Multi-aromatic ring oxime ester compound, photoresist and application thereof

Abstract

The invention provides an oxime ester compound with a multi-aromatic ring structure, a photoresist and application of the oxime ester compound. The oxime ester compound disclosed by the invention has a structure as shown in a formula (I), and the oxime ester compound is used as a photoresist prepared by a photoinitiator, has the characteristics of high sensitivity and low yellowing, and can be used for manufacturing a color display. # imgabs0 #

Description

Technical Field

[0001] The invention belongs to the technical field of organic chemistry and photocuring, and in particular relates to a polyaromatic ring oxime ester compound, a photoresist and applications thereof. Background Art

[0002] 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. Among them, one of the issues that 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 auxiliary initiator components used in conjunction with it. For example, the thioether oxime ester compounds proposed in patent CN1241562A are the most successfully used type of photoinitiators in photoresist formulations, such as commercial products. OXE 01 has relatively good sensitivity and low yellowing, is well known to those skilled in the art, and has been widely studied and used, especially in transparent photoresist and RGB color photoresist formulations.

[0003] Patent WO2002 / 100903 discloses oxime ester compounds with more complex substituents on the parent structure of diphenyl sulfide and oxime ester compounds based on carbazole, among which commercial products such as BASF's OXE 02, although the sensitivity is improved, its yellowing property is also stronger, which limits its use in transparent photoresists and color photoresists; Chinese patent CN101565472B, based on the aforementioned patent compounds, changes the side chain, but does not fundamentally change the sensitivity and yellowing property of the corresponding oxime ester compounds, such as PBG305 and PBG304 of Changzhou Qiangli Company; 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, such as NCI-831 of Japan Aidico Company and BASF Company 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 photoresists, limiting its application in transparent and RGB color photoresists.

[0004] In the prior art, oxime ester compounds used as photoresist initiators mostly use diaryl sulfide or carbazole as the parent structure. In order to meet the needs of this industry, it is still necessary to develop new photoinitiator products with higher sensitivity and lower yellowing. Summary of the invention

[0005] In order to solve one of the above problems existing in the prior art, the present invention provides a new oxime ester compound with a polyaryl compound as the parent skeleton, which has very high sensitivity and low yellowing property, can be used as a highly active photoinitiator in photocurable compositions, especially for the manufacture of photoresists, and shows high sensitivity and low yellowing properties.

[0006] In a first aspect, the present invention provides an oxime ester compound having a polyaromatic ring structure, which has a structure shown in formula (I):

[0007] in,

[0008]

[0009] Ar1 is selected from a substituted or unsubstituted group W, and the unsubstituted group W is selected from the structures represented by formula A-1 to formula A-3:

[0010]

[0011] wherein the group A is selected from C6-C20 arylene or C4-C20 heteroarylene, and the group A′ is selected from C4-C20 heteroarylene;

[0012] The substituents in the group W may be one or more, and each is independently selected from deuterium, halogen, CN, NO2, C1-C10 alkyl, CF3, C1-C10 alkoxy, and optionally, two adjacent substituents in the group W form a parallel ring structure with the aromatic ring or heteroaromatic ring to which they are connected;

[0013] "*-" indicates Ar1 and R1 or a group The location of the bond;

[0014] R1 is selected from NO2, CN, -C(=O)R9, -C(=O)C(=O)R 10 , -C(=O)P(=O)R9R9', or R9, R9' are each independently selected from -OR4, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C4-C20 heteroaryl; R 10 is selected from C1-C6 alkyl, substituted or unsubstituted 3-10 membered saturated nitrogen-containing heterocyclic group, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C4-C20 heteroaryl, -OR4, -HNR5, -NR4R5; R9, R9' and R 10 The substituents in the C3-C10 saturated heterocyclic group, C6-C20 aryl group, and C4-C20 heteroaryl group are selected from one or more of the following groups: halogen, phenyl, C1-C4 alkyl group, C3-C7 cycloalkyl group, C1-C4 alkoxy group, C1-C4 alkoxy group substituted with one or more F, C1-C4 alkylthio group, -C(=O)COOR4;

[0015] R2 and R2' are each independently selected from a hydrogen atom, a deuterium atom, a C1-C10 alkyl group, a C1-C10 alkyl group substituted by one or more phenyl groups, C3-C7 cycloalkyl groups, C3-C7 heterocyclyl groups, C1-C4 alkoxy groups, C1-C4 alkyl acyloxy groups, a C5-C7 cycloalkylmethyl group substituted by one or more C1-C4 alkyl groups, a C3-C10 alkyl group inserted by one or more O atoms, a C3-C7 cycloalkyl group, a C6-C20 aryl group, a C4-C20 heteroaryl group, a C1-C4 alkyl group, a C3-C7 cycloalkyl group, a C6-C20 aryl group, a C4-C20 heteroaryl group, a C1-C4 alkyl group, a C3-C7 cycloalkyl group, a C5-C7 cycloalkylmethyl group, a C3-C10 alkyl group inserted by one or more O atoms, a C3-C7 cycloalkyl group, a C6-C20 aryl group, a C4-C20 heteroaryl group, a C1-C4 alkyl group ... F, Cl, C1-C4 alkoxy, C1-C4 alkylthio, C6-C20 aryl substituted by one or more C1-C4 alkyl, C3-C7 cycloalkyl, F, Cl, C1-C4 alkoxy, C1-C4 alkylthio, -C(=O)COOR4, C4-C20 heteroaryl substituted by one or more C1-C4 alkyl, C3-C7 cycloalkyl, F, Cl, C1-C4 alkoxy, C1-C4 alkylthio, -C(=O)COOR4; phenyl, C3-C7 cycloalkyl and C3-C7 heterocyclic groups referred to by R2 and R2' are unsubstituted or substituted by one or more F, Cl, C1-C4 alkyl, C1-C4 alkoxy, COCOOR4;

[0016] R4 and R5 are each independently selected from C1-C8 alkyl, C1-C8 alkyl substituted by one or more F atoms, phenyl, C3-C7 cycloalkyl, C3-C7 heterocyclyl, R3COO, C3-C8 alkyl intermixed by one or more oxygen atoms, sulfur atoms, C3-C7 cycloalkyl, C3-C7 heterocyclyl, C6-C20 aryl, C4-C20 heteroaryl, C6-C20 aryl, C4-C20 heteroaryl in R4 and R5 are unsubstituted or substituted by one or more of C1-C4 alkyl, C3-C7 cycloalkyl, F, Cl, C1-C4 alkoxy, C1-C4 alkylthio;

[0017] R3 is selected from C1-C7 alkyl, C1-C3 alkyl substituted by C3-C7 cycloalkyl, C2-C7 alkenyl, C1-C4 alkoxy, C6-C12 aryl, C6-C12 aryloxy, -COOR6, -C(=O)R6; wherein R6 is selected from C1-C6 alkyl, C6-C12 aryl;

[0018] n=0 or 1.

[0019] In some embodiments, in formula A-1 and formula A-2, group A is selected from phenylene, naphthylene, biphenylene, anthracene, fluorenylene or carbazolylene; in formula A-3, group A′ is selected from carbazolylene or benzocarbazolylene.

[0020] In some preferred embodiments, Ar1 is selected from the structures shown in Formula A-1-1 to Formula A-1-6, Formula A-2-1 to Formula A-2-4, Formula A-3-1 to Formula A-3-2:

[0021]

[0022]

[0023]

[0024] In formula A-1-4, formula A-1-5, formula A-1-4 and formula A-3-2, R7 and R8 are each independently selected from a hydrogen atom, a deuterium atom, a C1-C8 alkyl group, a C1-C8 alkyl group substituted with one or more F atoms, Cl atoms, a phenyl group, a C3-C7 cycloalkyl group, a C3-C7 heterocyclic group, COOR4', or PO(OR4')2, a C3-C7 cycloalkyl group, a C3-C7 heterocyclic group, a C6-C20 aryl group, a C4-C20 heteroaryl group, and the C6-C20 aryl group and the C4-C20 heteroaryl group in R7 and R8 are unsubstituted or substituted with one or more selected from halogen, NO2, a C1-C4 alkyl group, a C1-C4 alkoxy group, a C1-C4 alkylthio group, COOR4', or COR5';

[0025] R4' and R5' are each independently selected from C1-C8 alkyl, C1-C8 alkyl substituted by one or more F atoms, phenyl, C3-C7 cycloalkyl, C3-C7 heterocyclic group, R3COO, C3-C8 alkyl interspersed by one or more oxygen atoms, sulfur atoms, C3-C7 cycloalkyl, C3-C7 heterocyclic group, C6-C20 aryl, C4-C20 heteroaryl; the C6-C20 aryl and C4-C20 heteroaryl in R4' and R5' are unsubstituted or substituted by one or more of C1-C4 alkyl, C3-C7 cycloalkyl, F, Cl, C1-C4 alkoxy and C1-C4 alkylthio.

