Zinc phthalocyanine, green photosensitive resin composition and application thereof

Abstract

The invention relates to zinc phthalocyanine, a green photosensitive resin composition and application thereof, the zinc phthalocyanine is prepared by substituting benzene ring sites on the periphery of a parent nucleus of zinc phthalocyanine through multifunctional groups, and the structural formula of the zinc phthalocyanine is as follows: R1-R16 are independently selected from any one of hydrogen atoms, chlorine atoms, alkyl groups, aryl groups or heteroaryl substituent groups; and R1 to R16 at least comprise one naphthalimide group. The green photosensitive resin composition is obtained by mixing a coloring agent, resin containing a double-bond structure or / and an epoxy structure, a monomer containing the double-bond structure or / and the epoxy structure, a photoinitiator with 365nm high absorption characteristic, an additive for improving film-forming property or / and stability, and a solvent containing an ether group. Compared with the prior art, the zinc phthalocyanine disclosed by the invention has excellent solubility and high green color purity, and the obtained green photosensitive resin composition can be prepared into a thinner colored layer, has light and heat stability, and can be used as a color photoresist for preparing a color filter.

Description

Technical Field

[0001] The present invention relates to the technical field of dye preparation, in particular to a zinc phthalocyanine and green photosensitive resin composition and applications thereof. Background Art

[0002] With the rapid development of 5G communication, virtual reality and ultra-high-definition display technology, modern display and imaging devices have increasingly stringent performance requirements for optical components. In a liquid crystal display (LCD), a color filter converts the white light of the backlight unit into red (R), green (G) and blue (B) primary colors, and then produces a color image. Therefore, the color filter is a key component that determines the color purity and color gamut of the image. Among them, the green filter mainly filters out red light and blue light, so that the light passing through is mainly concentrated within the green band range, achieving accurate color separation and processing. The pigment dispersion method is a common method for preparing a green filter, that is, a photosensitive resin composition containing a colorant is coated on a transparent substrate with a black matrix, the formed pattern is exposed, the unexposed portion is removed with a solvent, and the pattern is thermally cured. The colored photosensitive resin composition used to prepare a green filter by the pigment dispersion method generally includes a green colorant, a resin, a monomer, a photoinitiator, an additive, a solvent, etc. At present, the green colorant is generally a zinc phthalocyanine compound, such as Pigment Green G58. Although the filter produced by this method has good photothermal stability, it still has the following shortcomings: (1) Zinc phthalocyanine pigment exists in the form of particles in the photoresist system and is easy to aggregate, which easily causes light refraction or light reflection, resulting in low transmittance of the prepared green filter; (2) Zinc phthalocyanine pigment is aggregated and its thermal stability is reduced in the subsequent post-baking process of preparing the green filter, resulting in significant changes in optical properties; (3) Zinc phthalocyanine pigment has poor color purity, and color compensation pigments are often required to be added during use to make up for the lack of color purity, which may cause the transmittance spectrum of the zinc phthalocyanine pigment itself to shift and the transmittance to decrease, and the compatibility between the components of the green photosensitive resin composition to deteriorate, which is not conducive to the preparation of the filter.

[0003] To address the drawbacks of green pigment development, the industry is trending towards using green dye molecules instead of particulate pigments. Compared to green pigments, by directly dissolving green dye molecules in a film-forming medium, molecular green dyes do not require dispersants within the solubility range, which facilitates increased dosage and improved color saturation. Molecular green dyes also avoid the reduction in transmittance and contrast caused by light scattering and refraction. Furthermore, the clear structure-activity relationship of green dye molecules provides a molecular design foundation for targeted optimization of spectral properties. For example, by regulating the length of the conjugated chain or introducing electron-donating and accepting groups, precise tuning of the absorption peak position can be achieved. Although filters prepared from green dyes have advantages such as high transmittance, good color purity, and vibrant colors, during the film hardening process at 230°C or under the influence of light (especially ultraviolet light), the chemical bonds of the dye molecules change or even break, destroying the dye structure and causing it to lose its color. To meet industrial production requirements, green dyes must meet the following requirements: first, high solubility in industrial solvents; second, good color purity; and third, good light and heat stability. However, traditional green dyes often find it difficult to meet these requirements simultaneously: (1) The solubility of existing green dyes in industrial solvents (such as propylene glycol methyl ether acetate, abbreviated as PGMEA) is less than 5wt%, making it difficult to prepare high-concentration formulas. Multiple coatings and stacking are required to achieve the required optical density, which significantly reduces production efficiency and increases manufacturing costs. The green photosensitive resin composition prepared by the dye is prone to crystallization during storage and use, affecting the coating stability, uniformity and reproducibility; (2) The color purity of existing green dyes is low, with a single absorption peak at 550–700nm. It is impossible to achieve efficient absorption of blue light (400–500nm) and red light (600–700nm) at the same time, resulting in insufficient color purity. The corresponding color gamut is difficult to exceed 85% of the National Television Standards Committee (NTSC) standard of the United States; (3) Green dyes in a single molecule state may undergo changes in physical and chemical structure under photothermal conditions, ultimately affecting the overall optical performance and service life of the device.

[0004] At present, the research and development of green dyes mainly focuses on a series of zinc phthalocyanine derivatives based on the phthalocyanine parent nucleus (such as CN116178381A, CN108957951A, CN108107674A, CN119902413A). These zinc phthalocyanine green dyes have strong light absorption ability and photothermal stability, but there are two problems: (1) The solubility in the commonly used industrial solvent (PGMEA) is limited, which seriously limits its application adaptability in the preparation of green filters. Due to insufficient solubility, it is difficult for the dye to achieve the required high-concentration molecular dispersion state in the photoresist formula, resulting in insufficient coloration of the film layer obtained by coating. This problem makes it difficult to form a filter layer with sufficient optical density and color saturation through conventional thin film coating processes, and thus cannot meet the high standard requirements of the filter for green in terms of transmittance, color purity and optical uniformity. (2) The molecular design of these zinc phthalocyanine green dyes is mostly based on a single phthalocyanine chromophore system, resulting in the absorption characteristics of this type of material in the 400-700nm visible light region showing a single absorption peak centered at 650nm, and insufficient absorption in the blue light band (400-500nm), which significantly affects the performance of green filters configured with zinc phthalocyanine as the core pigment. In particular, it is difficult to meet the technical requirements of wide color gamut standards such as BT.2020 in advanced display applications that pursue high color gamut and high contrast. The above key performance defects urgently need to be effectively resolved through the rational optimization of molecular structure design and precise regulation of synthesis routes, or through systematic improvement of material processing technology. Summary of the Invention

[0005] The purpose of the present invention is to provide a zinc phthalocyanine, a green photosensitive resin composition and their application. The zinc phthalocyanine has excellent solubility and light and heat stability, and the green photosensitive resin composition can be made into a thinner colored layer and has high color purity.

