Modified oxime ester compound and preparation method thereof, and photocurable composition

Abstract

The present invention provides a modified oxime ester compound and a preparation method thereof, and a photocurable composition. The modified oxime ester compound has any one or more of the following general formulas I, II, III, and IV: The modified oxime ester compound of the present application has a large conjugated structure, and the amount of small molecular fragments generated by the oxime ester bond breaking under ultraviolet light irradiation is greatly reduced, thereby greatly reducing the probability of failure of the light-emitting device, and due to R 1 The substituent is an aromatic or heteroaryl substituent, so that it can be cured at a lower temperature, thereby better exerting the performance of the photoinitiator in accelerating the curing rate of ink and the like and improving the photosensitivity efficiency of the photoinitiator. At the same time, since the absorption wavelength of the modified oxime ester compound of the present application is further red-shifted, it can be cured at a longer ultraviolet wavelength.

Description

Technical Field

[0001] The invention relates to the technical field of oxime ester photoinitiator synthesis, and in particular to a modified oxime ester compound and a preparation method thereof, and a photocurable composition. Background Art

[0002] As effective free radical photoinitiators, oxime ester compounds have long been used in free radical photopolymerization due to their superior photoreactivity. After the NO bond of the oxime ester is broken, the acyloxy group may undergo a decarboxylation reaction to produce carbon dioxide, which solves the problem of inhibition of the photopolymerization process caused by oxygen in the air. Oxime ester initiators are widely used. They can be used not only in ordinary photocuring fields such as coatings and inks, but also in the preparation of various photoresists. They can also be used in high-end application fields such as guided isomerized films, photospacers, rib walls, nanoimprint materials, quantum dots, and OLEDs. However, on the one hand, when oxime ester initiators are irradiated with ultraviolet light, the oxime ester bond will break and produce small molecular fragments (outgas). If these small molecular fragments are not released, they are easy to stay in the reaction system, which will cause light-emitting equipment failure in some applications. On the other hand, based on the photolithography process, the photosensitive resin composition is selectively exposed and developed to form the desired photocured pattern. Conventional negative photoresist compositions require a post-curing temperature of 230°C or higher. However, the properties of existing oxime ester photoinitiators under low-temperature curing still need to be further improved. Therefore, there is an urgent need to find a photoinitiator that can be cured at low temperatures. Summary of the invention

[0003] The main purpose of the present invention is to provide a modified oxime ester compound and a preparation method thereof, and a photocurable composition, so as to solve the problem that the oxime ester photoinitiator in the prior art is difficult to take into account a small amount of small molecule fragments and low temperature curing.

[0004] In order to achieve the above object, according to one aspect of the present invention, a modified oxime ester compound is provided, and the modified oxime ester compound has any one or more of the following general formula I, general formula II, general formula III, and general formula IV:

[0005]

[0006]

[0007] R 1 For-R 11 or-COR 11 ; R 11 is selected from substituted or unsubstituted C 6 ~C 20 Aryl, substituted or unsubstituted C 3 ~C 20 Any one of the heteroaryl groups; R 2is selected from substituted or unsubstituted C 1 ~C 20 Alkyl, substituted or unsubstituted C 3 ~C 20 Cycloalkyl, substituted or unsubstituted C 6 ~C 20 Aryl, substituted or unsubstituted C 4 ~C 20 Heteroaryl, substituted or unsubstituted C 3 ~C 20 any one of the heterocycloalkyl groups; m is any integer from 0 to 2; A is empty, a single bond or C 1 ~C 5 An alkylene group; B is selected from -CR 12 R 13 -、-R 13 Any one of N-, -O-, -S-, where R 12 , R 13 are each independently selected from hydrogen, substituted or unsubstituted C 1 ~C 20 Straight chain alkyl, substituted or unsubstituted C 3 ~C 20 Branched alkyl, substituted or unsubstituted C 2 ~C 20 Straight chain olefins, substituted or unsubstituted C 4 ~C 20 Branched olefins, substituted or unsubstituted C 3 ~C 20 Cycloalkyl, substituted or unsubstituted C 4 ~C 20 Cycloalkylalkyl, substituted or unsubstituted C 4 ~C 20 Any one of the alkylcycloalkyl groups; Z is selected from -O-, -CH 2 - or a single key.

