Silicon phthalocyanine, blue photosensitive resin composition and application thereof

Abstract

The invention relates to silicon phthalocyanine, a blue photosensitive resin composition and application of the silicon phthalocyanine, the silicon phthalocyanine is prepared by substituting benzene ring sites on the periphery of a silicon phthalocyanine mother nucleus or / and silicon center axial sites through multifunctional groups, and the structural formula of the silicon phthalocyanine is shown in the specification, r1 to R18 are independently selected from any one of a hydrogen atom, a chlorine atom, an alkyl group, an aryl group or a heteroaryl substituent group. The blue 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 silicon phthalocyanine prepared by the invention has excellent solubility and photo-thermal stability, and the blue photosensitive resin composition can be prepared into a thinner colored layer, has high pigmentation degree, 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 silicon phthalocyanine, a blue photosensitive resin composition and applications thereof. Background Art

[0002] With the rapid adoption of flat-panel display products such as liquid crystal displays (LCDs) and organic light-emitting diodes (OLEDs), demand for color reproduction continues to rise. Color filters are crucial for improving the image quality of high-resolution displays. As a key component of the red, green, and blue (RGB) color filter, blue filters filter out red and green light, concentrating the light passing through primarily within the blue wavelength range, enabling accurate color separation and processing. Currently, triarylmethanes (e.g., Pigment Blue 10), anthraquinones (e.g., Pigment Blue 65), and copper phthalocyanines (e.g., Phthalocyanine Blue BX) are commonly used as blue colorants to prepare blue filters using a pigment dispersion method. While filters produced by this method exhibit good thermal and light stability, light scattering caused by the aggregation of the blue pigment is significant, reducing the dispersion stability and transmittance of the colorant, thereby reducing the brightness, contrast, and resolution of the blue filter. At the same time, the aggregation behavior of molecules within blue pigments is complex, and its impact on the optical properties of the pigments is difficult to predict, making the precise control of blue color purity a challenge and not conducive to the realization of high color purity and wide color gamut.

[0003] In order to solve the adverse effects of blue pigment aggregation, the development of blue dyes has emerged. The molecular structure of blue dyes is clear, and there is a clear structure-activity relationship between their molecular structure and photophysical properties; blue dyes dissolve in the medium and exist in molecular form, which reduces light scattering and thus has greater potential in achieving excellent optical properties. Although blue dyes can generally produce color filters with high transmittance and high contrast, their heat resistance and light resistance are poor, and chromaticity changes are prone to occur during the high-temperature heating step in the preparation of blue filters. In order to meet industrial production requirements, blue dyes need to have the following conditions: first, high solubility in industrial solvents; second, good color purity; third, good photothermal stability. However, traditional blue dyes often cannot meet the above requirements at the same time: (1) The developed blue dye molecules have low solubility in organic solvents and poor compatibility with other components in the photosensitive resin composition. (2) The developed blue dye molecules have poor light resistance and heat resistance when in a dispersed state, and are prone to changes in optical properties during the high-temperature post-baking process of subsequent device preparation and under long-term light exposure after service.

[0004] In order to develop blue dyes with good solubility and light and heat stability, a variety of blue dyes (such as CN119662037A, CN116203753B, CN119874755A, CN118785783A, and CN117567875A) have been developed based on the structural modification of triarylmethane, anthraquinone, and copper phthalocyanine cores. Although these dyes have good transmittance to light in the blue wavelength range, they still have the following shortcomings: (1) When heated, the blue dyes based on the triarylmethane core undergo internal bond scission, the chromophore is destroyed, and the thermal stability is poor, which cannot meet the conditions of industrial production. (2) Anthraquinone-based blue dyes have a small π-conjugation and weak interaction with surrounding molecules, resulting in poor thermal stability and the tendency for changes in the optical properties of the device to occur during the post-baking process. In addition, the anthraquinone core structure has few modification sites and low solubility in organic solvents, making it impossible to achieve high color concentrations through thin-layer coating, making it difficult to meet the optical standards of liquid crystal displays and image sensors. (3) Blue dyes based on copper phthalocyanine cores are limited by the strong π-π stacking effect in their molecular structure and often have defects such as poor solubility, insufficient dispersion ability, and poor compatibility with photosensitive resin compositions. In the subsequent high-temperature film formation process, reduced stability may shorten the service life of the device, thereby limiting its application in high-end blue filters and related devices. These key issues urgently need to be resolved through molecular structure modification or process optimization. Summary of the Invention

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

[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 silicon phthalocyanine, which is prepared by substituting the benzene ring sites around the silicon phthalocyanine mother core and / or the silicon center axial site by a multifunctional group, and its structural formula is as follows:

[0008]

[0009] General formula (Ⅰ);

[0010] Among them, R1~R 18 Each is independently selected from any one of a hydrogen atom, a chlorine atom, an alkyl group, an aryl group or a heteroaryl group.