[0006] The purpose of the present invention can be achieved by the following technical solutions:

[0007] One of the purposes of the present invention is to provide a zinc phthalocyanine, which is prepared by substituting the benzene ring sites around the zinc phthalocyanine mother nucleus with a multifunctional group, and its structural formula is as follows:

[0008]

[0009] Among them, R1~R 16 are independently selected from any one of hydrogen atom, chlorine atom, alkyl, aryl or heteroaryl substituents, and R1 to R 16 The present invention comprises at least one naphthalimide group.

[0010] Preferably, the alkyl group is selected from any one of an alkyl group having 1-18 carbon atoms, a carboxyalkyl group having 1-18 carbon atoms, an ether bond having 1-18 carbon atoms, an ester group having 1-18 carbon atoms, an olefin having 2-18 carbon atoms, a hydroxyalkyl group having 1-18 carbon atoms, an amino group having 1-18 carbon atoms, or an aldehyde group having 1-18 carbon atoms.

[0011] Preferably, the heteroaryl group is selected from any one of a condensed heterocyclic group, a monocyclic aromatic heterocyclic group and a polycyclic aromatic heterocyclic group.

[0012] 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 group, a halogenated aryl group and an arylamine group.

[0013] Preferably, the aryl group includes an unsubstituted aryl group (such as phenyl), an alkyl-substituted aryl group (such as tolyl) and a polyaryl group (such as biphenyl).

[0014] Preferably, the halogenated aryl group is a group formed by replacing an aryl group with at least one halogen atom selected from the group consisting of F, Cl, Br, and I.

[0015] More preferably, the halogenated aryl group is a group formed by replacing an aryl group with a Br atom.

[0016] Preferably, the aromatic amine group includes any one of a diphenylamine group and a triphenylamine group.

[0017] Preferably, the heteroatoms contained in the fused heterocyclic group include N, S, and O heteroatoms, the number of the heteroatoms is 1-7, and the types of heteroatoms in the fused heterocyclic group include any one, any two, or any three of N, S, and O heteroatoms.

[0018] Preferably, R1 to R 16 It contains at least 12 hydrogen atoms or chlorine atoms, and the remaining substituent groups are of the same type or different types.

[0019] More preferably, R1 to R 16 There are at least 12 hydrogen atoms or chlorine atoms, and the remaining substituent groups are of the same type.

[0020] Preferably, the structural formula of the naphthalimide group is as follows:

[0021]

[0022] Wherein, L is selected from one of the following formulas (A-1) to (A-15):

[0023]

[0024] Preferably, the curve in the general formula (II) represents R1 to R 16 The connecting bond with the zinc phthalocyanine mother core in formula (I).

[0025] Preferably, the curved lines in formulae (A-1) to (A-15) represent the bonds between L and its adjacent O atoms and N atoms.

[0026] Preferably, N1 and N2 are each independently selected from a hydrogen atom, or a substituted or unsubstituted group:

[0027] Any one of a C1 to C60 chain alkyl group, a C1 to C60 branched alkyl group, a C1 to C60 chain alkenyl group, a C1 to C60 chain alkynyl group, a C3 to C60 cycloalkyl group, a C4 to C60 cycloalkenyl group, a C4 to C60 cycloalkynyl group, a C1 to C60 alkoxy group, a C1 to C60 branched alkoxy group, a C1 to C60 thioalkoxy group, a C6 to C60 aryl group, a C3 to C60 heteroaryl group, and a C4 to C60 aryloxy group, and at least one of N1 and N2 is an amino functional group.

[0028] Preferably, N1 and N2 are each independently selected from any one of formulas (B-1) to (B-49):

[0029]

[0030] Preferably, the curved lines in formulae (B-1) to (B-49) represent the connecting bonds between N1, N2 and the naphthaleneimide group in general formula (II).

[0031] Preferably, the structural formula of the zinc phthalocyanine includes any one of the following:

[0032]

[0033]

[0034]

[0035]

[0036]

[0037]

[0038]

[0039]

[0040] A second object of the present invention is to provide a green photosensitive resin composition comprising the following components in parts by weight:

[0041]

[0042]

[0043] Wherein, the colorant includes the zinc phthalocyanine as described above; and the solid content of the green photosensitive resin composition is 13-38%.

[0044] Preferably, the green photosensitive resin composition comprises the following components in parts by weight:

[0045]

[0046] Further preferably, the colorant comprises zinc phthalocyanine as described above.

[0047] Further preferably, the solid content of the green photosensitive resin composition is 28%.

[0048] Preferably, the resin containing a double bond structure and / or an epoxy structure includes one or more of acrylic polyurethane resin, acrylic polyester resin, acrylic epoxy resin, acrylic polyether resin, acrylic alkyd resin, acrylic melamine resin, and acrylic silicone resin.

[0049] Preferably, the monomer containing a double bond structure or / and an epoxy structure includes one or more of dipentaerythritol pentaacrylate, trimethylolpropane triacrylate, polyvinyl cinnamate monomer, N-benzylmaleimide, epoxy acrylate, and epoxy acrylamide.

