WO2025044765A1 - Oxime ester compound, photoresist, and use thereof - Google Patents

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

CROSS-REFERENCE TO RELATED APPLICATIONS

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

Technical Field

The invention belongs to the technical field of organic chemistry and photocuring, and in particular relates to a new oxime ester compound, a photoresist containing the oxime ester compound and application thereof.

Background Art

Since the emergence of photocuring technology in the 1970s, it 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 most concerned issues for photocuring technology technicians is the curing efficiency or sensitivity. The key factors affecting the curing efficiency are the photoinitiator structure and the auxiliary initiator components used in conjunction 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 the sensitivity of OXE 02 is improved, its yellowing property is also stronger, which limits its use in transparent photoresists and color photoresists. Based on the aforementioned patent compounds, the modification of the side chain of Chinese patent CN101565472B does not fundamentally change the sensitivity and yellowing property 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 nitro group or the large conjugated structure of benzocarbazole, the ultraviolet absorption spectrum of the corresponding oxime ester compounds is significantly red-shifted. For example, NCI-831 of Japan Aidico and BASF The two commercial products of OXE 03 have more effective absorption of the 365nm emission light of the light source, showing higher sensitivity, but at the same time, the significantly red-shifted ultraviolet absorption spectrum also gives the compound a yellower color and significant yellowing in the photoresist. Therefore, they are more suitable for use in black photoresist formulations and are difficult to use in transparent and RGB color photoresists.

Patent CN112004800 and patent WO2022075452 disclose a technical solution 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 formulation.

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.

Summary of the invention

In order to solve one of the above technical problems existing in the prior art, the present invention provides a novel oxime ester compound. The present invention unexpectedly found that this type of compound has very high sensitivity and can meet the process requirements for the use of photoresists. The novel oxime ester compound provided by the present invention has both a dicarbonyl amide group and an oxime ester group, and can be used as a photoinitiator in photocuring technology, especially showing high sensitivity and low yellowing characteristics in photoresists, and can be used in the manufacture of color displays.

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

in,

R ₁ is selected from NR ₄ R ₅ ;

_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,

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.

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, -COCOOR ₄ ;

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, -COCOOR ₄ ;

_R3 is selected from C1-C3 alkyl, C3-C7 cycloalkyl substituted C1-C3 alkyl, C3-C6 alkenyl, C1-C4 alkoxy, phenyl, phenoxy;

R ₄ , R ₅ , R ₄ ′ and R ₅ ′ 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, R ₃ COO-, -R ₆ CONR ₆ ';

Optionally, NR ₄ R constitutes a three-membered, four-membered, five-membered, six-membered or seven-membered nitrogen-containing heterocyclic ring, the nitrogen-containing heterocyclic ring further having an additional heteroatom, the additional heteroatom selected from one or two nitrogen atoms, an oxygen atom, a sulfur atom and a 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, R ₃ COO-, -R ₆ CONR ₆ ', C3-C7 cycloalkyl, substituted or unsubstituted phenyl, R ₆ CO-, R ₆ COCO-, R ₆ SO ₂ -; optionally, the nitrogen-containing heterocyclic ring has a parallel ring structure, a bicyclic structure and a spirocyclic structure, for example, a benzo nitrogen-containing heterocyclic ring;

_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 by one or more substituents selected from methyl, F, Cl, nitro;

R ₆ 'is selected from hydrogen, C1-C4 alkyl;

n is 0 or 1;

Ar ₁ is selected from the structures shown in Formula A-1 to Formula A-5:

wherein 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, two adjacent groups of R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ 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, -OR ₄ ', -COOR ₄ ', -P(=O)(OR ₄ ') 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, -COCOOR ₄ ,

The substituents in the C6-C20 aryl group and the C4-C20 heteroaryl group are selected from one or more of halogen, NO ₂ , C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, -COOR ₄ ', and -COR ₅ ';

Optionally, _R7 and _R8 together with the carbon atom to which they are directly attached form a five-membered, six-membered or seven-membered ring;

In formula A-2 and formula A-3, R ₉ 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, -OR ₄ ', -COOR ₄ ', -P(=O)(OR ₄ ') 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, -COCOOR ₄ ,

The substituents in the C6-C20 aryl group and the C4-C20 heteroaryl group are selected from one or more of halogen, NO ₂ , C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, -COOR ₄ ', and -COR ₅ ';

In formula A-4, X ₁ is selected from a single bond, O, S, NR ₉ , CR ₇ R ₈ , Y is selected from O, S, C=O, S=O, R ₇ and R ₈ are defined as in formula A-1, and R ₉ is defined as in formula A-2 and formula A-3;

In formula A-5, X ₂ is selected from O, S, NR ₇ , CR ₇ R ₈ , R ₇ and R ₈ are defined the same as in formula A-2,

Ar ₂ and Ar ₃ are each independently selected from substituted or unsubstituted C6-C20 arylene groups, and the substituents in Ar ₂ and Ar ₃ 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.

In this application, -COCOO- means -CO- represents carbonyl, -COO- represents -COCO- means -SO ₂ - indicates

In some embodiments, examples of C6-C20 aryl and substituted C6-C20 aryl include phenyl, naphthyl, 4-fluorophenyl, and 4-methoxynaphthalen-1-yl.

In some embodiments, _R1 is selected from the group consisting of:

_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.

In some embodiments, R ₁ is selected from N(CH ₃ ) ₂ ,

In some embodiments, R ₄ and R ₅ are each independently selected from C1-C4 alkyl, C3-C7 cycloalkyl, C3-C7 heterocyclyl, benzyl, 4-methylbenzyl, C1-C3 alkyl substituted with one or more substituents selected from C3-C7 cycloalkyl and C3-C7 heterocyclyl, C2-C4 alkyl substituted with one or more substituents selected from C1-C4 alkoxy and R ₃ COO-, and C3-C8 alkyl interrupted by one or more oxygen atoms and/or sulfur atoms.

In some embodiments, R ₁ is selected from NR ₄ R ₅ , R ₄ and R ₅ are each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, phenyl, CH ₃ COO-substituted methyl, CH ₃ COO-substituted ethyl.

