Phthalocyanine compounds, their preparation and use

Abstract

The present application relates to the technical field of compounds, in particular to phthalocyanine compounds and preparation and application thereof. The present application proposes two strategies for applying phthalocyanine dyes to optical filters: first, in view of the poor solubility of phthalocyanine, the solubility groups are modified on the phthalocyanine mother nucleus, which effectively improves the solubility of the phthalocyanine dye; second, in view of the problem that the phthalocyanine dye is prone to aggregation, a series of cationic phthalocyanines are prepared, the repulsion between cations is used to inhibit the aggregation of the dye in the solid state, thereby further improving the photo-thermal stability of the phthalocyanine dye.

Description

Technical Field

[0001] This invention relates to the field of compound technology, and in particular to phthalocyanine compounds and their preparation and application. Background Technology

[0002] With the rapid popularization of flat panel display products such as Liquid Crystal Display (LCD) and Organic Light Emitting Diode (OLED), people's requirements for display color display are constantly increasing. Color filters are key raw materials for color display in LCD panels, OLEDs, and other flat panel display products. There are many methods for preparing color filters, such as dyeing, pigment dispersion, and printing. Among them, the pigment dispersion method for preparing color filters involves coating a coloring photosensitive resin composition onto a colored glass substrate with a pre-prepared black matrix. After photolithography processes such as exposure and development, the color pattern of the color filter is formed. Then, heating and other treatments are performed, and the above process is repeated to form the pattern of all colors of the color filter. Finally, an indium tin oxide conductive layer is formed, resulting in a color filter with multiple color patterns.

[0003] Currently, pigment dispersion methods using photolithography to form red-green-blue (RGB) patterned pixels are widely used to manufacture color filters because they can produce filters with excellent stability. While filters produced by this method have good thermal and photochemical stability, their particulate nature leads to light scattering, reducing brightness, contrast, and resolution. Furthermore, the aggregation behavior of molecules within the pigment and its impact on the pigment's optical properties are difficult to predict, making precise control of color purity challenging and hindering the achievement of high color purity and a wide color gamut. Dyes can be an attractive alternative to overcome this limitation because they dissolve in the medium and exist in molecular form, thus reducing light scattering. Moreover, dye molecules have well-defined structures, and their molecular structure has a clear structure-activity relationship with photophysical properties, giving them an advantage in achieving superior optical performance. Although dyes can generally produce color filters with high transmittance and high contrast, their poor heat and light resistance can easily lead to colorimetric changes during the high-temperature heating process in color filter manufacturing. In addition, they should be highly soluble in industrial solvents and have sharp absorption peaks to obtain excellent optical performance. Specifically:

[0004] (1) Traditional dyes exhibit low solubility in alkaline aqueous solutions or organic solvents, making it difficult to obtain colorable curable compositions with the desired spectrum.

[0005] (2) Dyes in a molecularly dispersed state are more likely to aggregate, thus causing changes in optical properties.

[0006] (3) Dyes in a molecularly dispersed state have poor light and heat resistance, and their optical properties are prone to change during the high-temperature baking process of subsequent device fabrication and long-term light exposure after service.

[0007] To address the aforementioned problems, it is known to use phthalocyanine dyes as colorants (see, for example, Patent Document 1). When phthalocyanine dyes are used as colorants, the hue or brightness of the displayed image can be improved by utilizing the inherent color purity or vividness of the phthalocyanine dye itself. Furthermore, modifying the phthalocyanine core with groups such as alkyl chains can effectively improve the solubility of the phthalocyanine dye in organic solvents.

[0008] Existing dyes include zinc phthalocyanine dyes and copper phthalocyanine dyes, which possess a wide variety of pigment precursors (CN202080008015.6, CN202180044374.1, CN202180038558.7, CN202211637638.7, CN202310360311.8). When using dyes in liquid crystal displays and image sensors to obtain colored images, it is generally required that the layer formed by the colored photosensitive composition be thin and have high coloring intensity. In addition to requirements for optical performance, considering the high-temperature process required to fabricate the dye into the device and the long-term light exposure during subsequent service, the dye is required to have good thermal and photostability.

[0009] Phthalocyanine cores possess good optical properties and photothermal stability, making them suitable for use in optical filters. However, phthalocyanine dyes present two main problems: First, phthalocyanines have poor solubility, especially in solvents commonly used in industrial production, such as propylene glycol monomethyl ether acetate (PGMEA). This poor solubility results in thinner colored layers that lack high coloring strength, failing to meet industrial standards. Second, the large planar structure of phthalocyanines makes them prone to aggregation, altering the dye's optical properties and directly affecting its photothermal stability. Summary of the Invention

[0010] To address the aforementioned problems, the present invention aims to provide a phthalocyanine compound and its preparation and application. The present invention proposes the following two strategies for applying phthalocyanine dyes to optical filters: First, to address the poor solubility of phthalocyanines, solubility groups are modified on the phthalocyanine core, effectively improving the solubility of the phthalocyanine dye; second, to address the problem of phthalocyanine dye aggregation, the present invention prepares a series of cationic phthalocyanines, utilizing the repulsive effect between cations to inhibit dye aggregation in the solid state, thereby further improving the photothermal stability of the phthalocyanine dye.

[0011] The objective of this invention can be achieved through the following technical solutions:

[0012] The first object of this invention is to provide a phthalocyanine compound, the chemical structural formula of which is shown below:

[0013]

[0014] Wherein, M is a metal atom; R1 to R4 are independently selected from one of the following groups: substituted or unsubstituted fused heterocyclic groups, monocyclic aromatic heterocyclic groups, or polycyclic aromatic heterocyclic groups.

[0015] In one embodiment of the present invention, M is selected from Cu, Zn, Fe, Mn or Ni.

[0016] In one embodiment of the present invention, R1 to R4 are independently selected from one of formulas (A-1) to (A-6):

[0017]

[0018]

[0019] In this context, the dashed lines represent the bonds connecting R1 to R4 to the parent nucleus in formula (I); L1 to L9 are independently selected from hydrogen atoms or alkanes; X is selected from N, O, or S; and Y is selected from halogen atoms.

