A dimeric triarylmethane compound for blue photoresist pigments and its synthesis method

Abstract

This invention discloses a dimerized triarylmethane compound for blue photoresist color paste and its synthesis method. The compound is a dimerized blue triarylmethane compound A, which is prepared by the following steps: (1) reacting reactant B with diacid chloride as an acylation reagent to obtain intermediate C; (2) removing the Boc group from intermediate C to obtain intermediate D; (3) cyclizing intermediate D with potassium thiocyanate and acyl chloride reagent to obtain intermediate E; (4) reacting intermediate E with 4,4-bis(diethylamino)benzophenone to obtain F; (5) salting intermediate F to obtain the target dimerized triarylmethane compound A. The dimerized triarylmethane compound of this invention has excellent color performance and is suitable for blue photoresist color paste. It can significantly improve the brightness, transparency, contrast and dispersibility of the color paste, while also possessing high hiding power, strong tinting strength and good thermal and light stability.

Description

Technical Field

[0001] This invention relates to the field of color photoresist technology, specifically to a dimeric triarylmethane compound for blue photoresist pigment 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 candidates 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 compounds that combine high stability, ease of synthesis, and excellent dispersibility. Summary of the Invention

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

[0005] The technical problem to be solved by this invention is to overcome the technical defects of the prior art and further improve the stability of compounds used in photoresist. This invention provides a dimerized triarylmethane compound for blue photoresist pigments and its synthesis method. The dimerized triarylmethane compound molecule provided by this invention greatly improves the weather resistance, such as light and heat resistance, through dimerization. Furthermore, due to the greater steric hindrance resulting from dimerization and the presence of more lipid-soluble groups in the molecule itself, its solubility and dispersibility are improved.

[0006] These triarylmethane compounds can be mixed with other colorants to form mixed or dye-type 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 dimeric triarylmethane compound for blue photoresist pigments, with the following chemical structural formula:

[0009] ;

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

[0011] R 1 Represents hydrogen atoms, halogen atoms, alkyl substituents, and aryl substituents;

[0012] X represents a linking group;

[0013] Y represents the counter ion.

[0014] Preferably, the linking group is an alkyl substituent or an aryl substituent.

[0015] Preferably, the counterion is a fluoride anion or a sulfonate anion.

[0016] Preferably, the linking group is an alkyl substituent or an aryl substituent with 1 to 20 carbon atoms; wherein the hydrogen atom contained in the alkyl substituent or aryl substituent can be replaced by a halogen atom, the -CH- contained in the alkyl substituent can be replaced by -CO- or -O-, and the aryl substituent can be a common aromatic, aromatic fused ring, or aromatic heterocyclic ring.

[0017] Preferred, R 1 The term represents a hydrogen atom; the linking group is an alkyl substituent with 1 to 20 carbon atoms; the counter ion is one or more of the following: trifluoromethanesulfonate anion, bis(trifluoromethanesulfonyl)imide anion, and p-toluenesulfonate anion.

[0018] More preferably, the linking group is an alkyl substituent with 1 to 3 carbon atoms. The -CH- in the alkyl substituent can be replaced by -O-. Preferably, when the alkyl substituent of the linking group contains an ether bond, the ether bond is not at the end of the substituent. More preferably, X is selected from -CH2-, -CH2-CH2-CH2-, and -CH2-O-CH2-.

[0019] The method for synthesizing a dimeric triarylmethane compound for a blue photoresist pigment, as described above, includes the following steps:

[0020] (1) Using diacyl chloride as an acylation reagent, reacting with reactant B, intermediate C is obtained;

[0021] (2) Remove the Boc group from intermediate C to obtain intermediate D;

[0022] (3) Intermediate D cyclizes with potassium thiocyanate and acyl chloride to obtain intermediate E;

[0023] (4) Intermediate E reacts with 4,4-bis(diethylamino)benzophenone to give F;

[0024] (5) Intermediate F is exchanged with salt to obtain the target dimeric triarylmethane compound A.

[0025] The synthetic route of the synthetic method is as follows:

[0026] ;

[0027] The symbols in the formula represent the following meanings:

[0028] R 1 Represents hydrogen atoms, halogen atoms, alkyl substituents, and aryl substituents;

[0029] X represents a linking group, such as an alkyl substituent or an aryl substituent;

[0030] Y represents a counter ion, which can include fluoride anions and sulfonate anions;

[0031] Preferably, the linking group is an alkyl substituent or an aryl substituent with 1 to 20 carbon atoms; wherein the hydrogen atom contained in the alkyl substituent or aryl substituent can be replaced by a halogen atom, the -CH- contained in the alkyl substituent can be replaced by -CO- or -O-, and the aryl substituent can be a common aromatic, aromatic fused ring, or aromatic heterocyclic ring.

[0032] Preferably, in step (1), the acylation reagent is a diacyl chloride type reagent, and the bridging group constructed therefrom is an alkyl group or an alkyl group containing heteroatoms such as oxygen and nitrogen, more preferably an alkyl group containing heteroatoms such as oxygen and nitrogen. Preferably, the bridging group is an alkyl group containing oxygen atoms.

