Low-gas-displacement high-sensitivity oxime ester compound as well as preparation method and application thereof

Abstract

The invention provides a high-sensitivity oxime ester compound with low gas displacement as well as a preparation method and application thereof. The low-gas-displacement high-sensitivity oxime ester compound has a structure as shown in a formula I, wherein a symbol E represents that O-N bonds in oximido are distributed in a trans form, and the O-N bonds and carbonyl are located on the opposite side; r1 is selected from C1-C6 alkyl and R1 'OCH2CH2, R1' is selected from C1-C4 alkyl, and R2 is selected from C1-C7 alkyl and C5-C7 cycloalkyl substituted C1-C2 alkylene. The compound has the advantages that the gas displacement is obviously reduced in a photocuring composition formula, especially a high-sensitivity photoresist formula, and the performance is obviously superior to that in the prior art.

Description

Technical Field

[0001] This invention relates to a low-gas-displacement, highly sensitive oxime ester compound, its preparation method, and its applications. Background Technology

[0002] Carbazole oxime esters are known to have high sensitivity and are commonly used photoinitiators in the photoresist industry. However, due to the photodecomposition process of oxime esters, these highly sensitive bisoxime esters also produce a high amount of carbon dioxide gas, which is a major component of the photoresist degassing emissions. High emissions are one of the factors affecting the performance of photoresists. Industry professionals require that the photoinitiators used not only have high sensitivity but also low emissions to reduce the adverse effects of gas emissions on the performance of photoresists, such as the quality of the film residue. Summary of the Invention

[0003] To address the aforementioned technical problems, this invention provides a low-displacement, highly sensitive oxime ester compound, its preparation method, and its applications.

[0004] In a first aspect, the present invention provides a low-displacement, highly sensitive oxime ester compound having a structure as shown in Formula I. Formula I In Equation I, the symbol E This indicates that the ON bonds in the oxime group are distributed in the trans configuration, opposite to the carbonyl group; R1 is selected from C1-C6 alkyl or R1'OCH2CH2; R1' is selected from C1-C4 alkyl; R2 is selected from C1-C7 alkyl, C5-C7 cycloalkyl-substituted C1-C2 alkylene groups.

[0005] In some embodiments of the low-displacement, high-sensitivity oxime ester compound of the present invention, R1 is selected from methyl, ethyl, isopropyl, 2-methoxyethyl; R2 is selected from C1-C3 alkyl, C5 or C6 cycloalkyl-substituted methylene, C5 or C6 cycloalkyl-substituted ethylene.

[0006] According to some embodiments of the low-displacement, high-sensitivity oxime ester compound of the present invention, the compound is selected from: A second aspect of the present invention provides a method for preparing a high-sensitivity oxime ester compound with low exhaust volume, comprising the following steps: Step (1): The raw material M1 is subjected to Friedel-Crafts acylation reaction with 2,4,6-trimethylbenzoyl chloride to obtain intermediate M2; Raw material M1 has the following structure: Intermediate M2 has the following structure: ; The reaction of raw material M1 with 2,4,6-trimethylbenzoyl chloride is as follows: Step (2): Intermediate M2 is subjected to Friedel-Crafts acylation reaction with acyl chloride compound R2CH2COCl to obtain intermediate M3; Acyl chloride compound R2CH2COCl has the following structure: Intermediate M3 has the following structure: ; The reaction between intermediate M2 and the acyl chloride compound R2CH2COCl is as follows: Step (3): Intermediate M3 is reacted with nitrite or nitrous acid under acidic conditions to obtain trans isomer M4 and cis isomer M4. ， A mixture; The trans isomer M4 has the following structure: cis isomer M4 ， It has the following structure: The reaction of intermediate M3 with nitrite esters or nitrite is as follows: Step (4): Purify the product obtained in step (3) to obtain the pure trans isomer M4; Step (5): The trans isomer M4 is esterified with CH3COCl or (CH3CO)2O to obtain the compound described in Formula I; In M4 and Equation I, the symbol E This indicates that the ON bonds in the oxime group are distributed in the trans configuration, opposite to the carbonyl group; in M4 ’ middle Z This indicates that the ON bonds in the oxime group are arranged in a cis configuration, on the same side as the carbonyl group; R1 is selected from C1-C6 alkyl groups; R1'OCH2CH2; R1' is selected from C1-C4 alkyl groups. R2 is selected from C1-C7 alkyl, C5-C7 cycloalkyl-substituted C1-C2 alkylene groups.

[0007] In some embodiments of the preparation method described in this invention, R1 is selected from methyl, ethyl, isopropyl, and 2-methoxyethyl.

[0008] In some embodiments of the preparation method described in this invention, R2 is selected from C1-C3 alkyl, C5 or C6 cycloalkyl-substituted methylene, and C5 or C6 cycloalkyl-substituted ethylene.

[0009] According to some embodiments of the preparation method of the present invention, in steps (1) and (2), the Friedel-Crafts acylation reaction is carried out in a chlorinated hydrocarbon solvent in the presence of a catalyst.

[0010] According to some embodiments of the preparation method described in this invention, the molar ratio of raw material M1 to 2,4,6-trimethylbenzoyl chloride is 1:(1-1.1); for example: 1:1, 1:1.02, 1:1.04, 1:1.05, 1:1.07, 1:1.1 or any value between them.

[0011] According to some embodiments of the preparation method described in this invention, the molar ratio of intermediate M2 to acyl chloride R2CH2COCl is 1:(1-1.1); for example: 1:1, 1:1.02, 1:1.04, 1:1.05, 1:1.07, 1:1.1 or any value between them.

[0012] According to some embodiments of the preparation method described in this invention, the chlorinated hydrocarbon solvent is selected from 1,2-dichloroethane, dichloromethane, or o-dichlorobenzene.

[0013] According to some embodiments of the preparation method described in this invention, the catalyst comprises aluminum trichloride.

[0014] According to some embodiments of the preparation method described in this invention, the catalyst comprises anhydrous aluminum trichloride.

[0015] According to some embodiments of the preparation method of the present invention, the molar ratio of the catalyst to the 2,4,6-trimethylbenzoyl chloride or acyl chloride R2CH2COCl is (0.5-2):1, for example, 0.5:1, 0.7:1, 0.9:1, 1.1:1, 1.3:1, 1.5:1, 1.7:1, 1.9:1 or any value between them.

[0016] According to some embodiments of the preparation method of the present invention, the molar ratio of the catalyst to the 2,4,6-trimethylbenzoyl chloride or acyl chloride R2CH2COCl is 1:1.

[0017] According to some embodiments of the preparation method of the present invention, in step a, the temperature of the Friedel-Crafts acylation reaction is -15 to 25°C; for example, -15°C, -10°C, 0°C, 10°C, 20°C, 25°C.

[0018] According to some embodiments of the preparation method described in this invention, the temperature of the Friedel-Crafts acylation reaction is -10 to 10°C.