[0020] In one embodiment of the invention, L1 to L9 are independently selected from one of the groups represented by the following formulas (B-1) to (B-5):

[0021]

[0022] In this context, the dashed lines represent the connecting bonds between groups L1 to L9 and groups R1 to R4, and n is an integer from 0 to 36.

[0023] In one embodiment of the present invention, the phthalocyanine compound is selected from one of the following formulas (1-1) to (1-125), where n is an integer from 0 to 36:

[0024]

[0025]

[0026]

[0027]

[0028]

[0029]

[0030] A second object of the present invention is to provide a method for preparing the above-mentioned phthalocyanine compound, comprising the following steps:

[0031] (S1) The first compound and the second compound are mixed and reacted, and then post-processed to obtain the first intermediate product;

[0032] (S2) The first intermediate obtained in step (S1) is mixed with the third compound and reacted, and then post-processed to obtain the second intermediate.

[0033] (S3) The second intermediate obtained in step (S2) is mixed with the fourth compound and reacted, and then post-processed to obtain the phthalocyanine compound.

[0034] In one embodiment of the present invention, in step (S1), the first compound is selected from one of 4-nitrophthalonitrile, 3-nitrophthalonitrile, 4′-bromo[1,1′-biphenyl]-3,4-dicarboxylonitrile, 1-hydroxy[1,1′-biphenyl]-3,4-dicarboxylonitrile, 4-isoquinolinyl-1,2-phthalonitrile, 4′-nitro[1,1′-biphenyl]-3,4-dicarboxylonitrile, and 4′-amino[1,1′-biphenyl]-3,4-dicarboxylonitrile;

[0035] The second compound is selected from one of 4-hydroxypyridine, 3-hydroxypyridine, imidazole, 2-methylimidazolium, 4-pyridinethiol, 3-pyridinethiol, 1-hydroxy-1,2,3-triazole, and 1-mercapto-1,2,3-triazole;

[0036] The molar ratio of the first compound to the second compound is 1:1 to 1.2;

[0037] During the reaction, the temperature is 20℃~80℃ and the time is 3h~24h;

[0038] In step (S2), the third compound is selected from one of zinc acetate, copper chloride, manganese acetate, and iron acetate;

[0039] The molar ratio of the first intermediate to the third compound is 2–3:1;

[0040] During the reaction, the temperature is 20℃~135℃ and the time is 18h~24h;

[0041] In step (S3), the fourth compound is selected from one of the following: iododecane, bromodecane, chlorodecane, isopropyl iodine, isopropyl bromide, isopropyl chloride, propyl 3-iodopropionate, propyl 3-bromopropionate, propyl 3-chloropropionate, 4-(dimethylamino)-2-methylbutyroyl bromide, 4-(dimethylamino)-2-methylbutyroyl chloride, 4-(dimethylamino)-2-methylbutyroyl iodine, 5-iodo-N,N,N-trimethyl-1-pentamine, 5-bromo-N,N,N-trimethyl-1-pentamine, and 5-N,N,N-trimethyl-1-pentamine.

[0042] The molar ratio of the second intermediate to the fourth compound is 1:10 to 20;

[0043] During the reaction, the temperature was 20℃~120℃ and the time was 48h~72h.

[0044] A third objective of this invention is to provide an application of phthalocyanine compounds in the preparation of dyes.

[0045] A fourth object of the present invention is to provide a dye containing the above-mentioned phthalocyanine compound.

[0046] A fifth object of the present invention is to provide an application of the above-mentioned dye in the preparation of optical filters.

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

[0048] This invention provides a class of high-performance ionic phthalocyanine dyes suitable for color filters. These dyes improve their solubility in organic solvents by modifying their solubility groups. By transforming the neutral phthalocyanine structure into positively charged cationic phthalocyanines, the repulsive effect between cations inhibits dye aggregation in the solid state, thereby further improving the photothermal stability of the phthalocyanine dyes. These phthalocyanine dyes exhibit good solubility and high photothermal stability, and their application in color filters can effectively improve the image performance and lifespan of the devices. Attached Figure Description

[0049] Figure 1 The NMR spectrum of the phthalocyanine composition (1-84, n=10) is shown.

[0050] Figure 2 The image shows the UV absorption spectrum of the phthalocyanine composition (1-84, n=10). Detailed Implementation

[0051] This invention provides a phthalocyanine compound, the chemical structural formula of which is shown below:

[0052]

[0053] Wherein, M is a metal atom; R1 to R4 are independently selected from one of the following groups: substituted or unsubstituted fused heterocyclic groups, monocyclic aromatic heterocyclic groups, or polycyclic aromatic heterocyclic groups.

[0054] In one embodiment of the present invention, M is selected from Cu, Zn, Fe, Mn or Ni.

[0055] In one embodiment of the present invention, R1 to R4 are independently selected from one of formulas (A-1) to (A-6):

[0056]

[0057]

[0058] In this context, the dashed lines represent the bonds connecting R1 to R4 to the parent nucleus in formula (I); L1 to L9 are independently selected from hydrogen atoms or alkanes; X is selected from N, O, or S; and Y is selected from halogen atoms.

[0059] In one embodiment of the invention, L1 to L9 are independently selected from one of the groups represented by the following formulas (B-1) to (B-5):

[0060]

[0061] In this context, the dashed lines represent the connecting bonds between groups L1 to L9 and groups R1 to R4, and n is an integer from 0 to 36.

[0062] In one embodiment of the present invention, the phthalocyanine compound is selected from one of the following formulas (1-1) to (1-125), where n is an integer from 0 to 36:

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069] This invention provides a method for preparing the above-mentioned phthalocyanine compound, comprising the following steps:

[0070] (S1) The first compound and the second compound are mixed and reacted, and then post-processed to obtain the first intermediate product;

[0071] (S2) The first intermediate obtained in step (S1) is mixed with the third compound and reacted, and then post-processed to obtain the second intermediate.