[0033] In step (1), the acylation reagent is malonyl chloride, glutaryl chloride, or 2,2'-diacetyl chloride oxide.

[0034] Preferably, in step (1), the molar ratio of the diacyl chloride reagent to reactant B is 1:1 to 1:2.5, and more preferably, the molar ratio is 1:1.5 to 1:2.

[0035] Preferably, in step (1), the acid-binding agent used is one or more of triethylamine, N,N-diisopropylethylamine, pyridine, trimethylamine, and diethylamine, more preferably one of triethylamine and N,N-diisopropylethylamine.

[0036] Preferably, in step (1), the solvent used is one or more of dichloromethane, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, N-methylpyrrolidone, chloroform or xylene, more preferably one of dichloromethane, acetonitrile, and tetrahydrofuran.

[0037] Preferably, in step (1), the molar ratio of the acid-binding agent to the diacyl chloride reagent is 1:1 to 1:5, more preferably 1:2 to 1:4.

[0038] Preferably, in step (1), the reaction temperature is 0℃~70℃, more preferably 0℃~40℃.

[0039] Preferably, in step (1), the catalyst used in the reaction is 4-dimethylaminopyridine.

[0040] Preferably, in step (2), the deBoc group removal reagent used is one or more of trifluoroacetic acid, hydrochloric acid, formic acid, p-toluenesulfonic acid, and acetic acid; more preferably, it is one of trifluoroacetic acid, hydrochloric acid, and formic acid.

[0041] Preferably, in step (2), the molar ratio of intermediate C to the Boc group removal reagent is 1:4 to 1:20, more preferably 1:4 to 1:10.

[0042] Preferably, in step (2), the solvent used is one or more of dichloromethane, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, N-methylpyrrolidone, chloroform or xylene, more preferably one of dichloromethane, acetonitrile, and tetrahydrofuran.

[0043] Preferably, in step (2), the reaction temperature is 0℃~70℃, more preferably 0℃~40℃.

[0044] Preferably, in step (3), the acyl chloride reagent used is benzoyl chloride or its derivative.

[0045] Preferably, in step (3), the molar ratio of intermediate D to acyl chloride reagent is 1:2 to 1:8, more preferably 1:2 to 1:4.

[0046] Preferably, in step (3), the molar ratio of intermediate D to potassium thiocyanate is 1:2 to 1:10, more preferably 1:2 to 1:4.

[0047] Preferably, in step (3), the acid used is one or more of hydrochloric acid, acetic acid, chloroacetic acid, formic acid, and sulfuric acid, more preferably one of acetic acid and chloroacetic acid.

[0048] Preferably, in step (3), the alkali used is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and cesium carbonate, more preferably one of sodium hydroxide and potassium hydroxide.

[0049] Preferably, in step (3), the solvent used is one or more of dichloromethane, tetrahydrofuran, acetone, dichloroethane, and chloroform, more preferably one of tetrahydrofuran and acetone.

[0050] Preferably, in step (3), the reaction temperature is 0℃~70℃, more preferably 0℃~40℃.

[0051] Preferably, in step (4), the Lewis acid used is one or more of phosphorus oxychloride, concentrated sulfuric acid, phosphorus trichloride, and phosphorus pentachloride, more preferably one of phosphorus oxychloride and concentrated sulfuric acid.

[0052] Preferably, in step (4), the molar ratio of intermediate E to 4,4-bis(diethylamino)benzophenone is 1:1.5 to 1:10, more preferably 1:1.5 to 1:5.

[0053] Preferably, in step (4), the solvent used is one or more of dichloroethane, xylene, toluene, chloroform, and dichloromethane, more preferably one of xylene and toluene.

[0054] Preferably, in step (4), the reaction temperature is 0℃~200℃, more preferably 50℃~150℃.

[0055] Preferably, in step (5), the counter anionic reagent used is one or more of sodium trifluoromethanesulfonate, lithium bis(trifluoromethanesulfonyl)imide, and sodium p-toluenesulfonate, more preferably one of sodium trifluoromethanesulfonate and lithium bis(trifluoromethanesulfonyl)imide.

[0056] Preferably, in step (5), the molar ratio of intermediate F to counter anionic reagent is 1:2 to 1:10, more preferably 1:2 to 1:5.

[0057] Preferably, in step (5), the solvent used is one or more of dichloroethane, dichloromethane, N,N-dimethylformamide, methanol, and tetrahydrofuran, more preferably one of dichloromethane and N,N-dimethylformamide.

[0058] Preferably, in step (5), the reaction temperature is 0℃~100℃, more preferably 30℃~70℃.

