Blue dye compound and photoresist

Abstract

The application provides a blue dye compound and a photoresist, and belongs to the technical field of dye compounds.The blue dye compound comprises a compound of formula I.The application designs the molecular structure of the blue dye compound, and a dye compound with good optical performance, high thermal stability, uniform dyeing and a simple preparation method is obtained.

Description

Technical Field

[0001] This invention belongs to the field of dye compound technology, specifically relating to a blue dye compound and a photoresist. Background Technology

[0002] In recent years, the display industry has developed rapidly. Compared with thin film transistor liquid crystal display (TFT-LCD), organic light-emitting diode (OLED) has advantages such as simple structure, fast response rate, self-illumination without backlight module, and thinness.

[0003] To achieve full-color display, one type of OLED display relies on the self-emissive process of red, green, and blue materials in the light-emitting layer. However, due to the varying lifespans of these materials, particularly the short lifespan of blue light-emitting materials, color shift issues arise during subsequent use. To address this problem, modern processes employ an alternative method: superimposing a white organic light-emitting diode (WOLED) with a color filter (CF) to achieve full-color display. The color filter comprises red, green, and blue color resist units. It uses white light generated by the WOLED at the bottom as its light source, producing corresponding colors by transmitting light of specific wavelengths. WOLEDs offer advantages such as high contrast, high saturation, good light uniformity, and high energy efficiency. The red, green, and blue photoresists play a crucial role in the color filter, and researchers currently primarily adjust the color by adding different pigments.

[0004] With the development of blue dyes for photoresists, their costs have been continuously reduced, and their advantages over pigments have become increasingly prominent. Compared to pigments, they have better dispersibility and optical properties. However, the blue dye compounds provided by existing technologies have low transmittance at a wavelength of 450nm, which cannot meet the stringent requirements of high-resolution optical devices for narrowband spectral transmittance. Some dyes are prone to photobleaching under light, limiting their application in long-term surgery and in vivo dynamic monitoring. At the same time, existing blue dyes also have disadvantages such as poor thermal stability, uneven dyeing, and complex synthesis processes.

[0005] Therefore, how to provide a dye compound with good optical properties and high thermal stability, uniform dyeing, and simple preparation method has become an urgent technical problem to be solved. Summary of the Invention

[0006] To address the shortcomings of existing technologies, the present invention aims to provide a blue dye compound and a photoresist. By designing the molecular structure of the blue dye compound, the present invention yields a dye compound with good optical properties, high thermal stability, uniform dyeing, and a simple preparation method.

[0007] To achieve this objective, the present invention adopts the following technical solution:

[0008] In a first aspect, the present invention provides a blue dye compound, said blue dye compound comprising compounds having the structure shown in Formula I:

[0009] Formula I;

[0010] Where Q represents a substituted or unsubstituted C5-C20 divalent saturated hydrocarbon group;

[0011] T 1 T 2 Each can independently represent any one of substituted or unsubstituted C6-C20 arylene or substituted or unsubstituted C3-C20 heteroarylene;

[0012] R k1 R k2 R1-R 16 Each of the following can be independently represented: hydrogen atom, deuterium atom, substituted or unsubstituted C1-C20 straight-chain or branched alkyl group, substituted or unsubstituted C6-C20 aryl group, or substituted or unsubstituted C7-C30 aralkyl group;

[0013] R a1 -R a8 Each independently represents any one of the following: substituted or unsubstituted C1-C20 straight-chain or branched alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C20 aryl, or substituted or unsubstituted C3-C20 heteroaryl. R a1 R a2 The elements are either not connected or connected in a loop, R a3 R a4 The elements are either not connected or connected in a loop, R a5 R a6 The elements are either not connected or connected in a loop, R a7 R a8 They are either not connected or connected in a loop;

[0014] T 1 T 2 R k1 R k2 R1-R 16 R a1 -R a8The 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;

[0015] p represents 0 or 1;

[0016] q represents an integer from 1 to 20;

[0017] Y n- The denot represents an anion, n represents an integer from 1 to 20, and m represents an integer from 1 to 10.