[0011] Preferably, R1 to R 18 They are of the same type or different types.

[0012] More preferably, the R1 to R 18 are of the same type, that is, they are all hydrogen atoms, chlorine atoms, alkyl groups, aryl groups, or heteroaryl groups.

[0013] 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.

[0014] 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.

[0015] 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.

[0016] 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).

[0017] 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.

[0018] More preferably, the halogenated aryl group is a group formed by replacing an aryl group with a Br atom.

[0019] Preferably, the aromatic amine group includes any one of a diphenylamine group and a triphenylamine group.

[0020] 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.

[0021] Preferably, the R1 to R 18 Each independently selected from any one of formulae (B-1) to (B-55).

[0022]

[0023]

[0024] Preferably, the curved lines in (B-1) to (B-55) represent connecting bonds. Preferably, the structural formula of the silicon phthalocyanine includes any one of the following:

[0025]

[0026]

[0027]

[0028]

[0029]

[0030] A second object of the present invention is to provide a blue photosensitive resin composition comprising the following components in parts by weight:

[0031]

[0032] Preferably, the blue photosensitive resin composition comprises the following components in parts by weight:

[0033]

[0034] Further preferably, the colorant includes silicon phthalocyanine as described above.

[0035] Further preferably, the solid content of the blue photosensitive resin composition is 28%.

[0036] 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.

[0037] 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.

[0038] 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.).

[0039] 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.

[0040] 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.

[0041] The third object of the present invention is to provide an application of the blue photosensitive resin composition in the field of color photoresist.

[0042] A fourth object of the present invention is to provide an application of the blue photosensitive resin composition in the preparation of a color filter.

[0043] Preferably, the blue photosensitive resin composition can be applied to filters of display and sensing devices such as liquid crystal displays and image sensors.

[0044] The present invention designs and develops a series of silicon phthalocyanine blue dyes: (1) To address the problem of poor solubility of silicon phthalocyanine, the present invention modifies the benzene ring sites and / or the silicon center axial sites around the silicon phthalocyanine mother core with solubility groups, effectively improving the solubility of the silicon phthalocyanine dye. Compared with zinc phthalocyanine and copper phthalocyanine, the axial modification sites of the silicon phthalocyanine mother core structure are more advantageous, making it easier to improve its physical and chemical properties through structural optimization. (2) To address the problem of easy aggregation of silicon phthalocyanine, the present invention introduces functional groups in the axial direction of the silicon phthalocyanine mother core structure based on the fact that the large π plane of the silicon phthalocyanine mother core structure is conducive to achieving high photothermal stability. This not only enhances solubility, but also effectively inhibits π-π stacking between the phthalocyanine π planes, thereby preventing dye aggregation in the solid state and further improving photothermal stability.

[0045] The present invention further synthesizes a blue photosensitive silicon phthalocyanine resin composition based on silicon phthalocyanine, overcoming the poor solubility of silicon phthalocyanine dyes and the reduced photothermal stability associated with improved solubility. Furthermore, the resulting colored layer from this blue photosensitive silicon phthalocyanine resin composition exhibits excellent solubility, photothermal stability, and high coloration, even at a relatively thin thickness. This blue photosensitive resin composition can be used as a color photoresist and in the preparation of color filters.

[0046] In summary, the present invention adopts a silicon phthalocyanine mother core structure for the first time. On the one hand, by modifying the large steric hindering groups at the benzene ring sites and / or the silicon center axial sites around the silicon phthalocyanine mother core to improve the solubility of the dye, while suppressing the phthalocyanine π plane aggregation of the silicon phthalocyanine dye under photothermal conditions, thereby improving its photothermal stability. On the other hand, the present invention adopts alkoxy and phenoxy molecular chain group modification, which not only enhances the thermal stability of the silicon phthalocyanine dye, but also effectively improves its solubility in organic solvents (PGMEA) and the compatibility with other components of the color photoresist, thereby providing a blue photosensitive resin composition based on silicon phthalocyanine. In addition, based on the excellent stability and high coloring degree of the silicon phthalocyanine mother core, the blue photosensitive resin composition can be used as a color photoresist in display and sensing device filters such as liquid crystal displays and image sensors.