[0059] Compared with the prior art, the beneficial effects of the present invention are:

[0060] (1) The dimeric triarylmethane compounds provided by this invention have higher thermal stability, light stability, excellent solubility, and good dispersibility;

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

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

[0063] Figure 1 The compound D1 prepared in Example 1 of this invention 1 H-NMR spectrum;

[0064] Figure 2 The compound E1 prepared in Example 1 of this invention 1 H-NMR spectrum;

[0065] Figure 3 The compound F1 prepared in Example 1 of this invention 1 H-NMR spectrum;

[0066] Figure 4 The UV-vis absorption spectrum of compound A1 prepared in Example 1 of this invention in PGMEA;

[0067] Figure 5 This is a thermogravimetric diagram of compound A1 prepared in Example 1 of the present invention. Detailed Implementation

[0068] 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.

[0069] Example 1 (Synthesis of compound A1);

[0070] A method for synthesizing a triarylmethane compound for blue photoresist pigment, comprising the following steps:

[0071] (1) The following reaction was carried out under nitrogen protection. A dry and clean 1000 mL three-necked flask was placed with a stir bar of appropriate size. 4-(Boc-amino)phenol (79.42 g, 0.38 mol, 1.9 eq.), DIPEA (77.4 g, 0.6 mol, 3.0 eq.), and DMAP (1.22 g, 0.01 mol, 0.05 eq.) were dissolved in 500 mL DCM and placed in an ice-salt bath. Malonyl chloride (28.19 g, 0.2 mol, 1.0 eq.) was slowly added dropwise at 0 °C. After the addition was complete, the reaction was carried out at room temperature for 3 hours.

[0072] After the reaction was completed, the reaction solution was filtered, the filtrate was washed with saturated sodium bicarbonate aqueous solution, then washed with water once, dried with anhydrous sodium sulfate, filtered again, the filtrate was collected, evaporated to dryness under reduced pressure, and then purified by column chromatography with a development system of PE / EA = 40:1-30:1, to obtain 87.57 g of white solid intermediate C1, with a yield of 94.7%.

[0073] The chemical structural formula of intermediate C1 is as follows:

[0074] ;

[0075] (2) Take a dry and clean 2000 mL three-necked flask and place a stir bar of appropriate size; dissolve intermediate C1 (87.57 g, 0.19 mol, 1 eq.) in 500 mL DCM, place it in an ice-salt bath, and slowly add trifluoroacetic acid (164.19 g, 1.44 mol, 8.0 eq.) at 0 °C. After the addition is complete, react at room temperature for 3 hours.

[0076] After the reaction was completed, 800 mL of saturated sodium bicarbonate aqueous solution was added to the reaction system, stirred for 20 minutes, extracted, and the organic phase was washed twice with 1% KOH aqueous solution, dried with anhydrous sodium sulfate, filtered again, and the filtrate was collected, evaporated to dryness under reduced pressure, and then purified by column chromatography with a development system of PE / EA = 40:1-30:1, to obtain 48.10 g of white solid intermediate D1, with a yield of 93.3%.

[0077] Its structure and purity were determined using NMR, as shown below: 1 H NMR (500 MHz, DMSO-d) δ 7.05 (d, J= 1.3 Hz, 2H), 7.03 (d, J = 1.2 Hz, 2H), 6.71 (d, J = 1.3 Hz, 2H), 6.70 (d, J= 1.3 Hz, 2H), 3.93 (s, 4H), 3.71 (s, 2H).

[0078] The chemical structural formula of the intermediate D1 is as follows:

[0079] ;

[0080] (3) The following reaction was carried out under nitrogen protection. A dry and clean 2000 mL three-necked flask was placed with a stir bar of appropriate size. Potassium thiocyanate (39.18 g, 0.40 mol, 2.4 eq.) was dissolved in 500 mL acetone and stirred at room temperature for 30 minutes. Then benzoyl chloride (51.95 g, 0.37 mol, 2.2 eq.) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 1 hour. An ice-salt bath was then performed. Intermediate D1 (48.1 g, 0.168 mol, 1.0 eq.) was added at 0 °C. Then 35 mL of 30% sodium hydroxide aqueous solution was added dropwise. The mixture was stirred for 30 minutes. Then chloroacetic acid (33.34 g, 0.35 mol, 2.1 eq.) was added dropwise. After the reaction was completed, the mixture was refluxed at 125 °C for 7 hours.

[0081] After the reaction was completed, the reaction solution was cooled to room temperature, ethyl acetate and water were added and stirred for 30 minutes, the mixture was extracted and separated, the organic phase was washed twice with water and once with saturated brine, the filtrate was dried with anhydrous sodium sulfate, filtered again, the filtrate was collected, evaporated to dryness under reduced pressure, and then purified by column chromatography with a development system of PE / EA = 10:1-5:1, to give a pale yellow oily intermediate E190.70 g, with a yield of 89.3%.

[0082] Its structure and purity were determined using NMR, as shown below: 1 H NMR (500 MHz, DMSO-d) δ 9.38 (s,2H), 7.85–7.81 (m, 4H), 7.54 (s, 2H), 7.51–7.46 (m, 4H), 7.45–7.42 (m, 4H),7.42–7.38 (m, 2H), 7.14–7.10 (m, 4H), 3.71 (s, 2H).

