Oxime ester compound, photoresist, and use thereof

Abstract

The present invention provides an oxime ester compound, a photoresist, and a use thereof. The oxime ester compound of the present invention has a structure represented by formula (I), and the photoresist prepared by using the oxime ester compound as a photoinitiator exhibits high sensitivity characteristics.

Description

Oxime ester compound, photoresist and application thereof

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to Chinese patent application No. CN202311101891.5 filed on August 29, 2023. The entire contents of the above-mentioned Chinese patent application are incorporated by reference into this application in their entirety. Technical Field

[0003] The invention belongs to the technical field of organic chemistry and photocuring, and particularly relates to a new oxime ester compound, a photoresist containing the oxime ester compound and applications thereof. Background Art

[0004] Since its emergence in the 1970s, photocuring technology has been widely used. For example, UV photocuring technology is widely used in the fields of coatings, printing inks, and electronic device manufacturing. One of the issues that photocuring technology technicians are most concerned about is the curing efficiency or sensitivity. The key factors affecting the curing efficiency are the structure of the photoinitiator and the co-initiator components used with it. Patent WO2002 / 100903 discloses oxime ester compounds with more complex substituents on the diphenyl sulfide parent structure and oxime ester compounds based on carbazole. Among them, commercial products such as BASF's Although OXE 02 has improved sensitivity, its yellowing property is also stronger, which greatly limits its use in transparent photoresists and color photoresists. Based on the aforementioned patent compounds, the modification of the side chain in Chinese patent CN101565472B does not fundamentally change the sensitivity and yellowing property of the corresponding oxime ester compound. Patent CN101528694A discloses an oxime ester compound with nitrocarbazole as the parent, and patent CN103153952A discloses an oxime ester compound with benzocarbazole as the parent. Due to the introduction of the nitro group of the chromophore or the large conjugated structure of benzocarbazole, the ultraviolet absorption spectrum of the corresponding oxime ester compound is significantly red-shifted. For example, NCI-831 of Japan Aidi Co., Ltd. and BASF's The two commercial OXE 03 products have more efficient absorption of the 365nm emission light of the light source, showing higher sensitivity. However, at the same time, the significantly red-shifted ultraviolet absorption spectrum also gives the compounds a yellower color and significant yellowing in photoresists. Therefore, they are more suitable for use in black photoresist formulations and are difficult to use in transparent and RGB color photoresists.

[0005] Patent CN112004800 and patent WO2022075452 disclose technical solutions having a formyl formate group and an oxime ester group in one molecule. The aromatic formyl formate group has poor hydrolysis resistance, resulting in poor storage stability and affecting the stability of the formula.

[0006] In order to improve the transmittance of transparent photoresist and the color purity of colored photoresist, technicians require that the photoinitiator used has lower yellowing and higher sensitivity, so the industry still needs to develop new photoinitiator products with higher sensitivity and lower yellowing.

[0007] Summary of the Invention

[0008] To address one of the aforementioned technical problems in the prior art, the present invention provides a novel oxime ester compound. The present invention unexpectedly discovered that this type of compound exhibits very high sensitivity, meeting the process requirements for photoresist use. The novel oxime ester compound provided by the present invention possesses both a dicarbonylamide group and an oxime ester group and can be used as a photoinitiator in photocuring technology. In particular, it exhibits high sensitivity and low yellowing properties in photoresists and can be used in the manufacture of color displays.

[0009] In a first aspect, the present invention provides an oxime ester compound having a structure as shown in formula (I):

[0010] in,

[0011] R1 is selected from NR4R5;

[0012] R2 is selected from a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1-C10 alkyl group, a C3-C10 alkyl group inserted by one or more O atoms, a substituted or unsubstituted C3-C7 cycloalkyl group, a substituted or unsubstituted C3-C7 heterocyclic group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C4-C20 heteroaryl group,

[0013] Wherein, the substituent in the C1-C10 alkyl group is selected from one or more of phenyl, C3-C7 cycloalkyl, C3-C7 heterocyclic group, C1-C4 alkoxy, and C1-C4 alkyl acyloxy.

[0014] The substituents in the C6-C20 aryl and C4-C20 heteroaryl are selected from one or more of C1-C4 alkyl, C3-C7 cycloalkyl, F, Cl, C1-C4 alkoxy, C1-C4 alkylthio, -COCOOR4;

[0015] The substituents in the C3-C7 cycloalkyl and C3-C7 heterocyclic groups are selected from one or more of F, Cl, C1-C4 alkyl, C1-C4 alkoxy, and -COCOOR4;

[0016] R3 is selected from C1-C3 alkyl, C3-C7 cycloalkyl substituted C1-C3 alkyl, C3-C6 alkenyl, C1-C4 alkoxy, phenyl, phenoxy;

[0017] R4, R5, R4' and R5' are each independently selected from H, substituted or unsubstituted C1-C8 alkyl, C3-C8 alkyl interrupted by one or more oxygen atoms and / or sulfur atoms, C3-C7 cycloalkyl, C3-C7 heterocyclyl, C6-C20 aryl, C4-C20 heteroaryl,

[0018] wherein the substituent in the C1-C8 alkyl group is selected from one or more of a F atom, a phenyl group, a C3-C7 cycloalkyl group, a C3-C7 heterocyclic group, a C1-C4 alkoxy group, R3COO-, and -R6CONR6';

[0019] Alternatively, NR4R constitutes a three-membered, four-membered, five-membered, six-membered or seven-membered nitrogen-containing heterocyclic ring, wherein the nitrogen-containing heterocyclic ring further has an additional heteroatom selected from one or two nitrogen atoms, one oxygen atom, one sulfur atom and one silicon atom; optionally, the nitrogen-containing heterocyclic ring has the following side chain substituents: C1-C4 alkyl, C1-C4 alkyl substituted with one or more substituents selected from F atom, phenyl, C3-C7 cycloalkyl, C3-C7 heterocyclic group, C1-C4 alkoxy, R3COO-, -R6CONR6', C3-C7 cycloalkyl, substituted or unsubstituted phenyl, R6CO-, R6COCO-, R6SO2-; optionally, the nitrogen-containing heterocyclic ring has a parallel ring structure, a bicyclic structure and a spirocyclic structure, such as a benzo nitrogen-containing heterocyclic ring;

[0020] R6 is selected from C1-C12 alkyl, C1-C4 alkyl substituted by one or more substituents selected from F and Cl, phenyl, thienyl, phenyl substituted by one or more substituents selected from methyl, F, Cl and nitro, and thienyl substituted by one or more substituents selected from methyl, F, Cl and nitro;

[0021] R6' is selected from hydrogen, C1-C4 alkyl;

[0022] n is 0 or 1;

[0023] Ar1 is selected from the structures shown in Formula A-1 to Formula A-5:

[0024] Among them, R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 and R 18 are independently selected from hydrogen atoms, deuterium atoms, C1-C4 alkyl groups, C1-C4 alkoxy groups, and optionally, R 11 、R 12 、R 13 、R 14 、R15 、R 16 、R 17 and R 18 The two adjacent carbon atoms in the benzene ring together with the carbon atoms on the connected benzene ring form a five-membered, six-membered or seven-membered ring;

[0025] In formula A-1, R7 and R8 are each independently selected from a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C7 cycloalkyl group, a substituted or unsubstituted C3-C7 heterocyclic group, a substituted or unsubstituted C6-C20 aryl group, or a substituted or unsubstituted C4-C20 heteroaryl group.

[0026] The substituents in the C1-C8 alkyl group are selected from one or more of a F atom, a Cl atom, a phenyl group, a C3-C7 cycloalkyl group, a C3-C7 heterocyclic group, -OR4', -COOR4', and -P(=O)(OR4')2,

[0027] The substituents on the C3-C7 cycloalkyl and C3-C7 heterocyclic groups are selected from one or more of F, Cl, C1-C4 alkyl, C1-C4 alkoxy, -COCOOR4,

[0028] The substituents in the C6-C20 aryl and C4-C20 heteroaryl are selected from one or more of halogen, NO2, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, -COOR4', and -COR5';

[0029] Alternatively, R7 and R8 together with the carbon atom to which they are directly attached form a five-membered, six-membered or seven-membered ring;

[0030] In formula A-2 and formula A-3, R9 is selected from substituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C3-C7 cycloalkyl, substituted or unsubstituted C3-C7 heterocyclic group, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C4-C20 heteroaryl,

[0031] The substituents in the C1-C8 alkyl group are selected from one or more of a F atom, a Cl atom, a phenyl group, a C3-C7 cycloalkyl group, a C3-C7 heterocyclic group, -OR4', -COOR4', and -P(=O)(OR4')2,

[0032] The substituents on the C3-C7 cycloalkyl and C3-C7 heterocyclic groups are selected from one or more of F, Cl, C1-C4 alkyl, C1-C4 alkoxy, -COCOOR4,

[0033] The substituents in the C6-C20 aryl and C4-C20 heteroaryl are selected from one or more of halogen, NO2, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, -COOR4', and -COR5';

[0034] In formula A-4, X1 is selected from a single bond, O, S, NR9, CR7R8, Y is selected from O, S, C=O, S=O, R7 and R8 are the same as those in formula A-1, and R9 is the same as those in formula A-2 and formula A-3;

[0035] In formula A-5, X2 is selected from O, S, NR7, CR7R8, and R7 and R8 are defined as in formula A-2.

[0036] Ar2 and Ar3 are each independently selected from a substituted or unsubstituted C6-C20 arylene group, and the substituents in Ar2 and Ar3 are selected from the group consisting of the following groups: a deuterium atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, and optionally, two adjacent substituents and the atoms of the aromatic ring to which they are connected form a five-membered, six-membered or seven-membered ring.

[0037] In this application, -COCOO- represents -CO- represents carbonyl, -COO- represents -COCO- indicates -SO2- indicates

[0038] In some embodiments, examples of the C6-C20 aryl group and substituted C6-C20 aryl group include phenyl, naphthyl, 4-fluorophenyl, and 4-methoxynaphth-1-yl.

[0039] In some embodiments, R1 is selected from the group consisting of:

[0040] R6 is selected from C1-C8 alkyl, C1-C4 alkyl substituted by one or more F, phenyl, phenyl substituted by one or more substituents selected from methyl, F.

