Colored photosensitive resin composition and color filter

Abstract

The invention provides a colored photosensitive resin composition and a color filter, and relates to the technical field of liquid crystal display. The coloring photosensitive resin composition is prepared from the following raw materials in percentage by mass: 40 to 60 percent of coloring agent, 2.5 to 4.5 percent of alkali-soluble resin, 2 to 3.5 percent of acrylate monomer, 0.05 to 0.1 percent of photopolymerization initiator, 0.02 to 0.03 percent of auxiliary agent and 35 to 52 percent of solvent, wherein the total mass of the raw materials is 100 percent; wherein the coloring agent is prepared from the following raw materials in percentage by mass: 8.3 to 9.8 percent of aluminum phthalocyanine dye, 17.7 to 18.5 percent of Y150 and 26 to 28.3 percent of G-Dye, wherein the total mass of the raw materials of the colored photosensitive resin composition is 100 percent. According to the invention, through collaborative optimization configuration of the components, relatively good sensitivity and developing performance can be maintained. The exposure area is fully cured, the non-exposure area is thoroughly dissolved, and the problems of non-contour line part residue and sheet-shaped object stripping are avoided.

Description

Technical Field

[0001] This application relates to the field of liquid crystal display technology, and more particularly to a coloring photosensitive resin composition and a color filter. Background Technology

[0002] In the manufacturing of color filters for liquid crystal displays (LCDs), traditional pigment-based systems suffer from reduced display quality due to light scattering issues. Therefore, dye-based and pigment-dye hybrid systems have been introduced to improve optical performance. However, when dyes are used as colorants, their molecular structure easily excites strong fluorescence under light, especially in complete darkness. This phenomenon significantly increases background brightness, weakening the filter's contrast and ultimately damaging the display's visual effect. As display technology advances towards higher resolutions, the demand for higher concentrations of color filters is increasingly urgent, requiring a higher colorant content in the coloring composition. However, increasing colorant concentration triggers a chain reaction: reduced photosensitivity leads to decreased exposure efficiency, and deteriorated solubility during development directly affects the quality of pixel outline formation. Specifically, material in non-outline areas is difficult to dissolve fully, often adhering to the substrate surface as undissolved residues or flaky flaking, inducing defects such as color shift. These problems not only degrade the optical quality of color filters but also significantly reduce the yield rate in the production process, increasing manufacturing costs and technical difficulty.

[0003] To address the aforementioned issues, existing technologies urgently need improvement. Summary of the Invention

[0004] The purpose of this application is to provide a coloring photosensitive resin composition and a color filter to solve the above-mentioned problems.

[0005] To achieve the above objectives, this application adopts the following technical solution: This application provides a coloring photosensitive resin composition, which, based on 100% of the total mass of the coloring photosensitive resin composition, comprises: 40-60% colorant, 2.5-4.5% alkali-soluble resin, 2-3.5% acrylate monomer, 0.05-0.1% photopolymerization initiator, 0.02-0.03% additives, and 35-52% solvent; The colorant, calculated based on the total mass of its raw materials (100%), comprises 8.3-9.8% aluminum phthalocyanine dye, 17.7-18.5% Y150, and 26-28.3% G-Dye.

[0006] Optionally, the chemical formula of the aluminum phthalocyanine dye is: ; Among them, A1, A2, A3, A4, B1, B2, B3, B4, C1, C2, C3, C4, D1, D2, D3, and D4 each independently include one or more of F, Cl, and Br.

[0007] Optionally, the method for preparing the aluminum phthalocyanine dye includes: A first slurry is obtained by mixing phthalonitrile, anhydrous aluminum chloride, 1,8-diazabicyclo[5.4.0]undec-7-ene and n-pentanol, and then subjected to a first cooling after heating and reflux. The first slurry after heating and reflux is mixed with methanol and water to obtain a green slurry. The green slurry is then subjected to drying, pulverizing, dispersing and dissolving in sequence to obtain the aluminum phthalocyanine dye.

[0008] Optionally, the mass ratio of the phthalonitrile, the anhydrous aluminum chloride, the 1,8-diazabicyclo[5.4.0]undec-7-ene, and the n-pentanol is 2.5-3:1:15:2.5-3.

[0009] Optionally, the temperature of the heating reflux is 133-138°C, and the time is 4.9-5.1 hours.

[0010] Optionally, the endpoint temperature of the first cooling is 28-32°C.

[0011] Optionally, after the pulverization, the particle size is no greater than 0.2 μm.

[0012] Optionally, the dispersion and dissolution process includes mixing the green slurry, which has undergone the drying and pulverization process once, with a dispersant and propylene glycol methyl ether.

[0013] The dispersant includes methacrylate.

[0014] Optionally, the preparation method of the G-Dye includes: A first solution was obtained by mixing tetrafluorophthalonitrile, potassium carbonate, and acetonitrile. After a second cooling, the solution was stirred with phenyl p-hydroxybenzoate and acetonitrile to obtain an intermediate. The intermediate was mixed with zinc chloride and phenylacetonitrile, and after reaction, it was washed, separated into solid and liquid components, and dried to obtain the G-Dye.

