Trans-trans dioxime acetate compound, preparation method therefor, and use thereof

Abstract

The present invention provides a trans-trans dioxime acetate compound having the structure shown in Formula I: where, in Formula I, the symbol E indicates that the O-N bond distribution in the oxime group is trans; R1 is selected from C1-C6 alkyl, C1-C2 alkylene substituted with C5-C7 cycloalkyl, and ethylene substituted with C1-C4 alkoxy; R2 and R2' are each independently selected from C1-C7 alkyl, C1-C2 alkylene substituted with C5-C7 cycloalkyl, and C5-C7 cycloalkyl. The compound of the present invention exhibits high sensitivity performance in photocurable composition formulations, especially in photoresists, with performance markedly superior to that of the existing technology.

Description

Trans-trans bisoxime acetate compounds, methods of making and using the same

[0001] Cross-reference to related applications

[0002] This application claims priority to Chinese Patent Application No. 202410544823.4, filed April 30, 2024, the entire contents of which are incorporated herein by reference in their entirety. TECHNICAL FIELD

[0003] The present invention relates to trans-trans bisoxime acetate compounds, methods of making and using the same. BACKGROUND

[0004] Photocuring technology has been widely used since its appearance in the 1970s, for example, UV photocuring technology is widely used in the fields of coatings, printing inks, and electronic device manufacturing. One of the most concerned issues for photocuring technology personnel is the curing efficiency or sensitivity. The key factor affecting the curing efficiency is the structure of the photoinitiator and the auxiliary initiator components used with it.

[0005] Patent WO2002 / 100903 discloses oxime ester compounds with more complex substituents on the diphenyl sulfide parent structure and oxime ester compounds with carbazole as the parent. Commercial products such as BASF's OXE 02, although the sensitivity is improved, but its yellowing is also stronger, which makes its use in transparent photoresist and color photoresist very limited. Chinese patent CN101565472B makes changes to the side chain based on the aforementioned patent compounds, but it does not fundamentally change the sensitivity and yellowing of the corresponding oxime ester compounds. Patent CN101528694A discloses oxime ester compounds with nitrocarbazole as the parent, and patent CN103153952A discloses oxime ester compounds with benzocarbazole as the parent. Due to the introduction of the chromophore group nitro or the large conjugated structure of benzocarbazole, the corresponding oxime ester compounds have a significant red shift in the ultraviolet absorption spectrum. For example, NCI-831 of Japan's ADEKA and OXE 03, two commercial products, have more effective absorption of 365 nm emitted light of the light source, showing higher sensitivity. However, they contain nitro groups or polyfluoroalkyl groups, which lack thermal stability or bring environmental impact that cannot be degraded. To improve the sensitivity of photoresist, the photoinitiator used by the technical personnel requires high sensitivity, and the industry still needs to develop new photoinitiator products with higher sensitivity.

[0006] Patent document CN117348340A discloses a negative photoresist taking compound A as a photoinitiator, and patent document CN104076606B discloses the preparation of compound B, but neither of them indicates the structure of the oxime group, and generally, the substituents on the double bond have cis or trans isomers, and the configuration of such compounds is more complex due to the two oxime groups.

[0007] SUMMARY

[0008] To solve the above technical problems, the present application provides a trans-trans double oxime acetate compound, a preparation method and application thereof. In a first aspect of the present application, a trans-trans double oxime acetate compound is provided, which has a structure as shown in formula I,

[0009] In formula I, symbol E represents that the O-N bond in the oxime group is in trans form.

[0010] R1 is selected from C1-C7 alkyl, C5-C7 cycloalkyl-substituted C1-C2 alkylene, and C1-C4 alkoxy-substituted ethylene.

[0011] R2 and R2' are each independently selected from C1-C7 alkyl, C5-C7 cycloalkyl-substituted C1-C2 alkylene, and C5-C7 cycloalkyl.

[0012] According to some embodiments of the compound of the present application, R1 is selected from C1-C4 alkyl.

[0013] According to some embodiments of the compound of the present application, R1 is selected from 2-methoxyethyl and 2-ethoxyethyl.

[0014] According to some embodiments of the compound of the present application, R2 and R2' are the same and selected from C1-C6 alkyl and C5 or C6 cycloalkyl-substituted methylene.

[0015] According to some embodiments of the compound of the present application, the compound is selected from:

[0016] In a second aspect of the present application, a preparation method of a trans-trans double oxime acetate compound is provided, which comprises the following steps:

[0017] Step (1): reacting raw material M1 with nitrite or nitrous acid under acidic conditions to obtain a mixture of cis-trans isomer M2' and trans-trans isomer M2;

[0018] Step (2): the anti-anti isomer M2 is obtained by purification after isomer conversion reaction of the product obtained in step (1);

[0019] Step (3): the compound described in formula I is obtained by esterification reaction of the anti-anti isomer M2 with CH3COCl or (CH3CO)2O;

[0020] wherein, symbol E represents that the O-N bond in the oxime group is in trans form, and Z represents that the O-N bond in the oxime group is in cis form;

[0021] R1 is selected from C1-C6 alkyl, C5-C7 cycloalkyl-substituted C1-C2 alkylene, C1-C4 alkoxy-substituted ethylene;

[0022] R2, R2' are each independently selected from C1-C7 alkyl, C5-C7 cycloalkyl-substituted C1-C2 alkylene, C5-C7 cycloalkyl.

[0023] According to some embodiments of the preparation method of the anti-anti bisoxime acetate compound according to the present application, the preparation method comprises the following steps:

[0024] Step a: the intermediate M1 is obtained by acidolysis treatment of the reaction product of the Friedel-Crafts acylation reaction of the raw material N-alkyl carbazole with acyl chloride R2CH2COCl and acyl chloride R2'CH2COCl;

[0025] Step b: the mixture of the cis-trans isomer M2' and the anti-anti isomer M2 is obtained by reaction of the intermediate M1 obtained in step a with nitrite or nitrous acid under acidic conditions;

[0026] Step c: the anti-anti isomer M2 is obtained by purification after isomer conversion reaction of the product obtained in step b;

[0027] Step d: the compound described in formula I is obtained by esterification reaction of the anti-anti isomer M2 with CH3COCl or (CH3CO)2O;

[0028] wherein, symbol E represents that the O-N bond in the oxime group is in trans form, and Z represents that the O-N bond in the oxime group is in cis form;

[0029] R1 is selected from C1-C6 alkyl, C5-C7 cycloalkyl-substituted C1-C2 alkylene, C1-C4 alkoxy-substituted ethylene;

[0030] R2, R2' are each independently selected from C1-C7 alkyl, C5-C7 cycloalkyl-substituted C1-C2 alkylene, C5-C7 cycloalkyl.

[0031] According to some embodiments of the preparation method of the present application, in step a, the molar ratio of N-alkylcarbazole to acyl chloride R2CH2COCl is 1:(1-1.2); for example, 1:1, 1:1.1, 1:1.2.

[0032] According to some embodiments of the preparation method of the present application, in step a, the molar ratio of N-alkylcarbazole to acyl chloride R2’CH2COCl is 1:(1-1.2); for example, 1:1, 1:1.1, 1:1.2.

[0033] According to some embodiments of the preparation method of the present application, in step a, the Friedel-Crafts acylation reaction is carried out in an organic solvent.

[0034] According to some embodiments of the preparation method of the present application, the organic solvent is selected from 1,2-dichloroethane or dichloromethane.

[0035] According to some embodiments of the preparation method of the present application, in step a, the Friedel-Crafts acylation reaction is carried out in the presence of a catalyst.

[0036] According to some embodiments of the preparation method of the present application, the catalyst comprises anhydrous aluminum chloride.

[0037] According to some embodiments of the preparation method of the present application, the molar ratio of the catalyst to the N-alkylcarbazole is (1-2.5):1; for example, 1:1, 1.2:1, 1.5:1, 2:1.

[0038] According to some embodiments of the preparation method of the present application, in step a, the temperature of the Friedel-Crafts acylation reaction is -20 to 30°C; for example, -20°C, -10°C, 0°C, 10°C, 20°C, 30°C.

[0039] According to some embodiments of the preparation method of the present application, the temperature of the Friedel-Crafts acylation reaction is -10 to 10°C.

[0040] According to some embodiments of the preparation method of the present application, the time of the Friedel-Crafts acylation reaction is 1-8h; for example, 1h, 2h, 3h, 4h, 6h, 8h.

[0041] According to some embodiments of the preparation method of the present application, in step (1), the molar ratio of the raw material M1 to nitrite or nitrous acid is 1:(2-3); for example, 1:2, 1:2.2, 1:2.4, 1:2.6, 1:3.

[0042] According to some embodiments of the preparation method of the present application, the nitrite ester is selected from isoamyl nitrite, butyl nitrite, sec-butyl nitrite, isobutyl nitrite, tert-butyl nitrite, methyl nitrite, ethyl nitrite, isopropyl nitrite or propyl nitrite.

[0043] According to some embodiments of the preparation method of the present application, in step (1), the reaction is carried out in an organic solvent.

[0044] According to some embodiments of the preparation method of the present application, the organic solvent is selected from DMSO, alcohols, ethers, esters, aromatic hydrocarbons or chlorinated alkanes.

[0045] According to some embodiments of the preparation method of the present application, 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, methyl tetrahydrofuran, 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 and ethyl butyrate; the aromatic hydrocarbon solvent is selected from benzene, toluene and chlorobenzene; and the chlorinated alkane is selected from dichloromethane and 1,2-dichloroethane.