[0041] In some embodiments, R1 is selected from N(CH3)2,

[0042] In some embodiments, R4 and R5 are each independently selected from C1-C4 alkyl, C3-C7 cycloalkyl, C3-C7 heterocyclyl, benzyl, 4-methylbenzyl, C1-C3 alkyl substituted by one or more substituents selected from C3-C7 cycloalkyl and C3-C7 heterocyclyl, C2-C4 alkyl substituted by one or more substituents selected from C1-C4 alkoxy and R3COO-, and C3-C8 alkyl interrupted by one or more oxygen atoms and / or sulfur atoms.

[0043] In some embodiments, R1 is selected from NR4R5, and R4 and R5 are each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, phenyl, CH3COO-substituted methyl, CH3COO-substituted ethyl.

[0044] In some embodiments, R2 is selected from C1-C6 alkyl, benzyl, cyclohexyl, cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, cyclohexylethyl, tetrahydrofuranylmethyl,

[0045] In some embodiments, R3 is selected from C1-C4 alkyl, C1-C4 alkyl substituted by C5-C7 cycloalkyl, C6-C10 aryl, -COOCH3.

[0046] In some embodiments, R3 is selected from methyl, ethyl, cyclohexylmethyl, 2-cyclohexylethyl, phenyl, -COOCH3.

[0047] In some embodiments, R6 is selected from C1-C8 alkyl, C1-C4 alkyl substituted with one or more F, phenyl, phenyl substituted with one or more substituents selected from methyl, F, nitro.

[0048] In some embodiments, the structure is selected from Formula A-1, A-2, A-3 or Formula A-5, wherein,

[0049] In formula A-1, R7 and R8 are each independently selected from a hydrogen atom or a C1-C4 alkyl group, preferably hydrogen, methyl, ethyl, n-propyl and n-butyl; optionally, R7 and R8 together with the carbon atom to which they are directly attached form a cyclopentyl ring or a cyclohexyl ring;

[0050] In formulas A-2 and A-3, R9 is selected from C1-C8 alkyl, C1-C8 alkyl substituted by one or more substituents selected from F atom, phenyl, C5-C6 cycloalkyl, C4-C6 heterocyclic group, OR4', -P(=O)(OR4')2, C5-C6 cycloalkyl, phenyl, or phenyl substituted by one or more of the following groups: F, NO2, C1-C4 alkyl, C1-C4 alkoxy, -C(=O)R5',

[0051] Wherein, R4' and R5' are each independently selected from C1-C8 alkyl, C3-C7 cycloalkyl, C3-C7 heterocyclyl, C6-C12 aryl; preferably, R9 is selected from methyl, ethyl, n-propyl, n-butyl, 2-ethylhexyl, phenyl, or the following groups:

[0052] In formula A-5, X2 is selected from O or S; Ar2 and Ar3 are each independently selected from a substituted or unsubstituted C6-C12 arylene group, a substituted or unsubstituted C5-C12 heteroarylene group, preferably, Ar2 and Ar3 are each independently selected from a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted anthrylene group, and the substituents in Ar2 and Ar3 are each independently selected from one or more of a C1-C4 alkyl group and a C1-C4 alkoxy group;

[0053] R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 and R 18 Each is independently selected from hydrogen or C1-C4 alkyl, preferably selected from hydrogen, methyl or ethyl.

[0054] In some embodiments, the oxime ester compound has a structure represented by formula (I-1), formula (I-2), or formula (I-3):

[0055] wherein R1, R2, R3, R7, R8 and R9 are defined the same as in formula (I).

[0056] In some embodiments, in formula (I-1), R1 is selected from NR4R5, wherein NR4R5 constitutes a three-membered to seven-membered nitrogen-containing heterocyclic ring, wherein the nitrogen-containing heterocyclic ring contains at least one nitrogen atom, optionally one oxygen atom, optionally one sulfur atom, and optionally one silicon atom. Preferably, the nitrogen-containing heterocyclic ring has a parallel ring structure, a bicyclic structure, and a spiro structure; R2 is selected from C1-C4 alkyl, C5-C8 alkyl, C1-C4 alkyl substituted by C5-C7 cycloalkyl, such as cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, or cyclohexylethyl; R3 is selected from C1-C4 alkyl.

[0057] In some embodiments, in formula (I-1), R1 is selected from

[0058] In some embodiments, in formula (I-2), R1 is selected from NR4R5, wherein NR4R5 constitutes a three-membered to seven-membered nitrogen-containing heterocyclic ring, wherein the nitrogen-containing heterocyclic ring contains at least one nitrogen atom, optionally one oxygen atom, optionally one sulfur atom, and optionally one silicon atom; R2 is selected from C1-C4 alkyl, C5-C8 alkyl, C1-C4 alkyl substituted by C5-C7 cycloalkyl, such as cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl or cyclohexylethyl; R3 is selected from C1-C4 alkyl; R7 and R8 are each independently selected from hydrogen or C1-C4 alkyl.

[0059] In some embodiments, in formula (I-2), R1 is selected from

[0060] In some embodiments, in formula (I-3), R1 is selected from NR4R5, wherein NR4R5 constitutes a three-membered to seven-membered nitrogen-containing heterocyclic ring containing at least one nitrogen atom, optionally one oxygen atom, optionally one sulfur atom, and optionally one silicon atom; R2 is selected from C1-C4 alkyl, C5-C8 alkyl, C1-C4 alkyl substituted with C5-C7 cycloalkyl, such as cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, or cyclohexylethyl; R3 is selected from C1-C4 alkyl; and R9 are each independently selected from the following C1-C4 alkyl groups:

[0061] In some embodiments, in formula (I-3), R1 is selected from

[0062] In some embodiments, the oxime ester compound is selected from the group consisting of the following compounds:

[0063] In some embodiments, the method for preparing the oxime ester compound comprises the following steps:

[0064] Step (1): reacting the raw material HAr1H with an acyl chloride compound R2CH2COCl, R2COCl or an acid anhydride compound under Friedel-Crafts acylation conditions to obtain an intermediate M1 or M1′;

[0065] Step (2): reacting the intermediate M1 or M1′ in step (1) with R1′COCOCl under Friedel-Crafts acylation conditions to obtain the intermediate M2 or M2′;

[0066] wherein R1′ is selected from methoxy, ethoxy or H3N;

[0067] Step (3): reacting the intermediate M2 or M2' in step (2) with an H-R1 organic amine compound HNR4R5 to obtain an intermediate M3 or M3';

[0068] Step (4): reacting the intermediate M3 of step (3) with a nitrite or nitrous acid under corresponding acidic conditions to obtain an intermediate M4, or reacting the intermediate M3' of step (3) with hydroxylamine hydrochloride under neutral or alkaline conditions to obtain an intermediate M4', which is a trans or cis configuration or a mixture of the two;

[0069] Step (5): reacting the intermediate M4 or M4' in step (4) with R3COCl or (R3CO)2O to obtain a compound of formula II or III;

[0070] wherein Ar1, R1, R2, R3, R4 and R5 are defined the same as in formula (I).

[0071] In some embodiments, when Ar1 in formula (I) is selected from -Ar2-X2-Ar 3- , and X2 is selected from O or S, the preparation method of the compound of formula (I) comprises the following steps:

[0072] Step (1): using the compound of formula IV as a raw material, reacting with an acylating agent, an acyl chloride compound R2CH2COCl or an acid anhydride compound under Friedel-Crafts acylation reaction conditions to obtain a compound of intermediate formula V; the compound of formula V undergoes a thioetherification reaction with a phenol or thiophenol compound of formula VII to obtain a compound of intermediate formula VI; wherein Z is selected from F, Cl, Br or I;

[0073] Step (2): reacting the intermediate compound represented by formula VI in step (1) with R1′COCOCl under Friedel-Crafts acylation conditions to obtain intermediate M2;

[0074] wherein R1′ is selected from methoxy or ethoxy; Ar1 ​​is -Ar2-X2-Ar3-;

[0075] Step (3): reacting the intermediate M2 of step (2) with an H-R1 organic amine compound HNR4R5 to obtain an intermediate M3;

[0076] Step (4): allowing the intermediate M3 of step (3) to undergo an oximation reaction with a nitrite or nitrous acid under acid catalysis to obtain an intermediate formula M4, which is a trans or cis configuration or a mixture of the two;

[0077] Step (5): The intermediate M4 of step (4) is subjected to an esterification reaction with R3COCl or (R3CO)2O to obtain an oxime ester product of formula (II).

[0078] wherein Ar2, Ar3, R1, R2, R3, R4 and R5 are defined the same as in formula (I).

[0079] In a second aspect, the present invention further provides a photocurable composition comprising a photoinitiator and at least one free radical polymerizable compound, wherein the photoinitiator comprises the oxime ester compound described in the first aspect of the present invention.

[0080] In some embodiments, the free radical polymerizable compound is selected from acrylate compounds, methacrylate compounds, and combinations thereof.

[0081] The photocurable composition of the present invention may further include other photoinitiators or co-initiators. The present invention does not particularly limit the specific types of the other initiators or co-initiators. A photoinitiator or co-initiator that is conducive to photocuring performance in the art may be selected.

[0082] The free radical polymerizable compounds of the present invention include low molecular weight double bond compounds, compounds containing two or more double bonds, and double bond compounds with relatively high molecular weight (eg, 500-3000).

[0083] Examples of the low molecular weight double bond compound include: alkyl acrylates, cycloalkyl acrylates, hydroxyalkyl acrylates, dialkylaminoalkyl acrylates, alkyl methacrylates, cycloalkyl methacrylates, hydroxyalkyl methacrylates, dialkylaminoalkyl methacrylates, such as methyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, ethyl methacrylate, silicone acrylate, acrylonitrile, vinyl acetate, vinyl ether, styrene, N-vinyl pyrrolidone, etc.

[0084] Examples of the compound containing two or more double bonds include diacrylates of ethylene glycol, polyethylene glycol, propylene glycol, neopentyl glycol, and 1,6-hexanediol, trihydroxymethane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, vinyl acrylate, and triallyl isocyanurate.

[0085] Examples of the relatively high molecular weight double bond compounds include a broad class of substances generally referred to as oligomers, such as acrylated epoxy resins, acrylated polyester resins, unsaturated polyester resins, acrylated polyether resins, and acrylated polyurethane resins.