In some embodiments, _R2 is selected from C1-C6 alkyl, benzyl, cyclohexyl, cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, cyclohexylethyl, tetrahydrofuranmethyl,

In some embodiments, R ₃ is selected from C1-C4 alkyl, C1-C4 alkyl substituted by C5-C7 cycloalkyl, C6-C10 aryl, -COOCH ₃ .

In some embodiments, R ₃ is selected from methyl, ethyl, cyclohexylmethyl, 2-cyclohexylethyl, phenyl, -COOCH ₃ .

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.

In some embodiments, the structure is selected from the structure shown in Formula A-1, A-2, A-3 or Formula A-5, wherein,

In formula A-1, R ₇ and R ₈ are each independently selected from a hydrogen atom or a C1-C4 alkyl group, preferably hydrogen, methyl, ethyl, n-propyl and n-butyl; optionally, R ₇ and R ₈ together with the carbon atom to which they are directly connected form a cyclopentyl ring or a cyclohexyl ring;

In formula A-2 and A-3, R ₉ 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, OR ₄ ', -P(=O)(OR ₄ ') ₂ , C5-C6 cycloalkyl, phenyl, or phenyl substituted by one or more of the following groups: F, NO ₂ , C1-C4 alkyl, C1-C4 alkoxy, -C(=O)R ₅ ',

Wherein, R ₄ 'and R ₅ 'are each independently selected from C1-C8 alkyl, C3-C7 cycloalkyl, C3-C7 heterocyclic group, C6-C12 Aryl; preferably, R ₉ is selected from methyl, ethyl, n-propyl, n-butyl, 2-ethylhexyl, phenyl, or the following groups:

In formula A-5, X ₂ is selected from O or S; Ar ₂ and Ar ₃ are each independently selected from a substituted or unsubstituted C6-C12 arylene group, a substituted or unsubstituted C5-C12 heteroarylene group, preferably, Ar ₂ and Ar ₃ 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 Ar ₂ and Ar ₃ are each independently selected from one or more of a C1-C4 alkyl group and a C1-C4 alkoxy group;

R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ are each independently selected from hydrogen or C1-C4 alkyl, preferably hydrogen, methyl or ethyl.

In some embodiments, the oxime ester compound has a structure shown in formula (I-1), formula (I-2) or formula (I-3):

wherein R ₁ , R ₂ , R ₃ , R ₇ , R ₈ and R ₉ are as defined in formula (I).

In some embodiments, in formula (I-1), R ₁ is selected from NR ₄ R ₅ , wherein NR ₄ R ₅ constitutes a three-membered to seven-membered nitrogen-containing heterocyclic ring containing at least one nitrogen atom, an optional oxygen atom, an optional a sulfur atom, optionally a silicon atom; preferably, the nitrogen-containing heterocyclic ring has a parallel ring structure, a bicyclic structure and a spirocyclic structure; R ₂ is selected from C1-C4 alkyl, C5-C8 alkyl, C1-C4 alkyl substituted by C5-C7 cycloalkyl, such as cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl or cyclohexylethyl; R ₃ is selected from C1-C4 alkyl.

In some embodiments, in formula (I-1), R ₁ is selected from

In some embodiments, in formula (I-2), R ₁ is selected from NR ₄ R ₅ , wherein NR ₄ R ₅ 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; R ₂ is selected from C1-C4 alkyl, C5-C8 alkyl, C1-C4 alkyl substituted by C5-C7 cycloalkyl, such as cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl or cyclohexylethyl; R ₃ is selected from C1-C4 alkyl; R ₇ and R ₈ are each independently selected from hydrogen or C1-C4 alkyl.

In some embodiments, in formula (I-2), R ₁ is selected from

In some embodiments, in formula (I-3), R ₁ is selected from NR ₄ R ₅ , wherein NR ₄ R ₅ 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; R ₂ is selected from C1-C4 alkyl, C5-C8 alkyl, C1-C4 alkyl substituted by C5-C7 cycloalkyl, such as cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl or cyclohexylethyl; R ₃ is selected from C1-C4 alkyl; R ₉ is each independently selected from the following groups of C1-C4 alkyl:

In some embodiments, in formula (I-3), R ₁ is selected from

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

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

Step (1): reacting the raw material HAr ₁ H with an acyl chloride compound R ₂ CH ₂ COCl, R ₂ COCl or an acid anhydride compound under Friedel-Crafts acylation conditions to obtain an intermediate M ₁ or M ₁ ′;

Step (2): reacting the intermediate M ₁ or M ₁ ′ in step (1) with R ₁ ′COCOCl under Friedel-Crafts acylation conditions to obtain the intermediate M ₂ or M ₂ ′;

wherein R ₁ ′ is selected from methoxy, ethoxy or H ₃ N;

Step (3): reacting the intermediate M ₂ or M ₂ ′ in step (2) with an HR ₁ organic amine compound HNR ₄ R ₅ to obtain an intermediate M ₃ or M ₃ ′;

Step (4): reacting the intermediate _M3 in step (3) with a nitrite or nitrous acid under corresponding acid conditions to obtain an intermediate _M4 , or reacting the intermediate _M3 ' in step (3) with hydroxylamine hydrochloride under neutral or alkaline conditions to obtain Intermediate M ₄ ', which is in trans or cis configuration or a mixture of both;

Step (5): reacting the intermediate M ₄ or M ₄ ' in step (4) with R ₃ COCl or (R ₃ CO) ₂ O to obtain a compound of formula II or III;

wherein Ar ₁ , R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are as defined in formula (I).

