide a naphthalimide derivative polymer dye, a yellow photosensitive resin composition, and its application, wherein the naphthalimide derivative polymer dye has high solubility, excellent lightfastness, and heat resistance.

[0008] The objective of this invention can be achieved through the following technical solutions: One objective of this invention is to provide a naphthalimide derivative polymer dye, the general structural formula of which is as follows: General formula (Ⅰ); Where n is a positive integer from 1 to 100, 0 < a ≤ 100, 0 ≤ b < 100, and a + b = 100; X1 to X4 are each independently selected from any one of hydrogen atom, alkyl, aryl or heteroaryl substituents, Y1 to Y5 are each independently selected from any one of hydrogen atom, alkyl, aryl or heteroaryl substituents, and Z is selected from any one of oxygen atom, nitrogen atom or sulfur atom; R1 to R3 are each independently selected from any one of hydrogen atoms, alkyl, alkenyl, ether, substituted alkyl, aryl, or heteroaryl substituents.

[0009] Preferably, when b=0, the naphthalimide derivative polymer dye is a homopolymer of naphthalimide derivative.

[0010] More preferably, when b=0, the naphthalimide derivative polymer dye is prepared by homopolymerization of naphthalimide derivative monomers.

[0011] Preferably, when b > 0, the naphthalimide derivative polymer dye is a copolymer of naphthalimide derivatives.

[0012] More preferably, when b > 0, the naphthalimide derivative polymer dye is prepared by copolymerization of 50% naphthalimide derivative monomer and 50% comonomer.

[0013] More preferably, the comonomer is a solubilizing non-chromophore monomer.

[0014] More preferably, the comonomer is a sterically hindered rigid group or a flexible long-chain comonomer.

[0015] More preferably, the general structural formula (II) of the naphthalimide derivative monomer is as follows: General formula (II).

[0016] More preferably, the general structural formula (Ⅲ) of the comonomer is as follows: General formula (Ⅲ).

[0017] More preferably, the naphthalimide derivative polymer dye is prepared from monomers in the following molar percentages: 50% naphthalimide derivative monomer and 50% comonomer.

[0018] Preferably, R1 to R3 are each independently selected from any one of the following: alkenyl groups having 2 to 22 carbons, alkyl groups having 1 to 22 carbons, carboxyl-substituted alkyl groups having 1 to 22 carbons, ether groups having 1 to 22 carbons, ester-substituted alkyl groups having 1 to 22 carbons, hydroxyl-substituted alkyl groups having 1 to 22 carbons, amino-substituted alkyl groups having 1 to 22 carbons, and aldehyde-substituted alkyl groups having 1 to 22 carbons.

[0019] More preferably, R1 to R3 are of the same type or different types, respectively.

[0020] Preferably, in R1 to R3, the heteroaryl group is selected from any one of fused heterocyclic groups, monocyclic aromatic heterocyclic groups, and polycyclic aromatic heterocyclic groups.

[0021] Preferably, the heteroatoms contained in the fused heterocyclic group include N, S, and O heteroatoms.

[0022] More preferably, the number of heteroatoms includes 1 to 7, specifically, it can be 1, 2, 3, 4, 5, 6 or 7.

[0023] More preferably, the heteroatom types in the fused heterocyclic group include any one, any two, or any three of N, S, and O heteroatoms.

[0024] Preferably, the fused heterocyclic group is obtained by bonding any one of a monocyclic aromatic or non-aromatic heterocyclic group or a polycyclic aromatic heterocyclic group with at least one of an aryl, a haloaryl, and an aromatic amino group.

[0025] More preferably, the aryl group includes unsubstituted aryl (such as phenyl), alkyl-substituted aryl, and polyaryl (such as biphenyl).

[0026] More preferably, the haloaryl group is a group formed by replacing an aryl group with at least one halogen atom selected from F, Cl, Br, and I.

[0027] More preferably, the haloaryl group is a group formed by replacing an aryl group with a Br atom.

[0028] More preferably, the aromatic amino group includes any one of diphenylamino group and triphenylamino group.