[0026] In some preferred embodiments, R7 and R8 are each independently selected from a hydrogen atom and a C1-C8 alkyl group, more preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a tert-butyl group.

[0027] In some embodiments, in formula A-1-5, CR7R8 together form a 5-7 membered ring.

[0028] In some embodiments, in Formulas A-1-1 to A-1-6, A-2-1 to A-2-4, A-3-1 to A-3-2, each R 11 ~R 26 Each R is independently selected from a hydrogen atom, a deuterium atom, F, Cl, CN, NO2, a C1-C4 alkyl group, CF3, and a C1-C4 alkoxy group. 11 ~R 26 The two adjacent substituents form a five-membered, six-membered or seven-membered ring structure with the connected benzene ring.

[0029] In some preferred embodiments, each R 11 ~R 26 Each is independently selected from hydrogen, F, CN, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl and CF3.

[0030] In some embodiments, R2 and R2' are each independently selected from C1-C7 alkyl, C1-C4 alkyl substituted by one or more phenyl, C5-C7 cycloalkyl, C3-C7 heterocyclyl. In some preferred embodiments, R2 and R2' are each independently selected from C1-C7 alkyl, C1-C4 alkyl substituted by one or more phenyl, cyclopentyl, cyclohexyl, thienyl, furyl.

[0031] In some embodiments, R3 is selected from C1-C4 alkyl, C1-C3 alkyl substituted by C5-C7 cycloalkyl, phenyl, -COOR6. In some preferred embodiments, R3 is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, cyclohexylmethyl, 2-cyclohexylethyl, phenyl, COOCH3.

[0032] In some embodiments, R9, R9' are each independently selected from -OR4, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted C5-C10 heteroaryl; the substituents in the C6-C10 aryl and C5-C10 heteroaryl in R9, R9' are selected from one or more of C1-C4 alkyl, F, C1-C4 alkoxy, C1-C4 alkoxy substituted with one or more F, C1-C4 alkylthio, COCOOR4.

[0033] In some embodiments, R 10 Selected from C1-C4 alkyl, substituted or unsubstituted 3-7 membered saturated nitrogen-containing heterocyclic group, substituted or unsubstituted C6-C10 aryl, -OR4, -NR4R5. 10 The ring atoms of the 3-7 membered saturated nitrogen-containing heterocyclic group contain 1 or more nitrogen atoms, preferably one or two nitrogen atoms. 10 The 3- to 7-membered saturated nitrogen-containing heterocyclic group may contain one or more heteroatoms other than nitrogen atoms, such as oxygen atoms, sulfur atoms, silicon atoms, and the like, as ring atoms.

[0034] In some preferred embodiments, R 10 The unsubstituted 3-7 membered saturated nitrogen-containing heterocyclic group is selected from the following groups:

[0035]

[0036] In some embodiments, R 10The substituents of the 3-7 membered saturated nitrogen-containing heterocyclic group and the C6-C10 aromatic group are selected from one or more of C1-C4 alkyl, F, phenyl, C1-C4 alkoxy, C1-C4 alkoxy substituted by one or more F, C1-C4 alkylthio, and -C(=O)COOR4.

[0037] In some embodiments, R 10 The substituents of the 3-7 membered saturated nitrogen-containing heterocyclic group are selected from C1-C4 alkyl, substituted or unsubstituted phenyl.

[0038] In some embodiments, R4 and R5 are each independently selected from C1-C4 alkyl, C1-C4 alkyl substituted with one or more F atoms, phenyl, C3-C7 cycloalkyl, C3-C7 heterocyclic group, C5-C7 cycloalkyl, C4-C6 heterocyclic group, C6-C10 aryl. In some preferred embodiments, R4 and R5 are each independently selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, methyl substituted with one or more F atoms, phenyl, C3-C7 cycloalkyl, C3-C7 heterocyclic group, cyclohexyl, tetrahydrofuranyl, thiolanyl, phenyl, phenyl substituted with one or more of C1-C4 alkyl, C1-C4 alkoxy, F.

[0039] In some preferred embodiments, R1 is selected from NO2, CN, or the following groups:

[0040]

[0041]

[0042] wherein R4, R5 and R2' are as defined above, R represents mono- or poly-substitution, and R is independently selected from C1-C4 alkyl, F, C1-C4 alkoxy or C1-C4 alkoxy substituted by one or more Fs.

[0043] In some embodiments, the compound has a structure represented by Formula (Ia) or Formula (Ib):

[0044]

[0045] Wherein, R2, R3 and R4 are defined as in formula (I), R 11 To R 22 The definition of is the same as that of formula A-1-1.

[0046] In some preferred embodiments, in Formula (Ia) or Formula (Ib), R 11 To R 22 Each is independently selected from a hydrogen atom, a deuterium atom, F, Cl, a methyl group, an ethyl group and CF3.

[0047] In some embodiments, the compound is selected from the structures shown in formula (I-1) to formula (I-40):

[0048]

[0049]

[0050]

[0051]

[0052]

[0053] In some embodiments, the preparation of the oxime ester compound comprises the following steps:

[0054] (1) Oximation reaction: reacting the compound represented by formula II with nitrite or nitrous acid under acidic conditions, or reacting the raw material represented by formula II with hydroxylamine hydrochloride under alkaline conditions to obtain an intermediate represented by formula III, wherein R1 is selected from NO2, CN, COR9, COCOR 10 or C(O)P(O)R9R9', Ar1, R2, R3 are as defined in Formula I, in Formula I to Formula III, n is 0 or 1, in Formula II to Formula III, m is 0 or 1;

[0055]

[0056] (2) Esterification reaction: The intermediate represented by formula III is reacted with R3COCl or (R3CO)2O to obtain the oxime ester compound represented by formula I.

[0057] In some embodiments, the preparation of the oxime ester compound comprises the following steps:

[0058] (1) Oximation reaction: reacting the compound represented by formula II′ with nitrite or nitrous acid under acidic conditions, or reacting the raw material represented by formula II′ with hydroxylamine hydrochloride under alkaline conditions to obtain the intermediate represented by formula III′, wherein Ar1, R2, R2′, and R3 are the same as those in formula I, and in formulas I to III′, n is 0 or 1, and in formulas II′ to III′, m is 0 or 1;

[0059]

[0060] (2) Esterification reaction: The intermediate represented by formula III′ is reacted with R3COCl or (R3CO)2O to obtain the oxime ester compound represented by formula I.

[0061] In some embodiments, R1 is NO2, and the preparation method of the compound represented by Formula II comprises:

[0062] In the first step, the raw material HAr1H is obtained by coupling with a halogenated aromatic compound through Suzuki coupling or Grignard reagent;

[0063] The second step is to react the raw material HAr1H with the acyl chloride compound ClOC(CH2) m R2 undergoes Friedel-Crafts acylation to obtain an intermediate of formula IV, wherein m is 0 or 1;

[0064] Step 3: The intermediate represented by Formula IV reacts with nitric acid to obtain the nitrated intermediate represented by Formula V;

[0065]

[0066] In some embodiments, R1 is CN, and the method for preparing the compound of Formula II comprises:

[0067] In the first step, the raw material NC-Ar2-B(OH)2 and Br-Ar3H are subjected to a Suzuki coupling reaction to obtain an intermediate shown in Formula VI, and the structure after coupling of Ar2 and Ar3 is Ar1;

[0068] In the second step, the intermediate shown in formula VI reacts with an acyl chloride compound ClOC(CH2) m R2 undergoes Friedel-Crafts acylation to obtain an intermediate of formula VII, wherein m is 0 or 1;

[0069]

[0070] In some embodiments, R1 is COR9, and R9 is selected from C6-C20 aryl or C5-C20 heteroaryl, and the preparation method of the compound represented by Formula II comprises:

[0071] In the first step, the raw material HAr1H is obtained by coupling with a halogenated aromatic compound through Suzuki coupling or Grignard reagent;

[0072] In the second step, the raw material HAr1H and the acyl chloride compound ClOCR9 undergo Friedel-Crafts acylation to obtain the intermediate represented by formula VIII;

[0073] Step 3: The intermediate shown in formula VIII and the acyl chloride compound ClOC(CH2) m R2 undergoes Friedel-Crafts acylation to obtain an intermediate of formula IX, wherein m is 0 or 1;

[0074]

[0075] In some embodiments, R1 is COR9, and R9 is OR4, and the method for preparing the compound of formula II comprises:

[0076] In the first step, the raw material R4OOC-Ar4-Br and (HO)2B-Ar5H are reacted by Suzuki coupling to obtain the intermediate of formula X, and the structure after coupling of Ar4 and Ar5 is Ar1;