[0072] (S3) The second intermediate obtained in step (S2) is mixed with the fourth compound and reacted, and then post-processed to obtain the phthalocyanine compound.

[0073] In one embodiment of the present invention, in step (S1), the first compound is selected from one of 4-nitrophthalonitrile, 3-nitrophthalonitrile, 4′-bromo[1,1′-biphenyl]-3,4-dicarboxylonitrile, 1-hydroxy[1,1′-biphenyl]-3,4-dicarboxylonitrile, 4-isoquinolinyl-1,2-phthalonitrile, 4′-nitro[1,1′-biphenyl]-3,4-dicarboxylonitrile, and 4′-amino[1,1′-biphenyl]-3,4-dicarboxylonitrile;

[0074] The second compound is selected from one of 4-hydroxypyridine, 3-hydroxypyridine, imidazole, 2-methylimidazolium, 4-pyridinethiol, 3-pyridinethiol, 1-hydroxy-1,2,3-triazole, and 1-mercapto-1,2,3-triazole;

[0075] The molar ratio of the first compound to the second compound is 1:1 to 1.2;

[0076] During the reaction, the temperature is 20℃~80℃ and the time is 3h~24h;

[0077] In step (S2), the third compound is selected from one of zinc acetate, copper chloride, manganese acetate, and iron acetate;

[0078] The molar ratio of the first intermediate to the third compound is 2–3:1;

[0079] During the reaction, the temperature is 20℃~135℃ and the time is 18h~24h;

[0080] In step (S3), the fourth compound is selected from one of the following: iododecane, bromodecane, chlorodecane, isopropyl iodine, isopropyl bromide, isopropyl chloride, propyl 3-iodopropionate, propyl 3-bromopropionate, propyl 3-chloropropionate, 4-(dimethylamino)-2-methylbutyroyl bromide, 4-(dimethylamino)-2-methylbutyroyl chloride, 4-(dimethylamino)-2-methylbutyroyl iodine, 5-iodo-N,N,N-trimethyl-1-pentamine, 5-bromo-N,N,N-trimethyl-1-pentamine, and 5-N,N,N-trimethyl-1-pentamine.

[0081] The molar ratio of the second intermediate to the fourth compound is 1:10 to 20;

[0082] During the reaction, the temperature was 20℃~120℃ and the time was 48h~72h.

[0083] This invention provides an application of phthalocyanine compounds in the preparation of dyes.

[0084] The present invention provides a dye containing the above-mentioned phthalocyanine compound.

[0085] This invention provides an application of the above-mentioned dye in the preparation of optical filters.

[0086] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments.

[0087] Unless otherwise specified, all reagents used in the following embodiments are commercially available reagents, and all detection methods and techniques used are conventional detection methods and techniques in the art.

[0088] Example 1-1

[0089] This embodiment provides the synthesis of phthalocyanine compositions (1-18, n=10).

[0090]

[0091] Under an argon atmosphere, 4-nitrophthalonitrile (500 mg) and 4-hydroxypyridine (302 mg) were dissolved in N,N-dimethylformamide (15 mL) and stirred at room temperature for 10 min. Then, potassium carbonate (2 g) was added, and the reaction was carried out at 80 °C for 3 h. The mixture was treated with water (50 mL) and extracted with dichloromethane / methanol (5%) (two 50 mL aliquots). Rapid purification by silica gel chromatography with dichloromethane / methanol (10%) yielded compound (C-1-1) as a white solid in 66% yield.

[0092]

[0093] Under an argon atmosphere, compound (C-1-1) (400 mg) and zinc(II) acetate dihydrate (110 mg) were dissolved in n-pentanol (15 mL) and stirred at room temperature for 10 min. Then, 1,8-diazabicyclo[5.4.0]undec-7-ene (300 μL) was added, and the mixture was refluxed for 18 h. The reaction mixture was cooled to room temperature and precipitated with cyclohexane (50 mL). The solid was filtered and washed with water and hexane. The solid was recrystallized from methanol / water to give compound (C-1-2), a green powder, in a yield of 68%.

[0094]

[0095] A mixture of compound (C-1-2) (240 mg), iododecane (20 mL), and acetone (10 mL) was stirred under reflux for 48 h. The solvent was removed under vacuum. The solid was resuspended in cyclohexane and filtered. The solid was washed with hexane, diethyl ether, and acetone to give the phthalocyanine composition, a green powder, in 95% yield.

[0096] Example 2-1

[0097] This embodiment provides the synthesis of phthalocyanine compositions (1-84, n=10).

[0098]

[0099] Under a nitrogen atmosphere, 8.65 g of 3-nitrophthalonitrile and 4.10 g of imidazole were dissolved in 100 mL of N,N-dimethylformamide. The mixture was stirred at room temperature for 24 h, during which time potassium carbonate (21 g in total, added every 2 h) was added in five portions. After the reaction was complete, the mixture was added to 500 mL of ice water, filtered, dried, and recrystallized to give compound (C-2-1) as a grayish-white solid in approximately 40% yield.

[0100]

[0101] Under an argon atmosphere, compound (C-1-1) (1.0 g) and zinc acetate (0.30 g) were dissolved in dry n-pentanol (70 mL), and 1,8-diazabicyclo[5.4.0]undec-7-ene (2 mL) was added as a catalyst. The mixture was stirred at 135 °C for 24 h. After cooling, n-hexane was added, and the green precipitate was collected by filtration and washed with n-pentanol and n-hexane. The dried crude product was dissolved in tetrahydrofuran and purified by column chromatography (silica gel) using tetrahydrofuran as the mobile phase to give compound (C-2-2), a green powder, in 80% yield.

[0102]

[0103] Compound (C-2-2) (100 mg) and iododecane (20 mL) were dissolved in N,N-dimethylformamide (5 mL) under nitrogen atmosphere and reacted at 120 °C for 72 h. Then, after cooling to room temperature, ethanol (40 mL) was added to precipitate the product, which was then filtered off to obtain the phthalocyanine composition (its NMR spectrum is shown below). Figure 1 As shown, the ultraviolet absorption diagram is as follows: Figure 2 (As shown), green powder, yield 92%.

