High-sensitivity oxime ester compound as well as preparation method and application thereof

Abstract

The invention provides a high-sensitivity oxime ester compound as well as a preparation method and application thereof, the high-sensitivity oxime ester compound has a structure as shown in a formula I, in which a symbol E represents that O-N bonds in oximido are distributed in a trans form and are opposite to carbonyl; r1 is selected from methyl, ethyl, isopropyl or sec-butyl; r2 is selected from hydrogen or methyl; and R3 is selected from ethyl, cyclohexyl methyl, cyclopentyl methyl, cyclopentyl ethyl or cyclohexyl ethyl. The compound disclosed by the invention has remarkably high sensitivity in a photocuring composition formula, especially a high-sensitivity photoresist formula, the performance of the compound is remarkably superior to that of the prior art, and the cis-isomer of the compound is very low in sensitivity. Formula I

Description

Technical Field

[0001] This invention relates to a highly sensitive oxime ester compound, its preparation method, and its application. Background Technology

[0002] Photoinitiators, also known as photosensitizers or photocuring agents, are compounds that absorb energy of a certain wavelength in the ultraviolet (250-420 nm) or visible (400-800 nm) light region, generating free radicals, cations, etc., thereby initiating monomer polymerization, cross-linking, and curing. Currently, photoinitiators generally have low photosensitivity and are subject to significant limitations in the types of light sources they can be used with; the vast majority are only suitable for ultraviolet excitation.

[0003] Oxime esters are known to be suitable photoinitiators for the formulation of photoresist compositions, exhibiting antioxidant and polymerization-inhibiting properties and good sensitivity even in very thin coatings. They are commonly used photoinitiators in the photoresist industry. However, industry professionals are constantly searching for oxime esters with higher sensitivity to improve the performance of photoresists. Summary of the Invention

[0004] To address the aforementioned technical problems, this invention provides a highly sensitive oxime ester compound, its preparation method, and its application. The oxime ester group of this invention has a trans structure, and its exposure sensitivity is significantly higher than that of the corresponding cis isomer compound.

[0005] In a first aspect, the present invention provides a 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 methyl, ethyl, isopropyl, or sec-butyl; R2 is selected from hydrogen or methyl; R3 is selected from ethyl, cyclohexylmethyl, cyclopentylmethyl, cyclopentylethyl, or cyclohexylethyl.

[0006] In some embodiments of the highly sensitive oxime ester compound of the present invention, R1 in Formula I is selected from ethyl, isopropyl, or sec-butyl.

[0007] In some embodiments of the highly sensitive oxime ester compound of the present invention, R3 in Formula I is selected from ethyl or cyclohexylmethyl.

[0008] According to some embodiments of the highly sensitive oxime ester compounds of the present invention, the compounds are selected from: A second aspect of the present invention provides a method for preparing the highly sensitive oxime ester compound described in the first aspect of the present invention, comprising the following steps: Step (1): The raw material M1 is subjected to Friedel-Crafts acylation reaction with R2-substituted benzoyl chloride to obtain intermediate M2; Raw material M1 has the following structure: R2-substituted benzoyl chloride has the following structure: Intermediate M2 has the following structure: , The Friedel-Crafts acylation reaction of starting material M1 with R2-substituted benzoyl chloride is shown below: Step (2): Intermediate M2 is subjected to Friedel-Crafts acylation reaction with acyl chloride compound R3CH2COCl to obtain intermediate M3; Acyl chloride compound R3CH2COCl has the following structure: Intermediate M3 has the following structure: , The Friedel-Crafts acylation reaction of intermediate M2 with acyl chloride compound R3CH2COCl is shown below: 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 shown below: 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 methyl, ethyl, isopropyl or sec-butyl; R2 is selected from hydrogen or methyl; R3 is selected from ethyl, cyclohexylmethyl, cyclopentylmethyl, cyclopentylethyl or cyclohexylethyl.