[0047] Compared with the prior art, the present invention has the following beneficial effects:

[0048] (1) The present invention replaces the benzene ring sites and / or the silicon center axial sites around the silicon phthalocyanine mother core with multifunctional groups, thereby providing a silicon phthalocyanine and a blue photosensitive resin composition prepared based on the silicon phthalocyanine. The silicon phthalocyanine has excellent solubility and light and heat stability, and the blue photosensitive resin composition can be made into a thinner colored layer and has a high degree of coloring.

[0049] (2) The present invention modifies the peripheral benzene ring sites and / or the silicon center axial sites of the silicon phthalocyanine core structure with solubility groups. By introducing polar or well-soluble substituents as axial ligands (such as ethers, esters, alkoxy or amino substituents, etc.), the strong π-π interaction between the phthalocyanine planes can be effectively destroyed, thereby improving the solubility of the molecule in polar or non-polar organic solvents, thereby achieving a higher concentration and more uniform dye dispersion system.

[0050] (3) The silicon phthalocyanine backbone of the present invention possesses a highly conjugated structure, imparting excellent thermal stability. The high Si-O or Si-N bond energy formed between the central silicon atom and the axial ligands imparts superior chemical stability to the entire molecule. This maintains its chemical structure and color tone even under long-term exposure to thermal stress in natural environments, thereby extending the lifespan of the dye material.

[0051] (4) The present invention is based on the fact that the silicon phthalocyanine core structure itself has good photo- and thermo-chemical stability, and replaces the peripheral benzene ring sites and / or the silicon center axial sites with functional groups, which not only enhances the solubility, but also effectively inhibits the π-π stacking between the phthalocyanine π planes, inhibits the aggregation of the phthalocyanine π planes under photo-thermal conditions, and further improves its photo-thermal stability.

[0052] (5) The silicon atom in the center of the silicon phthalocyanine of the present application has typical six-coordination ability, and has more structural expandability than conventional four-coordination metal phthalocyanine (e.g., zinc phthalocyanine, copper phthalocyanine). This six-coordination property allows the introduction of a multifunctional ligand in the axial direction of the silicon atom, thereby obtaining a highly adjustable steric configuration and intermolecular interaction mode, and more easily improving the physical and chemical properties of the material through structural modification.

[0053] (6) The present application has prepared a blue photosensitive resin composition based on the above-synthesized silicon phthalocyanine, which can be used to prepare a colored layer with a relatively thin thickness (1.5-2.0 μm) and high coloration degree as a color photoresist.

[0054] (7) The colored layer prepared by using the blue photosensitive resin composition prepared by the present application has excellent system compatibility, heat resistance, and solvent resistance, and can be applied to a color filter of a display and sensing device such as a liquid crystal display, an image sensor, etc.

[0055] (8) The color filter prepared by using the blue photosensitive resin composition prepared by the present application has excellent anti-migration property, and ΔE ab is less than 3.

[0056] (9) The color filter prepared by using the blue photosensitive resin composition prepared by the present application has good line neatness and development process margin. BRIEF DESCRIPTION OF DRAWINGS

[0057] Figure 1 The nuclear magnetic resonance hydrogen spectrum of the compound (17) prepared in Example 3 is shown in the following figure:

[0058] Figure 2 The nuclear magnetic resonance carbon spectrum of the compound (17) prepared in Example 3 is shown in the following figure:

[0059] Figure 3 The mass spectrum of the compound (17) prepared in Example 3 is shown in the following figure:

[0060] Figure 4 The actual figure of the blue photosensitive resin composition D1 prepared in Example 1-1 is shown in the following figure:

[0061] Figure 5 The ultraviolet-visible absorption spectrum of the blue photosensitive resin composition D1 prepared in Example 1-1 is shown in the following figure: DETAILED DESCRIPTION

[0062] This example is implemented on the premise of the technical solution of the present application, and gives a detailed implementation mode and specific operation process, but the protection scope of the present application is not limited to the following examples.

[0063] 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.