[0086] The acrylate group in the double bond compound of the present invention may also be replaced by a methacrylate group.

[0087] In some embodiments, the mass proportion of the oxime oxalate 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.

[0088] In a third aspect, the present invention further provides an ink or coating, which, in addition to containing the photocurable composition of the second aspect of the present invention, may also contain other necessary ingredients according to the ink color, printing application and other performance requirements.

[0089] In a fourth aspect, the present invention also provides an adhesive which, in addition to containing the photocurable composition of the second aspect of the present invention, may also add other necessary components such as a polymer with a molecular weight of 5000-100000 to improve the adhesive properties according to the performance requirements of the adhesive, and is used for bonding glass, plastic, metal components, etc.

[0090] In addition to the examples given here, those skilled in the art can easily add other necessary ingredients, such as stabilizers, surfactants, leveling agents, and dispersants according to the existing technology and the application requirements of the photocurable composition.

[0091] In a fifth aspect, the present invention further provides a photoresist, the raw materials of which include a photoinitiator, a multifunctional acrylate monomer, an alkali-soluble resin and a solvent, wherein the photoinitiator includes the oxime ester compound described in the first aspect of the present invention.

[0092] The multifunctional acrylate monomer in the photoresist raw material described herein refers to an acrylate monomer with a functionality of trifunctional or greater. The present invention does not specifically limit the specific type of the multifunctional acrylate monomer; those skilled in the art can select from among conventional multifunctional acrylate monomers in the art. Examples of the multifunctional acrylate include, but are not limited to, dipentaerythritol hexaacrylate and pentaerythritol acrylate.

[0093] The alkali-soluble resin in the photoresist raw material of the present invention refers to a polymer with an acidic group, which can be dissolved or dispersed when encountering an alkaline solution. The present invention does not make any special restrictions on the specific type of the alkali-soluble resin, and those skilled in the art can select and use it from the alkali-soluble resins conventional in the art. Examples of the alkali-soluble resin include, but are not limited to, polyacrylates or methacrylates with carboxylic acid groups, such as copolymers obtained by copolymerizing methacrylic acid, itaconic acid, maleic acid, etc. with common monomers in a suitable proportion. Examples of common monomers include, but are not limited to, methyl acrylate, butyl methacrylate, benzyl acrylate, hydroxyethyl acrylate, styrene, butadiene, maleic anhydride, etc. Examples of alkali-soluble resins include, but are not limited to, methyl methacrylate and methacrylic acid copolymers, benzyl methacrylate and methacrylic acid copolymers, methyl methacrylate and butyl methacrylate, and methacrylic acid and styrene copolymers.

[0094] In some embodiments, the photoresist is a transparent photoresist without pigment. Transparent photoresist can be used to manufacture optical films, polarizers, insulating films, passivation films, and sealing protective layers.

[0095] In some embodiments, the photoresist is a colored photoresist containing a pigment. The colored photoresist includes colored photoresist and black photoresist, wherein the colored photoresist includes red photoresist, green photoresist and blue photoresist. The pigment in the raw material of the red photoresist includes a red pigment such as CI Pigment Red 177. The pigment in the raw material of the green photoresist includes a green pigment such as CI Pigment Green 7. The pigment in the raw material of the blue pigment photoresist includes a blue pigment such as CI Pigment Blue 15:6 and Solvent Blue 25. The pigment in the raw material of the black photoresist includes a black pigment such as carbon black, titanium black, CI Pigment Black 1, etc. Black photoresist can be used to manufacture black matrix and cell gap spacers.

[0096] The present invention does not impose any particular limitation on the solvent of the photoresist raw material, and those skilled in the art can select the solvent according to their needs, such as propylene glycol monomethyl ether acetate.

[0097] In some embodiments, the photoinitiator may further include other photoinitiators or co-initiators known in the art, such as 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-piperidinylphenyl)-1-butanone, 2,4,6-trimethylbenzoylbenzene-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, and bis(2,6-difluoro-3-pyrrolophenyl)titanocene.

[0098] Furthermore, those skilled in the art may add a heat stabilizer or a light stabilizer, such as p-methoxyphenol, to the raw materials as needed. Other resins may also be added, such as polyalkyl methacrylate, ethyl cellulose, carboxymethyl cellulose, novolac resin, polyvinyl butyral, polyvinyl acetate, polyester, polyimide, etc.

[0099] By using the photoresist of the present invention as a raw material and following the color filter processing process, such as multiple coatings of different colored photoresists, exposure, and development, a color filter device with excellent optical properties can be obtained. This is an important component of a color display screen, wherein the color units exhibit pure colors and high transmittance, and the colorless portions exhibit low yellowing and high transmittance.

[0100] Photoresist is typically applied by spin coating, evenly distributing the material onto the substrate. After drying at 80-90°C, the solvent and other volatile components are separated, leaving a solid film. A mask is placed on top of the film and the material is exposed to a 365nm mercury lamp or LED light source for an appropriate exposure. The exposed material is then developed in an alkaline solution such as sodium carbonate or sodium hydroxide to remove the unexposed film and leave the exposed image. After cleaning and a post-baking process at 200-230°C, the image adheres better to the substrate. Following the designed process, different colors and patterns are produced, or combined with the necessary protective film processing procedures, to create a filter device.

[0101] In a sixth aspect, the present invention provides a black matrix or photo spacer, which is prepared from raw materials including the photoresist described in the fifth aspect of the present invention, wherein the pigment in the photoresist is a black pigment, preferably carbon black and titanium black.

[0102] In a seventh aspect, the present invention provides a color filter device, which is prepared from a raw material including the photoresist described in the fifth aspect of the present invention, wherein the pigment in the photoresist is a red pigment, a green pigment or a blue pigment.

[0103] In an eighth aspect, the present invention provides a printed article or display, which is obtained by photocuring the oxime oxalate compound described in the first aspect of the present invention as a photoinitiator.

[0104] In some embodiments, the printed article comprises a printed circuit board.

[0105] In some embodiments, the display includes a PCB display, an LCD display, or an OLED display.

[0106] In a ninth aspect, the present invention provides the use of the oxime ester compound described in the first aspect, the photocurable composition described in the second aspect, or the photoresist described in the fifth aspect in the preparation of colored or non-colored inks, coatings, adhesives, filters, displays, or in pattern printing, printing plates, 3D printing, PCB photoresists, PCB solder mask inks, substrate protective coatings, electronic device protective coatings, passivation films, liquid or dry film corrosion-resistant materials, sealants, dental materials, optical materials, optical films, optical fiber coatings, insulating films, polarizers, microlenses, and recording materials.

[0107] Any article such as a color filter, an LCD color display, an OLED color display, a PCB, or a printed matter obtained by using the compound of formula (I) of the present invention or a photoinitiator composition containing the compound of formula (I) and a photoresist containing the compound of formula (I) as raw materials and processing through necessary steps.

[0108] Compared with the prior art, the present invention has the following beneficial effects:

[0109] The compound of the present invention has significantly high sensitivity in the formulation of photocurable compositions, especially photoresists, and its performance is significantly better than that of the prior art. DETAILED DESCRIPTION

[0110] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments and drawings. The specific embodiments described herein are only used to illustrate the present invention and are not intended to constitute any limitation to the present invention.

[0111] The term "C1-C10 alkyl" used herein refers to a straight or branched chain alkyl group having 1 to 10 carbon atoms, including but not limited to methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and the like.

[0112] As used herein, the terms "C3-C10 alkyl group interrupted by one or more O or S atoms" or "C3-C10 alkyl group interrupted by one or more oxygen or sulfur atoms" have equivalent meanings and refer to a C3-C10 alkyl group interrupted by O or S one or more times, for example, 1-9 times, 1-5 times, 1-3 times, 2 times, or 1 time. If more than one spacer group is present, they may be of the same type or different. Two O atoms are separated by at least one methylene group, preferably at least two methylene groups (i.e., ethylene groups). These alkyl groups are linear or branched. For example: -CH2-CH2-O-CH2CH3-, -CH2-CH(CH3)-O-CH2-CH2O-CH3-, -CH2-CH2-S-CH2CH3, etc.

[0113] The term "alkoxy" used herein refers to an alkyl group separated by one O atom, for example, a C1-C4 alkoxy group refers to an alkyl group having 1-4 carbon atoms separated by one O atom, including but not limited to methoxy, ethoxy, propoxy, etc.

[0114] The term "alkylthio" as used herein is an alkyl group interrupted by one sulfur atom, for example, C1-C4 alkylthio is an alkyl group having 1 to 4 carbon atoms interrupted by one sulfur atom.

[0115] The term "cycloalkyl" as used herein refers to an alkyl group containing at least one ring, and C3-C7 cycloalkyl refers to a cyclic alkyl group having 3 to 7 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, especially cyclopentyl and cyclohexyl.

[0116] As used herein, the term "heterocyclic group" is used interchangeably with "heterocycle", "carboheterocycle", and "carboheterocyclic group" and includes aromatic cyclic groups and non-aromatic cyclic groups. Aromatic cyclic groups include heteroaromatic cyclic groups having 3-10 ring atoms, wherein at least one ring atom is selected from the group consisting of nitrogen, oxygen, sulfur, selenium, silicon, phosphorus, germanium, and boron atoms. Non-aromatic heterocyclic groups include saturated heterocyclic groups having 3-10 ring atoms and unsaturated non-aromatic heterocyclic groups having 3-10 ring atoms, wherein at least one ring atom is selected from the group consisting of nitrogen, oxygen, sulfur, selenium, silicon, phosphorus, germanium, and boron atoms. Preferred non-aromatic heterocyclic groups are those having 3 to 7 ring atoms, including at least one heteroatom such as nitrogen, oxygen, silicon, or sulfur. Examples of non-aromatic heterocyclic groups include oxiranyl, oxetanyl, tetrahydrofuranyl, tetrahydropyranyl, dioxolane, dioxanyl, aziridinyl, dihydropyrrolyl, tetrahydropyrrolyl, piperidinyl, oxazolidinyl, morpholinyl, piperazinyl, oxepinyl, thiepineyl, azepineyl and tetrahydrothiazolyl. In addition, the heterocyclic group may be optionally substituted.