[0083] The chemical structural formula of the intermediate E1 is as follows:

[0084] ;

[0085] (4) Take a dry and clean 2000 mL three-necked flask and place a stir bar of appropriate size; dissolve intermediate E1 (90.70 g, 0.15 mol, 1 eq.) in 500 mL xylene, add phosphorus oxychloride (46.00 g, 0.3 mol, 2.0 eq.) at room temperature, stir at room temperature for 0.5 hours, then add 4,4-bis(diethylamino)benzophenone (97.2 g, 0.3 mol, 2.0 eq.), and react at 105 °C for 7 hours after the reaction is completed.

[0086] After the reaction was completed, the reaction solution was cooled to room temperature, ethyl acetate and water were added and stirred for 30 minutes, the mixture was extracted and separated, the organic phase was washed twice with water and once with saturated brine, the filtrate was dried with anhydrous sodium sulfate, filtered again, the filtrate was collected, evaporated to dryness under reduced pressure, and then purified by column chromatography with a DCM / MeOH ratio of 30:1-10:1 to give a blue solid intermediate F1188.28 g, with a yield of 97.3%.

[0087] Its structure and purity were determined using NMR, as shown below: 1 H NMR (500 MHz, DMSO- d 6) δ 10.92 (s,2H), 7.74 – 7.68 (m, 4H), 7.58 – 7.52 (m, 4H), 7.49 – 7.40 (m, 15H), 7.16 –7.10 (m, 4H), 7.09 – 7.03 (m, 8H), 3.69 (s, 2H), 3.33 (q, J = 7.0 Hz, 16H), 1.15 (t, J = 7.0 Hz, 23H).

[0088] The chemical structural formula of the intermediate F1 is as follows:

[0089] ;

[0090] (5) Take a dry and clean 2000 mL three-necked flask and place a stir bar of appropriate size; dissolve intermediate F1 (188.28 g, 0.146 mol, 1 eq.) in 800 mL N,N-dimethylformamide, add lithium bis(trifluoromethanesulfonyl)imide (96.40 g, 0.336 mol, 2.3 eq.) at room temperature, and stir at 50 °C for 3 hours.

[0091] After the reaction was completed, the reaction solution was cooled to room temperature, and the reaction solution was added dropwise to 3 L of water. The mixture was stirred for 1 hour, filtered, and the filter cake was collected and dried under vacuum at 50 °C to obtain 213.59 g of blue triarylmethane compound A1 solid, with a yield of 82.19%.

[0092] The chemical structural formula of intermediate A1 is as follows:

[0093] ;

[0094] The UV-vis absorption spectrum of compound A1 in PGMEA is shown below. Figure 4 The thermogravimetric diagram of compound A1 is shown below. Figure 5 .

[0095] Example 2 (Synthesis of compound A2);

[0096] A method for synthesizing a triarylmethane compound for blue photoresist pigment, comprising the following steps:

[0097] (1) The following reaction was carried out under nitrogen protection. A dry and clean 1000 mL three-necked flask was placed with a stir bar of appropriate size. 4-(Boc-amino)phenol (79.42 g, 0.38 mol, 1.9 eq.), DIPEA (77.4 g, 0.6 mol, 3.0 eq.), and DMAP (1.22 g, 0.01 mol, 0.05 eq.) were dissolved in 500 mL DCM and placed in an ice-salt bath. Glutaryl chloride (33.80 g, 0.2 mol, 1.0 eq.) was slowly added dropwise at 0 °C. After the addition was complete, the reaction was carried out at room temperature for 3 hours.

[0098] After the reaction was completed, the reaction solution was filtered, the filtrate was washed with saturated sodium bicarbonate aqueous solution, then washed with water once, dried with anhydrous sodium sulfate, filtered again, the filtrate was collected, evaporated to dryness under reduced pressure, and then purified by column chromatography with a development system of PE / EA = 40:1-30:1, to obtain 95.71 g of white solid intermediate C2, with a yield of 93.0%.

[0099] The chemical structural formula of intermediate C2 is as follows:

[0100] ;

[0101] (2) Take a dry and clean 2000 mL three-necked flask and place a stir bar of appropriate size; dissolve intermediate C2 (95.71 g, 0.186 mol, 1 eq.) in 500 mL DCM, place it in an ice-salt bath, and slowly add trifluoroacetic acid (169.66 g, 1.49 mol, 8.0 eq.) at 0 °C. After the addition is complete, react at room temperature for 3 hours.

[0102] After the reaction was completed, 800 mL of saturated sodium bicarbonate aqueous solution was added to the reaction system, stirred for 20 minutes, extracted, and the organic phase was washed twice with 1% KOH aqueous solution, dried with anhydrous sodium sulfate, filtered again, and the filtrate was collected, evaporated to dryness under reduced pressure, and then purified by column chromatography with a development system of PE / EA = 40:1-30:1, to obtain 53.44 g of white solid intermediate D2, with a yield of 91.40%.