In some embodiments, when Ar ₁ in formula (I) is selected from -Ar ₂ -X ₂ -Ar _3- , and X ₂ is selected from O or S, the preparation method of the compound of formula (I) comprises the following steps:

Step (1): using the compound of formula IV as a raw material, reacting with an acylating agent, an acyl chloride compound R ₂ CH ₂ COCl or an acid anhydride compound under Friedel-Crafts acylation conditions to obtain an intermediate compound of formula V; the compound of formula V undergoes a thioetherification reaction with a phenol or thiophenol compound of formula VII to obtain an intermediate compound of 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 R ₁ 'COCOCl under Friedel-Crafts acylation conditions to obtain intermediate M ₂ ;

wherein R ₁ ' is selected from methoxy or ethoxy; Ar ₁ is -Ar ₂ -X ₂ -Ar ₃ -;

Step (3): reacting the intermediate M ₂ of step (2) with an HR ₁ organic amine compound HNR ₄ R ₅ to obtain an intermediate M ₃ ;

Step (4): the intermediate M ₃ of step (3) is subjected to an oximation reaction with a nitrite or nitrous acid under acid catalysis to obtain an intermediate M ₄ , which is a trans or cis configuration or a mixture of the two;

Step (5): The intermediate M ₄ in step (4) is subjected to an esterification reaction with R ₃ COCl or (R ₃ CO) ₂ O to obtain an oxime ester product of formula (II),

wherein Ar ₂ , Ar ₃ , R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are as defined in formula (I).

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.

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

The photocurable composition of the present invention may further include other photoinitiators or co-initiators. The present invention does not specifically limit the specific types of the other initiators or co-initiators. It is sufficient to select photoinitiators or co-initiators that are helpful for photocuring performance in the art.

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).

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.

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

Examples of the relatively high molecular weight double bond compounds include a large 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.

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

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.

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.

In a fourth aspect, the present invention further 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.

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 prior art and the application requirements of the photocurable composition.

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.

The multifunctional acrylate monomer in the photoresist raw material of the present invention refers to a trifunctional or higher functionality acrylate monomer. The present invention does not specifically limit the specific type of the multifunctional acrylate monomer, and those skilled in the art can select and use from conventional multifunctional acrylate monomers in the art. Examples of the multifunctional acrylate include, but are not limited to: dipentaerythritol hexaacrylate, pentaerythritol acrylate.

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 specifically limit the specific type of the alkali-soluble resin, and those skilled in the art can select and use it from the conventional alkali-soluble resins 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, and 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, copolymers of methyl methacrylate and methacrylic acid, copolymers of benzyl methacrylate and methacrylic acid, copolymers of methyl methacrylate and butyl methacrylate, and copolymers of methacrylic acid and styrene.

In some embodiments, the photoresist is a transparent photoresist without pigment. The transparent photoresist can be used to manufacture optical films, polarizers, insulating films, passivation films, sealing protective layers, etc.

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

The present invention does not specifically limit the solvent of the photoresist raw material, and those skilled in the art can select it according to needs, such as propylene glycol monomethyl ether acetate.

In some embodiments, the photoinitiator may also include other photoinitiators or co-initiators known in the art, such as 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.

In addition, those skilled in the art may also 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, phenolic resin, polyvinyl butyral, polyvinyl acetate, polyester, polyimide, etc.

By using the photoresist of the present invention as a raw material, through the color filter processing process such as multiple coating, exposure, development and other existing technical processes of different color photoresists, a color filter device with excellent optical properties can be obtained, which is an important component of a color display screen, wherein the color unit has pure color and high transmittance, and the colorless part has low yellowing and high transmittance.

The photoresist coating is usually evenly distributed on the substrate by spin coating, and then dried at 80-90℃ to separate the volatile components such as solvents, leaving the solids as films, and placing a mask on the top of the film. The film is exposed to a radiation light source such as a 365nm mercury lamp or LED lamp for a suitable exposure amount. The exposed material is developed in a solution of alkaline substances such as sodium carbonate or sodium hydroxide to remove the unexposed film and leave the exposed image. After that, it is washed and baked at 200-230℃ to make the image better adhere to the substrate. According to the designed procedure, different colors and patterns are produced, or combined with the necessary protective film processing procedures to obtain the filter device.

In a sixth aspect, the present invention provides a black matrix or photo spacer, 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 black pigment, preferably carbon black and titanium black.

In a seventh aspect, the present invention provides a color filter device, which comprises the color filter device described in the fifth aspect of the present invention. The raw materials of the photoresist are prepared, wherein the pigment in the photoresist is a red pigment, a green pigment or a blue pigment.

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.

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

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

In the ninth aspect, the present invention provides the use of the oxime ester compound described in the first aspect or 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.

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 the photoinitiator composition containing the compound of formula (I) as a raw material and processing through necessary steps.

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

The compound of the present invention has significantly high sensitivity in the formulation of photocurable composition, especially photoresist, and its performance is significantly better than that of the prior art.

DETAILED DESCRIPTION

In order to make the purpose, technical solution 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 explain the present invention and are not intended to constitute any limitation to the present invention.

The term "C1-C10 alkyl" as 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.

As used herein, the terms "C3-C10 alkyl group interrupted by one or more O atoms or S atoms" or "C3-C10 alkyl group interrupted by one or more oxygen atoms or sulfur atoms" have equivalent meanings, and refer to a C3-C10 alkyl group interrupted by O or S once or more times, for example 1-9 times, 1-5 times, 1-3 times, or 2 times or 1 time. If there is more than one spacer group, they are 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.

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

The term "alkylthio" as used herein refers to an alkyl group interrupted by a S atom, for example, a C1-C4 alkylthio group is an alkyl group interrupted by a S atom. Atoms are spaced apart from alkyl groups having 1 to 4 carbon atoms.

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, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, especially cyclopentyl and cyclohexyl.

The term "heterocyclic group" as used herein is used interchangeably with "heterocycle", "carbocyclic ring", 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 atoms, oxygen atoms, sulfur atoms, selenium atoms, silicon atoms, phosphorus atoms, germanium atoms, 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 atoms, oxygen atoms, sulfur atoms, selenium atoms, silicon atoms, phosphorus atoms, germanium atoms, 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 oxirane, 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.

The term "aryl or aromatic group" as used herein 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, fluorene, pyrene, , perylene and azulene, preferably phenyl, biphenyl, biphenyl, triphenylene, fluorene and naphthalene. Examples of non-condensed 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-quadrenyl. In addition, the aryl group may be optionally substituted.