[0117] As used herein, the term "aryl or aromatic group" includes both non-fused and fused systems. The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms. Examples of aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenanthrene, phenanthrene, fluorene, pyrene, , perylene and azulene, preferably phenyl, biphenyl, biphenyl, triphenylene, fluorene and naphthalene. Examples of non-fused aryl groups include phenyl, biphenyl-2-yl, biphenyl-3-yl, biphenyl-4-yl, p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl, m-terphenyl-2-yl, o-tolyl, m-tolyl, p-tolyl, p-(2-phenylpropyl)phenyl, 4'-methylbiphenyl, 4"-tert-butyl-p-terphenyl-4-yl, o-cumyl, m-cumyl, p-cumyl, 2,3-xylyl, 3,4-xylyl, 2,5-xylyl, mesityl and m-quaterphenyl. In addition, the aryl group may be optionally substituted.

[0118] As used herein, the term "heteroaryl" includes monocyclic or polycyclic ring systems, such as fused ring systems. C4-C20 heteroaryl includes, but is not limited to, thienyl, benzo[b]thienyl, naphtho[2,3-b]thienyl, thianthrenyl, furyl, dibenzofuranyl, benzopyranyl, xanthenyl, thioxanthenyl, phenothiazine, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinolyl, quinazolinyl, Cinnolinyl, pteridinyl, carbazolyl, β-carbolinyl, phenanthridinyl, acridinyl, perylene, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl, phenazinyl, 7-phenanthrenyl, anthraquinone-2-yl (= 9,10-dioxo-9,10-dihydroanthracen-2-yl), 3-benzo[b]thienyl, 5-benzo[b]thienyl, 2-benzo[b]thienyl, 4-dibenzofuranyl, 4,7-dibenzofuranyl pyranyl, 4-methyl-7-dibenzofuranyl, 2-xanthenyl, 8-methyl-2-xanthenyl, 3-xanthenyl, 2-phenoxathiol, 2,7-phenothiol, 2-pyrrolyl, 3-pyrrolyl, 5-methyl-3-pyrrolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 2-methyl-4-imidazolyl, 2-ethyl-4-imidazolyl, 2-ethyl-5-imidazolyl, 1H-tetrazol-5-yl, 3-pyrazolyl, 1-methyl-3-imidazolyl -pyrazolyl, 1-propyl-4-pyrazolyl, 2-pyrazinyl, 5,6-dimethyl-2-pyrazinyl, 2-indolizinyl, 2-methyl-3-isoindolyl, 2-methyl-1-isoindolyl, 1-methyl-2-indolyl, 1-methyl-3-indolyl, 1,5-dimethyl-2-indolyl, 1-methyl-3-indazolyl, 2,7-dimethyl-8-purinyl, 2-methoxy-7-methyl-8-purinyl, 2-quinolizinyl, 3-Isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, 3-methoxy-6-isoquinolyl, 2-quinolyl, 6-quinolyl, 7-quinolyl, 2-methoxy-3-quinolyl, 2-methoxy-6-quinolyl, 6-phthalazinyl, 7-phthalazinyl, 1-methoxy-6-phthalazinyl, 1,4-dimethoxy-6-phthalazinyl, 1,8-naphthyridin-2-yl, 2-quinolyl, 6-quinolyl, 2,3-dimethyl-6-quinolyl, 2,3-dimethoxy-6-quinolyl, 2-quinazolinyl, 7-quinazolinyl, 2-dimethylamino-6-quinazolinyl, 3-cinnolinyl, 6-cinnolinyl, 7-cinnolinyl, 3-methoxy-7-cinnolinyl, 2-pteridinyl, 6-pteridinyl, 7-pteridinyl, 6,7-dimethoxy-2-pteridinyl, 2-carbazolyl, 3-carbazolyl, 9-methyl-2-carbazolyl, 9-methyl-3-carbazolyl, β-carbolin-3-yl, 1-methyl-β-carbolin-3-yl, 1-methyl-β-carbolin-6-yl, 3-phenanthridinyl, 2-acridinyl, 3-acridinyl, 2-perylene-1, 1-methyl-5-perylene-1, 5-phenanthrolinyl, 6-phenanthrolinyl, 1-phenazinyl, 2-phenazinyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-phenothiazinyl, 3-phenothiazinyl, 10-methyl-3-phenothiazinyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 4-methyl-3-furazanyl, 2-phenazinyl, 10-methyl-2-phenazinyl, and the like. Preferably, it is thienyl, benzo[b]thienyl, thianthrenyl, thioxanthenyl, 1-methyl-2-indolyl or 1-methyl-3-indolyl; more preferably, it is thienyl. In addition, the heteroaryl group may be optionally substituted.

[0119] Experimental materials and equipment:

[0120] Light source equipment:

[0121] 365nm LED surface light source, Shanghai Futanxi Technology Co., Ltd.;

[0122] Test equipment:

[0123] Differential scanning calorimeter: HSC-1, Beijing Hengjiu Experimental Equipment Co., Ltd.

[0124] Stereo microscope, HY-950S, Beijing Huanyu Technology Co., Ltd., line width unit is μm;

[0125] Yellowness meter, fully automatic colorimeter SC-80C, Beijing Jingyi Kangguang Optical Instrument Co., Ltd.

[0126] Experimental Materials:

[0127] Genomer 4212: aliphatic polyurethane acrylate, a product of RAHN;

[0128] DPHA: dipentaerythritol hexaacrylate, a product of Tianjin Tianjiao Chemical Co., Ltd.

[0129] HDDA: 1,6-hexanediol diacrylate, a product of Tianjin Tianjiao Chemical Co., Ltd.

[0130] Compound preparation

[0131] Preparation Example 1 4-(2-morpholin-4-yl-2-oxoacetyl)-4'-(3-cyclohexyl-2-acetoxyiminopropionyl)diphenyl sulfide:

[0132] Step 1a. Place 22g (0.118mol) of diphenyl sulfide and 100g of o-dichlorobenzene (hereinafter referred to as DCB) in a 250mL three-necked flask, cool to -10°C, add 17.28g (0.13mol) of anhydrous aluminum chloride, stir, and add 21.65g (0.124mol) of 3-cyclohexylpropionyl chloride dropwise over 30min. Then, stir and react at 10°C overnight. The reaction solution is acidified and washed with water until neutral. DCB is removed by vacuum rotary evaporation to obtain 37.98g of a light yellow oil with a yield of 99.1% and an HPLC purity of 98.56%. The oil solidifies after cooling, with a DSC melting point of 38.1°C; this is the intermediate 4-(3-cyclohexylpropionyl)diphenyl sulfide.

[0133] Step 1b. Place 11.7 g (0.088 mol) of anhydrous aluminum chloride and 60 g of 1,2-dichloroethane (DCE) in a 100 mL three-necked flask, stir, and cool to 0°C. Add 9.5 g (0.0293 mol) of the product from Step 1a, controlling the temperature not to exceed 10°C. Then, add 3.95 g (0.0322 mol) of monomethyl oxalyl chloride dropwise, and react at 5-10°C for 3 h. Add the reaction solution dropwise to a 0°C solution of 15 g of hydrochloric acid and 50 mL of water, stir for 1 h, and allow to separate. Add 50 mL of water to the organic phase, stir for 30 min, and allow to separate. Distill the separated organic phase under reduced pressure to 60°C, leaving 13.6 g of a pale yellow solid. 15 g of toluene and 15 g of heptane were added to dissolve the solid, and the temperature was lowered to precipitate crystals. The temperature was lowered to -15°C, the precipitated crystals were filtered, and the pressure was reduced and dried to obtain 11.4 g of white crystals with a yield of 94.8%, HPLC purity of 99.25%, and a DSC melting point of 76.8°C; this was the intermediate 4-(2-methoxy-2-oxoacetyl)-4'-(3-cyclohexylpropionyl) diphenyl sulfide.

[0134] Step 1c. 4 g (9.7 mmol) of the product obtained in step 1b was added to a 50 mL single-necked bottle, 2 g (22.96 mmol) of morpholine, the reaction was stirred at 50 ° C for 2 h, 15 mL of hot ethanol was added, the temperature was lowered to precipitate white crystals, filtered, and dried under reduced pressure to give 4.1 g, a yield of 90.8%, HPLC content of 98.60%, DSC melting point: 110.1 ° C; intermediate 4- (2-morpholin-4-yl-2-oxoacetyl) -4'- (3-cyclohexylpropionyl) diphenyl sulfide;

[0135] Step 1d. In a 50 mL three-necked flask, place 3.8 g (8.2 mmol) of the product from Step 1c, 15 g of DMSO, and 1.0 g (9.8 mmol) of butyl nitrite, stir, and incubate at 30°C. HCl gas is continuously introduced in small amounts and the reaction is allowed to proceed for 4 h. The reaction solution is added to 20 mL of dichloromethane (DCM) and 50 mL of water and stirred for 30 min. The lower organic layer is separated, and the upper aqueous phase is extracted once more with 20 mL of DCM. The combined DCM phases are dried over 1 g of Na2SO4 for 4 h. The desiccant is filtered, and the filtrate is rotary evaporated to dryness, leaving a residue weighing 4.4 g of a light yellow solid. The obtained light yellow solid was dissolved in 20 g of ethyl acetate and then heated. 5 g of heptane was added and the mixture was cooled to crystallize. The temperature was then lowered to -10°C overnight. The precipitated crystals were filtered and dried under reduced pressure to obtain a white crystalline powder weighing 3.24 g, with a yield of 80%, an HPLC purity of 99.73%, and a DSC melting point of 152.9°C. This was the intermediate 4-(2-morpholin-4-yl-2-oxoacetyl)-4'-(3-cyclohexyl-2-hydroxyiminopropionyl) diphenyl sulfide.

[0136] Step 1e. To a 50 mL single-necked flask, add 3 g (6 mmol) of the product from Step 1d, 15.0 g of DCM, and 0.74 g (7.2 mmol) of acetic anhydride. Heat to 40°C and stir magnetically for 4 h. Wash with water three times, 3.0 g each time, until the pH reaches 6-7. Evaporate to dryness under reduced pressure, and remove the remaining solvent using an oil vacuum pump to obtain 3.0 g of a pale yellow viscous oil (90% yield, 98.85% purity by HPLC). Upon standing, the product becomes a glassy solid, the target compound being 4-(2-morpholin-4-yl-2-oxoacetyl)-4'-(3-cyclohexyl-2-acetoxyiminopropionyl) diphenyl sulfide.

