Oxime oxalate compound, photoresist and application of oxime oxalate compound

Abstract

The invention provides an oxime oxalate compound, a photoresist and application of the oxime oxalate compound. The oxime oxalate compound disclosed by the invention has a structure as shown in a formula (I), and when the oxime oxalate compound is used as a photoinitiator, the prepared photoresist shows a higher sensitivity characteristic. # imgabs0 #

Description

Technical Field

[0001] The invention belongs to the technical field of photocuring, and in particular relates to a new oxime oxalate compound, a photoresist containing the oxime oxalate compound and applications thereof. Background Art

[0002] Since its emergence in the 1970s, photocuring technology has been widely used. For example, UV photocuring technology is widely used in the fields of coatings, printing inks, and electronic device manufacturing. Among them, one of the issues that technicians are most concerned about is the curing efficiency or sensitivity.

[0003] The key factors affecting the curing efficiency are the photoinitiator structure and the auxiliary initiator components used in conjunction with it. For example, the thioether oxime ester compounds proposed in patent CN1241562A are the most successful photoinitiators used in photoresist formulations. For example, commercial products OXE 01 has relatively good sensitivity and low yellowing property. It is well known, widely studied and used by technicians in this field. It is especially effective in transparent photoresist and RGB color photoresist formulations. Later, patent WO2002 / 100903 disclosed 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 OXE 02, although its sensitivity 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 Chinese patent CN101565472B 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.

[0004] In order to improve the photolithography production efficiency and photolithography effect, it is necessary to develop higher sensitivity photoinitiators and photoresists. Summary of the invention

[0005] In order to solve one of the above technical problems existing in the prior art, the present invention provides a novel oxime oxalate compound. The present invention unexpectedly finds that this type of compound has very high sensitivity and sufficient thermal stability, which can meet the process requirements of photoresist use. The novel oxime oxalate compound provided by the present invention has an aryl or heteroaryl compound as a parent skeleton, has a strong electron-withdrawing group and an oxime oxalate group, can be used as a photoinitiator in photocuring technology, especially shows high sensitivity characteristics in photoresist, and can be used for the manufacture of color displays.

[0006] In a first aspect, the present invention provides an oxime oxalate compound having a structure as shown in formula (I):

[0007]

[0008] In formula (I), R 1 is selected from a strong electron withdrawing group, preferably an aroyl group, a nitro group, a trihalomethyl group, a sulfonic acid group or a trihalomethylsulfonyl group optionally substituted with one or more substituents selected from methyl, halogen, hydroxyl or amino;

[0009] Ar 1 Selected from the structures shown in Formula A-1 to Formula A-6:

[0010]

[0011] Among them, R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 are each independently selected from hydrogen, deuterium, F, Cl, cyano, nitro, C1-C4 alkyl, C1-C4 alkoxy, optionally, R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 The two adjacent carbon atoms in the ring together with the carbon atoms on the connected benzene ring form a five-membered, six-membered or seven-membered ring;

[0012] In formula A-2, R 7 and R 8 Each is independently selected from hydrogen, deuterium, substituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C3-C7 cycloalkyl, substituted or unsubstituted C3-C7 heterocyclyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C4-C20 heteroaryl; wherein the substituent in the C1-C8 alkyl is selected from F, Cl, phenyl, C3-C7 cycloalkyl, C3-C7 heterocyclyl, -OR 4 ′, -COOR 4 ′、-PO(OR 4 ′) 2 One or more of; the substituents on the C3-C7 cycloalkyl and C3-C7 heterocyclic groups are selected from F, Cl, C1-C4 alkyl, C1-C4 alkoxy, -COCOOR 4 One or more of; the substituents in the C6-C20 aryl and C4-C20 heteroaryl are selected from halogen, NO 2 , C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, -COOR 4 ′, -COR5 '; optionally, R 7 and R 8 Together with the carbon atom directly connected thereto, it forms a 5-7 membered ring;

[0013] In formula A-3 and formula A-4, R 9 Selected from C1-C12 alkyl, -R 4 COOR 4 ′, -R 4 CONR 5 R 5 ', one or more F atoms, Cl atoms, phenyl, C3-C7 cycloalkyl, C3-C7 heterocyclic group, -OR 4 ′, -COOR 4 '-C(=O)NR 4 R 4 ', -P(=O)(OR 4 ′) 2 substituted C1-C8 alkyl, C3-C7 cycloalkyl, C3-C7 heterocyclic group, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C4-C20 heteroaryl, wherein the substituents in the C6-C20 aryl and C4-C20 heteroaryl are selected from halogen, NO 2 , C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, -SO 2 R 4 ′, -COOR 4 ', -C(=O)R 5 One or more of ';

[0014] In formula A-5, X 1 Selected from single bond, O, S, NR 9 , CR 7 R 8 , Y is selected from O, S, C=O and S=O, R 7 and R 8 The definition is the same as that of formula A-2, R 9 The definition of is the same as that of Formula A-3 and Formula A-4;

[0015] In formula A-6, X 2 Selected from O, S, NR 7 or CR 7 R 8 , R 7 and R 8 The definition is the same as that of formula A-2, Ar 2 and Ar 3 are each independently selected from substituted or unsubstituted C6-C20 arylene, substituted or unsubstituted C4-C20 heteroarylene, Ar 2 and Ar 3The substituents in are each independently selected from the group consisting of: deuterium, F, Cl, CN, NO 2 , C1-C4 alkyl, CF 3 , C1-C4 alkoxy, optionally, two adjacent substituents and the aryl or arylene atoms to which they are connected form a five-membered, six-membered or seven-membered ring;

[0016] R 2 selected from hydrogen, deuterium, C1-C11 alkyl, C1-C4 alkyl substituted by one or more selected from phenyl, C3-C7 cycloalkyl, C3-C7 heterocyclyl, C1-C4 alkoxy, C1-C4 alkyl acyloxy, C1-C4 alkoxy acyl, C3-C10 alkyl inserted by one or more O atoms, C3-C7 cycloalkyl, C6-C20 aryl, C4-C20 heteroaryl, C6-C20 aryl or C4-C20 heteroaryl substituted by one or more selected from the following groups: C1-C4 alkyl, C3-C7 cycloalkyl, F, Cl, nitro, CN, C1-C4 alkoxy, C1-C4 alkylthio, inserted by oxygen or sulfur or by R 5 COO-、-R 5 CONR 5 'substituted C2-C10 alkoxy, inserted by oxygen or sulfur or by R 5 COO-、-R 5 CONR 5 'Substituted C2-C10 alkylthio, -COCOOR 4 ;

[0017] Among them, R 2 The C3-C7 cycloalkyl and C3-C7 heterocyclic groups involved are unsubstituted or substituted with one or more F, Cl, C1-C4 alkyl, C1-C4 alkoxy, -COCOOR 4 Replacement; R 2 The hydrogen atoms on the carbon of the alkyl or alkoxy group involved are replaced by one or more fluorine atoms;

[0018] R 4 and R 4 ' are each independently selected from C1-C8 alkyl, substituted by one or more F atoms, phenyl, C3-C7 cycloalkyl, C3-C7 heterocyclyl, C1-C4 alkoxy, R 5 COO-、-R 5 CONR 5 'Substituted C1-C8 alkyl, C3-C8 alkyl intercalated with one or more oxygen atoms or sulfur atoms; C3-C7 cycloalkyl, C3-C7 heterocyclic group, C6-C20 aryl, C4-C20 heteroaryl;

[0019] R 5 and R 5' 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, C1-C4 alkoxy, C3-C8 alkyl substituted by one or more oxygen atoms or sulfur atoms; C3-C7 cycloalkyl, C3-C7 heterocyclyl, C6-C20 aryl, C4-C20 heteroaryl;

[0020] Optionally, R 4 , R 4 ′、R 5 and R 5 The heterocyclic ring, C6-C20 aryl group, C4-C20 heteroaryl group involved in the invention may have the following side chain substituents: C1-C4 alkyl group, substituted by one or more F atoms, phenyl group, C3-C7 cycloalkyl group, C3-C7 heterocyclic group, C1-C4 alkoxy group, R 6 COO-、-R 6 CONR 6 'Substituted C1-C4 alkyl, C3-C7 cycloalkyl, substituted or unsubstituted phenyl, R 6 CO-, R 6 COCO-,R 6 SO 2 -; where R 6 is selected from C1-C12 alkyl, C1-C4 alkyl substituted by one or more F or Cl, phenyl, thienyl, phenyl or thienyl substituted by one or more methyl, F, Cl or nitro; R 6 ' is selected from hydrogen, C1-C4 alkyl;

[0021] R 3 Selected from C1-C12 alkyl, C1-C4 alkyl substituted by C3-C7 cycloalkyl, C6-C12 aryl;

[0022] n is selected from 0 or 1;

[0023] “*” indicates Ar 1 With R 1 or group Bonding location.

[0024] According to some embodiments of the present invention, in formula (I), R 1 is selected from benzoyl, nitro, trifluoromethyl, sulfonic acid, trifluoromethylsulfonyl substituted by three substituents selected from methyl, -F, hydroxyl or amino. In some preferred embodiments, in formula (I), R 1 Selected from trimethylbenzoyl (eg 2,4,6-trimethylbenzoyl), nitro and trifluoromethyl.

[0025] According to some embodiments of the present invention, in formula (I), R 2selected from C1-C8 alkyl, cyclopentylmethyl, cyclohexylmethyl, tetrahydrofuranylmethyl, phenyl, selected from C1-C4 alkyl, C1-C4 fluoroalkyl, F, nitro, CN, C1-C4 alkoxy, C1-C4 fluoroalkoxy, C1-C4 alkylthio, inserted by oxygen or sulfur or by R 5 COO-、-R 5 CONR 5 'substituted C2-C8 alkoxy, inserted by oxygen or sulfur or by R 5 COO-、-R 5 CONR 5 'Substituted C2-C8 alkylthio, -COCOOR 4 Substituted C6-C12 aryl.

