A triarylmethane dye and its application

Abstract

This invention provides a triarylmethane dye and its applications, specifically a triarylmethane dye, a coloring composition, and a filter. By designing the structure of the triarylmethane dye, this invention yields a triarylmethane dye with excellent performance and high thermal stability.

Description

Technical Field

[0001] This invention belongs to the field of dye materials technology, specifically relating to a triarylmethane dye and its application, and more specifically to a triarylmethane dye, a coloring composition and a filter. Background Technology

[0002] LCD screens are closely related to our daily work and life. They rely on internal color filters to display rich color images. Color filters are composed of fine, strip-shaped filter segments of two or more different hues arranged parallel or interlaced on the surface of a transparent substrate such as glass, or by arranging these fine filter segments in a fixed vertical and horizontal arrangement. Currently, the color layer of color filters mainly consists of a resin composition containing colorants, which are generally dyes or pigments. Coloring methods for the color layer include pigment dispersion, inkjet printing, electrolytic deposition, and printing. Generally speaking, when using pigments, the heat resistance and solvent resistance are better, but the brightness is not ideal; when using dyes, brightness can be guaranteed, but thermal stability is poor.

[0003] Therefore, how to provide a dye with good thermal stability has become an urgent technical problem to be solved. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the present invention aims to provide a triarylmethane dye and its applications, specifically a triarylmethane dye, a coloring composition, and a filter. By designing the structure of the triarylmethane dye, the present invention yields a triarylmethane dye with excellent performance and high thermal stability.

[0005] To achieve this objective, the present invention adopts the following technical solution:

[0006] In a first aspect, the present invention provides a triarylmethane dye having the structure shown in Formula I:

[0007] Formula I;

[0008] Wherein, X represents any one of O, S, substituted or unsubstituted C1-C10 straight-chain or branched alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C20 arylene, or substituted or unsubstituted C3-C20 heteroarylene.

[0009] R b1 R b2 Each of the following can be independently represented as any one of substituted or unsubstituted C1-C10 straight-chain or branched alkyl groups or substituted or unsubstituted C3-C10 cycloalkyl groups;

[0010] T 1 T 2 Each can independently represent any one of substituted or unsubstituted C6-C20 arylene or substituted or unsubstituted C3-C20 heteroarylene;

[0011] R k1 R k2 R1-R 16 Each of the following can be independently represented: hydrogen atom, deuterium atom, substituted or unsubstituted C1-C10 straight-chain or branched alkyl group, substituted or unsubstituted C3-C10 cycloalkyl group, or substituted or unsubstituted C6-C20 aryl group;

[0012] R a1 -R a8 Each of the following can be independently represented: a substituted or unsubstituted C1-C10 straight-chain or branched alkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C6-C20 aryl group, or a substituted or unsubstituted C3-C20 heteroaryl group.

[0013] T 1 T 2 R b1 R b2 R k1 R k2 R1-R 16 R a1 -R a8 The substituents described herein each independently represent any one of the following: deuterium atom, halogen atom, cyano group, amino group, C1-C10 straight-chain or branched alkyl group, C3-C10 cycloalkyl group, and C6-C10 aryl group;

[0014] p and q each independently represent integers from 0 to 3;

[0015] s represents an integer from 1 to 20;

[0016] The denot represents an anion, n represents an integer from 1 to 20, and m represents an integer from 1 to 10.

[0017] This invention designs the structure of triarylmethane dyes to obtain triarylmethane dyes with excellent performance and high thermal stability.

[0018] In this invention, unless otherwise specified, the heteroatom of the heteroaryl group is selected from atoms or groups of atoms in N, O, S, P, B, Si or Se, preferably N, O or S.

[0019] In this invention, the way of expressing a ring structure with "—" or "------" indicates that the connection point is located at any position on the ring structure where bonding can occur.

[0020] In this invention, the expression Ca-Cb represents that the group has ab carbon atoms. Unless otherwise specified, the number of carbon atoms generally does not include the number of carbon atoms of the substituents.

[0021] In this invention, "each independently" means that when there are multiple subjects, they can be the same or different from each other.

[0022] In this invention, the C1-C10 straight-chain or branched alkyl groups can be straight-chain or branched alkyl groups of C2, C3, C4, C5, C6, C7, C8, C9, C10, etc., and exemplary include but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-octyl, n-heptyl, n-nonyl or n-decyl, etc.

[0023] In this invention, the C3-C10 cycloalkyl groups can all be cycloalkyl groups of C4, C5, C6, C7, C8, C9, C10, etc., and exemplary include but are not limited to: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.