[0104] Examples 3-1 to 30-1

[0105] Examples 3-1 to 30-1 sequentially synthesized phthalocyanine compounds with chemical structures as described in formulas 1-18, 1-84, 1-2, 1-5, 1-9, 1-13, 1-14, 1-16, 1-22, 1-23, 1-35, 1-42, 1-49, 1-51, 1-54, 1-59, 1-61, 1-64, 1-67, 1-68, 1-71, 1-75, 1-77, 1-81, 1-83, 1-88, 1-93, 1-94, 1-96, and 1-97; wherein n is 10 in each case.

[0106] Examples 3-1 to 30-1 were synthesized according to the methods of Examples 1-1 and 2-1, with the only difference being the different reaction raw materials.

[0107] Example 1: Preparation of Green Photosensitive Resin Composition E1

[0108] Using the phthalocyanine dye prepared in Example 1 above, a colored photosensitive resin composition E1 was formulated and subjected to photolithography development to compare the relevant properties of the photosensitive resin composition. Specifically, a lithography method well known to those skilled in the art was applied.

[0109] Green photosensitive resin composition E1 comprises the following components in parts by weight:

[0110] 200 parts of colorant L1 (composed of 100 parts of dye formula (1-18, n=10) and 100 parts of solvent Q1);

[0111] 50 multifunctional monomers M1;

[0112] 50 portions of the multifunctional monomer M2;

[0113] 100 parts of alkali-soluble resin N;

[0114] 0.2 parts additive 01;

[0115] 0.3 parts additive 02;

[0116] 5 parts of photoinitiator P;

[0117] 50 parts of solvent Q2.

[0118] The above substances are fully dissolved and mixed, and the solid content is controlled at about 20% to obtain the green photosensitive resin composition E1.

[0119] Among them, the multifunctional monomer M1: dipentaerythritol hexaacrylate (analytical grade, purchased from Sartoma);

[0120] Multifunctional monomer M2: propionyl trimethylolpropane trimethacrylate (analytical grade, purchased from Taiwan Double Bond Chemical Co., Ltd.);

[0121] Alkali-soluble resin N: Trade name Sarbox SB400 (analytical grade, purchased from Sardoma);

[0122] Additive 01: Trade name F-556 (purchased from DIC Corporation);

[0123] Additive 02: KH570 (γ-methacryloyloxypropyltrimethoxysilane, purchased from Bailingwei);

[0124] Photoinitiator P: Trade name IRGACURE OXE 01 (purchased from BASF);

[0125] Solvent Q1: PGMEA (propylene glycol methyl ether acetate, purchased from Dow Chemical);

[0126] Solvent Q2: PM (propylene glycol methyl ether, purchased from Dow Chemical).

[0127] Example 2: Preparation of Green Photosensitive Resin Composition E2

[0128] Using the phthalocyanine dye prepared in Example 2 above, a colored photosensitive resin composition E2 was formulated and subjected to photolithography development to compare the relevant properties of the photosensitive resin composition. Specifically, a lithography method well known to those skilled in the art was applied.

[0129] Green photosensitive resin composition E2 comprises the following components in parts by weight:

[0130] 200 parts of colorant L2 (composed of 100 parts of dye formula (1-84, n=10) and 100 parts of solvent Q1);

[0131] 50 multifunctional monomers M1;

[0132] 50 portions of the multifunctional monomer M2;

[0133] 100 parts of alkali-soluble resin N;

[0134] 0.2 parts additive 01;

[0135] 0.3 parts additive 02;

[0136] 5 parts of photoinitiator P;

[0137] 50 parts of solvent Q2.

[0138] The above substances are fully dissolved and mixed, and the solid content is controlled at about 20% to obtain the green photosensitive resin composition E2.

[0139] Example 3: Preparation of Green Photosensitive Resin Composition E3

[0140] Green photosensitive resin composition E3 comprises the following components in parts by weight:

[0141] 200 parts of colorant L3 (composed of 100 parts of dye formula (1-2) and 100 parts of solvent Q1);

[0142] 50 multifunctional monomers M1;

[0143] 50 portions of the multifunctional monomer M2;

[0144] 100 parts of alkali-soluble resin N;

[0145] 0.2 parts additive 01;

[0146] 0.3 parts additive 02;

[0147] 5 parts of photoinitiator P;

[0148] 50 parts of solvent Q2.

[0149] The above substances were mixed evenly, and the solid content was controlled at about 20% to obtain the green photosensitive resin composition E3.

[0150] Example 4: Preparation of Green Photosensitive Resin Composition E4

[0151] Green photosensitive resin composition E4 comprises the following components in parts by weight:

[0152] 200 parts of colorant L4 (composed of 100 parts of dye formula (1-5) and 100 parts of solvent Q1);

[0153] 50 multifunctional monomers M1;

[0154] 50 portions of the multifunctional monomer M2;

[0155] 100 parts of alkali-soluble resin N;

[0156] 0.2 parts additive 01;

[0157] 0.3 parts additive 02;

[0158] 5 parts of photoinitiator P;

[0159] 50 parts of solvent Q2.

[0160] The above substances were mixed evenly, and the solid content was controlled at about 20% to obtain the green photosensitive resin composition E4.

[0161] Example 5: Preparation of Green Photosensitive Resin Composition E5

[0162] The green photosensitive resin composition E5 comprises the following components in parts by weight: 200 parts of colorant L5 (composed of 100 parts of dye formula (1-9) and 100 parts of solvent Q1);

[0163] 50 multifunctional monomers M1;

[0164] 50 portions of the multifunctional monomer M2;

[0165] 100 parts of alkali-soluble resin N;

[0166] 0.2 parts additive 01;

[0167] 0.3 parts additive 02;

[0168] 5 parts of photoinitiator P;

[0169] 50 parts of solvent Q2.

[0170] The above substances were mixed evenly, and the solid content was controlled at about 20% to obtain the green photosensitive resin composition E5.