[0026] In some embodiments, R 4 , R 4 ' are each independently selected from C1-C4 alkyl, C3-C7 cycloalkyl, C3-C7 heterocyclyl, benzyl, 4-methylbenzyl, C1-C3 alkyl substituted with a C3-C7 cycloalkyl or C3-C7 heterocyclyl, C1-C4 alkoxy, R 5 COO-substituted C2-C4 alkyl, C3-C8 alkyl intermixed with one or more oxygen atoms or sulfur atoms, C6-C12 aryl, C4-C12 heteroaryl.

[0027] In some embodiments, R 5 , R 5 ' are each independently selected from C1-C4 alkyl, C1-C4 alkyl substituted by one or more F atoms, phenyl, C3-C7 cycloalkyl, C3-C7 heterocyclyl, C1-C4 alkoxy, C3-C7 cycloalkyl, C3-C7 heterocyclyl, C6-C12 aryl, C4-C12 heteroaryl.

[0028] Optionally, R 4 , R 4 ′、R 5 and R 5 The heterocyclic ring, C6-C12 aryl, and C4-C12 heteroaryl involved in the invention have the following side chain substituents: C1-C4 alkyl, one or more F atoms, phenyl, C3-C7 cycloalkyl, C3-C7 heterocyclic group, C1-C4 alkoxy, R 6 COO-、-R 6 CONR 6 'Substituted C1-C4 alkyl, C3-C7 cycloalkyl, unsubstituted phenyl or substituted phenyl, R 6 CO-, R 6 COCO-,R 6 SO 2 -; where R6 Selected from C1-C4 alkyl, CF 3 , phenyl, thienyl, phenyl or thienyl substituted by one or more methyl, F, nitro; R 6 ' is selected from hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl and tert-butyl.

[0029] In some preferred embodiments, in formula (I), R 2 Selected from methyl, ethyl, propyl, n-butyl, pentyl, hexyl, n-heptane, isooctane, cyclohexyl, cyclopentyl, cyclopentylmethyl, cyclohexylmethyl, cyclohexylethyl, thienylmethyl, phenyl, benzyl, fluorinated, methyl, methoxy, tetrafluoropropoxy, CH 3 OCH 2 CH(CH 3 )O-substituted phenyl.

[0030] According to some embodiments of the present invention, in formula (I), R 3 is selected from C1-C4 alkyl, C1-C4 alkyl substituted by C5-C7 cycloalkyl, C6-C10 aryl. 3 Selected from methyl, ethyl, cyclohexylmethyl, 2-cyclohexylethyl, phenyl.

[0031] According to some embodiments of the present invention, in formula (I), Ar 1 Selected from the structures represented by formula A-1, A-2, A-3, A-4 or A-6.

[0032] In some embodiments, in Formula A-2, R 7 , R 8 Each is independently selected from a hydrogen atom, a C1-C4 alkyl group, preferably hydrogen, a methyl group, an ethyl group, a n-propyl group and a n-butyl group. 7 and R 8 Together with the carbon atom directly connected thereto, it forms a cyclopentyl ring or a cyclohexyl ring.

[0033] In some embodiments, in Formula A-3 and Formula A-4, R 9 Selected from C1-C8 alkyl, -R 4 COOR 4 ′, -R 4 CONR 5 R 5 ', replaced by one or more F, phenyl, C5-C6 cycloalkyl, C4-C6 heterocyclic group, OR 4 ′, -COOR 4 ', -P(=O)(OR 4 ′) 2Substituted C1-C8 alkyl, C5-C6 cycloalkyl, phenyl, thienyl, phenyl or thienyl substituted with one or more of the following groups: F, NO 2 , C1-C4 alkyl, C1-C4 alkoxy, -SO 2 R 4 ′, -COOR 4 ', -C(=O)R 5 ′; where R 4 , R 4 ′、R 5 and R 5 ' are each independently selected from C1-C8 alkyl, C3-C7 cycloalkyl, C3-C7 heterocyclyl, C6-C12 aryl, C4-C12 heteroaryl. In some embodiments, R 9 Selected from methyl, ethyl, n-propyl, n-butyl, 2-ethylhexyl, or the following groups:

[0034]

[0035] In some embodiments, in Formula A-6, X 2 Selected from O or S; Ar 2 and Ar 3 Each is independently selected from a substituted or unsubstituted C6-C12 arylene group, and a substituted or unsubstituted C5-C12 heteroarylene group.

[0036] In some embodiments, in Formula A-6, Ar 2 and Ar 3 are each independently selected from substituted or unsubstituted phenylene, substituted or unsubstituted thienylene, substituted or unsubstituted naphthylene, substituted or unsubstituted anthrylene, Ar 2 and Ar 3 The substituents in are each independently selected from one or more of the following groups: F, CN, NO 2 , C.F. 3 , C1-C4 alkyl, C1-C4 alkoxy.

[0037] According to some embodiments of the present invention, in Formula A-1 to Formula A-6, R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 Each is independently selected from hydrogen, F, C1-C4 alkyl; preferably hydrogen, F, methyl and ethyl.

[0038] According to some preferred embodiments of the present invention, the compound has a structure shown in formula (I-1) to formula (I-5):

[0039]

[0040]

[0041] Among them, each R Ar are selected identically or differently from H, F, CN, NO 2 , C.F. 3 , C1-C4 alkyl, C1-C4 alkoxy; R 1 , R 2 , R 3 , R 9 The same as defined in formula (I).

[0042] According to some embodiments of the present invention, examples of the compound include but are not limited to compounds represented by the following formulae 1 to 57:

[0043]

[0044]

[0045]

[0046]

[0047]

[0048]

[0049] According to some embodiments of the present invention, the preparation of the oxalic acid oxime ester compound comprises the following steps:

[0050] (1): Make the raw material R 1 -Ar 1 H and acyl chloride compound R 2 CH 2 COCl or anhydride undergoes Friedel-Crafts acylation to obtain intermediate M 1 ;or,

[0051] Make the raw material R 1 -Ar 1 H and acyl chloride compound R 2 COCl or anhydride undergoes Friedel-Crafts acylation to obtain intermediate M 1 ′;

[0052]

[0053] (2): The intermediate M obtained in step (1) 1 React with nitrite or nitrous acid under acidic conditions to obtain nitro intermediate M2 ,or,

[0054] The intermediate M obtained in step (1) 1 ' reacts with hydroxylamine hydrochloride under neutral or alkaline conditions to obtain intermediate M 2 ′;

[0055]

[0056] (3): The intermediate M obtained in step (2) 2 With R 3 OOCCOCl reacts to obtain a compound of formula II; or,

[0057] The intermediate M obtained in step (2) 2 ′ and R 3 OOCCOCl reacts to obtain a compound of formula III;

[0058]

[0059] Among them, Ar 1 , R 1 , R 2 , R 3 The same as defined in formula (I).

[0060] In the present invention, when R in the compound of formula (I) 1 When is nitro, the compound can also be prepared by a method comprising the following steps:

[0061] S1: Make the raw material H-Ar 1 H and acyl chloride compound R 2 CH 2 COCl or anhydride undergoes Friedel-Crafts acylation to obtain intermediate M 1A ;or,

[0062] Make the raw material H-Ar 1 H and acyl chloride compound R 2 COCl or anhydride undergoes Friedel-Crafts acylation to obtain intermediate M 1A ′;

[0063]

[0064] S2: The intermediate M obtained in step S1 1A or M 1A 'React with nitrating agent to obtain nitro intermediate M 1 or M 1 ′;

[0065]

[0066] S3: The intermediate M obtained in step S2 1 React with nitrite or nitrous acid under acidic conditions to obtain intermediate M 2 ,or,

[0067] The intermediate M obtained in step S2 1 ' reacts with hydroxylamine hydrochloride under neutral or alkaline conditions to obtain intermediate M 2 ′;

[0068]

[0069] S4: The intermediate M obtained in step S3 is 2 With R 3 OOCCOCl reacts to obtain a compound of formula II; or,

[0070] The intermediate M obtained in step S3 2 ′ and R 3 OOCCOCl reacts to obtain a compound of formula III;

[0071]

[0072] Among them, R 1 is nitro, Ar 1 , R 2 , R 3 The same as defined in formula (I).

[0073] In some embodiments, M can also be directly obtained by using existing technology or commercially purchasing 2 or M 2 ′, directly with R 3 OOCCOCl undergoes esterification reaction to obtain a compound of formula II or a compound of formula III.

[0074] 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 oxalate compound described in the first aspect of the present invention.

[0075] In some embodiments, the free radical polymerizable compound is selected from acrylate compounds, methacrylate compounds, and combinations thereof.

[0076] 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.

[0077] 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).

[0078] 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.

[0079] 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.

[0080] 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.

[0081] The acrylate group in the double bond compound of the present invention may also be replaced by a methacrylate group.

[0082] In some embodiments, the mass percentage of the oxime oxalate compound in the photocurable composition is 0.1-8.0%.

[0084] 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.

[0085] 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.

[0086] 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.

[0087] 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 oxalate compound described in the first aspect of the present invention.

[0088] 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.

[0089] 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.

[0090] 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.

[0091] 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.

[0092] 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.

[0093] 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.

[0094] 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.

[0095] 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.

[0096] 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.

[0097] 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.

[0098] 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.

