Silicon phthalocyanine, green photosensitive resin composition and application thereof

Abstract

The invention relates to silicon phthalocyanine, a green photosensitive resin composition and application of the silicon phthalocyanine, the silicon phthalocyanine is prepared by substituting a benzene ring site at the periphery of a silicon phthalocyanine mother nucleus or / and a silicon center axial site through a multifunctional group, and the structural formula of the silicon phthalocyanine is as follows: R1-R18 are independently selected from any one of hydrogen atoms, chlorine atoms, alkyl groups, aryl groups or heteroaryl substituent groups; and R1 to R18 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 silicon phthalocyanine has excellent solubility and photo-thermal stability, and the prepared green photosensitive resin composition has high color purity 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 green photosensitive resin composition and applications thereof. Background Art

[0002] Liquid crystal displays (LCDs), organic light-emitting diodes (OLEDs), and image sensors have become widely used display and sensing technologies in consumer electronics, healthcare, industrial automation, security, and other fields. Color filters are a crucial component of LCD and OLED displays and complementary metal oxide semiconductor (CMOS) image sensors. The green filter, a key component of the red, green, and blue (RGB) color filter, primarily filters out red and blue light, concentrating the light passing through it primarily within the green wavelength range, enabling accurate color separation and processing. Currently, the pigment dispersion method is a common method for producing green color filters. Various phthalocyanine compounds, such as Phthalocyanine Green G36 and Phthalocyanine Green G58, are commonly used as colorants. While filters produced by this method exhibit excellent heat and light resistance and a long service life, the large pigment particles affect transmittance and dispersion stability, thereby reducing the filter's brightness, contrast, and resolution, making it impossible to achieve high brightness, high color purity, and a wide color gamut.

[0003] In contrast, green dyes have certain advantages and can serve as attractive alternatives to overcome the above limitations. Green dyes dissolve in the medium and exist in molecular form, which reduces light scattering. In addition, green dyes have a clear molecular structure and a clear structure-activity relationship between their molecular structure and photophysical properties, making them more promising in achieving excellent optical properties. Although green dyes can generally produce color filters with high transmittance and high contrast, they have poor heat resistance and light resistance and are prone to chromaticity changes during the high-temperature heating step in the preparation of green filters. In addition, to meet industrial production requirements, green dyes need to have the following conditions: first, high solubility in industrial solvents; second, good color purity; and third, good photothermal stability. However, traditional green dyes often find it difficult to meet these requirements: (1) Traditional green dyes exhibit low solubility in organic solvents, and therefore it is difficult to obtain a colored curable composition with the desired spectrum. (2) To achieve green color purity, green dyes need to have good absorption capabilities for both the blue light band (400–500 nm) and the red light band (600–700 nm). The absorption band of green dyes in the visible light region is usually a single absorption peak, making it difficult to achieve good absorption of blue and red light simultaneously, resulting in poor green color purity. (3) Green dyes in a molecularly dispersed state have poor light and heat resistance, and are prone to changes in optical properties during the high-temperature post-baking process in subsequent device preparation and under long-term light exposure after service.

[0004] In terms of green dyes, currently, a variety of phthalocyanine green dyes based on planar tetragonal structures, including zinc phthalocyanine dyes and copper phthalocyanine dyes, have been developed mainly based on the phthalocyanine mother core (such as CN202080008015.6, CN202180044374.1, CN202180038558.7, CN202211637638.7, and CN202310360311.8). These dyes have strong light absorption capabilities, but there are the following problems in practical applications: (1) These green dyes have poor solubility in commonly used industrial solvents (such as propylene glycol monomethyl ether acetate PGMEA), resulting in the inability to achieve high color concentration through thin layer coating, making it difficult to meet the optical standards of liquid crystal displays and image sensors; (2) The zinc phthalocyanine and copper phthalocyanine dyes developed above all have planar tetragonal structures. The large planar conjugated structure of phthalocyanine makes it easy for the dye molecules to aggregate, which not only causes a physical shift in the optical properties, but also weakens the photothermal stability of the material itself. In addition, during the subsequent high-temperature film formation process, the reduced stability may cause changes in the optical properties and shorten the service life of the device. (3) The absorption of phthalocyanine green dyes is mainly concentrated in the red light band, and the absorption is poor in the blue light band. This absorption characteristic has obvious limitations in achieving high green color purity. It is often unable to fully filter out light of interfering wavelengths, which in turn hinders the goal of achieving high green color purity. These key issues urgently need to be solved 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 green photosensitive resin composition and its application. The silicon phthalocyanine has excellent solubility and photothermal stability. Based on the silicon phthalocyanine, a green photosensitive resin composition with high color purity can be prepared.

[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 independently selected from any one of hydrogen atom, chlorine atom, alkyl, aryl or heteroaryl substituents, R1 to R 18 The present invention comprises at least one naphthalimide group.

[0011] 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.

[0012] Preferably, the heteroaryl group is selected from any one of a fused heterocyclic group, a monocyclic aromatic heterocyclic group and a polycyclic aromatic heterocyclic group, and 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 group of an aryl group, a halogenated aromatic group and an aromatic amino 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 18 In the above, except for the naphthalene imide group, the other substituent groups are of the same type or different types.