[0019] According to some embodiments of the preparation method described in this invention, the Friedel-Crafts acylation reaction time is 1-8 h; for example, 1 h, 2 h, 3 h, 4 h, 6 h, 8 h.

[0020] According to some embodiments of the preparation method described in this invention, the molar ratio of raw material M3 to nitrite or nitrous acid in step (3) is 1:(1-1.5); for example, it is 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5 or any value between them.

[0021] Preferably, the nitrite is selected from isoamyl nitrite, butyl nitrite, sec-butyl nitrite, isobutyl nitrite, tert-butyl nitrite, methyl nitrite, ethyl nitrite, isopropyl nitrite, or propyl nitrite.

[0022] According to some embodiments of the preparation method described in this invention, the reaction is carried out in an organic solvent.

[0023] According to some embodiments of the preparation method of the present invention, the organic solvent is selected from DMSO, alcohol solvents, ether solvents, ester solvents, aromatic solvents or chlorinated alkane solvents.

[0024] According to some embodiments of the preparation method of the present invention, the alcohol solvent is selected from methanol, ethanol, isopropanol, propanol and 2,2,3,3-tetrafluoropropanol.

[0025] According to some embodiments of the preparation method of the present invention, the ether solvent is selected from diethyl ether, tetrahydrofuran, methyltetrahydrofuran, methyl tert-butyl ether, diisopropyl ether, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether and polyethylene glycol dimethyl ether.

[0026] According to some embodiments of the preparation method of the present invention, the ester solvent is selected from ethyl acetate, butyl acetate, sec-butyl acetate, ethyl butyrate, ethylene glycol methyl ether acetate, and propylene glycol methyl ether acetate.

[0027] According to some embodiments of the preparation method of the present invention, the aromatic solvent is selected from benzene, toluene and chlorobenzene; the chloroalkane is selected from dichloromethane, 1,2-dichloroethane, chlorobenzene and fluorobenzene.

[0028] According to some embodiments of the preparation method described in this invention, the reaction temperature is 0-35°C, for example 0°C, 5°C, 10°C, 20°C, 25°C, 30°C, 35°C or any value between them.

[0029] According to some embodiments of the preparation method described in this invention, in step (4), the intermediates M4 and M4 obtained in step (3) are...， The mixture was recrystallized in an organic solvent to obtain a high-purity intermediate M4.

[0030] In some embodiments of the preparation method described in this invention, the organic solvent for recrystallization is an alcohol, such as ethanol or methanol.

[0031] According to some embodiments of the preparation method described in this invention, in step (4), the intermediates M4 and M4 obtained in step (3) are... ， The mixture was separated and purified by silica gel column chromatography to obtain high-purity intermediate M4.

[0032] According to some embodiments of the preparation method of the present invention, in step (5), the molar ratio of the high-purity intermediate M4 obtained in step (4) to CH3COCl or (CH3CO)2O is 1:(1-1.5); for example, it is 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5 or any value between them.

[0033] According to some embodiments of the preparation method of the present invention, the esterification reaction is carried out in an aprotic solvent, preferably selected from dichloromethane, ethyl acetate, toluene and methyl tert-butyl ether.

[0034] According to some embodiments of the preparation method described in this invention, when the reaction raw material is CH3COCl, an acid-binding agent needs to be added to the reaction system.

[0035] Preferably, the acid-binding agent is selected from pyridine and triethylamine; more preferably, the molar ratio of the acid-binding agent to the CH3COCl is (1-1.2):1; for example, 1:1, 1.05:1, 1.1:1, 1.15:1, 1.2:1 or any value between them.

[0036] According to some embodiments of the preparation method of the present invention, the temperature of the esterification reaction is 20-60°C, for example 20°C, 30°C, 35°C, 40°C, 50°C, 60°C or any value between them.

[0037] According to some embodiments of the preparation method described in this invention, the esterification reaction time is 3-10 h; for example, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h, 10 h or any value between them.

[0038] According to some embodiments of the preparation method described in this invention, a method for preparing a high-sensitivity oxime ester compound with low exhaust volume includes the following steps: S1, raw material M1 and 2,4,6-trimethylbenzoyl chloride are subjected to a Friedel-Crafts acylation reaction in a chlorinated hydrocarbon solvent in the presence of a catalyst to obtain intermediate M2; then, acyl chloride compound R3CH2COCl is added to the system to carry out a Friedel-Crafts acylation reaction to obtain intermediate M3. S2, reacting intermediate M3 with nitrite or nitrous acid under acidic conditions to yield trans isomer M4 and cis isomer M4. ， A mixture; S3, purify the product obtained in step S2 to obtain pure trans isomer M4; S4, the trans isomer M4 is subjected to esterification with CH3COCl or (CH3CO)2O to obtain the compound described in Formula I.

[0039] A third aspect of the present invention provides a photocurable composition comprising a photoinitiator and a free radical polymerizable compound, wherein the photoinitiator comprises a low-gas-displacement, high-sensitivity oxime ester compound as described in the first aspect of the present invention or a low-gas-displacement, high-sensitivity oxime ester compound obtained by the preparation method of the second aspect of the present invention.

[0040] According to some embodiments of the photocurable composition of the present invention, the free radical polymerizable compound is selected from acrylate compounds, methacrylate compounds, and combinations thereof.

[0041] According to some embodiments of the photocurable composition of the present invention, the free radical polymerizable compound includes one or more of alkyl acrylates, cycloalkyl acrylates, hydroxyalkyl acrylates, dialkylaminoalkyl acrylates, alkyl methacrylates, cycloalkyl methacrylates, hydroxyalkyl methacrylates, dialkylaminoalkyl methacrylates, acrylic epoxy resins, acrylic polyester resins, unsaturated polyester resins, acrylic polyether resins, and acrylic polyurethane resins.

[0042] According to some embodiments of the photocurable composition of the present invention, the free radical polymerizable compound includes one or more of methyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, ethyl methacrylate, polysiloxane acrylate, diacrylate of vinyl acetate, diacrylate of styrene, diacrylate of ethylene glycol, diacrylate of polyethylene glycol, diacrylate of propylene glycol, diacrylate of neopentyl glycol, diacrylate of 1,6-hexanediol, trihydroxymethane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, vinyl acrylate, and triallyl isocyanurate.

[0043] According to some embodiments of the photocurable composition of the present invention, the low-gas-displacement, high-sensitivity oxime ester compound in the photocurable composition accounts for 0.1-8.0% by mass, for example 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5% or any value between them.

[0044] According to some embodiments of the photocurable composition of the present invention, the photocurable composition of the present invention may also include other photoinitiators or co-initiators. The present invention does not specifically limit the specific types of the other initiators or co-initiators, and any photoinitiator or co-initiator that is helpful to the photocuring performance can be selected.

[0045] This invention also provides an adhesive that, in addition to containing the photocurable composition described in the third aspect of this invention, may also contain other necessary components, such as polymers with a weight-average molecular weight of 5,000-100,000, to improve adhesive properties, for bonding glass, plastics, metal components, etc. Furthermore, those skilled in the art can easily add other necessary components, such as stabilizers, surfactants, leveling agents, and dispersants, according to existing technology and the intended use of the photocurable composition.