[0103] The chemical structural formula of the intermediate D2 is as follows:

[0104] ;

[0105] (3) The following reaction was carried out under nitrogen protection. A dry and clean 2000 mL three-necked flask was placed with a stir bar of appropriate size. Potassium thiocyanate (39.96 g, 0.41 mol, 2.4 eq.) was dissolved in 500 mL acetone and stirred at room temperature for 30 minutes. Then benzoyl chloride (52.51 g, 0.37 mol, 2.2 eq.) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 1 hour. An ice-salt bath was then performed. Intermediate D2 (53.44 g, 0.17 mol, 1.0 eq.) was added at 0 °C. Then 35 mL of 30% sodium hydroxide aqueous solution was added dropwise. The mixture was stirred for 30 minutes. Then chloroacetic acid (34.29 g, 0.36 mol, 2.1 eq.) was added dropwise. After the reaction was completed, the mixture was refluxed at 125 °C for 7 hours.

[0106] After the reaction was completed, the reaction solution was cooled to room temperature, ethyl acetate and water were added and stirred for 30 minutes, the mixture was extracted and separated, the organic phase was washed twice with water and once with saturated brine, the filtrate was dried with anhydrous sodium sulfate, filtered again, the filtrate was collected, evaporated to dryness under reduced pressure, and then purified by column chromatography with a development system of PE / EA = 10:1-5:1, to give a pale yellow oily intermediate E288.58 g, yield 82.35%.

[0107] The chemical structural formula of the intermediate E2 is as follows:

[0108] ;

[0109] (4) Take a dry and clean 2000 mL three-necked flask and place a stir bar of appropriate size; dissolve intermediate E2 (88.58 g, 0.14 mol, 1 eq.) in 500 mL xylene, add phosphorus oxychloride (42.93 g, 0.28 mol, 2.0 eq.) at room temperature, stir at room temperature for 0.5 hours, then add 4,4-bis(diethylamino)benzophenone (90.72 g, 0.28 mol, 2.0 eq.), and react at 105 °C for 7 hours after the reaction is completed.

[0110] After the reaction was completed, the reaction solution was cooled to room temperature, ethyl acetate and water were added and stirred for 30 minutes, the mixture was extracted and separated, the organic phase was washed twice with water and once with saturated brine, the filtrate was dried with anhydrous sodium sulfate, filtered again, the filtrate was collected, evaporated to dryness under reduced pressure, and then purified by column chromatography with a DCM / MeOH ratio of 30:1-10:1 to give a blue solid intermediate F2168.79 g, yield 91.43%.

[0111] The chemical structural formula of the intermediate F2 is as follows:

[0112] ;

[0113] (5) Take a dry and clean 2000 mL three-necked flask and place a stir bar of appropriate size; dissolve intermediate F2 (168.79 g, 0.128 mol, 1 eq.) in 800 mL N,N-dimethylformamide, add lithium bis(trifluoromethanesulfonyl)imide (84.52 g, 0.295 mol, 2.3 eq.) at room temperature, and stir at 50 °C for 3 hours.

[0114] After the reaction was completed, the reaction solution was cooled to room temperature, and the reaction solution was added dropwise to 3 L of water. The mixture was stirred for 1 hour, filtered, and the filter cake was collected and dried under vacuum at 50 °C to obtain 198.87 g of blue triarylmethane compound A2 solid, with a yield of 85.94%.

[0115] The chemical structural formula of intermediate A2 is as follows:

[0116] ;

[0117] Example 3 (Synthesis of compound A3);

[0118] A method for synthesizing a triarylmethane compound for blue photoresist pigment, comprising the following steps:

[0119] (1) The following reaction was carried out under nitrogen protection. A dry and clean 1000 mL three-necked flask was placed with a stir bar of appropriate size. 4-(Boc-amino)phenol (79.42 g, 0.38 mol, 1.9 eq.), DIPEA (77.4 g, 0.6 mol, 3.0 eq.), and DMAP (1.22 g, 0.01 mol, 0.05 eq.) were dissolved in 500 mL DCM and placed in an ice-salt bath. 2,2'-diacetyl chloride oxide (34.20 g, 0.2 mol, 1.0 eq.) was slowly added dropwise at 0 °C. After the addition was complete, the reaction was carried out at room temperature for 3 hours.

[0120] After the reaction was completed, the reaction solution was filtered, the filtrate was washed with saturated sodium bicarbonate aqueous solution, then washed with water once, dried with anhydrous sodium sulfate, filtered again, the filtrate was collected, evaporated to dryness under reduced pressure, and then purified by column chromatography with a development system of PE / EA = 40:1-30:1, to obtain 92.98 g of white solid intermediate C3, with a yield of 90.0%.

[0121] The chemical structural formula of the intermediate C3 is as follows:

[0122] ;

[0123] (2) Take a dry and clean 2000 mL three-necked flask and place a stir bar of appropriate size; dissolve intermediate C3 (92.98 g, 0.18 mol, 1 eq.) in 500 mL DCM, place it in an ice-salt bath, and slowly add trifluoroacetic acid (164.19 g, 1.44 mol, 8.0 eq.) at 0 °C. After the addition is complete, react at room temperature for 3 hours.

