A novel blue triarylmethane dye for blue photoresist color paste and a synthesis method thereof

Abstract

The application discloses a triarylmethane dye for blue photoresist color paste and a synthesis method thereof. The dye is a triarylmethane dye P, which is prepared through the following steps: (1) dissolving an alkyl or aryl triamine MA in a solvent, adding a palladium catalyst, a ligand and an alkali, and reacting with an aryl halide under an inert atmosphere to obtain an intermediate IA; (2) dissolving a dihalogenated diaryl ketone MB in a solvent, adding a palladium catalyst, a ligand and an alkali, and reacting with a disubstituted amine under an inert atmosphere to obtain a target intermediate IB; and (3) condensing the intermediate IA and the intermediate IB to obtain a novel blue triarylmethane dye P. The triarylmethane dye has excellent color performance, is suitable for mixed or dye-based blue photoresist color paste, and can significantly improve the brightness, transparency, contrast and dispersibility of the color paste, and meanwhile, has high hiding power, strong coloring power, and good thermal stability and light stability. In addition, the synthesis method is simple in process and suitable for industrial production.

Description

Technical Field

[0001] This invention relates to the field of color photoresist technology, specifically to a novel blue triarylmethane dye for blue photoresist color paste and its synthesis method. Background Technology

[0002] In the flat panel display manufacturing industry, the performance of the color filter (CF) in TFT-LCD (Thin Film Transistor Liquid Crystal Display) directly affects the color performance of the display. Currently, the industry mainly uses pigment nano-dispersion photoresist systems. Although these systems possess good weather resistance and initial color saturation, the low solubility of pigment molecules leads to the formation of large aggregates in the photoresist, resulting in severe backlight scattering. This significantly reduces the contrast of the color filter and increases energy consumption. This deficiency makes it difficult to meet the stringent requirements of next-generation display technologies for wide color gamut and low power consumption.

[0003] To achieve precise spectral control, color filters rely on the selective absorption characteristics of colorant molecules (380~780nm visible light band). Triarylmethane dyes are considered ideal candidate materials due to their wide spectral range (yellow-blue-red), high molar extinction coefficient, excellent fluorescence properties, and structural tunability. However, current technologies still lack solutions for blue triarylmethane dyes that combine high stability, ease of synthesis, and excellent dispersibility.

[0004] This invention effectively overcomes the aforementioned technical barriers through innovative molecular design and simplified processes. For example, the trimerized triarylmethane structure greatly improves its photothermal stability, and its good solubility results in excellent dispersibility, thus improving contrast and brightness. Summary of the Invention

[0005] The technical problem to be solved by this invention is to overcome the technical defects of the prior art, such as further improving the stability of dye colorant molecules for photoresists. This invention provides a novel blue triarylmethane dye for blue photoresist color paste and its synthesis method. The novel triarylmethane dye molecule provided by this invention achieves greater steric hindrance by trimerizing triarylmethanes, which helps prevent intermolecular stacking of dye molecules. Furthermore, multiple triarylmethane units are linked by a central linking group with a strong cyclic backbone. Simultaneously, each independent triarylmethane structure can convert received light and heat energy into kinetic energy through rotational motion, preventing itself from being activated and causing molecular decomposition, thereby greatly improving the molecule's light and heat resistance.

[0006] These dye molecules can be mixed with other colorants to formulate mixed or dye-based blue photoresist pastes, which can be used to improve various properties of the pastes, such as brightness, contrast and weather resistance.

[0007] The technical solution adopted by the present invention to solve the above-mentioned technical problems is as follows:

[0008] A novel blue triarylmethane dye for blue photoresist color paste has the following chemical structural formula:

[0009]

[0010] The symbols in the formula represent the following meanings:

[0011] R 1 -R 4 Each of these can independently represent a hydrogen atom, an alkyl group optionally having a substituent, a cycloalkyl group optionally having a substituent, and an aryl group optionally having a substituent;

[0012] Ar represents various substituted or unsubstituted aromatic groups. For example, Ar represents a substituted or unsubstituted aromatic group consisting of 6 to 20 carbon atoms.

[0013] A represents an alkyl group optionally having a substituent, a cycloalkyl group optionally having a substituent, and an aryl group optionally having a substituent; the substituents of the alkyl, cycloalkyl, or aryl group include, but are not limited to, hydrogen, alkyl, aryl, halogen, hydroxyl, and carbonyl groups;

[0014] B b- This represents a β-valent anion; for example, Cl... - ,Br - I - ;

[0015] a and c represent integers greater than 1;

[0016] Multiple R1, R2, R3, R4 and Ar may be the same or different.