[0050] Preferably, the photoinitiator with high absorption characteristics at 365nm includes one or more of oximes, benzoins, acetophenones, imidazoles (for example, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl oxime), α,α-diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-methyl-2-morpholino-1-(4-methylphenylthio)propane-1-one, thioxanthone, 1,2'-bis(2-chlorophenyl)-tetraphenylbiimidazole, etc.).

[0051] Preferably, the additives for improving film-forming property and / or stability include one or more of a surface flattening agent, a defoaming agent, a stabilizer, and a plasticizer.

[0052] Preferably, the solvent containing an ether group includes one or more of propylene glycol monomethyl ether, propylene glycol methyl ether acetate, propylene glycol monoethyl ether, 3-methoxybutyl acetate, and N,N-dimethylformamide.

[0053] The third object of the present invention is to provide a use of the green photosensitive resin composition as a color photoresist in the preparation of a color filter.

[0054] Preferably, the green photosensitive resin composition can be applied to filters of display and sensing devices such as liquid crystal displays and image sensors.

[0055] The present invention designs and develops a series of zinc phthalocyanines: First, to address the poor solubility of zinc phthalocyanine, the present invention replaces the benzene ring sites around the zinc phthalocyanine core with large steric groups, effectively improving the solubility of the zinc phthalocyanine dye. Furthermore, these large steric groups prevent the dye from aggregating in the solid state by inhibiting the π-π interaction between π planes, thereby further improving the stability of the phthalocyanine dye. Second, to address the insufficient color purity of zinc phthalocyanine green dyes, the present invention compensates for the zinc phthalocyanine dye's insufficient absorption in the blue light region (400–500nm) by coupling a functional group with blue light absorption properties (naphthalimide group), thereby synthesizing a high-color-purity green dye.

[0056] The present invention further synthesizes a high-color-purity green dye-green photosensitive resin composition based on zinc phthalocyanine. This overcomes the poor solubility of zinc phthalocyanine dyes and improves the low color purity of zinc phthalocyanine derivatives as green dyes. Furthermore, the colored layer prepared from the zinc phthalocyanine-based green photosensitive resin composition exhibits excellent solubility, photothermal stability, high coloration, and high color purity, even at a relatively thin thickness. This green photosensitive resin composition can be used as a color photoresist and in the preparation of color filters.

[0057] In summary, the present invention adopts a zinc phthalocyanine core structure, and modifies a photochemically stable blue region absorption module (naphthalimide group) on the phthalocyanine plane to compensate for the absorption of zinc phthalocyanine itself in the visible light region of 400-500nm, thereby achieving the regulation of the photochemical and photophysical properties of the dye, and obtaining a dye with excellent color purity and stable photochemical and photophysical properties. In addition, the modification of the alkoxy and phenoxy molecular chain groups not only enhances the thermal stability of the dye, but also effectively improves the solubility of the phthalocyanine dye in organic solvents and its compatibility with other components of the color photoresist, thereby providing a green photosensitive resin composition based on zinc phthalocyanine. In addition, based on its excellent stability and high color purity, the green photosensitive resin composition can be used as a color photoresist in filters of display and sensing devices such as liquid crystal displays and image sensors.

[0058] Compared with the prior art, the present invention has the following beneficial effects:

[0059] (1) The present invention replaces the benzene ring sites around the zinc phthalocyanine mother core with various substituents including naphthalimide groups, thereby providing a zinc phthalocyanine and a green photosensitive resin composition prepared based on the zinc phthalocyanine. The zinc phthalocyanine has excellent solubility and light and heat stability. The green photosensitive resin composition can be made into a thinner colored layer and has high color purity.

[0060] (2) The present invention compensates for the problem of insufficient blue light absorption characteristics of zinc phthalocyanine dye by introducing a functional group (naphthalimide group) with blue light absorption characteristics, thereby synthesizing a zinc phthalocyanine green dye with high green color purity.

[0061] (3) The present invention adopts a large π-conjugated zinc phthalocyanine mother core structure with high chemical bond energy, so zinc phthalocyanine has good photo- and thermo-chemical stability. Substitution of the benzene ring sites around the zinc phthalocyanine mother core by substituent groups not only further suppresses the strong π-π interaction of the phthalocyanine plane, improves its photo- and thermo-stability, but also enhances the solubility of the dye in organic solution.

[0062] (4) The zinc phthalocyanine green dye synthesized in the present invention overcomes the problem of poor solubility and can be well adapted to commonly used industrial solvents such as color photoresist solvent PGMEA. Based on this, the present invention prepares a zinc phthalocyanine green photosensitive resin composition, which can be used as a color photoresist to prepare a colored layer with a relatively thin thickness (1.5-2.0 μm) and a high degree of coloring.

[0063] (5) The coloring layer prepared using the green 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.

[0064] (6) The color filter prepared by the green photosensitive resin composition prepared by the present invention has excellent anti-migration property, ΔE ab Both are less than 3.

[0065] (7) The color filter prepared by using the green photosensitive resin composition prepared by the present invention has good edge line regularity and development process margin. BRIEF DESCRIPTION OF THE DRAWINGS

[0066] Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of compound (10) prepared in Example 4;

[0067] Figure 2 This is the mass spectrum of compound (10) prepared in Example 4;

[0068] Figure 3 This is a physical picture of the green photosensitive resin composition D1 prepared in Example 1-1;

[0069] Figure 4 is the UV-visible absorption spectrum of the green photosensitive resin composition D1 prepared in Example 1-1;

[0070] Figure 5 2-1 and 2-2 are CIE chromaticity diagrams of Example 1-1 and Comparative Example 2-1. DETAILED DESCRIPTION

[0071] The present invention is described in detail below with reference to the accompanying drawings and specific embodiments. This embodiment is implemented based on the technical solution of the present invention, and provides a detailed implementation method and specific operation process, but the protection scope of the present invention is not limited to the following embodiments.

[0072] Unless otherwise specified, the reagents, methods, instruments and equipment used in the present invention are conventional reagents, methods, instruments and equipment in the art. Unless otherwise specified, the reagents and materials used in the following examples are commercially available.