[0077] The second step is to react the intermediate of formula X with the acyl chloride compound ClOC(CH2) m R2 undergoes Friedel-Crafts acylation to obtain an intermediate of formula XI, wherein m is 0 or 1;

[0078]

[0079] In some embodiments, R1 is COCOR 10 , and R 10 is a C1-C4 alkyl group or OR4, and the preparation method of the compound represented by formula II comprises:

[0080] In the first step, the raw material HAr1H is obtained by coupling with a halogenated aromatic compound through Suzuki coupling or Grignard reagent;

[0081] The second step is to react the raw material HAr1H with the acyl chloride compound ClOC(CH2) m R2 undergoes Friedel-Crafts acylation to obtain an intermediate of formula IV, wherein m is 0 or 1;

[0082] Step 3: Intermediate of Formula IV and acyl chloride compound R 10 COCOCl reaction yields the intermediate of formula XII, where m is 0 or 1;

[0083]

[0084] In some embodiments, R1 is COCOR 10 , and R 10 It is HNR5, NR4R5, The preparation method of the compound shown in formula II comprises:

[0085] In the first step, the raw material HAr1H is obtained by coupling with a halogenated aromatic compound through Suzuki coupling or Grignard reagent;

[0086] The second step is to react the raw material HAr1H with the acyl chloride compound ClOC(CH2) m R2 undergoes Friedel-Crafts acylation to obtain an intermediate of formula IV, wherein m is 0 or 1;

[0087] The third step is to react the intermediate of formula IV with methyl oxalyl chloride or ethyl oxalyl chloride compound R 10 COCOCl reaction yields the intermediate of formula XII, wherein R 10 is OCH3 or OCH2CH3, m is 0 or 1;

[0088]

[0089] The fourth step is to react the intermediate of formula XII with an amino compound H2NR5, HNR4R5, The reaction takes place to obtain an amide compound of formula XIII intermediate,

[0090]

[0091] In some embodiments, R1 is C(O)P(O)R9R9', and the preparation method of the compound represented by Formula II comprises:

[0092] In the first step, the raw material HOOC-Ar4-Br and (HO)2B-Ar5H are reacted by Suzuki coupling to obtain the intermediate of formula XIV, and the structure after coupling of Ar4 and Ar5 is Ar1;

[0093] The second step is to react the intermediate of formula XIV with an acyl chloride compound ClOC(CH2) m R2 undergoes Friedel-Crafts acylation to obtain an intermediate of formula XV, wherein m is 0 or 1;

[0094]

[0095] The third step is to react the intermediate of formula XV with an acyl chloride reagent to convert the carboxylic acid group into an acyl chloride group to obtain an intermediate of formula XVI, wherein the acyl chloride reagent includes oxalyl chloride, thionyl chloride, and phosphorus trichloride;

[0096] The fourth step is to react the intermediate of formula XVI with methyl phosphite CH3OPR9R9' or ethyl phosphite CH3CH2OPR9R9' to obtain the intermediate of formula XVII;

[0097]

[0098] In some embodiments, R1 is C(O)C(O)P(O)R9R9', and the method for preparing the compound of Formula II comprises:

[0099] In the first step, the raw material HAr1H is obtained by coupling with a halogenated aromatic compound through Suzuki coupling or Grignard reagent;

[0100] The second step is to react the raw material HAr1H with the acyl chloride compound ClOC(CH2) m R2 undergoes Friedel-Crafts acylation to obtain an intermediate of formula IV, wherein m is 0 or 1;

[0101] The third step is to react the intermediate of formula IV with methyl oxalyl chloride or ethyl oxalyl chloride compound R 10 COCOCl reaction yields the intermediate of formula XII, wherein R 10is OCH3 or OCH2CH3, m is 0 or 1;

[0102]

[0103] In the fourth step, the intermediate of formula XII undergoes hydrolysis reaction with a dilute hydrochloric acid solution to obtain an intermediate of formula XVIII.

[0104] The fifth step is to react the intermediate of formula XVIII with an acyl chloride reagent to convert the carboxylic acid group into an acyl chloride group to obtain the intermediate of formula XIX;

[0105] Step 6: The intermediate of formula XIX reacts with methyl phosphonate CH3OPR9R9' or ethyl phosphite CH3CH2OPR9R9' to obtain the intermediate of formula XX;

[0106]

[0107] In some embodiments, R1 is The preparation method of the compound shown in formula II comprises:

[0108] In the first step, the key intermediate HAr1H is obtained by coupling with halogenated aromatic compounds via Suzuki coupling or Grignard reagent;

[0109] Step 2: The key intermediate HAr1H reacts with the acyl chloride compound ClOC(CH2) m R2 undergoes Friedel-Crafts acylation to obtain an intermediate of formula IV, wherein m is 0 or 1;

[0110] The third step is to react the intermediate IV with the acyl chloride compound ClOC(CH2) m R2' is reacted to obtain the intermediate formula II', wherein m is 0 or 1, and n is 0 or 1;

[0111]

[0112] In a second aspect, the present invention 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.

[0113] In some embodiments, the free radical polymerizable compound is selected from acrylate compounds, methacrylate compounds, and combinations thereof.

[0114] In the present invention, the acrylic acid ester compound includes a resin containing acrylic acid ester. The methacrylic acid ester compound includes a resin containing methacrylic acid ester.

[0115] 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.

[0116] 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).

[0117] 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.

[0118] 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.

[0119] 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.

[0120] The acrylate group in the double bond compound of the present invention may also be replaced by a methacrylate group.

[0121] In some embodiments, the mass percentage of the oxime ester compound in the photocurable composition is 0.1%-8.0%, for example 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8% or any value therebetween.

[0122] 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.

[0123] 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.

[0124] 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.

[0125] 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.

[0126] 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.

[0127] 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.

[0128] 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.

[0129] 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 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.

[0130] The present invention does not specifically limit the solvent of the photoresist raw material. Those skilled in the art can select ester solvents, ether solvents and aromatic hydrocarbon solvents as needed, such as propylene glycol monomethyl ether acetate, ethylene glycol methyl ether acetate, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, ethylene glycol diethyl ether, toluene, and xylene; propylene glycol monomethyl ether acetate is preferred.

[0131] 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.

[0132] 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.

[0133] 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.

[0134] 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.

[0135] 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.

[0136] 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.

[0137] In an eighth aspect, the present invention provides a printed article or display, which is obtained by photocuring the oxime ester compound described in the first aspect of the present invention as a photoinitiator.

[0138] In some embodiments, the printed article comprises a printed circuit board.

[0139] In some embodiments, the display comprises an LCD display or an OLED display.

[0140] In the ninth aspect, the present invention provides the use of the oxime ester compound with a polyaromatic ring structure 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 anti-corrosion materials, sealants, dental materials, optical materials, optical films, optical fiber coatings, insulating films, polarizers, microlenses, and recording materials.

[0141] 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 photocurable composition containing the compound of formula (I) as a raw material and processing through necessary steps.

[0142] Compared with the prior art, the present invention has the following beneficial effects:

[0143] The invention introduces a strong electron-withdrawing group into a polyaryl matrix to synthesize a novel oxime ester compound, which has significantly higher sensitivity performance in photocuring, especially in photoresist, than the existing photoinitiator. DETAILED DESCRIPTION

[0144] 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 embodiments. 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.

[0145] The term "C1-C8 alkyl" as used herein refers to a straight or branched chain alkyl group having 1 to 8 carbon atoms, including but not limited to methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, isooctyl, and the like.

[0146] The terms "C3-C10 alkyl group inserted by one or more O atoms or S atoms" or "C3-C10 alkyl group interspersed by one or more oxygen atoms or sulfur atoms" as used herein have equivalent meanings, and refer to a C3-C10 alkyl group that is interrupted by O or S once or multiple times, for example, 1-9 times, 1-5 times, 1-3 times, 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.

[0147] 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.

[0148] The term "alkylthio" as used herein is an alkyl group interrupted by one S atom, for example, C1-C4 alkylthio is an alkyl group having 1-4 carbon atoms interrupted by one S atom.

[0149] 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.

[0150] 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.

[0151] As used herein, the term "mn-membered" group refers to a ring having m to n ring atoms, such as "3-10 membered saturated heterocyclic group" means the heterocyclic group has 3 to 10 ring atoms.

[0152] As used herein, the term "alkenyl" refers to a straight or branched hydrocarbon group containing one or more double bonds and having a specified number of carbon atoms. For example, "C2-C7 alkenyl" refers to a group containing 2 to 7 carbon atoms. Alkenyl includes, but is not limited to, ethenyl, propenyl, butenyl, 1-methyl-2-buten-1-yl, heptenyl, octenyl, etc.

[0153] 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.