[0017] In the compounds represented by the above structural formulas, 'a' represents the number of cationic units in the molecule, and 'c' represents the number of anionic units in the molecular aggregate. Preferably, 5 ≥ a ≥ 1; 5 ≥ c ≥ 1. More preferably, 4 ≥ a ≥ 1; 3 ≥ c ≥ 1. Preferably, multiple R1s are the same, multiple R2s are the same, multiple R3s are the same, multiple R4s are the same, and multiple Ars are the same.

[0018] Preferred, R 1 -R 4Each of these groups independently represents a hydrogen atom, an alkyl group with 1 to 20 carbon atoms optionally having a substituent, a cycloalkyl group with 3 to 20 carbon atoms optionally having a substituent, and an aryl group with 6 to 20 carbon atoms optionally having a substituent. The hydrogen atoms in the alkyl or aryl substituents are optionally replaced by halogen atoms, and the -CH- group in the alkyl substituent is optionally replaced by -CO- or -O-; the halogen atom is chlorine, bromine, or iodine. The alkyl group with 1 to 20 carbon atoms optionally having a substituent is a straight-chain or branched alkyl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, etc. Preferably, the optional cycloalkyl group having 3 to 20 carbon atoms is a saturated cycloalkyl group having 3 to 20 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, etc. The aryl group is a monocyclic aryl (such as phenyl) or a polycyclic aryl (such as naphthyl, anthracene).

[0019] Preferably, R1 and R3 are the same, and R2 and R4 are the same.

[0020] Preferably, R1 and R3 are the same and both are -CH2CH3; R2 and R4 are the same and both are -CH2CH3.

[0021] or .

[0022] Preferably, Ar represents a naphthyl group;

[0023] Preferably, A represents a saturated cycloalkyl group formed by 3 to 10 carbon atoms; more preferably, A is cyclohexane.

[0024] In this invention, the dashed bond “------” represents the connecting bond between adjacent units or groups. In a preferred embodiment, R1 and R3 are the same and both are CH2CH3; R2 and R4 are the same and both are CH2CH3.

[0025] or .

[0026] In a preferred embodiment, Ar represents .

[0027] In a preferred embodiment, A is .

[0028] The method for synthesizing a novel triarylmethane dye for blue photoresist pigment paste, as described above, includes the following steps:

[0029] (1) Dissolve the triamine raw material MA in a solvent, add palladium catalyst, ligand and base, and react with aryl halogen under an inert atmosphere to obtain intermediate IA; the triamine raw material is alkyltriamine or aryltriamine; the halogen in the aryl halogen is chlorine, bromine or iodine;

[0030] (2) Dissolve the dihalodiaryl ketone MB in a solvent, add palladium catalyst, ligand and base, and react with disubstituted amine under an inert atmosphere to obtain the target intermediate IB; the halogen in the dihalodiaryl ketone MB is chlorine, bromine or iodine;

[0031] (3) Intermediate IA and intermediate IB are condensed to obtain a novel blue triarylmethane dye P;

[0032] The above synthetic route is as follows:

[0033]

[0034] The symbols in the formula represent the following meanings:

[0035] R 1 -R 4 Each of these can independently represent a hydrogen atom, an alkyl group optionally having a substituent, a cycloalkyl group optionally having a substituent, and an aryl group optionally having a substituent;

[0036] Ar represents various substituted or unsubstituted aromatic groups;

[0037] A represents an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, or an aryl group that may have a substituent;

[0038] B b- Indicates a b-valent anion;

[0039] A and c represent integers greater than 1;

[0040] Multiple R1, R2, R3, R4 and Ar may be the same or different.

[0041] Preferred, R 1 -R 4 Each of the following independently represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, optionally having a substituent; wherein the hydrogen atom in the alkyl or aryl substituent is optionally replaced by a halogen atom, and the -CH- in the alkyl substituent is optionally replaced by -CO- or -O-; Ar represents a substituted or unsubstituted aromatic group consisting of 6 to 20 carbon atoms; A represents a saturated cycloalkyl group consisting of 3 to 10 carbon atoms; and R1 and R3 are the same, as are R2 and R4.

[0042] In some implementations, R 1 -R4 The group is an alkyl substituent with 1 to 20 carbon atoms or an aryl substituent with 6 to 20 carbon atoms; wherein the hydrogen atom contained in the alkyl substituent or aryl substituent may be replaced by a halogen atom, and the -CH- contained in the alkyl substituent may be replaced by -CO- or -O-, wherein the halogen atom is selected from chlorine, bromine or iodine; the aryl substituent Ar is a common aromatic, aromatic fused ring or aromatic heterocyclic ring.