[0099] 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.

[0100] In some embodiments, the printed article comprises a printed circuit board.

[0101] In some embodiments, the display comprises an LCD display or an OLED display.

[0102] In the ninth aspect, the present invention provides the use of the oxime oxalate 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.

[0103] 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.

[0104] Compared with the prior art, the present invention has the following beneficial effects:

[0105] The invention introduces a strong electron-withdrawing group into an aromatic or heteroaromatic matrix to synthesize a novel oxalic acid oxime ester compound, which has significantly higher sensitivity performance in photocuring, especially in photoresist, than the existing photoinitiator. DETAILED DESCRIPTION

[0106] 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.

[0107] The term "C1-C4 alkyl" used herein refers to a straight or branched chain alkyl group having 1 to 4 carbon atoms, including but not limited to methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl and the like.

[0108] As used herein, the term "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" has the same meaning and refers to a C3-C10 alkyl group interrupted by O or S one or more times, for example 1-9 times, 1-5 times, 1-3 times 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: -CH 2 -CH 2 -O-CH 2 CH 3 -、-CH 2 -CH(CH 3 )-O-CH 2 -CH 2 O-CH 3 -、-CH 2 -CH 2 -S-CH 2 CH 3 wait.

[0109] 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.

[0110] 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.

[0111] 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.

[0112] 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.

[0113] 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,

[0114] Examples of non-fused aryl groups include phenyl, biphenyl-2-yl, biphenyl-3-yl, biphenyl-4-yl, p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl, m-terphenyl-2-yl, o-tolyl, m-tolyl, p-tolyl, p-(2-phenylpropyl)phenyl, 4'-methylbiphenyl, 4"-tert-butyl-p-terphenyl-4-yl, o-cumyl, m-cumyl, p-cumyl, 2,3-xylyl, 3,4-xylyl, 2,5-xylyl, mesityl and m-quadrenyl. In addition, the aryl group may be optionally substituted.

[0115] 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.

[0116] The term "aroyl" as used herein refers to an aromatic group connected through a carbonyl group, including but not limited to benzoyl, naphthoyl, benzothioyl, furoyl, thenoyl, isothiazole, pyridine, quinoline, isoquinoline, indole, thienopyridine, benzofuroyl, benzothiazole. In addition, the aromatic group can be optionally substituted, such as mono-, di- or tri-substituted.

[0117] 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.

[0118] Experimental materials and equipment:

[0119] Light source equipment:

[0120] 365nm LED surface light source, Shanghai Futanxi Technology Co., Ltd.;

[0121] Test equipment:

[0122] DSC: HSC-1, Beijing Hengjiu Experimental Equipment Co., Ltd.

[0123] Stereo microscope: HY-950S, Beijing Huanyu Technology Co., Ltd., line width unit is μm.

[0124] Experimental Materials:

[0125] Genomer 4212: aliphatic polyurethane acrylate, a product of RAHN;

[0126] DPHA: dipentaerythritol hexaacrylate, a product of Tianjin Tianjiao Chemical Co., Ltd.;

[0127] HDDA: 1,6-hexanediol diacrylate, a product of Tianjin Tianjiao Chemical Co., Ltd.;

[0128] Compound preparation

[0129] Preparation Example 1: 4-Nitroacetophenone oxime, O-(2-cyclohexylmethoxy-2-oxoacetic acid) ester

[0130]

[0131] 1pro. Preparation of intermediate oxalyl chloride monocyclohexyl methyl ester:

[0132] In a 250mL three-necked flask, add 127g (1mol) of oxalyl chloride, put in a magnetic stirrer, install a condenser, a drying tube, an exhaust duct and an exhaust absorption bottle, add dropwise 57.1g (0.5mol) of cyclohexylmethanol at room temperature at 15°C with stirring, add the mixture after 3h, raise the temperature to 65°C, and stir for 2h; modify the distillation apparatus, recover the oxalyl chloride at normal pressure, and then collect the main fraction by reduced pressure distillation, which is 80.2g of monocyclohexylmethyl oxalyl chloride, with a yield of 78.4% and a content of 98.53% according to GC analysis.

[0133] 1a. In a 50mL three-necked flask, add 3.3g (20mmol) of p-nitroacetophenone, 20g of ethanol, 1.66g (24mmol) of hydroxylamine hydrochloride, and 2.14g (26mmol) of sodium acetate. Stir and heat under reflux for 4h. Remove ethanol by distillation under reduced pressure, dissolve the residue with 50mL of 1,2-dichloroethane (hereinafter referred to as DCE), wash with 20mL of water for 30min, separate the lower organic layer, wash once with 20mL of water, and wash with 0.5g of Na 2 SO 4 Dry for 4 h, filter the desiccant, evaporate 20 mL of the solvent from the filtrate, let the remaining solution cool, precipitate crystals, filter, and dry the filter cake to obtain 2.82 g of an off-white solid with a yield of 78.3%. The HPLC purity was 99.05% (95.5% for the trans isomer and 3.55% for the cis isomer). The DSC melting point was 175.8°C; the intermediate 4-nitroacetophenone oxime was obtained.

[0134] 1b. In a 50 mL single-necked bottle, add 1 g (5.6 mmol) of the product obtained in operation 1a, add 15.0 g of DCE, then add 1.24 g (6.2 mmol) of oxalyl chloride monocyclohexyl methyl ester and 0.63 g (6.2 mmol) of triethylamine, 20 ° C, magnetic stirring for 2 h; wash 3 times with 5 ° C water, each time with 5.0 g of water, for 5 min, until pH = 6-7; anhydrous Na 2 SO 4 The organic phase was dried for 2 h, the solution was evaporated to dryness under reduced pressure, and the residual solvent was then pumped out with an oil vacuum pump to obtain 1.8 g of an off-white solid residue with a yield of 92.8%, a HPLC purity of 98.05%, and a DSC melting point of 117.6° C.; the target compound was 4-nitroacetophenone oxime, O-(2-cyclohexylmethoxy-2-oxoacetic acid) ester; 1 H-NMR (CDCl 3 , δ [ppm]) data: 0.9865-1.3053 (m, 3H, cyclohexane CH 2 ), 1.6702-1.8148 (m, 8H, cyclohexane CH 2 +CH), 2.5264 (s, 3H, CH 3 ), 4.1683-4.1821(d,2H,CH 2 ), 7.9349-7.9535(d,2H,ArH), 8.2749-8.2932(d,2H,ArH).

[0135] Preparation Example 2: 4-Trifluoromethylacetophenone oxime, O-(2-cyclohexylmethoxy-2-oxoacetic acid) ester

[0136]

[0137] 2a. According to the operation 1a of Preparation Example 1, p-trifluoromethylacetophenone was used instead of p-nitroacetophenone in operation 1a. After reaction and post-treatment, a crude product was obtained, which was recrystallized from a mixture of ethanol and ethyl acetate to obtain white granular crystals with a yield of 90% and a HPLC purity of 99.86% (including 96.81% of the trans isomer and 3.05% of the cis isomer); DSC melting point: 105.6°C, which was the intermediate 4-trifluoromethylacetophenone oxime.

[0138] 2b. According to the method of operation 1b of Preparation Example 1, the product of operation 2a was esterified with to give a white solid in a yield of 92%, HPLC purity of 96.38%, DSC melting point: 54.4 ° C; the target 4-trifluoromethylacetophenone oxime, O-(2-cyclohexylmethoxy-2-oxoacetic acid) ester; 1 H-NMR (CD 3 Cl 3, δ [ppm]) data: 0.9900-1.3006 (m, 3H, cyclohexane CH 2 ), 1.6706-1.8022 (m, 8H, cyclohexane CH 2 +CH), 2.5001(s,3H,CH 3 ), 4.1631-4.1771(d,2H,CH 2 ), 7.6808-7.6997(d,2H,ArH), 7.8632-7.8817(d,2H,ArH).

[0139] Preparation Example 3: 1-[6-nitro-9-(4-nitrophenyl)carbazole-3-yl]-1-octanone oxime, O-(2-cyclohexylmethoxy-2-oxoacetic acid) ester

[0140]

[0141] 3Pro. Preparation of intermediate N-(4-nitrophenyl)carbazole:

[0142] In a 100mL three-necked flask, 10g (0.06mol) of carbazole, 9.29g (0.066mol) of p-fluoronitrobenzene, 30g of N,N-dimethylformamide (DMF for short), and 3.7g (0.066mol) of solid KOH were placed. Electromagnetic stirring was turned on, and the solution turned black. The temperature was raised to 100°C and the reaction was carried out for 10h. The reaction solution was cooled to precipitate yellow crystals, which were filtered and the filter cake was rinsed with water and then with ethanol. After drying, it weighed 14.85g, with a yield of 85.8%, HPLC purity of 98.3%, and DSC melting point of 208°C.

[0143] 3a. Put 4g (13.8mmol) of the product obtained by operation 3Pro and 25g of o-dichlorobenzene (DCB) into a 100mL three-necked flask, stir and add 2g (14.6mmol) of anhydrous AlCl 3 , put it in a low temperature bath and cool it to -10°C, slowly add 2.36g (14.6mmol) of octanoyl chloride, and control the temperature not to exceed -10°C. After the dropwise addition, naturally heat it to 0°C and react overnight; after acid hydrolysis, wash with water, evaporate DCB under reduced pressure to obtain 6g of orange-yellow solid, and slurry it with 30mL of ethanol, cool it and filter it. After drying, the yellow powder weighs 5.34g, with a yield of 93.3%, HPLC purity of 99.4%, and DSC melting point: 130.6°C; it is the intermediate 3-octanoyl-9-(4-nitrophenyl)carbazole.