[0024] In this invention, specific examples of the C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, etc.) alkoxy groups can be exemplified by the above-mentioned straight-chain or branched alkyl groups connected to O to obtain monovalent groups.

[0025] In this invention, the C6-C20 arylene groups can all be arylene groups of C6, C9, C10, C12, C14, C16, C18, C20, etc., including monocyclic arylene groups or fused-ring arylene groups. A monocyclic arylene group means that the group contains at least one phenylene group. When it contains at least two phenyl groups, the phenyl groups are linked by a single bond, including but not limited to: phenylene, biphenylene, terphenylene, etc.; a fused-ring arylene group means that the group contains at least two aromatic rings, and the aromatic rings share two adjacent carbon atoms that are fused together, including but not limited to: naphthylene, naphthylphenylene, phenylnaphthylene, anthracene, phenanthrene, fluorene, etc.; the aforementioned listed groups include all possible connection methods.

[0026] In this invention, the C3-C20 heteroaryl groups can all be heteroaryl groups of C3, C4, C5, C6, C9, C10, C12, C14, C16, C18, C20, etc., including monocyclic heteroaryl groups or fused-ring heteroaryl groups. A monocyclic heteroaryl group means that the molecule contains at least one heteroaryl group. When the molecule contains one heteroaryl group and other groups (such as aryl, heteroaryl, alkyl, etc.), the heteroaryl group and other groups are connected by a single bond, exemplarily including but not limited to: furanyl, thiopheneyl, pyrrolyl, pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, oxazolyl, thiazolyl, imidazolyl, etc. The term "fused-ring heteroaryl" refers to a molecule containing at least one heteroaryl ring and one aromatic ring (aromatic heterocycle or aromatic ring), and the two rings share two adjacent atoms fused together in a group, including but not limited to: benzofuranyl, benzothiopheneyl, isobenzofuranyl, isobenzothiopheneyl, dibenzofuranyl, dibenzothiopheneyl, carbazoyl, etc.; the aforementioned groups include all possible connection methods.

[0027] In this invention, the C6-C20 aryl groups can be aryl groups of C6, C9, C10, C12, C14, C16, C18, C20, etc., preferably C6-C10 aryl groups, including monocyclic aryl groups or fused-ring aryl groups. A monocyclic aryl group means that the group contains at least one phenyl group. When it contains at least two phenyl groups, the phenyl groups are linked by a single bond, including but not limited to: phenyl, biphenyl, terphenyl, etc.; a fused-ring aryl group means that the group contains at least two aromatic rings, and the aromatic rings share two adjacent carbon atoms fused together, including but not limited to: naphthyl, naphthylphenyl, phenylnaphthyl, anthraceneyl, phenanthryl, fluoreneyl, etc.; the aforementioned listed groups include all feasible connection methods.

[0028] In this invention, the C3-C20 heteroaryl groups can be heteroaryl groups of C3, C4, C5, C6, C9, C10, C12, C14, C16, C18, C20, etc., including monocyclic heteroaryl groups or fused-ring heteroaryl groups. A monocyclic heteroaryl group means that the molecule contains at least one heteroaryl group. When the molecule contains one heteroaryl group and other groups (such as aryl, heteroaryl, alkyl, etc.), the heteroaryl group and other groups are connected by a single bond, exemplarily including but not limited to: furanyl, thiophene, pyrrole, pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, oxazolyl, thiazolyl, imidazole, etc. The term "fused-ring heteroaryl" refers to a molecule containing at least one aromatic heterocycle and one aromatic ring (aromatic heterocycle or aromatic ring), and the two share two adjacent atoms fused together in a group, including but not limited to: benzofuranyl, benzothiophenyl, isobenzofuranyl, isobenzothiophenyl, dibenzofuranyl, dibenzothiophenyl, carbazoleyl, etc.; the aforementioned groups include all possible connection methods.

[0029] The halogen atom includes fluorine, chlorine, bromine, or iodine; the same descriptions used below have the same meaning.

[0030] In this invention, the integers from 0 to 3 can be 0, 1, 2, or 3.

[0031] The integers from 1 to 20 can be 1, 2, 4, 6, 8, 10, 12, 14, 16, 18, or 20, etc.

[0032] The integers from 1 to 10 can be 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.

[0033] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. The purpose and beneficial effects of the present invention can be better achieved and realized through the following preferred technical solutions.

[0034] Preferably, X represents O, S, substituted or unsubstituted C1-C10 straight-chain or branched alkyl, and the substituted substituent represents any one of deuterium atom, halogen atom, cyano, amino, C1-C5 straight-chain or branched alkyl.