[0073] Example 1:

[0074] Synthesis of compound (1):

[0075]

[0076] Dissolve 4-bromonaphthalic anhydride (1 mmol) and p-bromophenol (2 mmol) in ethanol (30 mL) and stir at 90°C under nitrogen for 24 hours. After the reaction, cool to room temperature and pour the mixture into ice water to precipitate a solid. Filter the mixture to obtain a solid, which is then dried to obtain Intermediate 1.

[0077] Intermediate 1 (1 mmol), 4-(2-methoxyethoxy)aniline (1 mmol), tetrakistriphenylphosphine palladium (0.05 mmol), and potassium tert-butoxide (1.5 mmol) were heated under reflux at 110°C for 24 h in a toluene (20 mL) solution. After completion of the reaction, the mixture was cooled to room temperature and extracted with dichloromethane and saturated brine. The organic layer was collected and dried over anhydrous magnesium sulfate, and then the organic solvent was evaporated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography on silica gel (eluent: dichloromethane: petroleum ether = 4:1) to obtain Intermediate 2.

[0078] Intermediate 2 (4 mmol), 4-nitrophthalonitrile (4 mmol), and potassium carbonate (8 mmol) were dissolved in N'N-dimethylformamide (50 mL) and stirred at 160°C for 24 h under nitrogen. After the reaction, the mixture was cooled to room temperature and poured into ice water to precipitate a solid. The mixture was filtered to obtain a solid, which was then dried and purified by column chromatography on silica gel (eluent: petroleum ether: dichloromethane = 6:1) to obtain Intermediate 3.

[0079] Intermediate 3 (4 mmol) and zinc chloride (1 mmol) were dissolved in n-pentanol (20 mL) and stirred at 160°C under nitrogen for 24 h. After the reaction, the mixture was cooled to room temperature and the organic solvent was removed by evaporation under reduced pressure to obtain a crude product. The crude product was dried and purified by column chromatography on silica gel (eluent: dichloromethane:methanol = 45:1) to obtain compound (1) as a green solid in a yield of 77%.

[0080] After high-resolution mass spectrometry, ESI source, and positive ion mode detection, the molecular formula of compound (1) is C 144 H 112 N 16 O 20 Zn, detected value 2450.7366, theoretical value 2450.7367; detected element content (%): C, 70.55; H, 4.61; N, 9.13; O, 13.04; Zn, 2.67. Theoretical element content (%): C, 70.54; H, 4.60; N, 9.14; O, 13.05; Zn, 2.67. The above analytical results indicate that the obtained product is the expected product.

[0081] The starting reactants were replaced with corresponding reactants respectively, and the synthesis of the compounds involved in Examples 2-4 was completed by referring to the preparation method of Example 1. The specific results are shown in Table 1.

[0082] Table 1

[0083]

[0084]

[0085] Figure 1 -2 are the nuclear magnetic resonance hydrogen spectrum and mass spectrum of compound (10) prepared in Example 4, respectively, which prove the successful preparation of compound (10).

[0086] Example 5:

[0087] Synthesis of compound (24):

[0088]

[0089] Dissolve 4-bromonaphthalic anhydride (1 mmol) and p-bromophenol (2 mmol) in ethanol (30 mL) and stir at 90°C under nitrogen for 24 hours. After the reaction, cool to room temperature and pour the mixture into ice water to precipitate a solid. Filter the mixture to obtain a solid, which is then dried to obtain Intermediate 1.

[0090] Intermediate 1 (1 mmol), 3,5-diisopropylaniline (1 mmol), tetrakistriphenylphosphine palladium (0.05 mmol), and potassium tert-butoxide (1.5 mmol) were heated under reflux at 110°C for 24 h in a toluene (20 mL) solution. After completion of the reaction, the mixture was cooled to room temperature and extracted with dichloromethane and saturated brine. The organic layer was collected and dried over anhydrous magnesium sulfate, and then the organic solvent was evaporated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography on silica gel (eluent: dichloromethane:petroleum ether = 5:1) to obtain Intermediate 4.

[0091] Intermediate 4 (4 mmol), 3-nitrophthalonitrile (4 mmol), and potassium carbonate (8 mmol) were dissolved in N'N-dimethylformamide (50 mL) and stirred at 160°C for 24 h under nitrogen. After the reaction, the mixture was cooled to room temperature and poured into ice water to precipitate a solid. The mixture was filtered to obtain a solid, which was then dried and purified by column chromatography on silica gel (eluent: petroleum ether: dichloromethane = 7:1) to obtain Intermediate 5.

[0092] Intermediate 5 (4 mmol) and zinc chloride (1 mmol) were dissolved in n-pentanol (20 mL) and stirred at 160°C under nitrogen for 24 h. After the reaction, the mixture was cooled to room temperature and the organic solvent was removed by evaporation under reduced pressure to obtain a crude product. The crude product was dried and purified by column chromatography on silica gel (eluent: dichloromethane:methanol = 47:1) to obtain compound (24) as a green solid in a yield of 78%.

[0093] After high-resolution mass spectrometry, ESI source, and positive ion mode detection, the molecular formula of compound (24) is C 156 H 136 N 16 O 12 Zn, detected value 2490.9926, theoretical value 2490.9927; detected element content (%): C, 75.19; H, 5.50; N, 8.98; O, 7.70; Zn, 2.62. Theoretical element content (%): C, 75.18; H, 5.50; N, 8.99; O, 7.70; Zn, 2.62. The above analytical results indicate that the obtained product is the expected product.

[0094] The starting reactants were replaced with corresponding reactants, and the synthesis of the compounds involved in Examples 6-8 was completed by referring to the preparation method of Example 5. The specific results are shown in Table 2.

[0095] Table 2

[0096]

[0097] Example 9:

[0098] Synthesis of compound (37):

[0099]

[0100] Dissolve 4-bromonaphthalic anhydride (1 mmol) and p-bromophenol (2 mmol) in ethanol (30 mL) and stir at 90°C under nitrogen for 24 hours. After the reaction, cool to room temperature and pour the mixture into ice water to precipitate a solid. Filter the mixture to obtain a solid, which is then dried to obtain Intermediate 1.