[0043] Preferably, in step (1), the palladium catalyst includes, but is not limited to, palladium acetate, tetratriphenylphosphine palladium, 1,1'-bis(diphenylphosphine)ferrocene palladium dichloride, and bis(dibenzylacetone)palladium; in step (1), the ligand includes, but is not limited to, Xphos, Ruphos, Sphos, and Xantphos; in step (1), the base includes, but is not limited to, potassium tert-butoxide, sodium tert-butoxide, and cesium carbonate; preferably, in step (1), in the palladium-catalyzed coupling reaction, the molar ratio of aryl halogen to triamine raw material is 2:1 to 6:1, more preferably 2.2:1 to 4.5:1.

[0044] Preferably, in step (1), the molar ratio of the triamine raw material to the palladium catalyst in the palladium-catalyzed coupling reaction is 1:0.006 to 1:0.1, more preferably 1:0.01 to 1:0.1. Preferably, in step (1), the molar ratio of the triamine raw material to the ligand in the palladium-catalyzed coupling reaction is 1:0.01 to 1:0.5, more preferably 1:0.01 to 1:0.25.

[0045] Preferably, in step (1), the molar ratio of triamine raw material to base in the palladium-catalyzed coupling reaction is 1:3 to 1:6, more preferably 1:3 to 1:4.

[0046] Preferably, in step (1), the reaction temperature in the palladium-catalyzed coupling reaction is 20℃~150℃, more preferably 95℃~100℃.

[0047] Preferably, the solvent used in step (1) includes, but is not limited to, toluene, xylene, tetrahydrofuran, and 1,4-dioxane.

[0048] Preferably, in step (2), the palladium catalyst includes, but is not limited to, palladium acetate, tetratriphenylphosphine palladium, 1,1'-bis(diphenylphosphine)ferrocene palladium dichloride, and bis(dibenzylideneacetone) palladium;

[0049] In step (2), the ligand includes, but is not limited to, Xphos, Ruphos, Sphos, and Xantphos;

[0050] In step (2), the alkali includes, but is not limited to, potassium tert-butoxide, sodium tert-butoxide, and cesium carbonate.

[0051] Preferably, in step (2), the molar ratio of the disubstituted amine to the dihalodiaryl ketone in the palladium-catalyzed coupling reaction is 2:1 to 5:1, more preferably 2:1 to 3.2:1. Preferably, in step (2), the molar ratio of the dihalodiaryl ketone to the palladium catalyst in the palladium-catalyzed coupling reaction is 1:0.006 to 1:0.1, more preferably 1:0.05 to 1:0.1.

[0052] Preferably, in step (2), the molar ratio of the dihalodiaryl ketone to the ligand in the palladium-catalyzed coupling reaction is 1:0.01 to 1:0.5, more preferably 1:0.01 to 1:0.25. Preferably, in step (2), the molar ratio of the dihalodiaryl ketone to the base in the palladium-catalyzed coupling reaction is 1:3 to 1:6, more preferably 1:3 to 1:4.

[0053] Preferably, in step (2), the reaction temperature in the palladium-catalyzed coupling reaction is 20℃~150℃, more preferably 95℃~100℃.

[0054] Preferably, the solvent used in step (2) includes, but is not limited to, toluene, xylene, tetrahydrofuran, and 1,4-dioxane.

[0055] Preferably, in step (3), the condensation reagent used in the dehydration condensation reaction includes, but is not limited to, phosphorus oxychloride, phosphorus pentachloride, phosphorus pentoxide, etc., and more preferably phosphorus oxychloride.

[0056] Preferably, in step (3), the temperature of the condensation reaction is 20℃~150℃, more preferably 30℃~80℃.

[0057] Preferably, in step (3), the solvent used includes, but is not limited to, dichloromethane, xylene, o-dichlorobenzene, dichloroethane, etc.

[0058] In this application, "above" includes the number itself. For example, integers greater than or equal to 1 include 1.

[0059] In this application, the disclosed terms "1≤a≤5" and "1≤c≤5" mean that they cover all integer values ​​and any subset combinations within this numerical range. Specifically, "1≤a≤5" means that the value of a includes all integers such as 1, 2, 3, ..., 5, and "1≤c≤5" means that the value of c also includes all integers such as 1, 2, 3, ..., 5; at the same time, this range covers any subset formed by the above integers (such as a taking values ​​of 1~3, 3~5, c taking values ​​of 1~3, 2~4, etc., or discrete combinations of values ​​such as a=1, 3, 5, etc.). Compared with the prior art, the beneficial effects of this invention are:

[0060] (1) The novel triarylmethane dye molecule provided by the present invention has higher thermal stability, light stability, excellent solubility, and good dispersibility;

