Ion-type naphthalene diimide derivative, preparation method thereof, photosensitive resin composition and application thereof

Abstract

This invention relates to an ionic naphthalimide derivative and its preparation method, a photosensitive resin composition, and its application. In the derivative, R1 to R6 are each independently selected from hydrogen and a group containing a positive ion. The group is selected from substituted or unsubstituted fused heterocyclic groups, monocyclic aromatic heterocyclic groups, and polycyclic aromatic heterocyclic groups. The method includes: synthesis of 2,6-dihalonaphthalene-1,4,5,8-tetracarboxylic dianhydride; synthesis of a first intermediate; synthesis of a second intermediate; and synthesis of the naphthalimide derivative. The composition includes the naphthalimide derivative, a solvent, a multifunctional monomer, a base-soluble resin, a photoinitiator, and additives. The composition is used in filters for display devices and sensing devices. Compared with the prior art, this invention has good photothermal and chemical stability.

Description

Technical Field

[0001] This invention belongs to the field of dye technology and relates to an ionic naphthalimide derivative and its preparation method, a photosensitive resin composition and its application. Background Technology

[0002] With the development of display technology, flat panel displays have become the mainstream in the market. Among flat panel displays, LCDs (electronic modulation optics, composed of multiple sections filled with liquid crystals and arranged in front of a light source (backlight) to produce color images) occupy the largest market share due to their numerous advantages such as low cost, low power consumption, and flexibility. Color filters, which convert white backlight into red (R), green (G), and blue (B) colored light, are a key component in the development of display technology because they have the greatest potential to improve image quality. Only 6.3% of backlight can pass through the entire panel; a large amount of backlight is blocked by components such as polarizing filters, thin-film transistor (TFT) arrays, liquid crystal (LC) cells, and color filters. In particular, the transmittance through color filters is the lowest (30%). Therefore, developing color filters with high transmittance is essential for saving energy consumption and improving the quality of displays.

[0003] Currently, pigment dispersion methods using photolithography to form RGB patterned pixels are widely used in the production of color filters because they can produce color filters with high stability. Although color filters produced by this method have good thermal and photochemical stability, they exhibit low color properties due to the aggregation behavior of the pigment particles used as colorants. Dyes can be an attractive alternative to overcome this limitation because they dissolve in the medium and exist in molecular form, thus reducing light scattering. However, while dyes can generally produce color filters with high transmittance and high contrast, they have poor heat and light resistance, and are prone to colorimetric changes during the high-temperature heating process in the color filter production step. Furthermore, they should be highly soluble in industrial solvents and have strong absorption peaks to obtain excellent optical performance. Specifically, the problems are:

[0004] (1) Dyes in a molecularly dispersed state are generally inferior in terms of lightfastness and heat resistance compared to pigments that form molecular aggregates. In particular, the problem is that the optical properties are altered by high-temperature processes when forming indium tin oxide (ITO) films, which are widely used as electrodes for liquid crystal displays, etc.

[0005] (2) Dyes in a molecularly dispersed state are generally less solvent resistant than pigments that form molecular aggregates.

[0006] (3) Dyes tend to inhibit free radical polymerization, which makes it difficult to design colorable curable compositions for systems that use free radical polymerization as a curing method;

[0007] (4) Traditional dyes exhibit low solubility in alkaline aqueous solutions or organic solvents, making it difficult to obtain coloring curable compositions with the desired spectrum;

[0008] (5) Dyes often interact with other components in coloring curable compositions, making it difficult to control the solubility (developability) of the exposed and unexposed portions;

[0009] (6) When the molar absorptivity (ε) of the dye is low, a large amount of dye needs to be added. Therefore, the amount of other components in the coloring curable composition, such as polymerizable compounds (monomers), binders or photopolymerization initiators, must be reduced relatively, thereby reducing the curability of the coloring curable composition, as well as its heat resistance and developability after curing.