[0009] In some embodiments of the preparation method described in this invention, R1 is selected from ethyl, isopropyl, or sec-butyl; R3 is selected from ethyl or cyclohexylmethyl.

[0010] 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.

[0011] According to some embodiments of the preparation method described in this invention, the molar ratio of raw material M1 to benzoyl chloride substituted by R2 is 1:(1-1.1); for example: 1:1, 1:1.02, 1:1.05, 1:0.07, 1:1.1 or any value between them.

[0012] According to some embodiments of the preparation method described in this invention, the molar ratio of intermediate M2 to acyl chloride R3CH2COCl is 1:(1-1.1); 1:1, 1:1.02, 1:1.05, 1:0.07, 1:1.1 or any value between them.

[0013] 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.

[0014] According to some embodiments of the preparation method of the present invention, the catalyst includes aluminum trichloride, preferably anhydrous aluminum trichloride.

[0015] According to some embodiments of the preparation method of the present invention, the molar ratio of the total amount of catalyst to the R2-substituted benzoyl chloride or acyl chloride R3CH2COCl is (0.5-2):1, for example, 0.5:1, 0.7:1, 0.9:1, 1:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1, 2:1 or any value between them.

[0016] The molar ratio of the catalyst to the R2-substituted benzoyl chloride or acyl chloride R3CH2COCl is 1:1.

[0017] According to some embodiments of the preparation method of the present invention, in steps (1) and (2), 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 or any value between them.

[0018] According to some embodiments of the preparation method of the present invention, in steps (1) and (2), the temperature of the Friedel-Crafts acylation reaction is -10 to 10°C.

[0019] According to some embodiments of the preparation method of the present invention, in steps (1) and (2), the Friedel-Crafts acylation reaction time is 1-8 h; for example, 1 h, 2 h, 3 h, 4 h, 6 h, 8 h or any value between them.

[0020] And / or, in step (3), the molar ratio of raw material M3 to nitrite or nitrite is 1:(1-1.5); for example, 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 of the present invention, the reaction is carried out in an organic solvent, preferably selected from DMSO, alcohol solvents, ether solvents, ester solvents, aromatic solvents or chlorinated alkane solvents.

[0023] 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.

[0024] 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.

[0025] 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.

[0026] According to some embodiments of the preparation method of the present invention, the aromatic solvent is selected from benzene, toluene and chlorobenzene.

[0027] According to some embodiments of the preparation method described in this invention, 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, or 35°C.

[0029] According to some embodiments of the preparation method described in this invention, in step (4), 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 according to the present invention, the organic solvent 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 of the present invention, 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.

[0035] According to some embodiments of the preparation method of the present invention, the molar ratio of the acid-binding agent to the CH3COCl is (1-1.2):1; for example, 1:1, 1.1:1, 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 of the present invention, the method for preparing the highly sensitive oxime ester compound includes the following steps: S1, raw material M1 and R2-substituted benzoyl 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 shown 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 highly sensitive oxime ester compound as described in the first aspect of the present invention or a highly sensitive 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 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 high-sensitivity oxime ester compound described in the first aspect of the present invention or the 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 pigment in the photoresist is a black pigment.

[0060] According to some embodiments of the photoresist of the present invention, the pigments in the photoresist are carbon black and titanium black.

[0061] 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.

[0062] 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.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] 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.

[0068] According to some embodiments of the display described in this invention, the display includes a PCB display, an LCD display, and an OLED display.

[0069] 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.

[0070] According to some embodiments of the printed article of the present invention, the printed article includes a printed circuit board and a color filter.

[0071] The eighth aspect of the present invention provides the application of the high-sensitivity oxime ester compound described in the first aspect of the present invention, the high-sensitivity oxime ester compound obtained by the preparation method of the second aspect of the present invention, the photocurable composition described in the third aspect of the present invention, or the photoresist described in 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 photoresist, PCB solder resist ink, substrate protective coating, electronic device protective coating, passivation film, liquid or dry film resist material, sealant, dental material, optical material, optical film, optical fiber coating, insulating film, polarizer, microscope lens, and recording material.