[0019] More preferably, R1 to R 18 In the above formula (1), except for the naphthalene imide group, the other substituent groups are of the same type.

[0020] More preferably, R 17 ~R 18 They are of the same type or different types.

[0021] More preferably, R 17 ~R 18 Of the same kind.

[0022] Preferably, the structural formula of the naphthalimide group is as follows:

[0023]

[0024] General formula (II);

[0025] L is each independently selected from any one of the following formulae (A-1) to (A-15):

[0026]

[0027] Preferably, the curves in general formula (II) represent the bonds of R1to R 18 to the silicon phthalocyanine mother nucleus in formula (I).

[0028] Preferably, the curves in formulae (A-1) to (A-15) represent the bonds of L to its adjacent O atom and N atom.

[0029] Preferably, in general formula (II), N1, N2are each independently selected from a hydrogen atom, or a substituted or unsubstituted group:

[0030] one of C1to C60linear alkyl, C1to C60branched alkyl, C1to C60linear alkenyl, C1to C60linear alkynyl, C3to C60cycloalkyl, C4to C60cycloalkenyl, C4to C60cycloalkynyl, C1to C60alkoxy, C1to C60branched alkoxy, C1to C60thioalkoxy, C6to C60aryl, C3to C60heteroaryl, C4to C60aryloxy, and at least one of N1, N2is an amine functional group.

[0031] Preferably, N1, N2are each independently selected from one of formulae (B-1) to (B-49).

[0032]

[0033] Preferably, the curves in (B-1) to (B-49) represent the bonds of N1, N2to the naphthalimide group in general formula (II).

[0034] Preferably, the structural formula of the silicon phthalocyanine includes any one of the following:

[0035]

[0036]

[0037]

[0038]

[0039]

[0040]

[0041]

[0042]

[0043] A second object of the present invention is to provide a green photosensitive resin composition comprising the following components in parts by weight:

[0044] Colorants 2–10;

[0045] Resins containing double bond structures and / or epoxy structures 10–30;

[0046] Monomers 2–8 containing double bond structures and / or epoxy structures;

[0047] Photoinitiator 0.2–0.9 with high absorption characteristics at 365nm;

[0048] Additives to improve film forming and / or stability 0.1–0.6;

[0049] Solvents containing ether groups 50–90;

[0050] Wherein, the colorant includes the silicon phthalocyanine as described above; and the solid content of the green photosensitive resin composition is 15-38%.

[0051] Preferably, the green photosensitive resin composition comprises the following components in parts by weight:

[0052] Colorant 4;

[0053] Resin 20 containing a double bond structure and / or an epoxy structure;

[0054] Monomer 5 containing a double bond structure and / or an epoxy structure;

[0055] Photoinitiator 0.5 with high absorption characteristics at 365 nm;

[0056] Additives for improving film forming properties and / or stability 0.25;

[0057] Solvents containing ether groups 70;

[0058] Further preferably, the colorant includes silicon phthalocyanine as described above.

[0059] Further preferably, the solid content of the green photosensitive resin composition is 29%.

[0060] 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.

[0061] 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.

[0062] 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.).

[0063] 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.

[0064] 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.

[0065] 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.

[0066] Preferably, the green photosensitive resin composition can be applied to filters of display and sensing devices such as liquid crystal displays and image sensors.

[0067] The present invention designs and develops a series of silicon phthalocyanines: (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, thereby effectively improving the solubility of silicon phthalocyanine dyes; (2) To address the problem of easy aggregation of silicon phthalocyanine dyes, the present invention introduces functional groups on the axial side of the silicon phthalocyanine mother core to inhibit the π-π interaction between π planes and prevent the aggregation of the dye in the solid state, thereby further improving the stability of the phthalocyanine dyes; (3) To address the problem of insufficient color purity of silicon phthalocyanine green dyes, the present invention compensates for the poor absorption of silicon phthalocyanine dyes in the blue light region (400-500nm) by coupling functional groups with blue light absorption characteristics (naphthalimide groups), and successfully synthesizes a high-color-purity green dye-green photosensitive resin composition.

[0068] The present invention is based on the silicon phthalocyanine mother core structure, and modifies the peripheral benzene ring sites and / or the silicon center axial sites with light-stable blue light absorbing functional groups (naphthalimide groups), which compensates for the absorption of silicon phthalocyanine itself in the visible light region of 400-500nm, realizes the regulation of the photochemical and photophysical properties of the dye, and thus obtains a dye with excellent color purity and stable photochemical and photophysical properties. In addition, the present invention adopts alkoxy and phenoxy molecular chain group modification, which not only enhances the photothermal stability of the silicon phthalocyanine dye, but also effectively improves its solubility in organic solvents (PGMEA) and compatibility with other components of the color photoresist, thereby providing a green photosensitive resin composition based on silicon phthalocyanine. Based on the excellent photothermal stability and high coloration of the silicon phthalocyanine mother core, 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.