[0064] Example 1

[0065] Synthesis of compound (1):

[0066]

[0067] 4-(2-Methoxyethoxy)phenol (2 mmol), phthalocyanine dichlorosilane (1 mmol), and sodium hydride (5 mmol) were dissolved in toluene (20 mL) and stirred at 180°C under nitrogen for 72 h. After 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 dried and purified by column chromatography on a silica gel column (eluent: dichloromethane:methanol = 40:1) to obtain compound (1) as a blue solid with a yield of 75%.

[0068] After high-resolution mass spectrometry, ESI source, and positive ion mode detection, the molecular formula of compound (1) is C 50 H 38 N8O6Si, detected value 875.2755, theoretical value 875.2756; detected element content (%): C, 68.65; H, 4.37; N, 12.82; O, 10.96; Si, 3.21. Theoretical element content (%): C, 68.64; H, 4.38; N, 12.81; O, 10.97; Si, 3.21. These analytical results indicate that the obtained product is the expected product.

[0069] The starting reactants were replaced with corresponding reactants respectively, and the synthesis of the compounds involved in Examples 2 to 4 was completed by referring to the preparation method of Example 1. The specific results are shown in Table 1.

[0070] Table 1

[0071]

[0072] Figure 1 -3 are the nuclear magnetic resonance hydrogen spectrum, carbon spectrum and mass spectrum of compound (17) prepared in Example 3, respectively, which proves that the preparation of compound (17) is successful.

[0073] Example 5:

[0074] Synthesis of compound (37):

[0075]

[0076] 4-tert-Butylphenol (4 mmol), 4-nitrophthalonitrile (4 mmol), and potassium carbonate (8 mmol) were dissolved in N'N-dimethylformamide (50 mL) and stirred at 80°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 dried to obtain the crude product of Intermediate 1. The crude product was dried and purified by column chromatography on silica gel (eluent: petroleum ether: dichloromethane = 4:1) to obtain Intermediate 1.

[0077] Intermediate 1 (4 mmol) and silicon tetrachloride (1 mmol) were dissolved in quinoline (20 mL) and stirred at 220°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 blue solid in a yield of 76%.

[0078] After high-resolution mass spectrometry, ESI source, and positive ion mode detection, the molecular formula of compound (37) is C 76 H 80 C l2 N8O4Si, detected value 1267.5521, theoretical value 1267.5522; detected element content (%): C, 71.99; H, 6.35; Cl, ​​5.59; N, 8.84; O, 5.04; Si, 2.20. Theoretical element content (%): C, 71.96; H, 6.36; Cl, ​​5.59; N, 8.83; O, 5.04; Si, 2.21. These analytical results indicate that the obtained product is the expected product.

[0079] The starting reactants were replaced with corresponding reactants respectively, and the synthesis of the compounds involved in Examples 6 to 8 was completed by referring to the preparation method of Example 5. The specific results are shown in Table 2.

[0080] Table 2

[0081]

[0082]

[0083] Example 9:

[0084] Synthesis of compound (49):

[0085]

[0086] 4-(2-Methylpropyl)phenylmethanol (4 mmol), 3-nitrophthalonitrile (4 mmol), and potassium carbonate (8 mmol) were dissolved in N'N-dimethylformamide (50 mL) and stirred at 80°C for 24 hours 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 dried to obtain the crude product of Intermediate 2. The crude product was dried and purified by column chromatography on silica gel (eluent: petroleum ether: dichloromethane = 5:1) to obtain Intermediate 2.

[0087] Intermediate 2 (4 mmol) and silicon tetrachloride (1 mmol) were dissolved in quinoline (20 mL) and stirred at 220°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 = 54:1) to obtain compound (49) as a blue solid in a yield of 73%.

[0088] After high-resolution mass spectrometry, ESI source, and positive ion mode detection, the molecular formula of compound (49) is C 76 H 80 Cl2N8O4Si, assay value 1267.5521, theoretical value 1267.5522; assayed element content (%): C, 71.99; H, 6.35; Cl, ​​5.59; N, 8.84; O, 5.04; Si, 2.20. Theoretical element content (%): C, 71.96; H, 6.36; Cl, ​​5.59; N, 8.83; O, 5.04; Si, 2.21. These analytical results indicate that the product obtained is the expected product.

[0089] The starting reactants were replaced with corresponding reactants respectively, and the synthesis of the compounds involved in Examples 10 to 12 was completed by referring to the preparation method of Example 9. The specific results are shown in Table 3.