[0124] After the reaction was completed, 800 mL of saturated sodium bicarbonate aqueous solution was added to the reaction system, stirred for 20 minutes, extracted, and the organic phase was washed twice with 1% KOH aqueous solution, dried with anhydrous sodium sulfate, filtered again, and the filtrate was collected, evaporated to dryness under reduced pressure, and then purified by column chromatography with a development system of PE / EA = 40:1-30:1, to obtain 54.50 g of white solid intermediate D3, with a yield of 95.5%.

[0125] The chemical structural formula of the intermediate D3 is as follows:

[0126] .

[0127] (3) The following reaction was carried out under nitrogen protection. A dry and clean 2000 mL three-necked flask was placed with a stir bar of appropriate size. Potassium thiocyanate (40.43 g, 0.41 mol, 2.4 eq.) was dissolved in 500 mL acetone and stirred at room temperature for 30 minutes. Then benzoyl chloride (53.13 g, 0.38 mol, 2.2 eq.) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 1 hour. An ice-salt bath was then performed. Intermediate D3 (54.50 g, 0.172 mol, 1.0 eq.) was added at 0 °C. Then 35 mL of 30% sodium hydroxide aqueous solution was added dropwise. The mixture was stirred for 30 minutes. Then chloroacetic acid (34.69 g, 0.36 mol, 2.1 eq.) was added dropwise. After the reaction was completed, the mixture was refluxed at 125 °C for 7 hours.

[0128] After the reaction was completed, the reaction solution was cooled to room temperature, ethyl acetate and water were added and stirred for 30 minutes, the mixture was extracted and separated, the organic phase was washed twice with water and once with saturated brine, the filtrate was dried with anhydrous sodium sulfate, filtered again, the filtrate was collected, evaporated to dryness under reduced pressure, and then purified by column chromatography with a development system of PE / EA = 10:1-5:1, to give a pale yellow oily intermediate E398.38 g, yield 90.11%.

[0129] The chemical structural formula of the intermediate E3 is as follows:

[0130] .

[0131] (4) Take a dry and clean 2000 mL three-necked flask and place a stir bar of appropriate size; dissolve intermediate E3 (98.38 g, 0.155 mol, 1 eq.) in 500 mL xylene, add phosphorus oxychloride (47.53 g, 0.31 mol, 2.0 eq.) at room temperature, stir at room temperature for 0.5 hours, then add 4,4-bis(diethylamino)benzophenone (100.44 g, 0.31 mol, 2.0 eq.), and react at 105 °C for 7 hours after the reaction is completed.

[0132] After the reaction was completed, the reaction solution was cooled to room temperature, ethyl acetate and water were added and stirred for 30 minutes, the mixture was extracted and separated, the organic phase was washed twice with water and once with saturated brine, the filtrate was dried with anhydrous sodium sulfate, filtered again, the filtrate was collected, evaporated to dryness under reduced pressure, and then purified by column chromatography with a DCM / MeOH ratio of 30:1-10:1 to give a blue solid intermediate F3187.53 g, yield 91.61%.

[0133] The chemical structural formula of the intermediate F3 is as follows:

[0134] .

[0135] (5) Take a dry and clean 2000 mL three-necked flask and place a stir bar of appropriate size; dissolve intermediate F3 (187.53 g, 0.142 mol, 1 eq.) in 800 mL N,N-dimethylformamide, add lithium bis(trifluoromethanesulfonyl)imide (93.76 g, 0.33 mol, 2.3 eq.) at room temperature, and stir at 50 °C for 3 hours.

[0136] After the reaction was completed, the reaction solution was cooled to room temperature, and the reaction solution was added dropwise to 3 L of water. The mixture was stirred for 1 hour, filtered, and the filter cake was collected and dried under vacuum at 50 °C to obtain 235.29 g of blue triarylmethane compound A3 solid, with a yield of 91.55%.

[0137] The chemical structural formula of intermediate A3 is as follows:

[0138] .

[0139] Comparative Example 1 (Synthesis of Compound A-1)

[0140] A method for synthesizing a blue triarylmethane compound for blue photoresist pigment paste, comprising the following steps:

[0141] (1) The following reaction was carried out under nitrogen protection. A dry and clean 1000 mL three-necked flask was placed with a stir bar of appropriate size. Potassium thiocyanate (27.61 g, 0.28 mol, 1.4 eq.) was dissolved in 300 mL acetone and stirred at room temperature for 30 minutes. Then benzoyl chloride (33.55 g, 0.24 mol, 1.2 eq.) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 1 hour. An ice-salt bath was then used. N-ethyl-o-toluidine (27.2 g, 0.2 mol, 1.0 eq.) was added at 0 °C. Then 35 mL of 30% sodium hydroxide aqueous solution was added dropwise. The mixture was stirred for 30 minutes. Then chloroacetic acid (34.69 g, 0.36 mol, 3.1 eq.) was added dropwise. After the reaction was completed, the mixture was refluxed at 125 °C for 7 hours.