[0010] Patent CN107548395A discloses a specific N and P active material for the organic photoelectric conversion layer in an organic photodiode. This patent uses naphthalimide (NDI) as the core structure, but after side chain modification, the structure does not exhibit good transmission performance in the blue light region, and therefore cannot be used as a blue dye in the filters of display devices and sensing devices. Summary of the Invention

[0011] The purpose of this invention is to overcome at least one defect of the prior art and provide an ionic naphthalimide derivative and its preparation method, a photosensitive resin composition and its application. This invention has good photothermal and chemical stability.

[0012] The objective of this invention can be achieved through the following technical solutions:

[0013] One of the technical solutions of the present invention is to provide an ionic naphthalimide derivative, the structural formula of which is:

[0014]

[0015] R1 to R6 are each independently selected from hydrogen and a group containing a positive ion, wherein the group is selected from substituted or unsubstituted fused heterocyclic groups, monocyclic aromatic heterocyclic groups, and polycyclic aromatic heterocyclic groups.

[0016] Furthermore, each of R1 to R6 is independently selected from hydrogen, or one of the following structural groups:

[0017]

[0018] In this context, the dashed lines represent the bonds connecting R1 to R6 to the parent nucleus in general formula (Ⅰ), L1 to L9 are each independently selected from hydrogen, or one of straight-chain alkyl, branched alkyl, or ester groups, X includes oxygen or sulfur, Y includes chlorine, bromine, or iodine halogen, and n is an integer from 1 to 10.

[0019] Furthermore, each of L1 to L9 is independently selected from hydrogen, or one of the following structural groups:

[0020]

[0021] In this context, the dashed lines represent the connection keys between L1 to L9 and R1 to R6, and n is an integer from 0 to 36.

[0022] Furthermore, each of R1 to R6 is independently selected from hydrogen, or one of the following structural groups:

[0023]

[0024]

[0025] In this context, the dashed lines represent the bonds connecting R1 to R6 to the parent nucleus in general formula (Ⅰ), and L1 includes straight-chain alkyl, branched-chain alkyl, or ester groups.

[0026] Furthermore, the derivative is selected from one of the following structures:

[0027]

[0028]

[0029]

[0030]

[0031]

[0032]

[0033] One of the technical solutions of the present invention is to provide a method for preparing an ionic naphthalimide derivative, the method comprising the following steps:

[0034] (1) Synthesis of 2,6-dihalonaphthalene-1,4,5,8-tetracarboxylic dianhydride: The first halogenated compound was added to the mixture of 1,4,5,8-naphthalenetetracarboxylic anhydride (NDA) and concentrated acid to carry out the reaction. After the reaction was completed, the mixture was cooled, washed to remove acid and water, and dried to obtain 2,6-dihalonaphthalene-1,4,5,8-tetracarboxylic dianhydride.

[0035] (2) Synthesis of the first intermediate: 2,6-dihalonaphthalic-1,4,5,8-tetracarboxylic dianhydride, heterocyclic amine and acid were mixed and reacted in an inert gas. After the reaction was completed, the mixture was cooled, filtered to obtain a solid, vacuum dried and purified to obtain the first intermediate.

[0036] (3) Synthesis of the second intermediate: The first intermediate, heterocyclic amine and solvent are mixed and reacted in an inert gas. After the reaction is complete, the mixture is cooled, the aqueous layer is extracted, the combined organic extracts are dried and purified to obtain the second intermediate.

[0037] (4) Synthesis of naphthalimide derivatives: The second intermediate, the second halogenated compound and the solvent are mixed and reacted in an inert gas. After the reaction is completed, the mixture is cooled, precipitated and filtered out to obtain ionic naphthalimide derivatives.

[0038] As a preferred technical solution, the inert gas in steps (2) to (4) includes nitrogen or argon.

[0039] Furthermore, the concentrated acid in step (1) includes concentrated sulfuric acid, and the first halogenated compound includes dibromohydantoin (DBH).

[0040] The molar ratio of 1,4,5,8-naphthalenetetracarboxylic anhydride, concentrated acid, and the first halogenated compound is 1 mol:(3-5 L):(2-4 mol).