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, furanyl, dibenzofuranyl, benzopyranyl, xanthene, 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, 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 ...2-ethyl-3-imidazolyl, 2-ethyl-3-imidazolyl, 2-methyl-3-imidazolyl, 2-ethyl-3-imidazolyl, 2-ethyl-3-imidazolyl, 2-ethyl-3-imidazolyl, 2-methyl-3-imidazolyl, 2-ethyl-3-imidazolyl, 2-ethyl-3-imidazolyl, 2-methyl-3-imidazolyl, 2-ethyl-3-imidazolyl, 2-ethyl-3-imidazolyl, 2-methyl-3-imidazolyl, 2-ethyl-3-imidazolyl, 2-ethyl-3-imidazolyl, 2-methyl-3-imidazolyl, 2-ethyl-3-imidazolyl, 2-ethyl-3-imidazolyl, 2-methyl-3-imidazolyl, 2-ethyl-3-imidazolyl, 2-methyl-3-imidazolyl, 2-ethyl-3-imidazolyl, 2-methyl-3-imidazo -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-diazobenzene, 1-methyl-5-perylene-1-diazobenzene, 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.

Experimental materials and equipment:

Light source equipment:

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

Test equipment:

Differential Scanning Calorimeter: HSC-1, Beijing Hengjiu Experimental Equipment Co., Ltd.

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

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

Experimental Materials:

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

DPHA: dipentaerythritol hexaacrylate, a product of Tianjin Tianjiao Chemical Co., Ltd.;

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

Compound preparation

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

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

Step 1b. Add 11.7g (0.088mol) of anhydrous aluminum chloride and 60g of 1,2-dichloroethane (hereinafter referred to as DCE) into a 100mL three-necked flask, stir and cool to 0℃; add 9.5g (0.0293mol) of the product of step 1a, and control the temperature not to exceed 10℃. Then add 3.95g (0.0322mol) of monomethyl oxalyl chloride dropwise, and react at 5-10℃ for 3h. Add the reaction solution dropwise to a solution of 15g hydrochloric acid and 50mL water at 0℃, stir for 1h, and stand for stratification. Add 50mL of water to the organic phase, stir for 30min, and stand for stratification. The separated organic phase is distilled under reduced pressure to 60℃, and the residue is 13.6g of light 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 DSC melting point of 76.8°C; the intermediate 4-(2-methoxy-2-oxoacetyl)-4'-(3-cyclohexylpropionyl) diphenyl sulfide;

Step 1c. 4 g (9.7 mmol) of the product obtained in step 1b and 2 g (22.96 mmol) of morpholine were added to a 50 mL single-mouth bottle, stirred and reacted 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 obtain 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;

Step 1d. Add 3.8 g (8.2 mmol) of the product obtained in step 1c, 15 g DMSO and 1.0 g (9.8 mmol) of butyl nitrite into a 50 mL three-necked flask, stir and keep warm at 30 °C. Continuously introduce HCl gas in small amounts and react for 4 h. Add the reaction solution to 20 mL of dichloromethane (hereinafter referred to as DCM) and 50 ml of water, stir for 30 min, separate the lower organic layer, extract the upper aqueous phase with 20 ml of DCM again, combine the DCM, dry with 1 g of Na2SO4 for 4 h, filter the desiccant, and evaporate the filtrate to dryness. The residue weighs 4.4 g of light yellow solid. The obtained light yellow solid was added with 20g of ethyl acetate and heated to dissolve, 5g of heptane was added, the temperature was lowered to crystallize, the temperature was lowered to -10°C overnight, the precipitated crystals were filtered, and the white crystalline powder weighed 3.24g after reduced pressure drying, the yield was 80%, the HPLC purity was 99.73%, and the DSC melting point was 152.9°C; the intermediate 4-(2-morpholin-4-yl-2-oxoacetyl)-4'-(3-cyclohexyl-2-hydroxyiminopropionyl) diphenyl sulfide was obtained;

Step 1e. In a 50mL single-mouth bottle, add 3g (6mmol) of the product obtained in step 1d, add 15.0g DCM, and then add 0.74g (7.2mmol) acetic anhydride, heat to 40°C, and react for 4h with magnetic stirring. Wash with water 3 times, 3.0g of water each time, until pH = 6-7. Evaporate to dryness under reduced pressure, and then use an oil vacuum pump to drain the residual solvent to obtain 3.0g of a light yellow viscous oily residue, with a yield of 90% and a HPLC purity of 98.85%. After standing, it becomes a glassy solid; the target compound is 4-(2-morpholin-4-yl-2-oxoacetyl)-4'-(3-cyclohexyl-2-acetoxyiminopropionyl) diphenyl sulfide.

¹ H-NMR (CD ₃ CN, δ [ppm]) data: 0.9971-1.2288 (m, 3H, cyclohexane CH ₂ ), 1.5794-1.6823 (m, 8H, cyclohexane CH ₂ +CH), 2.1995 (s, 3H, COCH ₃ ), 2.7104 (d, 2H, CH ₂ ), 3.3042-3.3149-3.3256 (t, 2H, morpholine ring CH ₂ ), 3.5497-3.5604-3.5707 (t, 2H, morpholine ring CH ₂ ), 3.6553-3.6655-3.6758 (t, 2H, morpholine ring CH ₂ ), 3.7145-3.7240-3.7333 (t, 2H, morpholine ring CH ₂ ), 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).

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

Steps 2a-2e. The steps 1a-1e of Preparation Example 1 were followed, wherein piperidine was used instead of morpholine in step 1c to obtain the corresponding intermediate and target product from step 2c: 4-(2-piperidinyl-2-oxoacetyl)-4'-(3-cyclohexyl-2-acetoxyiminopropionyl) diphenyl sulfide; the appearance was light yellow glass, and the HPLC purity was 97.65%.