[0137] 1 H-NMR (CD3CN, δ [ppm]) data: 0.9971-1.2288 (m, 3H, cyclohexane CH2), 1.5794-1.6823 (m, 8H, cyclohexane CH2+CH), 2.1995 (s, 3H, COCH3), 2.7104 (d, 2H, CH2), 3.3042-3.3149-3.3256 (t, 2H, morpholine ring CH2), 3.5497-3.5604-3.5707 (t , 2H, morpholine ring CH2), 3.6553-3.6655-3.6758 (t, 2H, morpholine ring CH2), 3.7145-3.7240-3.7333 (t, 2H, morpholine ring CH2), 7.5028-7.5115-7.5204-7.5291 (quartet, 4H, ArH), 7.8864-7.9038 (d, 2H, ArH), 8.0185-8.0360 (d, 2H, ArH).

[0138] Preparation Example 2 4-(2-piperidinyl-2-oxoacetyl)-4'-(3-cyclohexyl-2-acetoxyiminopropionyl) diphenyl sulfide:

[0139] Steps 2a-2e. According to steps 1a-1e of Preparation Example 1, wherein in step 2c, piperidine is used instead of morpholine in step 1c, and the corresponding intermediate and target product are obtained starting from 2c: 4-(2-piperidinyl-2-oxoacetyl)-4'-(3-cyclohexyl-2-acetoxyiminopropionyl) diphenyl sulfide; the appearance is a light yellow glassy state, and the HPLC purity is 97.65%.

[0140] 1 H-NMR (CDCl3, δ [ppm]) data: 0.8636-1.7523 (m, 17H, cyclohexane CH2+CH+piperidine ring CH2), 1.9400 (s, 3H, CH3CO), 2.5984-2.6138 (d, 2H, CH2), 3.2278-3.2395-3.2517 (t, 2H, piperidine ring CH2), 3.6024-3.6134-3.6259 (t, 2H, piperidine ring CH2), 7.4312-7.4487 (d, 2H, ArH), 7.4933-7.5107 (d, 2H, ArH), 7.8305-7.8479-7.8639-7.8811 (quartet, 4H, ArH).

[0141] Preparation Example 3 4-[2-(3,4-Benzopiperidinyl)-2-oxoacetyl]-4'-(3-cyclohexyl-2-acetoxyiminopropionyl)diphenyl sulfide:

[0142] Steps 3a-3e. The reaction was performed according to steps 1a-1e of Preparation Example 1, except that 4,5-benzopiperidine was used instead of morpholine in step 1c in step 3c. The corresponding intermediate and target product were obtained starting from 3c: 4-[2-(3,4-benzopiperidinyl)-2-oxoacetyl]-4'-(3-cyclohexyl-2-acetoxyiminopropionyl) diphenyl sulfide; the product had a light yellow glassy appearance and a HPLC purity of 99.52% (96.3% of the major isomer and 3.22% of the minor isomer).

[0143] 1H-NMR (CDCl3, δ [ppm]) data: 0.9407-1.2379 (m, 3H, cyclohexane CH2), 1.6361-1.7195 (m, 8H, cyclohexane CH2+CH), 2.2876 (s, 3H, CH3CO), 2.7705-2.7864 (d, 2H, CH2), 2.9017-2.9150-2.9283 (t,) + 3.0150-3.0282-3.0416 (t) for the above two groups combined, 3.6517-3.6649-3.6780 (t,) + 4.017-4.01 51-4.0287(t,)the above two groups total 2H, 4.5823(s,)+4.9291(t,)the above two groups total 2H, 7.1494-7.1653(d)+7.2173-7.2329(d,)the two groups total 2H, 7.4384-7.4540(d,)+7.4717-7.4895(d,)the two groups total 6H, 7.9090-7.9270(d,)+7.9433-7.9611(d,)the two groups total 2H, 8.0770-8.0961+8.0928-8.1106(d+d)the two groups total 2H.

[0144] Preparation Example 4 6-(2-morpholin-4-yl-2-oxoacetyl)-2-(3-cyclohexyl-2-acetoxyiminopropionyl)fluorene:

[0145] Steps 4a-4e. The reaction was carried out according to steps 1a-1e of Preparation Example 1, except that fluorene was used in place of diphenyl sulfide in step 1a in step 4a. The corresponding intermediate and target product were obtained starting from step 4a: 6-(2-morpholin-4-yl-2-oxoacetyl)-2-(3-cyclohexyl-2-acetoxyiminopropionyl)fluorene; the product was a light yellow powder with a DSC melting point of 108.1°C and an HPLC purity of 98.05%.

[0146] 1H-NMR (CDCl3, δ [ppm]) data: 1.0201-1.2619 (m, 5H, CH2 of cyclohexane), 1.6018-1.7306 (m, 6H, CH2+CH of cyclohexane), 2.2761 (s, 3H, CH3CO), 2.7777-2.7948 (d, 2H, CH2), 3.4144-3.4250-3.4380 (t, 2H, CH2 of morpholine), 3.6669-3.6800-3.6908 (t, 2H, CH2 of morpholine), 3.8236 (s, 4H, 2CH2 of morpholine), 4.0536 (s, 2H, CH2 of fluorene), 7.9351-7.9501 (d, 1H, ArH), 7.9557-7.9703 (d, 1H, ArH), 8.0324-8.0524 (d, 1H, ArH), 8.1695 (s, 1H, ArH), 8.1757-8.1997 (d, 1H, ArH), 8.3191 (s, 1H, ArH).

[0147] Preparation Example 5 6-[2-(3-methylpiperidinyl)-2-oxoacetyl]-3-(1-acetoxyiminooctyl)-N-(4-nitrophenyl)carbazole:

[0148] Step 5a. Place 4 g (13.8 mmol) of N-(4-nitrophenyl) carbazole and 20 g of o-dichlorobenzene (hereinafter referred to as DCB) in a 100 mL three-necked flask, cool to -10°C, add 3.14 g (23.6 mmol) of anhydrous aluminum chloride, stir, and dropwise add 2.36 g (14.6 mmol) of octanoyl chloride over 30 minutes. Then, stir and react at 0°C overnight. The reaction solution was acidified and washed with water until neutral. DCB was removed by vacuum rotary evaporation to obtain 6.0 g of a yellow solid, which was recrystallized from 30 ml of ethanol to obtain 5.33 g of a yellow crystalline powder, with a yield of 93.2%, an HPLC purity of 99.4%, and a DSC melting point of 130.6°C. This is the intermediate 3-octanoyl-N-(4-nitrophenyl) carbazole.

[0149] Step 5b. Place 5.13 g (38.6 mmol) of anhydrous aluminum trichloride and 30 g of 1,2-dichloroethane (DCE) in a 100 mL three-necked flask, stir, and cool to 0°C. Add 5.0 g (12.1 mmol) of the product from Step 5a, controlling the temperature not to exceed 10°C. Then, add 1.63 g (13.3 mmol) of monomethyl oxalyl chloride dropwise and react at 5-10°C for 3 h. Add the reaction solution dropwise to a 0°C solution of 6 g of hydrochloric acid and 20 mL of water, stir for 1 h, and allow to separate. Add 20 mL of water to the organic phase, stir for 30 min, and allow to separate. The separated organic phase was distilled under reduced pressure to 60°C, 30 mL of ethanol was added to the residue, and the mixture was stirred and heated. The mixture was cooled to room temperature, filtered, and the filter cake was dried under reduced pressure to obtain 5.58 g of a yellow powder with a yield of 91.1%, a HPLC purity of 98.1%, and a DSC melting point of 178.7°C. This was the intermediate 3-octanoyl-6-(2-methoxy-2-oxoacetyl)-N-(4-nitrophenyl)carbazole.

[0150] Step 5c. 2 g (4 mmol) of the product obtained in step 5b was added to a 50 mL single-necked bottle, 10 g (0.1 mol) of 3-methylpiperidine, and the reaction was stirred at 65 ° C for 8 h. The reaction mixture was cooled and 30 ml of DCM and 30 ml of water were added. The lower organic phase was separated and washed once with water, and the DCM was evaporated to dryness to give a yellow solid. The solid was slurried with a mixture of tetrahydrofuran and n-heptane, filtered, and the filter cake was dried under reduced pressure to give 1.76 g, a yield of 77.5%, HPLC content of 97.7%, DSC melting point: 202.3 ° C; the intermediate 3-octanoyl-6-[2-(3-methylpiperidinyl)-2-oxoacetyl]-N-(4-nitrophenyl) carbazole;

[0151] Step 5d. In a 50 mL three-necked flask, add 0.8 g (1.4 mmol) of the product from Step 5c, 5 g of ethanol, 0.1 g (1.6 mmol) of hydroxylamine hydrochloride, and 0.14 g (1.6 mmol) of pyridine. Stir and maintain at 50°C for 14 h. The reaction mixture was evaporated to dryness under reduced pressure, dissolved in 5 mL of DCM, washed with 10 mL of water, and dried over 1 g of anhydrous Na2SO4 for 4 h. The desiccant was filtered, and the filtrate was rotary evaporated to dryness, leaving 1.0 g of a light yellow solid. The obtained light yellow solid was dissolved in 4 g of toluene, and 3 g of heptane was added. The mixture was cooled to crystallize, and the temperature was lowered to -10°C overnight. The precipitated crystals were filtered and dried under reduced pressure to obtain a yellow crystalline powder weighing 0.65 g, with a yield of 79.3%, an HPLC purity of 97.3%, and a DSC melting point of 178.7°C. This was the intermediate 3-(1-hydroxyiminooctyl)-6-[2-(3-methylpiperidinyl)-2-oxoacetyl]-N-(4-nitrophenyl)carbazole.