[0069] In summary, the present invention utilizes a large π-conjugated silicon phthalocyanine core structure with high chemical bond energy to impart excellent photo- and thermochemical stability to its silicon phthalocyanine derivatives. By introducing functional groups with blue light absorption properties, the insufficient blue light absorption characteristics of silicon phthalocyanine dyes are overcome, resulting in the synthesis of a green dye. Furthermore, axial substitution of the chlorine atoms of silicon phthalocyanine suppresses the strong π-π interactions within the phthalocyanine plane, enhancing the dye's solubility in organic solutions and overcoming the poor solubility of silicon phthalocyanine dyes and the resulting decrease in chemical stability after improved solubility.

[0070] Compared with the prior art, the present invention has the following beneficial effects:

[0071] (1) The present invention replaces the benzene ring sites around the silicon phthalocyanine mother core and / or the silicon center axial site with various substituents including naphthalimide groups, thereby providing a silicon phthalocyanine and a green photosensitive resin composition prepared based on the silicon phthalocyanine. The silicon phthalocyanine has excellent solubility and light and heat stability, and the green photosensitive resin composition has high color purity.

[0072] (2) The present invention modifies the peripheral benzene ring sites and / or the silicon center axial sites of the silicon phthalocyanine mother core structure with solubility groups, effectively improving the solubility of silicon phthalocyanine and making it well compatible with commonly used industrial solvents such as color photoresist solvent PGMEA.

[0073] (3) The silicon phthalocyanine core structure of the present invention has good photo- and thermo-chemical stability. Substitution of the peripheral benzene ring sites and / or the silicon center axial sites by functional groups not only enhances the solubility but also effectively inhibits the π-π stacking between the phthalocyanine π planes and inhibits the aggregation of the phthalocyanine π planes under photo-thermal conditions, thereby further improving its photo-thermal stability.

[0074] (4) The present invention modifies the benzene ring sites and / or the silicon center axial sites around the silicon phthalocyanine mother core with a photostable blue light absorbing functional group - a naphthalimide group, which can compensate for the problem of weak absorption of silicon phthalocyanine dyes in the blue light region (400-500nm), thereby synthesizing a silicon phthalocyanine green dye having a high green color purity.

[0075] (5) Compared with zinc phthalocyanine and copper phthalocyanine, the silicon phthalocyanine of the present invention has an axial modification site in its core structure, making it easier to improve the physical and chemical properties of the material through structural modification.

[0076] (6) The present invention prepares a green photosensitive resin composition based on the synthesized silicon phthalocyanine, which can be used as a color photoresist to prepare a colored layer with a thin thickness (1.5-2.0 μm) and high coloring degree.

[0077] (7) 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.

[0078] (8) 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.

[0079] (9) 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

[0080] Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of compound (1) prepared in Example 1;

[0081] Figure 2 The mass spectrum of compound (1) prepared in Example 1;

[0082] Figure 3 This is a physical picture of the green photosensitive resin composition D1 prepared in Example 1-1;

[0083] Figure 4 is the UV-visible absorption spectrum of the green photosensitive resin composition D1 prepared in Example 1-1;

[0084] Figure 5 2-1 and 2-2 are CIE chromaticity diagrams of Example 1-1 and Comparative Example 2-1. DETAILED DESCRIPTION

[0085] The application will be described in detail below in conjunction with the accompanying drawings and specific embodiments. The embodiments are implemented on the premise of the technical solutions of the application, and detailed implementation modes and specific operation processes are given, but the protection scope of the application is not limited to the following examples.

[0086] Unless otherwise specified, the reagents, methods, instruments and equipment used in the application 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.

[0087] Example 1:

[0088] Synthesis of compound (1):

[0089]

[0090] Dissolve 4-bromonaphthalic anhydride (1 mmol) and p-bromophenol (2 mmol) in ethanol (30 mL), stir at constant temperature 90°C for 24 h under nitrogen protection. After the reaction is completed, cool to room temperature, pour the mixture into ice water to precipitate the solid, and then extract the mixture by suction filtration to obtain the solid, and the solid after drying is the intermediate 1.

[0091] Dissolve intermediate 1 (1 mmol), 4-(2-methoxyethoxy) aniline (1 mmol), tetrakis triphenylphosphine palladium (0.05 mmol), and potassium tert-butoxide (1.5 mmol) in toluene (20 mL) and heat to reflux at 110°C for 24 h. After the reaction is completed, cool to room temperature, extract with dichloromethane and saturated brine. Collect the organic layer and dry with anhydrous magnesium sulfate, then evaporate the organic solvent under reduced pressure to obtain the crude product. Purify the crude product by column chromatography on a silica gel column (eluent: dichloromethane: petroleum ether = 4:1) to obtain the intermediate 2.

[0092] Dissolve intermediate 2 (2 mmol), phthalocyanine dichloride (1 mmol), and sodium hydride (5 mmol) in toluene (20 mL), stir at constant temperature 180°C for 72 h under nitrogen protection. After the reaction is completed, cool to room temperature, extract with dichloromethane and saturated brine. Collect the organic layer and dry with anhydrous magnesium sulfate, then evaporate the organic solvent under reduced pressure to obtain the crude product. Dry the crude product, then purify it by column chromatography on a silica gel column (eluent: dichloromethane:methanol = 40:1) to obtain compound (1) as a green solid with a yield of 55%.