[0018] This invention designs the molecular structure of a blue dye compound, and further designs the presence of a conjugated group in the blue dye compound. The presence of this conjugated group changes the electron cloud distribution of the molecule, which has a significant impact on the absorption spectrum of the dye, giving it high selective absorption and transmission capability at 450 nm of blue light. This can meet the stringent requirements of high-resolution optical devices for narrowband spectral transmittance, resulting in a dye compound with good optical performance, high thermal stability, uniform dyeing, and simple preparation method.

[0019] In this invention, by designing a blue dye compound with a triarylmethane system as the basic skeleton and using substituted or unsubstituted C5-C20 divalent saturated hydrocarbon groups (Q groups) as linking groups, the overall performance of the dye is precisely controlled, thereby preparing a dye compound that has strong absorption capacity at 450 nm of blue light, is relatively stable under light irradiation, has strong thermal stability, and produces uniform dyeing.

[0020] In this invention, a divalent saturated hydrocarbon group refers to a chain-like alkylene group, a cycloalkylene group, or a divalent group obtained by combining chain-like alkylene groups and cycloalkylene groups.

[0021] 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.

[0022] 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.

[0023] 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.

[0024] In this invention, "each independently" means that when there are multiple subjects, they can be the same or different from each other.

[0025] In this invention, the C5-C20 divalent saturated hydrocarbon group can be a divalent group of C6, C8, C9, C10, C12, C14, C16, C18, etc. (such as chain alkylene, cycloalkylene, or a divalent group obtained by combining chain alkyl and cycloalkyl). The chain alkylene is exemplary including but not limited to: methylene, ethylene, n-propylene, n-butylene, isobutylene, n-pentylene, etc., and the cycloalkylene is exemplary including but not limited to: cyclopropylene, cyclobutylene, cyclopentylene, or cyclohexylene, etc.

[0026] 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.

[0027] 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.

[0028] In this invention, the C1-C20 straight-chain or branched alkyl groups can be straight-chain or branched alkyl groups of C2, C4, C6, C8, C10, C12, C14, C16, C18, etc., and are more preferably C1-C10 straight-chain or branched alkyl groups, including but 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.

[0029] 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.

[0030] 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.

[0031] In this invention, specific examples of the C7-C30 (e.g., C9, C10, C12, C14, C16, C18, C20, C22, C24, C26 or C28, etc.) aryl groups can be exemplified by the monovalent groups obtained by connecting the above-mentioned aryl groups with alkyl groups.

[0032] 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.

[0033] The halogen atom includes fluorine, chlorine, bromine, or iodine; the same descriptions used below have the same meaning.

[0034] In this invention, the integers from 1 to 20 can be 1, 2, 4, 6, 8, 10, 12, 14, 16, 18, or 20, etc.

[0035] The integers from 1 to 10 can be 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.

[0036] It should also be noted that when p represents 0, T 2 denoted as any one of substituted or unsubstituted C6-C20 aryl or substituted or unsubstituted C3-C20 heteroaryl; when p represents 1, T 2 It represents any one of substituted or unsubstituted C6-C20 arylene or substituted or unsubstituted C3-C20 heteroarylene.

[0037] 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.

[0038] Preferably, Q represents any one of the following groups:

[0039] , , ;

[0040] The wavy lines indicate connection points;

[0041] R b1 R b2 Each can independently represent a straight-chain or branched alkyl group of C1-C10 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C10);

[0042] u1, u2, v1, and v2 each independently represent an integer between 0 and 3, for example, 0, 1, 2, or 3.

[0043] Preferably, Q represents any one of the following groups:

[0044] , , ;

[0045] The wavy lines indicate connection points.

[0046] In this invention, by selecting a Q group with a specific structure, the prepared blue dye compound exhibits excellent comprehensive properties. When the Q group is selected from a structure containing a six-membered ring ( , Because of the chair-boat tautomerism of the six-membered ring and the rapid conversion between α and β bonds, excited state energy can be dissipated, which can further improve the photostability and thermal stability of blue dye compounds, preventing the molecular chains of blue dye compounds from easily twisting, bending or breaking.