[0046] In a fourth aspect, the present invention provides a photoresist, wherein the raw materials for preparing the photoresist include a photoinitiator, a multifunctional acrylate monomer, an alkali-soluble resin, and an organic solvent, wherein the photoinitiator includes the low-gas-displacement, high-sensitivity oxime ester compound described in the first aspect of the present invention or the low-gas-displacement, high-sensitivity oxime ester compound obtained by the preparation method described in the second aspect of the present invention.

[0047] According to some embodiments of the photoresist of the present invention, the multifunctional acrylate monomer is selected from acrylate monomers with a functionality ≥3. The present invention does not specifically limit the type of the multifunctional acrylate monomer, and those skilled in the art can select from conventional multifunctional acrylate monomers.

[0048] According to some embodiments of the photoresist of the present invention, the multifunctional acrylate monomer includes dipentaerythritol hexaacrylate and / or pentaerythritol acrylate.

[0049] According to some embodiments of the photoresist of the present invention, the alkali-soluble resin is a resin having acidic groups, which can be dissolved or dispersed when exposed to an alkaline solution. The present invention does not specifically limit the type of alkali-soluble resin, and those skilled in the art can select from conventional alkali-soluble resins.

[0050] According to some embodiments of the photoresist of the present invention, the alkali-soluble resin includes polyacrylate or methacrylate having carboxylic acid groups.

[0051] According to some embodiments of the photoresist of the present invention, the alkali-soluble resin includes one or more of methacrylic acid, itaconic acid, and maleic acid, and one or more of methyl acrylate, methyl methacrylate, butyl methacrylate, benzyl acrylate, benzyl methacrylate, hydroxyethyl acrylate, styrene, butadiene, and maleic anhydride, such as methyl methacrylate and methacrylic acid copolymer, benzyl methacrylate and methacrylic acid copolymer, methyl methacrylate and butyl methacrylate, and methacrylic acid and styrene copolymer.

[0052] According to some embodiments of the photoresist of the present invention, the organic solvent is selected from one or more of ester solvents, aromatic solvents, and haloalkane solvents.

[0053] According to some embodiments of the photoresist of the present invention, the organic solvent is selected from one or more of propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, toluene, xylene, and tetrachloroethane.

[0054] According to some embodiments of the photoresist of the present invention, the photoinitiator further includes one or more of the following: 2,2-dimethoxy-2-phenylacetophenone, 2-dimethylamino-2-benzyl-1-(4-morpholinylphenyl)-1-butanone, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinylphenyl)-1-butanone, 2-dimethylamino-2-benzyl-1-(4-piperidinylphenyl)-1-butanone, 2,4,6-trimethylbenzoylbenzene-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2-isopropylthioxanthonone, 2,4-diethylthioxanthonone, and bis(2,6-difluoro-3-pyrrolephenyl)dicenoctanetane.

[0055] According to some embodiments of the photoresist of the present invention, the photoinitiator further includes commercially available oxime ester photoinitiators, such as OXE01, OXE02, OXE03, OXE04, PBG305, PBG304, PBG3057, NCI1919, NCI831, etc.

[0056] According to some embodiments of the photoresist of the present invention, the raw materials for preparing the photoresist further contain pigments.

[0057] According to some embodiments of the photoresist of the present invention, the pigment is a red pigment, a green pigment, a blue pigment, or a black pigment.

[0058] According to some embodiments of the photoresist of the present invention, the red pigment includes CI Pigment Red 177, the green pigment includes CI Pigment Green 7, the blue pigment includes CI Pigment Blue 15:6 and Solvent Blue 25, and the black pigment includes carbon black, titanium black and CI Pigment Black 1.

[0059] According to some embodiments of the photoresist of the present invention, the raw materials for preparing the photoresist further include heat stabilizers or light stabilizers, such as p-methoxyphenol. Other resins may also be added, such as polyalkyl methacrylate, ethyl cellulose, carboxymethyl cellulose, linear phenolic resin, polyvinyl butyral, polyvinyl acetate, polyester, polyimide, etc.

[0060] Using the photoresist of this invention as raw material, and through existing technology processes such as multiple coatings, exposures, and developments of different colored photoresists, a color filter device with excellent optical performance can be obtained. This device is an important component of a color display screen, in which the color units exhibit pure color and high light transmittance, while the colorless parts exhibit low yellowing and high light transmittance.

[0061] Photoresist is typically applied using a spin-coating method to evenly distribute it onto a substrate. After drying at 80-90°C, volatile components such as solvents are separated, leaving a solid film. A mask is placed on top of this film, and the substrate is exposed to appropriate exposure levels under a 365nm mercury lamp or LED light source. The exposed material is then developed in an alkaline solution such as sodium carbonate or sodium hydroxide to remove unexposed portions of the film, leaving the exposed image. Following this, a cleaning and post-baking process at 200-230°C is performed to ensure better adhesion of the image to the substrate. By following the designed procedure and fabricating different colors and patterns, or by combining this with necessary protective film processing, the optical filter device is obtained.

[0062] In a fifth aspect, the present invention provides a black matrix prepared from a photoresist comprising the photoresist described in the fourth aspect of the present invention, wherein the pigment in the photoresist is a black pigment, preferably carbon black and titanium black.

[0063] The present invention also provides an optical spacer, which is prepared from a photoresist including the one described in the fourth aspect of the present invention, wherein the pigment in the photoresist is a black pigment, preferably carbon black and titanium black.

[0064] In a sixth aspect, the present invention provides a color filter device prepared from a photoresist comprising the photoresist described in the fourth aspect of the present invention, wherein the pigment in the photoresist is a red pigment, a green pigment, or a blue pigment.

[0065] A seventh aspect of the present invention provides a display obtained by photocuring using a low-gas-displacement, high-sensitivity oxime ester compound as described in the first aspect of the present invention or a low-gas-displacement, high-sensitivity oxime ester compound obtained by the preparation method of the second aspect of the present invention as a photoinitiator.

[0066] According to some embodiments of the display described in this invention, the display includes a PCB display, an LCD display, and an OLED display.

[0067] The present invention also provides a printed article, which is obtained by photocuring using the low-gas-displacement, high-sensitivity oxime ester compound described in the first aspect of the present invention or the low-gas-displacement, high-sensitivity oxime ester compound obtained by the preparation method of the second aspect of the present invention as a photoinitiator.

[0068] According to some embodiments of the printed article of the present invention, the printed article includes a printed circuit board and a color filter.

[0069] The eighth aspect of the present invention provides the application of the low-gas-displacement, high-sensitivity oxime ester compound of the first aspect of the present invention, the low-gas-displacement, high-sensitivity oxime ester compound obtained by the preparation method of the second aspect of the present invention, the photocurable composition of the third aspect of the present invention, or the photoresist of the fourth aspect of the present invention in the preparation of colored or uncolored inks, coatings, adhesives, filters, displays, pattern printing, printing plates, 3D printing, PCB photoresists, PCB solder resist inks, substrate protective coatings, electronic device protective coatings, passivation films, liquid or dry film resists, sealants, dental materials, optical materials, optical films, fiber optic coatings, insulating films, polarizers, microscope lenses, and recording materials.