[0093] After high-resolution mass spectrometry, ESI source, and positive ion mode detection, the molecular formula of compound (1) is C 86 H 58 N 12 O 10Si, detected value 1447.4224, theoretical value 1447.4241; detected element content (%): C, 71.38; H, 4.02; N, 11.62; O, 11.06; Si, 1.92. Theoretical element content (%): C, 71.36; H, 4.04; N, 11.61; O, 11.05; Si, 1.94. These analytical results indicate that the product obtained is the expected product.

[0094] Figure 1 -2 are the nuclear magnetic resonance hydrogen spectrum and mass spectrum of compound (1) prepared in Example 1, respectively, which prove the successful preparation of compound (1).

[0095] The starting reactants were replaced with corresponding reactants respectively, and the synthesis of the compound involved in Example 2 was completed by referring to the preparation method of Example 1. The specific results are shown in Table 1.

[0096] Table 1

[0097]

[0098] Example 3:

[0099] Synthesis of compound (25):

[0100]

[0101] Dissolve 4-bromonaphthalic anhydride (1 mmol) and 4-aminobutanol (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 3.

[0102] Intermediate 3 (1 mmol), 4-hexylaniline (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 = 7:1) to obtain Intermediate 4.

[0103] Intermediate 4 (2 mmol), dichlorosilane phthalocyanine (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 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 dried and purified by column chromatography on a silica gel column (eluent: dichloromethane:methanol = 45:1) to obtain compound (25) as a green solid with a yield of 56%.

[0104] After high-resolution mass spectrometry, ESI source, and positive ion mode detection, the molecular formula of compound (25) is C 76 H 70 N 12 O6Si, detected value 1275.5384, theoretical value 1275.5383; detected element content (%): C, 71.55; H, 5.53; N, 13.18; O, 7.54; Si, 2.20. Theoretical element content (%): C, 71.56; H, 5.53; N, 13.18; O, 7.53; Si, 2.20. The above analysis results indicate that the obtained product is the expected product.

[0105] The starting reactants were replaced with corresponding reactants respectively, and the synthesis of the compound involved in Example 4 was completed by referring to the preparation method of Example 3. The specific results are shown in Table 2.

[0106] Table 2

[0107]

[0108] Example 5:

[0109] Synthesis of compound (42):

[0110]

[0111] 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.

[0112] 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.

[0113] Intermediate 2 (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 then dried to obtain the crude product of Intermediate 5. The crude product was dried and purified by column chromatography on silica gel (eluent: petroleum ether: dichloromethane = 5:1) to obtain Intermediate 5.

[0114] Intermediate 5 (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 = 53:1) to obtain compound (42) as a green solid in a yield of 51%.

[0115] After high-resolution mass spectrometry, ESI source, and positive ion mode detection, the molecular formula of compound (42) was C₁₄H₁₄Cl₂N₁₆O₂OSi, the detected value was 2484.7492, and the theoretical value was 2484.7491. The detected element content (%) was: C, 69.59; H, 4.55; C, 2.84; N, 9.03; O, 12.86; Si, 1.13. The theoretical element content (%) was: C, 69.59; H, 4.54; C, 2.85; N, 9.02; O, 12.87; Si, 1.13. The above analytical results showed that the obtained product was the expected product.

[0116] The starting reactants were replaced with corresponding reactants, and the synthesis of the compound involved in Example 6 was completed by referring to the preparation method of Example 5. The specific results are shown in Table 3.

[0117] Table 3

[0118]

[0119] Example 7:

[0120] Synthesis of compound (55):

[0121]

[0122] Dissolve 4-bromonaphthalic anhydride (1 mmol) and 5-amino-1-pentanol (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 6.

[0123] Intermediate 6 (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 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 = 6:1) to obtain Intermediate 7.

[0124] Intermediate 7 (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 then dried to obtain the crude product of Intermediate 8. The crude product was dried and purified by column chromatography on silica gel (eluent: petroleum ether: dichloromethane = 3:1) to obtain Intermediate 8.

[0125] Intermediate 8 (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 (55) as a green solid in a yield of 53%.

[0126] After high-resolution mass spectrometry, ESI source, and positive ion mode detection, the molecular formula of compound (55) is C 140 H 136 Cl2N 16 O 20Si, detected value 2460.9368, theoretical value 2460.9369; detected element content (%): C, 68.32; H, 5.56; Cl, ​​2.88; N, 9.10; O, 13.00; Si, 1.14. Theoretical element content (%): C, 68.31; H, 5.57; Cl, ​​2.88; N, 9.10; O, 13.00; Si, 1.14. These analytical results indicate that the product obtained is the expected product.

[0127] The starting reactants were replaced with corresponding reactants respectively, and the synthesis of the compound involved in Example 8 was completed by referring to the preparation method of Example 7. The specific results are shown in Table 4.