[0152] Step 5e. To a 50 mL single-necked flask, add 0.52 g (0.8 mmol) of the product from Step 5d, 5.0 mL of DCM, and 0.1 g (1 mmol) of acetic anhydride. Heat to 40°C and stir magnetically for 5 h. Wash with water three times, 3.0 g each time, until the pH reaches 6-7. Evaporate to dryness under reduced pressure, and remove the remaining solvent using an oil vacuum pump to obtain 0.52 g of a yellow glassy solid. The yield is 93%, and the HPLC purity is 98.14% (92.5% trans isomer + 5.64% cis isomer). This is the target compound, 6-[2-(3-methylpiperidinyl)-2-oxoacetyl]-3-(1-acetoxyiminooctyl)-N-(4-nitrophenyl)carbazole.

[0153] 1 H-NMR (CDCl3, δ [ppm]) data: 0.8058-0.8201 (t, 3H, CH3), 0.8468-0.8821 (m, 5H, CH3+CH2), 1.0190-1.0333 (d, 2H, CH2), 1.2493-1.6962 (m, 15H, CH2+CH), 2.2982 (s, 3H, CH3CO), 2.9724-2.9894-3.0063 (t, 2H, CH2), 7.4436-7 .4618(d,2H,ArH),7.4922-7.5112(d,2H,ArH),7.7832-7.7858-7.8014-7.8043(d+d,2.8H,ArH),7.8975-7.9 152(d,0.6H,ArH),8.1042-8.1221(d,0.6H,ArH),8.5357-8.5548(d+s,3H,ArH),8.7737-8.7774(s,1H,ArH).

[0154] Preparation Example 6 4-(2-morpholin-4-yl-2-oxoacetyl)-4'-(4-cyclohexyl-2-acetoxyiminobutyryl)diphenyl sulfide:

[0155] Step 6a. Place 22 g (0.118 mol) of diphenyl sulfide and 100 g of o-dichlorobenzene (hereinafter referred to as DCB) in a 250 mL three-necked flask, cool to -10°C, add 17.28 g (0.13 mol) of anhydrous aluminum chloride, stir, and add 23.4 g (0.124 mol) of 4-cyclohexylbutyryl chloride dropwise over 30 minutes. Then, stir and react at 10°C overnight. The reaction solution is acidified and washed with water until neutral. DCB is removed by rotary evaporation under reduced pressure to obtain 39.22 g of a light yellow oil with a yield of 98.2% and an HPLC purity of 98.6%, which is the intermediate 4-(4-cyclohexylbutyryl) diphenyl sulfide.

[0156] Step 6b. Place 11.7 g (0.088 mol) of anhydrous aluminum chloride and 60 g of 1,2-dichloroethane (DCE) in a 100 mL three-necked flask, stir, and cool to 0°C. Add 9.92 g (0.0293 mol) of the product from Step 6a, controlling the temperature not to exceed 10°C. Then, add 3.95 g (0.0322 mol) of monomethyl oxalyl chloride dropwise, and react at 5-10°C for 3 h. Add the reaction solution dropwise to a 0°C solution of 15 g of hydrochloric acid and 50 mL of water, stir for 1 h, and allow to separate. Add 50 mL of water to the organic phase, stir for 30 min, and allow to separate. The separated organic phase was distilled under reduced pressure to 60° C., leaving 12.2 g of a light yellow oil with a yield of 98% and a purity of 97.25% by HPLC; this was the intermediate 4-(2-methoxy-2-oxoacetyl)-4′-(4-cyclohexylbutanoyl) diphenyl sulfide.

[0157] Step 6c. In a 50 mL single-necked flask, 3.2 g (7.2 mmol) of the product obtained in Step 6b and 8.7 g (0.1 mol) of morpholine were added and stirred at 50°C for 2 h. 15 mL of hot ethanol was added, and the temperature was lowered to precipitate white crystals, which were filtered and dried under reduced pressure to obtain 2.9 g of the intermediate 4-(2-morpholin-4-yl-2-oxoacetyl)-4'-(4-cyclohexylbutanoyl)diphenyl sulfide. The yield was 79.7%, the HPLC content was 99.0%, and the DSC melting point was 108.7°C.

[0158] Step 6d. In a 50 mL three-necked flask, add 2.2 g (4.6 mmol) of the product from Step 6c, 10 g of DMSO, and 0.6 g (5.6 mmol) of butyl nitrite. Stir and incubate at 20°C. Continue to introduce small amounts of HCl gas and allow the reaction to proceed for 4 h. Add the reaction mixture to 20 mL of dichloromethane (DCM) and 50 mL of water, stir for 30 min, and separate the lower organic layer. The upper aqueous phase was extracted once more with 20 mL of DCM, combined with DCM, and dried over 1 g of Na2SO4 for 4 h. The desiccant was filtered, and the filtrate was rotary evaporated to dryness. The residue weighed 2.2 g of a light yellow oil, which was subjected to silica gel column chromatography. The eluent was a heptane-ethyl acetate mixture, and the eluent was collected and rotary evaporated to dryness to obtain a light yellow oil weighing 1.94 g, with a yield of 82.9% and a purity of 98.3% by HPLC; this was the intermediate 4-(2-morpholin-4-yl-2-oxoacetyl)-4'-(4-cyclohexyl-2-hydroxyiminobutyryl) diphenyl sulfide;

[0159] Step 6e. To a 50 mL single-necked flask, add 1 g (1.96 mmol) of the product from Step 6d, 5.0 g of methyl tert-butyl ether, and 0.25 g (2.45 mmol) of acetic anhydride. Heat to 40°C and stir magnetically for 4 h. Wash with water three times, 3.0 g each time, until the pH reaches 6-7. Evaporate to dryness under reduced pressure, and remove the remaining solvent using an oil vacuum pump to obtain 1.0 g of a pale yellow viscous oil. The yield is 92.6%, and the HPLC purity is 98%. This is the target compound, 4-(2-morpholin-4-yl-2-oxoacetyl)-4'-(4-cyclohexyl-2-acetoxyiminobutanoyl)diphenyl sulfide.

[0160] 1 H-NMR (CD3CN, δ [ppm]) data: 0.89445-1.2888 (m, 6H, cyclohexane CH2), 1.3958-1.4120-1.4278-1.4418 (quartet, 2H, CH2), 1.6314-1.7424 (m, 5H, cyclohexane CH2+CH), 2.2516 (s, 3H, COCH3), 2.7611-2.7778-2.7934 (t, 2H, CH2), 3. 3808-3.3903-3.4001 (t, 2H, morpholine ring CH2) 3.6519-3.6616-3.6711 (t, 2H, morpholine ring CH2), 3.7747 (s, 4H, morpholine ring CH2), 7.4218-7.4386-7.4423-7.4588 (quartet, 4H, ArH), 7.8756-7.8925 (d, 2H, ArH), 8.0413-8.0583 (d, 2H, ArH).

[0161] Preparation Example 7 4-(2-methoxy-2-oxoacetyl)-4'-(3-cyclohexyl-2-acetoxyiminopropionyl)diphenyl sulfide:

[0162] Step 7a. According to the operation of step 1d in Preparation Example 1, the product obtained in step 1b of Preparation Example 1 was used instead of the product obtained in step 1c, and α-oximation reaction was performed to give white crystals in a yield of 78%, HPLC purity of 99.4%, DSC melting point: 110.1 ° C; the intermediate 4-(2-methoxy-2-oxoacetyl)-4'-(3-cyclohexyl-2-hydroxyiminopropionyl) diphenyl sulfide;

[0163] Step 7b. According to the operation of step 1e in Preparation Example 1, the product obtained in step 7a was esterified to give white crystals with a yield of 85.0%, HPLC purity of 99.24%, DSC melting point: 58.8 ° C; the target product is 4-(2-methoxy-2-oxoacetyl)-4'-(3-cyclohexyl-2-acetoxyiminopropionyl) diphenyl sulfide.

[0164] 1 H-NMR (CD3CN, δ [ppm]) data: 1.0085-1.7078 (m, 11H, cyclohexane CH2+CH), 2.1996 (s, 3H, CH3CO), 2.7090-2.7245 (d, 2H, CH2), 3.9347 (s, 3H, OCH3), 7.4805-7.4983-7.5159-7.5339 (quartet, 4H, ArH), 7.9434-7.9613 (d, 2H, ArH), 8.0204-8.0379 (d, 2H, ArH).

[0165] Preparation Example 8 4-(3-cyclohexyl-2-acetoxyiminopropionyl)diphenyl sulfide:

[0166] Step 8a. According to the procedure of Step 1c of Preparation Example, the product 4-(3-cyclohexylpropionyl)diphenyl sulfide obtained in Step 1a was subjected to α-oximation reaction to obtain white crystals with a yield of 85%, HPLC purity, DSC melting point: 38.5 ° C; the intermediate 4-(3-cyclohexyl-2-hydroxyiminopropionyl)diphenyl sulfide;

[0167] Step 8b. According to the procedure of Preparation Example 1 in step 1e, the product obtained in step 8a was esterified to give white crystals with a yield of 80%, HPLC purity of 98.8%, and a DSC melting point of 52.9°C; the target product was 4-(3-cyclohexyl-2-acetoxyiminopropionyl)diphenyl sulfide.

[0168] Preparation of alkali-soluble resin

[0169] Dissolve 20g of benzyl methacrylate, 3g of methacrylic acid, 7g of hydroxyethyl methacrylate, 1.5g of azobisisobutyronitrile, and 0.5g of dodecanethiol in 200mL of toluene and place in a constant pressure dropping funnel. Place 100mL of toluene in a 500mL four-necked flask, replace the atmosphere with nitrogen, heat to 80°C, and add the solution in the funnel dropwise. Let react for 6h, then cool and filter to obtain 24g of a white alkali-soluble resin.

[0170] Black color paste preparation

[0171] 50 g of the alkali-soluble resin prepared by the above method, 50 g of P30 carbon black, 100 g of DPHA, and 250 g of propylene glycol methyl ether acetate were put into a 500 mL beaker and mixed at a speed of 5000 r / min for 15 min using a high-speed shear mixer to obtain a black color paste.

[0172] Red color paste preparation

[0173] 50 g of the alkali-soluble resin prepared by the above method, 50 g of Ciba IRGALITE RED 2BXL-Q pigment, 100 g of DPHA, and 250 g of propylene glycol methyl ether acetate were placed in a 500 mL beaker and mixed at 5000 r / min using a high-speed shear mixer for 15 min to prepare a red color paste.