[0090] Table 3

[0091]

[0092]

[0093] Example 13:

[0094] Synthesis of compound (65):

[0095]

[0096] 2,4,6-tri-tert-butylphenol (4 mmol), 3,4,5,6-tetrachlorobenzene-1,2-dicarbonitrile (4 mmol), and potassium carbonate (8 mmol) were dissolved in N'N-dimethylformamide (50 mL) and stirred at 80°C for 24 hours 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 dried to obtain the crude product of Intermediate 3. The crude product was dried and purified by column chromatography on silica gel (eluent: petroleum ether: dichloromethane = 3:1) to obtain Intermediate 3.

[0097] Intermediate 3 (4 mmol) and silicon tetrachloride (1 mmol) were dissolved in quinoline (20 mL) and stirred at 220°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 (65) as a blue solid in a 67% yield.

[0098] After high-resolution mass spectrometry, ESI source, and positive ion mode detection, the molecular formula of compound (65) is C 104 H 132 Cl 14 N8O4Si, detected value 2081.5726, theoretical value 2081.5725; detected element content (%): C, 59.98; H, 6.39; Cl, ​​23.84; N, 5.38; O, 3.07; Si, 1.34. Theoretical element content (%): C, 59.98; H, 6.39; Cl, ​​23.83; N, 5.38; O, 3.07; Si, 1.35. These analytical results indicate that the product obtained is the expected product.

[0099] The starting reactants were replaced with corresponding reactants respectively, and the synthesis of the compound involved in Example 14 was completed by referring to the preparation method of Example 13. The specific results are shown in Table 4.

[0100] Table 4

[0101]

[0102] Example 15:

[0103] Synthesis of compound (71):

[0104]

[0105] 4-tert-Butylphenol (4 mmol), 4-nitrophthalonitrile (4 mmol), and potassium carbonate (8 mmol) were dissolved in N'N-dimethylformamide (50 mL) and stirred at 80°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 dried to obtain the crude product of Intermediate 1. The crude product was dried and purified by column chromatography on silica gel (eluent: petroleum ether: dichloromethane = 4:1) to obtain Intermediate 1.

[0106] Intermediate 1 (4 mmol) and silicon tetrachloride (1 mmol) were dissolved in quinoline (20 mL) and stirred at 220°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 blue solid.

[0107] 4-tert-Butylphenol (2 mmol), compound (37) (1 mmol), and sodium hydride (5 mmol) were dissolved in toluene (20 mL) and stirred at 180°C under nitrogen for 72 h. After 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 dried and purified by column chromatography on a silica gel column (eluent: dichloromethane:methanol = 45:1) to obtain compound (71) as a blue solid with a yield of 65%.

[0108] After high-resolution mass spectrometry, ESI source, and positive ion mode detection, the molecular formula of compound (71) is C 96 H 106 N8O6Si, detected value 1496.8110, theoretical value 1496.8111; detected element content (%): C, 77.08; H, 7.13; N, 7.48; O, 6.43; Si, 1.88. Theoretical element content (%): C, 77.07; H, 7.14; N, 7.49; O, 6.42; Si, 1.88. These analytical results indicate that the product obtained is the expected product.

[0109] The starting reactants were replaced with corresponding reactants respectively, and the synthesis of the compounds involved in Examples 16 to 18 was completed by referring to the preparation method of Example 15. The specific results are shown in Table 5.

[0110] Table 5

[0111]

[0112] It should be noted that other compounds claimed in this application can be obtained by referring to the preparation methods of the above-mentioned embodiments, so they are not listed here one by one.

[0113] Example 19:

[0114] Synthesis of compound (79):

[0115]

[0116] p-Methoxyethylphenol (4 mmol), 3-nitrophthalonitrile (4 mmol), and potassium carbonate (8 mmol) were dissolved in N'N-dimethylformamide (50 mL) and stirred at 80°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 dried to obtain the crude product of Intermediate 4. The crude product was dried and purified by column chromatography on silica gel (eluent: petroleum ether: dichloromethane = 6:1) to obtain Intermediate 4.

[0117] Intermediate 4 (4 mmol) and silicon tetrachloride (1 mmol) were dissolved in quinoline (20 mL) and stirred at 220°C under nitrogen for 24 h. After the reaction, the mixture was cooled to room temperature and the organic solvent was evaporated under reduced pressure to obtain a crude product. The crude product was dried and purified by column chromatography on silica gel (eluent: dichloromethane:methanol = 55:1) to obtain Intermediate 5.