[0061] (2) The novel triarylmethane dye molecule provided by the present invention can be mixed with other colorants to prepare mixed or dye-type photoresist pastes, and has good compatibility;

[0062] (3) The synthesis method provided by the present invention has a simple route, a wide range of reagent sources, and is easy to scale up. Attached Figure Description

[0063] Figure 1 The compound IA1 prepared in Example 1 of this invention 1 H-NMR spectrum;

[0064] Figure 2 The compound IB1 prepared in Example 1 of this invention 1 H-NMR spectrum;

[0065] Figure 3 The compound P1 prepared in Example 1 of this invention 1 H-NMR spectrum;

[0066] Figure 4 The compound P2 prepared in Example 2 of this invention 1 H-NMR spectrum;

[0067] Figure 5 The compound P3 prepared in Example 3 of this invention 1 H-NMR spectrum;

[0068] Figure 6 The UV-vis absorption spectrum of compound P1 prepared in Example 1 of this invention in PGMEA;

[0069] Figure 7 This is a thermogravimetric diagram of compound P1 prepared in Example 1 of the present invention. Detailed Implementation

[0070] To better understand the content of this invention, further description is provided below with reference to specific embodiments and accompanying drawings. It should be understood that these embodiments are only for further illustration of the invention and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the description of this invention, those skilled in the art may make some non-essential modifications or adjustments to the invention, which still fall within the protection scope of this invention.

[0071] Example 1 (Synthesis of compound P1);

[0072] A method for synthesizing a novel triarylmethane dye for blue photoresist pigment paste, comprising the following steps:

[0073] (1) Take a dry and clean 250 mL three-necked flask, place a stir bar of appropriate size on it; add 1,3,5-triaminocyclohexane (1.29 g, 10 mmol, 1.0 eq.), 1-bromonaphthalene (5.18 g, 25 mmol, 2.5 eq.), potassium tert-butoxide (3.37 g, 30 mmol, 3.0 eq.), Xphos (95 mg, 0.2 mmol, 0.02 eq.), palladium acetate (23 mg, 0.1 mmol, 0.01 eq.), and toluene (180 mL), replace with nitrogen for protection, and heat under reflux overnight for 16 h. Take a sample and spot it on a TLC plate. The reactants were completely reacted. Let it cool naturally to room temperature (20~25℃), filter, collect the filtrate and evaporate to dryness. Column chromatography of the residue yielded the target product IA12.75 g, with a yield of 54.2%.

[0074] The chemical structural formula of the intermediate IA1 is as follows:

[0075]

[0076] 1H NMR (400 MHz, Chloroform-d) δ 8.12 – 8.03 (m, 1H), 7.75 (dt, J =8.4, 1.5 Hz, 1H), 7.63 (dt, J = 7.6, 1.4 Hz, 1H), 7.53 (td, J = 7.2, 1.6 Hz,2H), 7.36 – 7.24 (m, 1H), 7.10 (dd, J = 8.1, 1.4 Hz, 1H), 3.81 – 3.74 (m,1H), 1.98 (dt, J = 12.4, 5.7 Hz, 1H), 1.85 – 1.77 (m, 1H).

[0077] The compound IA1 1 See the H-NMR spectrum. Figure 1 .

[0078] (2) Take a dry and clean 250 mL three-necked flask and place a stir bar of appropriate size; add 4,4'-dibromobenzophenone (3.4 g, 10 mmol, 1.0 eq.), diethylamine (1.83 g, 25 mmol, 2.5 eq.), potassium tert-butoxide (3.37 g, 30 mmol, 3.0 eq.), Xphos (95 mg, 0.2 mmol, 0.02 eq.), palladium acetate (23 mg, 0.1 mmol, 0.01 eq.), and toluene (180 mL), replace with nitrogen for protection, and heat under reflux overnight for 16 h. Spot the sample onto a TLC plate. The reaction proceeds completely. Allow to cool naturally to room temperature (20~25℃), filter, and collect the filtrate by rotary evaporation. Column chromatography of the residue yielded the target product IB 12.14 g, with a yield of 66.1%.

[0079] The chemical structural formula of the intermediate IB1 is as follows:

[0080]

[0081] 1H NMR (400 MHz, Chloroform-d) δ 7.69 (d, J = 7.9 Hz, 2H), 6.77 (d, J= 7.9 Hz, 2H), 3.31 (q, J = 7.0 Hz, 4H), 1.16 (t, J = 7.0 Hz, 6H).

[0082] The compound IB1 1 See the H-NMR spectrum. Figure 2 .