[0144] 3b. In a 100 mL three-necked flask, 4.15 g (10 mmol) of the product obtained in operation 3a and 30 g of DCE were placed. The oil bath was heated to 45°C, and 1.06 g (11 mmol) of 65% nitric acid was added dropwise. The reaction was stirred for 4 h. The reaction solution was washed with water until the aqueous phase was neutral. The DCE was evaporated under reduced pressure. The residue was slurried with ethyl acetate and filtered. After the filter cake was dried, the yellow powder weighed 3.6 g, with a yield of 78.6%, HPLC purity of 96.42%, and DSC melting point: 221.2°C; the intermediate 6-nitro-3-octanoyl-9-(4-nitrophenyl)carbazole was obtained.

[0145] 3c. In a 50 mL single-necked bottle, 2 g (4.4 mmol) of the product obtained in operation 3b was added, 10 g of pyridine, 0.46 g (6.6 mmol) of hydroxylamine hydrochloride, and the reaction was carried out in an oil bath at 90 ° C. with electromagnetic stirring for 10 h; the pyridine was evaporated to dryness, the residue was slurried with 30 mL of water, filtered, the filter cake was drained under reduced pressure, and recrystallized from acetone and toluene. After drying, the yellow powder product weighed 1.85 g, HPLC purity 97.32% (major isomer 91.12%, minor isomer 6.2%), yield 89.8%, DSC melting point: 216.6 ° C; the intermediate 1-[6-nitro-9-(4-nitrophenyl)carbazole-3-yl]-1-octanone oxime.

[0146] 3d. In a 50 mL single-mouth bottle, 0.8 g (1.6 mmol) of the product obtained in operation 3c and 8 g of DCM were added, and then 0.42 g (2 mmol) of monocyclohexylmethyl oxalyl chloride and 0.2 g (2 mmol) of triethylamine were added, and the mixture was stirred at 20 ° C overnight. The reaction solution was washed with water 3 times, 4 g of water each time, and the DCM was evaporated to dryness. The residue was recrystallized from a mixture of ethanol and DCM, filtered, and the filter cake was dried to obtain 0.88 g of a yellow product with an HPLC purity of 97.52% (91.52% for the main isomer and 6.0% for the minor isomer), a yield of 81.5%, and a DSC melting point of 112.5 ° C; the target 1-[6-nitro-9-(4-nitrophenyl)carbazole-3-yl]-1-octanone oxime, O-(2-cyclohexylmethoxy-2-oxoacetic acid) ester, 1 H-NMR (CD 3 Cl 3 , δ [ppm]) data: 0.8418-1.8354 (m, 24H, cyclohexane CH 2 +CH+HeptylCH 3 +CH 2 ), 3.0482-3.0653-3.0824(t,2H,CH 2 ), 4.1889-4.2025(d,2H,OCH 2), 7.4751-7.4940(d); 7.7993-7.8180(d); 7.9749-7.9929(d); 8.3918-8.4106(d); the total of these four groups of integrals is 4H, 8.5688-8.5739-8.5884(s+d,5H,ArH), 9.1250(s,1H,ArH)).

[0147] Preparation Example 4: 1-[6-nitro-9-(4-nitrophenyl)carbazole-3-yl]-1-octanone oxime, O-(2-ethoxy-2-oxoacetic acid) ester

[0148]

[0149] 4a. Referring to the operation 3d of Preparation Example 3, ethyl oxalyl chloride was used instead of cyclohexyl methyl oxalyl chloride to give a yellow powder with a HPLC purity of 97.88% (91.78% for the major isomer and 6.1% for the minor isomer), a yield of 74%, and a DSC melting point of 132 ° C (decomposition); the target compound was 1-[6-nitro-9-(4-nitrophenyl)carbazole-3-yl]-1-octanone oxime, O-(2-ethoxy-2-oxoacetic acid) ester, 1 H-NMR (CD 3 Cl 3 , δ[ppm]) data: 0.8255-0.8974 (m, 8H, 2CH 3 +CH 2 ), 1.2495-1.7173(m,8H,4CH 2 ), 3.0490-3.0665-3.0832(t,2H,CH 2 ), 4.4268-4.4429-4.4582-4.4726(quartet,2H,OCH 2 ), 7.4745-7.4937(d); 7.8017-7.8205(d); 7.9736-7.8205(d); 8.3829-8.4067(d); the total of these four groups of integrals is 4H, 8.5670-8.5866(m,5H,ArH), 9.1172(s,1H,ArH)).

[0150] Preparation Example 5: 1-[6-nitro-9-(2-ethylhexyl)carbazole-3-yl]-1-(3-cyclohexyl)acetone oxime, O-(2-cyclohexylmethoxy-2-oxoacetic acid) ester

[0151]

[0152] 5a. Add 6.4 g (20 mmol) of N-(2-ethylhexyl) carbazole and 25 g of DCB into a 100 mL three-necked flask, stir and add 2.92 g (22 mmol) of anhydrous AlCl 3 , put it in a low temperature bath and cool it to -10°C, slowly add 3.48g (20mmol) of 3-cyclohexylpropionyl chloride, and control the temperature not to exceed -10°C. After the dropwise addition, naturally heat it to 0°C and react overnight; after acid hydrolysis, wash with water, and evaporate DCB under reduced pressure to obtain a light yellow oil, weighing 8.32g, with a yield of 100% and a HPLC purity of 97.2%; the intermediate 3-(3-cyclohexylpropionyl)-9-(2-ethylhexyl)carbazole.

[0153] 5b. In a 100 mL three-necked flask, 8.32 g (20 mmol) of the product obtained in operation 5a and 30 g of DCE were placed. The oil bath was heated to 45°C, and 4 g (20 mmol) of 35% nitric acid was added dropwise. The reaction was stirred for 4 h, and the reaction solution was washed with water until the aqueous phase was neutral. The DCE was evaporated under reduced pressure, and the residue was slurried with heptane and filtered. After the filter cake was dried, the yellow powder weighed 5.6 g, the yield was 60.5%, the HPLC purity was 96.42%, and the DSC melting point was 111.6°C; the intermediate 6-nitro-3-(3-cyclohexylpropionyl)-9-(2-ethylhexyl)carbazole.

[0154] 5c. In a 50 mL single-necked bottle, 2 g (4.4 mmol) of the product obtained in operation 5b was added, 10 g of ethanol, 0.45 g (6.4 mmol) of hydroxylamine hydrochloride and 0.53 g (6.4 mmol) of sodium acetate were added, and the reaction was carried out in an oil bath at 90 ° C. with electromagnetic stirring for 2 h; the ethanol was evaporated, the residue was slurried with 30 mL of water, filtered, the filter cake was drained under reduced pressure, and recrystallized from ethanol. After drying, the yellow crystalline powder weighed 1.68 g, HPLC purity 98.30% (major isomer 94.82%, minor isomer 3.48%), yield 81%, DSC melting point: 177 ° C; the intermediate 3-cyclohexyl-1-[6-nitro-9-(2-ethylhexyl))carbazole-3-yl]-1-acetone oxime.

[0155] 5d. In a 50 mL single-mouth bottle, 0.8 g (1.6 mmol) of the product obtained in operation 5c and 5 g of DCM were added, and then 0.24 g (2 mmol) of monomethyl oxalyl chloride and 0.2 g (2 mmol) of triethylamine were added. The mixture was stirred at 20 ° C overnight. The reaction solution was washed with water 3 times, 4 g of water each time, and the DCM was evaporated to dryness. The residue was recrystallized from a mixture of ethanol and DCM, filtered, and the filter cake was dried to obtain 0.72 g of yellow crystals, HPLC purity 97.82% (major isomer 93.50%, minor isomer 4.32%), yield 76.6%, DSC melting point: 105.7 ° C; the target 3-cyclohexyl-1-[6-nitro-9-(2-ethylhexyl)carbazole-3-yl]-1-acetone oxime, O-(2-methoxy-2-oxoacetic acid) ester, 1 H-NMR (CD 3 Cl 3 , δ [ppm]) data: 0.8308-2.0534 (m, 28H, methylenecyclohexane CH 2 +CH+3-HeptylCH 3 +CH 2 +CH), 3.0354-3.0533-3.0711(t,2H,CH 2 ),

[0156] 3.9923(s,3H,OCH 3 ), 4.2250-4.2435(d,2H,NCH 2 ), 7.4216-7.4403(d); 7.4668-7.4849(d); 7.9977-

[0157] 8.0195 (d); 8.3960-8.4145 (d); the total of these four groups of integrals is 4H, 8.4791 (s, 1H, ArH), 9.0505 (s, 1H, ArH)). Preparation Example 6: 3-cyclohexyl-1-[4-(4-nitrophenylthio)phenyl]-1,2-propanedione-2-oxime, O-(2-cyclohexylmethoxy-2-oxoacetate

[0158]

[0159] 6a. Add 5 g (21.6 mmol) of 4-nitrodiphenyl sulfide and 25 g of DCE into a 100 mL three-necked flask, place in a low temperature bath and stir to cool to -10 °C. After cooling, add 5.76 g (43.2 mmol) of anhydrous AlCl 3, slowly add 4.54g (26mmol) 3-cyclohexylpropionyl chloride dropwise, control the temperature not to exceed 10°C, after the addition is completed, naturally heat to 15°C and react overnight; after acid hydrolysis, wash with water, evaporate DCE under reduced pressure to obtain 8.5g of brown oil, crystallize with ethyl acetate and heptane, and vacuum dry to obtain 5.98g of yellow solid powder, yield: 75%, HPLC purity 97.57%, DSC melting point: 77.6°C; the intermediate 3-cyclohexyl-1-[4-(4-nitrophenylthio)phenyl]-1-propanone.