[0128] Table 4

[0129]

[0130] Example 9:

[0131] Synthesis of compound (59):

[0132]

[0133] 4-Bromonaphthalene anhydride (1 mmol) and p-bromophenol (2 mmol) were dissolved in ethanol (30 mL) and stirred at 90°C under nitrogen for 24 hours. 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 to obtain Intermediate 1.

[0134] Intermediate 1 (1 mmol), 3,5-di-tert-butylaniline (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 = 3:1) to obtain Intermediate 9.

[0135] Intermediate 7 (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 then dried to obtain the crude product of Intermediate 10. The crude product was dried and purified by column chromatography on silica gel (eluent: petroleum ether: dichloromethane = 2:1) to obtain Intermediate 10.

[0136] Intermediate 10 (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 = 52:1) to obtain compound (59) as a green solid in a 52% yield.

[0137] After high-resolution mass spectrometry, ESI source, and positive ion mode detection, the molecular formula of compound (59) is C 164 H 152 C l2 N 16 O 12 Si, detected value 2637.1029, theoretical value 2637.1028; detected element content (%): C, 74.66; H, 5.82; C, 2.68; N, 8.50; O, 7.28; Si, 1.07. Theoretical element content (%): C, 74.67; H, 5.81; C, 2.69; N, 8.50; O, 7.28; Si, 1.06. The above analysis 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 compound involved in Example 10 was completed by referring to the preparation method of Example 9. The specific results are shown in Table 5.

[0139] Table 5

[0140]

[0141] Example 11:

[0142] Synthesis of compound (66):

[0143]

[0144] Dissolve 4-bromonaphthalene anhydride (1 mmol) and 7-amino-1-heptanol (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.

[0145] Intermediate 11 (1 mmol), tetrahydropyrrole (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 toluene (20 mL). 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.

[0146] Intermediate 12 (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 then dried to obtain the crude product of Intermediate 13. The crude product was then dried and purified by column chromatography on silica gel (eluent: petroleum ether: dichloromethane = 6:1) to obtain Intermediate 13.

[0147] Intermediate 13 (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 compound (66) as a green solid in a 50% yield.

[0148] After high-resolution mass spectrometry, ESI source, and positive ion mode detection, the molecular formula of compound (66) is C 128 H 136 C l2 N 16 O 12 Si, detected value 2188.9775, theoretical value 2188.9776; detected element content (%): C, 70.22; H, 6.25; Cl, ​​3.23; N, 10.25; O, 8.76; Si, 1.28. Theoretical element content (%): C, 70.21; H, 6.25; Cl, ​​3.24; N, 10.24; O, 8.77; Si, 1.28. These analytical results indicate that the product obtained is the expected product.

[0149] The starting reactants can be replaced with corresponding reactants respectively. The synthesis of the compound involved in Example 12 can be completed by referring to the preparation method of Example 11. The specific results are shown in Table 6.

[0150] Table 6

[0151]

[0152] Example 13:

[0153] Synthesis of compound (72):

[0154]

[0155] 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.

[0156] Intermediate 1 (1 mmol), n-hexylamine (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 14.

[0157] Intermediate 14 (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 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 to obtain the crude product of Intermediate 15. The crude product was then dried and purified by column chromatography on silica gel (eluent: petroleum ether: dichloromethane = 5:1) to obtain Intermediate 15.

[0158] Intermediate 15 (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 (72) as a green solid in a 50% yield.

[0159] After high-resolution mass spectrometry, ESI source, and positive ion mode detection, the molecular formula of compound (72) is C 128 H 108 Cl 14 N 16 O 12Si, detected value 2586.3758, theoretical value 2586.3759; detected element content (%): C, 59.44; H, 4.21; Cl, ​​19.18; N, 8.67; O, 7.42; Si, 1.08. Theoretical element content (%): C, 59.43; H, 4.21; Cl, ​​19.19; N, 8.66; O, 7.42; Si, 1.09. These analytical results indicate that the product obtained is the expected product.

[0160] The starting reactants can be replaced with corresponding reactants respectively. The synthesis of the compound involved in Example 14 can be completed by referring to the preparation method of Example 13. The specific results are shown in Table 7.

[0161] Table 7

[0162]

[0163] Example 15:

[0164] Synthesis of compound (77):

[0165]

[0166] Dissolve 4-bromonaphthalic anhydride (1 mmol) and 5-amino-1-pentanol (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 6.

[0167] Intermediate 6 (1 mmol), 2-methylpiperidine (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 = 7:1) to obtain Intermediate 16.

[0168] Intermediate 16 (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 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 to obtain the crude product of intermediate 17. The crude product was then dried and purified by column chromatography on silica gel (eluent: petroleum ether: dichloromethane = 6:1) to obtain intermediate 17.

[0169] Intermediate 17 (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 (77) as a green solid in a yield of 56%.

[0170] After high-resolution mass spectrometry, ESI source, and positive ion mode detection, the molecular formula of compound (77) is C 124 H 124 Cl 14 N 16 O 12 Si, detected value 2554.5010, theoretical value 2554.5011; detected element content (%): C, 58.30; H, 4.88; Cl, ​​19.43; N, 8.78; O, 7.51; Si, 1.10. Theoretical element content (%): C, 58.30; H, 4.89; Cl, ​​19.43; N, 8.77; O, 7.51; Si, 1.10. These analytical results indicate that the product obtained is the expected product.