[0070] Using the compound of Formula I of this invention or a photoinitiator composition containing Formula I and a photoresist containing Formula I as raw materials, color filters, LCD color displays, OLED color displays, PCBs, and printed materials can be obtained through necessary processing steps.

[0071] The beneficial effects of the present invention include: the compounds of the present invention have significantly low photolysis and / or thermal degassing amounts in photocurable composition formulations, especially photoresists. Detailed Implementation

[0072] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. The specific embodiments described herein are for illustrative purposes only and are not intended to limit the invention in any way. Furthermore, descriptions of well-known structures and techniques are omitted in the following description to avoid unnecessarily obscuring the concepts of this disclosure. Such structures and techniques have also been described in many publications.

[0073] The term "C1-C7 alkyl" as used in this application refers to a straight-chain or branched chain alkyl group having 1-7 carbon atoms, including but not limited to methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.

[0074] As used in this application, the term "cycloalkyl" refers to an alkyl group containing at least one ring. C5-C7 cycloalkyl refers to a cyclic alkyl group having 5-7 carbon atoms, such as cyclopentyl, cyclohexyl, cycloheptyl, especially cyclopentyl and cyclohexyl.

[0075] Experimental materials and equipment: Light source equipment: 365nm LED surface light source, Shanghai Futanxi Technology Co., Ltd.

[0076] Test equipment: Differential scanning calorimeter: HSC-1, Beijing Hengjiu Experimental Equipment Co., Ltd.; Stereo microscope: HY-950S, Beijing Huanyu Technology Co., Ltd., linewidth unit is μm; Yellowness meter: SC-80C fully automatic colorimeter, Beijing Jingyi Kangguang Optical Instrument Co., Ltd.

[0077] Experimental materials: Genomer 4212: Aliphatic polyurethane acrylate, a product of RAHN Corporation; DPHA: Dipentaerythritol hexaacrylate, a product of Tianjin Tianjiao Chemical Co., Ltd. HDDA: 1,6-hexanediol diacrylate, a product of Tianjin Tianjiao Chemical Co., Ltd. Comparative compound C-1: self-made; Comparative compound C-2: self-made; Comparative compound C-3: OXE03, a product of BASF, Germany.

[0078] Compound preparation Preparation Example 1: 6-(2,4,6-trimethylbenzoyl)-3-(2E-2-acetoxyiminobutyryl)-9-ethylcarbazole I-1 Step 1a. In a 250 mL three-necked flask, add 5 g (0.026 mol) of 9-ethylcarbazole and 50 mL of dichloromethane, stir to dissolve, weigh 3.58 g (0.027 mol) of anhydrous aluminum trichloride, add to the reaction flask, stir and cool to 0 °C, add 4.91 g (0.027 mol) of 2,4,6-trimethylbenzoyl chloride dropwise, stir and react for 4 h after the addition is complete; add another 3.58 g (0.027 mol) of anhydrous aluminum trichloride, maintain 0 °C, add 2.87 g (0.027 mol) of n-butyryl chloride dropwise, keep the reaction at 0 °C for 4 h, acidify the reaction solution with hydrochloric acid and water, wash with water to remove most of the dichloromethane, add 50 mL of methanol while hot, cool, white crystals precipitate, filter, dry under reduced pressure, and obtain 9.63 g of white powder, HPLC purity 97.1%, which is intermediate I. -1A, yield 90%, DSC melting point 152.7℃; I-1A Step 1b. In a 100 mL three-necked flask, add 3 g (7.3 mmol) of intermediate I-1A obtained in step 1a, dissolve in 30 mL of ethyl acetate, weigh 1.0 g (9 mmol) of isoamyl nitrite, add 1 mL of concentrated hydrochloric acid, stir at 25 °C for 5 h, add 30 mL of water, stir and wash with water, separate the aqueous layer to obtain a yellow ethyl acetate solution, wash once with 30 mL of water, HPLC analysis shows that it contains 86.1% of the major isomer and 6.8% of the minor isomer; remove most of the ethyl acetate by vacuum distillation, add 30 mL of methanol while hot, cool to precipitate a yellow solid, which is crude intermediate C-2B, separated by silica gel column chromatography, the eluent is a methanol-dichloromethane mixture with a volume ratio of 1:20, after rotary evaporation to obtain 2.5 g of off-white solid, yield 77.9%, HPLC analysis shows that the purity of I-1B is 98.6%; melting point 66.4-69.2 °C; I-1B Step 1c. In a 50 mL three-necked flask, add 3.0 g (6.8 mmol) of intermediate I-1B obtained in step 1b and 30 mL of dichloromethane, and add 0.76 g (7.5 mmol) of acetic anhydride dropwise. Stir the reaction mixture at 35 °C for 5 h. Wash the reaction solution with water, remove most of the dichloromethane by vacuum distillation, add 12 mL of methanol while hot, and cool to precipitate a light yellow solid. After drying, 2.6 g of the solid was obtained, with a yield of 79.1% and a purity of 99.5% according to HPLC analysis. Melting range: 53.0-58.1 °C. 1 H-NMR data confirm that it is the compound shown in Formula I-1; 1H-NMR data (CDCl3, δ [ppm]) 1.2030-1.2221-1.2412(t,3H,CH3), 1.4508-1.4688-1.4868(t,3H,CH3), 2.1418(s ,6H,2ArCH3), 2.2997(s,3H,ArCH3), 2.3832(s,3H,COCH3), 2.8387-2.8578-2.8769-2.8961(quartet,2H,CH 2), 4.3739-4.3919-4.4102-4.4283(quartet,2H,N-CH2), 6.9539(s,2H,2ArH), 7.4300-7.4691(m,2H,2ArH) , 8.0298(s,1H,ArH), 8.2605 / 8.2648-8.2822 / 8.2865(dd,1H,ArH), 8.6064(s,1H,ArH), 8.8290 / 8.8331(d,H, ArH).

[0079] Preparation Example 2: 6-(2,4,6-trimethylbenzoyl)-3-(2E-2-acetoxyiminobutyryl)-9-methylcarbazole I-2 Step 2a. Following the procedure in step 1a of Preparation Example 1, 9-methylcarbazole was used instead of 9-ethylcarbazole to complete a two-step Friedel-Crafts acylation reaction, followed by a two-step reaction of α-oxime and esterification to finally obtain the target product I-2; the appearance was a light yellow crystalline powder, the overall yield was 66.5%, the HPLC purity was 99.03%, and the melting range was 69.4-75.3℃.