¹ H-NMR (CDCl ₃ , δ [ppm]) data: 0.8636-1.7523 (m, 17H, cyclohexane CH ₂ +CH+piperidinyl ring CH ₂ ), 1.9400 (s, 3H, CH ₃ CO), 2.5984-2.6138 (d, 2H, CH ₂ ), 3.2278-3.2395-3.2517 (t, 2H, piperidine ring CH ₂ ), 3.6024-3.6134-3.6259 (t, 2H, piperidine ring CH ₂ ), 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).

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

Steps 3a-3e. The steps 1a-1e of Preparation Example 1 were followed, wherein 4,5-benzopiperidine was used instead of morpholine in step 1c in step 3c, and the corresponding intermediate and target product were obtained from step 3c: 4-[2-(3,4-benzopiperidinyl)-2-oxoacetyl]-4'-(3-cyclohexyl-2-acetoxyiminopropanoyl)diphenyl sulfide; the appearance was light yellow glass, and the HPLC purity was 99.52% (of which the main isomer content was 96.3%, and the minor isomer content was 3.22%).

¹ H-NMR (CDCl ₃ , δ [ppm]) data: 0.9407-1.2379 (m, 3H, cyclohexane CH ₂ ), 1.6361-1.7195 (m, 8H, cyclohexane CH ₂ +CH), 2.2876 (s, 3H, CH ₃ CO), 2.7705-2.7864 (d, 2H, CH ₂ ), 2.9017-2.9150-2.9283(t,)+3.0150-3.0282-3.0416(t) the above two groups are 2H, 3.6517-3.6649-3.6780(t,)+4.0017-4.0151-4.0287(t,) the above two groups are 2H, 4.5823(s,)+4.9291(t,) the above two groups are 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.

Preparation Example 4 6-(2-morpholin-4-yl-2-oxoacetyl)-2-(3-cyclohexyl-2-acetoxyiminopropanoyl)fluorene:

Steps 4a-4e. The process was carried out in accordance with steps 1a-1e of Preparation Example 1, wherein fluorene was used instead of diphenyl sulfide in step 1a in step 4a, and the corresponding intermediate and target product were obtained starting from step 4a: 6-(2-morpholin-4-yl-2-oxoacetyl)-2-(3-cyclohexyl-2-acetoxyiminopropanoyl)fluorene; the product was a light yellow powder, with a DSC melting point of 108.1°C and a HPLC purity of 98.05%.

¹ H-NMR (CDCl ₃ , δ [ppm]) data: 1.0201-1.2619 (m, 5H, CH ₂ of cyclohexane), 1.6018-1.7306 (m, 6H, CH ₂ +CH of cyclohexane), 2.2761 (s, 3H, CH ₃ CO), 2.7777-2.7948 (d, 2H, CH ₂ ), 3.4144-3.4250-3.4380 (t, 2H, CH ₂ of morpholine), 3.6669-3.6800-3.6908 (t, 2H, CH ₂ of morpholine), 3.8236 (s, 4H, 2CH ₂ of morpholine), 4.0536 (s, 2H, CH ₂ 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).

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

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

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

Step 5c. Add 2 g (4 mmol) of the product obtained in step 5b and 10 g (0.1 mol) of 3-methylpiperidine into a 50 mL single-mouth bottle, stir and react at 65 ° C for 8 h, cool the reaction solution, add 30 ml of DCM and 30 ml of water, separate the lower organic phase and wash it with water once, evaporate the DCM to obtain a yellow solid, and beat it with a mixture of tetrahydrofuran and n-heptane, filter, and dry the filter cake under reduced pressure to obtain 1.76 g, yield 77.5%, HPLC content 97.7%, DSC melting point: 202.3°C; intermediate 3-octanoyl-6-[2-(3-methylpiperidinyl)-2-oxoacetyl]-N-(4-nitrophenyl)carbazole;

Step 5d. Add 0.8 g (1.4 mmol) of the product obtained in step 5c, 5 g of ethanol, 0.1 g (1.6 mmol) of hydroxylamine hydrochloride and 0.14 g (1.6 mmol) of pyridine into a 50 mL three-necked flask, stir and keep warm at 50°C; react for 14 h. Evaporate the reaction solution to dryness under reduced pressure, add 5 ml of DCM to dissolve, add 10 mL of water to wash, dry with 1 g of anhydrous Na ₂ SO 4 for 4 h, filter the desiccant, and evaporate the filtrate to dryness. The residue weighs 1.0 g of light yellow solid. The obtained light yellow solid was added with 4g toluene and dissolved by heating, and 3g heptane was added, and the temperature was lowered to crystallize, and the temperature was lowered to -10°C overnight, and the precipitated crystals were filtered out, and the yellow crystalline powder weighed 0.65g after reduced pressure drying, with a yield of 79.3%, a HPLC purity of 97.3%, and a DSC melting point of 178.7°C; the intermediate 3-(1-hydroxyiminooctyl)-6-[2-(3-methylpiperidinyl)-2-oxoacetyl]-N-(4-nitrophenyl)carbazole was obtained;

Step 5e. In a 50mL single-mouth bottle, add 0.52g (0.8mmol) of the product obtained in step 5d, add 5.0mL DCM, and then add 0.1g (1mmol) of acetic anhydride, heat to 40°C, and react with magnetic stirring for 5h. Wash with water 3 times, 3.0g of water each time, until pH = 6-7; evaporate to dryness under reduced pressure, and then use an oil vacuum pump to drain the residual solvent to obtain 0.52g of a yellow glassy solid residue, with a yield of 93% and a HPLC purity of 98.14% (92.5% for trans isomers + 5.64% for cis isomers); the target compound is 6-[2-(3-methylpiperidinyl)-2-oxoacetyl]-3-(1-acetoxyiminooctyl)-N-(4-nitrophenyl)carbazole.

¹ H-NMR (CDCl ₃ , δ [ppm]) data: 0.8058-0.8201(t,3H,CH ₃ ), 0.8468-0.8821(m,5H,CH ₃ +CH ₂ ), 1.0190-1.0333(d,2H,CH ₂ ),1.2493-1.6962(m,15H,CH ₂ +CH),2.2982(s,3H,CH ₃ CO),2.9724-2.9894-3.0063(t,2H,CH ₂ ),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),7.897 5-7.9152(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).