[0046] According to some embodiments of the preparation method of the present application, the temperature of the reaction is 5-25℃; for example, 5℃, 10℃, 20℃ or 25℃.

[0047] According to some embodiments of the preparation method of the present application, the reaction time is 4-8h; for example, 4h, 6h, 7h or 8h.

[0048] According to some embodiments of the preparation method of the present application, in step (2), the product obtained in step (1) is subjected to isomerization reaction at 80-100℃.

[0049] According to some embodiments of the preparation method of the present application, the isomerization reaction is carried out in a solvent or without solvent.

[0050] According to some embodiments of the preparation method of the present application, the product of the isomerization reaction is purified by column chromatography or recrystallization to obtain the trans-trans isomer M2.

[0051] According to some embodiments of the preparation method of the present application, in step (3), the molar ratio of the trans-trans isomer M2 to CH3COCl or (CH3CO)2O is 1:(2-2.5); for example, 1:2, 1:2.2, 1:2.3 or 1:2.5.

[0052] According to some embodiments of the preparation method of the present application, the esterification reaction is carried out in an aprotic solvent.

[0053] According to some embodiments of the preparation method of the present application, the aprotic solvent is selected from dichloromethane, ethyl acetate, toluene and methyl tert-butyl ether.

[0054] According to some embodiments of the preparation method of the present application, when the reaction raw material is CH3COCl, an acid binding agent needs to be added to the reaction system.

[0055] According to some embodiments of the preparation method of the present application, the acid binding agent is selected from pyridine and triethylamine.

[0056] According to some embodiments of the preparation method of the present application, 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.

[0057] According to some embodiments of the preparation method of the present application, the temperature of the esterification reaction is 20-60℃; for example, 20℃, 30℃, 35℃, 40℃, 50℃, 60℃.

[0058] According to some embodiments of the preparation method of the present application, the time of the esterification reaction is 3-5h; for example, 3h, 4h, 5h.

[0059] According to some embodiments of the preparation method of the present application, taking compound I-1 as an example, the preparation method is as follows:

[0060] Step (1): the Friedel-Crafts acylation reaction of the raw material N-ethylcarbazole with two moles of butyryl chloride is carried out in a solvent 1,2-dichloroethane or dichloromethane with anhydrous aluminum chloride as a catalyst, and the intermediate I-M1 is obtained by acidolysis treatment; the reaction is usually carried out at -20 to 30℃, preferably -10 to 10℃; the aluminum chloride complex in the reaction solution is generally dissociated with dilute hydrochloric acid aqueous solution, then washed with water, and the solvent is removed; the residue is a solid, which is crystallized with a common solvent such as ethanol to further improve the purity of the intermediate I-M1;

[0061] Step (2): the intermediate I-M1 reacts with nitrite or nitrous acid under acid conditions to obtain a mixture of trans-cis isomer I-M2' and trans-trans isomer I-M2;

[0062] The nitrite is selected from isopentyl nitrite, butyl nitrite, sec-butyl nitrite, isobutyl nitrite, tert-butyl nitrite and other compounds that are liquid at room temperature; the volatile methyl nitrite, ethyl nitrite, isopropyl nitrite and propyl nitrite can also be used in a container with good sealing.

[0063] Nitrous acid generated directly from sodium nitrite and hydrochloric acid gas or hydrochloric acid solution is also an optional raw material scheme;

[0064] Step (3): further purifying the trans-trans isomer I-M2 through isomerization reaction, column chromatography or recrystallization;

[0065] The isomerization reaction is carried out by heating the mixture of the trans-cis isomer and the trans-trans isomer in a solvent or without a solvent to 80-100°C, in which the trans-cis isomer is thermally converted into the trans-trans isomer, and the trans-trans isomer I-M2 is further purified through column chromatography or recrystallization;

[0066] Step (4): esterifying the intermediate I-M2 in step (3) with CH3COCl or (CH3CO)2O to obtain the compound of formula I-1; wherein the O-N bond of the oxime ester group is in the trans configuration; the esterification reaction is carried out in an aprotic solvent such as dichloromethane, toluene, methyl tert-butyl ether, and when acetyl chloride is used, an equimolar amount of base needs to be added simultaneously as an acid-binding agent to neutralize the by-produced hydrochloric acid, and the reaction solution is washed with water, dried, and recrystallized to obtain the trans-trans bisoxime acetate compound;

[0067] In a third aspect of the present application, a photocuring composition is provided, which comprises a photoinitiator and a free-radical polymerizable compound, wherein the photoinitiator comprises the trans-trans bisoxime acetate compound of the first aspect of the present application or the trans-trans bisoxime acetate compound obtained by the preparation method of the second aspect of the present application.

[0068] According to some embodiments of the photocuring composition of the present application, the free-radical polymerizable compound is selected from acrylate compounds, methacrylate compounds, and combinations thereof.

[0069] According to some embodiments of the photocuring composition of the present application, the free-radical polymerizable compound comprises one or more of an alkyl acrylate, a cycloalkyl acrylate, a hydroxyalkyl acrylate, a dialkylaminoalkyl acrylate, an alkyl methacrylate, a cycloalkyl methacrylate, a hydroxyalkyl methacrylate, a dialkylaminoalkyl methacrylate, an acrylated epoxy resin, an acrylated polyester resin, an unsaturated polyester resin, an acrylated polyether resin, and an acrylated polyurethane resin.

[0070] According to some embodiments of the photocurable composition of the present application, the free-radically polymerizable compound includes one or more of methyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, ethyl methacrylate, polysiloxane acrylate, vinyl acetate, styrene, diacrylate of ethylene glycol, diacrylate of polyethylene glycol, diacrylate of propylene glycol, diacrylate of neopentyl glycol, diacrylate of 1,6-hexanediol, triacrylate of trihydroxymethane, tetraacrylate of pentaerythritol, hexaacrylate of dipentaerythritol, vinyl acrylate, triallyl isocyanurate.

[0071] According to some embodiments of the photocurable composition of the present application, the mass ratio of the trans-trans bisoxime acetate compound in the photocurable composition is 0.1-8.0%, 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 therebetween.

[0072] According to some embodiments of the photocurable composition of the present application, other photoinitiators or co-initiators can also be included in the photocurable composition of the present application, and the present application does not make any special limitation on the specific types of the other initiators or co-initiators, and any photoinitiator or co-initiator that is helpful to the photocuring performance in the art can be selected.

[0073] The present application also provides an adhesive, which, in addition to the photocurable composition of the third aspect of the present application, can also add other necessary ingredients according to the performance requirements of the adhesive, such as a polymer with a molecular weight of 5000-100000 to improve the adhesive performance, for use in bonding glass, plastic, metal components, etc. In addition, those skilled in the art can easily add other necessary ingredients according to the prior art and the needs of the use of the photocurable composition, such as stabilizers, surfactants, leveling agents, dispersants.

[0074] In the fourth aspect of the present application, a photoresist is provided, and 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 trans-trans bisoxime acetate compound of the first aspect of the present application or the trans-trans bisoxime acetate compound obtained by the preparation method of the second aspect of the present application.

[0075] According to some embodiments of the photoresist of the present application, the multifunctional acrylate monomer is selected from acrylate monomers with a functionality of ≥3. The present application does not make any special limitation on the specific types of the multifunctional acrylate monomer, and those skilled in the art can select and use it from the conventional multifunctional acrylate monomers in the art.

[0076] According to some embodiments of the photoresist according to the present application, the multifunctional acrylate monomer includes dipentaerythritol hexaacrylate and / or pentaerythritol acrylate.

[0077] According to some embodiments of the photoresist according to the present application, the alkali-soluble resin is a resin having an acid group which can be dissolved or dispersed when coming into contact with an alkaline solution. The present application does not particularly limit the specific kind of the alkali-soluble resin, and one skilled in the art can select and use it from among conventional alkali-soluble resins in the art.

[0078] According to some embodiments of the photoresist according to the present application, the alkali-soluble resin includes a polyacrylate or a polymethacrylate having a carboxylic acid group.

[0079] According to some embodiments of the photoresist according to the present application, the alkali-soluble resin includes a copolymer of one or more of methacrylic acid, itaconic acid, maleic acid and one or more of methyl acrylate, methyl methacrylate, butyl methacrylate, benzyl acrylate, benzyl methacrylate, hydroxyethyl acrylate, styrene, butadiene, maleic anhydride, such as methyl methacrylate and methacrylic acid copolymer, benzyl methacrylate and methacrylic acid copolymer, methyl methacrylate and butyl methacrylate copolymer, and methacrylic acid and styrene copolymer.

[0080] According to some embodiments of the photoresist according to the present application, the organic solvent is selected from one or more of ester-based solvents, aromatic hydrocarbon-based solvents, and halogenated alkane-based solvents.

[0081] According to some embodiments of the photoresist according to the present application, the organic solvent is selected from one or more of propylene glycol monomethyl ether acetate, ethylene glycol methyl ether acetate, toluene, xylene, and tetrachloroethane.

[0082] According to some embodiments of the photoresist according to the present application, the photoinitiator further includes one or more of 2,2-dimethoxy-2-phenylacetophenone, 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)-1-butanone, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-1-butanone, 2-dimethylamino-2-benzyl-1-(4-piperidinophenyl)-1-butanone, 2,4,6-trimethylbenzoylbenzophenone, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, and bis(2,6-difluoro-3-pyrrolophenyl)titanocene.

[0083] According to some embodiments of the photoresist of the present application, the photoinitiator further comprises commercially available oxime ester photoinitiators, such as OXE01, OXE02, OXE03, OXE04, PBG305, PBG304, PBG3057, NCI1919, NCI831, and the like.