[0083] (3) Take a dry and clean 100 mL three-necked flask and place a stir bar of appropriate size; add the obtained intermediates IA1 (5 g, 9.8 mmol, 1.0 eq.) and IB1 (7.04 g, 21.7 mmol, 2.2 eq.) and dry chlorobenzene solvent (50 mL); then add phosphorus oxychloride (3.33 g, 21.7 mmol, 2.2 eq.) dropwise to the above solvent under ice-water bath conditions; after the phosphorus oxychloride is added, raise the above reaction system to 45~50℃ and react for 24 hours; after the reaction is completed, pour the reaction solution into 100 mL of dichloromethane and 100 mL of water, separate the liquids, dry the organic phase with anhydrous sodium sulfate and then evaporate to dryness, and column chromatography of the residue yields the target product P1 10.3 g, with a yield of 68.3%;

[0084] The chemical structural formula of compound P1 is as follows:

[0085]

[0086] Figure 3

[0087] 1H NMR (400 MHz, Chloroform-d) δ 8.13 (dd, J = 8.0, 1.3 Hz, 1H), 8.05 (dd, J = 7.9, 1.4 Hz, 1H), 7.62 (td, J = 7.9, 1.3 Hz, 1H), 7.53 – 7.49 (m,1H), 7.44 – 7.40 (m, 6H), 7.05 – 7.01 (m, 4H), 3.78 (q, J = 5.7 Hz, 1H), 3.29(q, J = 7.0 Hz, 8H), 1.89 (ddt, J = 77.5, 12.4, 5.7 Hz, 2H), 1.16 (t, J = 7.0Hz, 12H).

[0088] The compound P1 1 See the H-NMR spectrum. Figure 3 The UV-vis absorption spectrum of compound P1 in PGMEA is shown in [reference needed]. Figure 6 The thermogravimetric diagram of compound P1 is shown below. Figure 7 .

[0089] Example 2 (Synthesis of compound P2)

[0090] A method for synthesizing a novel triarylmethane dye for blue photoresist pigment paste, comprising the following steps:

[0091] (1) Take a dry and clean 250 mL three-necked flask and place a stir bar of appropriate size; add 4,4'-dibromobenzophenone (3.4 g, 10 mmol, 1.0 eq.), N-ethyl-o-methylaniline (3.03 g, 25 mmol, 2.5 eq.), potassium tert-butoxide (3.37 g, 30 mmol, 3.0 eq.), Xphos (95 mg, 0.2 mmol, 0.02 eq.), palladium acetate (23 mg, 0.1 mmol, 0.01 eq.), and toluene (180 mL), replace with nitrogen for protection, and heat under reflux overnight for 16 h. Spot the sample onto a TLC plate. The reaction proceeds completely. Allow to cool naturally to room temperature (20~25℃), filter, and collect the filtrate by rotary evaporation. Column chromatography of the residue yielded the target product IB2 2.37 g, with a yield of 52.3%.

[0092] The chemical structural formula of the intermediate IB2 is as follows:

[0093]

[0094] (2) Take a dry and clean 100 mL three-necked flask and place a stir bar of appropriate size; add the obtained intermediates IA1 (5 g, 9.8 mmol, 1.0 eq.) and IB2 (9.73 g, 21.7 mmol, 2.2 eq.) and dry chlorobenzene solvent (50 mL); then add phosphorus oxychloride (3.33 g, 21.7 mmol, 2.2 eq.) dropwise to the above solvent under ice-water bath conditions; after the phosphorus oxychloride is added, raise the above reaction system to 45~50℃ and react for 24 hours; after the reaction is completed, pour the reaction solution into 100 mL of dichloromethane and 100 mL of water, separate the liquids, dry the organic phase with anhydrous sodium sulfate and then evaporate to dryness, and precipitate the residue by column chromatography to obtain the target product P2 9.1 g, with a yield of 48.6%;

[0095] The chemical structural formula is as follows:

[0096]

[0097] 1H NMR (400 MHz, Chloroform-d) δ 8.13 (dd, J = 8.0, 1.3 Hz, 1H), 8.05 (dd, J = 7.8, 1.4 Hz, 1H), 7.65 – 7.60 (m, 1H), 7.57 – 7.53 (m, 4H), 7.51(td, J = 7.8, 1.3 Hz, 1H), 7.42 (s, 2H), 7.37 – 7.31 (m, 4H), 7.20 – 7.14 (m,4H), 7.09 – 7.02 (m, 2H), 6.95 – 6.92 (m, 2H), 3.88 (q, J = 7.4 Hz, 4H), 3.79(q, J = 5.7 Hz, 1H), 2.26 (d, J = 0.7 Hz, 6H), 1.99 (dd, J = 12.5, 5.7 Hz,1H), 1.79 (dt, J = 12.4, 5.7 Hz, 1H), 1.27 (t, J = 7.5 Hz, 6H).