[0142] After the reaction was completed, the reaction solution was cooled to room temperature, ethyl acetate and water were added and stirred for 30 minutes, the mixture was extracted and separated, the organic phase was washed twice with water and once with saturated brine, the filtrate was dried with anhydrous sodium sulfate, filtered again, the filtrate was collected, evaporated to dryness under reduced pressure, and then purified by column chromatography with a development system of PE / EA = 10:1-5:1, to give a pale yellow oily intermediate C-152.99 g, yield 90.0%.

[0143] The chemical structural formula of intermediate C-1 is as follows:

[0144] .

[0145] (2) Take a dry and clean 1000 mL three-necked flask and place a stir bar of appropriate size; dissolve intermediate C-1 (52.99 g, 0.18 mol, 1 eq.) in 300 mL xylene, add phosphorus oxychloride (27.60 g, 0.18 mol, 1.0 eq.) at room temperature, stir at room temperature for 0.5 hours, then add 4,4-bis(diethylamino)benzophenone (58.32 g, 0.18 mol, 1.0 eq.), and react at 105 °C for 7 hours after the reaction is completed.

[0146] After the reaction was completed, the reaction solution was cooled to room temperature, ethyl acetate and water were added and stirred for 30 minutes, the mixture was extracted and separated, the organic phase was washed twice with water and once with saturated brine, the filtrate was dried with anhydrous sodium sulfate, filtered again, the filtrate was collected, evaporated to dryness under reduced pressure, and then purified by column chromatography with a DCM / MeOH ratio of 30:1-10:1 to give 104.53 g of blue solid intermediate B-1, yield 91.11%.

[0147] The chemical structural formula of intermediate B-1 is as follows:

[0148] ;

[0149] (3) Take a dry and clean 1000 mL three-necked flask and place a stir bar of appropriate size; dissolve intermediate B-1 (104.53 g, 0.164 mol, 1 eq.) in 400 mL N,N-dimethylformamide, add lithium bis(trifluoromethanesulfonyl)imide (60.57 g, 0.21 mol, 1.3 eq.) at room temperature, and stir at 50 °C for 3 hours.

[0150] After the reaction was completed, the reaction solution was cooled to room temperature, and the reaction solution was added dropwise to 3 L of water. The mixture was stirred for 1 hour, filtered, and the filter cake was collected and dried under vacuum at 50 °C to obtain 132.30 g of blue triarylmethane compound A-1 solid, with a yield of 91.46%.

[0151] The chemical structural formula of intermediate A-1 is as follows:

[0152] .

[0153] Effect Experiment Example

[0154] I. Determination of UV-Vis Absorption Spectroscopy of Triarylmethane Dye Molecules

[0155] The triarylmethane dyes 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. The absorption spectra were measured using a UV-Vis spectrophotometer. The molar extinction coefficient of the dyes was calculated using the following formula:

[0156] Α = εcl

[0157] 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.

[0158] The UV-Vis absorption spectra of the triarylmethane dye molecules prepared in Examples 1-3 and Comparative Example 1 are shown in Table 1.

[0159] Table 1. UV-Vis absorption spectra of triarylmethane dye molecules prepared in Examples 1-3 and Comparative Example 1

[0160]

[0161] As shown in Table 1, the triarylmethane dye molecules prepared in Examples 1, 2, and 3 show a slight red shift compared to Comparative Example 1, while the triarylmethane dye molecules prepared in Examples 1 and 3 show a slight blue shift compared to Comparative Example 2. Furthermore, the triarylmethane dye molecules prepared in Example 1 have the highest molar absorptivity.

[0162] II. Solubility Test of Triarylmethane Dye Molecules

[0163] The solubility of triarylmethane 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 minutes, and allowed to stand for 24 hours. The mixture was then filtered three times using a filter membrane. The filtrate was dried, and the solubility S of the dye was calculated.

[0164] S = 100M S / mL

[0165] In the formula, M S The value is the mass of the dye after drying, in g; mL is the mass of the solution, in g.

[0166] The solubility test results of the triarylmethane dye molecules prepared in Examples 1-3 and Comparative Example 1 are shown in Table 2.

[0167] Table 2. Solubility test results of triarylmethane dye molecules prepared in Examples 1-3 and Comparative Example 1

[0168]

[0169] As shown in Table 2, the triarylmethane dye molecules prepared in Examples 1-3 all have good solubility in PGMEA and DMF, among which the triarylmethane dye molecules prepared in Example 1 have the best solubility in PGMEA and DMF.

[0170] III. Thermal stability test of triarylmethane dye molecules

[0171] 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 .

[0172] The thermal stability test results of the triarylmethane dye molecules prepared in Examples 1-3 and Comparative Example 1 are shown in Table 3.

[0173] Table 3. Thermal stability test results of triarylmethane dye molecules prepared in Examples 1-3 and Comparative Example 1

[0174]

[0175] 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 324~349 ℃, the weight loss rate at 230 ℃ is less than 5%, indicating that the above dye molecules have good thermal stability.