[0084] According to some embodiments of the photoresist of the present application, the raw materials for preparing the photoresist further comprise pigments.

[0085] According to some embodiments of the photoresist of the present application, the pigments are red pigments, green pigments, blue pigments, or black pigments.

[0086] According to some embodiments of the photoresist of the present application, the red pigments comprise C.I. Pigment Red 177, the green pigments comprise C.I. Pigment Green 7, the blue pigments comprise C.I. Pigment Blue 15:6 and Solvent Blue 25, and the black pigments comprise carbon black, titanium black, and C.I. Pigment Black 1.

[0087] According to some embodiments of the photoresist of the present application, the raw materials for preparing the photoresist further comprise heat stabilizers or light stabilizers, such as p-methoxyphenol. Other resins, such as polyalkyl methacrylate, ethyl cellulose, carboxymethyl cellulose, linear phenol-formaldehyde resin, polyvinyl butyral, polyvinyl acetate, polyester, polyimide, and the like, can also be added.

[0088] Using the photoresist of the present application as raw materials, through the existing technical processes such as coating, exposure, and development of multiple different color photoresists in the process of manufacturing color filters, a color filter device with excellent optical performance can be obtained, which is an important component of color display screens. The color units therein have pure colors and high transmittance, and the colorless parts have low yellowing degree and high transmittance.

[0089] The coating of the photoresist is usually performed by the method of spin coating to uniformly distribute the photoresist on the substrate, and then dried at 80-90°C to separate the volatile components such as solvents, leaving the solid components into a film. A mask is placed on the top of the film, and then exposed to a suitable amount of light under a radiation light source containing a 365 nm mercury lamp or an LED lamp. The exposed material is developed in an alkaline solution such as sodium carbonate or sodium hydroxide to remove the unexposed film, leaving the exposed image. Then, the image is washed and post-baked at 200-230°C to better adhere to the substrate. According to the designed program, the photoresist of different colors and patterns is manufactured, or combined with the necessary protective film processing program to obtain the filter device.

[0090] In a fifth aspect, the present application provides a black matrix prepared from the photoresist according to the fourth aspect of the present application, wherein the pigment in the photoresist is black pigment, preferably carbon black and titanium black.

[0091] In a fifth aspect, the present application provides a black matrix prepared from the photoresist according to the fourth aspect of the present application, wherein the pigment in the photoresist is black pigment, preferably carbon black and titanium black.

[0092] In a sixth aspect, the present application provides a color filter device prepared from the photoresist according to the fourth aspect of the present application, wherein the pigment in the photoresist is red pigment, green pigment or blue pigment.

[0093] In a seventh aspect, the present application provides a display prepared by photo-curing the anti-anti form bisoxime acetate compound according to the first aspect of the present application or the anti-anti form bisoxime acetate compound prepared by the method according to the second aspect of the present application as a photoinitiator.

[0094] According to some embodiments of the display of the present application, the display includes PCB display, LCD display and OLED display.

[0095] In an eighth aspect, the present application provides the use of the anti-anti form bisoxime acetate compound according to the first aspect of the present application, the anti-anti form bisoxime acetate compound prepared by the method according to the second aspect of the present application, the photo-curing composition according to the third aspect of the present application or the photoresist according to the fourth aspect of the present application in the preparation of colored or uncolored ink, paint, adhesive, filter, display, pattern printing, printing plate, 3D printing, PCB photoresist, PCB solder mask ink, base material protective coating, electronic device protective coating, passivation film, liquid or dry film resist, sealant, dental material, optical material, optical film, optical fiber coating, insulation film, polarizer, microscopic lens and recording material.

[0096] According to some embodiments of the printed article of the present application, the printed article includes printed circuit board, color filter.

[0097] In an eighth aspect, the present application provides the use of the anti-anti form bisoxime acetate compound according to the first aspect of the present application, the anti-anti form bisoxime acetate compound prepared by the method according to the second aspect of the present application, the photo-curing composition according to the third aspect of the present application or the photoresist according to the fourth aspect of the present application in the preparation of colored or uncolored ink, paint, adhesive, filter, display, pattern printing, printing plate, 3D printing, PCB photoresist, PCB solder mask ink, base material protective coating, electronic device protective coating, passivation film, liquid or dry film resist, sealant, dental material, optical material, optical film, optical fiber coating, insulation film, polarizer, microscopic lens and recording material.

[0098] The color filter, LCD color display screen, OLED color display screen, PCB and printed article can be prepared by using the compound of formula (I) or the photoinitiator composition containing the compound of formula (I) and the photoresist containing the compound of formula (I) as raw materials and processing through necessary procedures.

[0099] The beneficial effects of the present application include that the compounds described in the present application have a significantly high sensitivity performance in the formulation of photocuring compositions, especially photoresists, and the performance is significantly better than the prior art. DETAILED DESCRIPTION

[0100] In order to make the objects, technical solutions and advantages of the present application clearer, the present application is further described in detail below with examples. The specific examples described herein are only used to explain the present application and do not constitute any limitation on the present application. In addition, in the following description, the description of well-known structures and technologies is omitted to avoid unnecessary confusion of the concept of the present disclosure. Such structures and technologies are also described in many publications.

[0101] The term "C1-C7 alkyl" used in the present application refers to a linear or branched chain alkyl group having 1-7 carbon atoms, including but not limited to methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, etc.

[0102] The term "cycloalkyl" used in the present application refers to an alkyl group having at least one ring, and C5-C7 cycloalkyl refers to a cyclic alkyl group having 5-7 carbon atoms, such as cyclopentyl, cyclohexyl, cyclooctyl, especially cyclopentyl and cyclohexyl.

[0103] Experimental materials and equipment:

[0104] Light source equipment:

[0105] 365nm LED surface light source, Shanghai Futanxi Science and Technology Co., Ltd.

[0106] Test equipment:

[0107] Differential scanning calorimeter: HSC-1, Beijing Hengju Experimental Equipment Co., Ltd.;

[0108] Stereo microscope: HY-950S, Beijing Huanru Technology Co., Ltd., line width unit: μm;

[0109] Yellowness meter: Full-automatic colorimeter SC-80C, Beijing Jingyi Kangguang Optical Instrument Co., Ltd.

[0110] Experimental materials:

[0111] Genomer 4212: aliphatic polyurethane acrylate, product of RAHN Company;

[0112] DPHA: dipentaerythritol hexaacrylate, product of Tianjin Tianjia Chemical Co., Ltd.;

[0113] HDDA: 1,6-hexanediol diacrylate, product of Tianjin Tianjia Chemical Co., Ltd.;

[0114] Comparative compound C-1 : NCI 831, product of Japanese company ADEKA;

[0115] Comparative compound C-2: OXE03, product of German company BASF.

[0116] Preparation of compounds

[0117] Preparation example 1 3,6-di(2E-2-acetyloxyiminobutanoyl)-9-ethylcarbazole

[0118] Step 1a. In a 100 mL three-necked flask, put 9-ethylcarbazole 20 g (0.102 mol) and 200 g dichloromethane (hereinafter referred to as DCM), cool to -10 °C, put anhydrous aluminum chloride 28.68 g (0.215 mol), stir, drop butyryl chloride 22.92 g (0.215 mol) within 30 min, then stir the reaction at 0 °C for 2 h. Carry out acidolysis and water washing of the reaction liquid to neutral, remove DCM by rotary evaporation, add ethyl acetate 80 mL while hot, precipitate white crystals, cool to 0 °C and filter, dry the filter cake to obtain white crystals 31.65 g as intermediate I-1A; yield 92.1%, HPLC content 99.81%, DSC melting point: 117.4 °C;

[0119] Step 1b. In a 100 mL three-necked flask, put 10 g (30 mmol) of the intermediate I-1A sample obtained in step 1a, 50 ml of ethyl acetate, cool to 5-10 °C, drop 7.05 g (68.5 mmol) of butyl nitrite, stir and incubate at 5-10 °C, then continuously pass in HCl gas in small amounts, react for 5 h. When HPLC analysis shows that the monoxime compound is reduced to below 1%, add the reaction liquid to 50 mL of dilute sodium carbonate aqueous solution, stir for 30 min, separate the lower aqueous phase, wash the upper organic phase with 20 mL of water once, dry the organic phase with 1 g of Na2SO4 for 4 h, filter to remove the drying agent, rotary evaporate the filtrate to dryness, the remaining 10 g of light yellow sticky crude product contains 20% of a secondary isomer and 73% of a major isomer according to HPLC analysis; yield 85%; divide it into two equal parts, one part is subjected to thermal conversion reaction, and the other part is subjected to column chromatography separation;

[0120] Step 1c. Isomer conversion reaction operation: the intermediate crude product 5g obtained in step 1b was dissolved in 10 mL of ethyl acetate and heated to reflux for 3 h. HPLC analysis showed 3% of the minor isomer and 88.5% of the major isomer. Most of the ethyl acetate was removed by distillation, and 30 mL of methanol was added to the remaining material. Crystallization occurred upon cooling, and the precipitated crystals were filtered and dried under reduced pressure to obtain 3.8 g of light yellow crystalline powder with a yield of 66.4%. HPLC analysis showed a purity of 98.8% for the major isomer, and the melting point was 181.7°C (decomposition). NMR analysis showed that it was a symmetrical trans-trans bisoxime compound I-1B. 1 H-NMR data (CDC13, δ [ppm]): 1.1046-1.1235-1.1424 (t, 6H, 2CH3), 1.4355-1.4538-1.4717 (t, 3H, CH3), 2.7146-2.7336-2.7526-2.7715 (quartet, 4H, 2CH2), 4.3487-4.3671-4.3855-4.4032 (quartet, 2H, CH2), 7.4151-7.4368 (d, 2H, 2ArH), 8.1661 / 8.1703-8.1879 / 8.1922 (dd, 2H, 2ArH), 8.79970 / 8.8013 (d, 2H, 2ArH), 9.4862 (s, 2H, 2N-OH), identified as an E-E bisoxime compound, also known as a trans-trans bisoxime compound;