[0160] 6b. In a 100mL three-necked flask, 1.94g (5.3mmol) of the product obtained in operation 6a was added, 10gDMSO, 0.82g (7.9mmol) butyl nitrite was added, and the oil bath was 30°C. Hydrochloric acid gas was continuously introduced in small amounts, and the reaction was stirred electromagnetically for 6h; the reaction solution was poured into 100mL of water, the aqueous phase was extracted with 20gDCM, and the DCM solution was washed with water, the DCM solution was evaporated to dryness, and the residue was recrystallized from 9g of ethanol, filtered, and the filter cake was drained under reduced pressure. After drying, a light yellow crystalline powder weighing 1.61g was obtained, with a HPLC purity of 98.11%, a yield of 77%, and a DSC melting point of 160°C; the intermediate 3-cyclohexyl-1-[4-(4-nitrophenylthio)phenyl]-1-acetone oxime.

[0161] 6c. In a 50 mL single-necked bottle, add 0.8 g (2 mmol) of the product obtained in operation 6b and 8 g of DCM, then add 0.46 g (2.2 mmol) of oxalyl chloride monocyclohexylmethyl ester and 0.22 g (2.2 mmol) of triethylamine, stir at 20 ° C for 2 h, wash the reaction solution with water 3 times, 2 g of water each time, and wash with 0.2 g of anhydrous Na 2 SO 4 The organic phase was dried, the desiccant was filtered off and the DCM was evaporated to dryness. The residue was slurried with heptane, filtered and the filter cake was dried under reduced pressure to obtain 0.8 g of a light yellow powder with a HPLC purity of 96.33% and a DSC melting point of 90° C. The target compound was 3-cyclohexyl-1-[4-(4-nitrophenylthio)phenyl]-1,2-propanedione-2-oxime, O-(2-cyclohexylmethoxy-2-oxoacetic acid) ester. 1 H-NMR (CD 3 Cl 3 , δ [ppm]) data: 0.9646-1.7599 (m, 22H, two cyclohexane CH 2 +CH), 2.8104-2.8241(d,2H,CH 2 ), 4.1328-4.1450(d,2H,OCH 2), 7.4441-7.4618 (d, 2H, ArH); 7.4711-7.4878 (d, 2H, ArH); 8.0737-8.0908 (d, 2H, ArH), 8.1647-8.1825 (d, 2H, ArH). Preparation Example 7: 1-[6-nitro-9-(2-ethylhexyl)carbazol-3-yl]-1-[2-(2,2,3,3-tetrafluoropropoxy)]benzophenone oxime, O-(2-methoxy-2-oxoacetate

[0162]

[0163] 7a. In a 250mL three-necked flask, 7.2g (25.8mmol) of N-(2-ethylhexyl) carbazole, 30g of o-dichlorobenzene, 3.62g (27.1mmol) of aluminum chloride were added, a thermometer was installed, magnetic stirring was applied, and an exhaust gas absorption device was installed; the temperature was cooled to -15°C with stirring, and the reaction solution turned black; 4.1g (25.8mmol) of o-fluorobenzoyl chloride was dissolved in 10g of o-dichlorobenzene and slowly added dropwise to the reaction flask. After the addition, the reaction was kept at -10°C for 6h; at -10°C, the reaction solution was slowly dripped into an excess of dilute hydrochloric acid solution, stirred at room temperature for 30min, separated, washed with water until neutral, and dried to obtain 15g of a black oil; column chromatography was performed for separation and purification, and the solvent was removed to obtain 8g of a light yellow oil with a yield of 77.5% and a purity of 98.15% by HPLC; the intermediate 3-(2-fluorobenzoyl)-9-(2-ethylhexyl) carbazole was obtained;

[0164] 7b. In a 100mL three-necked flask, 5.1g (12.7mmol) of the product of operation 7a and 25g of DCE were placed, and the mixture was kept warm to 50°C. 2.2g (14mmol) of 40% nitric acid was added dropwise, and the reaction was continued for 3h after the addition. The reaction solution was washed with water, the solvent DCE was removed, and the mixture was recrystallized from ethyl acetate to obtain a yellow solid with a dry weight of 4.6g, a yield of 81.1%, a HPLC purity of 96.82%, and a DSC melting point of 145.7°C; the intermediate 6-nitro-3-(2-fluorobenzoyl)-9-(2-ethylhexyl)carbazole;

[0165] 7c. In a 100mL dry single-mouth bottle, a magnetic stirrer was placed; 2.3g (17.4mmol) of tetrafluoropropanol, 10g of tetrahydrofuran, 1.2g (50mmol) of sodium hydrogen hydride were added, and the mixture was stirred until no bubbles appeared. 4.5g (10mmol) of the product of operation 7b was added, and the temperature was raised to 50°C for 60h; tetrahydrofuran and tetrafluoropropanol were removed by rotary evaporation under reduced pressure, dissolved with DCE, washed with water to pH = 7, and the solvent was removed by rotary evaporation under reduced pressure to obtain 4.5g of a brown viscous substance; the yield was 80.5%; the HPLC content was 96.5%; the intermediate 6-nitro-3-[2-(2,2,3,3-tetrafluoropropoxy)benzoyl]-9-(2-ethylhexyl)carbazole;

[0166] 7d. Place a magnetic stirrer in a 50 mL single-necked bottle; add 2.0 g (3.6 mmol) of the product of operation 7b, 6 g of pyridine, 0.4 g (5.7 mmol) of hydroxylamine hydrochloride to the reaction flask, protect with nitrogen, and heat to 80 ° C for 24 h; remove pyridine by vacuum rotary evaporation, dissolve with DCE, wash with water to neutrality, and vacuum rotary evaporation to dryness to give 2.0 g of a brown viscous material, a yield of 96.8%, HPLC content 98.4% (major isomer 68.90%, minor isomer 29.5%); intermediate 1-[6-nitro-9-(2-ethylhexyl)carbazole-3-yl]-1-[2-(2,2,3,3-tetrafluoropropoxy)]benzophenone oxime;

[0167] 7d. Place a magnetic stirrer in a 50 mL single-necked bottle; add 1.25 g (2.18 mmol) of the product of operation 7c and 5 g of DCM to the reaction bottle to form a dark brown clear solution, cool to -10 ° C, add 0.3 g (2.45 mmol) of methyl oxalyl chloride, and react at -5 ° C in the dark for 2 h; wash three times with water, dry with 0.5 g of anhydrous sodium sulfate for 2 h, filter the desiccant, and evaporate the organic solution to dryness under reduced pressure. The residue was crystallized from ethyl acetate and heptane to give 1.1 g of a dry yellow powder solid; yield 76.5%, HPLC content 98.2% (major isomer 66.5%, minor isomer 31.7%), DSC melting point 75.2 ° C. The target compound is 1-[6-nitro-9-(2-ethylhexyl)carbazole-3-yl]-1-[2-(2,2,3,3-tetrafluoropropoxy)]benzophenone oxime, O-(2-methoxy-2-oxoacetate).

[0168] 1 H-NMR (CD 3 Cl 3 ,δ[ppm]) data: 0.8558(t,3H,CH 3 ), 0.9173(t,3H,CH 3 )), 1.2562-1.4398 (m, 9H, CH 2 +CH), 3.9161 / 3.9469(s,3H,OCH 3 ), 4.2152-4.2336(d,2H,NCH 2 ), 4.2987-4.3272-4.3555(t,OCH 2 CF 2 ),5.3455-5.4503-5.4780(t,1H,CF 2H),7.0663-7.0871(d,1H,ArH),7.2428-7.2779(t,1H,ArH),7.3447-7.3491-7.3635-7.3679(d+d,1H,ArH),7 .3899-7.4128(d,1H,ArH),7.4420-7.4637(d,1H,ArH),7.5345-7.5550-7.5734(t,1H,ArH),7.8479-7.8523-

[0169] 7.8697-7.8741(d+d,1H,ArH),8.0393-8.0436(d,1H,ArH),8.3568-8.3626-8.3796-8.3852(d+d,1H,ArH),8.8937-8.8994(d,1H,ArH).

[0170] Preparation Example 8: 1-[6-(2,4,6-trimethylbenzoyl)-11-(2-ethylhexyl)benzocarbazole-8-yl]-1-[2-(2,2,3,3-tetrafluoropropoxy)]benzophenone oxime, O-(2-methoxy-2-oxoacetate

[0171]

[0172] 8a. Obtain the intermediate oxime compound 54A according to the method of Example 24 of the specification of patent document CN103153952A

[0173]

[0174] 8b. Place a magnetic stirrer in a 50 mL single-necked bottle; add 3.0 g (4.1 mmol) of the intermediate oxime compound 54A obtained in operation 8a, 15 g of DCM solvent and 0.5 g (5 mmol) of triethylamine, cool to 0°C, add 0.56 g (4.6 mmol) of methyl chlorooxalyl ester dropwise, and react at 0°C in the dark for 2 h; wash three times with water, dry with 0.5 g of anhydrous sodium sulfate for 2 h, filter the desiccant, and evaporate the organic solution under reduced pressure to dryness, leaving 2.5 g of a yellow solid; yield 74.6%, HPLC content 98.2% (major isomer 72.4%, minor isomer 25.8%), melting point 80.5-85.0°C. The target compound is 1-[6-(2,4,6-trimethylbenzoyl)-11-(2-ethylhexyl)benzocarbazole-8-yl]-1-[2-(2,2,3,3-tetrafluoropropoxy)]benzophenone oxime, O-(2-methoxy-2-oxoacetate). 1 H-NMR (CD 3 Cl 3,δ[ppm]) data: 0.77920-0.8100-0.8275(t,3H,CH 3 ), 0.8443-0.8775-0.9107(t,3H,CH 3 ), 1.1660-1.4795(m,8H,4CH 2 ), 2.1954(s,6H,2ArCH 3 ),2.2470-2.3197(m,1H,CH),2.3852(s,3H,ArCH 3 ),3.8156 / 3.8431(s,3H,OCH 3 ), 4.3288-4.3576-4.3859(t,2H,CH 2 O), 4.6655-4.7443 (m, 2H, NCH 2 ),5.4382 / 5.4517 / 5.4647-5,5704 / 5.58375.5970-5.7027 / 5.7159 / 5.7291(ttt,1H,CHF 2 ),6.9352 / 6.9477(s,2H,2ArH),7.0367-7.0576(d,1H,ArH),7.1576-7.2130( m,2H,2ArH),7.4421-7.5910(m,3H,3ArH),7.6855-7.7723(m,2H,2ArH),8.22 726-8.4122(m,2H,2ArH),8.6298-8.6470 / 8.7866-8.7989(d,1H,ArH),9.452 8 / 9.4571-9.4736 / 9.4780-9.5000 / 9.5039-9.5211 / 9.5251(d / dd / d,1H,ArH).