[0154] 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, phenanthrolinyl, oxazinyl, 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, 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-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-methyl-5-perylene-1-methyl-5-perylene-1-methyl-6-phenanthridinyl, 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.

[0155] It should be noted that, unless the substituent on the group is defined separately, the group does not contain a substituent. For example, "C1-C4 alkyl" means methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, etc. without a substituent. "Substituted C1-C4 alkyl" means that one or hydrogen of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, etc. can be replaced by one or more other groups.

[0156] Experimental materials and equipment:

[0157] Light source equipment:

[0158] 365nm LED surface light source, Shanghai Futanxi Technology Co., Ltd.

[0159] Test equipment:

[0160] Stereo microscope, HY-950S, Beijing Huanyu Technology Co., Ltd., line width unit is μm.

[0161] Yellowness meter, fully automatic colorimeter SC-80C, Beijing Jingyi Kangguang Optical Instrument Co., Ltd.

[0162] Experimental Materials:

[0163] Compound OXE01 is a product of BASF, Germany.

[0164] Genomer 4212: Aliphatic polyurethane acrylate, a product of RAHN.

[0165] DPHA: Dipentaerythritol penta-hexaacrylate, a product of Tianjin Tianjiao Chemical Co., Ltd.

[0166] HDDA: 1,6-hexanediol diacrylate, a product of Tianjin Tianjiao Chemical Co., Ltd.

[0167] Compound preparation

[0168] Preparation Example 1 Preparation of 4-(3-cyclohexyl-2-acetoxyiminopropionyl)-4"-(2-ethoxy-2-oxoacetyl)-p-terphenyl

[0169]

[0170] 1a. Add 6.91g (0.03mol) of p-terphenyl and 40mL of 1,2-dichloroethane (hereinafter referred to as DCE) into a 100mL three-necked flask, stir at room temperature until the solution becomes clear, cool to -10℃, add 4.40g (0.033mol) of aluminum chloride, keep the reaction solution at -10∽-5℃, add 5.5g (0.0315mol) of 3-cyclohexylpropionyl chloride to the reaction solution within 30min, continue stirring for 4h after the addition is complete; add the reaction solution dropwise to a solution of 5g of concentrated hydrochloric acid and 20g of water at 5℃, stir for 30min, let stand for 30min, separate the lower organic layer phase; add 20mL of water to the organic phase, stir and wash for 30min, stand for 30min, and separate the organic phase; repeat washing the organic phase with water twice; dry the organic phase with 2.0g of anhydrous sodium sulfate overnight, and filter to remove the desiccant; remove the solvent DCE from the organic phase by vacuum distillation with a water pump until the liquid temperature is 80°C, and obtain 10.41g of a crude product; stir the crude product with 40g of ethanol, heat to 70°C, then cool to 0°C, filter, and obtain a white solid powder, which is vacuum dried at 40°C and weighs 9.52g, with a yield of 86.55%, and an HPLC content of 99.2%, which is intermediate 1a, 4-(3-cyclohexylpropionyl)-p-terphenyl.

[0171] 1b. Add 5g (0.0136mol) of intermediate 1a and 40mL of DEC into a 100mL three-necked flask, stir at room temperature until the solution is clear, cool to -5°C, add 6.34g (0.0474mol) of aluminum chloride, keep the reaction solution at -5∽0°C, add 2.21g (0.0162mol) of monoethyl oxalyl chloride dropwise to the reaction solution within 30min, continue stirring for 2h after the addition is complete; add the reaction solution dropwise to a solution of 7g of concentrated hydrochloric acid and 30g of water at 5°C, stir for 30min, let stand for 30min, separate the lower organic phase; add 30mL of water to the organic phase, stir and wash for 30min, let stand for 30min , separate the organic phase; wash the organic phase with water twice; dry the organic phase with 2.0g of anhydrous sodium sulfate overnight, and filter to remove the desiccant; remove the solvent DCE from the organic phase by vacuum distillation with a water pump until the liquid temperature is 80°C, to obtain 6.10g of a crude product; stir and heat the crude product with 30g of ethanol and 10g of DEC to 70°C and dissolve it, filter it hot, and slowly cool the filtrate to 5°C in a round-bottom flask, filter the precipitated solid, and obtain white crystals, which are vacuum dried at 40°C and weigh 5.50g, with a yield of 86.34% and an HPLC content of 99.21%, which is intermediate 1b, 4-(3-cyclohexylpropionyl)-4'-(2-ethoxy-2-oxoacetyl)-p-terphenyl.

[0172] 1c. First, add 4.68g (0.01mol) of intermediate 1b, 10g of dimethyl sulfoxide and 10g of dichloromethane to a 100mL three-necked flask, stir to dissolve, and add 1.13g (0.011mol) of butyl nitrite; keep the temperature at 25°C, drop 0.1g of concentrated hydrochloric acid; stir for 5h, put the reaction solution into 100mL of water, and add 10g of dichloromethane, stir for 30min and then stand, separate the liquids, extract the aqueous phase with 20g of dichloromethane once, combine the organic phases, and wash twice with 20mL of water each time until the aqueous phase is neutral; dry the organic phase with 2.0g of anhydrous sodium sulfate overnight, filter to remove the desiccant; evaporate the organic phase solvent dichloromethane under reduced pressure, add 2.0g of ethanol and 2.0g of dichloroethane, heat to dissolve completely, cool to crystallize,

[0173] The precipitated solid was filtered to obtain off-white flocculent crystals, which were dried in vacuum and weighed 3.56 g, with a yield of 71.8% and an HPLC content of 99%. This was intermediate 1c, 4-(3-cyclohexyl-2-hydroxyiminopropionyl)-4'-(2-ethoxy-2-oxoacetyl)-p-terphenyl.

[0174] 1d. In a 100mL single-mouth bottle, add 2.0g (0.004mol) of intermediate 1c, 10g of dichloromethane, and 0.52g (0.005mol) of acetic anhydride; stir and react at 25°C for 5 hours; wash 3 times with 10mL of water each time until the aqueous phase has a Ph of 6-7; distill off the solvent dichloromethane in the organic phase to obtain a light yellow oily liquid; add 12g of anhydrous ethanol, heat to 40°C to dissolve; slowly cool to precipitate crystals, then slowly cool to -15°C and keep overnight; filter to obtain off-white flaky crystals, dry and weigh to obtain 1.63g of the product, with a yield of 78.4%, HPLC content of 98.78%, and DSC melting point: 129.45°C;

[0175] 1 H-NMR data (CDCl3, δ ppm): 1.0425-1.2757 (m, 5H, cyclohexane CH2), 1.4354-1.4533-1.4711 (t, 3H, CH3), 1.6819-1.7370 (m, 6H, CH2+CH of cyclohexane), 2.2850 (s, 3H, CH3CO), 2.7820-2.7991 (d, 2H, CH2-Cyc.), 4.5776-4.4755-4.4 933-4.5112 (quartet, 2H, OCH2), 7.7484-7.7587 (m, 6H, ArH), 7.7790-7.8002 (d, 2H, ArH), 8.1219-8.1383 (d, 2H, ArH), 8.2034-8.2247 (d, 2H, ArH); the target compound 4-(3-cyclohexyl-2-acetoxyiminopropanoyl)-4'-(2-ethoxy-2-oxoacetyl)-p-terphenyl.

[0176] Preparation Example 2 Preparation of 4-(3-cyclohexyl-2-acetoxyiminopropionyl)-3"-fluoro-4"-(2-ethoxy-2-oxoacetyl)-p-terphenyl

[0177]

[0178] 2pre. Preparation of 3-fluoro-p-terphenyl

[0179] In a 100mL three-necked flask, 5.0g (0.0253mol) of 4-biphenylboric acid and 4.86g (0.0278mol) of m-fluorobromobenzene were added and dissolved in 15mL of ethanol; 7g (0.0506mol) of K2CO3 was dissolved in 10mL of water and added to the reaction flask to mix with the ethanol solution; 0.15g (0.1mmol) of tetrakis(triphenylphosphine)palladium was weighed and added to the reaction solution, the reaction solution was heated to 70°C, nitrogen was replaced 3 times, nitrogen protection was maintained, the reaction was carried out at 70°C for 4h, the temperature was lowered, the precipitated solid was filtered, the filter cake was light yellow, 40mL of DCE was added, the mixture was heated to 50°C, and it was washed with 20mL of water. The DCE solution was cooled and crystals were precipitated, which weighed 5.33g after drying, with a yield of 84.8% and an HPLC content of 98.72%, which was 3-fluoro-p-terphenyl.