[0174] Compound hydrolysis resistance test

[0175] Compound I-27 obtained in Preparation Example 1 and Comparative Compound A obtained in Preparation Example 7 were prepared into 2% solutions in analytically pure propylene glycol methyl ether acetate (50 g each). Each solution was then divided into five sealed bottles and stored in a 25°C incubator protected from light. After one week, one bottle from each solution was removed and analyzed by HPLC under the same conditions. The analysis was then repeated weekly to observe changes in the main content. The results are listed in Table 1.

[0176] Table 1

[0177] The data in Table 1 indicate that the oxime ester groups in both solutions were hydrolyzed, and the oxime intermediate content increased slightly, albeit modestly. The methyl ester hydrolyzate, arylformic acid, increased rapidly in the solution of the compound from Preparation Example 7, while no corresponding hydrolyzate, arylformic acid, was found in the solution from Preparation Example 1. This suggests that hydrolysis primarily occurred at the arylformic acid methyl ester end of Comparative Compound A, indicating that arylformic acid methyl ester exhibits poor hydrolysis resistance, while arylformamide does not hydrolyze.

[0178] Photoresist composition examples and comparative examples

[0179] The compounds prepared in Preparation Examples 1-6 and Comparative Compound B were used as initiators, mixed and dissolved in PMA according to the proportions in Table 2, and then mixed with black color paste according to the proportions in Table 2. The dosage unit is gram.

[0180] After mixing all components, apply a film to a glass slide using a 10μm wire rod and oven dry at 90°C for 5 minutes. Using a 365nm area light source, a quartz mask with 138μm lines and a 41-step exposure ruler, develop the film with a 1% Na2CO3 solution at 25°C. Rinse with purified water for 10 seconds and oven dry at 90°C for 30 minutes. Observe the number of steps remaining in the film. Measure the line width of the developed image using an electron microscope and record the number. A larger number of steps remaining after curing and a larger line width indicate a higher sensitivity, indicating a more sensitive formulation.

[0181] Table 2

[0182] The mixtures of the examples and comparative examples in Table 2 were coated, cured, developed, and measured, and the data are shown in Table 3.

[0183] Table 3

[0184] From the data in Table 3, it can be seen that under the same dosage conditions, the compounds provided by the present invention are significantly better than the comparative compound B in both the film retention number and the developed line width after curing in the black system. The compound of general formula I of the present invention has the characteristic of high sensitivity.

[0185] The compounds prepared in Preparation Examples 1-6 and Comparative Compound B were used as initiators, dissolved in PMA according to the amounts in Table 4, and then mixed with red color paste according to the proportions in Table 4 (the amount unit is gram).

[0186] After mixing all components, a film was applied to a glass slide using a 10μm wire rod and oven-dried at 90°C for 5 minutes. Cured using a 365nm surface light source using a 41-step exposure ruler and a 138μm mask. The film was developed using a 1% NaOH solution at 25°C, rinsed with purified water for 10 seconds, and oven-dried at 90°C for 30 minutes. The number of film steps remaining was observed and recorded. The line width of the developed image was measured using an electron microscope. Line widths are reported in μm in Table 5.

[0187] Table 4

[0188] Table 5

[0189] It can be seen from the data in Table 5 that under the same dosage conditions, the compound provided by the present invention has significantly better film retention and development line width after curing in the red formula system than the comparative compound B.

[0190] Transparent Photocurable Composition Examples and Comparative Examples

[0191] The compounds prepared in Preparation Examples 1-5 and Comparative Compound B were used as photoinitiators and mixed with the other components in Table 6 according to the ratios in Table 6. The amount used is in grams. The transparent composition can be used as an optical film, adhesive, sealing coating, etc.

[0192] After mixing all the components evenly, a film was coated on a glass slide using a 50 μm wire rod and cured using a 365 nm light source. The film weight was measured after curing and then soaked in acetone at room temperature for 36 h and the film weight was measured again. The gel conversion rate was calculated and recorded in Table 7.

[0193] Table 6

[0194] Table 7

[0195] From the data in Table 7, it can be seen that the photogel conversion rate of the transparent composition containing the compound provided by the present invention as a photoinitiator is significantly higher than that of the comparative example.

[0196] Yellowing test

[0197] The compounds prepared in Preparation Examples 1-3 and Preparation Example 6, as well as Comparative Compounds A and B, were used as initiators. The initiators were dissolved in a 60°C oven and then mixed uniformly with the other components according to the ratios listed in Table 8 (amounts reported in g). Films were applied to glass plates using a 25 μm wire rod and cured under a 365 nm LED light source. The films were oven-dried at 230°C for 30 minutes, then cooled to room temperature. The yellowness values ​​of the samples for each Example and Comparative Example were measured with an automatic colorimeter and recorded in Table 9.

[0198] Table 8

[0199] Table 9

[0200] From the data in Table 9, it can be seen that compounds I-27, I-28, I-29, and I-31 provided by the present invention have more excellent low-yellowing properties. Under the same dosage conditions, the yellowness value of the paint film is significantly lower than that of the comparative compound.

[0201] The technical solution of the present invention is not limited to the above-mentioned specific embodiments. Any technical variations made according to the technical solution of the present invention fall within the protection scope of the present invention.

Claims

1. An oxime ester compound having a structure as shown in formula (I), In formula (I), R1 is selected from NR4R5; R2 is selected from a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1-C10 alkyl group, a C3-C10 alkyl group inserted by one or more O atoms, a substituted or unsubstituted C3-C7 cycloalkyl group, a substituted or unsubstituted C3-C7 heterocyclic group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C4-C20 heteroaryl group, in, The substituent in the C1-C10 alkyl group is selected from one or more of phenyl, C3-C7 cycloalkyl, C3-C7 heterocyclic group, C1-C4 alkoxy, and C1-C4 alkyl acyloxy. The substituents in the C6-C20 aryl and C4-C20 heteroaryl are selected from one or more of C1-C4 alkyl, C3-C7 cycloalkyl, F, Cl, C1-C4 alkoxy, C1-C4 alkylthio, -COCOOR4, The substituents in the C3-C7 cycloalkyl and C3-C7 heterocyclic groups are selected from one or more of F, Cl, C1-C4 alkyl, C1-C4 alkoxy, -COCOOR4; R3 is selected from C1-C3 alkyl, C3-C7 cycloalkyl substituted C1-C3 alkyl, C3-C6 alkenyl, C1-C4 alkoxy, phenyl, phenoxy; R4, R5, R4' and R5' are each independently selected from H, substituted or unsubstituted C1-C8 alkyl, C3-C8 alkyl interrupted by one or more oxygen atoms and / or sulfur atoms, C3-C7 cycloalkyl, C3-C7 heterocyclyl, C6-C20 aryl, C4-C20 heteroaryl, Wherein, the substituent in the C1-C8 alkyl group is selected from one or more of F atom, phenyl, C3-C7 cycloalkyl, C3-C7 heterocyclic group, C1-C4 alkoxy, R3COO-, -R6CONR6'; Optionally, NR4R5 constitutes a three-membered to seven-membered nitrogen-containing heterocyclic ring, the nitrogen-containing heterocyclic ring further has an additional hetero atom, the additional hetero atom is selected from one or two nitrogen atoms, one oxygen atom, one sulfur atom and one silicon atom, and optionally, the nitrogen-containing heterocyclic ring has the following side chain substituents: C1-C4 alkyl, C1-C4 alkyl substituted with one or more substituents selected from F atom, phenyl, C3-C7 cycloalkyl, C3-C7 heterocyclic group, C1-C4 alkoxy, R3COO-, -R6CONR6', C3-C7 cycloalkyl, substituted or unsubstituted phenyl, R6CO-, R6COCO-, R6SO2-; optionally, the nitrogen-containing heterocyclic ring has a cyclic structure, a bicyclic structure and a spirocyclic structure; R6 is selected from C1-C12 alkyl, C1-C4 alkyl substituted by one or more substituents selected from F, Cl, phenyl, thienyl, phenyl substituted by one or more substituents selected from methyl, F, Cl, nitro, Thienyl substituted with one or more substituents selected from methyl, F, Cl, nitro; R6' is selected from hydrogen, C1-C4 alkyl; n is 0 or 1; Ar1 is selected from the structures shown in Formula A-1 to Formula A-5: in, R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are each independently selected from a hydrogen atom, a deuterium atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, and optionally, R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 The two adjacent carbon atoms in the benzene ring together with the carbon atoms on the connected benzene ring form a five-membered, six-membered or seven-membered ring; In formula A-1, R7 and R8 are each independently selected from a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C7 cycloalkyl group, a substituted or unsubstituted C3-C7 heterocyclic group, a substituted or unsubstituted C6-C20 aryl group, or a substituted or unsubstituted C4-C20 heteroaryl group. The substituent in the C1-C8 alkyl group is selected from one or more of a F atom, a Cl atom, a phenyl group, a C3-C7 cycloalkyl group, a C3-C7 heterocyclic group, -OR4', -COOR4', and -PO(OR4')2, The substituents on the C3-C7 cycloalkyl and C3-C7 heterocyclic groups are selected from one or more of F, Cl, C1-C4 alkyl, C1-C4 alkoxy, -COCOOR4, The substituents in the C6-C20 aryl and C4-C20 heteroaryl are selected from one or more of halogen, NO2, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, -COOR4', -COR5'; Optionally, R7 and R8 together with the carbon atom to which they are directly attached form a five-membered to seven-membered ring; In formula A-2 and formula A-3, R9 is selected from substituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C3-C7 cycloalkyl, substituted or unsubstituted C3-C7 heterocyclic group, substituted or unsubstituted C6-C20 aryl group, substituted or unsubstituted C4-C20 heteroaryl group, The substituents in the C1-C8 alkyl group are selected from F atoms, Cl atoms, phenyl groups, C3-C7 cycloalkyl groups, C3-C7 heteroalkyl groups, One or more of a cyclic group, -OR4', -COOR4', -P(=O)(OR4')2, The substituents on the C3-C7 cycloalkyl and C3-C7 heterocyclic groups are selected from one or more of F, Cl, C1-C4 alkyl, C1-C4 alkoxy, -COCOOR4, The substituents in the C6-C20 aryl and C4-C20 heteroaryl are selected from one or more of halogen, NO2, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, -COOR4', -COR5'; In formula A-4, X1 is selected from a single bond, O, S, NR9, CR7R8, Y is selected from O, S, C=O, S=O, R7 and R8 are defined as in formula A-1, and R9 is defined as in formula A-2 and formula A-3; In formula A-5, X2 is selected from O, S, NR7, CR7R8, and R7 and R8 are defined as in formula A-2. Ar2 and Ar3 are each independently selected from substituted or unsubstituted C6-C20 arylene groups, and the substituents in Ar2 and Ar3 are selected from the group consisting of: deuterium atoms, C1-C4 alkyl groups, C1-C4 alkoxy groups, and optionally, two adjacent substituents and the atoms of the aromatic ring to which they are connected form a five-membered, six-membered or seven-membered ring.