[0029] Preferably, R1 to R3 are each independently selected from one of the following formulas (B-1) to (B-49), where n is any integer from 1 to 20 in formula (B-1), and the curve represents the connection bond between R1 to R3 and the mother core in general formula (I): Preferably, its structural formula includes any one of the following formulas (C-1) to (C-48), where n is a positive integer from 1 to 100, 0 < a ≤ 100, 0 ≤ b < 100, and a + b = 100: .

[0030] More preferably, its structural formula includes any one of the following formulas (1) to (76), where n is a positive integer from 1 to 100: .

[0031] A second objective of this invention is to provide a yellow photosensitive resin composition comprising the following components in parts by weight: Colorant 2~10; 10-30% of resins containing double bond structures and / or epoxy structures; 2-8 monomers containing double bond structures and / or epoxy structures; Photoinitiator with high absorption characteristics at 365 nm, 0.2~0.9; Additives that improve film-forming properties and / or stability, at a concentration of 0.1–0.6%. Solvents containing ether groups: 50-90%; The colorant includes the aforementioned naphthalimide derivative polymer dye; the solid content of the yellow photosensitive resin composition is 15-38%.

[0032] Preferably, the resin containing a double bond structure and / or an epoxy structure includes one or more of the following: acrylic polyurethane resin, acrylic polyester resin, acrylic epoxy resin, acrylic polyether resin, acrylic alkyd resin, acrylic melamine resin, and acrylic silicone resin; the monomer containing a double bond structure and / or an epoxy structure includes one or more of the following: dipentaerythritol pentaacrylate, trimethylolpropane triacrylate, polyvinyl alcohol cinnamate monomer, N-benzylmaleimide, epoxy acrylate, and epoxy acrylamide; the photoinitiator with high absorption characteristics at 365 nm includes one or more of the following: oximes, benzoins, acetophenones, and imidazoles; the additives that improve film-forming properties and / or stability include one or more of the following: surface leveling agents, defoamers, stabilizers, and plasticizers; and the solvent containing an ether group includes one or more of the following: propylene glycol monomethyl ether, propylene glycol methyl ether acetate, propylene glycol monoethyl ether, 3-methoxybutyl acetate, and N,N-dimethylformamide.

[0033] A third objective of this invention is to provide an application of the aforementioned yellow photosensitive resin composition in the field of color photoresist.

[0034] The fourth objective of this invention is to provide an application of the aforementioned yellow photosensitive resin composition in the preparation of color filters.

[0035] Preferably, the yellow photosensitive resin composition can be used in filters of display and sensing devices such as liquid crystal displays and image sensors.

[0036] When dyes are used to form colored images for applications such as liquid crystal displays (LCDs) and image sensors, it is typically required that the colored photosensitive composition form an extremely thin layer, and that it exhibits a high color concentration even at a thin thickness. This necessitates high solubility of the dye in the solvent. Furthermore, the lightfastness or heat resistance of the color pixels may not be sufficient for practical applications, leading to difficulties in coping with recent high-brightness backlighting issues. Indium tin oxide (ITO), which is widely used as an electrode in flat panel displays (FPDs) such as LCDs, suffers from the aforementioned problems of altered photochemical and photophysical properties due to the high temperatures involved in film formation.

[0037] Based on the above problems, this invention innovatively proposes a new type of yellow dye based on naphthalimide for use as a dye in filters for display and sensing devices such as liquid crystal displays and image sensors. This invention proposes the following three strategies for applying naphthalimide dyes to filters: First, addressing the lack of application of naphthalimide in displaying colors using reflected or transmitted light in fields such as liquid crystal displays, image sensors, fiber materials, and inkjet printing, this invention designs and develops a series of naphthalimide derivatives for dye application. Second, addressing the poor thermal stability of traditional yellow dyes (such as azo dyes), this invention polymerizes naphthalimide through free radical polymerization. The highly fused rigid framework and strong intermolecular interactions effectively improve the thermal stability of the naphthalimide dye. Third, addressing the poor solubility of naphthalimide polymer dyes, this invention, based on the advantage of the π-plane of naphthalimide in achieving high photothermal stability, introduces functional groups around the naphthalimide and adds other comonomers during the polymerization process to improve solubility. The molecule proposed in this invention has high photothermal stability and solubility, and can be used as a dye in filters for display and sensing devices such as liquid crystal displays and image sensors.