[0101] Intermediate 1 (1 mmol), 3,4,5-trimethylaniline (1 mmol), tetrakistriphenylphosphine palladium (0.05 mmol), and potassium tert-butoxide (1.5 mmol) were heated under reflux at 110°C for 24 h in a toluene (20 mL) solution. After completion of the reaction, the mixture was cooled to room temperature and extracted with dichloromethane and saturated brine. The organic layer was collected and dried over anhydrous magnesium sulfate, and then the organic solvent was evaporated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography on silica gel (eluent: dichloromethane: petroleum ether = 4:1) to obtain Intermediate 6.

[0102] Intermediate 6 (4 mmol), 3,4,5,6-tetrachlorophthalonitrile (4 mmol), and potassium carbonate (8 mmol) were dissolved in N'N-dimethylformamide (50 mL) and stirred at 160°C for 24 h under nitrogen. After the reaction, the mixture was cooled to room temperature and poured into ice water to precipitate a solid. The mixture was filtered to obtain a solid, which was then dried and purified by column chromatography on silica gel (eluent: petroleum ether: dichloromethane = 3:1) to obtain Intermediate 7.

[0103] Intermediate 7 (4 mmol) and zinc chloride (1 mmol) were dissolved in n-pentanol (20 mL) and stirred at 160°C under nitrogen for 24 h. After the reaction, the mixture was cooled to room temperature and the organic solvent was removed by evaporation under reduced pressure to obtain a crude product. The crude product was dried and purified by column chromatography on silica gel (eluent: dichloromethane:methanol = 50:1) to obtain compound (37) as a green solid in a yield of 77%.

[0104] After high-resolution mass spectrometry, ESI source, and positive ion mode detection, the molecular formula of compound (37) is C 140 H 100 Cl 12 N 16 O 12Zn, detected value 2688.3340, theoretical value 2688.3341; detected element content (%): C, 62.54; H, 3.76; Cl, ​​15.81; N, 8.32; O, 7.15; Zn, 2.42. Theoretical element content (%): C, 62.53; H, 3.75; Cl, ​​15.82; N, 8.33; O, 7.14; Zn, 2.43. These analytical results indicate that the product obtained is the expected product.

[0105] The starting reactants were replaced with corresponding reactants, and the synthesis of the compounds involved in Examples 10-12 was completed by referring to the preparation method of Example 9. The specific results are shown in Table 3.

[0106] Table 3

[0107]

[0108] Example 13:

[0109] Synthesis of compound (53):

[0110]

[0111] Dissolve 4-bromonaphthalene anhydride (1 mmol) and ethanolamine (2 mmol) in ethanol (30 mL) and stir at 90°C under nitrogen for 24 hours. After the reaction, cool to room temperature and pour the mixture into ice water to precipitate a solid. Filter the mixture to obtain a solid, which is then dried to obtain Intermediate 8.

[0112] Intermediate 8 (1 mmol), methylbutylamine (1 mmol), tetrakistriphenylphosphine palladium (0.05 mmol), and potassium tert-butoxide (1.5 mmol) were heated under reflux at 110°C for 24 h in a toluene (20 mL) solution. After the reaction was completed, the mixture was cooled to room temperature and extracted with dichloromethane and saturated brine. The organic layer was collected and dried over anhydrous magnesium sulfate, and then the organic solvent was evaporated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography on silica gel (eluent: dichloromethane: petroleum ether = 7:1) to obtain Intermediate 9.

[0113] Intermediate 9 (4 mmol), 4-nitrophthalonitrile (4 mmol), and potassium carbonate (8 mmol) were dissolved in N'N-dimethylformamide (50 mL) and stirred at 160°C for 24 h under nitrogen. After the reaction, the mixture was cooled to room temperature and poured into ice water to precipitate a solid. The mixture was filtered to obtain a solid, which was then dried and purified by column chromatography on silica gel (eluent: petroleum ether: dichloromethane = 4:1) to obtain Intermediate 10.

[0114] Intermediate 10 (4 mmol) and zinc chloride (1 mmol) were dissolved in n-pentanol (20 mL) and stirred at 160°C under nitrogen for 24 h. After the reaction, the mixture was cooled to room temperature and the organic solvent was removed by evaporation under reduced pressure to obtain a crude product. The crude product was dried and purified by column chromatography on silica gel (eluent: dichloromethane:methanol = 43:1) to obtain compound (53) as a green solid in a yield of 71%.

[0115] After high-resolution mass spectrometry, ESI source, and positive ion mode detection, the molecular formula of compound (53) is C 112 H 112 N 16 O 12 Zn, detected value 1938.8048, theoretical value 1938.8049; detected element content (%): C, 69.35; H, 5.82; N, 11.56; O, 9.90; Zn, 3.37. Theoretical element content (%): C, 69.36; H, 5.82; N, 11.55; O, 9.90; Zn, 3.37. The above analytical results indicate that the obtained product is the expected product.

[0116] The starting reactants were replaced with corresponding reactants, and the synthesis of the compounds involved in Examples 14-16 was completed by referring to the preparation method of Example 13. The specific results are shown in Table 4.

[0117] Table 4

[0118]

[0119] Example 17:

[0120] Synthesis of compound (71):

[0121]

[0122] Dissolve 4-bromonaphthalene anhydride (1 mmol) and 3-amino-1-propanol (2 mmol) in ethanol (30 mL) and stir at 90°C under nitrogen for 24 hours. After the reaction, cool to room temperature and pour the mixture into ice water to precipitate a solid. Filter the mixture to obtain a solid, which is then dried to obtain Intermediate 11.

[0123] Intermediate 11 (1 mmol), cyclopropylmethylamine (1 mmol), tetrakistriphenylphosphine palladium (0.05 mmol), and potassium tert-butoxide (1.5 mmol) were heated under reflux at 110°C for 24 h in a toluene (20 mL) solution. After completion of the reaction, the mixture was cooled to room temperature and extracted with dichloromethane and saturated brine. The organic layer was collected and dried over anhydrous magnesium sulfate, and then the organic solvent was evaporated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography on silica gel (eluent: dichloromethane: petroleum ether = 5:1) to obtain Intermediate 12.