[0047] Preferably, the T 1 T 2 Each of the following groups, whether substituted or unsubstituted, independently represents any one of the following: phenylene, naphthylene; wherein each of the substituted substituents independently represents at least one of the following: deuterium atom, halogen atom, cyano, amino, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, phenyl.

[0048] 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.

[0049] 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.

[0050] 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.

[0051] Preferably, the Ra2 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.

[0052] Preferably, the Y n- [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.

[0053] Preferably, p represents 1.

[0054] Preferably, q represents an integer from 1 to 10, such as 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

[0055] Preferably, m represents an integer from 1 to 5, such as 1, 2, 3, 4 or 5.

[0056] Preferably, the compound with the structure shown in Formula I includes the following compounds:

[0057] .

[0058] 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.

[0059] In a second aspect, the present invention provides a photoresist comprising the blue dye compound as described in the first aspect.

[0060] Compared with the prior art, the present invention has the following beneficial effects:

[0061] This invention designs the molecular structure of a blue dye compound to obtain a dye compound with good optical properties and high thermal stability, which also has uniform dyeing and a simple preparation method. The blue dye compound has high selective absorption and transmission at a wavelength of 450 nm, and also has high thermal stability. Detailed Implementation

[0062] 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.

[0063] Example 1

[0064] This embodiment provides a blue dye compound A3 and its synthesis method, which is as follows:

[0065] (1) Synthesis of intermediate C1

[0066]

[0067] 4,4'-Dibromobenzophenone (20 g, 60 mmol), N-ethyl-2-methylaniline (16 g, 120 mmol), sodium tert-butoxide (16 g, 168 mmol), tri-tert-butylphosphine (6 g, 30 mmol), and palladium acetate (0.134 g, 0.6 mmol) were dispersed in 200 mL of toluene and reacted at 115 °C for 48 h. After the reaction was completed, the mixture was cooled to room temperature and extracted with water. The extract was then dried with magnesium sulfate and concentrated to give intermediate C1 (23.6 g, yield 88%).

[0068] Intermediate C1 was characterized using ¹H NMR and LC-MS. The results are as follows: ¹H NMR (400 MHz, CDCl3) δ 7.81 - 7.20 (m, 10H), 7.15 - 6.85 (dd, 6H), 3.50 (q, J = 7.2 Hz, 4H), 2.15 (s, 6H), 1.6 (t, 6H); LC-MS (C 31 H 32 N2O): 448.5.

[0069] (2) Synthesis of intermediate A1

[0070]

[0071] 1-Iodonaphthalene (5.1 g, 20 mmol), isophorone diamine (1.7 g, 10 mmol), sodium tert-butoxide (2.7 g, 28 mmol), tri-tert-butylphosphine (1 g, 5 mmol), and palladium acetate (0.05 g, 0.2 mmol) were dispersed in 50 mL of xylene and reacted at 130–135 °C for 48 h. After the reaction was completed, the mixture was cooled to room temperature and extracted with water. The extract was then dried with magnesium sulfate and concentrated to give intermediate A1 (2.99 g, yield 71%).

[0072] Characterization of intermediate A1: 1 H NMR (500 MHz, Chloroform-d) δ 7.88 - 7.67 (m,4H), 7.47 - 7.16 (m, 10H), 5.63 (dd, 2H), 3.77 - 3.50 (dt, 3H), 1.77 - 1.59(m, 6H), 1.48 - 1.13 (m, 9H); LC-MS (C 30 H 34 N2): 421.9.

[0073] (3) Synthesis of intermediate A2

[0074]

[0075] Intermediate A1 (2.5 g, 6 mmol), intermediate C1 (5.8 g, 13 mmol), and 30 mL of chlorobenzene were stirred and mixed thoroughly at 45–50 °C. Phosphorus oxychloride (1.99 g, 13 mmol) was added dropwise, and the mixture was stirred at 45–50 °C for 20 h. After the reaction was complete, 100 mL of chloroform and 100 mL of water were added to dissolve the mixture, and the chloroform layer was separated. The chloroform layer was washed with water, dried with magnesium sulfate, and concentrated under reduced pressure. The residue was diluted with chloroform and purified by silica gel column chromatography to give compound A2 (6.9 g, 90% yield).