[0015] Optionally, the mass ratio of the tetrafluorophthalonitrile, the potassium carbonate, and the acetonitrile is 1.5-1.8:0.5:24-25.

[0016] Optionally, the endpoint temperature of the second cooling is 2°C.

[0017] Optionally, the stirring time is 7.8-8.3 hours.

[0018] Optionally, the mass ratio of the intermediate, the zinc chloride, and the phenylacetonitrile is 0.7:0.15-0.2:0.5; the reaction temperature is 160-180℃, and the reaction time is 4.9-5.2h.

[0019] Optionally, the molecular weight of the alkali-soluble resin is 10,000-50,000, and the acid value is 100 mg·KOH / g; or, The molecular weight of alkali-soluble resins is not higher than 10,000, and the acid value is not higher than 50 mg·KOH / g.

[0020] Optionally, the photopolymerization initiator includes an oxime ester initiator; the oxime ester initiator includes PBG-345 and / or PBG-327.

[0021] Optionally, the acrylate monomer includes at least one of methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, and tert-butyl methacrylate.

[0022] Optionally, the adjuvant includes F-554 and / or KBM-503M.

[0023] Optionally, the solvent includes PGMEA and / or PGDA.

[0024] This application also provides a color filter, the raw material of which includes the aforementioned coloring photosensitive resin composition.

[0025] Compared with the prior art, the beneficial effects of this application include: This application provides a coloring photosensitive resin composition and a color filter. By introducing a specific combination of aluminum phthalocyanine dye, Y150, and G-Dye into the colorant and precisely controlling their proportions, the fluorescence phenomenon of the dye can be effectively suppressed. Compared with a single dye or randomly mixed colorants, this optimized dye system can effectively reduce the brightness in a completely black state, thereby improving the contrast of the color filter and thus improving the optical performance of the display. It achieves good photosensitivity and development performance under high concentrations of colorant, while effectively suppressing fluorescence through the combination of specific dyes, thus producing a color filter with high contrast and high quality. Through the synergistic optimization of its components, this application can maintain good photosensitivity and development performance even at high concentrations of colorant. It ensures sufficient curing of the exposed area and complete dissolution of the unexposed area, thereby ensuring the clear formation of pixel outlines and effectively avoiding the problems of residue and peeling flakes in non-outline areas. Attached Figure Description

[0026] To more clearly illustrate the technical solutions of the embodiments of this application, the accompanying drawings used in the embodiments will be briefly described below. It should be understood that the following drawings only show some embodiments of this application and should not be regarded as a limitation on the scope of this application.

[0027] Figure 1 The image shows the line falling off when aluminum phthalocyanine and G-Dye are mixed in a certain proportion in Example 4. Figure 2 This refers to the edge case in Example 4 where aluminum phthalocyanine and G-Dye are mixed in a certain proportion; Figure 3 The line drop situation in Comparative Example 1 where only G-Dye was used as the coloring component; Figure 4 In Comparative Example 2, the coloring component is only used at the edge of aluminum phthalocyanine. Figure 5 The results are for the transmissibility test of Example 4, Comparative Example 1, and Comparative Example 2. Detailed Implementation

[0028] As used in this article: "Prepared from" is synonymous with "comprising". The terms "comprising", "including", "having", "containing", or any other variations thereof as used herein are intended to cover non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that includes the listed elements is not necessarily limited to those elements, but may include other elements not expressly listed or elements inherent to such composition, step, method, article, or apparatus.

[0029] The conjunction "composed of..." excludes any unspecified elements, steps, or components. If used in a claim, this phrase makes the claim closed, excluding materials other than those described, except for associated conventional impurities. When the phrase "composed of..." appears in a clause of the body of a claim rather than immediately following it, it limits only the elements described in that clause; other elements are not excluded from the claim as a whole.

[0030] When a quantity, concentration, or other value or parameter is expressed as a range, a preferred range, or a range defined by a series of upper and lower preferred values, this should be understood as specifically disclosing all ranges formed by any pair of any upper or preferred value with any lower or preferred value, regardless of whether the range is disclosed individually. For example, when the range “1–5” is disclosed, the described range should be interpreted as including ranges “1–4”, “1–3”, “1–2”, “1–2 and 4–5”, “1–3 and 5”, etc. When numerical ranges are described herein, unless otherwise stated, the range is intended to include its endpoints and all integers and fractions within that range.

[0031] In these embodiments, unless otherwise specified, the portions and percentages are all by weight.

[0032] "Parts by mass" refers to the basic unit of measurement that expresses the mass ratio of multiple components. One part can represent any unit mass, such as 1g or 2.689g. If we say that component A has "a" parts by mass and component B has "b" parts by mass, it means the ratio of the mass of component A to the mass of component B is a:b. Alternatively, it can mean that the mass of component A is aK and the mass of component B is bK (where K is any number representing a multiplier). It is important to understand that, unlike parts by mass, the sum of the mass parts of all components is not limited to 100 parts.

[0033] "And / or" is used to indicate that one or both of the described situations may occur, for example, A and / or B includes (A and B) and (A or B).