[0124] Intermediate 12 (4 mmol), 3-nitrophthalonitrile (4 mmol), and potassium carbonate (8 mmol) were dissolved in N'N-dimethylformamide (50 mL) and stirred at 160°C under nitrogen for 24 h. After the reaction, the mixture was cooled to room temperature and poured into ice water to precipitate a solid. The mixture was filtered to obtain a solid, which was then dried and purified by column chromatography on silica gel (eluent: petroleum ether: dichloromethane = 6:1) to obtain Intermediate 13.

[0125] Intermediate 13 (4 mmol) and zinc chloride (1 mmol) were dissolved in n-pentanol (20 mL) and stirred at 160°C under nitrogen for 24 h. After the reaction, the mixture was cooled to room temperature and the organic solvent was removed by evaporation under reduced pressure to obtain a crude product. The crude product was dried and purified by column chromatography on silica gel (eluent: dichloromethane:methanol = 41:1) to obtain compound (71) as a green solid in a yield of 79%.

[0126] After high-resolution mass spectrometry, ESI source, and positive ion mode detection, the molecular formula of compound (71) is C 112 H 104 N 16 O 12 Zn, detected value 1930.7424, theoretical value 1930.7423; detected element content (%): C, 69.66; H, 5.43; N, 11.60; O, 9.93; Zn, 3.38. Theoretical element content (%): C, 69.65; H, 5.43; N, 11.60; O, 9.94; Zn, 3.38. The above analytical results indicate that the obtained product is the expected product.

[0127] The starting reactants were replaced with corresponding reactants, and the synthesis of the compounds involved in Examples 18-20 was completed by referring to the preparation method of Example 17. The specific results are shown in Table 5.

[0128] Table 5

[0129]

[0130] Example 21:

[0131] Synthesis of compound (91):

[0132]

[0133] Dissolve 4-bromonaphthalene anhydride (1 mmol) and 6-amino-1-hexanol (2 mmol) in ethanol (30 mL) and stir at 90°C under nitrogen for 24 hours. After the reaction, cool to room temperature and pour the mixture into ice water to precipitate a solid. Filter the mixture to obtain a solid, which is then dried to obtain Intermediate 14.

[0134] Intermediate 14 (1 mmol), N,N-dimethylethylenediamine (1 mmol), tetrakistriphenylphosphine palladium (0.05 mmol), and potassium tert-butoxide (1.5 mmol) were heated under reflux at 110°C for 24 h in a toluene (20 mL) solution. After completion of the reaction, the mixture was cooled to room temperature and extracted with dichloromethane and saturated brine. The organic layer was collected and dried over anhydrous magnesium sulfate, and then the organic solvent was evaporated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography on silica gel (eluent: dichloromethane: petroleum ether = 8:1) to obtain Intermediate 15.

[0135] Intermediate 15 (4 mmol), 3,4,5,6-tetrachlorophthalonitrile (4 mmol), and potassium carbonate (8 mmol) were dissolved in N'N-dimethylformamide (50 mL) and stirred at 160°C under nitrogen for 24 h. After the reaction, the mixture was cooled to room temperature and poured into ice water to precipitate a solid. The mixture was filtered to obtain a solid, which was then dried and purified by column chromatography on silica gel (eluent: petroleum ether: dichloromethane = 4:1) to obtain Intermediate 16.

[0136] Intermediate 16 (4 mmol) and zinc chloride (1 mmol) were dissolved in n-pentanol (20 mL) and stirred at 160°C under nitrogen for 24 h. After the reaction, the mixture was cooled to room temperature and the organic solvent was removed by evaporation under reduced pressure to obtain a crude product. The crude product was dried and purified by column chromatography on silica gel (eluent: dichloromethane:methanol = 50:1) to obtain compound (91) as a green solid in a yield of 75%.

[0137] After high-resolution mass spectrometry, ESI source, and positive ion mode detection, the molecular formula of compound (91) is C 120 H 128 Cl 12 N 20 O 12Zn, detected value 2532.5674, theoretical value 2532.5673; detected element content (%): C, 56.90; H, 5.09; Cl, ​​16.79; N, 11.05; O, 7.58; Zn, 2.59. Theoretical element content (%): C, 56.90; H, 5.09; Cl, ​​16.79; N, 11.06; O, 7.58; Zn, 2.58. The above analytical results indicate that the obtained product is the expected product.

[0138] The starting reactants were replaced with corresponding reactants respectively, and the synthesis of the compounds involved in Examples 22-24 was completed by referring to the preparation method of Example 21. The specific results are shown in Table 6.

[0139] Table 6

[0140]

[0141] Example 1-1

[0142] Preparation of green photosensitive resin composition D1

[0143] A green photosensitive resin composition D1 was prepared using the zinc phthalocyanine dye of formula (1) prepared in Example 1, and subjected to photolithographic development to compare the properties of the photosensitive resin composition. The photolithographic development method is a conventional method used by those skilled in the art.

[0144] formula:

[0145] 3 parts by weight of a colorant, 20 parts by weight of a resin containing a double bond structure, 4 parts by weight of a monomer containing a double bond structure, 0.5 parts by weight of a photoinitiator having high absorption characteristics at 365 nm, 0.25 parts by weight of an additive for improving film-forming properties and / or stability, and 72 parts by weight of an ether-containing solvent are thoroughly mixed and dissolved, and the solid content is controlled at about 28% to obtain a green photosensitive resin composition. Figure 3 shown.

[0146] in,

[0147] Colorant: zinc phthalocyanine (Formula (1))

[0148] Resins containing double bond structures or / and epoxy structures: acrylic polyester resin (analytical grade), purchased from Titan Corporation;

[0149] Monomers containing double bond structures or / and epoxy structures: dipentaerythritol pentaacrylate monomer (analytical grade), purchased from Titan Corporation;

[0150] Photoinitiator with high absorption characteristics at 365 nm: α,α-diethoxyacetophenone (analytical grade), purchased from Titan Company;

[0151] Additives for improving film-forming property and / or stability: defoaming agent (analytical grade), purchased from Titan Company;

[0152] Ether-containing solvents: Propylene glycol methyl ether acetate (analytical grade), purchased from Titan Corporation.