[0076] Characterization of intermediate A2: 1 H NMR (500 MHz, Chloroform-d) δ 7.91 - 7.68 (m,15H), 7.54 - 7.01 (m, 29H), 5.51 - 5.42 (dd, 6H), 4.21 - 4.03 (m, 4H), 3.48 -3.37 (m, 2H), 2.28 (dt, 8H), 1.81 - 1.63 (m, 15H), 1.54 - 1.17 (m, 19H); LC-MS(C 92 H 98 N6 + ): 1286.7.

[0077] (4) Synthesis of compound A3

[0078]

[0079] After dissolving 12-tungstic phosphate·n hydrate (3.68 g, 1.28 mmol) by heating in a mixture of 60 mL methanol and 60 mL water, intermediate A2 (2.56 g, 2 mmol) was added, and the mixture was stirred at room temperature for 1 h. The precipitate was filtered, washed with water, and dried under reduced pressure to give compound A3 (6.4 g, 95% yield).

[0080] Characterization of compound A3: 1H NMR (500 MHz, Chloroform-d) δ 8.11 - 8.07 (d,2H), 7.78 - 7.56 (m, 20H), 7.46 - 7.08 (dt, 22H), 5.41 - 5.33 (dt, 8H), 4.16- 3.93 (m, 4H), 3.31 - 3.27 (m, 8H), 2.28 - 1.81 (m, 18H), 1.68 - 1.37 (m, 16H); MALDI-TOF MS (C 92 H 98 N6 + ): calcd. 1285.9867.

[0081] Example 2

[0082] This embodiment provides a method for synthesizing compound B3, as detailed below:

[0083] (1) Prepare intermediate C1 according to the synthesis method provided in step (1) of Example 1;

[0084] (2) Synthesis of intermediate B1

[0085]

[0086] Following the synthesis method provided in step (2) of Example 1, isophorone diamine was replaced with an equimolar amount of bicyclo[2.2.1]heptane dimethylamine to obtain intermediate B1 (3.0 g, yield 74%).

[0087] Intermediate B1 was characterized as follows: 1 H NMR (500 MHz, Chloroform-d) δ 7.78 - 7.51 (m,6H), 7.36 - 7.07 (m, 10H), 3.65 - 3.50 (dd, 4H), 2.30 (dq, 2H), 1.86 - 1.71(m, 3H), 1.55 - 1.37 (m, 3H); LC-MS (C 29 H 28 N2): 403.1.

[0088] (3) Synthesis of intermediate B2

[0089]

[0090] Referring to the synthesis method provided in step (3) of Example 1, intermediate A1 was replaced with an equimolar amount of intermediate B1 to obtain intermediate B2 (7.1 g, yield 93%).

[0091] Characterization of intermediate B2: 1 H NMR (500 MHz, Chloroform-d) δ 8.06 - 7.86 (m,4H), 7.67 - 7.41 (m, 14H), 7.23 - 7.14 (m, 8H), 7.09 - 7.02 (m, 13H), 6.71 -6.48 (m, 8H), 5.11 - 4.89 (dt, 6H), 3.89 - 3.57 (dq, 8H), 2.18 - 1.69 (m,14H), 1.55 - 1.31 (m,17H); LC-MS (C 91 H 92 N6): 1267.1.

[0092] (4) Synthesis of compound B3

[0093]

[0094] Referring to the synthesis method provided in step (4) of Example 1, intermediate A2 was replaced with an equimolar amount of intermediate B2 to obtain compound B3 (6.37 g, yield 92%).

[0095] Compound B3 was characterized by: ¹H NMR (500 MHz, Chloroform-d) δ 8.15 (dd, 2H), 7.90 - 7.87 (m, 2H), 7.66 - 7.43 (m, 11H), 7.22 - 7.16 (m, 13H), 7.08 - 7.04 (m, 11H), 6.70 - 6.50 (dt, 8H), 5.10 - 4.91 (dd, 8H), 3.88 - 3.59 (dq, 6H), 2.17 - 1.71 (m, 18H), 1.54 - 1.33 (m, 13H); MALDI-TOF MS (C 91 H 92 N6): calcd.1267.9351.