[0041] The reaction temperature is 60-100℃, and the time is 12-36h;

[0042] In steps (2) and (3), the heterocyclic amine uses a group with an amino group and a positive ion. The group is selected from one of the following: substituted or unsubstituted fused heterocyclic groups, monocyclic aromatic heterocyclic groups, and polycyclic aromatic heterocyclic groups.

[0043] The acid in step (2) includes acetic acid.

[0044] The ratio of 2,6-dihalonaphthalic-1,4,5,8-tetracarboxylic dianhydride, heterocyclic amine, and acid is 1 mol:(3-10 mol):(10-50 L).

[0045] The reaction temperature is 100-150℃, and the time is 2-6 hours;

[0046] The solvents used in steps (3) and (4) include N,N-dimethylformamide (DMF);

[0047] In step (3), the ratio of the first intermediate, heterocyclic amine, and solvent is 1 mol:(3-10 mol):(10-50 L).

[0048] The reaction temperature is 100-150℃, and the time is 8-18 hours;

[0049] The second halogenated compounds in step (4) include iodobutane, bromobutane, chlorobutane, iodononane, bromononane, chlorononane, isopropyl iodine, isopropyl bromide, isopropyl chloride, propyl 3-iodopropionate, propyl 3-bromopropionate, propyl 3-chloropropionate, iodomethane, bromomethane, and chloromethane.

[0050] The molar ratio of the second intermediate, the second halogenated compound, and the second solvent is 1 mol:(4-6 mol):(1-10 L).

[0051] The reaction temperature is 100-150℃ and the time is 24-72h.

[0052] As a preferred technical solution, the heterocyclic amine in steps (2) and (3) is selected from one of the following structures:

[0053]

[0054] Wherein, the dashed line connects the amino group, L1 to L9 are each independently selected from hydrogen, or one of straight-chain alkyl, branched alkyl, or ester groups, X includes oxygen or sulfur, Y includes chlorine, bromine, or iodine halogen, and n is an integer from 1 to 10.

[0055] As a preferred technical solution, the heterocyclic amine in steps (2) and (3) is selected from one of the following structures:

[0056]

[0057] In this context, the dashed line connects amino groups, and L1 includes straight-chain alkyl, branched alkyl, or ester groups.

[0058] As a preferred technical solution, the mixing temperature in step (1) is room temperature, and the time is 3-30 min;

[0059] Cool to room temperature, pour the product into ice water, and add a saturated sodium sulfite (Na2SO3) aqueous solution to remove the hydrogen bromide generated in the reaction;

[0060] The washing and deacidification reagent includes water, and the number of times is one to five;

[0061] The washing and dehydration reagent includes ethanol, and the number of times is one to five;

[0062] The drying temperature is 50-100℃.

[0063] As a preferred technical solution, in step (2), the mixture is cooled to room temperature and then poured into ice water;

[0064] The temperature for vacuum drying is 30-80℃;

[0065] Purification was performed using silica gel column chromatography, with the eluent consisting of a mixture of dichloromethane and acetone in a volume ratio of 1:(1-3).

[0066] As a preferred technical solution, in step (3), the mixture is cooled to room temperature and quenched with a saturated sodium bicarbonate (NaHCO3) aqueous solution;

[0067] The extraction reagents include dichloromethane, and the number of extractions is one to five.

[0068] The dried reagents include magnesium sulfate (MgSO4);

[0069] Purification was performed using silica gel column chromatography, with the eluent consisting of a mixture of petroleum ether and dichloromethane in a volume ratio of 1:(1-3).

[0070] As a preferred technical solution, in step (4), the product is cooled to room temperature, ethanol is added to precipitate the product, and then filtered out.

[0071] One of the technical solutions of the present invention is to provide a photosensitive resin composition, the composition comprising the aforementioned ionic naphthalimide derivative, the composition comprising the following components and their weight percentages:

[0072]

[0073] Furthermore, the multifunctional monomer is selected from one or more of pentaerythritol hexaacrylate and propoxytrimethylolpropane trimethacrylate, and the solvent is selected from one or more of propylene glycol methyl ether acetate and propylene glycol methyl ether.