[0080] 1 1H-NMR data (CDCl3, δ [ppm]): 1.2007-1.2194-1.2389 (t, 3H, CH3), 2.1340 (s, 6H, 2ArCH3), 2.2996 (s, 3H, ArCH3), 2.3849 (s,3H,COCH3), 2.8345-2.8537-2.8728-2.8919(quartet,2H,CH2), 3.9165(s,3H,N-CH3), 6.9536(s,2H,2ArH), 7.4297-7.4499-7.4 708(t,2H,2ArH), 8.0368(s,1H,ArH), 8.2745 / 8.2784-8.2963 / 8.3003(dd,1H,ArH), 8.6040(s,1H,ArH), 8.8214 / 8.8256(d,1H,ArH).

[0081] Preparation Example 3: 6-(2,4,6-trimethylbenzoyl)-3-(2E-2-acetoxyiminopropionyl)-9-ethylcarbazole I-4 Steps 3a-3c. Follow steps 1a-1c of Preparation Example 1, except that in step 3a, propionyl chloride is used instead of n-butyryl chloride in the second Friedel-Crafts reaction, followed by two steps of α-oxime and esterification to finally obtain the target product I-4; the appearance is a light yellow crystalline powder, the total yield is 58.5%, the HPLC purity is 99.1%, and the DSC melting point is 70.1℃. 1 H-NMR data (CDCl3, δ[ppm]) 1.4652-1.4833-1.5013(t,3H,CH3), 2.1383(s,6H,2ArCH3), 2.2990 (s,3H, ArCH3), 2.3578(s,3H,CH3), 2.3861(s,3H,COCH3), 4.3889-4.4071-4.4252-4.4433(quartet,2H,N-CH2),6.9543(s,2H,2ArH),7.4421-7.4639(d,1H,ArH),7.4562-7.47 80(d,1H,ArH), 8.0686(s,1H,ArH), 8.3005 / 8.3048-8.3224 / 8.3266(dd,1H,ArH), 8.5565(s,1H,ArH), 8.8461 / 8.8504 (d,H,ArH).

[0082] Preparation Example 4: 6-(2,4,6-trimethylbenzoyl)-3-(2E-2-acetoxyimino-3-cyclohexylpropionyl)-9-ethylcarbazole I-15 Steps 4a-4c. Follow steps 1a-1c of Preparation Example 1, except that in step 4a, 3-cyclohexylpropionyl chloride is used instead of n-butyryl chloride in the second Friedel-Crafts reaction. After two steps of α-oxime and esterification, the target product I-15 is finally obtained. It is a light yellow crystalline powder with an overall yield of 66.8% and an HPLC purity of 99.2%. The DSC melting point is 142.4℃. 1 H-NMR data confirm that it is the target compound I-15; 1H-NMR data (CDCl3, δ [ppm]): 1.0286-1.1156 (m, 5H, Cy-CH2), 1.4689-1.4870-1. 5050(t,3H,CH3), 1.6266-1.7588(m,6H,Cy-CH2+CH), 2.1375(s,6H,2ArCH3), 2.2922(s,3H,ArCH3), 2.3845(s,3H,COCH3), 2.8021-2.8190(d,2H,CH2), 4.3913-4.4095-4.4277-4.4458(q uartet,2H,N-CH2), 6.9512(s,2H,2ArH), 7.4310-7.4526(d,1H,ArH), 7.4611-7.4830 (d,1H,ArH), 8.0344(s,1H,ArH), 8.3127 / 8.3170-8.3344 / 8.3387(dd,1H,ArH), 8.5933(s,1H,ArH), 8.8576 / 8.8620 (d,H, ArH).

[0083] Preparation Example 5: 6-(2,4,6-trimethylbenzoyl)-3-(2E-2-acetoxyiminobutyryl)-9-(2-methoxyethyl)carbazole I-19 Steps 5a-5c. Follow steps 1a-1c of Preparation Example 1, except that in step 5a, 9-(2-methoxyethyl)carbazole is used instead of 9-ethylcarbazole. The target product I-19 is obtained. It is yellow, viscous, and oily in appearance, with an overall yield of 51.5% and an HPLC purity of 98.05%. 1H-NMR data (CDCl3, δ[ppm]): 1.1996-1.2188-1.2378(t,3H,CH3), 2.1383(s,6H,2ArCH3), 2.2968(s,3H,ArCH3), 2.3825(s,3H,COCH3), 2.8341-2.8532-2.8724-2. 8915(quartet,2H,CH2),3.2695(s,3H,OCH3),3.7757-3.7894-3.8028(t,2H,OCH2),4.4988-4.51 26-4.5263(t,2H,N-CH2), 6.9510(s,2H,2ArH), 7.4743-7.4991-7.5211(t,2H,2ArH), 8.0163(s, 1H,ArH), 8.2470 / 8.2513-8.2688 / 8.2731(dd,1H,ArH), 8.5899(s,1H,ArH), 8.8109 / 8.8153(d,H, ArH).

[0084] Preparation Example 6: 6-(2,4,6-trimethylbenzoyl)-3-(2E-2-acetoxyimino-3-cyclohexylpropionyl)-9-(2-methoxyethyl)carbazole I-22 Steps 6a-6c. Follow steps 1a-1c of Preparation Example 1, except that in step 6a, 9-(2-methoxyethyl)carbazole is used instead of 9-ethylcarbazole, and in the second Friedel-Crafts reaction, 3-cyclohexylpropionyl chloride is used instead of n-butyryl chloride in step 1a. After two steps of α-oxime and esterification, the target product I-22 is finally obtained. It is a yellow viscous oil with an overall yield of 50.2% and an HPLC purity of 98.5%. 11H-NMR data (CDCl3, δ [ppm]): 1.0289–1.2566 (m, 5H, Cy-CH2), 1.6019–1.7574 (m, 6H, Cy-CH2+CH), 2.1372 (s, 6H, 2ArCH3), 2.2926 (s, 3H, ArCH3). 2.3824(s,3H,COCH3), 2.8011-2.8181(d,2H,CH2), 3.27782(s,3H,OCH3), 3.7804-3.7940-3.8077(t,2H,OCH 2), 4.5030-4.5166-4.5305(t,2H,N-CH2), 6.9489(s,2H,2ArH), 7.4719-7.5017(d,1H,ArH), 7.4935-7.5237 (d,1H,ArH), 8.0140(s,1H,ArH), 8.2933 / 8.2976-8.3152 / 8.3194(dd,1H,ArH), 8.5867(s,1H,ArH), 8.8441 / 8.8485 (d,H, ArH).