[0034] To better illustrate the technical solution provided in this application, a detailed description of the technical solution provided in this application will be given before proceeding with the specific implementation.

[0035] In a first aspect, this application provides a coloring photosensitive resin composition, which, calculated based on 100% of the total mass of the coloring photosensitive resin composition, comprises: 40-60% colorant, 2.5-4.5% alkali-soluble resin, 2-3.5% acrylate monomer, 0.05-0.1% photopolymerization initiator, 0.02-0.03% additives, and 35-52% solvent; The colorant, calculated based on the total mass of its raw materials (100%), comprises 8.3-9.8% aluminum phthalocyanine dye, 17.7-18.5% Y150, and 26-28.3% G-Dye.

[0036] It is understandable that in existing technologies, increasing the concentration of colorant in the coloring composition to achieve high concentration often results in a decrease in pixel outline formation properties such as photosensitivity and solubility during development. This may lead to undissolved coloring composition residues in non-outline areas during development, or undissolved photoresist that directly becomes peel-off flakes on the substrate, causing problems such as color shift, reduced quality, and decreased production yield. The coloring photosensitive resin composition of this embodiment, through the synergistic optimization of its components, maintains good photosensitivity and development performance even at high colorant concentrations. It ensures sufficient curing of exposed areas and complete dissolution of unexposed areas, thereby guaranteeing clear pixel outline formation and effectively avoiding the problems of residues and peel-off flakes in non-outline areas. Therefore, the technical solution of this application effectively solves the problem of decreased processing performance caused by high-concentration colorants, improving the quality and production efficiency of color filters.

[0037] In an optional embodiment, the chemical formula of the aluminum phthalocyanine dye is: ; Among them, A1, A2, A3, A4, B1, B2, B3, B4, C1, C2, C3, C4, D1, D2, D3, and D4 each independently include one or more of F, Cl, and Br.

[0038] This application's solution, by specifying the exact chemical formula of the aluminum phthalocyanine dye in the colorant, enables the coloring photosensitive resin composition to achieve more stable and controllable coloring performance, ensuring that the aluminum phthalocyanine dye possesses the expected absorption spectral characteristics, thereby exhibiting a precise green hue and high color purity in the composition. This precise chemical structure definition allows the aluminum phthalocyanine dye to better synergize with components such as the alkali-soluble resin, acrylate monomer, and photopolymerization initiator in the coloring photosensitive resin composition, forming a uniform and stable dispersion system. This avoids problems such as uneven color, color deviation, or performance degradation caused by uncertain dye properties.

[0039] In an optional embodiment, the method for preparing the aluminum phthalocyanine dye includes: A first slurry is obtained by mixing phthalonitrile, anhydrous aluminum chloride, 1,8-diazabicyclo[5.4.0]undec-7-ene and n-pentanol, and then subjected to a first cooling after heating and reflux. The first slurry after heating and reflux is mixed with methanol and water to obtain a green slurry. The green slurry is then subjected to drying, pulverizing, dispersing and dissolving in sequence to obtain the aluminum phthalocyanine dye.

[0040] In an optional embodiment, the mass ratio of the phthalonitrile, the anhydrous aluminum chloride, the 1,8-diazabicyclo[5.4.0]undec-7-ene, and the n-pentanol is 2.5-3:1:15:2.5-3.

[0041] Optionally, the mass ratio of the phthalonitrile, the anhydrous aluminum chloride, the 1,8-diazabicyclo[5.4.0]undec-7-ene, and the n-pentanol can be 2.5:1:15:2.5, 3:1:15:3, or any value between 2.5 and 3:1:15:2.5-3.

[0042] In one optional embodiment, the heating reflux temperature is 133-138°C, and the time is 4.9-5.1 hours.

[0043] Optionally, the reflux temperature can be 133℃, 134℃, 135℃, 136℃, 137℃, 138℃, or any value between 133℃ and 138℃; the time can be 4.9h, 5h, 5.1h, or any value between 4.9h and 5.1h.

[0044] In one alternative implementation, the endpoint temperature of the first cooling is 28-32°C.

[0045] Optionally, the endpoint temperature of the first cooling can be 28°C, 29°C, 30°C, 31°C, 32°C, or any value between 28°C and 32°C.

[0046] In one optional embodiment, after the pulverization, the particle size is no greater than 0.2 μm.

[0047] Optionally, the particle size of the pulverized particles can be 0.05μm, 0.1μm, 0.15μm, 0.2μm, or any value not greater than 0.2μm.

[0048] In an optional embodiment, the dispersion and dissolution process includes mixing the green slurry, which has undergone the drying and pulverization process once, with a dispersant and propylene glycol methyl ether.

[0049] The dispersant includes methacrylate.

[0050] In an optional embodiment, the method for preparing the G-Dye includes: A first solution was obtained by mixing tetrafluorophthalonitrile, potassium carbonate, and acetonitrile. After a second cooling, the solution was stirred with phenyl p-hydroxybenzoate and acetonitrile to obtain an intermediate. The intermediate was mixed with zinc chloride and phenylacetonitrile, and after reaction, it was washed, separated into solid and liquid components, and dried to obtain the G-Dye.