[0074] As a preferred technical solution, the alkali-soluble resin includes Sarbox SB400 from Sartoma Corporation, the photoinitiator includes IRGACURE OXE 01 from BASF Corporation, and the additive is selected from one or more of F-556 from DIC Corporation and KH570 (γ-methacryloyloxypropyltrimethoxysilane) from Bailingwei Corporation.

[0075] One of the technical solutions of the present invention is to provide a method for preparing a photosensitive resin composition, the method comprising the following steps:

[0076] A colorant, a multifunctional monomer, an alkali-soluble resin, an additive, and a photoinitiator are taken, wherein the colorant includes derivatives and a solvent. The solvent is added and the mixture is fully dissolved and mixed to obtain a photosensitive resin composition.

[0077] As a preferred technical solution, the solid content of the composition is 10-30%.

[0078] One of the technical solutions of the present invention is to provide an application of a photosensitive resin composition, wherein the composition is applied to filters of display devices and sensing devices.

[0079] Compared with the prior art, the present invention has the following beneficial effects:

[0080] (1) This invention employs a closed-ring fused-ring π-conjugated core structure such as naphthalimide (NDI). Its closed-ring and π-conjugated characteristics can give the molecular skeleton high chemical bond energy, thus providing a basis for good photothermal chemical stability. At the same time, the optical properties of naphthalimide derivatives can be adjusted by substitution at the core or imide position while maintaining photothermal stability.

[0081] (2) This invention transforms the neutral naphthalimide structure into a positively charged cationic structure by substitution. The modification of the outer molecular chain segments can improve the solubility of the dye in the solvent and its compatibility with other components of the color photoresist. The repulsion between cations inhibits the aggregation of the dye in the solid state, thereby further improving the photothermal stability of the dye and its anti-migration ability in the color photoresist. This type of dye has good solubility and high photothermal stability. When applied to color filters, it can effectively improve the image performance and service life of the device. Detailed Implementation

[0082] The present invention will now be described in detail with reference to 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.

[0083] Unless otherwise specified, the equipment used in the following embodiments is conventional equipment in the art; unless otherwise specified, the reagents used are commercially available products or prepared by conventional methods in the art. In the following embodiments, unless otherwise described in detail, conventional experimental methods in the art can be used.

[0084] Example 1-1:

[0085] An ionic naphthalimide derivative and its preparation method are described below:

[0086] The synthesis of S1, 2,6-dibromonaphthalene-1,4,5,8-tetracarboxylic dianhydride is shown in the following reaction equation:

[0087]

[0088] The specific steps are as follows:

[0089] In a 150 mL thick-walled pressure-resistant bottle, 1,4,5,8-naphthalenetetracarboxylic anhydride (NDA, 20 mmol) and concentrated sulfuric acid (60 mL) were added sequentially. The mixture was stirred at room temperature for 5 min to dissolve the anhydride. Dibromohydantoin (DBH, 45 mmol) was added in batches (to prevent clumping). The mixture was sealed and stirred at 80 °C for 24 h. After the substitution reaction was completed, the mixture was cooled to room temperature. The product was poured into ice water, and saturated sodium sulfite (Na2SO3) aqueous solution was added to remove the hydrogen bromide generated in the reaction. The product was washed three times with water to remove acid, and three times with ethanol to remove water. The product was dried at 80 °C to obtain 2,6-dibromonaphthalene-1,4,5,8-tetracarboxylic dianhydride with a yield of 83%.

[0090] The synthesis of S2 and intermediate 1 is shown in the following reaction equation:

[0091]

[0092] The specific steps are as follows:

[0093] In a 150 mL thick-walled pressure-resistant bottle, a mixture of 2,6-dibromonaphthalene-1,4,5,8-tetracarboxylic dianhydride (2 mmol), starting material 1-1 (3,5-diisopropylpyridine-4-amine, 6 mmol), and acetic acid (30 mL) was stirred at 120 °C for 2 h under nitrogen (N2) protection. After the substitution reaction was completed, the mixture was cooled to room temperature, poured into ice water, filtered to obtain a solid, dried under vacuum at 50 °C, and purified by column chromatography on a silica gel column using dichloromethane and petroleum ether in a volume ratio of 2:3 to obtain an orange-red solid intermediate 1 with a yield of 77%.