[0180] 2a.-2d. According to the operation of 1a.-1d. of Preparation Example 1, the product 3-fluoro-p-terphenyl obtained in the operation of 2pre. was used instead of p-terphenyl to obtain the target 4-(3-cyclohexyl-2-acetoxyiminopropionyl)-3"-fluoro-4"-(2-ethoxy-2-oxoacetyl)-p-terphenyl; off-white powder, HPLC content 99.01%, DSC melting point: 87.5°C; 1 H-NMR data (CDCl3, δppm): 1.0513-1.2742 (m, 5H, cyclohexane CH2), 1.4094-1.4272-1.4451 (t, 3H, CH3), 1.6366-1.7349 (m, 6H, CH2+CH of cyclohexane), 2.2837 (s, 3H, CH3CO), 2.7807-2.7978 (d, 2H, CH2-Cyc.),

[0181] 4.4359-4.4538-4.4716-4.895(quartet,2H,OCH2),7.4218-7.4515(d,1H,ArH),

[0182] 7.5791-7.5997(d,1H,ArH), 7.7167-7.7743(m,6H,ArH), 8.0093-8.0285-8.0481(t,1H,ArH), 8.2047-8.2258(d,2H,ArH).

[0183] Preparation Example 3 Preparation of Compound 4-(3-cyclohexyl-2-acetoxyiminopropionyl)-4"-(2-butoxy-2-oxoacetyl)-p-terphenyl

[0184]

[0185] 3pre. Preparation of mono-n-butyl oxalyl chloride

[0186] In a 100mL three-necked flask equipped with a reflux condenser and a tail gas absorption device, 30.8g (0.24mol) of oxalyl chloride was added, cooled to -5°C, 0.1g of N,N-dimethylformamide was added dropwise, stirred, 11.12g (0.15mol) of n-butanol was added dropwise, and the mixture was completed within 1 hour. The mixture was heated to 40°C, stirred until there were no bubbles, changed to an atmospheric distillation device, and distilled at atmospheric pressure to 70°C at the distillation head. The mixture was cooled to 30°C, and changed to a vacuum distillation device until the distillation head temperature stabilized at 64°C to receive the main fraction, and 18g of a colorless liquid product was obtained. The GC content after methanol derivatization was 99.1%, and the yield was 72.9%.

[0187] 3a. Materials and operation are the same as 1a.

[0188] 3b.-3d. According to the operation of 1b-1d., the monobutyl oxalyl chloride obtained in operation 3pre. was used instead of the monoethyl oxalyl chloride to obtain the target 4-(3-cyclohexyl-2-acetoxyiminopropionyl)-4"-(2-butoxy-2-oxoacetyl)-p-terphenyl, which was an off-white powder crystal with an HPLC content of 97.90% and a DSC melting point of 102.0°C; 1 H-NMR data (CDCl3, δppm): 0.9681-0.9866-1.0052 (t, 3H, CH3), 1.0520-1.2581 (m, 5H, cyclohexane CH2), 1.4491-1.5055 (quartet, 2H, CH2), 1.6161-1.7566 (m, 6H, CH2+CH of cyclohexane), 1.7738-1.8281 (quintet, 2H, CH2), 2.2846 (s, 3H, CH3CO), 2.7817-2.7988 (d, 2H, CH2-Cyc.), 4.44085-4.4253-4.4421 (t, 2H, OCH2),

[0189] 7.7483-7.8054(m,8H,ArH), 8.1061-8.1273(d,2H,ArH), 8.2033-8.2245(d,2H,ArH).

[0190] Preparation Example 4 Preparation of 4-(1-acetoxyiminobutyryl)-4"-nitro-p-terphenyl

[0191]

[0192] 4a. Add 4.66g (0.02mol) 4-bromobiphenyl and 20mL DCE into a 50mL three-necked flask, stir at room temperature until the solution becomes clear, cool to -10°C, add 2.96g (0.022mol) aluminum chloride, keep the reaction solution at -10∽-5°C, add 2.24g (0.021mol) n-butyryl chloride dropwise to the reaction solution within 30min, continue stirring for 6h after the addition is complete; add the reaction solution dropwise to a solution of 3g concentrated hydrochloric acid and 10g water at 5°C, stir for 30min, let stand for 30min, separate the lower organic phase; add 10mL water to the organic phase, stir Stir and wash for 30 minutes, let stand for 30 minutes, and separate the organic phase; the organic phase is washed with water twice; the organic phase is dried with 1.0g of anhydrous sodium sulfate overnight, and the desiccant is filtered out; the solvent DCE in the organic phase is removed by vacuum distillation with a water pump until the liquid temperature reaches 80°C, and 6.0g of a solid crude product is obtained; 20g of ethyl acetate is stirred with the crude product and heated to 70°C to dissolve, then cooled to 0°C, filtered, and light yellow crystals are obtained, which are vacuum dried at 40°C, weighing 5.2g, with a yield of 85.75%, HPLC content of 98.2%, and DSC melting point of 100.9°C, which is intermediate 4a, 4'-bromo-4-n-butyrylbiphenyl.

[0193] 4b. The intermediate 2 g (6.6 mmol) obtained in operation 4a. was reacted with 1.22 g (3.6 mmol) of 4-nitrobenzeneboronic acid, and a coupling reaction was carried out according to the operation of Preparation Example 2pre. to obtain 2.14 g of light yellow crystalline powder with a yield of 93.8%, which was the intermediate 4-butyryl-4"-nitro-p-terphenyl, with an HPLC content of 98.0% and a DSC melting point of 128.6°C.

[0194] 4c. In a 50mL three-necked flask, put into operation 4b. The intermediate 2g (5.8mmol), 0.48g (7mmol) sodium nitrite, 10mL DMSO, maintain the reaction temperature at 25°C, and introduce hydrogen chloride gas into the reaction solution; 5h sampling analysis, intermediate 4b. Remaining 0.5%; the reaction solution was put into 50mL of water, and 20g of dichloromethane was added, stirred for 30min and then allowed to stand, separated, the aqueous phase was extracted once with 20g of dichloromethane, the organic phases were combined, and washed twice with 20mL of water each time until the aqueous phase was neutral; the organic phase was dried overnight with 2.0g of anhydrous sodium sulfate, and the desiccant was removed by filtration; the organic phase was evaporated to dryness under reduced pressure, the solvent dichloromethane was added, 5.0g of ethanol, 1.0g of dichloromethane, heated to dissolve, cooled and crystallized,

[0195] The precipitated solid was filtered to obtain a yellow crystalline powder, which was dried in vacuum and weighed 2.1 g. The yield was 92.2%, the HPLC content was 97.5%, and the DSC melting point was 184.6°C. This was intermediate 4c.

[0196] 4d. In a 50 mL single-mouth bottle, add 2.0 g (4.8 mmol) of intermediate 4c, 10 g of dichloromethane, and 0.62 g (6 mmol) of acetic anhydride; stir and react at 40 °C for 5 hours; wash three times with 10 mL of water each time until the aqueous phase has a Ph of 6-7; distill off the solvent dichloromethane in the organic phase to obtain a light yellow oily liquid; add 15 g of ethyl acetate, heat to 50 °C to dissolve; slowly cool to precipitate crystals, then slowly cool to 0 °C, filter to obtain a light yellow crystalline powder, dry and weigh to obtain 1.66 g of the product, with a yield of 83%, HPLC content of 98.05%, and DSC melting point: 162.9 °C.

[0197] 1 H-NMR data (CDCl3, δppm): 1.1920-1.2110-1.2301 (t, 3H, CH3), 2.2932 (s, 3H, CH3CO), 2.8062-2.8253-2.8443-2.8635 (quartet, 2H, CH2), 7.7271-7.8103 (m, 8H, ArH),

[0198] 8.1862-8.2074 (d, 2H, ArH), 8.3154-8.3373 (d, 2H, ArH); the target compound is I-4-(1-acetoxyiminobutyryl)-4"-nitro-p-terphenyl.

[0199] Black photoresist of Examples 1 to 4 and Comparative Example 1

[0200] Preparation of alkali soluble resin

[0201] 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 put them into a constant pressure dropping funnel. Put 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. Preparation example of black color paste:

[0202] 50 g of alkali-soluble resin, 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.

[0203] The compounds prepared in Preparation Examples 1 to 4 and the comparative compound OXE 01 were used as photoinitiators, mixed and dissolved in PMA according to the proportions in Table 1, and then mixed with black color paste according to the proportions. After the components were mixed evenly, a 10 μm wire rod was used to coat the film on a glass slide, and the film was dried in an oven at 90°C for 5 minutes. A 41-step exposure ruler was used as a mask, a 365nm surface light source was used, and a 1% Na2CO3 solution was used for development at 25°C. The film was then soaked and cleaned with pure water for 10 seconds, and the film was dried in an oven at 90°C for 10 minutes. The film order was observed and recorded.