[0096] Example 3

[0097] This embodiment provides a method for synthesizing compounds A5 and A6, as detailed below:

[0098] (1) Prepare intermediate C1 according to the synthesis method provided in step (1) of Example 1;

[0099] (2) Prepare intermediate A1 according to the synthesis method provided in step (2) of Example 1;

[0100] (3) Synthesis of intermediate A4 / intermediate A4-2

[0101]

[0102] Intermediate A1 (2.5 g, 6 mmol), intermediate C1 (2.9 g, 6.5 mmol), and 30 mL of chlorobenzene were stirred and mixed thoroughly at 0 °C. Phosphorus oxychloride (1.4 g, 9 mmol) was added dropwise, and the mixture was stirred at 0 °C for 20 h. After the reaction was completed, 100 mL of chloroform and 100 mL of water were added to dissolve the mixture, and the chloroform layer was separated. The chloroform layer was washed with water, dried with magnesium sulfate, and concentrated under reduced pressure. The residue was diluted with chloroform and purified by silica gel column chromatography to obtain intermediates A4 and A4-2 (4.1 g, yield 80%) (A4 and A4-2 are isomers and cannot be separated).

[0103] The intermediate A4 (A4-2) was characterized as follows: 1 H NMR (500 MHz, Chloroform-d) δ 7.95 - 7.82(dt, 3H), 7.68 - 7.44 (m, 15H), 7.31 - 6.93 (m, 10H), 5.36 - 5.28 (m, 4H),3.87 (dq, 4H), 3.58 - 3.41 (m, 3H), 2.29 - 1.75 (m, 8H), 1.63 - 1.57 (m, 4H), 1.37 - 0.93 (dt, 15H); LC-MS (C 61 H 66 N4): 853.6.

[0104] (4) Synthesis of compound A5 / compound A6

[0105]

[0106] Referring to the synthesis method provided in step (4) of Example 1, intermediate A2 was replaced with equimolar amounts of intermediates A4 and A4-2 to obtain a mixture of compounds A5 and A6 (4.3 g, yield 85%) (A5 and A6 are isomers and cannot be separated).

[0107] Compounds A5 and A6 were characterized as follows: 1H NMR (500 MHz, Chloroform-d) δ 8.07 -8.01 (m, 1H), 7.87 (dd, 2H), 7.69 - 7.47 (m, 6H), 7.36 - 7.21 (m,18H), 6.78 -6.59 (dd, 3H), 5.33 - 5.21 (m, 4H), 3.54 - 3.43 (m, 4H), 2.28 (d, 4H), 1.83 -1.74 (m, 8H), 1.52 - 1.33(d, 16H); MALDI-TOF MS (C 61 H 66 N4): calcd. 854.2436.

[0108] Example 4

[0109] This embodiment provides a method for synthesizing compound B5, as detailed below:

[0110] (1) Prepare intermediate C1 according to the synthesis method provided in step (1) of Example 1;

[0111] (2) Prepare intermediate B1 according to the synthesis method provided in step (2) of Example 3;

[0112] (3) Synthesis of intermediate B4

[0113]

[0114] Intermediate B1 (2.4 g, 6 mmol), intermediate C1 (3.2 g, 7.2 mmol), and 30 mL of chlorobenzene were stirred and mixed thoroughly at 0 °C. Phosphorus oxychloride (1.4 g, 9 mmol) was added dropwise, and the mixture was stirred at 0 °C for 20 h. After the reaction was completed, 100 mL of chloroform and 100 mL of water were added to dissolve the mixture, and the chloroform layer was separated. The chloroform layer was washed with water, dried with magnesium sulfate, and concentrated under reduced pressure. The residue was diluted with chloroform and purified by silica gel column chromatography to obtain intermediate B4 (5.2 g, yield 93%).