[0072] 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.

[0073] The beneficial effects of the present invention include: the compounds of the present invention have significantly low photolysis and / or thermal degassing in photocurable composition formulations, especially photoresists, while having high sensitivity properties. Detailed Implementation

[0074] 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.

[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: OXE02, a product of BASF, Germany; Comparative compound C-3: prepared according to Example 13 of literature CN1514845A.

[0078] Note: In C-1 Z This indicates that the ON bond in the oxime ester group is in the cis double bond configuration, and is on the same side as the carbonyl group on the double bond.

[0079] Compound preparation Preparation Example 1: 6-Benzoyl-3-(2E-2-acetoxyiminobutyryl)-9-ethylcarbazole I-1 Step 1a. In a 250 mL three-necked flask, add 10 g (0.051 mol) of 9-ethylcarbazole and 100 mL of dichloromethane, stir to dissolve, weigh 6.81 g (0.051 mol) of anhydrous aluminum trichloride, add to the reaction flask, stir and cool to 0 °C, add 7.17 g (0.051 mol) of benzoyl chloride dropwise, stir and react for 4 h after the addition is complete; add another 6.81 g (0.051 mol) of anhydrous aluminum trichloride, keep at 0 °C, add 6.0 g (0.056 mol) of n-butyryl chloride dropwise, keep at the temperature for 4 h after the addition is complete, 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 16.43 g of white powder, HPLC purity 98.8%, intermediate I-1A, yield 87.2%, DSC melting point 136.9 °C; I-1A Step 1b. In a 100 mL three-necked flask, add 10 g (27.1 mmol) of intermediate I-1A obtained in step 1a, dissolve in 50 mL of dimethyl sulfoxide, weigh 3.35 g (32.5 mmol) of butyl nitrite, purge with 1 g of dry hydrochloric acid gas, stir at 25 °C for 5 h, add 100 mL of water, extract with 100 mL of ethyl acetate, 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, separate by silica gel column chromatography, eluent is a methanol-dichloromethane mixture with a volume ratio of 1:20, first obtain the eluent of the major component, then the eluent of the minor component; after evaporating the solvent from the eluent of the major component, 5.85 g of off-white solid, i.e., intermediate I-1B, yield 54.3%, HPLC analysis I -1B purity 98.85%; DSC melting point 171.7℃; I-1B Step 1c. In a 50 mL three-necked flask, add 2.0 g (5 mmol) of intermediate I-1B obtained in step 1b and 6 mL of dichloromethane, and add 0.56 g (5.5 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 6 mL of methanol while hot, and cool to precipitate a light yellow solid. After drying, 1.8 g of the solid was obtained, with a yield of 81.4% and a purity of 99.2% as determined by HPLC. Melting point: 34.8-41.3 °C. 1 H-NMR data confirm that it is the compound shown in Formula I-1; 1H-NMR data (CDCl3, δ[ppm]) 1.2002-1.2193-1.2383(t,3H,CH3), 1.4702-1.4883-1.5062(t,3H,CH3), 2.2890(s,3H,COCH3),2.8340-2.8531-2.8722-2.8914(quartet,2H,CH2),4.4047-4.4229-4.4410-4.45 90(quartet,2H,N-CH2),7.4698-7.5523(m,4H,4ArH),7.6045-7.6223-7.6415(t,H,ArH),7.8449-7.8623 (d,2H,2ArH), 8.0574 / 8.0614-8.0790 / 8.0829(dd,1H,ArH), 8.2716 / 8.2757-8.2933 / 8.2976 (dd,1H,ArH), 8.6455 / 8.6495(d,1H,ArH), 8.8447 / 8.8491(d,1H, ArH).