[0051] In an optional embodiment, the mass ratio of the tetrafluorophthalonitrile, the potassium carbonate, and the acetonitrile is 1.5-1.8:0.5:24-25.

[0052] Optionally, the mass ratio of tetrafluorophthalonitrile, potassium carbonate, and acetonitrile can be 1.5:0.5:24, 1.6:0.5:24.5, 1.7:0.5:24.5, 1.8:0.5:25, or any value between 1.5 and 1.8:0.5:24-25.

[0053] In one optional implementation, the endpoint temperature of the second cooling is 2°C.

[0054] In one optional embodiment, the stirring time is 7.8-8.3 hours.

[0055] Optionally, the stirring time can be 7.8h, 7.9h, 8h, 8.1h, 8.2h, 8.3h, or any value between 7.8h and 8.3h.

[0056] In one optional embodiment, the mass ratio of the intermediate, the zinc chloride, and the phenylacetonitrile is 0.7:0.15-0.2:0.5; the reaction temperature is 160-180℃, and the reaction time is 4.9-5.2h.

[0057] Optionally, the mass ratio of the intermediate, the zinc chloride, and the phenylacetonitrile can be 0.7:0.15:0.5, 0.7:0.16:0.5, 0.7:0.17:0.5, 0.7:0.18:0.5, 0.7:0.19:0.5, 0.7:0.2:0.5, or any value between 0.7:0.15 and 0.2:0.5.

[0058] In one optional embodiment, the alkali-soluble resin has a molecular weight of 10,000-50,000 and an acid value of 100 mg·KOH / g; or, The molecular weight of alkali-soluble resins is not higher than 10,000, and the acid value is not higher than 50 mg·KOH / g.

[0059] In an optional embodiment, the photopolymerization initiator includes an oxime ester initiator; the oxime ester initiator includes PBG-345 and / or PBG-327.

[0060] In an optional embodiment, the acrylate monomer includes at least one selected from methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, and tert-butyl methacrylate.

[0061] In an optional embodiment, the adjuvant includes F-554 and / or KBM-503M.

[0062] In an optional embodiment, the solvent includes PGMEA and / or PGDA.

[0063] Secondly, this application also provides a color filter, the raw materials of which include the aforementioned coloring photosensitive resin composition.

[0064] The implementation schemes of this application will be described in detail below with reference to specific embodiments. However, those skilled in the art will understand that the following embodiments are only for illustrating this application and should not be regarded as limiting the scope of this application. Unless otherwise specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments used without specified manufacturers are all conventional products that can be purchased commercially.

[0065] Example 1 This embodiment provides a coloring photosensitive resin composition: The total mass of the coloring photosensitive resin composition comprises: 54.3 parts by weight of colorant, 2 parts by weight of alkali-soluble resin S1, 1.8 parts by weight of alkali-soluble resin S2, 3.8 parts by weight of alkali-soluble resin S2, 2.8 parts by weight of DPHA (acrylate monomer), 0.072 parts by weight of PBG-327 (photopolymerization initiator, purchased from Changzhou Qiangli Electronic New Materials Co., Ltd.), 0.016 parts by weight of additive F-554 (manufactured by DIC Corporation of Japan), and 0.012 parts by weight of additive KBM-503M (manufactured by Shin-Etsu Corporation), 7.0 parts by weight of PGDA, and 32.0 parts by weight of propylene glycol monomethyl ether acetate mixed as a solvent.

[0066] The total mass of the coloring photosensitive resin composition includes 8.3 parts by weight of aluminum phthalocyanine dye, 17.7 parts by weight of Y150, and 28.3 parts by weight of G-Dye.

[0067] Among them, the molecular weight of alkali-soluble resin S1 is 15800 and the acid value is 102.8 mg·KOH / g, while the molecular weight of alkali-soluble resin S2 is 9800 and the acid value is 91.3 mg·KOH / g.

[0068] The specific preparation steps of aluminum phthalocyanine dye are as follows: First, 225 parts of phthalonitrile and 78 parts of anhydrous aluminum chloride are added to 1250 parts of n-pentanol in a reaction vessel and stirred. Then, 266 parts of 1,8-diazabicyclo[5.4.0]undec-7-ene are added, and the mixture is heated and refluxed at 136°C for 5 hours. The reaction solution, cooled to 30°C while stirring, is injected into a mixed solvent of 5000 parts of methanol and 10000 parts of water to obtain a green slurry. The slurry is filtered, washed with a mixed solvent of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of aluminum phthalocyanine chloride. Next, the pigment aluminum phthalocyanine in the above colorant is dispersed using a bead mill or similar device until the average particle size of the pigment reaches below 0.2 μm. A resin dispersant and PGME are added to the pigment to completely dissolve it, thus obtaining a high color gamut aluminum phthalocyanine dye with the following structure: .