[0176] This invention designs an innovative class of triarylmethane dye compounds, which are particularly suitable for formulating high-performance blue photoresist color pastes. This dye not only significantly improves the brightness of the color paste but also possesses the following excellent properties: outstanding optical properties, excellent dispersibility, and superior color strength. Furthermore, the compound exhibits outstanding thermal stability. In terms of the preparation process, the operation procedure developed in this invention is simple and efficient, with significant advantages in production cost, making it very suitable for large-scale industrial production.

[0177] 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 dimeric triarylmethane compound for blue photoresist pigment, characterized in that, The chemical structural formula of the dimeric triarylmethane compound is as follows: The symbols in the formula represent the following meanings: R 1 Represents a hydrogen atom; X represents a linking group; X is selected from -CH2-, -CH2-CH2-CH2-, and -CH2-O-CH2-. Y represents the counter ion; the counter ion is a bis(trifluoromethanesulfonyl)imide anion.

2. The method for synthesizing a dimeric triarylmethane compound for blue photoresist pigment as described in claim 1, characterized in that, Includes the following steps: (1) Using a diacyl chloride reagent as an acylation reagent, react with reactant B to obtain intermediate C; (2) Remove the Boc group from intermediate C to obtain intermediate D; (3) Intermediate D cyclizes with potassium thiocyanate and an acyl chloride reagent to obtain intermediate E; in step (3), the acyl chloride reagent used is benzoyl chloride; (4) Intermediate E reacts with 4,4-bis(diethylamino)benzophenone to obtain F; (5) Intermediate F undergoes salt exchange to obtain the target dimeric triarylmethane compound A; The synthetic route of the synthetic method is as follows: The symbols in the formula represent the following meanings: R 1 Represents a hydrogen atom; X represents a linking group, wherein X is selected from -CH2-, -CH2-CH2-CH2-, and -CH2-O-CH2-. Y represents the counter ion, which is a bis(trifluoromethanesulfonyl)imide anion.

3. The method for synthesizing a dimeric triarylmethane compound for blue photoresist pigment as described in claim 2, characterized in that, In step (1), the molar ratio of the diacyl chloride reagent to reactant B is 1:1 to 1:2.5; In step (1), an acid-binding agent is used, and the acid-binding agent used is one or more of triethylamine, N,N-diisopropylethylamine, pyridine, trimethylamine, and diethylamine; In step (1), a solvent is used, and the solvent used is one or more of dichloromethane, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, N-methylpyrrolidone, chloroform or xylene; In step (1), the molar ratio of the acid-binding agent to the diacyl chloride reagent is 1:1 to 1:5; In step (1), the reaction temperature is 0℃~70℃; In step (1), a catalyst is used during the reaction, and the catalyst used is 4-dimethylaminopyridine.

4. The method for synthesizing a dimeric triarylmethane compound for blue photoresist pigment as described in claim 2, characterized in that, In step (2), a deBoc group removal reagent is used, and the deBoc group removal reagent used is one or more of trifluoroacetic acid, hydrochloric acid, formic acid, p-toluenesulfonic acid, and acetic acid; In step (2), the molar ratio of intermediate C to the Boc-removing reagent is 1:4 to 1:20; In step (2), the reaction temperature is 0℃~70℃.

5. The method for synthesizing a dimeric triarylmethane compound for blue photoresist pigment as described in claim 2, characterized in that, In step (3), the molar ratio of intermediate D to acyl chloride reagent is 1:2 to 1:8; In step (3), the molar ratio of intermediate D to potassium thiocyanate is 1:2 to 1:10; In step (3), an acid is used, and the acid used is one or more of hydrochloric acid, acetic acid, chloroacetic acid, formic acid, and sulfuric acid; In step (3), an alkali is used, and the alkali used is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and cesium carbonate; In step (3), a solvent is used, and the solvent used is one or more of dichloromethane, tetrahydrofuran, acetone, dichloroethane, and chloroform; In step (3), the reaction temperature is 0℃~70℃.

6. The method for synthesizing a dimeric triarylmethane compound for blue photoresist pigment as described in claim 2, characterized in that, In step (4), Lewis acids are used, and the Lewis acid used is one or more of phosphorus oxychloride, phosphorus trichloride, and phosphorus pentachloride; In step (4), the molar ratio of intermediate E to 4,4-bis(diethylamino)benzophenone is 1:1.5 to 1:10; In step (4), a solvent is used, and the solvent used is one or more of dichloroethane, xylene, toluene, chloroform, and dichloromethane; In step (4), the reaction temperature is 0℃~200℃.

7. The method for synthesizing a dimeric triarylmethane compound for blue photoresist pigment as described in claim 2, characterized in that, In step (5), an anti-anionic reagent is used, and the anti-anionic reagent used is lithium bis(trifluoromethanesulfonyl)imide; In step (5), the molar ratio of intermediate F to the counter anionic reagent is 1:2 to 1:10; In step (5), a solvent is used, and the solvent used is one or more of dichloroethane, dichloromethane, N,N-dimethylformamide, methanol, and tetrahydrofuran; In step (5), the reaction temperature is 0℃~100℃.

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