[0204] A 138 μm line width mask plate was used as a mask, and a 365 nm surface light source was used to cure the plate. A 1% NaOH solution was used for development at 25°C, and the film was soaked and cleaned with pure water for 10 seconds. After drying in a 90°C oven for 30 minutes, the line width of the developed image was measured with a microscope. The unit of the line width is μm.

[0205] Table 1

[0206]

[0207] The mixed solutions of Examples 1 to 4 and Comparative Example 1 in Table 1 were coated, cured, developed, and measured. The data are shown in Table 2. The results show that under the same dosage conditions, compared with Comparative Example 1, the larger the number of film retention steps after curing of Examples 1 to 4 of the present invention, the larger the value of the developed line width, indicating a higher sensitivity, indicating a higher sensitivity of the formula.

[0208] Table 2

[0209] Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Development steps 16 17 16 16 12 Developed line width / μm 147 148 147 147 141

[0210] It can be seen that under the same dosage conditions, the compounds provided in Preparation Examples 1 to 4 of the present invention have significantly better sensitivity test results of film retention and development line width after curing in a black system than the comparative compound OXE01, indicating that the polyaromatic ring structure oxime ester compound of the present invention has the characteristic of high sensitivity.

[0211] Examples 5 to 8 and Comparative Example 2 Red Photoresist

[0212] Preparation of alkali soluble resin

[0213] Dissolve 20 g of benzyl methacrylate, 3 g of methacrylic acid, 7 g of hydroxyethyl methacrylate, 1.5 g of azobisisobutyronitrile, and 0.5 g of dodecanethiol in 200 mL of toluene and put into a constant pressure dropping funnel. Put 100 mL of toluene in a 500 mL four-necked bottle, replace with nitrogen, heat to 80°C, add the solution in the funnel dropwise, react for 6 hours, then cool and filter to obtain 24 g of white alkali-soluble resin.

[0214] Preparation of red color paste

[0215] 50 g of alkali-soluble resin, 50 g of Ciba IRGALITE RED 2BXL-Q pigment, 100 g of DPHA, and 250 g of propylene glycol methyl ether acetate were put into a 500 mL beaker, and mixed for 15 min at a speed of 5000 r / min using a high-speed shear mixer to obtain a red color paste.

[0216] The compounds prepared in Preparation Examples 1 to 4 of the present application and the comparative compound OXE 01 were used as initiators, mixed and dissolved in PMA according to the proportions in Table 3, and then mixed with the red color paste in proportion. After the components were mixed evenly, a 10 μm wire rod was used to coat the film on a glass slide, dried in an oven at 90°C for 5 minutes, and a 41-step exposure ruler and a 138 μm mask were used for 365 nm surface light source curing, and 1% NaOH solution was used for development at 25°C, and then soaked and cleaned with pure water for 10 seconds. After drying in an oven at 90°C for 30 minutes, the film retention order was observed and recorded, and the line width of the developed image was measured with an electron microscope. The line width unit is μm and is recorded in Table 4.

[0217] Table 3

[0218] Example 5 Example 6 Example 7 Example 8 Comparative Example 2 Preparation Example 1 Compound / g 0.08 0 0 0 0 Preparation Example 2 Compound / g 0 0.08 0 0 0 Preparation Example 3 Compound / g 0 0 0.08 0 0 Preparation Example 4 Compound / g 0 0 0 0.08 0 Comparative compound OXE01 / g 0 0 0 0 0.08 PMA / g 2 2 2 2 2 Red color paste / g 4.5 4.5 4.5 4.5 4.5

[0219] Table 4

[0220] Example 5 Example 6 Example 7 Example 8 Comparative Example 2 Development steps 19 20 19 19 14 Developed line width / μm 150 152 151 151 143

[0221] The results in Table 4 show that the compounds provided in Preparation Examples 1 to 4 of the present invention, under the same dosage conditions, have significantly better film retention and development line width after curing in the red formulation system than the comparative compound OXE 01.

[0222] Transparent photoresist of Examples 9 to 10 and Comparative Example 3

[0223] The compounds prepared in Preparation Examples 1 to 2 of the present invention and the comparative compound OXE 01 were used as photoinitiators, mixed evenly with the corresponding components in Table 5, and then coated on a glass slide using a 50 μm wire rod. The films were cured using a 365 nm light source, and the film weight was measured after curing. The film weight was then measured again after being immersed in acetone at room temperature for 36 h, and the gel conversion rate was calculated.

[0224] Table 5

[0225] Example 9 Example 10 Comparative Example 3 Preparation Example 1 Compound / g 0.5 0 0 Preparation Example 2 Compound / g 0 0.5 0 Comparative compound OXE01 / g 0 0 0.5 Genomer4212 / g 5 5 5 HDDA / g 4.5 4.5 4.5

[0226] The results show that the transparent photoresists prepared in Examples 9 and 10 using the compounds provided in Preparation Examples 1 to 2 of the present invention as photoinitiators have photogel conversion rates of 93.5% and 93.7%, respectively, which are significantly higher than the transparent photoresist prepared in Comparative Example 3 using compound OXE 01 as a photoinitiator (85.2%), and can meet the requirements for uses such as optical films and adhesives.

[0227] Examples 11 to 13 and Comparative Example 4

[0228] The photoresist components of Examples 11 to 13 and Comparative Example 4 are shown in Table 6. The initiator was dissolved in a 60°C oven and mixed evenly with the other components in Table 6. A 25 μm wire rod was used to coat the film on a glass plate and a 365 nm LED light source was used for curing. After being heated in a 230°C oven for 30 minutes and then cooled to room temperature, the yellowness values ​​of each Example and Comparative Example were measured with an automatic colorimeter, and the data are listed in Table 7.

[0229] Table 6

[0230] Embodiment 11 Example 12 Embodiment 13 Comparative Example 4 Preparation Example 1 Compound / g 0.08 0 0 0 Preparation Example 2 Compound / g 0 0.08 0 0 Preparation Example 3 Compound / g 0 0 0.08 0 Comparative compound OXE01 / g 0 0 0 0.08 Genomer4212 / g 1 1 1 1 HDDA / g 1 1 1 1

[0231] Table 7

[0232] Embodiment 11 Example 12 Embodiment 13 Comparative Example 4 Paint film yellowness / Yid 6.21 6.15 6.10 7.53

[0233] The data in Table 7 show that the compound provided by the present invention has a more excellent low yellowing property. Under the same dosage conditions, the yellowness value of the paint film is significantly lower than that of the comparative compound OXE01.

[0234] In summary, the compound provided by the present invention has higher exposure sensitivity than the existing commercially available oxime ester photoinitiators or comparative examples, and is suitable for photoresist formulations, especially for use in RGB color photoresists and transparent optical adhesive formulations.

[0235] 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

1. An oxime ester compound having a polyaromatic ring structure, which has a structure shown in formula (I), in, Ar1 is selected from a substituted or unsubstituted group W, and the unsubstituted group W is selected from the structures represented by formula A-1 to formula A-3: wherein the group A is selected from C6-C20 arylene or C4-C20 heteroarylene, and the group A′ is selected from C4-C20 heteroarylene; The substituents in the group W are one or more and are independently selected from deuterium, halogen, CN, NO2, C1-C10 alkyl, CF3, C1-C10 alkoxy, and optionally, two adjacent substituents in the group W form a parallel ring structure with the aromatic ring or heteroaromatic ring to which they are connected; "*-" indicates Ar1 and R1 or a group The location of the bond; R1 is selected from NO2, CN, -C(=O)R9, -C(=O)C(=O)R 10 , -C(=O)P(=O)R9R9', or R9, R9' are each independently selected from -OR4, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C4-C20 heteroaryl; R 10 is selected from C1-C6 alkyl, substituted or unsubstituted 3-10 membered saturated nitrogen-containing heterocyclic group, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C4-C20 heteroaryl, -OR4, -HNR5, -NR4R5; R9, R9' and R 10 The substituents in the C3-C10 saturated heterocyclic group, C6-C20 aryl group, and C4-C20 heteroaryl group are selected from one or more of the following groups: halogen, phenyl, C1-C4 alkyl group, C3-C7 cycloalkyl group, C1-C4 alkoxy group, C1-C4 alkoxy group substituted with one or more F, C1-C4 alkylthio group, -C(=O)COOR4; R2 and R2' are each independently selected from a hydrogen atom, a deuterium atom, a C1-C10 alkyl group, a C1-C10 alkyl group substituted by one or more phenyl groups, C3-C7 cycloalkyl groups, C3-C7 heterocyclyl groups, C1-C4 alkoxy groups, C1-C4 alkyl acyloxy groups, a C5-C7 cycloalkylmethyl group substituted by one or more C1-C4 alkyl groups, a C3-C10 alkyl group inserted by one or more O atoms, a C3-C7 cycloalkyl group, a C6-C20 aryl group, a C4-C20 heteroaryl group, a C1-C4 alkyl group, a C3-C7 cycloalkyl group, a C6-C20 aryl group, a C4-C20 heteroaryl group, a C1-C4 alkyl group, a C3-C7 cycloalkyl group, a C5-C7 cycloalkylmethyl group, a C3-C10 alkyl group inserted by one or more O atoms, a C3-C7 cycloalkyl group, a C6-C20 aryl group, a C4-C20 heteroaryl group, a C1-C4 alkyl group ... F, Cl, C1-C4 alkoxy, C1-C4 alkylthio, C6-C20 aryl substituted by one or more C1-C4 alkyl, C3-C7 cycloalkyl, F, Cl, C1-C4 alkoxy, C1-C4 alkylthio, -C(=O)COOR4, C4-C20 heteroaryl substituted by one or more C1-C4 alkyl, C3-C7 cycloalkyl, F, Cl, C1-C4 alkoxy, C1-C4 alkylthio, -C(=O)COOR4; phenyl, C3-C7 cycloalkyl and C3-C7 heterocyclic groups referred to by R2 and R2' are unsubstituted or substituted by one or more F, Cl, C1-C4 alkyl, C1-C4 alkoxy, COCOOR4; R4 and R5 are each independently selected from C1-C8 alkyl, C1-C8 alkyl substituted by one or more F atoms, phenyl, C3-C7 cycloalkyl, C3-C7 heterocyclyl, R3COO, C3-C8 alkyl intermixed by one or more oxygen atoms, sulfur atoms, C3-C7 cycloalkyl, C3-C7 heterocyclyl, C6-C20 aryl, C4-C20 heteroaryl, C6-C20 aryl, C4-C20 heteroaryl in R4 and R5 are unsubstituted or substituted by one or more of C1-C4 alkyl, C3-C7 cycloalkyl, F, Cl, C1-C4 alkoxy, C1-C4 alkylthio; R3 is selected from C1-C7 alkyl, C1-C3 alkyl substituted by C3-C7 cycloalkyl, C2-C7 alkenyl, C1-C4 alkoxy, C6-C12 aryl, C6-C12 aryloxy, -COOR6, -C(=O)R6; wherein R6 is selected from C1-C6 alkyl, C6-C12 aryl; n=0 or 1.