[0085] Comparative compound C-1 was used to prepare 3-(2E-2-acetoxyiminooctanoyl)-6-(2E-2-acetoxyimino-3-cyclohexylpropionyl)-9-ethylcarbazole C-1 Step 7a. In a 250 mL three-necked flask, add 10 g (0.0512 mol) of 9-ethylcarbazole and 100 mL of dichloromethane, stir to dissolve, weigh 6.82 g (0.0512 mol) of anhydrous aluminum trichloride, add it to the reaction flask, stir and cool to 0 °C, add 8.33 g (0.0512 mol) of n-octanoyl chloride dropwise, stir and react for 4 h after the addition is complete; add another 6.82 g (0.0512 mol) of anhydrous aluminum trichloride, and maintain the reaction temperature. At 0℃, 8.94 g (0.0512 mol) of 3-cyclohexylpropionyl chloride was added dropwise. After the addition was complete, the reaction was kept at this temperature for 4 h. The reaction solution was acidified with hydrochloric acid and water, then washed with water to remove most of the dichloromethane. 200 mL of methanol was added while hot, and the mixture was cooled. White crystals precipitated. The crystals were filtered, dried under reduced pressure, and 22.61 g of white powder was obtained. The HPLC purity was 98.85%, which is intermediate C-1A with a yield of 96%. The DSC melting point was 51.1℃. C-1A Step 7b. In a 100 mL three-necked flask, add 6 g (0.013 mol) of intermediate C-1A obtained in step 7a, dissolve it in 15 mL of ethyl acetate, weigh 4.0 g (0.034 mol) of isoamyl nitrite, add 2 mL of concentrated hydrochloric acid, stir at 25 °C for 5 h, add 10 mL of water, stir and wash with water, separate the aqueous layer to obtain a yellow ethyl acetate solution, wash once with 10 mL of water, HPLC analysis shows that it contains 71.2% of the major isomer and 20.1% of the minor isomer; reflux the organic phase to remove water for 1 h, then continue reflux at 82 °C for 4 h, remove most of the ethyl acetate by vacuum distillation, add 30 mL of methanol while hot, cool to precipitate a yellow solid, which is intermediate C-1B, 4.57 g after drying, yield 68%, HPLC analysis shows a purity of 98.5%; C-1B Step 7c. In a 50 mL three-necked flask, add 1.5 g (2.9 mmol) of intermediate C-1B obtained in step 7b and 8 mL of dichloromethane, and add 0.62 g (6.1 mmol) of acetic anhydride dropwise. Stir the reaction mixture at 35 °C for 5 h. Wash the reaction solution with water, remove most of the dichloromethane by vacuum distillation, add 12 mL of methanol while hot, and cool to precipitate a yellow solid. After drying, 1.38 g of the solid was obtained, with a yield of 80%. HPLC analysis showed a purity of 98.4%; DSC melting point was 92.6 °C. 1 H-NMR data confirmed it to be the target compound C-1; 1 H-NMR data (CDCl3, δ[ppm]): 0.8437-0.8618-0.8787(t,3H,CH3), 1.0384-1.3303 (m,10H,5CH2),1.3705-1.4435(quintuplet,2H,CH2),1.4556-1.4736-1.4916(t,3H,CH3),1.5872- 1.7727(m,7H,3CH2+1CH), 2.3027(s,6H,2COCH3), 2.8189-2.8371(d,2H,CH2), 2.8401-2.8596- 2.8792(t,2H,CH2),4.3904-4.4086-4.4268-4.4446(quartet,2H,N-CH2),7.4695-7.4912 (d,2H,2ArH), 8.2860 / 8.2905-8.3079 / 8.3118(dd,1H,ArH), 8.3158 / 8.3205-8.3378 / 8.3422(dd,1H,ArH), 8.9460 / 8.9504(d,1H,ArH), 8.9836 / 8.9879(d,1H,ArH).

[0086] Preparation of compound C-2 C-2 Step 8a. In a 250 mL three-necked flask, 10 g (0.0512 mol) of 9-ethylcarbazole and 100 mL of dichloromethane were added and stirred to dissolve. 6.82 g (0.0512 mol) of anhydrous aluminum trichloride was weighed and added to the reaction flask. The mixture was stirred and cooled to 0 °C. 7.92 g (0.0512 mol) of o-methylbenzoyl chloride was added dropwise. After the addition was complete, the mixture was stirred and reacted for 4 h. 6.82 g (0.0512 mol) of anhydrous aluminum trichloride was added again. The mixture was kept at 0 °C. 5.5 g (0.0516 mol) of n-butyryl chloride was added dropwise. After the addition was complete, the mixture was kept at the temperature for 4 h. The reaction solution was acidified with hydrochloric acid and water, then washed with water to remove most of the dichloromethane. 200 mL of methanol was added while hot, and the mixture was cooled. White crystals precipitated. The crystals were filtered, dried under reduced pressure, and 28.64 g of white powder was obtained. The HPLC purity was 99.08%, indicating that it was intermediate C-2A with a yield of 97%. The DSC melting point was 127 °C. C-2A Step 8b. In a 100 mL three-necked flask, add 5 g (0.013 mol) of intermediate C-2A obtained in step 8a, dissolve it in 50 mL of ethyl acetate, weigh 4.0 g (0.034 mol) of isoamyl nitrite, add 2 mL of concentrated hydrochloric acid, stir and react at 25 °C for 5 h, add 50 mL of water, stir and wash with water, separate the aqueous layer to obtain a yellow ethyl acetate solution, wash once with 50 mL of water, HPLC analysis shows that it contains 91.1% of the major isomer and 8.0% of the minor isomer; remove most of the ethyl acetate by vacuum distillation, add 30 mL of methanol while hot, cool to precipitate a yellow solid, which is crude intermediate C-2B, separated by silica gel column chromatography, the eluent is a 1:10 mixture of dichloromethane and n-heptane, after rotary evaporation to obtain 3.6 g, yield 67%, HPLC analysis shows that the purity of C-2B is 98.2%; C-2B Step 8c. In a 50 mL three-necked flask, add 2.68 g (6.5 mmol) of intermediate C-2B obtained in step 8b and 20 mL of dichloromethane, and add 0.73 g (7.1 mmol) of acetic anhydride dropwise. Stir the reaction mixture at 35 °C for 5 h. Wash the reaction solution with water, remove most of the dichloromethane by vacuum distillation, add 12 mL of methanol while hot, and cool to precipitate a yellow solid. After drying, 3.08 g of the solid was obtained, with a yield of 83.2%. HPLC analysis showed a purity of 98.3%; DSC melting point was 61.8 °C. 1 H-NMR data confirmed that it was the target compound C-2; 1H-NMR data (CDCl3, δ[ppm]): 1.1990-1.1218-1.2371(t,3H,CH3), 1.4668-1.4849-1.5029(t,3H,CH3), 2.2922(s,3H,CH3), 2.3581(s,3H,CH3), 2.8334-2.8524-2.8716-2.8907(quartet,2H,CH2), 4.4012-4.4192-4.4375-4.4556 (quartet,2H,N-CH2),7.2883-7.4909 (m,6H,6ArH),8.0363 / 8.0406-8.0580 / 8.0622(dd,1H,ArH),8.2723 / 8.2765-8.2941 / 8.2983(dd,1H,ArH),8.6081 / 8.6122(d,1H,ArH), 8.8174 / 8.8216(d,1H,ArH).