[0121] Step 1c’. The intermediate crude product 5g obtained in step 1b was purified by silica gel column chromatography using dichloromethane-methanol (20:1 by volume) as the eluent. The minor isomer I-1B’ was obtained first, and the solvent was evaporated to obtain 0.6 g of a white solid with a purity of 98.5% by HPLC. The melting point was 77-88°C. The major isomer I-1B was obtained later, and the solvent was evaporated to obtain 3.0 g of a white solid with a purity of 99.1% by HPLC. The minor isomer I-1B ’ identified as an asymmetrical Z-E bisoxime compound I-1B’ by NMR analysis; 1H-NMR data (CDC13, δ [ppm]): 1.1520-1.1704-1.1888-1.2074 (t+t, 6H, 2CH3), 1.3922-1.4104-1.4284 (t, 3H, CH3), 2.5294-2.5481-2.5668-2.5855 (quartet, 2H, Z-CH2), 2.7614-2.7802-2.7992-2.8182 (quartet, 2H, E-CH2), 4.3175-4.3351-4.3532-4.3710 (quartet, 2H, CH2), 7.3833-7.4050 (d, 1H, Z-ArH), 7.4104-7.4321 (d, 1H, E-ArH), 8.0589 / 8.0630-8.0806 / 8.0847 (dd, 1H, Z-ArH), 8.1398 / 8.1441-8.1616 / 8.1657 (dd, H, E-ArH), 8.5755 / 8.5796 (d, 1H, Z-ArH), 8.6215 (s, 1H, Z-N-OH), 8.7806 / 8.7846 (d, 1H, E-ArH), 9.6924 (s, 1H, E-N-OH);

[0122] Step 1d. In a 50 mL single neck flask, add the intermediate I-1B from step 1c 3.93 g (10 mmol), add 20 ml DCM, then add 2.25 g (22 mmol) acetic anhydride, heat the oil bath to 40 °C, stir the reaction magnetically for 4 h. Wash with pure water 3 times, 5 ml water each time, wash to pH = 6-7. Dry the DCM under reduced pressure, add 10 ml ethyl acetate to the residue to recrystallize, precipitate yellow solid at low temperature, filter at 0 °C, dry to get 3.48 g yellow powder, yield 73%; HPLC purity 99.05%, DSC melting point 113.1 °C;

[0123] 1 H-NMR data proved to be a compound of formula I-1; 1H-NMR data (CDC13, δ [ppm]) 1.2139-1.2331-1.2520 (t, 6H, 2CH3), 1.4451-1.4631-1.4812 (t, 3H, CH3), 2.3085 (s, 6H, 2COCH3), 2.8470-2.8661-2.8852-2.9041 (quartet, 4H, 2CH2), 4.3814-4.3995-4.4177-4.4358 (quartet, 2H, N-CH2), 7.4632-7.4850 (d, 2H, 2ArH), 8.2766 / 8.2808-8.2983 / 8.3026 (dd, 2H, 2ArH), 8.9269 / 8.9311 (d, 2H, 2ArH).

[0124] Preparation Example 2 3,6-di(2E-2-acetyloxyimino butanoyl)-9-methylcarbazole

[0125] Step 2a. Follow the procedure of Preparation Example 1, Step 1a, using 9-methylcarbazole instead of 9-ethylcarbazole to give intermediate I-2A as off-white crystals in 95% yield, HPLC purity 99.17%; DSC melting point: 178.2°C;

[0126] Step 2b. Follow the procedure of Preparation Example 1, Step 1b, using intermediate I-2A instead of I-1A to give crude intermediate I-2B, HPLC analysis contains 81% of major isomer and 18% of minor isomer; yield 88%;

[0127] Step 2c. Follow the procedure of Preparation Example 1, Step 1c, to perform isomer conversion reaction on crude intermediate I-2B and then recrystallization to give yellow crystalline powder in 68.9% yield, HPLC analysis: major isomer trans-trans bisoxime intermediate I-2B purity 98.8%, melting point 216.6°C;

[0128] Step 2d. Follow the procedure of Preparation Example 1, Step 1d, to perform esterification reaction using intermediate I-2B instead of I-1B to give yellow crystals in 83.4% yield, HPLC purity 98.7%; DSC melting point 90.1°C; 1 H-NMR data proved to be the target I-2;

[0129] 1H-NMR data (CDC13, δ [ppm]): 1.4477-1.4655-1.4838 (t, 3H, CH3), 2.3156 (s, 6H, 2COCH3), 2.3759 (s, 6H, 2CH3), 4.3812-4.3993-4.4175-4.4357 (quartet, 2H, N-CH2), 7.4634-7.4852 (d, 2H, 2ArH), 8.3033 / 8.3076-8.3251 / 8.3294 (dd, 2H, 2ArH), 8.9465 / 8.9508 (d, 2H, 2ArH).

[0130] Preparation Example 3 3,6-Bis(2E-2-acetyloxyiminopropionyl)-9-ethylcarbazole

[0131] Steps 3a-3d. Following the procedure of Preparation Example 1, Steps la-Id, where in Step 3a propionyl chloride is used instead of n-butyryl chloride in Step la, the target product I-4 is obtained; appearance yellow powder crystals, overall yield 58.2%, HPLC purity 99.03%, DSC melting point: 164.2 °C. 1 H-NMR data (CDC13, δ [ppm]): 1.4477-1.4655-1.4838 (t, 3H, CH3), 2.3156 (s, 6H, 2COCH3), 2.3759 (s, 6H, 2CH3), 4.3812-4.3993-4.4175-4.4357 (quartet, 2H, N-CH2), 7.4634-7.4852 (d, 2H, 2ArH), 8.3033 / 8.3076-8.3251 / 8.3294 (dd, 2H, 2ArH), 8.9465 / 8.9508 (d, 2H, 2ArH).

[0132] Preparation Example 4 3,6-Bis(2E-2-acetyloxyiminopropionyl)-9-n-propylcarbazole

[0133] Steps 4a-4d. Following the procedure of Preparation Example 1, Steps la-Id, where in Step 4a 9-n-propylcarbazole is used instead of 9-ethylcarbazole and propionyl chloride is used instead of n-butyryl chloride in Step la, the target product I-5 is obtained; appearance yellow powder crystals, overall yield 51.5%, HPLC purity 98.21%, DSC melting point: 191.3 °C. 1H-NMR data (CDC13, δ [ppm]): 0.9424-0.9608-0.9793 (t, 3H, CH3), 1.8868-1.9049-1.9230-1.9412-1.9593-1.9774 (sixtet, 2H, CH2), 2.3158 (s, 6H, 2COCH3), 2.3751 (s, 6H, 2CH3), 4.3036-4.3214-4.3393 (t, 2H, N-CH2), 7.4659-7.4878 (d, 2H, 2ArH), 8.2993 / 8.3036-8.3210 / 8.3254 (dd, 2H, 2ArH), 8.9492 / 8.9536 (d, 2H, 2ArH).

[0134] Preparation Example 5 3,6-di(2E-2-acetyloxyimino-3-cyclohexylpropionyl)-9- ethylcarbazole

[0135] Step 5a-5d. Following the procedure of Preparation Example 1, Steps la-Id, where 3-cyclohexylpropionyl chloride was used instead of n-butyryl chloride in Step 5a, the final target product I-13 was obtained; appearance yellow powder crystal, overall yield 62.2%, HPLC purity 98.61%, DSC melting point: 162.5 °C. 1 H-NMR data (CDC13, δ [ppm]): 0.9424-0.9608-0.9793 (t, 3H, CH3), 1.8868-1.9049-1.9230-1.9412-1.9593-1.9774 (sixtet, 2H, CH2), 2.3158 (s, 6H, 2COCH3), 2.3751 (s, 6H, 2CH3), 4.3036-4.3214-4.3393 (t, 2H, N-CH2), 7.4659-7.4878 (d, 2H, 2ArH), 8.2993 / 8.3036-8.3210 / 8.3254 (dd, 2H, 2ArH), 8.9492 / 8.9536 (d, 2H, 2ArH).