[0171] The starting reactants were replaced with corresponding reactants respectively, and the synthesis of the compound involved in Example 16 was completed by referring to the preparation method of Example 15. The specific results are shown in Table 8.

[0172] Table 8

[0173]

[0174] Example 17:

[0175] Synthesis of compound (83):

[0176]

[0177] 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.

[0178] 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 = 2:1) to obtain Intermediate 18.

[0179] Intermediate 18 (4 mmol), 4-nitrophthalonitrile (4 mmol), and potassium carbonate (8 mmol) were dissolved in N'N-dimethylformamide (50 mL) and stirred at 80°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 to obtain the crude product of Intermediate 17. The crude product was then dried and purified by column chromatography on silica gel (eluent: petroleum ether: dichloromethane = 4:1) to obtain Intermediate 19.

[0180] Intermediate 19 (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 then dried and purified by column chromatography on silica gel (eluent: dichloromethane:methanol = 47:1) to obtain Intermediate 20.

[0181] Intermediate 18 (2 mmol), intermediate 20 (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 removed by evaporation 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 (83) as a green solid with a yield of 51%.

[0182] After high-resolution mass spectrometry, ESI source, and positive ion mode detection, the molecular formula of compound (83) is C 216 H 190 N 20 O 18Si, detected value 3382.4475, theoretical value 3382.4476; detected element content (%): C, 76.72; H, 5.65; N, 8.28; O, 8.51; Si, 0.83. Theoretical element content (%): C, 76.71; H, 5.66; N, 8.28; O, 8.51; Si, 0.83. These analytical results indicate that the product obtained is the expected product.

[0183] The starting reactants were replaced with the corresponding reactants, and the synthesis of the compound involved in Example 18 was completed by referring to the preparation method of Example 17. The specific results are shown in Table 9.

[0184] Table 9

[0185]

[0186] Example 19:

[0187] Synthesis of compound (89):

[0188]

[0189] Dissolve 4-bromonaphthalic anhydride (1 mmol) and 4-amino-1-butanol (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 21.

[0190] Intermediate 21 (1 mmol), 3,5-di-tert-butylaniline (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 = 5:2) to obtain Intermediate 22.

[0191] Intermediate 22 (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 then dried to obtain the crude product of intermediate 23. The crude product was then dried and purified by column chromatography on silica gel (eluent: petroleum ether: dichloromethane = 5:1) to obtain intermediate 23.

[0192] Intermediate 23 (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 = 45:1) to obtain intermediate 24.

[0193] Intermediate 22 (2 mmol), intermediate 24 (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 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 dried and purified by column chromatography on a silica gel column (eluent: dichloromethane:methanol = 40:1) to obtain compound (89) as a green solid in a 50% yield.

[0194] After high-resolution mass spectrometry, ESI source, and positive ion mode detection, the molecular formula of compound (89) is C 216 H 238 N 20 O 18 Si, detected value 3430.8233, theoretical value 3430.8232; detected element content (%): C, 75.64; H, 6.99; N, 8.16; O, 8.39; Si, 0.82. Theoretical element content (%): C, 75.63; H, 6.99; N, 8.17; O, 8.39; Si, 0.82. The above analytical results indicate that the obtained product is the expected product.

[0195] The starting reactants were replaced with corresponding reactants respectively, and the synthesis of the compound involved in Example 20 was completed by referring to the preparation method of Example 19. The specific results are shown in Table 10.

[0196] Table 10

[0197]

[0198] Example 21:

[0199] Synthesis of compound (95):

[0200]

[0201] 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.

[0202] Intermediate 1 (1 mmol), 2-(p-dimethylaminophenyl)ethylamine (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 = 6:1) to obtain Intermediate 25.

[0203] Intermediate 25 (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 then dried to obtain the crude product of intermediate 26. The crude product was dried and purified by column chromatography on silica gel (eluent: petroleum ether: dichloromethane = 4:1) to obtain intermediate 26.

[0204] Intermediate 26 (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 = 52:1) to obtain Intermediate 27.

[0205] Intermediate 25 (2 mmol), intermediate 27 (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 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 dried and purified by column chromatography on a silica gel column (eluent: dichloromethane:methanol = 40:1) to obtain compound (95) as a green solid in a yield of 48%.

[0206] After high-resolution mass spectrometry, ESI source, and positive ion mode detection, the molecular formula of compound (95) is C 204 H 172 N 26 O 18Si, detected value 3304.3251, theoretical value 3304.3252; detected element content (%): C, 74.15; H, 5.25; N, 11.03; O, 8.72; Si, 0.85. Theoretical element content (%): C, 74.16; H, 5.25; N, 11.02; O, 8.72; Si, 0.85. These analytical results indicate that the product obtained is the expected product.

[0207] The starting reactants were replaced with the corresponding reactants respectively, and the synthesis of the compound involved in Example 22 was completed by referring to the preparation method of Example 21. The specific results are shown in Table 11.