2. The oxime ester compound according to claim 1, characterized in that In formula A-1 and formula A-2, group A is selected from phenylene, naphthylene, biphenylene, anthrylene, fluorenylene or carbazolylene; in formula A-3, group A′ is selected from carbazolylene or benzocarbazolylene; Preferably, Ar1 is selected from the structures shown in Formula A-1-1 to Formula A-1-6, Formula A-2-1 to Formula A-2-4, Formula A-3-1 to Formula A-3-2: In formula A-1-4, formula A-1-5, formula A-1-4 and formula A-3-2, R7 and R8 are each independently selected from a hydrogen atom, a deuterium atom, a C1-C8 alkyl group, a C1-C8 alkyl group substituted with one or more F atoms, Cl atoms, a phenyl group, a C3-C7 cycloalkyl group, a C3-C7 heterocyclic group, COOR4', or PO(OR4')2, a C3-C7 cycloalkyl group, a C3-C7 heterocyclic group, a C6-C20 aryl group, a C4-C20 heteroaryl group, and the C6-C20 aryl group and the C4-C20 heteroaryl group in R7 and R8 are unsubstituted or substituted with one or more selected from halogen, NO2, a C1-C4 alkyl group, a C1-C4 alkoxy group, a C1-C4 alkylthio group, COOR4', or COR5'; R4' and R5' are each independently selected from C1-C8 alkyl, C1-C8 alkyl substituted by one or more F atoms, phenyl, C3-C7 cycloalkyl, C3-C7 heterocyclic group, R3COO, C3-C8 alkyl intermixed by one or more oxygen atoms, sulfur atoms, C3-C7 cycloalkyl, C3-C7 heterocyclic group, C6-C20 aryl, C4-C20 heteroaryl; C6-C20 aryl, C4-C20 heteroaryl in R4' and R5' are unsubstituted or substituted by one or more of C1-C4 alkyl, C3-C7 cycloalkyl, F, Cl, C1-C4 alkoxy, C1-C4 alkylthio; Preferably, R7 and R8 are each independently selected from a hydrogen atom and a C1-C8 alkyl group, more preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group; Optionally, in formula A-1-5, CR7R8 together form a 5-7 membered ring; Each R 11 ~R 26 Each is independently selected from a hydrogen atom, a deuterium atom, F, Cl, CN, NO2, a C1-C4 alkyl group, CF3, a C1-C4 alkoxy group; optionally, each R 11 ~R 26 The two adjacent substituents form a five-membered, six-membered or seven-membered ring structure with the connected benzene ring; Preferably, each R 11 ~R 26 Each is independently selected from hydrogen, F, CN, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl and CF3.

3. The oxime ester compound according to claim 1 or 2, characterized in that R2 and R2' are each independently selected from C1-C7 alkyl, C1-C4 alkyl substituted by one or more phenyl, C5-C7 cycloalkyl, C3-C7 heterocyclyl; preferably, R2 and R2' are each independently selected from C1-C7 alkyl, C1-C4 alkyl substituted by one or more phenyl, cyclopentyl, cyclohexyl, thienyl, furyl; R3 is selected from C1-C4 alkyl, C1-C3 alkyl substituted by C5-C7 cycloalkyl, phenyl, -COOR6, preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, cyclohexylmethyl, 2-cyclohexylethyl, phenyl, -COOCH3; R9, R9' are each independently selected from -OR4, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted C5-C10 heteroaryl; the substituents in the C6-C10 aryl and C5-C10 heteroaryl in R9, R9' are selected from one or more of C1-C4 alkyl, F, C1-C4 alkoxy, C1-C4 alkoxy substituted with one or more F, C1-C4 alkylthio, COCOOR4; R 10 is selected from C1-C4 alkyl, substituted or unsubstituted 3-7 membered saturated nitrogen-containing heterocyclic group, substituted or unsubstituted C6-C10 aryl, -OR4, -NR4R5, Preferably, R 10 The unsubstituted 3-7 membered saturated nitrogen-containing heterocyclic group is selected from the following groups: Where R 10 The substituents of the 3-7 membered saturated nitrogen-containing heterocyclic group and the C6-C10 aryl group are selected from one or more of C1-C4 alkyl, F, phenyl, C1-C4 alkoxy, C1-C4 alkoxy substituted by one or more F, C1-C4 alkylthio, -C(=O)COOR4; R4 and R5 are each independently selected from C1-C4 alkyl, C1-C4 alkyl substituted by one or more F atoms, phenyl, C3-C7 cycloalkyl, C3-C7 heterocyclic group, C5-C7 cycloalkyl, C4-C6 heterocyclic group, C6-C10 aryl; preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, methyl substituted by one or more F atoms, phenyl, C3-C7 cycloalkyl, C3-C7 heterocyclic group, cyclohexyl, tetrahydrofuranyl, thiolanyl, phenyl, phenyl substituted by one or more of C1-C4 alkyl, C1-C4 alkoxy, F; Preferably, R1 is selected from NO2, CN, or the following groups: wherein R4, R5 and R2' are as defined in formula (I), R represents mono- or poly-substitution, and R is independently selected from C1-C4 alkyl, F, C1-C4 alkoxy or C1-C4 alkoxy substituted by one or more Fs.

4. The compound according to any one of claims 1 to 3, characterized in that The compound has a structure represented by formula (Ia) or formula (Ib): Wherein, R2, R3 and R4 are defined as in formula (I), R 11 To R 22 The definition of is the same as that of formula A-1-1; Preferably, R 11 To R 22 Each is independently selected from a hydrogen atom, a deuterium atom, F, Cl, a methyl group, an ethyl group and CF3.

5. The oxime ester compound according to any one of claims 1 to 4, characterized in that: The compound is selected from the structures shown in formula (I-1) to formula (I-40):

6. The oxime ester compound according to any one of claims 1 to 5, characterized in that The preparation of the oxime ester compound comprises the following steps: (1) Oximation reaction: reacting the compound represented by formula II with nitrite or nitrous acid under acidic conditions, or reacting the raw material represented by formula II with hydroxylamine hydrochloride under alkaline conditions to obtain an intermediate represented by formula III, wherein R1 is selected from NO2, CN, COR9, COCOR 10 or C(O)P(O)R9R9', Ar1, R2, R3 are as defined in Formula I, in Formula I to Formula III, n is 0 or 1, in Formula II to Formula III, m is 0 or 1; (2) Esterification reaction: reacting the intermediate represented by formula III with R3COCl or (R3CO)2O to obtain an oxime ester compound represented by formula I; Alternatively, the method comprises: (1) Oximation reaction: reacting the compound represented by formula II′ with nitrite or nitrous acid under acidic conditions, or reacting the raw material represented by formula II′ with hydroxylamine hydrochloride under alkaline conditions to obtain the intermediate represented by formula III′, wherein Ar1, R2, R2′, and R3 are the same as those in formula I, and in formulas I to III′, n is 0 or 1, and in formulas II′ to III′, m is 0 or 1; (2) Esterification reaction: The intermediate represented by formula III′ is reacted with R3COCl or (R3CO)2O to obtain the oxime ester compound represented by formula I.