[0069] The specific preparation steps of G-Dye are as follows: 1.5g of tetrafluorophthalonitrile, 0.5g of potassium carbonate, and 25ml of acetonitrile are mixed and cooled. Phenylparaben and acetonitrile are added at 2℃ and stirred for 8 hours to obtain an intermediate. 0.7g of this intermediate, 0.15g of zinc chloride, and phenylacetonitrile are mixed and reacted at 170℃ for 5 hours. After the reaction, the mixture is washed with methanol, filtered, and dried under reduced pressure to obtain dye G-Dye.

[0070] Example 2 This embodiment provides a coloring photosensitive resin composition: The total mass of the coloring photosensitive resin composition comprises: 54.3 parts by weight of colorant, 2 parts by weight of alkali-soluble resin S1, 1.8 parts by weight of alkali-soluble resin S2, 3.8 parts by weight of alkali-soluble resin S2, 2.8 parts by weight of DPHA, 0.072 parts by weight of PBG-327, 0.016 parts by weight of additive F-554 and 0.012 parts by weight of additive KBM-503M, 7.0 parts by weight of PGDA and 32.0 parts by weight of propylene glycol monomethyl ether acetate mixed as a solvent.

[0071] The total mass of the coloring photosensitive resin composition includes 8.8 parts by weight of aluminum phthalocyanine dye, 17.7 parts by weight of Y150, and 27.8 parts by weight of G-Dye.

[0072] Among them, the molecular weight of alkali-soluble resin S1 is 15800 and the acid value is 102.8 mg·KOH / g, while the molecular weight of alkali-soluble resin S2 is 9800 and the acid value is 91.3 mg·KOH / g.

[0073] The specific preparation steps of aluminum phthalocyanine dye are as follows: First, 225 parts of phthalonitrile and 78 parts of anhydrous aluminum chloride are added to 1250 parts of n-pentanol in a reaction vessel and stirred. Then, 266 parts of 1,8-diazabicyclo[5.4.0]undec-7-ene are added, and the mixture is heated and refluxed at 136°C for 5 hours. The reaction solution, cooled to 30°C while stirring, is injected into a mixed solvent of 5000 parts of methanol and 10000 parts of water to obtain a green slurry. The slurry is filtered, washed with a mixed solvent of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of aluminum phthalocyanine chloride. Next, the pigment aluminum phthalocyanine in the above colorant is dispersed using a bead mill or similar device until the average particle size of the pigment reaches below 0.2 μm. A resin dispersant and PGME are added to the pigment to completely dissolve it, thus obtaining a high color gamut aluminum phthalocyanine dye with the following structure: .

[0074] The specific preparation steps of G-Dye are as follows: 1.5g of tetrafluorophthalonitrile, 0.5g of potassium carbonate, and 25ml of acetonitrile are mixed and cooled. Phenylparaben and acetonitrile are added at 2℃ and stirred for 8 hours to obtain an intermediate. 0.7g of this intermediate, 0.15g of zinc chloride, and phenylacetonitrile are mixed and reacted at 170℃ for 5 hours. After the reaction, the mixture is washed with methanol, filtered, and dried under reduced pressure to obtain dye G-Dye.

[0075] Example 3 This embodiment provides a coloring photosensitive resin composition: The total mass of the coloring photosensitive resin composition comprises: 54.3 parts by weight of colorant, 2 parts by weight of alkali-soluble resin S1, 1.8 parts by weight of alkali-soluble resin S2, 3.8 parts by weight of alkali-soluble resin S2, 2.8 parts by weight of DPHA, 0.072 parts by weight of PBG-327, 0.016 parts by weight of additive F-554 and 0.012 parts by weight of additive KBM-503M, 7.0 parts by weight of PGDA and 32.0 parts by weight of propylene glycol monomethyl ether acetate mixed as a solvent.

[0076] The total mass of the coloring photosensitive resin composition includes 9.3 parts by weight of aluminum phthalocyanine dye, 17.7 parts by weight of Y150, and 27.3 parts by weight of G-Dye.

[0077] Among them, the molecular weight of alkali-soluble resin S1 is 15800 and the acid value is 102.8 mg·KOH / g, while the molecular weight of alkali-soluble resin S2 is 9800 and the acid value is 91.3 mg·KOH / g.

[0078] The specific preparation steps of aluminum phthalocyanine dye are as follows: First, 225 parts of phthalonitrile and 78 parts of anhydrous aluminum chloride are added to 1250 parts of n-pentanol in a reaction vessel and stirred. Then, 266 parts of 1,8-diazabicyclo[5.4.0]undec-7-ene are added, and the mixture is heated and refluxed at 136°C for 5 hours. The reaction solution, cooled to 30°C while stirring, is injected into a mixed solvent of 5000 parts of methanol and 10000 parts of water to obtain a green slurry. The slurry is filtered, washed with a mixed solvent of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of aluminum phthalocyanine chloride. Next, the pigment aluminum phthalocyanine in the above colorant is dispersed using a bead mill or similar device until the average particle size of the pigment reaches below 0.2 μm. A resin dispersant and PGME are added to the pigment to completely dissolve it, thus obtaining a high color gamut aluminum phthalocyanine dye with the following structure: .