[0035] Preferably, X represents any one of O, S, methylene, ethylene, n-propylene, isopropylene, or fluorine-substituted isopropylene.

[0036] Preferably, the R b1 R b2 Each can independently represent any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl.

[0037] Preferably, p and q each independently represent 0, 1, or 2.

[0038] Preferably, the T 1 T 2 Each of the following groups, whether substituted or unsubstituted, can be represented independently: phenylene, naphthylene, anthraceneylene.

[0039] Preferably, the R k1 R k2 R1-R 16 Each of the following can be independently represented: hydrogen atom, deuterium atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl or phenyl.

[0040] Preferably, the R a1 R a3 R a5 R a7 Each independently represents any one of substituted or unsubstituted C1-C10 straight-chain or branched alkyl groups, or substituted or unsubstituted C3-C10 cycloalkyl groups, wherein R a2 R a4 R a6 R a8 Each can independently represent any one of substituted or unsubstituted C6-C20 aryl or substituted or unsubstituted C3-C20 heteroaryl.

[0041] Preferably, the R a1 R a3 R a5 R a7 Each of the following groups, whether substituted or unsubstituted, independently represents any one of the substituted or unsubstituted groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl; wherein each of the substituted substituents independently represents at least one of deuterium, halogen, cyano, amino, methyl or ethyl.

[0042] Preferably, the R a2 R a4 R a6 R a8 Each of the following groups, whether substituted or unsubstituted, independently represents any one of the following: phenyl, naphthyl, biphenyl; wherein each of the substituted substituents independently represents at least one of deuterium, halogen, cyano, amino, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl.

[0043] Preferably, the [PW] 12 O 40 3- [P2W] 18 O 62 6-]、[SiW 12 O 40 4- [P2W] 17 O 61 10- [P2W] 15 O 56 12- [H2P2W] 12 O 48 12- [NaP5W] 30 O 110 14- [SiW9O] 34 10- ]、[SiW 10 O 36 8- ]、[SiW 11 O 39 8- [W6O] 19 2- ]、[W 10 O 32 4- ]、[WO4 2- ]、 , , , , , Any one of them.

[0044] Preferably, s represents an integer from 1 to 10.

[0045] Preferably, m represents an integer from 1 to 5.

[0046] Preferably, the triarylmethane dye comprises the following compounds:

[0047] , .

[0048] It should be noted that the present invention does not impose any special limitations on the preparation method of the above-mentioned blue dye compound, and commonly used preparation methods in the art are applicable.

[0049] In a second aspect, the present invention provides a coloring composition comprising a triarylmethane dye as described in the first aspect.

[0050] Thirdly, the present invention provides a filter comprising a coloring layer prepared from a coloring composition as described in the second aspect.

[0051] Compared with the prior art, the present invention has the following beneficial effects:

[0052] This invention designs the structure of triarylmethane dyes to obtain triarylmethane dyes with excellent performance and high thermal stability. Detailed Implementation

[0053] To facilitate understanding of the present invention, the following embodiments are provided. Those skilled in the art should understand that these embodiments are merely illustrative and should not be construed as limiting the scope of the invention.

[0054] Example 1

[0055] This embodiment provides compound D1 and its synthesis method, which is as follows:

[0056] (1) Intermediate A1 ( Synthesis of )

[0057] Weigh 100 g (0.294 mol) of 4,4'-dibromobenzophenone, 99.42 g (0.735 mol) of N-ethyl-2-methylaniline, 84.79 g (1.23 mol) of sodium tert-butoxide, 29.75 g (2.94 mol) of tritert-tert-butylphosphine, and 2.69 g (2.94 mol) of tridibenzylacetone dipalladium (2.69 g (2.94 mol) and disperse them in 1300 mL of toluene solvent. The nitrogen gas was purged three times and the reaction was carried out at 110 °C for 5 h. After the reaction was completed, water was added after slight cooling and the mixture was cooled to room temperature. The mixture was filtered, and the mixture was slurried with n-heptane and ethanol under reflux. After cooling to room temperature, the mixture was filtered to obtain intermediate A1 (92.3 g, yield 70%).

[0058] Characterization of intermediate A1: 1 H NMR and LC-MS: 1 LC-MS (C 31 H 32 N2O): 448.5.