[0087] Preparation of alkali-soluble resins 20g of benzyl methacrylate, 3g of methacrylic acid, 7g of hydroxyethyl methacrylate, 1.5g of azobisisobutyronitrile, and 0.5g of dodecanethiol were dissolved in 200mL of toluene and placed in a constant-pressure dropping funnel. 100mL of toluene was added to a 500mL four-necked flask, purged with nitrogen, and the temperature was raised to 80℃. The solution from the funnel was added dropwise, and after reacting for 6 hours, the mixture was cooled and filtered to obtain 24g of a white alkali-soluble resin.

[0088] Preparation of black pigment Take 50g of the alkali-soluble resin prepared by the above method, 50g of Mitsubishi PK7 carbon black, 100g of DPHA, and 250g of propylene glycol methyl ether acetate and put them into a 500mL beaker. Mix them for 15 minutes at 5000r / min using a high-speed shear mixer to obtain a black color paste.

[0089] Examples and Comparative Examples of Photoresist Compositions The compounds prepared in Preparation Examples 1-6, along with comparative compounds C-1, C-2, and C-3, were used as photoinitiators. They were mixed and dissolved in PMA (propylene glycol methyl ether acetate) according to the proportions in Table 1, and then mixed with black pigment according to the proportions in Table 1. The amount is measured in grams.

[0090] Comparative compound C-1: self-made; Comparative compound C-2: self-made; Comparative compound C-3: photoinitiator OXE03, purchased from BASF, Germany.

[0091] After thoroughly mixing all components, a film was coated onto a glass slide using a 10μm wire rod. The film was dried in a 90℃ oven for 5 minutes. Using a 365nm surface light source and a 41-level exposure scale as a mask, development was performed using a 0.0425% KOH aqueous solution at 25℃. The film was then rinsed with purified water for 10 seconds and dried in a 90℃ oven for 30 minutes. The film retention level was observed and recorded as a sensitivity evaluation standard. A higher film retention level after curing indicates higher formulation sensitivity and better photoinitiator sensitivity. Increasing the amount of low-sensitivity photoinitiator can improve sensitivity to the level of Comparative Example 1. The corresponding photoinitiator dosage values ​​were recorded.

[0092] Table 1 records data from examples and comparative examples that achieved the same sensitivity value of 25.

[0093] Table 1

[0094] Based on the dosage in Table 1, the number of moles of oxime ester compound per 100g of photoresist formulation and the amount of carbon dioxide emitted per 100g of complete decomposition are calculated and listed in Table 2.

[0095] Table 2

[0096] The solid content percentage of the photoinitiator in Tables 1 and 2 refers to the mass percentage of the photoinitiator in the photoresist formulation.

[0097] In summary, in photoresist formulations, the compound described in this invention exhibits significantly lower exhaust volume compared to the comparative compound while maintaining the same sensitivity.

[0098] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A low-displacement, highly sensitive oxime ester compound having the structure shown in Formula I, Equation I in, In Equation I, the symbol E This indicates that the ON bonds in the oxime group are distributed in the trans configuration, opposite to the carbonyl group; R1 is selected from C1-C6 alkyl or R1'OCH2CH2; R1' is selected from C1-C4 alkyl; R2 is selected from C1-C7 alkyl, C5-C7 cycloalkyl-substituted C1-C2 alkylene groups.

2. The low-displacement, high-sensitivity oxime ester compound according to claim 1, characterized in that, R1 is selected from methyl, ethyl, isopropyl, 2-methoxyethyl; R2 is selected from C1-C3 alkyl, C5 or C6 cycloalkyl-substituted methylene, and C5 or C6 cycloalkyl-substituted ethylene.

3. The low-displacement, high-sensitivity oxime ester compound according to claim 1, characterized in that, The compound is selected from:

4. A method for preparing the low-gas-displacement, highly sensitive oxime ester compound according to any one of claims 1-3, comprising the following steps: Step (1): The raw material M1 is subjected to Friedel-Crafts acylation reaction with 2,4,6-trimethylbenzoyl chloride to obtain intermediate M2; Raw material M1 has the following structure: Intermediate M2 has the following structure: ; Step (2): Intermediate M2 is subjected to Friedel-Crafts acylation reaction with acyl chloride compound R2CH2COCl to obtain intermediate M3; Acyl chloride compound R2CH2COCl has the following structure: Intermediate M3 has the following structure: ; Step (3): Intermediate M3 is reacted with nitrite or nitrous acid under acidic conditions to obtain trans isomer M4 and cis isomer M4. ， A mixture; The trans isomer M4 has the following structure: cis isomer M4 ， It has the following structure: Step (4): Purify the product obtained in step (3) to obtain the pure trans isomer M4; Step (5): The trans isomer M4 is esterified with CH3COCl or (CH3CO)2O to obtain the compound described in Formula I; In M4 and Equation I, the symbol E This indicates that the ON bonds in the oxime group are distributed in the trans configuration, opposite to the carbonyl group; in M4 ’ middle Z This indicates that the ON bonds in the oxime group are arranged in a cis configuration, on the same side as the carbonyl group; R1 is selected from C1-C6 alkyl groups; R1'OCH2CH2; R1' is selected from C1-C4 alkyl groups. R2 is selected from C1-C7 alkyl, C5-C7 cycloalkyl-substituted C1-C2 alkylene groups.

5. The preparation method according to claim 4, characterized in that, In steps (1) and (2), the Friedel-Crafts acylation reaction is carried out in a chlorinated hydrocarbon solvent in the presence of a catalyst; Preferably, the molar ratio of raw material M1 to 2,4,6-trimethylbenzoyl chloride is 1:(1-1.1). And / or, the molar ratio of intermediate M2 to acyl chloride R2CH2COCl is 1:(1-1.1), And / or, the chlorinated hydrocarbon solvent is selected from 1,2-dichloroethane, dichloromethane, or o-dichlorobenzene; And / or, the catalyst comprises aluminum trichloride; And / or, the molar ratio of the catalyst to the 2,4,6-trimethylbenzoyl chloride or acyl chloride R2CH2COCl is (0.5-2):1; And / or, the temperature of the Friedel-Crafts acylation reaction is -15 to 25°C, preferably -10 to 10°C; And / or, in step (3), the molar ratio of raw material M3 to nitrite or nitrous acid is 1:(1-1.5); preferably, the nitrite is selected from isoamyl nitrite, butyl nitrite, sec-butyl nitrite, isobutyl nitrite, tert-butyl nitrite, methyl nitrite, ethyl nitrite, isopropyl nitrite, or propyl nitrite; the reaction is carried out in an organic solvent, preferably, the organic solvent is selected from DMSO, alcohol solvents, ether solvents, ester solvents, aromatic solvents, or chloroalkane solvents; more preferably, the alcohol solvent is selected from methanol, ethanol, isopropanol, propanol, and 2, 2,3,3-Tetrafluoropropanol; the ether solvent is selected from diethyl ether, tetrahydrofuran, methyltetrahydrofuran, methyl tert-butyl ether, diisopropyl ether, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, and polyethylene glycol dimethyl ether; the ester solvent is selected from ethyl acetate, butyl acetate, sec-butyl acetate, ethyl butyrate, ethylene glycol methyl ether acetate, and propylene glycol methyl ether acetate; the aromatic solvent is selected from benzene, toluene, and chlorobenzene; the chloroalkanes are selected from dichloromethane, 1,2-dichloroethane, chlorobenzene, and fluorobenzene; and / or, the reaction temperature is 0-35°C; And / or, in step (4), the intermediates M4 and M4 obtained in step (3) are... ， The mixture was recrystallized in an organic solvent to obtain a high-purity intermediate M4; And / or, in step (4), the intermediates M4 and M4 obtained in step (3) are... ， The mixture was separated and purified by silica gel column chromatography to obtain high-purity intermediate M4; And / or, in step (5), the molar ratio of the high-purity intermediate M4 obtained in step (4) to CH3COCl or (CH3CO)2O is 1:(1-1.5); the esterification reaction is carried out in an aprotic solvent, preferably, the aprotic solvent is selected from dichloromethane, ethyl acetate, toluene and methyl tert-butyl ether; And / or, when the reaction raw material is CH3COCl, an acid-binding agent needs to be added to the reaction system. Preferably, the acid-binding agent is selected from pyridine and triethylamine. More preferably, the molar ratio of the acid-binding agent to CH3COCl is (1-1.2):