[0098] The compound P2 1 See the H-NMR spectrum. Figure 4 .

[0099] Example 3 (Synthesis of compound P3)

[0100] A method for synthesizing a triarylmethane dye for blue photoresist pigment paste, comprising the following steps:

[0101] (1) Take a dry and clean 250 mL three-necked flask, place a stir bar of appropriate size on it; add 4,4'-dibromobenzophenone (3.4 g, 10 mmol, 1.0 eq.), N-ethyl-2,6-dimethylaniline (3.03 g, 25 mmol, 2.5 eq.), potassium tert-butoxide (3.37 g, 30 mmol, 3.0 eq.), Xphos (95 mg, 0.2 mmol, 0.02 eq.), palladium acetate (23 mg, 0.1 mmol, 0.01 eq.), and toluene (180 mL), replace with nitrogen for protection, and heat under reflux overnight for 16 h. Take a sample and spot it on a TLC plate. The reactants were completely reacted. Let it cool naturally to room temperature (20~25℃), filter, collect the filtrate and evaporate to dryness. Column chromatography of the residue gave 2.71 g of the target product IB3, with a yield of 56.8%.

[0102] The chemical structural formula of the intermediate IB3 is as follows:

[0103]

[0104] (2) Take a dry and clean 100 mL three-necked flask and place a stir bar of appropriate size; add the obtained intermediates IA1 (5 g, 9.8 mmol, 1.0 eq.) and IB3 (10.34 g, 21.7 mmol, 2.2 eq.) and dry chlorobenzene solvent (50 mL); then add phosphorus oxychloride (3.33 g, 21.7 mmol, 2.2 eq.) dropwise to the above solvent under ice-water bath conditions; after the phosphorus oxychloride is added, raise the above reaction system to 45~50℃ and react for 24 hours; after the reaction is completed, pour the reaction solution into 100 mL of dichloromethane and 100 mL of water, separate the liquids, dry the organic phase with anhydrous sodium sulfate and then evaporate to dryness, and precipitate the residue by column chromatography to obtain the target product P3 10.20 g, with a yield of 52.2%;

[0105] The chemical structural formula is as follows:

[0106]

[0107] 1H NMR (400 MHz, Chloroform-d) δ 8.13 (dd, J = 8.0, 1.3 Hz, 1H), 8.05 (dd, J = 7.9, 1.4 Hz, 1H), 7.62 (td, J = 7.9, 1.3 Hz, 1H), 7.57 – 7.49 (m,5H), 7.42 (s, 2H), 7.35 – 7.31 (m, 4H), 7.10 – 7.00 (m, 6H), 3.86 (q, J = 7.4Hz, 4H), 3.79 (p, J = 5.7 Hz, 1H), 2.22 (d, J = 0.5 Hz, 12H), 1.98 (dt, J =12.4, 5.7 Hz, 1H), 1.79 (dt, J = 12.4, 5.7 Hz, 1H), 1.23 (t, J = 7.4 Hz, 6H).

[0108] The compound P3 1 See the H-NMR spectrum. Figure 5 .

[0109] Comparative Example 1

[0110] Commercially available dye Basic Blue 7 was used as Comparative Example 1.

[0111] The chemical structural formula of Basic Blue 7 is as follows:

[0112]

[0113] Effect Experiment Example

[0114] I. Determination of the UV-Vis Absorption Spectroscopy of Triarylmethane Dye Molecules

[0115] The triarylmethane dye molecules prepared in Examples 1-3 and Comparative Example 1 were formulated into 10 μmol / L solutions using propylene glycol methyl ether acetate (PGMEA) as the solvent, and their absorption spectra were measured using a UV-Vis spectrophotometer. The molar extinction coefficient of the dye was calculated using the following formula:

[0116] Α = εcl

[0117] In the formula, A is the absorption intensity; ε is the molar extinction coefficient, L / (mol·cm); c is the concentration, mol / L; and l is the thickness of the absorption layer, cm.

[0118] The UV-Vis absorption spectra of the novel blue triarylmethane dyes prepared in Examples 1-3 and the dye molecules prepared in Comparative Example 1 are shown in Table 1.

[0119] Table 1. UV-Vis absorption spectra of the novel blue triarylmethane dyes prepared in Examples 1-3 and the dye molecules in Comparative Example 1.