[0115] Intermediate B4 was characterized as follows: 1H NMR (500 MHz, Chloroform-d) δ 7.91 - 7.76 (m,4H), 7.66 - 7.41 (m, 5H), 7.33 - 7.26 (m, 6H), 7.18 - 7.11 (m, 4H), 7.06 -6.93 (m, 8H), 6.67 (t, 2H), 6.51 (d, 3H), 5.22 (m, 1H), 4.18 (dq, 2H), 3.97(dd, 2H), 2.39 - 2.18 (m, 9H), 1.83 - 1.66 (m, 5H), 1.37 - 1.17 (m, 9H); LC-MS(C 60 H 60 N4): 835.3.

[0116] (4) Synthesis of compound B5

[0117]

[0118] Referring to the synthesis method provided in step (4) of Example 1, intermediate A2 was replaced with an equimolar amount of intermediate B4 to obtain compound B5 (6.37 g, yield 92%).

[0119] Characterization of compound B5: 1 H NMR (500 MHz, Chloroform-d) δ 8.12 - 8.03 (m,2H), 7.96 - 7.89 (m, 1H), 7.80 (m, 1H), 7.70 - 7.45 (m, 8H), 7.39 - 7.29 (m,6H), 7.11 - 6.96 MALDI-TOF MS(C 60 H 60 N4): calcd. 836.3965.

[0120] Example 5

[0121] This embodiment provides a method for synthesizing compound C, as detailed below:

[0122] (1) Prepare intermediate C1 according to the synthesis method provided in step (1) of Example 1;

[0123] (2) Synthesis of intermediate C2

[0124]

[0125] Referring to the synthesis method provided in step (2) of Example 1, isophorone diamine was replaced with an equimolar amount of 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane to obtain intermediate C2.

[0126] (3) Synthesis of intermediate C3

[0127]

[0128] Referring to the synthesis method provided in step (3) of Example 1, intermediate A1 was replaced with an equimolar amount of intermediate C2, and the amount of intermediate C2 was adjusted to 6 mmol to obtain intermediate C3.

[0129] (4) Synthesis of compound C

[0130]

[0131] Referring to the synthesis method provided in step (4) of Example 1, intermediate A2 was replaced with an equimolar amount of intermediate C3 to obtain compound C (5.8 g, yield 85%).

[0132] Compound C was characterized by: ¹H NMR (400 MHz, CDCl₃) δ 8.39 (d, J = 8.1 Hz, 1H), 7.78 (dq, 2H), 7.42 (qd, 2H), 7.36–7.10 (m, 16H), 7.01 (dt, 6H), 6.61 (dq, 2H), 6.38 (dd, 5H), 4.13 (dt, 1H), 3.69 (q, 4H), 3.23 (td, 1H), 2.14 (d, 7H), 1.81 (d, 4H), 1.54 (s, 1H), 1.30–0.95 (m, 17H), 0.86–0.70 (m, 4H); MALDI-TOF MS (C 66 H 73 N4 + ): calcd. 921.415.

[0133] Examples 6-7

[0134] Examples 6-7 provide compounds D3 and D5 and their synthetic methods, respectively. Compounds D3 and D5 are as follows:

[0135] ;

[0136] The synthesis method can be referred to the synthesis method provided in Example 5. Specifically, in step (1) of Example 5, N-ethyl-2-methylaniline is replaced with an equimolar amount of N-isopropylaniline. Other conditions and steps are referred to the synthesis method provided in Example 1 to prepare compound D3 (yield 76%) and compound D5 (yield 70%).

[0137] Characterization of compound D3: 1 H NMR (500 MHz, Chloroform-d) δ 8.13 - 8.05 (m,2H), 7.88 - 7.79 (m, 2H), 7.68 - 7.43 (m, 12H), 7.34 - 7.28 (m, 4H), 7.21 -7.10 (m, 13H), 7.03 - 6.88 (m, 12H), 5.31 (d, 2H), 5.17 (dt, 4H), 4.28 (dd,4H), 3.25 - 3.11 (m, 6H), 1.86 - 1.51 (m, 20H), 1.38 - 0.93 (m, 23H); MALDI-TOF MS (C 97 H 106 N6 + ): calcd. 1355.1127.