[0094] The synthesis of S3 and intermediate 2-1 is shown in the following reaction equation:

[0095]

[0096] The specific steps are as follows:

[0097] Intermediate 1 (0.54 mmol), starting material 1-1 (5 mmol), and anhydrous N,N-dimethylformamide (DMF) (20 mL) were added to a 50 mL double-necked flask. The mixture was heated under N2 protection and refluxed at 135 °C for 10 h. After the substitution reaction was completed, the mixture was cooled to room temperature and quenched with a saturated sodium bicarbonate (NaHCO3) aqueous solution. The aqueous layer was extracted with dichloromethane (3 × 100 mL). The combined organic extracts were dried over anhydrous magnesium sulfate (MgSO4) and purified by column chromatography on a silica gel column using petroleum ether and dichloromethane in a volume ratio of 1:1 to give a blue solid intermediate 2-1 in 85% yield.

[0098] S4. The synthesis of ionic naphthalimide derivatives is shown in the following reaction equation:

[0099]

[0100] The specific steps are as follows:

[0101] Intermediate 2-1 (5 mmol) and starting material 2-1 (iodononane, 20 mmol) were dissolved in anhydrous DMF (10 mL) and added to a 50 mL double-necked flask. The mixture was reacted at 120 °C for 48 h under N2 protection. After the substitution reaction was completed, the mixture was cooled to room temperature, and ethanol (40 mL) was added to precipitate the product and filter it out to obtain a blue powder ionic naphthalimide derivative with the structure of dye formula (15) and a yield of 90%.

[0102] Examples 1-2 to 1-12:

[0103] An ionic naphthalimide derivative and its preparation method are basically the same as those in Examples 1-1, with the following differences:

[0104] The starting material 1 used in step S3 is different from starting material 1-1 (3,5-diisopropylpyridine-4-amine). The specific structures of intermediates 2-2 to 2-16 corresponding to starting materials 1-2 to 1-16 are as follows:

[0105]

[0106]

[0107] The starting material 2 selected in step S4 is different from starting material 2-1 (iodononane). Starting materials 2-2 to 2-15 include bromononane, chlorononane, iodobutane, bromobutane, chlorobutane, isopropyl iodine, isopropyl bromide, isopropyl chloride, propyl 3-iodopropionate, propyl 3-bromopropionate, propyl 3-chloropropionate, iodomethane, bromomethane, and chloromethane.

[0108] The starting materials and intermediates used in Examples 1-1 to 1-12, as well as the molecular structures of the products, are shown in Table 1.

[0109] Table 1 shows the starting materials and intermediates used in Examples 1-1 to 1-12, and the molecular structures of the products.

[0110] Example In step S3, starting material 1 Intermediate 2 In step S4, starting material 2 Synthetic dye formula Example 1-1 Starting material 1-1 Intermediate 2-1 Starting material 2-1 Dye formula (15) Examples 1-2 Starting material 1-2 Intermediate 2-2 Starting material 2-6 Dye formula (4) Examples 1-3 Starting material 1-1 Intermediate 2-1 Starting material 2-4 Dye formula (12) Examples 1-4 Starting materials 1-3 Intermediate 2-3 Starting material 2-2 Dye formula (14) Examples 1-5 Starting material 1-2 Intermediate 2-2 Starting material 2-1 Dye formula (18) Examples 1-6 Starting materials 1-5 Intermediate 2-5 Starting material 2-8 Dye formula (41) Examples 1-7 Starting materials 1-8 Intermediate 2-8 Starting material 2-13 Dye formula (36) Examples 1-8 Starting materials 1-13 Intermediate 2-13 Starting material 2-3 Dye formula (22) Examples 1-9 Starting materials 1-15 Intermediate 2-15 Starting material 2-2 Dye formula (26) Examples 1-10 Starting materials 1-16 Intermediate 2-16 Starting material 2-1 Dye-based (30) Examples 1-11 Starting material 1-1 Intermediate 2-1 Starting material 2-12 Dye formula (43) Examples 1-12 Starting material 1-1 Intermediate 2-1 Starting materials 2-7 Dye formula (48)