[0153] Comparative Example 2-1

[0154] Preparation of green photosensitive resin composition E1

[0155] 3 parts by weight of a colorant, 20 parts by weight of a resin containing a double bond structure, 4 parts by weight of a monomer containing a double bond structure, 0.5 parts by weight of a photoinitiator having high absorption characteristics at 365 nm, 0.25 parts by weight of an additive for improving film-forming properties and / or stability, and 72 parts by weight of an ether-containing solvent are fully mixed and dissolved, and the solid content is controlled at about 28% to obtain a green photosensitive resin composition.

[0156] in,

[0157] Colorant: Zinc Phthalocyanine Dye L

[0158] Resins containing double bond structures or / and epoxy structures: acrylic polyester resin (analytical grade), purchased from Titan Corporation;

[0159] Monomers containing double bond structures or / and epoxy structures: dipentaerythritol pentaacrylate monomer (analytical grade), purchased from Titan Corporation;

[0160] Photoinitiator with high absorption characteristics at 365 nm: α,α-diethoxyacetophenone (analytical grade), purchased from Titan Company;

[0161] Additives for improving film-forming property and / or stability: defoaming agent (analytical grade), purchased from Titan Company;

[0162] Ether-containing solvents: Propylene glycol methyl ether acetate (analytical grade), purchased from Titan Corporation.

[0163] The chemical structure of zinc phthalocyanine dye L is as follows:

[0164]

[0165] The performance test of the photosensitive resin compositions D1 and E1 was carried out using the following steps:

[0166] The glass slide was cleaned and dried, and then coated with glue using a spin coater to obtain a uniform film layer of 1.5–2.0 μm. The film was pre-baked at 90°C for 120 seconds and exposed to 365 nm UV light at an exposure dose of 40 mJ / cm 2The distance between the mask and the coating was 180 μm, and then the film was developed at 25°C for 5 seconds and then post-baked at 230°C for 30 minutes. The subsequent related performance was tested, and the results are shown in Table 7.

[0167] Performance testing and evaluation methods:

[0168] (1) Chromaticity: Detected using a Konica Minolta CM-5 spectrophotometer.

[0169] (2) System compatibility: The photosensitive resin composition was stored in a dark environment at 0–10°C 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 film surface was examined under an optical microscope (OM) at x500.

[0170] The evaluation criteria are as follows:

[0171] ○: Viscosity change < ±5% mPa·s and no particles on the x500 surface;

[0172] △: Viscosity change < ±10% mPa·s and no particles on the x500 surface;

[0173] ×: Viscosity change > ±10% mPa·s or particles on the surface of x500;

[0174] (3) Heat resistance test: The heat resistance of the photosensitive resin composition was verified by color difference. The film was post-baked at 230°C for 20 minutes and repeated twice. The film thickness was measured by XP-2 step analyzer. The color difference was the color difference between the second post-baked sample and the first post-baked sample. The color difference was measured by Minolta CM-5. If ΔE ab <3, it indicates better heat resistance;

[0175] (4) Evaluation of solvent resistance:

[0176] Place the post-baked sample in isopropanol, soak it at room temperature for 5 minutes, bake it in an oven at 150℃ for 30 minutes, and measure the color difference before and after. If ΔE ab <3, indicating good solvent resistance.

[0177] (5) Evaluation of anti-migration performance:

[0178] According to the color filter manufacturing process, green or blue pixels are first prepared on thin film transistor (TFT) glass. Then the sample is coated and after the development is completed, the color filter surface is blown dry and the color difference before and after the pixel is measured. If ΔE ab <3, indicating good anti-migration properties.

[0179] (6) Line width, edge regularity, and development process margin:

[0180] The line width and edge uniformity were tested by x500 OM, and the mask line width was 140μm.

[0181] When evaluating process margin, other process conditions are fixed and the edge neatness, edge residue, or edge peeling of the image obtained with a development time between 40 and 100 seconds is examined. The peeling property is determined by referring to the adhesion measurement method in the art.

[0182] The evaluation criteria for edge neatness are as follows:

[0183] ○: The edges are neat and there is no residue at the edges after 50s of development;

[0184] △: After 50 seconds of development, the image edge has burrs, is not neat, or has residues at the edge;

[0185] ×: Image missing

[0186] The specific standards for evaluating the development process margin are as follows:

[0187] ○: The edges are neat and there is no residue or peeling at the edges after 40-100s of development;

[0188] △: The edges are neat and there is no residue or peeling at the edges after 50-80s of development;

[0189] ×: The edges are not neat, or there are residues or peeling at the edges after 50–80s of development.

[0190] The alkaline developer used above is an aqueous solution of an alkaline compound such as 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%.

[0191] The preparation of photosensitive resin compositions D2-D24 in Examples 1-2 to 1-24 was identical to that in Example 1-1, with the preparation method and materials being identical, the only difference being the colorant. Specific evaluation results are shown in Table 7.

[0192] Table 7

[0193]

[0194] Figure 4 This is the UV-visible absorption spectrum of the green photosensitive resin composition D1 prepared in Example 1-1. It can be seen from the figure that the green photosensitive resin composition prepared by the present invention has good absorption in the blue light region (400-500nm) and the red light region (600-700nm).

[0195] Figure 5 2-1 is a CIE chromaticity diagram of Example 1-1 and Comparative Example 2-1. It can be seen from the diagram that the green photosensitive resin composition prepared by the present invention has more excellent coloring and green color purity.