[0138] Characterization of compound D5: 1 H NMR (500 MHz, Chloroform-d) δ 8.11 - 8.06 (m,2H), 7.93 - 7.87 (m, 1H), 7.69 - 7.51 (m, 10H), 7.45 - 7.21 (m, 12H), 7.16 -6.93 (m, 6H), 5.37 (dd, 1H), 5.13 (ddt, 1H), 4.96 (m, 1H), 4.33 (d, 2H), 3.57(dd, 2H), 1.88 - 1.71 (m, 6H), 1.67 - 1.23 (m, 21H), 1.17 - 0.93 (m, 9H); MALDI-TOF MS (C 66 H 74 N4 + ): calcd. 922.5873.

[0139] Examples 8-9

[0140] Examples 8-9 respectively provide compounds E3 and E5 and their synthetic methods, wherein compounds E3 and E5 are respectively:

[0141] ;

[0142] The synthesis method can be referred to the synthesis method provided in Example 5. Specifically, in step (1) of Example 5, N-ethyl-2-methylaniline is replaced with an equimolar amount of N-butylaniline. Other conditions and steps are referred to the synthesis method provided in Example 1 to prepare compound E3 (yield of 71%) and compound E5 (yield of 80%).

[0143] Characterization of compound E3: 1 H NMR (500 MHz, Chloroform-d) δ 7.89 - 7.79 (dd,4H), 7.45 (dt, 4H), 7.40 - 7.32 (m, 16H), 7.26 - 7.13 (m, 18H), 7.01 (s, 4H), 6.90 (d, 2H), 5.31 - 5.26 (m, 3H), 4.00 - 3.81 (dt, 8H), 3.22 (q, 4H), 1.83 -1.66 (m, 16H), 1.56 - 1.31 (m, 18H), 1.14 - 0.86 (m, 17H); MALDI-TOF MS(C 101 H 114 N6 + ): calcd. 1411.0152.

[0144] Characterization of compound E5: 1 H NMR (500 MHz, Chloroform-d) δ 8.11 - 8.06 (m,1H), 7.91 - 7.86 (m, 2H), 7.78 (dt, 2H), 7.69 - 7.37 (m, 4H), 7.39 - 7.28 (m,6H), 7.16 - 7.08 (m, 14H), 6.89 (d, 1H), 6.65 (dd, 1H), 5.34 - 5.29 (m, 3H), 3.93 (dt, 2H), 3.47 - 3.29 (dt, 9H), 1.88 - 1.53 (m, 21H), 1.28 - 0.91 (m,12H); MALDI-TOF MS (C 68 H 78 N4+ ): calcd. 950.7381.

[0145] Examples 10-11

[0146] Examples 14-15 respectively provide compounds F3 and F5 and their synthetic methods, wherein compounds F3 and F5 are respectively:

[0147] ;

[0148] The synthesis method can be referred to the synthesis method provided in Example 5. Specifically, in step (1) of Example 5, N-ethyl-2-methylaniline is replaced with an equimolar amount of 2-methylindoline. Other conditions and steps are referred to the synthesis method provided in Example 1 to prepare compound F3 (yield of 86%) and compound F5 (yield of 77%).

[0149] Characterization of compound F3: 1 H NMR (500 MHz, Chloroform-d) δ 7.87 (dd, 3H),7.78 (m, 1H), 7.58 - 7.41 (m, 12H), 7.33 - 6.91 (m, 28H), 5.31 - 5.26 (m,4H), 3.85 (h, 4H), 3.22 (q, 2H), 2.83 (ddd, 4H), 2.73 (ddd, 4H), 1.87 - 1.40 (m, 16H), 1.31 (d, 6H), 1.18 - 0.99 (d, 14H); MALDI-TOF MS (C 97 H 98 N6 + ): calcd.1346.7168.

[0150] Characterization of compound F5: 1H NMR (500 MHz, Chloroform-d) δ 8.11 - 8.06 (m,1H), 7.89 (d, 1H), 7.86 - 7.75 (m, 4H), 7.68 - 7.38 (m, 4H), 7.34 - 7.28 (m,4H), 7.18 - 6.97 (m, 15H), 6.89 (d, 1H), 6.65 (dd, 1H), 5.34 (d, 1H), 4.34(h, 2H), 3.29 (dt, 2H), 2.63 - 2.47 (m, 4H), 1.91 - 1.83 (m, 5H), 1.74 - 1.56(m, 11H), 1.33 - 0.94 (m, 14H); MALDI-TOF MS (C 66 H 70 N4 + ): calcd. 918.4572.