[0111] Example 2-1:

[0112] A photosensitive resin composition and its preparation method are described below:

[0113] Take 200 parts by weight of colorant (composed of 100 parts by weight of ionic naphthalimide derivative (dye formula (15)) from Example 1-1 and 100 parts by weight of solvent Q1), 50 parts by weight of multifunctional monomer M1, 50 parts by weight of multifunctional monomer M2, 100 parts by weight of alkali-soluble resin N, 0.2 parts by weight of additive 01, 0.3 parts by weight of additive 02 and 5 parts by weight of photoinitiator P, add 100 parts by weight of solvent Q1 and 50 parts by weight of solvent Q2 and fully dissolve and mix, controlling the solid content at 20%, to obtain a blue photosensitive resin composition.

[0114] in,

[0115] Multifunctional monomer M1: dipentaerythritol hexaacrylate (analytical grade), purchased from Sartoma;

[0116] Multifunctional monomer M2: propionyl trimethylolpropane trimethacrylate (analytical grade), purchased from Double Bond Chemical Co., Ltd., Taiwan, China;

[0117] Alkali-soluble resin N: Trade name Sarbox SB400 (analytical grade), purchased from Sardoma;

[0118] Additive 01: Trade name F-556 (analytical grade), purchased from DIC Corporation;

[0119] Additive 02: KH570 (γ-methacryloyloxypropyltrimethoxysilane), purchased from Bailingwei Company;

[0120] Photoinitiator P: Trade name IRGACURE OXE 01 (analytical grade), purchased from BASF;

[0121] Solvent Q1: PGMEA (propylene glycol methyl ether acetate, analytical grade), purchased from Dow Chemical Company;

[0122] Solvent Q2: PGME (propylene glycol methyl ether, analytical grade), purchased from Dow Chemical Company.

[0123] Examples 2-2 to 2-12:

[0124] A photosensitive resin composition and its preparation method are basically the same as those in Examples 2-1, except that the dye used in the coloring agent is an ionic naphthalimide derivative corresponding to Examples 1-2 to 1-12.

[0125] Comparative Example 2-1:

[0126] A photosensitive resin composition and its preparation method are basically the same as those in Examples 2-1, except that the dye used in the coloring agent is CI Solvent Blue 106.

[0127] Comparative Example 2-2:

[0128] A photosensitive resin composition and its preparation method are basically the same as those in Example 2-1, except that the dye used in the coloring agent is intermediate 2-1.

[0129] The performance testing of the above photosensitive resin composition was performed using photolithography, with the specific steps as follows:

[0130] The glass slides were washed and dried, and then coated with adhesive using a rotary coater to obtain a uniform film layer of 1.5 μm. The film was pre-baked at 90℃ for 120 s and then exposed to 365 nm ultraviolet light at an exposure dose of 40 mJ / cm². 2 The distance between the mask and the coating was 180 μm. Development was performed at 23°C for 50 seconds, followed by baking at 230°C for 20 minutes. Subsequent performance tests were then conducted.

[0131] The specific steps of the performance testing and evaluation methods are as follows:

[0132] (1) Colorimetry: Detected using a Konica Minolta CM-5 spectrophotometer;

[0133] (2) System compatibility: The photosensitive resin composition was stored in the dark at 8°C, and its viscosity was tested for six months. Photolithography was performed according to the process conditions, and the presence of particles on the color filter surface was examined under a 500x optical microscope (OM).