[0136] Preparation Example 6 3-(2E-2-acetyloxyiminooctanoyl)-6-(2E-2-acetyloxyimino-3- cyclohexylpropionyl)-9-ethylcarbazole

[0137] Step 6a. In a 250 ml flask, put 9-ethylcarbazole 10 g (0.0512 mol) and dichloromethane 100 ml, stir to dissolve, weigh anhydrous aluminum chloride 6.82 g (0.0512 mol), put into the flask, stir to cool to 0 °C, drop in n-octanoyl chloride 8.33 g (0.0512 mol), after dropping, stir to react for 4 h; add anhydrous aluminum chloride 6.82 g (0.0512 mol), keep at 0 °C, drop in 3-cyclohexylpropionyl chloride 8.94 g (0.0512 mol), after dropping, keep to react for 4 h; acidolyze the reaction solution with hydrochloric acid and water, wash with water, add methanol 200 ml while hot after removing most of the dichloromethane, cool to precipitate white crystals, filter, and dry under reduced pressure to obtain white powder 22.61 g, with a purity of 98.85% by HPLC, which is intermediate I-20A, with a yield of 96%, and a DSC melting point of 51.1 °C;

[0138] Step 6b. In a 100 ml flask, put intermediate I-20A 6 g (0.013 mol) obtained in step 6a, dissolve in ethyl acetate 15 ml, weigh isoamyl nitrite 4.0 g (0.034 mol), drop in concentrated hydrochloric acid 2 ml, stir to react at 25 °C for 5 h, add 10 ml of water, stir to wash with water, separate the water layer to obtain a yellow ethyl acetate solution, wash once more with 10 ml of water, and analyze by HPLC, which contains 71.2% of the main isomer and 20.1% of the secondary isomer;

[0139] Step 6c. Reflux the organic phase to remove water for 1 h, continue to reflux at 82 °C for 4 h, remove most of the ethyl acetate by distillation under reduced pressure, add methanol 30 ml while hot, cool to precipitate yellow solids, which are intermediate I-20B, dry to obtain 4.92 g, with a yield of 73.2%, and a purity of 98.3% by HPLC analysis;

[0140] Step 6d. In a 50 ml flask, put intermediate I-20B 1.5 g (2.9 mmol) obtained in step 6b and dichloromethane 8 ml, drop in acetic anhydride 0.62 g (6.1 mmol), stir to react at 35 °C for 5 h, wash the reaction solution with water, remove most of the dichloromethane by distillation under reduced pressure, add methanol 12 ml while hot, cool to precipitate yellow solids, dry to obtain 1.38 g, with a yield of 80%, and a purity of 98.2% by HPLC analysis; the DSC melting point is 92.5 °C; 1 H-NMR data prove that it is the target compound I-20;

[0141] 1H-NMR data (CDC13, 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).

[0142] Preparation Example 7 3,6-Bis(2E-2-acetyloxyiminopropionyl)-9-cyclohexylmethylcarbazole

[0143] Steps 7a-7d. Following the procedure of Preparation Example 1, Steps la-Id, where 9-cyclohexylmethylcarbazole was used instead of 9-ethylcarbazole in Step 7a, the final target product I-21 was obtained as yellow powder crystals in a total yield of 60.5%, HPLC purity 98.55%, DSC melting point: 138.0 °C. 1 H-NMR data (CDC13, δ [ppm]): 1.0535-1.1913 (m, 6H, 3CH2), 1.2175-1.2366-1.2557 (t, 6H, 2CH3), 1.6073-1.7088 (m, 4H, 2CH2), 2.3110 (s, 6H, 2COCH3), 2.8488-2.8680-2.8871-2.9064 (quartet, 4H, 2CH2), 4.1634-4.1817 (d, 2H, N-CH2), 7.4679-7.4897 (d, 2H, 2ArH), 8.2794 / 8.2838-8.3011 / 8.3055 (dd, 2H, 2ArH), 8.9324 / 8.9368 (d, 2H, 2ArH).

[0144] Preparation 8 3,6-Bis(2E-2-acetyloxyimino-3-cyclohexylpropionyl)-9- cyclohexylmethylcarbazole

[0145] Steps 8a-8d. Following the procedure of Preparation 1, steps 1a-1d, where in step 8a, 9-cyclohexylmethylcarbazole was used instead of 9-ethylcarbazole and 3- cyclohexylpropionyl chloride was used instead of n-butyryl chloride in step 1a, the target product I-22 was obtained in the end; appearance of yellow powder crystal, overall yield 65.8%, HPLC purity 99.15%, DSC melting point: 168.5 °C.

[0146] 1 H-NMR data (CDC13, δ [ppm]): 1.0440-1.2755 (m, 15H, CH2), 1.5687-1.7764 (m, 17H, CH2+CH), 1.9618-2.0537 (m, 1H, CH), 2.3018 (s, 6H, 2COCH3), 2.8205-2.83375 (d, 4H, 2CH2), 4.1621-4.1803 (d, 2H, N-CH2), 7.4683-7.4902 (d, 2H, 2ArH), 8.3091 / 8.3134-8.3308 / 8.3351 (dd, 2H, 2ArH), 8.9858 / 8.9901 (d, 2H, 2ArH).

[0147] Preparation 9 3,6-Bis(2E-2-acetyloxyimino butyryl)-9-butylcarbazole

[0148] Steps 9a-9d. Following the procedure of Preparation 1, steps 1a-1d, where in step 9a, 9-butylcarbazole was used instead of 9-ethylcarbazole in step 1a, the target product I-24 was obtained in the end; appearance of yellow powder crystal, overall yield 66.3%, HPLC purity 98.85%, DSC melting point: 120.2 °C. 1H-NMR data (CDC13, δ [ppm]): 0.9152-0.9337-0.9520 (t, 3H, CH3), 1.2105-1.2297-1.2488 (t, 6H, 2CH3), 1.3130-1.3314-1.3498-1.3695-1.3884-1.4070 (sextet, 2H, CH2), 1.8130-1.8312-1.8503-1.8693-1.8870 (quintuptet, 2H, CH2), 2.3041 (s, 6H, 2COCH3), 2.8415-2.8606-2.8798-2.8989 (quartet, 4H, 2CH2), 4.3126-4.3306-4.3485 (t, 2H, N-CH2), 7.4489-7.4708 (d, 2H, 2ArH), 8.2637 / 8.2680-8.2856 / 8.2899 (dd, 2H, 2ArH), 8.9182 / 8.9224 (d, 2H, 2ArH).

[0149] Preparation Example 10 3,6-di(2E-2-acetyloxyiminopentanoyl)-9-ethylcarbazole

[0150] Steps 10a-10d. Following the procedure of Preparation Example 1, Steps la-Id, wherein n-valeryl chloride is used instead of n-butyryl chloride in Step 10a, the final target product I-25 is obtained; appearance yellow powder crystal, total yield 68.4%, HPLC purity 98.21%, DSC melting point: 103.7°C. 1 H-NMR data (CDC13, δ [ppm]): 0.9152-0.9337-0.9520 (t, 3H, CH3), 1.2105-1.2297-1.2488 (t, 6H, 2CH3), 1.3130-1.3314-1.3498-1.3695-1.3884-1.4070 (sextet, 2H, CH2), 1.8130-1.8312-1.8503-1.8693-1.8870 (quintuptet, 2H, CH2), 2.3041 (s, 6H, 2COCH3), 2.8415-2.8606-2.8798-2.8989 (quartet, 4H, 2CH2), 4.3126-4.3306-4.3485 (t, 2H, N-CH2), 7.4489-7.4708 (d, 2H, 2ArH), 8.2637 / 8.2680-8.2856 / 8.2899 (dd, 2H, 2ArH), 8.9182 / 8.9224 (d, 2H, 2ArH).

[0151] Preparation Example 11 3,6-Bis(2E-2-acetyloxyiminobutanoyl)-9-methylcarbazole

[0152] Steps 11a-11d. Following the procedure of Preparation Example 1, Steps 1a-1d, where in Step 11a, 9-methylcarbazole was used instead of 9-ethylcarbazole in Step 1a, n-pentanoyl chloride was used instead of n-butyryl chloride in Step 1a, and the target product I-26 was obtained in the end; appearance of yellow powder crystals, overall yield 69.5%, HPLC purity 98.8%, DSC melting point: 136.2°C.

[0153] 1 H-NMR data (CDC13, δ [ppm]): 1.007 0-1.025 4-1.043 9 (t, 6H, 2CH3), 1.631 0-1.649 6-1.668 6-1.687 6-1.706 5-1.725 3 (sextet, 2H, CH2), 2.305 5 (s, 6H, 2COCH3), 2.831 4-2.850 9-2.870 2 (t, 4H, 2CH2) 3.913 7 (s, 3H, N-CH3), 7.455 6-7.477 3 (d, 2H, 2ArH), 8.294 4 / 8.298 7-8.316 2 / 8.320 4 (dd, 2H, 2ArH), 8.941 8 / 8.945 9 (d, 2H, 2ArH).

[0154] Preparation Example 12 3,6-Bis(2E-2-acetyloxyiminobutanoyl)-9-isopropylcarbazole

[0155] Steps 12a-12d. Following the procedure of Preparation Example 1, Steps 1a-1d, where in Step 12a, 9-isopropylcarbazole was used instead of 9-ethylcarbazole in Step 1a, and the target product I-27 was obtained in the end; appearance of yellow powder crystals, overall yield 58.5%, HPLC purity 98.87%, DSC melting point: 102.9°C. 1H-NMR data (CDC13, δ [ppm]): 1.2150-1.2341-1.2532 (t, 6H, 2CH3), 1.7350-1.7524 (d, 6H, 2CH3), 2.3092 (s, 6H, 2COCH3), 2.8487-2.8678-2.8870-2.9060 (quartet, 4H, 2CH2), 4.9902-5.0078-5.0253-5.0429-5.0605-5.0780-5.0955 (heptet, 1H, N-CH), 7.5968-7.6190 (d, 2H, 2ArH), 8.2610 / 8.2655-8.2831 / 8.2874 (dd, 2H, 2ArH), 8.9546 / 8.9589 (d, 2H, 2ArH).