[0079] The specific preparation steps of G-Dye are as follows: 1.5g of tetrafluorophthalonitrile, 0.5g of potassium carbonate, and 25ml of acetonitrile are mixed and cooled. Phenylparaben and acetonitrile are added at 2℃ and stirred for 8 hours to obtain an intermediate. 0.7g of this intermediate, 0.15g of zinc chloride, and phenylacetonitrile are mixed and reacted at 170℃ for 5 hours. After the reaction, the mixture is washed with methanol, filtered, and dried under reduced pressure to obtain dye G-Dye.

[0080] Example 4 This embodiment provides a coloring photosensitive resin composition: The total mass of the coloring photosensitive resin composition comprises: 54.3 parts by weight of colorant, 2 parts by weight of alkali-soluble resin S1, 1.8 parts by weight of alkali-soluble resin S2, 3.8 parts by weight of alkali-soluble resin S2, 2.8 parts by weight of DPHA, 0.072 parts by weight of PBG-327, 0.016 parts by weight of additive F-554 and 0.012 parts by weight of additive KBM-503M, 7.0 parts by weight of PGDA and 32.0 parts by weight of propylene glycol monomethyl ether acetate mixed as a solvent.

[0081] The total mass of the coloring photosensitive resin composition includes 9.8 parts by weight of aluminum phthalocyanine dye, 17.7 parts by weight of Y150, and 26.8 parts by weight of G-Dye.

[0082] Among them, the molecular weight of alkali-soluble resin S1 is 15800 and the acid value is 102.8 mg·KOH / g, while the molecular weight of alkali-soluble resin S2 is 9800 and the acid value is 91.3 mg·KOH / g.

[0083] The specific preparation steps of aluminum phthalocyanine dye are as follows: First, 225 parts of phthalonitrile and 78 parts of anhydrous aluminum chloride are added to 1250 parts of n-pentanol in a reaction vessel and stirred. Then, 266 parts of 1,8-diazabicyclo[5.4.0]undec-7-ene are added, and the mixture is heated and refluxed at 136°C for 5 hours. The reaction solution, cooled to 30°C while stirring, is injected into a mixed solvent of 5000 parts of methanol and 10000 parts of water to obtain a green slurry. The slurry is filtered, washed with a mixed solvent of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of aluminum phthalocyanine chloride. Next, the pigment aluminum phthalocyanine in the above colorant is dispersed using a bead mill or similar device until the average particle size of the pigment reaches below 0.2 μm. A resin dispersant and PGME are added to the pigment to completely dissolve it, thus obtaining a high color gamut aluminum phthalocyanine dye with the following structure: .

[0084] The specific preparation steps of G-Dye are as follows: 1.5g of tetrafluorophthalonitrile, 0.5g of potassium carbonate, and 25ml of acetonitrile are mixed and cooled. Phenylparaben and acetonitrile are added at 2℃ and stirred for 8 hours to obtain an intermediate. 0.7g of this intermediate, 0.15g of zinc chloride, and phenylacetonitrile are mixed and reacted at 170℃ for 5 hours. After the reaction, the mixture is washed with methanol, filtered, and dried under reduced pressure to obtain the dye G-Dye. The line fading is as follows... Figure 1 As shown, the edge case is as follows Figure 2 As shown.

[0085] Example 5 This embodiment provides a coloring photosensitive resin composition: The total mass of the coloring photosensitive resin composition comprises: 54.3 parts by weight of colorant, 2 parts by weight of alkali-soluble resin S1, 1.8 parts by weight of alkali-soluble resin S2, 3.8 parts by weight of alkali-soluble resin S2, 2.8 parts by weight of DPHA, 0.072 parts by weight of PBG-327, 0.016 parts by weight of additive F-554 and 0.012 parts by weight of additive KBM-503M, 7.0 parts by weight of PGDA and 32.0 parts by weight of propylene glycol monomethyl ether acetate mixed as a solvent.

[0086] The total mass of the coloring photosensitive resin composition includes 9.8 parts by weight of aluminum phthalocyanine dye, 18.5 parts by weight of Y150, and 26 parts by weight of G-Dye.

[0087] Among them, the molecular weight of alkali-soluble resin S1 is 15800 and the acid value is 102.8 mg·KOH / g, while the molecular weight of alkali-soluble resin S2 is 9800 and the acid value is 91.3 mg·KOH / g.

[0088] The specific preparation steps of aluminum phthalocyanine dye are as follows: First, 225 parts of phthalonitrile and 78 parts of anhydrous aluminum chloride are added to 1250 parts of n-pentanol in a reaction vessel and stirred. Then, 266 parts of 1,8-diazabicyclo[5.4.0]undec-7-ene are added, and the mixture is heated and refluxed at 136°C for 5 hours. The reaction solution, cooled to 30°C while stirring, is injected into a mixed solvent of 5000 parts of methanol and 10000 parts of water to obtain a green slurry. The slurry is filtered, washed with a mixed solvent of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of aluminum phthalocyanine chloride. Next, the pigment aluminum phthalocyanine in the above colorant is dispersed using a bead mill or similar device until the average particle size of the pigment reaches below 0.2 μm. A resin dispersant and PGME are added to the pigment to completely dissolve it, thus obtaining a high color gamut aluminum phthalocyanine dye with the following structure: .