[0134] The evaluation criteria are as follows:

[0135] ○: Viscosity change value < ±5% mPa·s and no particles on the ×500 surface;

[0136] △: Viscosity change value < ±10% mPa·s and no particles on the ×500 surface;

[0137] ×: Viscosity change value > ±10% mPa·s or ×500 indicates particles on the surface;

[0138] (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 minutes, 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 ΔE ab A value less than 3 indicates good heat resistance;

[0139] (4) Solvent resistance evaluation: After drying, the sample was immersed in isopropanol at room temperature for 5 minutes, then baked in an oven at 150°C for 30 minutes. The color difference before and after was measured. If ΔE ab A value less than 3 indicates good solvent resistance;

[0140] (5) Evaluation of anti-migration performance: Following the manufacturing process of color filters, red or blue pixel A is first prepared on thin-film transistor (TFT) glass; then the sample is coated, and after development, the surface of the color filter is dried, and the color difference before and after pixel A is measured. If ΔE ab <3 indicates good resistance to transfection;

[0141] (6) Line width, edge neatness, and development process tolerance:

[0142] The linewidth and edge neatness of the mask were tested by ×500 OM, and the linewidth of the mask was 140μm.

[0143] When evaluating the margin of development process, other process conditions are fixed, and the edge neatness and edge residue or edge peeling of the image obtained with a development time between 40-100s are examined. The peeling is judged with reference to the adhesion measurement method in this field.

[0144] The evaluation criteria for edge neatness are as follows:

[0145] ○: After 50 seconds of development, the edges are neat and there is no residue at the edges;

[0146] △: The image developed for 50 seconds has rough, uneven edges or residue at the edges;

[0147] ×: Image missing;

[0148] The evaluation criteria for development process margin are as follows:

[0149] ○: After developing for 40-100 seconds, the edges are neat and there is no residue or peeling at the edges;

[0150] △: After developing for 50-80 seconds, the edges are neat and there is no residue or peeling at the edges;

[0151] ×: The edges are uneven after 50-80 seconds of development, or there is residue at the edges, or there is peeling at the edges;

[0152] 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, have an [OH-] concentration of 0.2-1.0%, preferably 0.4-0.6%. In this embodiment, an aqueous solution of sodium hydroxide with an [OH-] concentration of 0.4% is used.

[0153] The evaluation results of the photosensitive resin compositions in Examples 2-1 to 2-12 and Comparative Examples 2-1 and 2-2 are shown in Table 2.

[0154] Table 2 Evaluation results of the photosensitive resin compositions in Examples 2-1 to 2-12 and Comparative Examples 2-1 and 2-2

[0155]

[0156] As shown in Table 2, the CI solvent Blue 106 of Comparative Example 2-1 is slightly soluble in the color photoresist solvent PGMEA, while Examples 2-1 to 2-12 have good solubility in the color photoresist solvent PGMEA, and the blue color purity in the color photoresist solvent PGMEA is higher.

[0157] Compared with the blue photosensitive resin composition of Comparative Example 2-2 using neutral intermediate 2-1 as a colorant, the blue photosensitive resin compositions of Examples 2-1, 2-3, 2-11, and 2-12 with intermediate 2 as intermediate 2-1 have better heat resistance, solvent resistance, and anti-migration properties.

[0158] Meanwhile, the blue photosensitive resin compositions of Examples 2-1 to 2-12 also exhibit similar good processing properties as Comparative Examples 2-1 and 2-2, such as linewidth, system compatibility, edge neatness, and development process margin.

[0159] This invention provides a high-performance compound for use as a blue dye in filters for display and sensing devices such as liquid crystal displays and image sensors. The invention employs a closed-ring fused-ring π-conjugated core structure, such as naphthalimide (NDI). The closed-ring and π-conjugated characteristics of NDI enable the molecular backbone to possess high chemical bond energies, thus resulting in good chemical stability of the naphthalimide derivatives. The optical properties of NDI can be easily tuned by substitution at the NDI core or imide positions. This invention prepares a series of cationic naphthalimides, utilizing the repulsive effect between cations to inhibit dye aggregation in the solid state, thereby further improving the photothermal stability of the naphthalimide derivative dyes.

[0160] This invention overcomes the problems of poor photothermal stability of traditional dyes and their poor solubility in color photoresist systems. At the same time, it prepares a series of cationic naphthalimides to solve the problem of dye aggregation, thereby improving the photothermal stability of dyes and their anti-migration ability in color photoresists.