[0118] p-Methoxyethylphenol (2 mmol), intermediate 5 (1 mmol), and sodium hydride (5 mmol) were dissolved in toluene (20 mL) and stirred at 180°C under nitrogen for 72 h. After 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 dried and purified by column chromatography on silica gel (eluent: dichloromethane:methanol = 45:1) to obtain compound (79) as a blue solid in a yield of 63%.

[0119] After high-resolution mass spectrometry, ESI source, and positive ion mode detection, the molecular formula of compound (79) is C 90 H 94 N8O 12 Si, detected value 1507.6834, theoretical value 1507.6833; detected element content (%): C, 71.68; H, 6.28; N, 7.44; O, 12.72; Si, 1.87. Theoretical element content (%): C, 71.69; H, 6.28; N, 7.43; O, 12.73; Si, 1.86. These analytical results indicate that the obtained product is the expected product.

[0120] The starting reactants were replaced with corresponding reactants respectively, and the synthesis of the compounds involved in Examples 20 to 22 was completed by referring to the preparation method of Example 19. The specific results are shown in Table 6.

[0121] Table 6

[0122]

[0123] It should be noted that other compounds claimed in this application can be obtained by referring to the preparation methods of the above-mentioned embodiments, so they are not listed one by one here.

[0124] Example 23:

[0125] Synthesis of compound (87):

[0126]

[0127] 4-tert-Butyl-3-methylphenol (4 mmol), 3,4,5,6-tetrachlorobenzene-1,2-dicarbonitrile (4 mmol), and potassium carbonate (8 mmol) were dissolved in N'N-dimethylformamide (50 mL) and stirred at 80°C for 24 hours 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 dried to obtain the crude product of Intermediate 6. The crude product was dried and purified by column chromatography on silica gel (eluent: petroleum ether: dichloromethane = 5:1) to obtain Intermediate 6.

[0128] Intermediate 6 (4 mmol) and silicon tetrachloride (1 mmol) were dissolved in quinoline (20 mL) and stirred at 220°C under nitrogen for 24 h. After the reaction, the mixture was cooled to room temperature and the organic solvent was evaporated under reduced pressure to obtain a crude product. The crude product was dried and purified by column chromatography on silica gel (eluent: dichloromethane:methanol = 58:1) to obtain Intermediate 7.

[0129] 4-tert-Butyl-3-methylphenol (2 mmol), intermediate 7 (1 mmol), and sodium hydride (5 mmol) were dissolved in toluene (20 mL) and stirred at 180°C under nitrogen for 72 h. After 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 dried and purified by column chromatography on silica gel (eluent: dichloromethane:methanol = 49:1) to obtain compound (87) as a blue solid in a yield of 62%.

[0130] After high-resolution mass spectrometry, ESI source, and positive ion mode detection, the molecular formula of compound (87) is C 98 H 106Cl 12 N8O6Si, detected value 1946.4286, theoretical value 1946.4285; detected element content (%): C, 60.50; H, 5.49; Cl, ​​21.88; N, 5.75; O, 4.93; Si, 1.44. Theoretical element content (%): C, 60.50; H, 5.49; Cl, ​​21.87; N, 5.76; O, 4.93; Si, 1.44. These analytical results indicate that the product obtained is the expected product.

[0131] The starting reactants were replaced with the corresponding reactants respectively, and the synthesis of the compound involved in Example 24 was completed by referring to the preparation method of Example 23. The specific results are shown in Table 7.

[0132] Table 7

[0133]

[0134] Example 1-1

[0135] Preparation of blue photosensitive resin composition D1

[0136] A blue photosensitive resin composition D1 was prepared using the silicon phthalocyanine 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.

[0137] formula:

[0138] 5 parts by weight of a colorant, 17 parts by weight of a resin containing a double bond structure, 6 parts by weight of a monomer containing a double bond structure, 0.5 parts by weight of a photoinitiator, 0.25 parts by weight of an additive for improving film-forming properties and / or stability, and 77 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 blue photosensitive resin composition. Figure 4 The UV-visible absorption spectrum of the prepared blue photosensitive resin composition D1 is shown as Figure 5 shown.