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

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

Step 6b. Add 11.7g (0.088mol) of anhydrous aluminum chloride and 60g of 1,2-dichloroethane (hereinafter referred to as DCE) into a 100mL three-necked flask, stir and cool to 0°C; add 9.92g (0.0293mol) of the product of step 6a, and control the temperature not to exceed 10°C. Then add 3.95g (0.0322mol) of monomethyl oxalyl chloride dropwise, and react at 5-10°C for 3h. Add the reaction solution dropwise to a solution of 15g hydrochloric acid and 50mL water at 0°C, stir for 1h, and stand for stratification. Add 50mL of water to the organic phase, stir for 30min, and stand for stratification. The separated organic phase was distilled under reduced pressure to 60° C. The residue was 12.2 g of light yellow oil with a yield of 98% and a HPLC purity of 97.25%; the intermediate was 4-(2-methoxy-2-oxoacetyl)-4'-(4-cyclohexylbutyryl) diphenyl sulfide;

Step 6c. Add 3.2 g (7.2 mmol) of the product obtained in step 6b and 8.7 g (0.1 mol) of morpholine into a 50 mL single-mouth bottle, keep warm at 50°C and stir to react for 2 h. Add 15 mL of hot ethanol, cool down to precipitate white crystals, filter, and dry under reduced pressure to obtain 2.9 g, with a yield of 79.7%, HPLC content of 99.0%, and DSC melting point of 108.7°C; the intermediate 4-(2-morpholin-4-yl-2-oxoacetyl)-4'-(4-cyclohexylbutyryl) diphenyl sulfide;

Step 6d. Add 2.2 g (4.6 mmol) of the product obtained in step 6c, 10 g DMSO and 0.6 g (5.6 mmol) butyl nitrite into a 50 mL three-necked flask, stir and keep warm at 20°C. Continue to pass HCl gas in small amounts and react for 4 h. Add the reaction solution to 20 mL of dichloromethane (hereinafter referred to as DCM) and 50 mL of water, stir for 30 min, and separate the lower organic layer. The upper aqueous phase was extracted once again with 20 mL of DCM, combined with DCM, dried with 1 g of Na2SO4 for 4 h, the desiccant was filtered, and the filtrate was evaporated to dryness. The residue weighed 2.2 g of a light yellow oil, which was subjected to silica gel column chromatography, and the eluent was a heptane-ethyl acetate mixture. The eluent was collected and evaporated to dryness to obtain a light yellow oil weighing 1.94 g, with a yield of 82.9% and a HPLC purity of 98.3%; the intermediate 4-(2-morpholin-4-yl-2-oxoacetyl)-4'-(4-cyclohexyl-2-hydroxyiminobutyryl) diphenyl sulfide;

Step 6e. In a 50mL single-mouth bottle, add 1g (1.96mmol) of the product obtained in step 6d, add 5.0g of methyl tert-butyl ether, and then add 0.25g (2.45mmol) of acetic anhydride, heat to 40°C, and react for 4h under magnetic stirring. Wash with water 3 times, 3.0g of water each time, until pH = 6-7; evaporate to dryness under reduced pressure, and then use an oil vacuum pump to drain the residual solvent to obtain 1.0g of a light yellow viscous oily residue, with a yield of 92.6% and a HPLC purity of 98%; the target compound is 4-(2-morpholin-4-yl-2-oxoacetyl)-4'-(4-cyclohexyl-2-acetoxyiminobutyryl) diphenyl sulfide.

¹ H-NMR (CD ₃ CN, δ [ppm]) data: 0.89445-1.2888 (m, 6H, cyclohexane CH ₂ ), 1.3958-1.4120-1.4278-1.4418 (quartet, 2H, CH ₂ ), 1.6314-1.7424 (m, 5H, cyclohexane CH ₂ +CH), 2.2516 (s, 3H, COCH ₃ ), 2.7611-2.7778-2.7934 (t, 2H, CH ₂ ), 3.3808-3.3903-3.4001 (t, 2H, morpholine ring CH ₂ ) 3.6519-3.6616-3.6711 (t, 2H, morpholine ring CH ₂ ), 3.7747 (s, 4H, morpholine ring CH ₂ ), 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).

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

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 to carry out α-oximation reaction to obtain white crystals with a yield of 78%, HPLC purity of 99.4%, and DSC melting point of 110.1°C; the intermediate 4-(2-methoxy-2-oxoacetyl)-4'-(3-cyclohexyl-2-hydroxyiminopropionyl) diphenyl sulfide;

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

¹ H-NMR (CD ₃ CN, δ [ppm]) data: 1.0085-1.7078 (m, 11H, cyclohexane CH ₂ +CH), 2.1996 (s, 3H, CH ₃ CO), 2.7090-2.7245 (d, 2H, CH ₂ ), 3.9347 (s, 3H, OCH ₃ ), 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).

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

Step 8a. According to the operation of step 1c of the 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;

Step 8b. According to the operation of 1e in step 1 of the preparation example, the product obtained in step 8a was esterified to obtain white crystals with a yield of 80%, HPLC purity of 98.8%, and DSC melting point of 52.9°C; the target compound was 4-(3-cyclohexyl-2-acetoxyiminopropionyl)diphenyl sulfide.

Preparation of alkali soluble resin

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 bottle, replace with nitrogen, heat to 80°C, drop the solution in the funnel, react for 6h, cool and filter, and obtain 24g of white alkali-soluble resin.

Black color paste preparation

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

Red color paste preparation

Take 50g of the alkali-soluble resin prepared by the above method, 50g of Ciba IRGALITE RED 2BXL-Q pigment, 100g of DPHA and 250g of propylene glycol methyl ether acetate, put them into a 500mL beaker, use a high-speed shear mixer to mix at a speed of 5000r/min for 15min to obtain a red color paste.