[0171] Example 6: Preparation of Green Photosensitive Resin Composition E6

[0172] The green photosensitive resin composition E6 comprises the following components in parts by weight: 200 parts of colorant L6 (composed of 100 parts of dye formula (1-13) and 100 parts of solvent Q1);

[0173] 50 multifunctional monomers M1;

[0174] 50 portions of the multifunctional monomer M2;

[0175] 100 parts of alkali-soluble resin N;

[0176] 0.2 parts additive 01;

[0177] 0.3 parts additive 02;

[0178] 5 parts of photoinitiator P;

[0179] 50 parts of solvent Q2.

[0180] The above substances were mixed evenly, and the solid content was controlled at about 20% to obtain the green photosensitive resin composition E6.

[0181] Example 7: Preparation of Green Photosensitive Resin Composition E7

[0182] The green photosensitive resin composition E7 comprises the following components in parts by weight: 200 parts of colorant L7 (composed of 100 parts of dye formula (1-14) and 100 parts of solvent Q1);

[0183] 50 multifunctional monomers M1;

[0184] 50 portions of the multifunctional monomer M2;

[0185] 100 parts of alkali-soluble resin N;

[0186] 0.2 parts additive 01;

[0187] 0.3 parts additive 02;

[0188] 5 parts of photoinitiator P;

[0189] 50 parts of solvent Q2.

[0190] The above substances were mixed evenly, and the solid content was controlled at about 20% to obtain the green photosensitive resin composition E7.

[0191] Example 8: Preparation of Green Photosensitive Resin Composition E8

[0192] The green photosensitive resin composition E8 comprises the following components in parts by weight: 200 parts of colorant L8 (composed of 100 parts of dye formula (1-16, n=10) and 100 parts of solvent Q1); 50 parts of multifunctional monomer M1;

[0193] 50 portions of the multifunctional monomer M2;

[0194] 100 parts of alkali-soluble resin N;

[0195] 0.2 parts additive 01;

[0196] 0.3 parts additive 02;

[0197] 5 parts of photoinitiator P;

[0198] 50 parts of solvent Q2.

[0199] The above substances were mixed evenly, and the solid content was controlled at about 20% to obtain the green photosensitive resin composition E8.

[0200] Example 9: Preparation of Green Photosensitive Resin Composition E9

[0201] The green photosensitive resin composition E9 comprises the following components in parts by weight: 200 parts of colorant L9 (composed of 100 parts of dye formula (1-22, n=10) and 100 parts of solvent Q1); 50 parts of multifunctional monomer M1;

[0202] 50 portions of the multifunctional monomer M2;

[0203] 100 parts of alkali-soluble resin N;

[0204] 0.2 parts additive 01;

[0205] 0.3 parts additive 02;

[0206] 5 parts of photoinitiator P;

[0207] 50 parts of solvent Q2.

[0208] The above substances were mixed evenly, and the solid content was controlled at about 20% to obtain the green photosensitive resin composition E9.

[0209] Example 10: Preparation of Green Photosensitive Resin Composition E10

[0210] The green photosensitive resin composition E10 comprises the following components in parts by weight: 200 parts of colorant L10 (composed of 100 parts of dye formula (1-23, n=10) and 100 parts of solvent Q1); 50 parts of multifunctional monomer M1;

[0211] 50 portions of the multifunctional monomer M2;

[0212] 100 parts of alkali-soluble resin N;

[0213] 0.2 parts additive 01;

[0214] 0.3 parts additive 02;

[0215] 5 parts of photoinitiator P;

[0216] 50 parts of solvent Q2.

[0217] The above substances were mixed evenly, and the solid content was controlled at about 20% to obtain the green photosensitive resin composition E10.

[0218] Example 11 Preparation of Green Photosensitive Resin Composition E11

[0219] The green photosensitive resin composition E11 comprises the following components in parts by weight: 200 parts of colorant L11 (composed of 100 parts of dye formula (1-35) and 100 parts of solvent Q1);

[0220] 50 multifunctional monomers M1;

[0221] 50 portions of the multifunctional monomer M2;

[0222] 100 parts of alkali-soluble resin N;

[0223] 0.2 parts additive 01;

[0224] 0.3 parts additive 02;

[0225] 5 parts of photoinitiator P;

[0226] 50 parts of solvent Q2.

[0227] The above substances were mixed evenly, and the solid content was controlled at about 20% to obtain the green photosensitive resin composition E11.

[0228] Example 12 Preparation of Green Photosensitive Resin Composition E12

[0229] The green photosensitive resin composition E12 comprises the following components in parts by weight: 200 parts of colorant L12 (composed of 100 parts of dye formula (1-42) and 100 parts of solvent Q1);

[0230] 50 multifunctional monomers M1;

[0231] 50 portions of the multifunctional monomer M2;

[0232] 100 parts of alkali-soluble resin N;

[0233] 0.2 parts additive 01;

[0234] 0.3 parts additive 02;

[0235] 5 parts of photoinitiator P;

[0236] 50 parts of solvent Q2.

[0237] The above substances were mixed evenly, and the solid content was controlled at about 20% to obtain the green photosensitive resin composition E12.

[0238] Example 13 Preparation of Green Photosensitive Resin Composition E13

[0239] The green photosensitive resin composition E13 comprises the following components in parts by weight: 200 parts of colorant L13 (composed of 100 parts of dye formula (1-49) and 100 parts of solvent Q1);

[0240] 50 multifunctional monomers M1;

[0241] 50 portions of the multifunctional monomer M2;

[0242] 100 parts of alkali-soluble resin N;

[0243] 0.2 parts additive 01;

[0244] 0.3 parts additive 02;

[0245] 5 parts of photoinitiator P;

[0246] 50 parts of solvent Q2.

[0247] The above substances were mixed evenly, and the solid content was controlled at about 20% to obtain the green photosensitive resin composition E13.