[0089] The specific preparation steps of G-Dye are as follows: 1.5g of tetrafluorophthalonitrile, 0.5g of potassium carbonate, and 25ml of acetonitrile are mixed and cooled. Phenylparaben and acetonitrile are added at 2℃ and stirred for 8 hours to obtain an intermediate. 0.7g of this intermediate, 0.15g of zinc chloride, and phenylacetonitrile are mixed and reacted at 170℃ for 5 hours. After the reaction, the mixture is washed with methanol, filtered, and dried under reduced pressure to obtain dye G-Dye.

[0090] Comparative Example 1 This comparative example differs from Example 1 only in that it uses only 36.6 parts by weight of the G-Dye dye composition as the colorant, instead of the aluminum phthalocyanine composition; the resin composition is 2 parts by weight for S1 and 1.8 parts by weight for S2; all other steps and component compositions remain unchanged. The line fading is as follows: Figure 3 As shown.

[0091] Comparative Example 2 Compared to Example 2, this comparative example differs only in that the colorant used is only 36.6 parts by weight of the aluminum phthalocyanine composition, instead of the G-Dye dye composition; the resin composition is 2 parts by weight for S1 and 1.8 parts by weight for S2; the remaining steps and composition remain unchanged. The phthalocyanine edge is as shown... Figure 4 As shown, it is rather blurry.

[0092] The photosensitive coloring compositions provided in the examples and comparative examples were coated onto a 50mm x 50mm, 2mm thick glass substrate using a spin coater. The substrate was then dried at 100°C for 3 minutes, exposed to ultraviolet light using an ultra-high pressure mercury lamp until the cumulative light intensity reached 60mJ / cm, and developed with an alkaline developer at 23°C to obtain a coated substrate. Next, the substrate was heated to 230°C for 20 minutes, cooled, and the chromaticity of the resulting coating was measured using a microspectrophotometer (using an OLYMPUS Optical OSP-SP100), and recorded as luminance Y(C). The substrates produced after heat treatment at 230°C exhibited the chromaticity of the C light source shown in the table below. An alkaline developer consisting of 0.04% potassium hydroxide was used. The coloring results are shown in Table 1. Where × indicates poor, and ▲ indicates OK. It indicates excellence.

[0093] Table 1

[0094] As shown in Table 1, in the above embodiments, when the y value is 0.5700, the difference in x fluctuates within 1 / 100, and both the transmittance Y and CR values ​​show good performance, indicating good coloring performance comparable to the coloring and CR achieved using only Dye. In the comparative examples, using only G-Dye or only aluminum phthalocyanine resulted in good contrast and y performance, but using only G-Dye resulted in lower y and some issues with migration. Figure 5 The transmissibility test results for Example 4, Comparative Example 1, and Comparative Example 2 are as follows: Figure 5 As shown, the combination of G-Dye and aluminum phthalocyanine effectively reduces migration issues while maximizing optical performance. Aluminum phthalocyanine, as a pigment, offers significant advantages in optical performance compared to other pigments, avoiding the problems associated with using only dyes. It also better utilizes optical performance while maintaining the superior contrast and transmittance of the dye. In Example 4, the line edges performed particularly well, exhibiting neat edges and good taper performance after POB, meeting requirements and demonstrating good line retention. The migration issue was effectively resolved. Regarding reliability, the Eab value was within the acceptable range, indicating good chemical and lightfastness. In this example, the green dye improves the transmittance of the composition. The addition of aluminum phthalocyanine compounds further enhances the composition's performance, not only increasing the CR value but also achieving a wider color gamut, resulting in better reliability and migration resistance.

[0095] In the above embodiments, experimental verification shows that using a resin with a suitable molecular weight is effective. If a resin with a lower molecular weight is used, the DEV effect may be poor, the sensitivity may be low, and the line drop may be severe. If a resin with a higher molecular weight is used, the developability may be poor, and incomplete development may result in severe residue and contamination of the CF end. Therefore, a combination of two resins is used to achieve good sensitivity without leaving any residue on the film surface.

[0096] In the above composition, the addition of aluminum phthalocyanine significantly improves the y-value, provides a high degree of improvement in color gamut, and exhibits superior performance in terms of brightness and contrast.

[0097] Adding G-Dye can effectively improve its transmittance, but simply adding G-Dye will still have problems with migration performance. In order to solve its migration problem and improve transmittance at the same time, aluminum phthalocyanine is added, which greatly improves the performance of photoresist and avoids the occurrence of previous problems.