[0038] This invention provides a high-performance compound for use as a dye in filters for display and sensing devices such as liquid crystal displays and image sensors. This invention prepares a polymer dye from a naphthalimide derivative, exhibiting stronger intermolecular interactions than smaller molecules, thus demonstrating good photochemical and thermochemical stability. The solubility of the dye is improved by introducing sterically hindered groups around the naphthalimide and by introducing other comonomers, thus suppressing π-plane aggregation of the dye in the solvent. This invention synthesizes a yellow polymer dye based on naphthalimide and overcomes the problem of poor solubility in naphthalimide yellow polymer dyes.

[0039] Compared with the prior art, the present invention has the following beneficial effects: (1) The present invention provides a naphthalimide derivative polymer dye, which is obtained by free radical polymerization of naphthalimide derivative monomer and comonomer. The naphthalimide derivative polymer dye has high solubility, excellent lightfastness and heat resistance.

[0040] (2) The present invention introduces sterically hindered functional groups on the periphery of naphthalimide molecules to obtain naphthalimide derivative chromophore monomers, which effectively inhibits the intermolecular stacking and aggregation of naphthalimide π planar molecules and improves solubility. The present invention abandons the single homopolymerization method and further conducts free radical copolymerization of naphthalimide derivative chromophore monomers with sterically hindered rigid groups, flexible long chains and other solubilizing non-chromophore monomers to solve the shortcoming of limited solubility of naphthalimide homopolymer dyes and improve the solubility of polymers in industrial solvents.

[0041] (3) In this invention, naphthalimide itself has a large planar π conjugated fused ring rigid skeleton, which naturally endows the material with excellent basic heat resistance and light resistance. The naphthalimide derivative monomer is prepared into a high molecular polymer dye. The high molecular weight brings stronger intermolecular interaction, which further improves the overall light resistance and heat resistance compared with small molecule dyes.

[0042] (4) The naphthalimide derivative polymer dye synthesized in this invention has excellent solubility and can be well adapted to commonly used industrial solvents such as color photoresist solvent PGMEA. Naphthalimide has yellow optical properties. Based on this, this invention prepares a yellow photosensitive resin composition. This yellow photosensitive resin composition can be used as a color photoresist to prepare a thin (1.5-2.0 μm) colored layer with high color intensity.

[0043] (5) The coloring layer prepared by the yellow photosensitive resin composition prepared by the present invention has excellent system compatibility, heat resistance and solvent resistance, and can be applied to color filters of display and sensing devices such as liquid crystal displays and image sensors.

[0044] (6) The color filter prepared using the yellow photosensitive resin composition prepared in this invention has excellent stability, Δ E ab All are less than 3.

[0045] (7) The color filter prepared by the yellow photosensitive resin composition prepared by the present invention has good edge neatness and development process margin. Attached Figure Description

[0046] Figure 1 The 1H NMR spectrum of intermediate 5 prepared in Example 7; Figure 2 The 1H NMR spectrum of compound (1) prepared in Example 7; Figure 3 This is a photograph of the yellow photosensitive resin composition D1 prepared in Example 1-1; Figure 4 The UV-Vis absorption spectrum of the yellow photosensitive resin composition D1 prepared in Example 1-1 is shown. Figure 5 The CIE chromaticity diagrams for Examples 1-1 and Comparative Examples 2-1 are shown. Detailed Implementation

[0047] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments. These embodiments are based on the technical solution of the present invention and provide detailed implementation methods and specific operating procedures. However, the scope of protection of the present invention is not limited to the following embodiments.

[0048] Unless otherwise specified, the reagents, methods, instruments, and equipment used in this invention are conventional in the art. Unless otherwise specified, the reagents and materials used in the following examples are all commercially available.