[0151] Comparative Example 1

[0152] This comparative example provides compound 1 and its synthetic method. Compound 1 is:

[0153] ;

[0154] The synthesis method can be referred to the synthesis method provided in Example 1. Specifically, in step (1) of Example 1, isophorone diamine is replaced with an equimolar amount of m-phenylenediamine, and other conditions and steps are referred to the synthesis method provided in Example 1 to prepare compound 1 (yield of 85%).

[0155] Compound 1 was characterized as follows: 1 H NMR (500 MHz, Chloroform-d) δ 8.11 - 8.05 (m,2H), 7.89 - 7.83 (m, 2H), 7.78 (s, 2H), 7.67 - 7.56 (m, 8H), 7.47 - 7.38 (m,12H), 7.29 - 7.14 (m, 11H), 7.09 - 6.94 (m, 12H), 6.53 (dd, 2H), 5.46 (m,2H), 4.24 (dt, 4H), 3.87 (dq, 4H), 2.14 - 1.81 (m, 11H), 1.48 - 0.96 (m,12H); MALDI-TOF MS (C 88 H 84 N6 +): calcd. 1224.5872.

[0156] Comparative Example 2

[0157] This comparative example provides compound 2 and its synthesis method. Compound 2 is:

[0158] ;

[0159] The synthesis method can be referred to the synthesis method provided in Example 5. Specifically, in step (2) of Example 5, isophorone diamine is replaced with an equimolar amount of 4,4-diaminodiphenylmethane, and other conditions and steps are referred to the synthesis method provided in Example 5 to prepare compound 2 (yield of 91%).

[0160] Compound 2 was characterized as follows: 1 H NMR (500 MHz, Chloroform-d) δ 8.06 - 7.98 (m,2H), 7.89 - 7.84 (m, 6H), 7.76 - 7.59 (m, 12H), 7.52 - 7.33 (m, 14H), 7.21 -7.10 (m, 18H), 7.04 - 6.91 (m, 6H), 5.35 (dt, 2H), 4.48 (hept, 4H), 3.04 (dt,2H), 1.67 - 1.46 (m,12H), 1.33 - 1.04 (m, 12H); MALDI-TOF MS (C 95 H 90 N6 + ): calcd.1314.6792.

[0161] Comparative Example 3

[0162] This comparative example provides a commercially available blue dye, for .

[0163] The performance of the compounds provided in the above embodiments was tested, and the specific test methods are as follows:

[0164] UV (450 nm) absorbance: 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.

[0165] Thermal stability (TGA): The TGA data of the dyes were determined using the “STAR SYSTEM TGA2” manufactured by METTLER TOLEDO.

[0166] 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.

[0167] The performance test results are shown in Table 1 below:

[0168] Table 1 Performance Test Results

[0169]

[0170] As can be seen from the above, this invention designs the molecular structure of a blue dye compound to obtain a dye compound with good optical properties and high thermal stability, as well as uniform dyeing and simple preparation method. This blue dye compound has high selective absorption and transmission ability at a wavelength of 450 nm, and also has high thermal stability.

[0171] 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 blue dye compound, characterized in that, The blue dye compound is selected from any one of the following compounds having the structure shown in Formula I: compound C, compound D5, and compound F5: Equation I; Where Q represents any one of the following groups: , The wavy lines indicate connection points; T 1 T 2 Each independently represents a naphthyl group; R k1 R k2 R1-R 16 Each can independently represent either a hydrogen atom or a deuterium atom; 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 represents 0 or 1; q represents an integer from 1 to 10; Y n- [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- [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 the following, where m represents an integer from 1 to 5; 、 、 。 2. The blue dye compound according to claim 1, characterized in that, p represents 1.

3. The blue dye compound according to claim 1, characterized in that, The compounds with the structure shown in Formula I include the following compounds: 。 4. A photoresist, characterized in that, The photoresist includes the blue dye compound as described in any one of claims 1-3.

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