1. And / or, the temperature of the esterification reaction is 20-60°C.

6. A photocurable composition comprising a photoinitiator and a free radical polymerizable compound, wherein the photoinitiator comprises a low-gas-displacement, high-sensitivity oxime ester compound as described in any one of claims 1-3 or an oxime ester compound prepared by any one of claims 4-5; Preferably, the free radical polymerizable compound is selected from acrylate compounds, methacrylate compounds, and combinations thereof; Preferably, the free radical polymerizable compound includes one or more of the following: alkyl acrylate, cycloalkyl acrylate, hydroxyalkyl acrylate, dialkylaminoalkyl acrylate, alkyl methacrylate, cycloalkyl methacrylate, hydroxyalkyl methacrylate, dialkylaminoalkyl methacrylate, acrylic epoxy resin, acrylic polyester resin, unsaturated polyester resin, acrylic polyether resin, and acrylic polyurethane resin. More preferably, the free radical polymerizable compound includes one or more of the following: methyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, ethyl methacrylate, polysiloxane acrylate, diacrylate of vinyl acetate, diacrylate of styrene, diacrylate of ethylene glycol, diacrylate of polyethylene glycol, diacrylate of propylene glycol, diacrylate of neopentyl glycol, diacrylate of 1,6-hexanediol, trihydroxymethane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, vinyl acrylate, and triallyl isocyanurate. And / or, the low-displacement, high-sensitivity oxime ester compound accounts for 0.1-8.0% by mass in the photocurable composition.

7. A photoresist, wherein the raw materials for preparing the photoresist include a photoinitiator, a multifunctional acrylate monomer, an alkali-soluble resin, and an organic solvent, wherein, The photoinitiator includes the low-gas-displacement, high-sensitivity oxime ester compound as described in any one of claims 1-3 or the oxime ester compound prepared by any one of claims 4-5; Preferably, the multifunctional acrylate monomer is selected from acrylate monomers with a functionality of ≥3, more preferably dipentaerythritol hexaacrylate and / or pentaerythritol acrylate; Preferably, the alkali-soluble resin is a resin having acidic groups, more preferably a polyacrylate or methacrylate having carboxylic acid groups, and even more preferably a copolymer formed by one or more of methacrylic acid, itaconic acid, and maleic acid with methyl acrylate, methyl methacrylate, butyl methacrylate, benzyl acrylate, benzyl methacrylate, hydroxyethyl acrylate, styrene, butadiene, and maleic anhydride, such as methyl methacrylate and methacrylate copolymer, benzyl methacrylate and methacrylate copolymer, methyl methacrylate and butyl methacrylate, and methacrylate and styrene copolymer; Preferably, the organic solvent is selected from one or more of ester solvents, aromatic solvents, and haloalkane solvents, and more preferably from one or more of propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, toluene, xylene, and tetrachloroethane; Optionally, the photoinitiator further includes one or more of the following: 2,2-dimethoxy-2-phenylacetophenone, 2-dimethylamino-2-benzyl-1-(4-morpholinylphenyl)-1-butanone, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinylphenyl)-1-butanone, 2-dimethylamino-2-benzyl-1-(4-piperidinylphenyl)-1-butanone, 2,4,6-trimethylbenzoylbenzene-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2-isopropylthioxanthonone, 2,4-diethylthioxanthonone, and bis(2,6-difluoro-3-pyrrolephenyl)dicenoctanetane. Optionally, the raw materials for preparing the photoresist further contain pigments; preferably, the pigments are red pigments, green pigments, blue pigments, or black pigments; more preferably, the red pigments include CI pigment red 177, the green pigments include CI pigment green 7, the blue pigments include CI pigment blue 15:6 and solvent blue 25, and the black pigments include carbon black, titanium black, and CI pigment black 1. Preferably, the raw materials for preparing the photoresist also include a heat stabilizer or a light stabilizer.

8. A black matrix prepared from the photoresist of claim 7, wherein, The pigment in the photoresist is a black pigment, preferably carbon black or titanium black.

9. A color filter device, which is prepared from the photoresist according to claim 7, wherein, The pigment in the photoresist is a red pigment, a green pigment, or a blue pigment.

10. A display obtained by photocuring a low-gassing, high-sensitivity oxime ester compound as described in any one of claims 1-3 or an oxime ester compound prepared by any one of claims 4-5 as a photoinitiator; preferably, the display includes a PCB display, an LCD display, and an OLED display.

11. The use of the low-gas-displacement, high-sensitivity oxime ester compound of any one of claims 1-3, the oxime ester compound obtained by any one of claims 4-5, the photocurable composition of claim 6, or the photoresist of claim 7 in the preparation of colored or uncolored inks, coatings, adhesives, filters, displays, pattern printing, printing plates, 3D printing, PCB photoresists, PCB solder resist inks, substrate protective coatings, electronic device protective coatings, passivation films, liquid or dry film resists, sealants, dental materials, optical materials, optical films, fiber optic coatings, insulating films, polarizers, microscope lenses, and recording materials.

12. An adhesive comprising the photocurable composition of claim 6, Preferably, the adhesive further includes one or more of a polymer, stabilizer, surfactant, leveling agent, and dispersant. Preferably, the polymer has a weight-average molecular weight of 5,000-100,000.

13. An optical spacer, comprising the photoresist of claim 7, wherein, The pigment in the photoresist is a black pigment, preferably carbon black or titanium black.

14. A printed article comprising a low-gas-displacement, high-sensitivity oxime ester compound as described in any one of claims 1-3 or a low-gas-displacement, high-sensitivity oxime ester compound obtained by the preparation method as described in any one of claims 4-5, and photocured as a photoinitiator; Preferably, the printed article includes a printed circuit board and a color filter.

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