[0196] Comparison of experimental results shows that the zinc phthalocyanine dyes in Examples 1-1 to 1-24 have better solubility in the color photoresist solvent PGMEA than the zinc phthalocyanine dye L used in the comparative example. Furthermore, the dyes in Examples 1-1 to 1-24 have functional groups with blue light absorption properties coupled to the benzene ring sites around the zinc phthalocyanine parent core to compensate for the weak absorption of zinc phthalocyanine dyes in the blue light region (400–500nm). The color filters prepared with these zinc phthalocyanine dyes have higher green color purity and excellent heat resistance, light resistance, and solvent resistance. Furthermore, compared with the photosensitive resin composition E1 using zinc phthalocyanine dye L in the comparative example, the photosensitive resin compositions D1 to D24 using these zinc phthalocyanine dyes have similarly good process performance, such as system compatibility, edge line neatness, and development process margin.

[0197] In summary, the present invention effectively improves the solubility of zinc phthalocyanine dyes by replacing the benzene ring sites around the zinc phthalocyanine mother nucleus with functional groups; inhibits the aggregation of the dye in the solid state and further improves the stability of the phthalocyanine dye; improves the optical properties of traditional zinc phthalocyanine dyes, and prepares green dyes with high color purity and stable photochemical and photophysical properties; solves the problems of green color purity not meeting industrial production requirements and poor solubility and compatibility in color photoresist systems; the selected zinc phthalocyanine compounds with better performance can be used to prepare green photosensitive resin compositions, which can be used as color photoresists in filters of display and sensing devices such as liquid crystal displays and image sensors.

[0198] The above description of the embodiments is intended to facilitate understanding and use of the invention by those skilled in the art. It will be apparent that those skilled in the art can readily make various modifications to these embodiments and apply the general principles described herein to other embodiments without requiring inventive effort. Therefore, the present invention is not limited to the above-described embodiments. 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 present invention, should be within the scope of protection of the present invention.

Claims

1. A zinc phthalocyanine, characterized in that It is prepared by substituting the benzene ring sites around the zinc phthalocyanine core with multifunctional groups. Its structural formula is as follows: Among them, R1~R 16 are independently selected from any one of hydrogen atom, chlorine atom, alkyl, aryl or heteroaryl substituents, and R1 to R 16 The present invention comprises at least one naphthalimide group.

2. A zinc phthalocyanine according to claim 1, characterized in that, The alkyl group is selected from any one of an alkyl group having 1-18 carbon atoms, a carboxyalkyl group having 1-18 carbon atoms, an ether bond having 1-18 carbon atoms, an ester group having 1-18 carbon atoms, an olefin having 2-18 carbon atoms, a hydroxyalkyl group having 1-18 carbon atoms, an amino group having 1-18 carbon atoms, or an aldehyde group having 1-18 carbon atoms.

3. A zinc phthalocyanine according to claim 1, characterized in that, The heteroaryl group is selected from any one of a fused heterocyclic group, a monocyclic aromatic heterocyclic group and a polycyclic aromatic heterocyclic group; 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 to at least one of an aryl group, a halogenated aryl group and an arylamine group; Wherein, the aryl group includes unsubstituted aryl, alkyl-substituted aryl and polyaryl; The halogenated aryl group is a group formed after the aryl group is substituted by at least one halogen atom selected from F, Cl, Br, and I; The aromatic amine group includes any one of a diphenylamine group and a triphenylamine group; The heteroatoms contained in the fused heterocyclic group include N, S, and O heteroatoms, and the number of the heteroatoms is 1-7. The types of heteroatoms in the fused heterocyclic group include any one, any two, or any three of N, S, and O heteroatoms.

4. A zinc phthalocyanine according to claim 1, characterized in that, The structural formula of the naphthalene imide group is as follows: Wherein, L is selected from one of the following formulas (A-1) to (A-15), and the curved lines in the formulas (A-1) to (A-15) represent the bonds between L and its adjacent O atoms and N atoms:

5. A zinc phthalocyanine according to claim 4, characterized in that, N1 and N2 are each independently selected from a hydrogen atom, or a substituted or unsubstituted group: Any one of a C1 to C60 chain alkyl group, a C1 to C60 branched alkyl group, a C1 to C60 chain alkenyl group, a C1 to C60 chain alkynyl group, a C3 to C60 cycloalkyl group, a C4 to C60 cycloalkenyl group, a C4 to C60 cycloalkynyl group, a C1 to C60 alkoxy group, a C1 to C60 branched alkoxy group, a C1 to C60 thioalkoxy group, a C6 to C60 aryl group, a C3 to C60 heteroaryl group, and a C4 to C60 aryloxy group, and at least one of N1 and N2 is an amino functional group.

6. A zinc phthalocyanine according to claim 4, characterized in that, N1 and N2 are each independently selected from any one of formulas (B-1) to (B-49), wherein the curve represents the connection between N1, N2 and the naphthalene imide group in general formula (II):

7. The zinc phthalocyanine according to claim 1, characterized in that Its structural formula includes any of the following:

8. A green photosensitive resin composition, characterized in that: The composition comprises the following components in parts by weight: Wherein, the colorant comprises the zinc phthalocyanine according to any one of claims 1 to 7; and the solid content of the green photosensitive resin composition is 13-38%.

9. The green photosensitive resin composition according to claim 8, characterized in that: Resins containing double bond structures or / and epoxy structures include one or more of acrylic polyurethane resins, acrylic polyester resins, acrylic epoxy resins, acrylic polyether resins, acrylic alkyd resins, acrylic melamine resins, and acrylic silicone resins; monomers containing double bond structures or / and epoxy structures include one or more of dipentaerythritol pentaacrylate, trimethylolpropane triacrylate, polyvinyl cinnamate monomer, N-benzylmaleimide, epoxy acrylate, and epoxy acrylamide; photoinitiators with high absorption characteristics at 365nm include one or more of oximes, benzoins, acetophenones, and imidazoles; additives for improving film-forming properties and / or stability include one or more of surface flattening agents, defoaming agents, stabilizers, and plasticizers; solvents containing ether groups include one or more of propylene glycol monomethyl ether, propylene glycol methyl ether acetate, propylene glycol monoethyl ether, 3-methoxybutyl acetate, and N,N-dimethylformamide.

10. Use of the green photosensitive resin composition according to any one of claims 8 to 9 as a color photoresist in the preparation of a color filter.

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