2. The oxime ester compound according to claim 1, characterized in that In formula (I): R1 is selected from NR4R5, R2 is selected from C1-C8 alkyl, benzyl, cyclohexyl, cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, cyclohexylethyl, tetrahydrofuranmethyl, R3 is selected from C1-C4 alkyl, C1-C4 alkyl substituted by C5-C7 cycloalkyl, C6-C10 aryl, -COOCH3, preferably selected from methyl, ethyl, cyclohexylmethyl, 2-cyclohexylethyl, phenyl, -COOCH3; R4, R5, R4' and R5' are each independently selected from hydrogen, C1-C4 alkyl, C3-C7 cycloalkyl, C3-C7 heteroalkyl Cyclic group, benzyl, 4-methylbenzyl, C1-C3 alkyl substituted by one or more substituents selected from C3-C7 cycloalkyl, C3-C7 heterocyclic group, C2-C4 alkyl substituted by one or more substituents selected from C1-C4 alkoxy, R3COO-, C3-C8 alkyl interspersed by one or more heteroatoms selected from oxygen atoms, sulfur atoms; R6 is selected from C1-C8 alkyl, C1-C4 alkyl substituted by one or more F, phenyl, phenyl substituted by one or more substituents selected from methyl, F; n is 0 or 1; Ar1 is selected from the structure shown in formula A-1, A-2, A-3 or formula A-5, in, In formula A-1, R7 and R8 are each independently selected from a hydrogen atom or a C1-C4 alkyl group, preferably hydrogen, methyl, ethyl, n-propyl and n-butyl; optionally, R7 and R8 together with the carbon atom directly connected thereto form a cyclopentyl ring or a cyclohexyl ring; In formula A-2 and A-3, R9 is selected from C1-C8 alkyl, C1-C8 alkyl substituted by one or more substituents selected from F atom, phenyl, C5-C6 cycloalkyl, C4-C6 heterocyclic group, OR4', -P(=O)(OR4')2, C5-C6 cycloalkyl, phenyl, or phenyl substituted by one or more of the following groups: F, NO2, C1-C4 alkyl, C1-C4 alkoxy, -C(=O)R5', Wherein, R4' and R5' are each independently selected from C1-C8 alkyl, C3-C7 cycloalkyl, C3-C7 heterocyclic group, C6-C12 aryl; preferably, R9 is selected from methyl, ethyl, n-propyl, n-butyl, 2-ethylhexyl, phenyl, or the following groups: In formula A-5, X2 is selected from O or S; Ar2 and Ar3 are each independently selected from substituted or unsubstituted C6-C12 arylene groups, substituted or unsubstituted C5-C12 heteroarylene groups, preferably, Ar2 and Ar3 are each independently selected from substituted or unsubstituted phenylene groups, substituted or unsubstituted naphthylene groups, substituted or unsubstituted anthrylene groups, and the substituents in Ar2 and Ar3 are each independently selected from one or more of C1-C4 alkyl groups and C1-C4 alkoxy groups; R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 Each is independently selected from hydrogen or C1-C4 alkyl, preferably selected from hydrogen, methyl or ethyl.

3. The oxime ester compound according to claim 1 or 2, characterized in that The oxime ester compound has a structure shown in formula (I-1), formula (I-2) or formula (I-3): Wherein, R1, R2, R3, R7, R8 and R9 are defined the same as in formula (I).

4. The oxime ester compound according to any one of claims 1 to 3, characterized in that The compound is selected from the group consisting of the following compounds:

5. The oxime ester compound according to any one of claims 1 to 4, characterized in that The preparation of the compound comprises the following steps: Step (1): Reaction of HAr1H with an acyl chloride compound R2CH2COCl, R2COCl or an anhydride compound in a Friedel-Crafts acylation reaction Under the reaction conditions, a reaction occurs to obtain an intermediate M1 or M1'; Step (2): reacting the intermediate M1 or M1′ in step (1) with R1′COCOCl under Friedel-Crafts acylation conditions to obtain the intermediate M2 or M2′; Wherein, R1' is selected from methoxy, ethoxy or H3N, Step (3): reacting the intermediate M2 or M2' in step (2) with an H-R1 amino compound HNR4R5 to obtain an intermediate M3 or M3'; Step (4): reacting the intermediate M3 in step (3) with a nitrite or nitrous acid under acidic conditions to obtain an intermediate M4, or reacting the intermediate M3' in step (3) with hydroxylamine hydrochloride under neutral or alkaline conditions to obtain an intermediate M4', which is a trans or cis configuration or a mixture of the two; Step (5): reacting the intermediate M4 or M4' in step (4) with R3COCl or (R3CO)2O to obtain a compound of formula II or III; wherein Ar1, R1, R2, R3, R4 and R5 are defined the same as in formula (I).

6. The oxime ester compound according to any one of claims 1 to 5, characterized in that When Ar1 in the compound of formula (I) is selected from -Ar2-X2-Ar3-, and X2 is selected from O or S, the preparation method of the compound comprises the following steps: Step (1): using the compound represented by formula IV as a raw material, reacting with R2CH2COCl or an acid anhydride compound under Friedel-Crafts acylation conditions to obtain an intermediate compound represented by formula V; the compound represented by formula V undergoes a thioetherification reaction with a phenol or thiophenol compound represented by formula VII to obtain an intermediate compound represented by formula VI; wherein Z is selected from F, Cl, Br or I; Step (2): reacting the intermediate compound represented by formula VI in step (1) with R1'COCOCl under Friedel-Crafts acylation conditions to obtain intermediate M2; wherein R1' is selected from methoxy or ethoxy; Ar1 ​​is -Ar2-X2-Ar3-; Step (3): reacting the intermediate M2 of step (2) with an H-R1 organic amine compound HNR4R5 to obtain an intermediate M3; Step (4): subjecting the intermediate M3 of step (3) to an oximation reaction with a nitrite or nitrous acid under acid catalysis to obtain an intermediate of formula M4; Step (5): The intermediate M4 of step (4) is subjected to an esterification reaction with R3COCl or (R3CO)2O to obtain an oxime ester product of formula (II): wherein Ar2, Ar3, R1, R2, R3, R4 and R5 are defined the same as in formula (I).

7. A photocurable composition comprising a photoinitiator and at least one free radical polymerizable compound, wherein the photoinitiator comprises the oxime ester compound according to any one of claims 1 to 6; 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 includes methyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, ethyl methacrylate, polysiloxane acrylate, acrylonitrile, vinyl acetate, vinyl ether, styrene, N-vinyl pyrrolidone, ethylene glycol diacrylate, polyethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, 1,6- One or more of hexanediol diacrylate, trihydroxymethane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, vinyl acrylate, and triallyl isocyanurate; More preferably, the mass proportion of the oxime oxalate compound in the photocurable composition is 0.1-8.0%.

8. A photoresist, the raw materials of which include a photoinitiator, a multifunctional acrylate monomer, an alkali-soluble resin and an organic solvent, wherein: The photoinitiator comprises the oxime ester compound according to any one of claims 1 to 6; Preferably, the multifunctional acrylate monomer is selected from acrylate monomers with a functionality ≥ 3, more preferably dipentaerythritol hexaacrylate and / or pentaerythritol acrylate; Preferably, the alkali-soluble resin is a resin having an acidic group, more preferably a polyacrylate or methacrylate having a carboxylic acid group, and further preferably a copolymer formed by one or more of methacrylic acid, itaconic acid, and maleic acid and one or more of methyl acrylate, butyl methacrylate, benzyl acrylate, hydroxyethyl acrylate, styrene, butadiene, and maleic anhydride, such as a copolymer of methyl methacrylate and methacrylic acid, a copolymer of benzyl methacrylate and methacrylic acid, a copolymer of methyl methacrylate and butyl methacrylate, and a copolymer of methacrylic acid and styrene; Preferably, the organic solvent is selected from ester solvents, aromatic hydrocarbon solvents and halogenated alkane solvents, preferably propylene glycol monomethyl ether acetate, ethylene glycol methyl ether acetate, toluene, xylene, tetrachloroethane; Optionally, the photoinitiator further includes one or more of 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, di(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, and bis(2,6-difluoro-3-pyrrolophenyl)titanocene; Optionally, the photoresist raw material also contains a pigment; preferably, the pigment is a red pigment, a green pigment, a blue pigment or a black pigment; more preferably, 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.

9. A black matrix or photo spacer, prepared from a raw material comprising the photoresist according to claim 8, wherein: The pigment in the photoresist is a black pigment, preferably carbon black and titanium black.

10. A color filter device, prepared from a raw material comprising the photoresist according to claim 8, wherein: The pigment in the photoresist is a red pigment, a green pigment or a blue pigment.

11. A printed article or display, obtained by photocuring the oxime ester compound according to any one of claims 1 to 6 as a photoinitiator; preferably, the printed article comprises a printed circuit board, and the display comprises a PCB display, an LCD display, or an OLED display.

12. Use of the oxime ester compound according to any one of claims 1 to 6, the photocurable composition according to claim 7, or the photoresist according to claim 8 in the preparation of colored or non-colored inks, coatings, adhesives, filters, displays, or in pattern printing, printing plates, 3D printing, PCB photoresists, PCB solder mask inks, substrate protective coatings, electronic device protective coatings, passivation films, liquid or dry film corrosion-resistant materials, sealants, dental materials, optical materials, optical films, optical fiber coatings, insulating films, polarizers, microlenses, and recording materials.

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