[0049] Examples 1 and 2, synthesis of intermediates 1 and 2: Example 1, Synthesis of Intermediate 1: The preparation method of intermediate 1 is as follows: 4-bromo-1,8-naphthalenedicarboxylic anhydride (23 mmol), 3,5-dimethyl-4-aminophenol (23 mmol) and acetic acid (150 mL) were added to a two-necked flask and heated under N2 protection at 120 °C for 12 h under reflux. After the reaction was stopped, the mixture was cooled to room temperature, poured into water, filtered under reduced pressure and washed with a large amount of ethanol. The filter cake was collected to obtain 7.31 g of grayish-white solid (intermediate 1), with a yield of 80%.

[0050] Intermediate 2 was synthesized using the same or similar methods as intermediate 1, involving the substitution of amine groups and acid anhydrides. The difference lay in the different starting materials and substrates used. The structures, yields, and mass spectrometry data of the starting materials and intermediate compounds are shown in Table 1.

[0051] Table 1 Examples 3 and 4, Synthesis of Intermediates 3 and 4 Example 3, Synthesis of Intermediate 3: The preparation method of intermediate 3 is as follows: intermediate 1 (10 mmol), octadecylamine (10 mmol) and dimethyl sulfoxide (DMSO) (50 mL) were added to a two-necked flask and heated under N2 protection at 90 °C for 24 h under reflux. After the reaction was stopped, the mixture was cooled to room temperature, poured into water, filtered under reduced pressure and washed with a large amount of water. The filter cake was then washed with anhydrous ethanol and collected to obtain 5.1 g of yellow solid (intermediate 3), with a yield of 86%.

[0052] Intermediate 4 was synthesized using the same or similar methods as intermediate 3, involving the substitution of amine and bromine atoms. The difference lay in the different starting materials and substrates used. The structures, yields, and mass spectrometry data of the starting materials and intermediate compounds are shown in Table 2.

[0053] Table 2 Examples 5 and 6, Synthesis of Intermediates 5 and 6 Example 5, Synthesis of Intermediate 5: The preparation method of intermediate 5 is as follows: intermediate 3 (3 mmol), methacryloyl chloride (4.5 mmol), triethylamine (5 mL) and dichloromethane (DCM) (10 mL) were added to a single-necked flask and stirred at room temperature for 1 h. After the reaction was stopped, the mixture was poured into a separatory funnel, washed three times with pure water, and the organic phase was collected by separation. 5 g of silica gel powder was added to the collected dichloromethane and distilled under reduced pressure. After the silica gel powder was dried, the product was purified by column chromatography (eluent: dichloromethane: petroleum ether = 1:4) to obtain 1.2 g of yellow solid (intermediate 5), with a yield of 63%.

[0054] Intermediate 6 was synthesized using the same or similar methods as intermediate 5, involving the substitution of hydroxyl and chlorine atoms. The difference lay in the different starting materials and substrates used. The structures, yields, and mass spectrometry data of the starting materials and intermediate compounds are shown in Table 3.

[0055] Table 3 Example 7, Synthesis of compound (1): Intermediate 5 (3 mmol), triethylene glycol methyl ether methacrylate (3 mmol), azobisisobutyronitrile (AIBN) (0.3 mmol), and N,N-dimethylformamide (DMF) (6 mL) were added to a two-necked flask and heated at 65 °C for 24 h under N2 protection. After the reaction was stopped, the mixture was cooled to room temperature, poured into water, filtered under reduced pressure, and the filter cake was washed with a large amount of anhydrous ethanol. The filter cake was collected to give 2.5 g of yellow solid (compound (1)) with a yield of 89%.

[0056] Figure 1-2 The 1H NMR spectra of intermediate 5 and compound (1) in Example 7 respectively prove the successful preparation of compound (1).

[0057] It should be noted that other compounds claimed in this invention can be obtained by replacing the starting reactants with the corresponding reactants and referring to the preparation methods of the examples listed above, so they will not be listed one by one here.