[0080] Preparation Example 2: 6-(2,4,6-trimethylbenzoyl)-3-(2E-2-acetoxyimino-3-cyclohexylpropionyl)-9-(2-methoxyethyl)carbazole Ⅰ-3 Step 2a. 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 and 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%, which was intermediate I-3A with a yield of 97%. The DSC melting point was 127 °C. Ⅰ-3A Step 2b. In a 100 mL three-necked flask, add 5 g (0.013 mol) of intermediate I-3A obtained in step 2a, 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 the crude intermediate I-3B, 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 I-3B is 98.2%; I-3B Step 2c. In a 50 mL three-necked flask, add 2.68 g (6.5 mmol) of intermediate I-3B obtained in step 2b 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 I-3; 1 H-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).

[0081] Preparation Example 3: 6-(2-methylbenzoyl)-3-(2E-2-acetoxyimino-3-cyclohexylpropionyl)-9-ethylcarbazole I-4 Steps 3a-3c. Follow steps 2a-2c of Preparation Example 2, except that in step 3a, 3-cyclohexylpropionyl chloride is used instead of n-butyryl chloride in the second Friedel-Crafts reaction to obtain intermediate I-4A. After two steps of α-oxime and esterification, the target product I-4 is finally obtained. It is a light yellow crystalline powder with an overall yield of 66.8% and an HPLC purity of 99.1%. The DSC melting point is 149.0℃. 1 H-NMR data confirm that it is the target compound I-4; 1 1H-NMR data (CDCl3, δ [ppm]): 1.0282–1.2563 (m, 5H, Cy-CH2), 1.4632–1.4813–1.4993 (t, 3H, CH3), 1.5935–1.7560 (m, 6H, Cy-CH2+CH), 2.2878 (s, 3H, ArCH3), 2.3574 (s ,3H,COCH3), 2.8015-2.8185(d,2H,CH2), 4.3927-4.4108-4.4290-4.4471(quarte t,2H,N-CH2), 7.2829-7.4351(m,4H,4ArH), 7.4441-7.4645-7.4849(t,2H,2ArH), 8.0243 / 8.0285-8.0459 / 8.0502(dd,1H,ArH), 8.3066 / 8.3109-8.3284 / 8.3327(dd,1H,ArH), 8.6150 / 8.6190(d,1H,ArH), 8.8586 / 8.8632(d,1H,ArH).

[0082] Preparation Example 4: 6-(3-methylbenzoyl)-3-(2E-2-acetoxyimino-3-cyclohexylpropionyl)-9-ethylcarbazole I-6 Steps 4a-4c. Follow steps 2a-2c of Preparation Example 2, except that in step 4a, m-methylbenzoyl chloride is used instead of o-methylbenzoyl chloride in the first Friedel-Crafts reaction, and 3-cyclohexylpropionyl chloride is used instead of n-butyryl chloride in the second Friedel-Crafts reaction, to obtain intermediate I-6A. After two steps of α-oxime and esterification, the target product I-6 is finally obtained. It appears as a light yellow crystalline powder with an overall yield of 65.2% and an HPLC purity of 99.3%; the DSC melting point is 123.1℃. 1 H-NMR data confirms it to be the target compound I-6; 1H-NMR data (CDCl3, δ[ppm]): 1.0270-1.2572(m,5H,Cy-CH2), 1.4804-1.4984-1.5164(t,3H, CH3), 1.5989-1.7618(m,6H,Cy-CH2+CH), 2.2863(s,3H,COCH3), 2.4627(s,3H,ArCH3), 2.8 071-2.8241(d,2H,CH2),4.4162-4.4342-4.4524-4.4705(quartet,2H,N-CH2),7.3928-7 .4491(m,2H,2ArH),7.4801 / 7.4880-7.5021 / 7.5096(dd,2H,2ArH),7.6200-7.6369(d,1H, ArH), 7.6755(s,1H,ArH), 8.0584 / 8.0626-8.0799 / 8.0840(dd, 1H,ArH), 8.3093 / 8.3136-8.3311 / 8.3354(dd,1H,ArH), 8.6483 / 8.6524(d,1H,ArH), 8.8859 / 8.8901(d, 1H,ArH).