[0120]

[0121] As shown in Table 1, the maximum absorption wavelength of the triarylmethane dye molecules prepared in Examples 1-3 is significantly red-shifted compared to Comparative Example 1, and the absorption coefficient is significantly improved. Furthermore, the triaryl dye molecule prepared in Example 1 has the highest molar absorption coefficient.

[0122] II. Solubility Test of Dye Molecules

[0123] The solubility of the dye molecules prepared in Examples 1-3 and Comparative Example 1 in PGMEA and N,N-dimethylformamide (DMF) was tested. A certain amount of dye and organic solvent were weighed, sonicated at room temperature for 10 min, and allowed to stand for 24 h. The mixture was then filtered three times using a filter membrane. The filtrate was dried, and the solubility S of the dye was calculated.

[0124] S = 100M S / M L

[0125] In the formula, M S This refers to the mass of the dye after drying, in grams (g); in milliliters (M). L This is the mass of the solution, in grams (g).

[0126] The solubility test results of the dye molecules prepared in Examples 1-3 and Comparative Example 1 are shown in Table 2.

[0127] Table 2. Solubility test results of dye molecules prepared in Examples 1-3 and Comparative Example 1

[0128] dye <![CDATA[S PGMEA ]]> <![CDATA[S DMF ]]> Example 1 10.5 2.2 Example 2 13.4 2.8 Example 3 13.2 2.8 Comparative Example 1 0.1 0.3

[0129] As shown in Table 2, the triarylmethane dye molecules prepared in Examples 1-3 showed significantly higher solubility in both PGMEA and DMF compared to the known molecules in Comparative Example 1. Among them, the triarylmethane dye molecules prepared in Example 2 showed the best solubility in both PGMEA and DMF.

[0130] III. Thermal stability test of dye molecules

[0131] The fabrication of color filters involves a post-baking process at 200℃ or higher, as industrial applications require dye molecules to exhibit good thermal stability at this temperature. Thermogravimetric analysis (TGA) is used to evaluate the thermal stability of synthetic dyes. Under nitrogen protection, the synthetic dyes are heated from room temperature to 500℃ at a rate of 10℃ / min to determine their thermal decomposition temperature T. d .

[0132] The thermal stability test results of the dye molecules prepared in Examples 1-3 and Comparative Example 1 are shown in Table 3.

[0133] Table 3. Thermal stability test results of dye molecules prepared in Examples 1-3 and Comparative Example 1

[0134] dye <![CDATA[T d (℃)]]> Weight loss rate (230℃) / % Example 1 268.4 5.56 Example 2 250.0 7.55 Example 3 261.3 7.21 Comparative Example 1 - 44.94

[0135] As shown in Table 3, the T values ​​of the triarylmethane dye molecules prepared in Examples 1-3 are... d Within the temperature range of 250~270℃, the weight loss rate of the triarylmethane dye P1 obtained in Example 1 was <5% at 230℃, indicating that the thermal stability of the dye molecules was significantly improved compared to the original triarylmethane dyes.

[0136] This invention designs an innovative class of triarylmethane dyes, particularly suitable for formulating high-performance blue photoresist color pastes. These dyes not only significantly enhance the brightness of the color paste but also possess the following excellent properties: outstanding optical performance, excellent dispersibility, and superior tinting strength. Furthermore, the compounds exhibit remarkable thermal stability. In terms of the preparation process, the procedures developed in this invention are simple and efficient, making them highly suitable for large-scale industrial production.

[0137] The foregoing description is not intended to limit the invention, nor is the invention limited to the examples given. Any changes, modifications, additions, or substitutions made by those skilled in the art within the scope of the invention should also be considered within the protection scope of the invention.

Claims

1. A novel blue triarylmethane dye for blue photoresist color paste, characterized in that, The chemical structural formula of the triarylmethane-containing dye is as follows: The symbols in the formula represent the following meanings: R 1 -R 4 Each of these can independently represent a hydrogen atom, an alkyl group optionally having a substituent, a cycloalkyl group optionally having a substituent, and an aryl group optionally having a substituent; Ar represents various substituted or unsubstituted aromatic groups; A represents an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, or an aryl group that may have a substituent; B b- Indicates a b-valent anion; a and c represent integers greater than 1; Multiple R1, R2, R3, R4 and Ar may be the same or different.

2. The novel blue triarylmethane dye for blue photoresist color paste as described in claim 1, characterized in that, R 1 -R 4 Each of the following independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms optionally having a substituent, a cycloalkyl group having 3 to 20 carbon atoms optionally having a substituent, and an aryl group having 6 to 20 carbon atoms optionally having a substituent; Ar represents a substituted or unsubstituted aromatic group consisting of 6 to 20 carbon atoms; A represents a saturated cycloalkyl group consisting of 3 to 10 carbon atoms; and R1 and R3 are the same, and R2 and R4 are the same.