[0208] Table 11

[0209]

[0210] Example 23:

[0211] Synthesis of compound (101):

[0212]

[0213] Dissolve 4-bromonaphthalic anhydride (1 mmol) and 4-amino-1-butanol (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 21.

[0214] Intermediate 21 (1 mmol), 3-cyclopropylaniline (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 toluene (20 mL). 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 = 7:1) to obtain Intermediate 28.

[0215] Intermediate 28 (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 then dried to obtain the crude product of Intermediate 29. The crude product was dried and purified by column chromatography on silica gel (eluent: petroleum ether: dichloromethane = 3:1) to obtain Intermediate 29.

[0216] Intermediate 29 (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 then dried and purified by column chromatography on silica gel (eluent: dichloromethane:methanol = 46:1) to obtain intermediate 30.

[0217] Intermediate 28 (2 mmol), intermediate 30 (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 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 dried and purified by column chromatography on silica gel (eluent: dichloromethane:methanol = 45:1) to obtain compound (101) as a green solid in a yield of 51%.

[0218] After high-resolution mass spectrometry, ESI source, and positive ion mode detection, the molecular formula of compound (101) is C 186 H 166 N 20 O 18 Si, detected value 2998.2597, theoretical value 2998.2598; detected element content (%): C, 74.54; H, 5.57; N, 9.35; O, 9.61; Si, 0.94. Theoretical element content (%): C, 74.53; H, 5.58; N, 9.35; O, 9.61; Si, 0.94. These analytical results indicate that the product obtained is the expected product.

[0219] 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 12.

[0220] Table 12

[0221]

[0222] Example 25:

[0223] Synthesis of compound (107):

[0224]

[0225] 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.

[0226] Intermediate 1 (1 mmol), 4-n-butoxyaniline (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 31.

[0227] Intermediate 31 (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 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 to obtain the crude product of intermediate 32. The crude product was then dried and purified by column chromatography on silica gel (eluent: petroleum ether: dichloromethane = 2:1) to obtain intermediate 32.

[0228] Intermediate 32 (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 then dried and purified by column chromatography on silica gel (eluent: dichloromethane:methanol = 42:1) to obtain intermediate 33.

[0229] Intermediate 31 (2 mmol), intermediate 33 (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 = 44:1) to obtain compound (107) as a green solid in a yield of 52%.

[0230] After high-resolution mass spectrometry, ESI source, and positive ion mode detection, the molecular formula of compound (107) is C 200 H 154 Cl 12 N 20 O 24Si, detected value 3675.7527, theoretical value 3675.7528; detected element content (%): C, 65.37; H, 4.23; Cl, ​​11.58; N, 7.61; O, 10.45; Si, 0.76. Theoretical element content (%): C, 65.37; H, 4.22; Cl, ​​11.58; N, 7.62; O, 10.45; Si, 0.76. These analytical results indicate that the product obtained is the expected product.

[0231] The starting reactants were replaced with the corresponding reactants respectively, and the synthesis of the compound involved in Example 26 was completed by referring to the preparation method of Example 25. The specific results are shown in Table 13.

[0232] Table 13

[0233]

[0234] Example 27:

[0235] Synthesis of compound (113):

[0236]

[0237] Dissolve 4-bromonaphthalic anhydride (1 mmol) and 4-amino-1-butanol (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 21.

[0238] 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 = 3:1) to obtain Intermediate 34.

[0239] Intermediate 34 (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 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 to obtain the crude product of intermediate 32. The crude product was then dried and purified by column chromatography on silica gel (eluent: petroleum ether: dichloromethane = 3:2) to obtain intermediate 35.

[0240] Intermediate 35 (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 then dried and purified by column chromatography on silica gel (eluent: dichloromethane:methanol = 40:1) to obtain Intermediate 36.

[0241] Intermediate 34 (2 mmol), intermediate 36 (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 = 42:1) to obtain compound (113) as a green solid in a yield of 51%.

[0242] After high-resolution mass spectrometry, ESI source, and positive ion mode detection, the molecular formula of compound (113) is C 182 H 166 Cl 12 N 20 O 30 Si, detected value 3566.8127, theoretical value 3566.8128; detected element content (%): C, 61.28; H, 4.69; Cl, ​​11.94; N, 7.86; O, 13.45; Si, 0.79. Theoretical element content (%): C, 61.29; H, 4.69; Cl, ​​11.93; N, 7.85; O, 13.46; Si, 0.79. These analytical results indicate that the product obtained is the expected product.

[0243] The starting reactants can be replaced with corresponding reactants, so they are not listed here in detail. The synthesis of the compound involved in Example 28 can be completed by referring to the preparation method of Example 27. The specific results are shown in Table 14.

[0244] Table 14

[0245]

[0246]

[0247] Example 1-1

[0248] Preparation of green photosensitive resin composition D1

[0249] A green 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.

[0250] formula:

[0251] 4 parts by weight of a colorant, 20 parts by weight of a resin containing a double bond structure, 5 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 70 parts by weight of an ether-containing solvent are mixed and dissolved thoroughly, and the solid content is controlled at about 29% to obtain a green photosensitive resin composition. Figure 3 shown.