[0083] Preparation Example 5: 6-(2-methylbenzoyl)-3-(2E-2-acetoxyimino-3-cyclohexylpropionyl)-9-isopropylcarbazole I-10 Steps 5a-5c. Follow steps 2a-2c of Preparation Example 2, except that in step 5a, m-9-isopropylcarbazole is used instead of 9-ethylcarbazole in step 2a in the first Friedel-Crafts reaction, and 3-cyclohexylpropionyl chloride is used instead of n-butyryl chloride in step 2a in the second Friedel-Crafts reaction, to obtain intermediate I-10A. After two steps of α-oxime and esterification, the target product I-10 is finally obtained. It appears as a light yellow crystalline powder with an overall yield of 60.8% and an HPLC purity of 99.0%; melting point 69.7-75.7℃. 1 H-NMR data confirm that it is the target compound I-10; 11H-NMR data (CDCl3, δ [ppm]): 1.0276–1.2707 (m, 5H, Cy-CH2), 1.6026–1.7432 (m, 6H, Cy-CH2+CH), 1.7446–1.7619 (d, 6H, 2CH3) , 2.2897(s,3H,COCH3), 2.3620(s,3H,ArCH3), 2.8027-2.8195(d,2H,CH2), 4.9977-5.0145-5.0318-5.0493-5.0669 -5.0843-5.1011(heptet,1H,N-CH),7.2857-7.3042-7.3225(t,1H,ArH),7.3338-7.3528-7.3725-7.3911(quartet, 2H,2ArH) ,7.4176-7.4366-7.4553(t,1H,ArH),7.5648-7.5887-7.6131(t,1H, ArH),8.0040-8.0259(d, 1H,ArH), 8.2823-8.3044(d,1H,ArH), 8.6162(s,1H,ArH), 8.8608(s, 1H,ArH).

[0084] Preparation of 6-benzoyl-3-(2Z-2-acetoxyiminobutyryl)-9-ethylcarbazole by comparison with compound C-1 C-1 Step 4b. In operation 1b of Preparation Example 1, the reaction product was separated by silica gel column chromatography, first obtaining the eluent of the major component, and then the eluent of the minor component; after evaporating the solvent from the eluent of the minor component, 0.5 g of a white foamy solid was obtained, with a yield of 4.6%; HPLC analysis showed that the purity of C-1B was 97.6%. C-1B Step 4c. In a 50 mL three-necked flask, add 0.5 g (1.25 mmol) of intermediate C-1B obtained in step 4a and 5 mL of dichloromethane, and add 0.14 g (1.37 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 2 mL of methanol while hot, and cool to -10 °C to precipitate a light yellow solid. After drying, 0.4 g of the solid was obtained, with a yield of 72.6% and a purity of 98.2% according to HPLC analysis. The melting point is 40.1-47.5 °C. 1 H-NMR data confirm that it is the compound shown in formula C-1; 1H-NMR data (CDCl3, δ[ppm]) 1.2393-1.2577-1.2761(t,3H,CH3), 1.5105-1.5284-1.5464(t,3H,CH3), 1.879(s,3H,COCH3),2.7097-2.7300-2.7489-2.7661(quartet,2H,CH2),4.4303-4.4484-4.4 665-4.4846(quartet,2H,N-CH2),7.4858-7.5562(m,4H,4ArH),7.6148-7.6340-7.6532(t,1H, ArH), 7.8369-7.8551 (d,2H,2ArH), 8.0051 / 8.0091-8.0288 / 8.0328(dd,1H,ArH), 8.0933 / 8.0978-8.1150 / 8.1195 (dd,1H,ArH), 8.5493 / 8.5538(d,1H,ArH), 8.6210 / 8.6255(d,1H, ArH).

[0085] 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.

[0086] 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.