[0156] Preparation Example 13 3-(2E-2-acetyloxyimino propionyl)-6-(2E-2-acetyloxyimino butyryl)-9- ethyl carbazole

[0157] Step 13a. In a 250 ml three-necked flask, put 9-ethyl carbazole 10 g (0.0512 mol) and DCM 100 ml, stir to dissolve, weigh anhydrous aluminum chloride 6.82 g (0.0512 mol), put into the reaction flask, stir to cool to 0 °C, drop butyryl chloride 6.18 g (0.0512 mol), after dropping, stir to react for 4 h; add anhydrous aluminum chloride 6.82 g (0.0512 mol), keep at 0 °C, drop propionyl chloride 4.74 g (0.0512 mol), after dropping, keep to react for 4 h; use hydrochloric acid and water to acid hydrolyze the reaction solution, then water wash, after removing most of the DCM, add hot methanol 50 ml, cool to precipitate white crystals, filter, and dry under reduced pressure to obtain white powder 15.1 g, with HPLC purity 99.62%, which is intermediate I-29A, with a yield of 91.7%, and DSC melting point 119.5 °C;

[0158] Step 13b. In a 100 ml three-necked flask, put intermediate I-29A 5 g (0.0155 mol) obtained in step 13a, dissolve with ethyl acetate 25 ml, weigh butyl nitrite 3.53.0 g (0.0342 mol), drop concentrated hydrochloric acid 2 ml, stir to react at 25 °C for 5 h, add 10 ml water, stir to wash with water, separate the yellow ethyl acetate solution, and wash once more with 10 ml water; HPLC analysis shows that the solution contains 80.5% of the main isomer and 11.4% of the secondary isomer.

[0159] Step 13c. The organic phase was refluxed with water separation for 1 h, and then refluxed at 82°C for another 4 h. The solution was directly purified by column chromatography with DCM as eluent. The DCM was removed by distillation under reduced pressure to obtain a dark yellow oil, which was weighed as 4.29 g of intermediate I-29B with a yield of 73% and a purity of 98.5% by HPLC analysis.

[0160] Step 13d. In a 50 ml three-necked flask, 2 g (5.2 mmol) of intermediate I-29B obtained in step 13c and 8 ml of DCM were added, and 1.24 g (12.1 mmol) of acetic anhydride was added dropwise. The reaction was stirred at 35°C for 5 h. The reaction solution was washed with water, and most of the DCM was removed by distillation under reduced pressure. While hot, 12 ml of methanol was added, and yellow solid was precipitated upon cooling. After drying, 1.88 g was obtained with a yield of 78.3% and a purity of 98.9% by HPLC analysis. The melting point was 123.7°C by DSC. 1 H-NMR data proved that it was the target compound I-29. 1 H-NMR data (CDC13, δ [ppm]): 1.2172-1.2363-1.2555 (t, 3H, CH3), 1.4546-1.4727-1.4907 (t, 2H, CH3), 2.3101 (s, 3H, COCH3), 2.3159 (s, 3H, COCH3), 2.3769 (s, 3H, CH3), 2.8499-2.8690-2.8882-2.9073 (quartet, 2H, CH2), 4.3897-4.4078-4.4261-4.4443 (quartet, 2H, N-CH2), 7.4703-7.4922 (d, 2H, 2ArH), 8.2838 / 8.2881-8.3055 / 8.3098 (dd, 1H, ArH), 8.3145 / 8.3189-8.3364 / 8.3406 (dd, 1H, ArH), 8.9195 / 8.9237 (d, 1H, ArH), 8.9748 / 8.9790 (d, 1H, ArH).

[0161] Preparation Example 14 3-(2E-2-acetyloxyimino butanoyl)-6-(2E-2-acetyloxyimino octanoyl)-9- ethyl carbazole

[0162] Steps 14a-14d. According to the procedures of steps 6a-6d of Preparation Example 6, in the second Friedel-Crafts acylation reaction in step 14a, n-butyryl chloride was used instead of 3-cyclohexylpropionyl chloride in step 6a, and finally the target product I-32 was obtained. The appearance was dark yellow viscous substance, the total yield was 35.5%, and the purity was 96.17% by HPLC. 1H-NMR data (CDCI3, δ [ppm]): 0.8473-0.8651-0.8821 (t, 3H, CH3), 1.2185-1.2375-1.2568 (t, 3H, CH3), 1.2862-1.3383 (m, 4H, 2CH2), 1.3755-1.4294 (m, 2H, CH2), 1.4394-1.4575-1.4755 (t, 3H, CH3), 1.5921-1.6118-1.6308-1.6511-1.6688 (quintuplet, 2H, CH2), 2.3087 (s, 3H, COCH3), 2.3118 (s, 3H, COCH3), 2.8426-2.9079 (t + quartet, 4H, 2CH2), 4.3706-4.3886-4.4067-4.4248 (quartet, 2H, N-CH2), 7.4539-7.4758 (d, 2H, 2ArH), 8.2716 / 8.2756-8.2778 / 8.2826 (dd, 1 H, ArH), 8.2933 / 8.2976-8.3000 / 8.3043 (dd, 1 H, ArH), 8.9256 / 8.9302 (d, 1 H, ArH), 8.9378 / 8.9420 (d, 1 H, ArH).

[0163] Preparation example 15 3,6-bis(2E-2-acetyloxyiminobutanoyl)-9-(2-methoxyethyl)carbazole

[0164] Step 15a. In a 250 mL three-necked flask was placed: carbazole 20 g (0.12 mol), toluene 100 mL, a solution of potassium hydroxide 10 g (0.178 mol) in 15 mL of water, 2-bromoethyl methyl ether 20 g (0.144 mol), catalyst tetrabutylammonium bromide 2 g, the temperature was brought to 70°C, the reaction was stirred vigorously for 5 h, 100 mL of water was added, the phases were separated after standing, the aqueous phase was separated, the organic phase was washed twice with 50 mL of water, the toluene was removed by rotary evaporation under reduced pressure, 30 mL of methylcyclohexane was added while hot, the solution was stirred until it cleared, then it was cooled to precipitate a white crystalline solid, which was filtered and dried to obtain intermediate I-36A as a white crystalline solid 25.68 g, in 95% yield, with a HPLC purity of 99.2% and a DSC melting point of 75.9°C;

[0165] Step 15b. In a 100 mL flask, put the intermediate I-36A from step 15a 6 g (26.6 mmol) and 80 g DCM, cool to -10 °C, put in anhydrous aluminum chloride 7.46 g (56 mmol), stir, drop in n-butyryl chloride 5.96 g (56 mmol) in 30 min, then stir the reaction at 0 °C for 2 h. Acidolysis and water washing to neutral, remove DCM by rotary evaporation, add ethanol 20 ml while hot, cool to precipitate light yellow crystals, cool to 0 °C and filter, dry the filter cake to get light yellow crystals 7.85 g as intermediate I-36B; yield 80.6%, HPLC content 97.8%, DSC melting point: 115.9 °C;

[0166] Step 15c. In a 100 mL flask, put the intermediate I-36B from step 15b sample 4 g (11 mmol), ethyl acetate 20 mL, cool to 5-10 °C, drop in butyl nitrite 1.36 g (13.2 mmol), stir and incubate at 5-10 °C, then continuously add HCl gas in small amounts, react for 5 h. When the HPLC analysis of the monoxime compound is reduced to less than 1%, add the reaction solution to 50 ml of dilute sodium carbonate aqueous solution, stir for 30 min, separate the lower aqueous phase, wash the upper organic phase with 20 mL of water once, dry the organic phase with 1 g of Na2SO4 for 4 h, filter to remove the drying agent, and rotary evaporate the filtrate to dryness. The remaining material is 4 g of light yellow sticky crude product, which contains 12% of the secondary isomer and 83% of the main isomer according to HPLC analysis; perform silica gel column chromatography purification, elute with 1:200 methanol-DCM eluent, collect the main isomer containing component, and rotary evaporate the solvent to 2.88 g, which has a HPLC purity of 98.35% and is intermediate I-36C, with a yield of 61.8%;

[0167] Step 15d. In a 50 mL single-neck flask, add intermediate I-36C from step 15c 1.2 g (2.8 mmol), add DCM 6 mL, then add acetic anhydride 0.64 g (6.2 mmol), heat the oil bath to 40 °C, and magnetically stir the reaction for 4 h. Wash with pure water 3 times, each time with 5 mL of water, until the pH is 6-7. Dry the DCM under reduced pressure, recrystallize the remaining material with ethyl acetate 5 mL and methylcyclohexane 5 mL, cool to precipitate yellow solids, filter at 0 °C, and dry to get yellow powder 1.1 g, yield 76.4%; HPLC purity 99.15%, DSC melting point 120.1 °C; 1 H-NMR data prove to be a compound of formula I-36; 1H-NMR data (CDC13, δ [ppm]) 1.2085-1.2277-1.266 (t, 6H, 2CH3), 2.3027 (s, 6H, 2COCH3), 2.8389-2.8580-2.8772-2.8962 (quartet, 4H, 2CH2), 3.2227 (s, 3H, OCH3), 3.7397-3.7532-3.7666 (t, 2H, OCH2), 4.4664-4.4799-4.4935 (t, 2H, N-CH2), 7.4770-7.4989 (d, 2H, 2ArH), 8.2365 / 8.2407-8.2582 / 8.2626 (dd, 2H, 2ArH), 8.8946 / 8.8988 (d, 2H, 2ArH).