[0161] 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. An ionic naphthalimide derivative, characterized in that, The structural formula of the derivative is: Wherein, R2 and R5 are selected from hydrogen, R3 and R6 are selected from structural groups of the following formula (C-1), and R1 and R4 are selected from structural groups of the following formulas (C-1) to (C-16): In this context, the dashed lines represent the bonds connecting R1, R3, R4, and R6 to the parent nucleus in general formula (Ⅰ), and L1 is selected from one of the following structural groups: In this context, the dashed lines represent the connection keys between L1 and R1, R3, R4, and R6, and n is an integer from 0 to 36.

2. An ionic naphthalimide derivative, characterized by, The derivative is selected from one of the following structures: 。 3. A process for the preparation of an ionic naphthalimide derivative according to claim 2, characterized in that, The method includes the following steps: (1) Synthesis of 2,6-dihalonaphthalene-1,4,5,8-tetracarboxylic dianhydride: 1,4,5,8-naphthalenetetracarboxylic dianhydride and concentrated acid were added to a first halogenated compound and reacted to obtain 2,6-dihalonaphthalene-1,4,5,8-tetracarboxylic dianhydride. (2) Synthesis of the first intermediate: 2,6-dihalonaphthalene-1,4,5,8-tetracarboxylic dianhydride, starting material 1-1 and acid were mixed and reacted to obtain the first intermediate; (3) Synthesis of the second intermediate: The first intermediate, starting material 1 and solvent are mixed and reacted to obtain the second intermediate; (4) Synthesis of naphthalimide derivatives: The second intermediate, the second halogenated compound and the solvent are mixed and reacted to obtain ionic naphthalimide derivatives; The concentrated acid in step (1) includes concentrated sulfuric acid; The structural formula of starting material 1-1 in step (2) is: ； In step (3), starting material 1 is selected from one of the following structures: ； The second halogenated compounds in step (4) include iodobutane, bromobutane, chlorobutane, iodononane, bromononane, chlorononane, isopropyl iodine, isopropyl bromide, isopropyl chloride, propyl 3-iodopropionate, propyl 3-bromopropionate, and propyl 3-chloropropionate.

4. The method for preparing an ionic naphthalimide derivative according to claim 3, characterized in that, The first halogenated compound in step (1) includes dibromohydantoin. The molar ratio of 1,4,5,8-naphthalenetetracarboxylic anhydride, concentrated acid, and the first halogenated compound is 1 mol:(3-5 L):(2-4 mol). The reaction temperature is 60-100 ℃, and the time is 12-36 h; The acid in step (2) includes acetic acid. The ratio of 2,6-dihalonaphthalene-1,4,5,8-tetracarboxylic dianhydride, starting material 1-1, to acid is 1 mol:(3-10 mol):(10-50 L). The reaction temperature is 100-150 ℃, and the time is 2-6 h; The solvent in steps (3) and (4) includes N,N-dimethylformamide; In step (3), the ratio of the first intermediate, starting material 1, and solvent is 1 mol:(3-10 mol):(10-50 L). The reaction temperature is 100-150 ℃, and the time is 8-18 h; In step (4), the ratio of the second intermediate, the second halogenated compound, and the solvent is 1 mol:(4-6 mol):(1-10 L). The reaction temperature is 100-150 ℃, and the time is 24-72 h.

5. A photosensitive resin composition, characterized by comprising: The composition comprises the ionic naphthalimide derivative as described in claim 1 or 2, and the composition comprises the following components and their weight percentages: 80-120 parts of naphthalimide derivative, Solvent 220-280 parts, 80-120 parts of multifunctional monomers 80-120 parts of alkali-soluble resin, 4-6 parts of photoinitiator Additives: 0.4-0.6 parts.

6. The photosensitive resin composition according to claim 5, wherein The multifunctional monomer is selected from one or more of pentaerythritol hexaacrylate and propoxytrimethylolpropane trimethacrylate, and the solvent is selected from one or more of propylene glycol methyl ether acetate and propylene glycol methyl ether.

7. Use of the photosensitive resin composition according to claim 5, characterized in that, The composition is used in filters for display devices and sensing devices.

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