[0087] Examples and Comparative Examples of Photoresist Compositions The compounds prepared in Preparation Examples 1-5, Comparative Compound C-1, Comparative Compound C-2, and Comparative Compound C-3 were used as photoinitiators and dissolved in PMA (propylene glycol methyl ether acetate) according to the proportions in Table 1. They were then mixed with black pigment according to the proportions in Table 1. The amount is measured in grams.

[0088] Comparative compound C-1: self-made.

[0089] Comparative compound C-2: photoinitiator OXE02, purchased from BASF, Germany.

[0090] Comparative compound C-3: prepared according to Example 13 of literature CN1514845A.

[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 performance; the corresponding values ​​were recorded.

[0092] Table 1 records the sensitivity data.

[0093] Table 1

[0094] In summary, in photoresist formulations, the compounds described in this invention exhibit significantly higher sensitivity compared to the comparative compounds at the same dosage. The comparative compound C-1 is a cis isomer of compound I-1 of this invention, and its sensitivity is significantly lower than that of its corresponding trans isomer.

[0095] 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 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 methyl, ethyl, isopropyl, or sec-butyl; R2 is selected from hydrogen or methyl; R3 is selected from ethyl, cyclohexylmethyl, cyclopentylmethyl, cyclopentylethyl, or cyclohexylethyl.

2. The highly sensitive oxime ester compound according to claim 1, characterized in that, R1 is selected from ethyl, isopropyl, or sec-butyl; R3 is selected from ethyl or cyclohexylmethyl.

3. The highly sensitive oxime ester compound according to claim 1, characterized in that, The compound is selected from:

4. A method for preparing the 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 R2-substituted benzoyl chloride to obtain intermediate M2; Raw material M1 has the following structure: R2-substituted benzoyl chloride 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 R3CH2COCl to obtain intermediate M3; Acyl chloride compound R3CH2COCl 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 methyl, ethyl, isopropyl or sec-butyl; R2 is selected from hydrogen or methyl; R3 is selected from ethyl, cyclohexylmethyl, cyclopentylmethyl, cyclopentylethyl or cyclohexylethyl.

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 benzoyl chloride substituted with R2 is 1:(1-1.1); And / or, the molar ratio of intermediate M2 to acyl chloride R3CH2COCl is 1:(1-1.1); Preferably, in steps (1) and (2), the temperature of the Friedel-Crafts acylation reaction is independently -15 to 25°C. And / or, in steps (1) and (2), the chlorinated hydrocarbon solvent is selected from 1,2-dichloroethane, dichloromethane, or o-dichlorobenzene; And / or, in steps (1) and (2), the catalyst comprises aluminum trichloride; And / or, in steps (1) and (2), the molar ratio of the catalyst to R2-substituted benzoyl chloride or acyl chloride R3CH2COCl is (0.5-2):1, preferably 1:1; and / or, in step (3), the molar ratio of raw material M3 to nitrite or nitrite 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; And / or, the reaction is carried out in an organic solvent, preferably 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 chloroalkane is 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 highly sensitive oxime ester compound according to any one of claims 1-3 or a highly sensitive oxime ester compound obtained 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 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 highly sensitive oxime ester compound according to any one of claims 1-3 or the highly sensitive oxime ester compound obtained by the preparation method according to 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 fabricated from the photoresist of claim 7 or the black matrix of claim 8, wherein, The pigment in the photoresist is a red pigment, a green pigment, or a blue pigment.

10. A display obtained by photocuring a highly sensitive oxime ester compound as described in any one of claims 1-3 or a highly sensitive 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 high-sensitivity oxime ester compound of any one of claims 1-3, the high-sensitivity 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 photoresist, PCB solder resist ink, substrate protective coating, electronic device protective coating, passivation film, liquid or dry film resist material, sealant, dental material, optical material, optical film, fiber optic coating, insulating film, polarizer, microscope lens, and recording material.

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, which is obtained by photocuring using the highly sensitive oxime ester compound according to any one of claims 1-3 or the highly sensitive oxime ester compound obtained by the preparation method of claim 4 or 5 as a photoinitiator; Preferably, the printed article includes a printed circuit board and a color filter.

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