[0098] Compared to previous phthalocyanine compounds, aluminum phthalocyanine exhibits better solubility. Previous zinc and copper phthalocyanine compounds had high solvent solubility and required no dispersion treatment, leading to the assumption that there were almost no dispersants or alkali-soluble resins around the phthalocyanine compounds, resulting in a weaker affinity between the phthalocyanine compounds and alkali-soluble resins in the coloring resin composition. Phthalocyanine compounds, due to the π-π interactions between phthalocyanine rings and the aforementioned π-π interactions between functional groups, readily associate with each other. Furthermore, the presence of small fluorine atoms further increases the density of molecular packing, resulting in weak affinity for alkali-soluble resins and difficulty in penetrating the phthalocyanine compounds during alkali development. This reduces alkali solubility and easily leaves residues on the glass substrate. However, aluminum phthalocyanine demonstrates superior performance in terms of residue management and shows varying degrees of improvement in pigment dispersion.

[0099] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit them. Although this application 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 this application.

[0100] Furthermore, those skilled in the art will understand that although some embodiments herein include certain features included in other embodiments but not others, combinations of features from different embodiments are intended to be within the scope of this application and form different embodiments. For example, in the foregoing claims, any of the claimed embodiments can be used in any combination. The information disclosed in this background section is intended only to enhance the understanding of the general background of this application and should not be construed as an admission or in any way implying that such information constitutes prior art known to those skilled in the art.

Claims

1. A coloring photosensitive resin composition, characterized in that, The coloring photosensitive resin composition comprises, by weight (100%): 40-60% colorant, 2.5-4.5% alkali-soluble resin, 2-3.5% acrylate monomer, 0.05-0.1% photopolymerization initiator, 0.02-0.03% additives, and 35-52% solvent. The colorant, calculated based on 100% of the total mass of the raw materials in the coloring photosensitive resin composition, includes 8.3-9.8% aluminum phthalocyanine dye, 17.7-18.5% Y150, and 26-28.3% G-Dye.

2. The coloring photosensitive resin composition according to claim 1, characterized in that, The chemical formula of the aluminum phthalocyanine dye is: ； Among them, A1, A2, A3, A4, B1, B2, B3, B4, C1, C2, C3, C4, D1, D2, D3, and D4 each independently include one or more of F, Cl, and Br.

3. The coloring photosensitive resin composition according to claim 2, characterized in that, The preparation method of the aluminum phthalocyanine dye includes: A first slurry is obtained by mixing phthalonitrile, anhydrous aluminum chloride, 1,8-diazabicyclo[5.4.0]undec-7-ene and n-pentanol, and then subjected to a first cooling after heating and reflux. The first slurry after heating and reflux is mixed with methanol and water to obtain a green slurry. The green slurry is then subjected to drying, pulverizing, dispersing and dissolving in sequence to obtain the aluminum phthalocyanine dye.

4. The coloring photosensitive resin composition according to claim 3, characterized in that, At least one of the following conditions must be met: a. The mass ratio of the phthalonitrile, the anhydrous aluminum chloride, the 1,8-diazabicyclo[5.4.0]undec-7-ene, and the n-pentanol is 2.5-3:1:15:2.5-3; b. The heating reflux temperature is 133-138℃, and the time is 4.9-5.1h; c. The final temperature of the first cooling is 28-32℃; d. After the aforementioned crushing, the particle size is no greater than 0.2 μm; e. The dispersion and dissolution comprises: mixing the green slurry, which has undergone the drying and pulverization process once, with a dispersant and propylene glycol methyl ether; The dispersant includes methacrylate.

5. The coloring photosensitive resin composition according to claim 1, characterized in that, The preparation method of the G-Dye includes: A first solution was obtained by mixing tetrafluorophthalonitrile, potassium carbonate, and acetonitrile. After a second cooling, the solution was stirred with phenyl p-hydroxybenzoate and acetonitrile to obtain an intermediate. The intermediate was mixed with zinc chloride and phenylacetonitrile, and after reaction, it was washed, separated into solid and liquid components, and dried to obtain G-Dye.

6. The coloring photosensitive resin composition according to claim 5, characterized in that, At least one of the following conditions must be met: f. The mass ratio of the tetrafluorophthalonitrile, the potassium carbonate, and the acetonitrile is 1.5-1.8:0.5:24-25; g. The final temperature of the second cooling is 2°C; h. The stirring time is 7.8-8.3 hours; i. The mass ratio of the intermediate, the zinc chloride, and the phenylacetonitrile is 0.7:0.15-0.2:0.5; the reaction temperature is 160-180℃, and the reaction time is 4.9-5.2h.

7. The coloring photosensitive resin composition according to claim 1, characterized in that, The alkali-soluble resin has a molecular weight of 10,000-50,000 and an acid value of 100 mg·KOH / g; or, The molecular weight of alkali-soluble resins is not higher than 10,000, and the acid value is not higher than 50 mg·KOH / g.

8. The coloring photosensitive resin composition according to claim 1, characterized in that, The photopolymerization initiator includes oxime ester initiators; The oxime ester initiators include PBG-345 and / or PBG-327.

9. The coloring photosensitive resin composition according to any one of claims 1-8, characterized in that, At least one of the following conditions must be met: c. The acrylate monomer includes at least one of methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, and tert-butyl methacrylate; d. The adjuvants include F-554 and / or KBM-503M; e. The solvent includes PGMEA and / or PGDA.

10. A color filter, characterized in that, Its raw materials include the coloring photosensitive resin composition according to any one of claims 1-9.

Images