[0059] (2) Intermediate B1 ( Synthesis of )

[0060] Weigh 4,4-diaminodiphenyl ether (5 g, 24.97 mmol), 1-iodonaphthalene (13.32 g, 52.44 mmol), sodium tert-butoxide (12 g, 124.85 mmol), and methanesulfonic acid (2-dicyclohexylphosphine-2',6'-dimethoxy-1,1'-biphenyl)(2'-amino-1,1'-biphenyl-3-yl)palladium(II) (0.19 g, 0.25 mmol) and disperse them in 50 mL of toluene. The mixture was purged with nitrogen three times, heated to reflux, and reacted at 110 °C for 12 h. After the reaction was completed, water was added after slight cooling, and the mixture was cooled to room temperature. The mixture was filtered and separated by column chromatography to obtain intermediate B1 (7.35 g, yield 65%).

[0061] Intermediate B1 was characterized as follows: 1 H NMR and LC-MS: 1 H NMR (400 MHz, Chloroform-d) δ8.10-7.80 (dt, 5.85H), 7.57-7.28 (m, 11.9H), 6.66-6.54 (m, 4.1H), 5.93 (s,1H), 5.86 (s, 1H). LC-MS (C 32 H 24 N2O): 451.19.

[0062] (3) Intermediate C1 ( Synthesis of )

[0063] Intermediate B1 (10 g, 22.07 mmol), intermediate A1 (20.73 g, 46.25 mmol), and phosphorus oxychloride (8.46 g, 55.18 mmol) were weighed and dispersed in 100 mL of chlorobenzene. The mixture was heated to reflux and reacted for 24 h. After the reaction was completed, water and dichloromethane were added and stirred. The mixture was extracted and rotary evaporated to obtain intermediate C1 (27.54 g, yield 90%).

[0064] Intermediate C1 was characterized as follows: 1 H NMR and LC-MS: 1H NMR (400 MHz, CDCl3) δ 7.96-7.81(s, 3.96H), 7.65 -7.49 (m, 6H), 7.40-7.26 (m, 21H), 7.15-7.03 (m, 18H), 6.90-6.81 (m, 2.1H), 6.63 (dd, 2H), 4.25 (q, 4H), 3.81 (q, 4H), 2.43 (d, 6H), 2.26(s, 6H), 1.68-1.15 (t, 12H); LC-MS (C 94 H 86 N6O 2+ ): 657.9.

[0065] (4) Compound D1 ( Synthesis of )

[0066] Intermediate C1 (40 g, 21.52 mmol) was weighed and dissolved in 1000 g methanol. 70 g of tungstic phosphate·12 hydrate was weighed and dissolved in 1000 g deionized water. The methanol solution of intermediate C1 was added dropwise to the aqueous solution of phosphotungstic acid. The mixture was heated to reflux and reacted for 6 h. After the reaction was completed, the mixture was filtered to obtain compound D1 (59 g, yield 85%).

[0067] Characterization of compound D1: 1 H NMR (500 MHz, DMSO-d6) 8.15 (s, 0.99H), 7.89-7.65 (ddt, 7.9H), 7.53- 7.26 (m, 35.1H), 7.26-7.13 (m, 30.9H), 7.02-6.88 (m, 17.3H), 6.55 (dd, 3H), 4.60 (dq, 6H), 3.89 (q, 6H), 2.46- 2.19 (ddq, 17.9H), 1.69 - 1.21 (m, 18H).

[0068] Example 2

[0069] This embodiment provides compound D2 and its synthesis method, which is as follows:

[0070] (1) Intermediate A1 was obtained by referring to the synthesis method provided in Example 1;

[0071] (2) Intermediate B2 ( Synthesis of )

[0072] Weigh 3 g (11.8 mmol) of 4-(4-amino-3,5-dimethylbenzyl)-2,6-dimethylaniline, 6 g (23.6 mmol) of 1-iodonaphthalene, 3.4 g (35.38 mmol) of sodium tert-butoxide, 108 mg (0.118 mmol) of tribenzylacetone dipalladium, and 120 mg (0.59 mmol) of tritert-butylphosphine and disperse them in 30 mL of toluene. The mixture was purged with nitrogen three times, heated to reflux, and reacted at 110 °C for 12 h. After the reaction was completed, water was added after slight cooling, and the mixture was cooled to room temperature. The mixture was filtered and separated by column chromatography to obtain intermediate B2 (4.07 g, yield 68%).

[0073] Characterization of intermediate B2: 1 H NMR and LC-MS: 1 H NMR (400 MHz, Chloroform-d) δ7.90-7.50 (m, 8H), 7.50-7.30 (dt, 6H), 7.13-6.84 (dt, 4H), 5.55 (s, 2H), 3.35(s, 2H), 2.31 (s, 12H). LC-MS (C 37 H 34 N2): 505.8.