[0058] The molecular structure identification data of compounds (1) to (76) are shown in Table 4: Table 4 Example 1-1 Preparation of yellow photosensitive resin composition D1 Using the naphthalimide polymer dye (compound (1)) prepared in Example 7 above, a yellow photosensitive resin composition D1 was formulated and subjected to photolithography to compare the relevant properties of the photosensitive resin composition. The photolithography method described is a conventional method used by those skilled in the art.

[0059] formula: Take 4 parts by weight of colorant, 20 parts by weight of resin containing double bonds, 5 parts by weight of monomer containing double bonds, 0.5 parts by weight of photoinitiator, 0.25 parts by weight of additive to improve film-forming properties and / or stability, and 70 parts by weight of solvent containing ether groups. Mix and dissolve thoroughly, controlling the solid content to be around 29%, to obtain a yellow photosensitive resin composition, such as... Figure 3 As shown.

[0060] Among them, the colorant is: compound (1) naphthalimide polymer dye; Resins containing double bond structures and / or epoxy structures: acrylic polyester resin (analytical grade), purchased from Titan Corporation; Monomers containing double bond structures and / or epoxy structures: dipentaerythritol pentaacrylate monomer (analytical grade), purchased from Titan Corporation; Photoinitiator with high absorption characteristics at 365nm: α,α-diethoxyacetophenone (analytical grade), purchased from Titan Corporation; Additives to improve film-forming properties and / or stability: Defoamer (analytical grade), purchased from Titan Corporation; Solvent containing ether groups: Propylene glycol methyl ether acetate (analytical grade), purchased from Titan Corporation; Comparative Example 2-1 Preparation of yellow photosensitive resin composition E1 Take 4 parts by weight of Y138, 20 parts by weight of resin containing double bond structure, 5 parts by weight of monomer containing double bond structure, 0.5 parts by weight of photoinitiator, 0.25 parts by weight of additive to improve film-forming properties and / or stability, and 70 parts by weight of solvent containing ether group, mix and dissolve thoroughly, and control the solid content to about 29% to obtain yellow photosensitive resin composition E1.

[0061] The chemical structure of Y138 is as follows: The performance testing of photosensitive resin compositions D1 and E1 was conducted using the following steps: The glass slides were washed and dried, and then coated with adhesive using a spin coater to obtain a uniform film layer of 1.5–2.0 μm. After pre-baking at 90°C for 120 s, the film was exposed to 365 nm ultraviolet light at an exposure dose of 40 mJ / cm². 2The distance between the mask and the coating was 180 μm. After development at 23℃ for 50 s, the coating was then baked at 230℃ for 20 min. Subsequent related performance was then tested, and the results are shown in Table 5.

[0062] Performance testing and evaluation methods: (1) Colorimetry: Detected using a Konica Minolta CM-5 spectrophotometer.

[0063] (2) System compatibility: The photosensitive resin composition was stored in the dark at 0~10 ℃, and its viscosity was tested (for at least six months). The composition was then photolithographically processed according to the process conditions, and the presence of particles on the color filter surface was examined under an optical microscope (OM) at 500x magnification.

[0064] The evaluation criteria are as follows: ○: Viscosity change < ±5% mPa·s and no particles on the x500 surface; △: Viscosity change value < ±10% mPa·s and x500 surface is free of particles; ×: Viscosity change value > ±10% mPa·s or x500 indicates particles on the surface; (3) Heat resistance test: The heat resistance of the photosensitive resin composition was verified by color difference. The sample was post-baked at 230 ℃ for 20 min, and this post-baking was repeated twice. The film thickness was measured using an XP-2 step meter. The color difference was the difference between the second post-baked sample and the first post-baked sample, measured using a Minolta CM-5. If Δ E ab A value less than 3 indicates good heat resistance; (4) Solvent resistance evaluation: After baking, the sample was placed in PGMEA and immersed at room temperature for 5 minutes. After removal, it was baked in an oven at 150°C for 30 minutes. The color difference before and after baking was then measured. If Δ E ab A value less than 3 indicates good solvent resistance.

[0065] (5) Evaluation of anti-migration performance: Following the manufacturing process of color filters, yellow pixels are first fabricated on thin-film transistor (TFT) glass. Then, a sample is coated, and after development, the surface of the color filter is dried. The color difference before and after the pixel is measured. If Δ E ab A value less than 3 indicates good resistance to transfection.