[0168] Preparation Example 16 3,6-Bis(2E-2-acetyloxyimino pentanoyl)-9-(2-methoxyethyl)carbazole

[0169] Steps 16a-16d. Following the procedure of Preparation Example 15, steps 15a-15d, wherein n-butyryl chloride is used instead of n-butyryl chloride in step 15b, the final target product I-37 is obtained; appearance yellow powder crystal, total yield 37.8%, HPLC purity 99.18%, DSC melting point: 99.1 °C. 1 H-NMR data proved to be the compound shown in formula I-37; 1 H-NMR data (CDC13, δ [ppm]) 1.0121-1.0306-1.0491 (t, 6H, 2CH3), 1.6365-1.6553-1.6737-1.6933-1.7122-1.7307 (sextent, 4H, 2CH2), 2.3102 (s, 6H, 2COCH3), 2.8355-2.8546-2.8741 (t, 4H, 2CH2), 3.2233 (s, 3H, OCH3), 3.7382-3.7515-3.7648 (t, 2H, OCH2), 4.4573-4.4708-4.4844 (t, 2H, N-CH2), 7.4697-7.4915 (d, 2H, 2ArH), 8.2425 / 8.2469-8.2644 / 8.2687 (dd, 2H, 2ArH), 8.9147 / 8.9191 (d, 2H, 2ArH).

[0170] Preparation Example 17 3,6-Bis(2E-2-acetyloxyimino-3-cyclohexylpropionyl)-9-(2-methoxyethyl)carbazole

[0171] Steps 17a-17d. Operate according to the procedure of Preparation 15, steps 15a-15d, wherein in step 15b operate with 3-cyclohexylpropionyl chloride instead of n-butyryl chloride in step 15b, finally to give the target product I-39; appearance yellow powder crystals, total yield 40.6%, HPLC purity 99.28%, DSC melting point: 158.8°C. 1 H-NMR data proved to be the compound of formula I-39; 1 H-NMR data (CDCI3, δ [ppm]) 1.0396-1.2500 (m, 10H, CH2), 1.5831-1.7693 (m, 12H, CH2+CH), 2.2971 (s, 6H, 2COCH3), 2.8147-2.8318 (d, 4H, 2CH2), 3.2385 (s, 3H, OCH3), 3.7517-3.7653-3.7789 (t, 2H, OCH2), 4.4772-4.4908-4.5044 (t, 2H, N-CH2), 7.4834-7.5053 (d, 2H, 2ArH), 8.2758 / 8.2801-8.2977 / 8.3020 (dd, 2H, 2ArH), 8.9636 / 8.9680 (d, 2H, 2ArH).

[0172] Preparation 18 3,6-di(2E-2-acetyloxyimino-3-cyclohexylpropionyl)-9-(2-ethoxyethyl)carbazole

[0173] Step 18a. Operate according to the procedure of Example 15, step 15a, with equimolar amount of 2-bromoethyl ether instead of 2-bromoethyl methyl ether, the reaction and work-up gave the intermediate I-40A as yellow oil in 99% yield, HPLC purity 99.1%;

[0174] Steps 18b-18d. Operate according to the procedure of Preparation 15, steps 15b-15d, wherein in step 15b operate with the intermediate I-40A obtained in step 18a instead of intermediate I-36A in step 15b; with 3-cyclohexylpropionyl chloride instead of n-butyryl chloride in step 15b, finally to give the target product I-40; appearance yellow powder crystals, total yield 36.8%, HPLC purity 98.16%, DSC melting point: 117°C. 1 H-NMR data proved to be the compound of formula I-40; 1H-NMR data (CDC13, δ [ppm]): 0.8472-0.8643-0.8818 (t, 3H, CH3), 1.0691-1.7744 (m, 19H, 4CH2+ Cy), 2.3021 (s, 6H, 2COCH3), 2.8178-2.8779 (d+t, 4H, 2CH2), 3.2570 (s, 3H, OCH3), 3.7726-3.7861-3.7994 (t, 2H, OCH2), 4.5078-4.5213-4.5347 (t, 2H, N-CH2), 7.5117-7.5334 (d, 2H, 2ArH), 8.2768-8.3021-8.3284 (d+d, 2H, 2ArH), 8.9403 (s, 1H, ArH), 8.9774 (s, 1H, ArH).

[0175] Preparation 19 3-(2E-2-acetyloxyimino octanoyl)-6-(2E-2-acetyloxyimino-3- cyclohexylpropionyl)-9-(2-methoxyethyl)carbazole

[0176] Steps 19a-19d. Following the procedure of Example 6, steps 6a-6d, where in step 19a the intermediate I-36A from the procedure of Preparation 15, step 15a, is used instead of 9- ethylcarbazole in step 6a, and the final target product I-42 is obtained; appearance yellow powder crystals, overall yield 33.4%, HPLC purity 96.86%, DSC melting point: 104.1 °C. 1 H-NMR data prove the compound to be of formula I-42; 1 H-NMR data (CDC13, δ [ppm]): 0.8472-0.8643-0.8818 (t, 3H, CH3), 1.0691-1.7744 (m, 19H, 4CH2+ Cy), 2.3021 (s, 6H, 2COCH3), 2.8178-2.8779 (d+t, 4H, 2CH2), 3.2570 (s, 3H, OCH3), 3.7726-3.7861-3.7994 (t, 2H, OCH2), 4.5078-4.5213-4.5347 (t, 2H, N-CH2), 7.5117-7.5334 (d, 2H, 2ArH), 8.2768-8.3021-8.3284 (d+d, 2H, 2ArH), 8.9403 (s, 1H, ArH), 8.9774 (s, 1H, ArH).

[0177] Preparation of Comparative Compounds

[0178] Comparative Preparation 1 3-(2E-2-acetoxyimino butanoyl)-6-(2Z-2-acetoxyimino butanoyl)-9- ethyl carbazole

[0179] Step 1d. Follow the procedure of Step 1d of Preparation 1, replace intermediate I-1B with I-1B' in Step 1d, after esterification, wash with water, dry DCM, stir at 5-10°C in methyl tert-butyl ether, solid precipitates, filter, dry the filter cake under vacuum to get the product as yellow powder, HPLC purity 98.27%; melting point 26-35°C; which is the target product I-1'; 1 H-NMR data (CDC13, δ [ppm]): 1.2332-1.2521-1.2713 (t, 3H, Z-CH3), 1.2462-1.2651-1.2839 (t, 3H, E-CH3), 1.4803-1.4986-1.5166 (t, 3H, CH3), 1.8877 (s, 3H, Z-COCH3), 2.3089 (s, 3H, E-COCH3), 2.7295-2.7486-2.7674-2.7862 (quartet, 2H, Z-CH2), 2.8680-2.8870-2.9061-2.9253 (quartet, 2H, E-CH2), 4.4204-4.4386-4.4569-4.4750 (quartet, 2H, N-CH2), 7.5063-7.5282 (d, 1H, Z-ArH), 7.5178-7.5393 (d, 1H, E-ArH), 8.0380 / 8.0422-8.0597 / 8.0639 (dd, 1H, Z-ArH), 8.3088 / 8.3131-8.3306 / 8.3349 (dd, 1H, E-ArH), 8.6425 / 8.6466 (d, 1H, Z-ArH), 8.8850 / 8.8891 (d, 1H, E-ArH).

[0180] Preparation of base-soluble resin

[0181] Dissolve benzyl methacrylate 20 g, methacrylic acid 3 g, hydroxyethyl methacrylate 7 g, azobisisobutyronitrile 1.5 g, dodecanethiol 0.5 g in 200 mL of toluene and put into a constant pressure dropping funnel. Put 100 mL of toluene into a 500 mL four-necked flask, replace with nitrogen, heat to 80°C, drop the solution in the dropping funnel, after 6 h of reaction, cool and filter to get 24 g of white base-soluble resin.

[0182] Preparation of black colorant paste

[0183] Take 50 g of the alkali-soluble resin prepared by the above method, 50 g of Mitsubishi PK7 carbon black, 100 g of DPHA, 250 g of propylene glycol methyl ether acetate into a 500 mL beaker, mix with a high-speed shear mixer at a speed of 5000 r / min for 15 min to prepare a black color paste.

[0184] Red color paste preparation

[0185] Take 50 g of the alkali-soluble resin prepared by the above method, 50 g of DIC PR122 pink pigment, 100 g of DPHA, 250 g of propylene glycol methyl ether acetate into a 500 mL beaker, mix with a high-speed shear mixer at a speed of 5000 r / min for 15 min to prepare a red color paste.

[0186] Photoresist composition examples and comparative examples

[0187] The compounds prepared in Preparation Examples 1-19, the compound obtained in Comparative Preparation Example 1, and Comparative Compounds C-1 and C-2 were mixed and dissolved in PMA as photo initiators according to the proportions in Table 1, and then mixed with the black color paste according to the proportions in Table 1, with the amount unit being grams.

[0188] Comparative Compound C-1: photo initiator NCI 831, purchased from ADEKA Company, Japan.

[0189] Comparative Compound C-2: photo initiator OXE03, purchased from BASF Company, Germany.

[0190] After the components were mixed uniformly, a 10 μm wire rod was used to coat a film on a glass slide, which was dried in a 90°C oven for 5 min, a 365 nm surface light source was used, a 41-step exposure scale was used as a mask, a 0.0425% KOH aqueous solution was used for development at 25°C, and the film was cleaned by soaking in pure water for 10 s, and then observed after drying in a 90°C oven for 30 min, and the remaining film step number was recorded. The higher the remaining film step number after curing and development, the higher the sensitivity of the formula, and the better the sensitivity performance of the corresponding photo initiator.

[0191] The formula mixtures of the examples and comparative examples in Table 1 were coated, cured, developed, and measured, and the remaining film step number was recorded.

[0192] Table 1

[0193] From the data of the film remaining degree in Table 1, it can be seen that the compound provided by the present application has a film remaining degree significantly higher than that of the comparative compound C-1 and the comparative compound C-2 after curing in the black system under the same amount condition. The compound of the general formula I of the present application has a high sensitivity. It is also found that the sensitivity of the anti-anti bisoxime acetate compound I-1 and other compounds of the present application is significantly higher than that of the syn-anti bisoxime acetate compound I-1'.