[0248] Example 14 Preparation of Green Photosensitive Resin Composition E14

[0249] The green photosensitive resin composition E14 comprises the following components in parts by weight: 200 parts of colorant L14 (composed of 100 parts of dye formula (1-51) and 100 parts of solvent Q1);

[0250] 50 multifunctional monomers M1;

[0251] 50 portions of the multifunctional monomer M2;

[0252] 100 parts of alkali-soluble resin N;

[0253] 0.2 parts additive 01;

[0254] 0.3 parts additive 02;

[0255] 5 parts of photoinitiator P;

[0256] 50 parts of solvent Q2.

[0257] The above substances were mixed evenly, and the solid content was controlled at about 20% to obtain the green photosensitive resin composition E14.

[0258] Example 15 Preparation of Green Photosensitive Resin Composition E15

[0259] Green photosensitive resin composition E15 comprises the following components in parts by weight: 200 parts of colorant L15 (composed of 100 parts of dye formula (1-54) and 100 parts of solvent Q1);

[0260] 50 multifunctional monomers M1;

[0261] 50 portions of the multifunctional monomer M2;

[0262] 100 parts of alkali-soluble resin N;

[0263] 0.2 parts additive 01;

[0264] 0.3 parts additive 02;

[0265] 5 parts of photoinitiator P;

[0266] 50 parts of solvent Q2.

[0267] The above substances were mixed evenly, and the solid content was controlled at about 20% to obtain the green photosensitive resin composition E15.

[0268] Example 16 Preparation of Green Photosensitive Resin Composition E16

[0269] The green photosensitive resin composition E16 comprises the following components in parts by weight: 200 parts of colorant L16 (composed of 100 parts of dye formula (1-59) and 100 parts of solvent Q1);

[0270] 50 multifunctional monomers M1;

[0271] 50 portions of the multifunctional monomer M2;

[0272] 100 parts of alkali-soluble resin N;

[0273] 0.2 parts additive 01;

[0274] 0.3 parts additive 02;

[0275] 5 parts of photoinitiator P;

[0276] 50 parts of solvent Q2.

[0277] The above substances were mixed evenly, and the solid content was controlled at about 20% to obtain the green photosensitive resin composition E16.

[0278] Example 17 Preparation of Green Photosensitive Resin Composition E17

[0279] The green photosensitive resin composition E17 comprises the following components in parts by weight: 200 parts of colorant L17 (composed of 100 parts of dye formula (1-61) and 100 parts of solvent Q1);

[0280] 50 multifunctional monomers M1;

[0281] 50 portions of the multifunctional monomer M2;

[0282] 100 parts of alkali-soluble resin N;

[0283] 0.2 parts additive 01;

[0284] 0.3 parts additive 02;

[0285] 5 parts of photoinitiator P;

[0286] 50 parts of solvent Q2.

[0287] The above substances were mixed evenly, and the solid content was controlled at about 20% to obtain the green photosensitive resin composition E17.

[0288] Example 18 Preparation of Green Photosensitive Resin Composition E18

[0289] Green photosensitive resin composition E18 comprises the following components in parts by weight: 200 parts of colorant L18 (composed of 100 parts of dye formula (1-64) and 100 parts of solvent Q1);

[0290] 50 multifunctional monomers M1;

[0291] 50 portions of the multifunctional monomer M2;

[0292] 100 parts of alkali-soluble resin N;

[0293] 0.2 parts additive 01;

[0294] 0.3 parts additive 02;

[0295] 5 parts of photoinitiator P;

[0296] 50 parts of solvent Q2.

[0297] The above substances were mixed evenly, and the solid content was controlled at about 20% to obtain the green photosensitive resin composition E18.

[0298] Example 19 Preparation of Green Photosensitive Resin Composition E19

[0299] Green photosensitive resin composition E19 comprises the following components in parts by weight: 200 parts of colorant L19 (composed of 100 parts of dye formula (1-67) and 100 parts of solvent Q1);

[0300] 50 multifunctional monomers M1;

[0301] 50 portions of the multifunctional monomer M2;

[0302] 100 parts of alkali-soluble resin N;

[0303] 0.2 parts additive 01;

[0304] 0.3 parts additive 02;

[0305] 5 parts of photoinitiator P;

[0306] 50 parts of solvent Q2.

[0307] The above substances were mixed evenly, and the solid content was controlled at about 20% to obtain the green photosensitive resin composition E19.

[0308] Example 20: Preparation of Green Photosensitive Resin Composition E20

[0309] Green photosensitive resin composition E20 comprises the following components in parts by weight: 200 parts of colorant L20 (composed of 100 parts of dye formula (1-68) and 100 parts of solvent Q1);

[0310] 50 multifunctional monomers M1;

[0311] 50 portions of the multifunctional monomer M2;

[0312] 100 parts of alkali-soluble resin N;

[0313] 0.2 parts additive 01;

[0314] 0.3 parts additive 02;

[0315] 5 parts of photoinitiator P;

[0316] 50 parts of solvent Q2.

[0317] The above substances were mixed evenly, and the solid content was controlled at about 20% to obtain the green photosensitive resin composition E20.

[0318] Example 21 Preparation of Green Photosensitive Resin Composition E21

[0319] Green photosensitive resin composition E21 comprises the following components in parts by weight: 200 parts of colorant L21 (composed of 100 parts of dye formula (1-71) and 100 parts of solvent Q1);

[0320] 50 multifunctional monomers M1;

[0321] 50 portions of the multifunctional monomer M2;

[0322] 100 parts of alkali-soluble resin N;

[0323] 0.2 parts additive 01;

[0324] 0.3 parts additive 02;

[0325] 5 parts of photoinitiator P;

[0326] 50 parts of solvent Q2.

[0327] The above substances were mixed evenly, and the solid content was controlled at about 20% to obtain the green photosensitive resin composition E21.

[0328] Example 22 Preparation of Green Photosensitive Resin Composition E22

[0329] The green photosensitive resin composition E22 comprises the following components in parts by weight: 200 parts of colorant L22 (composed of 100 parts of dye formula (1-75) and 100 parts of solvent Q1);

[0330] 50 multifunctional monomers M1;

[0331] 50 portions of the multifunctional monomer M2;

[0332] 100 parts of alkali-soluble resin N;

[0333] 0.2 parts additive 01;

[0334] 0.3 parts additive 02;

[0335] 5 parts of photoinitiator P;

[0336] 50 parts of solvent Q2.