[0175] Preparation Example 9: 1-[6-(2,4,6-trimethylbenzoyl)-11-(2-ethylhexyl)benzocarbazole-8-yl]-1-(2-fluorophenyl)methanone oxime, O-(2-methoxy-2-oxoacetate)

[0176]

[0177] 9a. Obtain intermediate 57A according to the method of Example 24 of the specification of patent document CN103153952A

[0178]

[0179] 9b. Place a magnetic stirrer in a 50 mL single-necked bottle; add 3.0 g (5 mmol) of the intermediate 57A obtained in operation 9a, dissolve it with 10 ml of pyridine, add 0.42 g (6 mmol) of hydroxylamine hydrochloride, turn on stirring and heat to 90 ° C. Keep the reaction for 5 hours, evaporate the pyridine under reduced pressure, add 15 ml of DCM and 15 ml of water to dissolve, separate the layers, wash the organic phase with water again, and remove the organic phase to obtain 3.02 g of the intermediate oxime compound 57B; it is a mixture of cis and trans isomers, with a ratio of 69:29

[0180]

[0181] 9c. Place a magnetic stirrer in a 50 mL single-necked bottle; add 3.0 g (4.9 mmol) of the intermediate oxime compound 57B obtained in operation 9b, 15 g of DCM solvent and 0.51 g of triethylamine, cool to 0°C, add 0.61 g (5 mmol) of methyl chlorooxalyl ester dropwise, and react at 0°C in the dark for 2 h; wash three times with water, dry with 0.5 g of anhydrous sodium sulfate for 2 h, filter the desiccant, and evaporate the organic solution under reduced pressure to dryness, leaving 3.1 g of a yellow solid; yield 90.5%, HPLC content 97.4% (major isomer 70.5%, minor isomer 26.9%), melting point 61.1-65.0°C. The target compound is 1-[6-(2,4,6-trimethylbenzoyl)-11-(2-ethylhexyl)benzocarbazole-8-yl]-1-(2-fluorophenyl)methanone oxime, O-(2-methoxy-2-oxoacetate). 1 H-NMR (CD 3 Cl 3 , δ[ppm]) data: 0.77936-0.8112-0.8289 (t, 3H, CH 3 ), 0.8459-0.9318(m,3H,CH 3 ), 1.1488-1.4286(m,8H,4CH 2 ), 2.1982(s,6H,2ArCH 3 ),2.2480-2.3260(m,1H,CH),2.3818(s,3H,ArCH 3 ),3.88245 / 3.8597(s,3H,OCH 3 ), 4.6670-4.7989 (m, 2H, NCH 2), 6.9331 / 6.9465(s,2H,2ArH), 7.4414-7.5744(m,3H,3ArH),7.6911-7.7781(m,2H,2ArH),8.3353 / 8.3392(d,1H,ArH),8 .3647 / 8.3689-8.4219 / 8.4259(dd,1H,ArH),8.6251-8.6469(d,1H,ArH),9.4735-9.4943 / 9.5122-9.5160(d / d,1H,ArH).

[0182] Comparative compound A: 1-[9-(4-nitrophenyl)carbazole-3-yl]-1-octanone oxime, O-(2-methoxy-2-oxoacetic acid) ester

[0183] The preparation method is:

[0184] 10a. According to the method of Preparation Example 3 in Operation 3c, the product of Operation 3a was oximated to give a yellow solid powder with a yield of 69%, HPLC purity of 96.15% (major isomer 91.02%, minor isomer 5.13%), DSC melting point: 136 ° C; intermediate 1-[9-(4-nitrophenyl) carbazole-3-yl]-1-octanone oxime;

[0185] 10b. According to the method of operation 5d in Preparation Example 5, the product obtained in operation 10a was esterified to give a yellow glassy solid with a yield of 68% and a HPLC purity of 96.24% (major isomer 92.14%, minor isomer 4.1%); the target 1-[9-(4-nitrophenyl)carbazole-3-yl]-1-octanone oxime, O-(2-methoxy-2-oxoacetic acid) ester, 1 H-NMR (CD 3 Cl 3 , δ [ppm]) data: 0.8511-1.4537 (m, 13H, hexyl CH 3 +CH 2 ), 3.0315-3.0499-3.0664(t,2H,CH 2 ),

[0186] 3.9903(s,3H,OCH 3 ), 7.4216-7.4403(d); 7.4668-7.4849(d); 7.9977-8.0195(d); 8.3960-8.4145(d); the total of these four groups of integrals is 4H, 8.4791(s,1H,ArH), 9.0505(s,1H,ArH)).

[0187] Comparative compound B: 3-cyclohexyl-1-(4-phenylthiophenyl)-1,2-propanedione-2-oxime, O-(2-methoxy-2-oxoacetate)

[0188] The preparation method is:

[0189] 11a. In a 250 ml three-necked flask, 22 g (0.118 mol) of diphenyl sulfide and 100 g of o-dichlorobenzene (hereinafter referred to as DCB) were added, cooled to -10 ° C, 17.28 g (0.13 mol) of anhydrous aluminum chloride was added, stirred, 21.65 g (0.124 mol) of 3-cyclohexylpropionyl chloride was added dropwise within 30 min, and then stirred at 10 ° C for overnight reaction; the reaction solution was acidified and washed with water until neutral, and DCB was removed by vacuum rotary evaporation to obtain 37.98 g of a light yellow oil, with a yield of 99.1% and a HPLC purity of 98.56%. It solidified after cooling, and the DSC melting point was 38.1 ° C; the intermediate 3-cyclohexyl-1-(4-phenylthiophenyl)-1-propanone;

[0190] 11b. In a 100 ml three-necked flask, 20 g (0.062 mol) of the product obtained in operation 11a and 50 ml of DMSO were added dropwise, and 7.6 g (0.074 mol) of butyl nitrite and 2 ml of concentrated hydrochloric acid were added dropwise. The reaction was maintained at 35 °C for 5 h. The reaction solution was added to 200 ml of water and 80 ml of DCM and stirred for 30 min. The lower layer was separated and the upper aqueous phase was extracted once with 20 ml of DCM. The DCM solutions were combined, washed once with 20 ml of water, and then washed with 2 g of anhydrous MgSO 4 After drying for 4 hours, DCM was evaporated, and the residue (21 g) was dissolved in 15 ml of ethyl acetate and 25 ml of heptane at 50°C, cooled to precipitate crystals, and cooled to -15°C for 1 hour. The filter cake was filtered to obtain a dry weight of 18.5 g, a yield of 84.5%, a HPLC purity of 98.17%, and a DSC melting point of 116.1°C; the intermediate 3-cyclohexyl-1-(4-phenylthiophenyl)-1-acetone oxime was obtained;

[0191] 11c. In a 50 ml two-necked flask, 1.6 g (4.6 mmol) of the product obtained in operation 11b, 10 g of DCM, and 0.56 g (6.8 mmol) of 1-methylimidazole were placed at room temperature of 20°C, electromagnetic stirring was started, and 0.72 g (5.8 mmol) of monomethyl oxalyl chloride was added dropwise, and a white solid precipitated. The reaction was stirred for 1 h, and the solid was removed by vacuum extraction. The filtrate was washed with water twice and washed with anhydrous Na 2 SO 4After drying for 2 h, the desiccant was filtered off and the filtrate was evaporated to dryness. The residue was in a glassy state. The residual low-boiling substances were vacuum-evacuated and weighed 1.51 g. The yield was 74.7% and the HPLC purity was 98.02%. The target product was 3-cyclohexyl-1-(4-phenylthiophenyl)-1,2-propanedione-2-oxime, O-(2-methoxy-2-oxoacetic acid) ester. The product was placed in a room at 15-20°C away from light for 3 days and then analyzed and found to have been decomposed by 50%.

[0192] Comparative compound C: 1-(4-phenylthiophenyl)-1,2-(3-cyclohexylpropane)dione-2-oxime, O-acetate

[0193]

[0194] The preparation method is:

[0195] 12a. In a 100 ml three-necked flask, 2.5 g (0.071 mol) of the product obtained in operation 11b and 10 ml of DCM solvent were added dropwise, and the reaction was maintained at 40°C for 5 h. 20 ml of water was added to the reaction solution, stirred for 1 h, separated, and washed once with 10 ml of water. The organic phase was vacuum evaporated to dryness to obtain 2.53 g of an oily substance. 2 ml of ethyl acetate and 8 ml of heptane were added to the oily substance, cooled to -15°C, filtered to obtain precipitated crystals, which were dried to obtain 2.0 g, with a yield of 71.2%, HPLC purity of 98.81%, and DSC melting point of 52.9°C. The target compound was 1-(4-phenylthiophenyl)-1,2-(3-cyclohexylpropane)dione-2-oxime, O-acetate.