[0074] (3) Intermediate C2 ( Synthesis of )

[0075] Intermediate B2 (10 g, 19.75 mmol), intermediate A1 (18.59 g, 41.48 mmol), and phosphorus oxychloride (7.57 g, 49.38 mmol) were weighed and dispersed in 100 mL of chlorobenzene. The mixture was heated to reflux and reacted for 24 h. After the reaction was completed, water and dichloromethane were added and stirred. The mixture was extracted and rotary evaporated to obtain intermediate C2 (23.84 g, yield 88%).

[0076] Intermediate C2 was characterized as follows: 1 H NMR and LC-MS: 1 H NMR (400 MHz, CDCl3) δ 8.25 (s,2H), 7.95-7.72 (m, 8H), 7.65-7.29 (m, 23H), 7.32-7.05 (m, 11.9H), 6.80-6.72(m, 6H), 4.38 (q, 4H), 3.85-3.72(m,5.8H), 2.49-2.11 (ddq,25H),1.66-1.17 (dq,12H); LC-MS (C 99 H96 N6 2+ ): 685.3.

[0077] (4) Compound D2 ( Synthesis of )

[0078] Following the synthesis method in step (4) of Example 1, intermediate C1 was replaced with an equimolar amount of intermediate C2 to obtain compound D2 (76 g, yield 80%).

[0079] Characterization of compound D2: 1 H NMR (400 MHz, CDCl3) δ 8.25 (s, 2H), 7.95-7.72(m, 8H), 7.65-7.29 (m, 23H), 7.32-7.05 (m, 11.9H), 6.80-6.72 (m, 5.9H), 4.38(q, 4.1H), 3.85-3.72(m,5.9H), 2.49-2.11 (ddq,25H), 1.66-1.17 (dq,12H).

[0080] Comparative Example 1

[0081] This comparative example provides a dye compound DNP, the structure of which is as follows:

[0082] .

[0083] The performance of the dye compounds provided in the above embodiments and comparative examples was tested, and the specific test methods are as follows:

[0084] Thermal stability (TGA): The TGA data of the dyes were determined using the “STAR SYSTEM TGA2” manufactured by METTLER TOLEDO.

[0085] UV characteristic peak wavelength: The UV spectrum of the dye was determined using a "UV-1900" manufactured by SHIMADZU. 1 mg of the mixture or compound provided in the above examples or comparative examples was dissolved in dichloromethane for testing.

[0086] The performance test results are shown in Table 1 below:

[0087] Table 1

[0088]

[0089] As can be seen from the above, this invention has obtained a triarylmethane dye with excellent performance by designing the structure of the triarylmethane dye. This triarylmethane dye has high thermal stability.

[0090] The triarylmethane dyes provided by this invention exhibit UV characteristic peaks near wavelengths of 605-610 nm and possess high thermal stability.

[0091] The applicant declares that the detailed process flow of this invention is illustrated by the above embodiments, but this invention is not limited to the above detailed process flow, that is, it does not mean that this invention must rely on the above detailed process flow to be implemented. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of raw materials for the product of this invention, addition of auxiliary components, and selection of specific methods, etc., all fall within the protection scope and disclosure scope of this invention.

Claims

1. A triarylmethane dye, characterized in that, The triarylmethane dye has the structure shown in Formula I: Equation I; Wherein, X represents any one of O, S, methylene, ethylene, n-propylene, and isopropylene; R b1 R b2 Each can independently represent any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl; T 1 T 2 Each can independently represent either phenylene or naphthylene; R k1 R k2 R1-R 16 Each atom represents a hydrogen atom independently; R a1 R a3 R a5 R a7 Each of the following groups can be independently represented as an unsubstituted group: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl; R a2 R a4 R a6 R a8 Each of the following groups, whether substituted or unsubstituted, independently represents any one of the following groups: phenyl, naphthyl, biphenyl; wherein each of the substituted substituents independently represents at least one of deuterium, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl. p and q each independently represent 0, 1, or 2; s represents an integer from 1 to 10; [PW] 12 O 40 3- [P2W] 18 O 62 6- Any one of the following, where m represents an integer from 1 to 5.

2. The triarylmethane dye according to claim 1, characterized in that, The triarylmethane dyes include the following compounds: 、 。 3. A coloring composition, characterized in that, The coloring composition includes the triarylmethane dyes as described in claim 1 or 2.

4. A filter, characterized in that, The filter includes a coloring layer, which is prepared from a coloring composition as described in claim 3.

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