3. A method for synthesizing a novel blue triarylmethane dye for blue photoresist pigments as described in claim 1 or 2, characterized in that, Includes the following steps: (1) Dissolve the triamine raw material MA in a solvent, add palladium catalyst, ligand and base, and react with aryl halogen under an inert atmosphere to obtain intermediate IA; the triamine raw material is alkyltriamine or aryltriamine; the halogen in the aryl halogen is chlorine, bromine or iodine; (2) Dissolve the dihalodiaryl ketone MB in a solvent, add palladium catalyst, ligand and base, and react with disubstituted amine under an inert atmosphere to obtain the target intermediate IB; the halogen in the dihalodiaryl ketone MB is chlorine, bromine or iodine; (3) Intermediate IA and intermediate IB are condensed to obtain a novel blue triarylmethane dye P; The above synthetic route is as follows: The symbols in the formula represent the following meanings: R 1 -R 4 Each of these can independently represent a hydrogen atom, an alkyl group optionally having a substituent, a cycloalkyl group optionally having a substituent, and an aryl group optionally having a substituent; Ar represents various substituted or unsubstituted aromatic groups; A represents an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, or an aryl group that may have a substituent; B b- Indicates a b-valent anion; a and c represent integers greater than 1; Multiple R1, R2, R3, R4 and Ar may be the same or different.

4. The method for synthesizing a novel blue triarylmethane dye for blue photoresist pigment paste as described in claim 3, characterized in that, R 1 -R 4 Each of the following independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms optionally having a substituent, a cycloalkyl group having 3 to 20 carbon atoms optionally having a substituent, and an aryl group having 6 to 20 carbon atoms optionally having a substituent; Ar represents a substituted or unsubstituted aromatic group consisting of 6 to 20 carbon atoms; A represents a saturated cycloalkyl group consisting of 3 to 10 carbon atoms; and R1 and R3 are the same, and R2 and R4 are the same.

5. The method for synthesizing a novel blue triarylmethane dye for blue photoresist pigments as described in claim 4, characterized in that, In step (1), the molar ratio of the triamine raw material MA to the aryl halide is 1:2 to 1:6; In step (1), the molar ratio of the triamine raw material MA to the palladium catalyst is 1:0.006 to 1:0.1; In step (1), the molar ratio of the triamine raw material MA to the ligand is 1:0.01 to 1:0.5; In step (1), the molar ratio of the triamine raw material MA to the alkali is 1:3 to 1:6; In step (1), the solvents used include, but are not limited to, toluene, xylene, tetrahydrofuran, and 1,4-dioxane.

6. The method for synthesizing a novel blue triarylmethane dye as described in claim 4, characterized in that, In step (1), the reaction temperature is 20℃~150℃.

7. The method for synthesizing a novel blue triarylmethane dye as described in claim 4, characterized in that, In step (2), the molar ratio of the disubstituted amine to the dihalodiaryl ketone MB is 2:1 to 5:1; In step (2), the palladium catalyst includes, but is not limited to, palladium acetate, tetratriphenylphosphine palladium, 1,1'-bis(diphenylphosphine)ferrocene palladium dichloride, and bis(dibenzylideneacetone) palladium; In step (2), the ligands include, but are not limited to, Xphos, Ruphos, Sphos, and Xantphos; In step (2), the alkali includes, but is not limited to, potassium tert-butoxide, sodium tert-butoxide, and cesium carbonate; In step (2), the molar ratio of the disubstituted amine to the dihalodiaryl ketone is 2:1 to 5:1; In step (2), the molar ratio of the dihalodiaryl ketone MB to the palladium catalyst is 1:0.006 to 1:0.1; In step (2), the molar ratio of the dihalodiaryl ketone MB to the ligand is 1:0.01 to 1:0.5; in step (2), the molar ratio of the dihalodiaryl ketone MB to the base is 1:3 to 1:6; in step (2), the solvent used includes, but is not limited to, toluene, xylene, tetrahydrofuran, and 1,4-dioxane.

8. The method for synthesizing a novel blue triarylmethane dye as described in claim 4, characterized in that, In step (2), the reaction temperature is 20℃~150℃.

9. The method for synthesizing a novel blue triarylmethane dye as described in claim 4, characterized in that, In step (3), the condensation reagent used in the condensation reaction includes, but is not limited to, phosphorus oxychloride, phosphorus pentachloride, and phosphorus pentoxide.

10. The method for synthesizing a novel blue triarylmethane dye as described in claim 4, characterized in that, In step (3), the temperature of the condensation reaction is 25℃~150℃.

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