[0252] in,

[0253] Colorant: Silicon phthalocyanine (Formula (1))

[0254] Resins containing double bond structures or / and epoxy structures: acrylic polyester resin (analytical grade), purchased from Titan Corporation;

[0255] Monomers containing double bond structures or / and epoxy structures: dipentaerythritol pentaacrylate monomer (analytical grade), purchased from Titan Corporation;

[0256] Photoinitiator with high absorption characteristics at 365 nm: α,α-diethoxyacetophenone (analytical grade), purchased from Titan Company;

[0257] Additives for improving film-forming property and / or stability: defoaming agent (analytical grade), purchased from Titan Company;

[0258] Solvents containing ether groups: propylene glycol methyl ether acetate (analytical grade), purchased from Titan Corporation;

[0259] Comparative Example 2-1

[0260] Preparation of green photosensitive resin composition E1

[0261] 4 parts by weight of a colorant, 20 parts by weight of a resin containing a double bond structure, 5 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 70 parts by weight of an ether-containing solvent are thoroughly mixed and dissolved, and the solid content is controlled at about 29% to obtain a green photosensitive resin composition.

[0262] in,

[0263] Colorant: zinc phthalocyanine dye L, and other components are the same as those in Example 1-1.

[0264] The chemical structure of zinc phthalocyanine dye L is as follows:

[0265]

[0266] Zinc Phthalocyanine Dye L

[0267] The performance test of the photosensitive resin compositions D1 and E1 was performed using the following steps:

[0268] 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 5s, and then post-baked at 230℃ for 30min. Then the subsequent related performance is tested. The results are shown in Table 15.

[0269] Performance testing and evaluation methods:

[0270] (1) Chromaticity: Detected using a Konica Minolta CM-5 spectrophotometer.

[0271] (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 a magnification of x500.

[0272] The evaluation criteria are as follows:

[0273] ○: Viscosity change < ±5% mPa·s and no particles on the x500 surface;

[0274] △: Viscosity change < ±10% mPa·s and no particles on the x500 surface;

[0275] ×: Viscosity change > ±10% mPa·s or particles on the surface of x500;

[0276] (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;

[0277] (4) Evaluation of solvent resistance:

[0278] 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.

[0279] (5) Evaluation of anti-migration performance:

[0280] According to the manufacturing process of color filter, green 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.

[0281] (6) Line width, edge regularity, and development process margin:

[0282] The line width and edge uniformity were tested by x500 OM, and the mask line width was 140μm.

[0283] 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.

[0284] The evaluation criteria for edge neatness are as follows:

[0285] ○: The edges are neat and there is no residue at the edges after 50s of development;

[0286] △: After 50 seconds of development, the image edge has burrs, is not neat, or has residues at the edge;

[0287] ×: Image missing

[0288] The specific standards for evaluating the development process margin are as follows:

[0289] ○: The edges are neat and there is no residue or peeling at the edges after 40-100s of development;

[0290] △: The edges are neat and there is no residue or peeling at the edges after 50-80s of development;

[0291] ×: The edges are not neat, or there are residues or peeling at the edges after 50–80s of development.

[0292] 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%.

[0293] The preparation of photosensitive resin compositions D2-D28 in Examples 1-2 to 1-28 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 15.

[0294] Table 15

[0295]

[0296]

[0297] 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).

[0298] Figure 5 2-1 is the CIE chromaticity diagram of Example 1-1 and Comparative Example 2-1. It can be seen from the figure that the green photosensitive resin composition prepared by the present invention has a more excellent coloring degree and a higher green color purity.

[0299] Comparison of experimental results shows that the silicon phthalocyanine dyes in Examples 1-1 to 1-28 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 1-28 are synthesized by coupling functional groups with blue light absorption properties to the benzene ring sites around the silicon phthalocyanine mother core and / or the silicon center axial site to compensate for the silicon phthalocyanine dye's weak absorption in the blue light region (400–500nm). The color filters prepared with these 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, the photosensitive resin compositions D1 to D28 using the silicon phthalocyanine dye of the present invention have similar good process performance, such as system compatibility, edge line neatness, and development process margin.

[0300] In summary, the present invention effectively improves the solubility of silicon phthalocyanine dyes by replacing the benzene ring sites and / or the silicon center axial sites around the silicon phthalocyanine mother core 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 silicon phthalocyanine dyes, and prepares green dyes with high color purity and stable photochemical and photophysical properties; 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 green photosensitive resin compositions, and can be used as dyes in color filters of display and sensing devices such as liquid crystal displays and image sensors.

[0301] 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 are independently selected from any one of hydrogen atom, chlorine atom, alkyl, aryl or heteroaryl substituents, and R1 to R 18 The present invention comprises at least one naphthalimide 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 fused heterocyclic group, a monocyclic aromatic heterocyclic group and a polycyclic aromatic heterocyclic group, wherein 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 aromatic group and an aromatic amino 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.

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

5. The silicon 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. The silicon 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 silicon 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 silicon phthalocyanine according to any one of claims 1 to 7; and the solid content of the green photosensitive resin composition is 15-38%.

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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