7. The oxime ester compound according to claim 6, characterized in that When R1 is NO2, the preparation method of the compound represented by formula II comprises: In the first step, the raw material HAr1H is obtained by coupling with a halogenated aromatic compound through Suzuki coupling or Grignard reagent; The second step is to react the raw material HAr1H with the acyl chloride compound ClOC(CH2) m R2 undergoes Friedel-Crafts acylation to obtain an intermediate of formula IV, wherein m is 0 or 1; Step 3: The intermediate represented by Formula IV reacts with nitric acid to obtain the nitrated intermediate represented by Formula V; When R1 is CN, the preparation method of the compound represented by formula II comprises: In the first step, the raw material NC-Ar2-B(OH)2 and Br-Ar3H are subjected to a Suzuki coupling reaction to obtain an intermediate shown in Formula VI, and the structure after coupling of Ar2 and Ar3 is Ar1; In the second step, the intermediate shown in formula VI reacts with an acyl chloride compound ClOC(CH2) m R2 undergoes Friedel-Crafts acylation to obtain an intermediate of formula VII, wherein m is 0 or 1; When R1 is COR9, and R9 is selected from C6-C20 aryl or C5-C20 heteroaryl, the preparation method of the compound represented by formula II comprises: In the first step, the raw material HAr1H is obtained by coupling with a halogenated aromatic compound through Suzuki coupling or Grignard reagent; In the second step, the raw material HAr1H and the acyl chloride compound ClOCR9 undergo Friedel-Crafts acylation to obtain the intermediate represented by formula VIII; Step 3: The intermediate shown in formula VIII and the acyl chloride compound ClOC(CH2) m R2 undergoes Friedel-Crafts acylation to obtain an intermediate of formula IX, wherein m is 0 or 1; When R1 is COR9 and R9 is OR4, the preparation method of the compound represented by formula II comprises: In the first step, the raw material R4OOC-Ar4-Br and (HO)2B-Ar5H are reacted by Suzuki coupling to obtain the intermediate of formula X, and the structure after coupling of Ar4 and Ar5 is Ar1; The second step is to react the intermediate of formula X with the acyl chloride compound ClOC(CH2) m R2 undergoes Friedel-Crafts acylation to obtain an intermediate of formula XI, wherein m is 0 or 1; When R1 is COCOR 10 , and R 10 When is C1-C4 alkyl or OR4, the preparation method of the compound represented by formula II comprises: In the first step, the raw material HAr1H is obtained by coupling with a halogenated aromatic compound through Suzuki coupling or Grignard reagent; The second step is to react the raw material HAr1H with the acyl chloride compound ClOC(CH2) m R2 undergoes Friedel-Crafts acylation to obtain an intermediate of formula IV, wherein m is 0 or 1; Step 3: Intermediate of Formula IV and acyl chloride compound R 10 COCOCl reaction yields the intermediate of formula XII, where m is 0 or 1; When R1 is COCOR 10 , and R 10 It is HNR5, NR4R5, When, the preparation method of the compound represented by formula II comprises: In the first step, the raw material HAr1H is obtained by coupling with a halogenated aromatic compound through Suzuki coupling or Grignard reagent; The second step is to react the raw material HAr1H with the acyl chloride compound ClOC(CH2) m R2 undergoes Friedel-Crafts acylation to obtain an intermediate of formula IV, wherein m is 0 or 1; The third step is to react the intermediate of formula IV with methyl oxalyl chloride or ethyl oxalyl chloride compound R 10 COCOCl reaction yields the intermediate of formula XII, wherein R 10 is OCH3 or OCH2CH3, m is 0 or 1; The fourth step is to react the intermediate of formula XII with an amino compound H2NR5, HNR4R5, The reaction takes place to obtain an amide compound of formula XIII intermediate, When R1 is C(O)P(O)R9R9', the preparation method of the compound represented by formula II comprises: In the first step, the raw material HOOC-Ar4-Br and (HO)2B-Ar5H are reacted by Suzuki coupling to obtain the intermediate of formula XIV, and the structure after coupling of Ar4 and Ar5 is Ar1; The second step is to react the intermediate of formula XIV with an acyl chloride compound ClOC(CH2) m R2 undergoes Friedel-Crafts acylation to obtain an intermediate of formula XV, wherein m is 0 or 1; The third step is to react the intermediate of formula XV with an acyl chloride reagent to convert the carboxylic acid group into an acyl chloride group to obtain an intermediate of formula XVI, wherein the acyl chloride reagent includes oxalyl chloride, thionyl chloride, and phosphorus trichloride; The fourth step is to react the intermediate of formula XVI with methyl phosphite CH3OPR9R9' or ethyl phosphite CH3CH2OPR9R9' to obtain the intermediate of formula XVII; When R1 is C(O)C(O)P(O)R9R9', the preparation method of the compound represented by formula II comprises: In the first step, the raw material HAr1H is obtained by coupling with a halogenated aromatic compound through Suzuki coupling or Grignard reagent; The second step is to react the raw material HAr1H with the acyl chloride compound ClOC(CH2) m R2 undergoes Friedel-Crafts acylation to obtain an intermediate of formula IV, wherein m is 0 or 1; The third step is to react the intermediate of formula IV with methyl oxalyl chloride or ethyl oxalyl chloride compound R 10 COCOCl reaction yields the intermediate of formula XII, wherein R 10 is OCH3 or OCH2CH3, m is 0 or 1; In the fourth step, the intermediate of formula XII undergoes hydrolysis reaction with a dilute hydrochloric acid solution to obtain an intermediate of formula XVIII. The fifth step is to react the intermediate of formula XVIII with an acyl chloride reagent to convert the carboxylic acid group into an acyl chloride group to obtain the intermediate of formula XIX; Step 6: The intermediate of formula XIX reacts with methyl phosphonate CH3OPR9R9' or ethyl phosphite CH3CH2OPR9R9' to obtain the intermediate of formula XX; When R1 is When, the preparation method of the compound represented by formula II comprises: In the first step, the key intermediate HAr1H is obtained by coupling with halogenated aromatic compounds via Suzuki coupling or Grignard reagent; Step 2: The key intermediate HAr1H reacts with the acyl chloride compound ClOC(CH2) m R2 undergoes Friedel-Crafts acylation to obtain an intermediate of formula IV, wherein m is 0 or 1; The third step is to react the intermediate IV with the acyl chloride compound ClOC(CH2) m R2' is reacted to obtain the intermediate formula II', wherein m is 0 or 1, and n is 0 or 1; 8. 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 7; Preferably, the free radical polymerizable compound is selected from acrylate compounds, methacrylate compounds and combinations thereof; Preferably, the free radical polymerizable compound comprises one or more of alkyl acrylate, cycloalkyl acrylate, hydroxyalkyl acrylate, dialkylaminoalkyl acrylate, alkyl methacrylate, cycloalkyl methacrylate, hydroxyalkyl methacrylate, dialkylaminoalkyl methacrylate, acrylated epoxy resin, acrylated polyester resin, unsaturated polyester resin, acrylated polyether resin, acrylated polyurethane resin; More preferably, the free radical polymerizable compound comprises one or more of methyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, ethyl methacrylate, polysiloxane acrylate, acrylonitrile, vinyl acetate, vinyl ether, styrene, N-vinyl pyrrolidone, ethylene glycol diacrylate, polyethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, trihydroxymethane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, vinyl acrylate, and triallyl isocyanurate; More preferably, the mass proportion of the oxime ester compound in the photocurable composition is 0.1-8.0%.

9. 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 7; 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 polymethacrylate 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, ether solvents and aromatic solvents, preferably propylene glycol monomethyl ether acetate, ethylene glycol methyl ether acetate, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, ethylene glycol diethyl ether, toluene and xylene; 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.

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

11. A color filter device, prepared from a raw material comprising the photoresist according to claim 9, wherein: The pigment in the photoresist is a red pigment, a green pigment or a blue pigment.

12. A printed article or display, obtained by photocuring the oxime ester compound according to any one of claims 1 to 7 as a photoinitiator; preferably, the printed article comprises a printed circuit board, and the display comprises an LCD display or an OLED display.

13. Use of the oxime ester compound according to any one of claims 1 to 7, the photocurable composition according to claim 8, or the photoresist according to claim 9 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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