[0139] in,

[0140] Colorant: Silicon phthalocyanine (Formula (1))

[0141] Resins containing double bond structures or / and epoxy structures: acrylic polyester resin (analytical grade), purchased from Titan Corporation;

[0142] Monomers containing double bond structures or / and epoxy structures: dipentaerythritol pentaacrylate monomer (analytical grade), purchased from Titan Corporation;

[0143] Photoinitiator with high absorption characteristics at 365 nm: α,α-diethoxyacetophenone (analytical grade), purchased from Titan Company;

[0144] Additives for improving film-forming property and / or stability: defoaming agent (analytical grade), purchased from Titan Company;

[0145] Solvents containing ether groups: propylene glycol methyl ether acetate (analytical grade), purchased from Titan Corporation;

[0146] Comparative Example 2-1

[0147] Preparation of blue photosensitive resin composition E1

[0148] Take 5 parts by weight of a colorant (anthraquinone dye L1), 17 parts by weight of a resin containing a double bond structure, 6 parts by weight of a monomer containing a double bond structure, 0.5 parts by weight of a photoinitiator, 0.25 parts by weight of an additive for improving film-forming properties and / or stability, and 77 parts by weight of an ether-containing solvent, mix and dissolve them thoroughly, and control the solid content to about 28% to obtain a blue photosensitive resin composition.

[0149] Comparative Example 2-2

[0150] Preparation of blue photosensitive resin composition E2

[0151] Take 5 parts by weight of a colorant (triarylmethane dye L2), 17 parts by weight of a resin containing a double bond structure, 6 parts by weight of a monomer containing a double bond structure, 0.5 parts by weight of a photoinitiator, 0.25 parts by weight of an additive for improving film-forming properties and / or stability, and 77 parts by weight of an ether-containing solvent, mix and dissolve them thoroughly, and control the solid content to about 28% to obtain a blue photosensitive resin composition.

[0152] Comparative Examples 2-3

[0153] Preparation of blue photosensitive resin composition E3

[0154] Take 5 parts by weight of a colorant (copper phthalocyanine dye L3), 17 parts by weight of a resin containing a double bond structure, 6 parts by weight of a monomer containing a double bond structure, 0.5 parts by weight of a photoinitiator, 0.25 parts by weight of an additive for improving film-forming properties and / or stability, and 77 parts by weight of an ether-containing solvent, mix and dissolve them thoroughly, and control the solid content to about 28% to obtain a blue photosensitive resin composition.

[0155] in,

[0156] Colorants: Anthraquinone dye L1, triarylmethane dye L2, copper phthalocyanine dye L3

[0157] Resins containing double bond structures or / and epoxy structures: acrylic polyester resin (analytical grade), purchased from Titan Corporation;

[0158] Monomers containing double bond structures or / and epoxy structures: dipentaerythritol pentaacrylate monomer (analytical grade), purchased from Titan Corporation;

[0159] Photoinitiator with high absorption characteristics at 365 nm: α,α-diethoxyacetophenone (analytical grade), purchased from Titan Company;

[0160] Additives for improving film-forming property and / or stability: defoaming agent (analytical grade), purchased from Titan Company;

[0161] Solvents containing ether groups: propylene glycol methyl ether acetate (analytical grade), purchased from Titan Corporation;

[0162] The chemical structure of anthraquinone dye L1 is as follows:

[0163]

[0164] Anthraquinone dye L1

[0165] The chemical structure of triarylmethane dye L2 is as follows:

[0166]

[0167] Triarylmethane Dye L2

[0168] The chemical structure of copper phthalocyanine dye L3 is as follows:

[0169]

[0170] Copper Phthalocyanine Dye L3

[0171] The performance testing of the photosensitive resin compositions D1, E1, E2, and E3 was performed using the following steps:

[0172] 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 2 The distance between the mask plate and the coating film is 180μm, and then it is developed at 25℃ for 50s, and then post-baked at 230℃ for 30min. Then the subsequent related performance is tested. The results are shown in Table 8.

[0173] Performance testing and evaluation methods:

[0174] (1) Chromaticity: Detected using a Konica Minolta CM-5 spectrophotometer.

[0175] (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.

[0176] The evaluation criteria are as follows:

[0177] ○: Viscosity change < ±5% mPa·s and no particles on the x500 surface;

[0178] △: Viscosity change < ±10% mPa·s and no particles on the x500 surface;

[0179] ×: Viscosity change > ±10% mPa·s or particles on the surface of x500;

[0180] (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;

[0181] (4) Evaluation of solvent resistance:

[0182] 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.