[0196] Thermal stability test

[0197] The thermodynamic data of the compounds obtained in Preparation Examples 1 to 9 and Comparative Compound A and Comparative Compound B were analyzed by differential scanning calorimetry. The analysis results are listed in Table 1, unit: °C.

[0198] Table 1

[0199]

[0200] As can be seen from Table 1, the thermal decomposition starting temperatures of the compounds obtained in Preparation Examples 1 to 9 are all above 100° C., which are significantly higher than those of Comparative Example Compounds A and B, indicating that the oxalic acid oxime ester compounds of the present invention exhibit better thermal stability.

[0201] Examples 1 to 4 Black Photoresist

[0202] 1. Preparation of alkali-soluble resin

[0203] 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.

[0204] 2. Preparation of black color paste

[0205] 50 g of the alkali-soluble resin prepared in step 1 above, 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.

[0206] The compounds obtained in Preparation Examples 3, 5, 7 and 8 were used as photoinitiators, mixed and dissolved in the solvent PMA according to the ratio in Table 2, and then mixed with the black color paste according to the ratio in Table 2. The dosage unit is gram. 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 365 nm surface light source was used, a quartz mask with 138 μm lines and a 41-step exposure ruler were used as masks, and a 1% Na 2 CO 3 The solution was developed at 25℃, and then washed with pure water for 10s. After drying in a 90℃ oven for 30min, the film retention order was observed, and the line width of the developed image was measured with an electron microscope and recorded. 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 formula sensitivity is.

[0207] Table 2

[0208] Photoinitiator Photoinitiator dosage / g Black color paste dosage / g Solvent PMA dosage / g Example 1 Preparation Example 3 Compound 0.08 2 4.5 Example 2 Preparation Example 5 Compound 0.08 2 4.5 Example 3 Preparation Example 7 Compound 0.08 2 4.5 Example 4 Preparation Example 8 Compound 0.08 2 4.5 Comparative Example 1 Comparative Compound A 0.08 2 4.5 Comparative Example 2 Comparative Compound B 0.08 2 4.5 Comparative Example 3 Comparative Compound C 0.08 2 4.5

[0209] The mixtures prepared in Examples 1 to 4 and Comparative Examples 1 to 3 in Table 2 were coated, cured, developed, and measured, and the data results are shown in Table 3.

[0210] Table 3

[0211] Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Development steps 25 22 22 24 No Image No Image 16 Developed line width / μm 154 152 152 153 No Image No Image 143

[0212] The results show that under the same dosage conditions, the compounds of Preparation Example 3, Preparation Example 5, Preparation Example 7 and Preparation Example 8 provided by the present invention are significantly better than the comparative compound C in terms of the number of film retention steps and the development line width after curing in the black system, while the comparative compounds A and B do not show exposure images due to thermal instability. Therefore, it is shown that the compound of general formula I of the present invention has the characteristic of high sensitivity.

[0213] Example 5 Transparent Photoresist

[0214] After mixing the components evenly according to the ratio in Table 4, a 50 μm wire rod was used to coat the film on a glass slide and a mercury lamp light source was used for curing. After curing, the film weight was measured and then soaked in acetone at room temperature for 36 h. The film weight was measured again to calculate the gel conversion rate.

[0215] Table 4

[0216]

[0217]

[0218] The results show that the photo-gel conversion rate of the transparent photoresist prepared in Example 5 using the compound obtained in Preparation Example 6 of the present invention as a photoinitiator is 96.0%, which is significantly higher than the photo-gel conversion rate (87.0%) of the transparent photoresist prepared in Comparative Example 4 using Comparative Compound C as a photoinitiator. This indicates that the transparent photoresist of the present invention can be used as an optical film, adhesive, sealing coating, etc.

[0219] In summary, the oxalic acid oxime ester compounds provided by the present invention have higher exposure sensitivity and lower yellowing than the existing commercially available oxime ester photoinitiators and comparative compounds A, B and C, and are suitable for photoresist formulations, especially for use in RGB color photoresists and transparent optical adhesive formulations.

[0220] 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 oxalate compound having a structure as shown in formula (I), In formula (I), R1 is selected from aroyl, nitro, trihalomethyl, sulfonic acid or trihalomethylsulfonyl, which is optionally substituted with one or more substituents selected from methyl, halogen, hydroxyl or amino; Ar1 is selected from the structures shown in Formula A-1 to Formula A-6: in, R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 are each independently selected from hydrogen, deuterium, F, Cl, cyano, nitro, C1-C4 alkyl, C1-C4 alkoxy, optionally, R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 The two adjacent carbon atoms in the ring together with the carbon atoms on the connected benzene ring form a five-membered, six-membered or seven-membered ring; In formula A-2, R7 and R8 are each independently selected from hydrogen, deuterium, substituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C3-C7 cycloalkyl, substituted or unsubstituted C3-C7 heterocyclic group, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C4-C20 heteroaryl; wherein the substituent in the C1-C8 alkyl is selected from one or more of F, Cl, phenyl, C3-C7 cycloalkyl, C3-C7 heterocyclic group, -OR4′, -COOR4′, -PO(OR4′)2 ; the substituents on the C3-C7 cycloalkyl and C3-C7 heterocyclic groups are selected from one or more of F, Cl, C1-C4 alkyl, C1-C4 alkoxy, -COCOOR4; the substituents in the C6-C20 aryl and C4-C20 heteroaryl groups are selected from one or more of halogen, NO2, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, -COOR4′, -COR5′; optionally, R7 and R8 together with the carbon atoms directly connected thereto form a 5-7 membered ring; In formula A-3 and formula A-4, R9 is selected from C1-C12 alkyl, -R4COOR4′, -R4CONR5R5′, C1-C8 alkyl substituted by one or more F atoms, Cl atoms, phenyl, C3-C7 cycloalkyl, C3-C7 heterocyclic group, -OR4′, -COOR4′, -C(═O)NR4R4′, -P(═O)(OR4′)2, C3-C7 cycloalkyl, C3-C7 heterocyclic group, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C4-C20 heteroaryl, and the substituents in the C6-C20 aryl and C4-C20 heteroaryl are selected from one or more of halogen, NO2, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, -SO2R4′, -COOR4′, -C(═O)R5′; In formula A-5, X1 is selected from a single bond, O, S, NR9, CR7R8, Y is selected from O, S, C=O and S=O, R7 and R8 are defined as in formula A-2, and R9 is defined as in formula A-3 and formula A-4; In formula A-6, X2 is selected from O, S, NR7 or CR7R8, R7 and R8 are defined as in formula A-2, Ar2 and Ar3 are each independently selected from a substituted or unsubstituted C6-C20 arylene group, a substituted or unsubstituted C4-C20 heteroarylene group, and the substituents in Ar2 and Ar3 are each independently selected from the group consisting of the following groups: deuterium, F, Cl, CN, NO2, C1-C4 alkyl, CF3, C1-C4 alkoxy, and optionally, two adjacent substituents and the atoms of the aryl or arylene group to which they are connected form a five-membered, six-membered or seven-membered ring; R2 is selected from hydrogen, deuterium, C1-C11 alkyl, C1-C4 alkyl substituted by one or more of phenyl, C3-C7 cycloalkyl, C3-C7 heterocyclyl, C1-C4 alkoxy, C1-C4 alkyl acyloxy, C1-C4 alkoxy acyl, C3-C10 alkyl inserted by one or more O atoms, C3-C7 cycloalkyl, C6-C20 aryl, C4-C20 heteroaryl, one or more of the following groups Substituted C6-C20 aryl or C4-C20 heteroaryl: C1-C4 alkyl, C3-C7 cycloalkyl, F, Cl, nitro, CN, C1-C4 alkoxy, C1-C4 alkylthio, C2-C10 alkoxy inserted by oxygen or sulfur or substituted by R5COO-, -R5CONR5′, C2-C10 alkylthio inserted by oxygen or sulfur or substituted by R5COO-, -R5CONR5′, -COCOOR4; Wherein, the C3-C7 cycloalkyl and C3-C7 heterocyclic group involved in R2 are unsubstituted or substituted by one or more F, Cl, C1-C4 alkyl, C1-C4 alkoxy, -COCOOR4; the hydrogen atoms on the carbon of the alkyl or alkoxy involved in R2 are substituted by one or more fluorine; R4 and R4′ 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, C1-C4 alkoxy, R5COO-, -R5CONR5′, C3-C8 alkyl substituted by one or more oxygen atoms or sulfur atoms; C3-C7 cycloalkyl, C3-C7 heterocyclic group, C6-C20 aryl, C4-C20 heteroaryl; R5 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, C1-C4 alkoxy, C3-C8 alkyl substituted by one or more oxygen atoms, sulfur atoms; C3-C7 cycloalkyl, C3-C7 heterocyclyl, C6-C20 aryl, C4-C20 heteroaryl; Optionally, the heterocycle, C6-C20 aryl, C4-C20 heteroaryl referred to by R4, R4′, R5 and R5′ have the following side chain substituents: C1-C4 alkyl, C1-C4 alkyl substituted by one or more F atoms, phenyl, C3-C7 cycloalkyl, C3-C7 heterocyclic group, C1-C4 alkoxy, R6COO-, -R6CONR6′, C3-C7 cycloalkyl, substituted or unsubstituted phenyl, R6CO-, R6COCO-, R6SO2-; wherein R6 is selected from C1-C12 alkyl, C1-C4 alkyl substituted by one or more F, Cl, phenyl, thienyl, phenyl or thienyl substituted by one or more methyl, F, Cl, nitro; R6′ is selected from hydrogen, C1-C4 alkyl; R3 is selected from C1-C12 alkyl, C1-C4 alkyl substituted by C3-C7 cycloalkyl, C6-C12 aryl; n is selected from 0 or 1.