Compound hydrolysis resistance test

Compound I-27 obtained in Preparation Example 1 and comparative compound A obtained in Preparation Example 7 were prepared into 2% solution in analytically pure propylene glycol methyl ether acetate, 50 g each, and each was sealed in 5 bottles and stored in a 25°C incubator away from light. After one week, one bottle was taken out from each bottle for HPLC analysis under the same conditions, and then analyzed once every other week to observe the changes in the main content. The analysis results are listed in Table 1.

Table 1

From the data in Table 1, it can be seen that the oxime ester groups of both solutions were hydrolyzed, and the content of oxime intermediates increased, but the amplitude was not large. The methyl ester hydrolyzate - arylformic acid in the solution of the compound of Preparation Example 7 increased rapidly, while there was no corresponding hydrolyzate - arylformic acid in the analysis of the solution of the compound of Preparation Example 1, indicating that the hydrolysis mainly occurred at the arylformic acid methyl ester end of the comparative compound A, the hydrolysis resistance of arylformic acid methyl ester was poor, and arylformamide was not hydrolyzed.

Photoresist composition examples and comparative examples

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, with the dosage unit being grams.

After mixing all the components evenly, use a 10μm wire rod to coat the film on a glass slide, dry it in a 90℃ oven for 5min, use a 365nm surface light source, use a quartz mask with 138μm lines and a 41-step exposure ruler as a mask, use a 1% Na ₂ CO ₃ solution at 25℃ for development, and soak and clean it with pure water for 10s. After drying in a 90℃ oven for 30min, observe the film retention order. Use an electron microscope to measure the line width of the developed image and record it. If the number of film retention orders after curing is larger, the larger the value of the developed line width is, the higher the sensitivity is, which means the higher the sensitivity of the formula is.

Table 2

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.

Table 3

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 terms of the film retention number and the development line width after curing in the black system. The compound of general formula I of the present invention has the characteristic of high sensitivity.

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 amounts are in grams.

After mixing all the components evenly, use a 10μm wire rod to coat the film on a glass slide, dry it in a 90℃ oven for 5min, use a 41-step exposure ruler and a 138μm mask to cure with a 365nm surface light source, use a 1% NaOH solution at 25℃ for development, soak and clean it with pure water for 10s, and dry it in a 90℃ oven for 30min. Observe and record the film-retaining order. Use an electron microscope to measure the line width of the developed image. The line width unit is μm and is recorded in Table 5.

Table 4

Table 5

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 order and development line width after curing in the red formula system than the comparative compound B.

Transparent photocurable composition examples and comparative examples

The compounds prepared in Preparation Examples 1-5 and Comparative Compound B were used as photoinitiators and mixed with 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.

After mixing all the components evenly, a 50 μm wire rod was used to coat the film on a glass slide 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.

Table 6

Table 7

From the data in Table 7, it can be seen that the photo-gel conversion rate of the transparent composition using the compound provided by the present invention as a photoinitiator is significantly higher than that of the comparative example.

Yellowing test

The compounds prepared in Preparation Examples 1-3 and Preparation Example 6 and comparative compounds A and B were used as initiators. The initiators were dissolved in a 60°C oven and mixed evenly with other components according to the ratio in Table 8. The dosage unit was g. A 25μm wire rod was used to apply the film on a glass plate and a 365nm LED light source was used for curing. After being heated in an oven at 230°C for 30 minutes and then cooled to room temperature, the yellowness values of each embodiment and comparative example were measured by an automatic colorimeter and recorded in Table 9.

Table 8

Table 9

It can be seen from the data in Table 9 that the 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.

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

Claims (12)