[0337] The above substances were mixed evenly, and the solid content was controlled at about 20% to obtain the green photosensitive resin composition E22.

[0338] Example 23 Preparation of Green Photosensitive Resin Composition E23

[0339] The green photosensitive resin composition E23 comprises the following components in parts by weight: 200 parts of colorant L23 (composed of 100 parts of dye formula (1-77, n=10) and 100 parts of solvent Q1); 50 parts of multifunctional monomer M1;

[0340] 50 portions of the multifunctional monomer M2;

[0341] 100 parts of alkali-soluble resin N;

[0342] 0.2 parts additive 01;

[0343] 0.3 parts additive 02;

[0344] 5 parts of photoinitiator P;

[0345] 50 parts of solvent Q2.

[0346] The above substances were mixed evenly, and the solid content was controlled at about 20% to obtain the green photosensitive resin composition E23.

[0347] Example 24 Preparation of Green Photosensitive Resin Composition E24

[0348] The green photosensitive resin composition E24 comprises the following components in parts by weight: 200 parts of colorant L24 (composed of 100 parts of dye formula (1-81, n=10) and 100 parts of solvent Q1); 50 parts of multifunctional monomer M1;

[0349] 50 portions of the multifunctional monomer M2;

[0350] 100 parts of alkali-soluble resin N;

[0351] 0.2 parts additive 01;

[0352] 0.3 parts additive 02;

[0353] 5 parts of photoinitiator P;

[0354] 50 parts of solvent Q2.

[0355] The above substances were mixed evenly, and the solid content was controlled at about 20% to obtain the green photosensitive resin composition E24.

[0356] Example 25 Preparation of Green Photosensitive Resin Composition E25

[0357] The green photosensitive resin composition E25 comprises the following components in parts by weight: 200 parts of colorant L25 (composed of 100 parts of dye formula (1-83, n=10) and 100 parts of solvent Q1); 50 parts of multifunctional monomer M1;

[0358] 50 portions of the multifunctional monomer M2;

[0359] 100 parts of alkali-soluble resin N;

[0360] 0.2 parts additive 01;

[0361] 0.3 parts additive 02;

[0362] 5 parts of photoinitiator P;

[0363] 50 parts of solvent Q2.

[0364] The above substances were mixed evenly, and the solid content was controlled at about 20% to obtain the green photosensitive resin composition E25.

[0365] Example 26 Preparation of Green Photosensitive Resin Composition E26

[0366] Green photosensitive resin composition E26 comprises the following components in parts by weight: 200 parts of colorant L26 (composed of 100 parts of dye formula (1-88) and 100 parts of solvent Q1);

[0367] 50 multifunctional monomers M1;

[0368] 50 portions of the multifunctional monomer M2;

[0369] 100 parts of alkali-soluble resin N;

[0370] 0.2 parts additive 01;

[0371] 0.3 parts additive 02;

[0372] 5 parts of photoinitiator P;

[0373] 50 parts of solvent Q2.

[0374] The above substances were mixed evenly, and the solid content was controlled at about 20% to obtain the green photosensitive resin composition E26.

[0375] Example 27 Preparation of Green Photosensitive Resin Composition E27

[0376] Green photosensitive resin composition E27 comprises the following components in parts by weight: 200 parts of colorant L27 (composed of 100 parts of dye formula (1-93) and 100 parts of solvent Q1);

[0377] 50 multifunctional monomers M1;

[0378] 50 portions of the multifunctional monomer M2;

[0379] 100 parts of alkali-soluble resin N;

[0380] 0.2 parts additive 01;

[0381] 0.3 parts additive 02;

[0382] 5 parts of photoinitiator P;

[0383] 50 parts of solvent Q2.

[0384] The above substances were mixed evenly, and the solid content was controlled at about 20% to obtain the green photosensitive resin composition E27.

[0385] Example 28 Preparation of Green Photosensitive Resin Composition E28

[0386] Green photosensitive resin composition E28 comprises the following components in parts by weight: 200 parts of colorant L28 (composed of 100 parts of dye formula (1-94) and 100 parts of solvent Q1);

[0387] 50 multifunctional monomers M1;

[0388] 50 portions of the multifunctional monomer M2;

[0389] 100 parts of alkali-soluble resin N;

[0390] 0.2 parts additive 01;

[0391] 0.3 parts additive 02;

[0392] 5 parts of photoinitiator P;

[0393] 50 parts of solvent Q2.

[0394] The above substances were mixed evenly, and the solid content was controlled at about 20% to obtain the green photosensitive resin composition E94.

[0395] Example 29 Preparation of Green Photosensitive Resin Composition E29

[0396] Green photosensitive resin composition E29 comprises the following components in parts by weight:

[0397] 200 parts of colorant L29 (composed of 100 parts of dye formula (1-96) and 100 parts of solvent Q1);

[0398] 50 multifunctional monomers M1;

[0399] 50 portions of the multifunctional monomer M2;

[0400] 100 parts of alkali-soluble resin N;

[0401] 0.2 parts additive 01;

[0402] 0.3 parts additive 02;

[0403] 5 parts of photoinitiator P;

[0404] 50 parts of solvent Q2.

[0405] The above substances were mixed evenly, and the solid content was controlled at about 20% to obtain the green photosensitive resin composition E29.

[0406] Example 30: Preparation of Green Photosensitive Resin Composition E30

[0407] Green photosensitive resin composition E30 comprises the following components in parts by weight:

[0408] 200 parts of colorant L30 (composed of 100 parts of dye formula (1-97, n=10) and 100 parts of solvent Q1);

[0409] 50 multifunctional monomers M1;

[0410] 50 portions of the multifunctional monomer M2;

[0411] 100 parts of alkali-soluble resin N;

[0412] 0.2 parts additive 01;

[0413] 0.3 parts additive 02;

[0414] 5 parts of photoinitiator P;

[0415] 50 parts of solvent Q2.