2. The compound according to claim 1, characterized in that In formula (I): R1 is selected from benzoyl, nitro, trifluoromethyl, sulfonic acid, trifluoromethylsulfonyl substituted by three substituents selected from methyl, -F, hydroxyl or amino, preferably trimethylbenzoyl, nitro and trifluoromethyl; R2 is selected from C1-C8 alkyl, cyclopentylmethyl, cyclohexylmethyl, tetrahydrofuranylmethyl, phenyl, selected from C1-C4 alkyl, C1-C4 fluoroalkyl, F, nitro, CN, C1-C4 alkoxy, C1-C4 fluoroalkoxy, C1-C4 alkylthio, C2-C8 alkoxy inserted by oxygen or sulfur or substituted by R5COO-, -R5CONR5′, CONR5′ substituted C2-C8 alkylthio, -COCOOR4 substituted C6-C12 aryl; preferably, R2 is selected from methyl, ethyl, propyl, n-butyl, pentyl, hexyl, n-heptane, isooctane, cyclohexyl, cyclopentyl, cyclopentylmethyl, cyclohexylmethyl, cyclohexylethyl, thienylmethyl, phenyl, benzyl, phenyl substituted with fluorine, methyl, methoxy, tetrafluoropropoxy, CH3OCH2CH(CH3)O-; R4, R4' are each independently selected from C1-C4 alkyl, C3-C7 cycloalkyl, C3-C7 heterocyclyl, benzyl, 4-methylbenzyl, C1-C3 alkyl substituted by a C3-C7 cycloalkyl or C3-C7 heterocyclyl, C2-C4 alkyl substituted by a C1-C4 alkoxy or R5COO-, C3-C8 alkyl intercalated by one or more oxygen atoms or sulfur atoms, C6-C12 aryl, C4-C12 heteroaryl; R5, 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 heterocyclyl, C1-C4 alkoxy, C3-C7 cycloalkyl, C3-C7 heterocyclyl, C6-C12 aryl, C4-C12 heteroaryl; Optionally, the heterocycle, C6-C12 aryl, and C4-C12 heteroaryl involved by R4, R4′, R5, and R5′ have the following side chain substituents: C1-C4 alkyl, C1-C4 alkyl substituted with one or more F atoms, phenyl, C3-C7 cycloalkyl, C3-C7 heterocyclic group, C1-C4 alkoxy, R6COO-, -R6CONR6′, C3-C7 cycloalkyl, unsubstituted phenyl or substituted phenyl, R6CO-, R6COCO-, R6SO2-; wherein R6 is selected from C1-C4 alkyl, CF3, phenyl, thienyl, phenyl or thienyl substituted with one or more methyl, F, nitro groups; R6′ is selected from hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, and tert-butyl; R3 is selected from C1-C4 alkyl, C1-C4 alkyl substituted by C5-C7 cycloalkyl, C6-C10 aryl, preferably methyl, ethyl, cyclohexylmethyl, 2-cyclohexylethyl, phenyl.

3. The compound according to claim 1 or 2, characterized in that In formula (I), Ar1 is selected from the structure shown in formula A-1, A-2, A-3, A-4 or A-6, wherein, In formula A-2, R7 and R8 are each independently selected from a hydrogen atom, a C1-C4 alkyl group, preferably hydrogen, methyl, ethyl, n-propyl and n-butyl; optionally, R7 and R8 together with the carbon atom to which they are directly connected form a cyclopentyl ring or a cyclohexyl ring; In formula A-3 and formula A-4, R9 is selected from C1-C8 alkyl, -R4COOR4′, -R4CONR5R5′, C1-C8 alkyl substituted with one or more F, phenyl, C5-C6 cycloalkyl, C4-C6 heterocyclic group, -OR4′, -COOR4′, -P(═O)(OR4′)2, C5-C6 cycloalkyl, phenyl, thienyl, phenyl or thienyl substituted with one or more of the following groups: F, NO2, C1-C4 alkyl, C1-C4 alkoxy, -SO2R4′, -COOR4′, -C(═O)R5′; wherein R4, R4′, R5 and R5′ are each independently selected from C1-C8 alkyl, C3-C7 cycloalkyl, C3-C7 heterocyclyl, C6-C12 aryl, C4-C12 heteroaryl; preferably, R9 is selected from methyl, ethyl, n-propyl, n-butyl, 2-ethylhexyl, or the following groups: In formula A-6, X2 is selected from O or S; Ar2 and Ar3 are each independently selected from substituted or unsubstituted C6-C12 arylene groups, substituted or unsubstituted C5-C12 heteroarylene groups, preferably, Ar2 and Ar3 are each independently selected from substituted or unsubstituted phenylene groups, substituted or unsubstituted thienylene groups, substituted or unsubstituted naphthylene groups, substituted or unsubstituted anthrylene groups, and the substituents in Ar2 and Ar3 are each independently selected from one or more of the following groups: F, CN, NO2, CF3, C1-C4 alkyl groups, C1-C4 alkoxy groups; R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 Each is independently selected from hydrogen, F, C1-C4 alkyl; preferably hydrogen, F, methyl and ethyl.

4. The compound according to any one of claims 1 to 3, characterized in that The compounds have structures shown in formula (I-1) to formula (I-5): Among them, each R Ar The same or different ones are selected from H, F, CN, NO2, CF3, C1-C4 alkyl, C1-C4 alkoxy; R1, R2, R3, R9 are defined the same as in formula (I).

5. The compound according to any one of claims 1 to 4, which is selected from the compounds shown in numbers 1 to 57:

6. The compound according to any one of claims 1 to 5, characterized in that The preparation of the compound comprises the following steps: (1): subjecting the raw material R1-Ar1H to a Friedel-Crafts acylation reaction with an acyl chloride compound R2CH2COCl or an acid anhydride to obtain an intermediate M1; or The raw material R1-Ar1H is subjected to Friedel-Crafts acylation reaction with an acyl chloride compound R2COCl or an acid anhydride to obtain an intermediate M1′; (2): reacting the intermediate M1 obtained in step (1) with a nitrite or nitrous acid under acidic conditions to obtain a nitro intermediate M2, or The intermediate M1′ obtained in step (1) is reacted with hydroxylamine hydrochloride under neutral or alkaline conditions to obtain the intermediate M2′; (3): reacting the intermediate M2 obtained in step (2) with R3OOCCOCl to obtain a compound of formula II; or, The intermediate M2′ obtained in step (2) is reacted with R3OOCCOCl to obtain a compound of formula III; Wherein, Ar1, R1, R2, and R3 are defined the same as in formula (I).

7. The compound according to claim 6, characterized in that When R1 is nitro, the preparation method of the compound comprises the following steps: S1: The raw material H-Ar1H is subjected to Friedel-Crafts acylation reaction with the acyl chloride compound R2CH2COCl or anhydride to obtain the intermediate M 1A ; Alternatively, the raw material H-Ar1H is subjected to Friedel-Crafts acylation reaction with an acyl chloride compound R2COCl or an acid anhydride to obtain an intermediate M 1A ′; S2: The intermediate M obtained in step S1 1A or M 1A ′ reacts with a nitrating agent to obtain a nitro intermediate M1 or M1′; S3: reacting the intermediate M1 obtained in step S2 with a nitrite or nitrous acid under acidic conditions to obtain an intermediate M2, or, reacting the intermediate M1′ obtained in step S2 with hydroxylamine hydrochloride under neutral or alkaline conditions to obtain the intermediate M2′; S4: reacting the intermediate M2 obtained in step S3 with R3OOCCOCl to obtain a compound of formula II; or, The intermediate M2′ obtained in step S3 is reacted with R3OOCCOCl to obtain a compound of formula III; Wherein, R1 is nitro, and Ar1, R2, and R3 are defined the same as in formula (I).

8. A photocurable composition comprising a photoinitiator and at least one free radical polymerizable compound, wherein the photoinitiator comprises the oxime oxalate 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 oxalate 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 oxalate 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, aromatic hydrocarbon solvents and halogenated alkane solvents, preferably propylene glycol monomethyl ether acetate, ethylene glycol methyl ether acetate, toluene, xylene, tetrachloroethane; Optionally, the photoinitiator further includes one or more of 2,2-dimethoxy-2-phenylacetophenone, 2-dimethylamino-2-benzyl-1-(4-morpholinylphenyl)-1-butanone, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinylphenyl)-1-butanone, 2-dimethylamino-2-benzyl-1-(4-piperidinylphenyl)-1-butanone, 2,4,6-trimethylbenzoylbenzene-diphenylphosphine oxide, di(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, and bis(2,6-difluoro-3-pyrrolophenyl)titanocene; Optionally, the photoresist raw material also contains a pigment; preferably, the pigment is a red pigment, a green pigment, a blue pigment or a black pigment; more preferably, the red pigment includes CI Pigment Red 177, the green pigment includes CI Pigment Green 7, the blue pigment includes CI Pigment Blue 15:6 and Solvent Blue 25, and the black pigment includes carbon black, titanium black and CI Pigment Black 1.

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 oxalate 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 oxalate 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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