[0194] The compound prepared from Preparation Example 1-13 and Preparation Example 15, the compound obtained from Comparative Preparation Example 1, and the comparative compound C-1 and the comparative compound C-2 were used as the photoinitiator, dissolved in propylene glycol methyl ether acetate (PMA) in the amount shown in Table 2, and then mixed with the red color paste in the proportion shown in Table 2, with the unit of the amount being gram.

[0195] After the components were mixed uniformly, a 10 μm wire bar was used to coat a film on a glass slide, the film was dried in a 90°C oven for 5 min, 365 nm surface light source curing was performed using a 41-step exposure ruler, development was performed using a 0.0425% KOH solution at 25°C, and the film was cleaned by soaking in pure water for 10 s, and then dried in a 90°C oven for 30 min, after which the film remaining degree was observed and recorded in Table 2.

[0196] Table 2

[0197] From the data of the film remaining degree in Table 2, it can be seen that the compound provided by the present application has a film remaining degree significantly higher than that of the comparative compound C-1 and the comparative compound C-2 after curing in the red formula system under the same amount condition; it is also found that the sensitivity of the anti-anti bisoxime acetate compound I-1 and other compounds of the present application is significantly higher than that of the syn-anti bisoxime acetate compound I-1'.

[0198] In summary, whether in the black photoresist formula or in the color photoresist formula such as the red photoresist formula, the compound of the present application has a sensitivity significantly higher than that of the syn-anti bisoxime acetate compound I-1', the comparative compound C-1 and the comparative compound C-2.

[0199] The above describes the preferred embodiments of the present application in detail, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as the disclosed content of the present application, and all fall within the protection scope of the present application.

Claims

1. A trans-trans bisoxime acetate compound having a structure according to Formula I, ###000001### Formula I wherein In formula I, symbol E represents that the O-N bond in the oxime group is in trans form; R1is selected from C1-C6alkyl, C5-C7cycloalkyl-substituted C1-C2alkylene, C1-C4alkoxy-substituted ethylene; R2, R2' are each independently selected from C1-C7alkyl, C5-C7cycloalkyl-substituted C1-C2alkylene, C5-C7cycloalkyl. Preferably, R1is selected from C1-C4alkyl, 2-methoxyethyl. Preferably, R2and R2' are the same and selected from C1-C6alkyl, C5or C6cycloalkyl-substituted methylene.

2. The compound of claim 1, wherein The compound is selected from:

3. A method for preparing the trans-trans bisoxime acetate compound according to any one of claims 1-2, comprising the following steps: Step (1): reacting the starting material M1 with a nitrite or nitrous acid under acidic conditions to obtain a mixture of cis-trans isomer M2' and trans-trans isomer M2; Step (2): purifying the product obtained in step (1) after isomer conversion to obtain the trans-trans isomer M2; Step (3): esterification of the trans-trans isomer M2 with CH3COCl or (CH3CO)20 to obtain the compound according to Formula I; In formula I, symbol E represents that the O-N bond in the oxime group is in trans form; symbol Z represents that the O-N bond in the oxime group is in cis form; R1is selected from C1-C6alkyl, C5-C7cycloalkyl-substituted C1-C2alkylene, C1-C4alkoxy-substituted ethylene; R2, R2' are each independently selected from C1-C7alkyl, C5-C7cycloalkyl-substituted C1-C2alkylene, C5-C7cycloalkyl.

4. The production method according to claim 3, characterized by, In step (1), the molar ratio of the starting material M1to nitrite or nitrous acid is 1:(2-3); 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, in step (1), the reaction is carried out in an organic solvent, preferably, the organic solvent is selected from DMSO, alcohols, ethers, esters, aromatic hydrocarbons or chlorinated alkanes; 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, methyl tetrahydrofuran, 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 and ethyl butyrate; the aromatic hydrocarbon solvent is selected from benzene, toluene and chlorobenzene; the chlorinated alkane is selected from dichloromethane and 1,2-dichloroethane; And / or, the temperature of the reaction is 5-25℃; And / or, the time of the reaction is 4-8h; And / or, in step (2), the isomer conversion of the product obtained in step (1) is carried out at 80-100℃; And / or, in step (3), the molar ratio of the trans-trans isomer M2to CH3COCl or (CH3CO)2O is 1:(2-2.5); And / or, 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 into 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 the CH3COCl is (1-1.2):1; and / or, the temperature of the esterification reaction is 20-60℃; and / or, the time of the esterification reaction is 3-5h.

5. A photocuring composition, comprising a photoinitiator and a free-radical polymerizable compound, wherein the photoinitiator comprises the trans-trans bisoxime acetate compound according to any one of claims 1-2 or the trans-trans bisoxime acetate compound prepared by the method according to any one of claims 3-4; Preferably, the free-radical polymerizable compound is selected from acrylate compounds, methacrylate compounds and combinations thereof; Preferably, the free-radical polymerizable compound comprises one or more of alkyl acrylate, cycloalkyl acrylate, hydroxyalkyl acrylate, dialkylaminoalkyl acrylate, alkyl methacrylate, cycloalkyl methacrylate, hydroxyalkyl methacrylate, dialkylaminoalkyl methacrylate, acrylated epoxy resin, acrylated polyester resin, unsaturated polyester resin, acrylated polyether resin, acrylated polyurethane resin; More preferably, the free-radical polymerizable compound comprises one or more of methyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, ethyl methacrylate, polysiloxane acrylate, vinyl acetate, styrene, diacrylate of ethylene glycol, diacrylate of polyethylene glycol, diacrylate of propylene glycol, diacrylate of neopentyl glycol, diacrylate of 1,6-hexanediol, triacrylate of trihydroxy methane, tetraacrylate of pentaerythritol, hexaacrylate of dipentaerythritol, vinyl acrylate, triallyl isocyanurate. and / or, the mass fraction of the trans-trans bisoxime acetate compound in the photocuring composition is 0.1-8.0%.

6. A photoresist, the raw materials for the preparation of the photoresist comprising a photoinitiator, a multifunctional acrylate monomer, an alkali-soluble resin, and an organic solvent, wherein, The photoinitiator comprises the trans-trans bisoxime acetate compound according to any one of claims 1-2 or the trans-trans bisoxime acetate compound prepared by the method according to any one of claims 3-4; Preferably, the multifunctional acrylate monomer is selected from acrylate monomers with functionality ≥3, more preferably, is dipentaerythritol hexaacrylate and / or pentaerythritol acrylate; Preferably, the alkali-soluble resin is a resin with acidic groups, more preferably, is a polyacrylate or polymethacrylate with carboxylic acid groups, further preferably, is a copolymer of one or more of methacrylic acid, itaconic acid, maleic acid with one or more of methyl acrylate, methyl methacrylate, butyl methacrylate, benzyl acrylate, benzyl methacrylate, hydroxyethyl acrylate, styrene, butadiene, maleic anhydride, such as methyl methacrylate and methacrylic acid copolymer, benzyl methacrylate and methacrylic acid copolymer, methyl methacrylate and butyl methacrylate copolymer, and methacrylic acid and styrene copolymer. Preferably, the organic solvent is selected from one or more of ester solvents, aromatic hydrocarbon solvents and halogenated alkane solvents, preferably one or more of propylene glycol monomethyl ether acetate, ethylene glycol methyl ether acetate, toluene, xylene and tetrachloroethane; Optionally, the photoinitiator further comprises one or more of 2,2-dimethoxy-2-phenylacetophenone, 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)-1-butanone, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-1-butanone, 2-dimethylamino-2-benzyl-1-(4-piperidinophenyl)-1-butanone, 2,4,6-trimethylbenzoylbenzoic acid-diphenyl phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenyl phosphine oxide, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, bis(2,6-difluoro-3-pyrrolophenyl)titanocene; Optionally, the photolithography resist further comprises a pigment; preferably, the pigment is a red pigment, a green pigment, a blue pigment or a black pigment; more preferably, the red pigment comprises C.I. Pigment Red 177, the green pigment comprises C.I. Pigment Green 7, the blue pigment comprises C.I. Pigment Blue 15:6 and Solvent Blue 25, and the black pigment comprises carbon black, titanium black and C.I. Pigment Black 1. The pigment in the photolithography resist is a black pigment, preferably carbon black and titanium black.

7. A black matrix prepared from a photoresist comprising the photoresist of claim 6, wherein, The pigment in the photolithography resist is a red pigment, a green pigment or a blue pigment.

8. A color filter device prepared from a black matrix comprising the photoresist of claim 6 and the black matrix of claim 7, wherein, 9. A display obtained by photo-curing of a reverse-trans double oxime acetate compound of any one of claims 1-2 or a reverse-trans double oxime acetate compound obtained by the method of any one of claims 3-4 as a photoinitiator; preferably, the display comprises a PCB display, an LCD display and an OLED display.

10. Use of the reverse-trans double oxime acetate compound of any one of claims 1-2, the reverse-trans double oxime acetate compound obtained by the method of any one of claims 3-4, the photo-curing composition of claim 5 or the photolithography resist of claim 6 in the preparation of a pigmented or non-pigmented ink, a paint, an adhesive, a filter, a display, a pattern printing, a printing plate, a 3D printing, a PCB photoresist, a PCB solder mask ink, a substrate protective coating, an electronic device protective coating, a passivation film, a liquid or dry film resist, a sealant, a dental material, an optical material, an optical film, an optical fiber coating, an insulation film, a polarizer, a microlens and a recording material. ​

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