[0416] The above substances were mixed evenly, and the solid content was controlled at about 20% to obtain the green photosensitive resin composition E30.

[0417] Comparative Example 1: Preparation of Green Photosensitive Resin Composition R1

[0418] A colored photosensitive resin composition R1 was formulated using pigment green 36 and then subjected to photolithography development to compare the relevant properties of the photosensitive resin compositions. Specifically, a lithography method well known to those skilled in the art was applied.

[0419] The green photosensitive resin composition R1 comprises the following components in parts by weight:

[0420] 200 parts of colorant R (composed of 100 parts of pigment green 36 and 100 parts of solvent Q1);

[0421] 50 multifunctional monomers M1;

[0422] 50 portions of the multifunctional monomer M2;

[0423] 100 parts of alkali-soluble resin N;

[0424] 0.2 parts additive 01;

[0425] 0.3 parts additive 02;

[0426] 5 parts of photoinitiator P;

[0427] 50 parts solvent Q2;

[0428] The above substances were mixed evenly, and the solid content was controlled at about 20% to obtain a green photosensitive resin composition R1.

[0429] Performance testing:

[0430] The lithography method includes the following steps:

[0431] The glass slides were washed and dried, and then coated with adhesive using a rotary coater to obtain a uniform film layer of 1.5-2.0 μm. The film was pre-baked at 90℃ for 120 s and then exposed to 365 nm ultraviolet light at an exposure dose of 40 mJ / cm². 2The distance between the mask and the coating was 180 μm. The film was developed at 23 °C for 50 s and then baked at 230 °C for 20 min. The subsequent related performance was tested, and the results are shown in Table 1.

[0432] Performance testing and evaluation methods:

[0433] (1) Colorimetry: Detected using a Konica Minolta CM-5 spectrophotometer.

[0434] (2) System compatibility (referred to as “A” in Table 1): The photosensitive resin composition was stored in the dark at 0-10℃, 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 filter surface was examined under an optical microscope (OM) at 500x magnification.

[0435] The evaluation criteria are as follows:

[0436] ○: Viscosity change < ±5% mPa·s and X500 surface free of particles;

[0437] △: Viscosity change < ±10% mPa·s and X500 surface free of particles;

[0438] ×: Viscosity change value > ±10% mPa.s or x500 indicates particles on the surface;

[0439] (3) Heat resistance test: The heat resistance of the photosensitive resin composition was verified by color difference. The sample was post-baked at 230℃ for 20 minutes, and this post-baking was repeated twice. The film thickness was measured using an XP-2 step meter. The color difference was the difference between the second post-baked sample and the first post-baked sample, measured using a Minolta CM-5. If ΔE ab A value less than 3 indicates good heat resistance;

[0440] (4) Solvent resistance evaluation:

[0441] After drying, the sample was immersed in isopropanol at room temperature for 5 minutes, then baked in an oven at 150°C for 30 minutes. The color difference before and after baking was then measured. If ΔE ab A value less than 3 indicates good solvent resistance.

[0442] (5) Evaluation of anti-migration performance:

[0443] Following the manufacturing process of color filters, green or blue pixel A is first prepared on TFT glass. Then, a sample is coated, and after development, the surface of the color filter is dried. The color difference before and after pixel A is measured. If ΔE ab A value less than 3 indicates good resistance to transfection.

[0444] (6) Line width, edge neatness, and development process tolerance:

[0445] The linewidth and edge neatness were tested at x500 OM, and the mask linewidth was 140μm.

[0446] When evaluating process margin, other process conditions are kept constant, and the edge neatness and edge residue or edge peeling of the image obtained with a development time between 40s and 100s are examined. The peeling property is determined by referring to the adhesion measurement method in this field.

[0447] The evaluation criteria for edge neatness (referred to as "B" in Table 1) are as follows:

[0448] ○: After 50 seconds of development, the edges are neat and there is no residue at the edges;

[0449] △: The image developed for 50 seconds has rough, uneven edges or residue at the edges;

[0450] ×: Image missing.

[0451] The specific criteria for evaluating the development process margin (referred to as "C" in Table 1) are as follows:

[0452] ○: After developing for 40-100 seconds, the edges are neat and there is no residue or peeling at the edges;

[0453] △: After developing for 50-80 seconds, the edges are neat and there is no residue or peeling at the edges;

[0454] ×: The edges are uneven after 50-80 seconds of development, or there is residue at the edges, or there is peeling at the edges;

[0455] The alkaline developing solutions used above, such as aqueous solutions of alkaline compounds like sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, calcium carbonate, ammonia, diethylamine, or tetramethylammonium hydroxide, [OH] - The concentration is 0.2-1.0%, preferably 0.4-0.6%.

[0456] The evaluation results are shown in the table below:

[0457] Table 1. Summary of performance analysis of the green photosensitive resin compositions prepared in Examples 1-30 and comparative examples.

[0458]

[0459]

[0460] The experimental results show that the CI pigment green 36 in the comparative example is insoluble in PGMEA, while the dyes involved in Examples 1-30 have good solubility in the color photoresist solvent PGMEA, and the green color purity in the color photoresist solvent PGMEA is higher. At the same time, the photosensitive resin compositions E1-E30 obtained using these 30 dyes have similar good process performance as Comparative Example 1 (photosensitive resin composition R1 using CI pigment green 36), such as system compatibility, edge neatness, and development process margin.

[0461] The above description of the embodiments is provided to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the interpretation of the present invention, without departing from the scope of the invention, should be within the protection scope of the present invention.

Claims

1. A phthalocyanine compound, characterized in that, The phthalocyanine compound is selected from one of the following structural formulas: 。 2. The use of the phthalocyanine compound as described in claim 1 in the preparation of dyes.

3. A dye, characterized in that, The dye contains the phthalocyanine compound as described in claim 1.

4. The use of the dye as described in claim 3 in the preparation of optical filters.

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