[0066] (6) Line width, edge neatness, and development process tolerance: The linewidth and edge neatness were tested at x500 OM, and the mask linewidth was 140 μm.

[0067] When evaluating process margin, other process conditions are fixed, and the edge neatness and edge residue or edge peeling of the image obtained with a development time between 40 s and 100 s are examined. The peeling property is determined by referring to the adhesion measurement method in this field.

[0068] The evaluation criteria for edge neatness are as follows: ○: Developed for 50 seconds, the edges are neat and there is no residue at the edges; △: The image developed for 50 seconds has rough, uneven edges or residue at the edges; ×: Image missing The specific criteria for evaluating the development process margin are as follows: ○: Developed for 40~100 seconds, the edges are neat and there is no residue or peeling at the edges; △: Develop for 50~80 seconds. The edges are neat and there is no residue or peeling at the edges. ×: The edges are uneven after developing for 50~80 seconds, or there is residue at the edges, or there is peeling at the edges; The alkaline developing solutions used above, such as aqueous solutions of alkaline compounds like sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, calcium carbonate, ammonia, diethylamine, or tetramethylammonium hydroxide, [OH] - The concentration is 0.2-1.0%, preferably 0.4-0.6%.

[0069] The preparation of photosensitive resin compositions D2-D76 in Examples 1-2 to 1-76 was carried out in accordance with Example 1-1, using the same preparation method and materials, with the only difference being the colorant. Specific evaluation results are shown in Table 5.

[0070] Table 5 Figure 4 The image shows the UV-Vis absorption spectrum of the yellow photosensitive resin composition D1 prepared in Example 1-1. As can be seen from the figure, the yellow photosensitive resin composition prepared in this invention has good absorption in the blue light region (400-500nm).

[0071] Figure 5 The figures show the CIE chromaticity diagrams for Examples 1-1 and Comparative Examples 2-1. As can be seen from the figures, the yellow photosensitive resin composition prepared by the present invention has superior colorimetric properties and higher yellow color purity.

[0072] The experimental results show that, compared with Y138 used in the comparative example, the dyes in Examples 1-1 to 1-76 exhibit better solubility in the color photoresist solvent PGMEA; they also possess excellent heat resistance and solvent resistance. Furthermore, the photosensitive resin compositions D1 to D76 using these dyes demonstrate similar good processing properties to the photosensitive resin composition E1 using Y138 in the comparative example, such as system compatibility, edge neatness, and development process margin.

[0073] This invention improves the solubility of dyes by introducing functional groups around naphthalimide and adding other comonomers during polymerization; it also improves the stability of naphthalimide polymer dyes by inhibiting dye aggregation in the solid state; it solves the problems of thermal stability and solvent resistance not meeting industrial production requirements, as well as poor solubility and compatibility in color photoresist systems, and selects naphthalimide polymers with better performance as dyes for use in filters of display and sensing devices such as liquid crystal displays and image sensors.

[0074] The above description of the embodiments is provided to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention.

Claims

1. A naphthalimide derivative polymer dye, characterized in that, Its general structural formula is as follows: General formula (Ⅰ); Where n is a positive integer from 1 to 100, 0 < a ≤ 100, 0 ≤ b < 100, and a + b = 100; X1 to X4 are each independently selected from any one of hydrogen atom, alkyl, aryl or heteroaryl substituents, Y1 to Y5 are each independently selected from any one of hydrogen atom, alkyl, aryl or heteroaryl substituents, and Z is selected from any one of oxygen atom, nitrogen atom or sulfur atom; R1 to R3 are each independently selected from any one of hydrogen atoms, alkyl, alkenyl, ether, substituted alkyl, aryl, or heteroaryl substituents.