An oxime ester compound having a structure as shown in formula (I),
In formula (I), R ₁ is selected from NR ₄ R ₅ ; _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, 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. 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, -COCOOR ₄ , 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, -COCOOR ₄ ; _R3 is selected from C1-C3 alkyl, C3-C7 cycloalkyl substituted C1-C3 alkyl, C3-C6 alkenyl, C1-C4 alkoxy, phenyl, phenoxy; R ₄ , R ₅ , R ₄ ′ and R ₅ ′ 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, R ₃ COO-, -R ₆ CONR ₆ '; Optionally, NR ₄ R ₅ constitutes a three-membered to seven-membered nitrogen-containing heterocyclic ring, the nitrogen-containing heterocyclic ring further has an additional heteroatom, the additional heteroatom is 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, R ₃ COO-, -R ₆ CONR ₆ ', C3-C7 cycloalkyl, substituted or unsubstituted phenyl, R ₆ CO-, R ₆ COCO-, R ₆ SO ₂ -; optionally, the nitrogen-containing heterocyclic ring has a parallel ring structure, a bicyclic structure and a spiro ring 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; R ₆ 'is selected from hydrogen, C1-C4 alkyl; n is 0 or 1; Ar ₁ 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, two adjacent ones of R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ 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, -OR ₄ ', -COOR ₄ ', and -PO(OR ₄ ') 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, -COCOOR ₄ , The substituents in the C6-C20 aryl group and the C4-C20 heteroaryl group are selected from one or more of halogen, NO ₂ , C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, -COOR ₄ ', and -COR ₅ '; Alternatively, _R7 and _R8 together with the carbon atom to which they are directly attached form a five- to seven-membered ring; In formula A-2 and formula A-3, R ₉ 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, -OR ₄ ', -COOR ₄ ', -P(=O)(OR ₄ ') 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, -COCOOR ₄ , The substituents in the C6-C20 aryl group and the C4-C20 heteroaryl group are selected from one or more of halogen, NO ₂ , C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, -COOR ₄ ', and -COR ₅ '; In formula A-4, X ₁ is selected from a single bond, O, S, NR ₉ , CR ₇ R ₈ , Y is selected from O, S, C=O, S=O, R ₇ and R ₈ are defined as in formula A-1, and R ₉ is defined as in formula A-2 and formula A-3; In formula A-5, X ₂ is selected from O, S, NR ₇ , CR ₇ R ₈ , R ₇ and R ₈ are defined the same as in formula A-2, Ar ₂ and Ar ₃ are each independently selected from substituted or unsubstituted C6-C20 arylene groups, and the substituents in Ar ₂ and Ar ₃ 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. The oxime ester compound according to claim 1, characterized in that in formula (I): R ₁ is selected from NR ₄ R ₅ , _R2 is selected from C1-C8 alkyl, benzyl, cyclohexyl, cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, cyclohexylethyl, tetrahydrofuranylmethyl, R ₃ is selected from C1-C4 alkyl, C1-C4 alkyl substituted by C5-C7 cycloalkyl, C6-C10 aryl, -COOCH ₃ , preferably selected from methyl, ethyl, cyclohexylmethyl, 2-cyclohexylethyl, phenyl, -COOCH ₃ ; R ₄ , R ₅ , R ₄ 'and R ₅ 'are each independently selected from hydrogen, C1-C4 alkyl, C3-C7 cycloalkyl, C3-C7 hetero 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, R ₃ COO-, C3-C8 alkyl interrupted by one or more heteroatoms selected from oxygen atom, sulfur atom; _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; Ar ₁ is selected from the structure represented by formula A-1, A-2, A-3 or formula A-5, in, In formula A-1, R ₇ and R ₈ are each independently selected from a hydrogen atom or a C1-C4 alkyl group, preferably hydrogen, methyl, ethyl, n-propyl and n-butyl; optionally, R ₇ and R ₈ together with the carbon atom to which they are directly connected form a cyclopentyl ring or a cyclohexyl ring; In formula A-2 and A-3, R ₉ 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, OR ₄ ', -P(=O)(OR ₄ ') ₂ , C5-C6 cycloalkyl, phenyl, or phenyl substituted by one or more of the following groups: F, NO ₂ , C1-C4 alkyl, C1-C4 alkoxy, -C(=O)R ₅ ', Wherein, R ₄ 'and R ₅ 'are each independently selected from C1-C8 alkyl, C3-C7 cycloalkyl, C3-C7 heterocyclyl, C6-C12 aryl; preferably, R ₉ is selected from methyl, ethyl, n-propyl, n-butyl, 2-ethylhexyl, phenyl, or the following groups:
In formula A-5, X ₂ is selected from O or S; Ar ₂ and Ar ₃ are each independently selected from a substituted or unsubstituted C6-C12 arylene group, a substituted or unsubstituted C5-C12 heteroarylene group, preferably, Ar ₂ and Ar ₃ 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 Ar ₂ and Ar ₃ are each independently selected from one or more of a C1-C4 alkyl group and a C1-C4 alkoxy group; R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ are each independently selected from hydrogen or C1-C4 alkyl, preferably hydrogen, methyl or ethyl. 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 R ₁ , R ₂ , R ₃ , R ₇ , R ₈ and R ₉ are as defined in formula (I). 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:




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 HAr ₁ H with an acyl chloride compound R ₂ CH ₂ COCl, R ₂ COCl or an anhydride compound in a Friedel-Crafts reaction Under the reaction conditions, the reaction takes place to obtain the intermediate M ₁ or M ₁ ';
Step (2): reacting the intermediate M ₁ or M ₁ ′ in step (1) with R ₁ ′COCOCl under Friedel-Crafts acylation conditions to obtain the intermediate M ₂ or M ₂ ′;
wherein R ₁ 'is selected from methoxy, ethoxy or H ₃ N, Step (3): reacting the intermediate M ₂ or M ₂ ′ in step (2) with an HR ₁ amino compound HNR ₄ R ₅ to obtain an intermediate M ₃ or M ₃ ′;
Step (4): reacting the intermediate M ₃ in step (3) with a nitrite or nitrous acid under acidic conditions to obtain an intermediate M ₄ , or reacting the intermediate M ₃ ′ in step (3) with hydroxylamine hydrochloride under neutral or alkaline conditions to obtain an intermediate M ₄ ′, which is a trans or cis configuration or a mixture of the two;
Step (5): reacting the intermediate M ₄ or M ₄ ' in step (4) with R ₃ COCl or (R ₃ CO) ₂ O to obtain a compound of formula II or III;
wherein Ar ₁ , R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are as defined in formula (I). The oxime ester compound according to any one of claims 1 to 5, characterized in that, when Ar ₁ in the compound of formula (I) is selected from -Ar ₂ -X ₂ -Ar ₃ -, and X ₂ 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 R ₂ CH ₂ COCl or an 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 R ₁ 'COCOCl under Friedel-Crafts acylation conditions to obtain intermediate M ₂ ;
wherein R ₁ ' is selected from methoxy or ethoxy; Ar ₁ is -Ar ₂ -X ₂ -Ar ₃ -; Step (3): reacting the intermediate M ₂ of step (2) with an HR ₁ organic amine compound HNR ₄ R ₅ to obtain an intermediate M ₃ ;
Step (4): the intermediate M ₃ of step (3) is subjected to an oximation reaction with a nitrite or nitrous acid under acid catalysis to obtain an intermediate of formula M ₄ ;
Step (5): The intermediate M ₄ in step (4) is subjected to an esterification reaction with R ₃ COCl or (R ₃ CO) ₂ O to obtain an oxime ester product of formula (II):
wherein Ar ₂ , Ar ₃ , R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are as defined in formula (I). 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%. 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 includes 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 C.I. Pigment Red 177, the green pigment includes C.I. Pigment Green 7, the blue pigment includes C.I. Pigment Blue 15:6 and Solvent Blue 25, and the black pigment includes carbon black, titanium black and C.I. Pigment Black 1. A black matrix or photo spacer is prepared from raw materials including the photoresist according to claim 8, wherein the pigment in the photoresist is a black pigment, preferably carbon black and titanium black. A color filter device is prepared from a raw material including the photoresist according to claim 8, wherein the pigment in the photoresist is a red pigment, a green pigment or a blue pigment. A printed article or display, obtained by photocuring the oxime ester compound described in any one of claims 1 to 6 as a photoinitiator; preferably, the printed article includes a printed circuit board, and the display includes a PCB display, an LCD display, and an OLED display. 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.