[0183] (5) Evaluation of anti-migration performance:

[0184] According to the color filter manufacturing process, first prepare blue pixels on thin film transistor (TFT) glass. Then apply the sample, and after the development is completed, blow dry the color filter surface and measure the color difference before and after the pixel. If ΔE ab <3, indicating good anti-migration properties.

[0185] (6) Line width, edge regularity, and development process margin:

[0186] The line width and edge uniformity were tested by x500 OM, and the mask line width was 140μm.

[0187] 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.

[0188] The evaluation criteria for edge neatness are as follows:

[0189] ○: The edges are neat and there is no residue at the edges after 50s of development;

[0190] △: After 50 seconds of development, the image edge has burrs, is not neat, or has residues at the edge;

[0191] ×: Image missing

[0192] The specific standards for evaluating the development process margin are as follows:

[0193] ○: The edges are neat and there is no residue or peeling at the edges after 40-100s of development;

[0194] △: The edges are neat and there is no residue or peeling at the edges after 50-80s of development;

[0195] ×: The edges are not neat, or there are residues or peeling at the edges after 50–80s of development.

[0196] 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%.

[0197] 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 8.

[0198] Table 8

[0199]

[0200]

[0201] Comparison of experimental results shows that the silicon phthalocyanine dyes of Examples 1-1 to 1-24 exhibit superior solubility in the color photoresist solvent PGMEA, compared to the anthraquinone dye L1 used in Comparative Example 2-1, the triarylmethane dye L2 used in Comparative Example 2-2, and the copper phthalocyanine dye L3 used in Comparative Example 2-3. They also exhibit excellent heat resistance, light resistance, and solvent resistance. Furthermore, compared to the photosensitive resin composition E1 using anthraquinone dye L1, the photosensitive resin composition E2 using triarylmethane dye L2, and the photosensitive resin composition E3 using copper phthalocyanine dye L3, the blue photosensitive resin compositions D1 to D24 prepared using the silicon phthalocyanine dyes of the present invention exhibit similarly good process performance, such as system compatibility, edge line uniformity, and development process margin.

[0202] In summary, the present invention effectively improves the solubility of silicon phthalocyanine dyes by modifying functional groups at the benzene ring sites and / or the silicon center axial sites around the silicon phthalocyanine mother core; inhibits the aggregation of the dye in the solid state, further improving the stability of the phthalocyanine dye; solves the problems of thermal stability and solvent resistance not meeting industrial production requirements, and poor solubility and compatibility in color photoresist systems; the selected silicon phthalocyanine compounds with better performance can be used to prepare blue photosensitive resin compositions, and can be used as color photoresists in color filters of display and sensing devices such as liquid crystal displays and image sensors.

[0203] 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 silicon phthalocyanine, characterized in that It is prepared by substituting the benzene ring sites and / or the silicon center axial sites around the silicon phthalocyanine core with multifunctional groups. Its structural formula is as follows: Among them, R1~R 18 Each is independently selected from any one of a hydrogen atom, a chlorine atom, an alkyl group, an aryl group or a heteroaryl group.

2. The silicon 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. The silicon phthalocyanine according to claim 1, characterized in that: The heteroaryl group is selected from any one of a condensed heterocyclic group, a monocyclic aromatic heterocyclic group, and a polycyclic aromatic heterocyclic group.

4. The silicon phthalocyanine according to claim 3, characterized in that: 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; The aryl group includes an unsubstituted aryl group, an alkyl-substituted aryl group, and a polyaryl group; 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; and the arylamine 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.

5. The silicon phthalocyanine according to claim 1, characterized in that: The R1~R 18 Each is independently selected from any one of formulas (B-1) to (B-55), wherein the curved line represents a connecting bond:

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

7. A blue photosensitive resin composition, characterized in that: The composition comprises the following components in parts by weight: Wherein, the colorant comprises the silicon phthalocyanine according to any one of claims 1 to 6; and the solid content of the blue photosensitive resin composition is 14-39%.

8. The blue photosensitive resin composition according to claim 7, characterized in that: The resin containing a double bond structure or / and 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; 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; the photoinitiator with high absorption characteristics at 365nm includes oximes, benzoins, acetophenones, imidazolines, and the like. The invention also includes one or more of azoles, 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.; 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.

9. Use of the blue photosensitive resin composition according to any one of claims 7 to 8 in the field of color photoresist.

10. Use of the blue photosensitive resin composition according to any one of claims 7 to 8 in preparing a color filter.

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