2. The naphthalimide derivative polymer dye according to claim 1, characterized in that, R1 to R3 are each independently selected from any one of the following: alkenyl groups having 2 to 22 carbons, alkyl groups having 1 to 22 carbons, carboxyl-substituted alkyl groups having 1 to 22 carbons, ether groups having 1 to 22 carbons, ester-substituted alkyl groups having 1 to 22 carbons, hydroxyl-substituted alkyl groups having 1 to 22 carbons, amino-substituted alkyl groups having 1 to 22 carbons, and aldehyde-substituted alkyl groups having 1 to 22 carbons.

3. The naphthalimide derivative polymer dye according to claim 1, characterized in that, In R1 to R3, the heteroaryl group is selected from any one of fused heterocyclic groups, monocyclic aromatic heterocyclic groups, and polycyclic aromatic heterocyclic groups. The heteroatoms contained in the fused heterocyclic group include N, S, and O heteroatoms. The number of heteroatoms includes 1 to 7. The types of heteroatoms in the fused heterocyclic group include any one, any two, or any three of N, S, and O heteroatoms. In R1 to R3, the fused heterocyclic group is obtained by bonding any one of a monocyclic aromatic or non-aromatic heterocyclic group or a polycyclic aromatic heterocyclic group with at least one of an aryl group, a haloaryl group, and an aromatic amino group. The aryl group includes unsubstituted aryl groups, alkyl-substituted aryl groups, and polyaryl groups. The haloaryl group is a group formed by replacing an aryl group with at least one halogen atom from F, Cl, Br, and I. The aromatic amino group includes any one of a diphenylamino group and a triphenylamino group.

4. The naphthalimide derivative polymer dye according to claim 1, characterized in that, R1 to R3 are each independently selected from one of the following formulas (B-1) to (B-49), where n is any integer from 1 to 20 in formula (B-1), and the curve represents the connection bond between R1 to R3 and the mother core in general formula (Ⅰ): 。 5. The naphthalimide derivative polymer dye according to claim 1, characterized in that, Its structural formula is selected from any one of the following formulas (C-1) to (C-48), where n is a positive integer from 1 to 100, 0 < a ≤ 100, 0 ≤ b < 100, and a + b = 100: 。 6. The naphthalimide derivative polymer dye according to claim 1, characterized in that, Its structural formula is selected from any one of the following formulas (1) to (76), where n is a positive integer from 1 to 100: 。 7. A yellow photosensitive resin composition, characterized in that, The components include the following parts by weight: Colorant 2~10; 10-30% of resins containing double bond structures and / or epoxy structures; 2-8 monomers containing double bond structures and / or epoxy structures; Photoinitiator with high absorption characteristics at 365 nm, 0.2~0.9; Additives that improve film-forming properties and / or stability, at a concentration of 0.1–0.6%. Solvents containing ether groups: 50-90%; The colorant includes the naphthalimide derivative polymer dye as described in any one of claims 1 to 6; the solid content of the yellow photosensitive resin composition is 15 to 38%.

8. The yellow photosensitive resin composition according to claim 7, characterized in that, Resins containing double bonds and / or epoxy structures include one or more of the following: acrylic polyurethane resin, acrylic polyester resin, acrylic epoxy resin, acrylic polyether resin, acrylic alkyd resin, acrylic melamine resin, and acrylic silicone resin; monomers containing double bonds and / or epoxy structures include one or more of the following: dipentaerythritol pentaacrylate, trimethylolpropane triacrylate, polyvinyl alcohol cinnamate monomer, N-benzylmaleimide, epoxy acrylate, and epoxy acrylamide; photoinitiators with high absorption characteristics at 365 nm include one or more of the following: oximes, benzoin derivatives, acetophenones, and imidazole derivatives; additives that improve film-forming properties and / or stability include one or more of the following: surface leveling agents, defoamers, stabilizers, and plasticizers; solvents containing ether groups include one or more of the following: propylene glycol monomethyl ether, propylene glycol methyl ether acetate, propylene glycol monoethyl ether, 3-methoxybutyl acetate, and N,N-dimethylformamide.

9. The application of the yellow photosensitive resin composition as described in any one of claims 7 to 8 in the field of color photoresist.

10. The use of the yellow photosensitive resin composition as described in any one of claims 7 to 8 in the preparation of color filters.

Images