[0008] Furthermore, the above R 11 is selected from substituted or unsubstituted C 6 ~C 10 Aryl, substituted or unsubstituted C 3 ~C 10 Any one of the heteroaryl groups; preferably R 11 is selected from any one of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted thiazolyl, substituted or unsubstituted thienyl; preferably R 11 Any one selected from phenyl, 4-methoxyphenyl, 4-nitrophenyl, 6-methoxy-2-naphthyl, 2-thiazolyl, 2-thienyl; further, preferably R 1Any one selected from the group consisting of phenyl, 4-methoxyphenyl, 4-nitrophenyl, 6-methoxy-2-naphthyl, 2-thiazolyl, 2-thienyl and benzoyl.

[0009] Furthermore, the above R 2 In, substituted C 1 ~C 20 The substituents in the alkyl group are selected from C 3 ~C 12 Any one of cycloalkyl, halogen, cyano, and nitro; preferably substituted C 1 ~C 20 The substituents in the alkyl group are selected from C 3 ~C 6 Any of the cycloalkyl groups; preferably substituted C 1 ~C 20 The substituent in the alkyl group is cyclohexyl; preferably substituted C 1 ~C 20 Any one or more -CH 2 - is substituted by O- or -S-; preferably substituted by C 6 ~C 20 The substituents in the aryl group are selected from C 1 ~C 6 Alkyl, C 1 ~C 10 Alkoxy, C 1 ~C 10 Alkylthio, C 1 ~C 8 Acyl, C 1 ~C 8 The acyloxy group, C 1 ~C 8 Any one of oxyacyl, halogen, cyano, and nitro; preferably substituted C 6 ~C 20 The substituents in the aryl group are selected from C 1 ~C 3 Alkyl, C 1 ~C 6 Alkoxy, C 1 ~C 6 Alkylthio, C 1 ~C 4 Acyl, C 1 ~C 4 The acyloxy group, C 1 ~C 4 Any of the oxygen acyl groups; preferably substituted C 6 ~C 20The substituents in the aryl group are selected from any one of methyl, ethyl, propyl, methoxy, ethoxy, propoxy, methylthio, ethylthio, propylthio, formyl, acetyl, propionyl, formyloxy, acetoxy, propionyloxy, oxyformyl, oxyacetyl, and oxypropionyl; preferably substituted C 4 ~C 20 The substituents in the heteroaryl group are selected from C 1 ~C 8 A straight chain alkyl or C 3 ~C 8 Any one of the branched alkyl groups; preferably substituted C 4 ~C 20 The substituents in the heteroaryl group are selected from C 1 ~C 4 A straight chain alkyl or C 3 ~C 6 Any one of the branched alkyl groups; preferably substituted C 4 ~C 20 The substituents in the heteroaryl are selected from any one of methyl, ethyl, propyl, butyl, isopropyl, isobutyl and isopentyl; preferably substituted C 3 ~C 20 The substituents in the heterocycloalkyl group are selected from C 1 ~C 6 Straight chain alkyl, C 3 ~C 6 Any one of the branched alkyl groups; preferably substituted C 3 ~C 20 The substituents in the heterocycloalkyl are selected from any one of methyl, ethyl, propyl, butyl, isopropyl, isobutyl and isopentyl; preferably substituted C 3 ~C 20 The substituents in the cycloalkyl group are selected from C 1 ~C 10 Straight chain alkyl, C 3 ~C 10 Any one of the branched alkyl groups; preferably substituted C 3 ~C 20 The substituents in the cycloalkyl group are selected from C 1 ~C 6 Straight chain alkyl, C 3 ~C 6 Any one of the branched alkyl groups; preferably substituted C 3 ~C 20 The substituents in the cycloalkyl group are selected from any one of methyl, ethyl, propyl, butyl, isopropyl, isobutyl and isopentyl.

[0010] Furthermore, the above R 2 is selected from substituted or unsubstituted C 1 ~C10 Alkyl, substituted or unsubstituted C 3 ~C 12 Cycloalkyl, substituted or unsubstituted C 6 ~C 10 Aryl, substituted or unsubstituted C 4 ~C 10 Heteroaryl, substituted or unsubstituted C 3 ~C 10 Any one of the heterocycloalkyl groups; preferably R 2 is selected from substituted or unsubstituted C 1 ~C 6 A straight chain alkyl or substituted or unsubstituted C 3 ~C 6 Branched alkyl, substituted or unsubstituted C 3 ~C 6 cycloalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted C 4 ~C 6 Heteroaryl, substituted or unsubstituted C 3 ~C 6 Any one of the heterocycloalkyl groups; preferably R 2 Any one selected from methyl, ethyl, cyclohexylethyl, propyl, butyl, isopropyl, isobutyl, isopentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, tolyl, trimethylphenyl, thienyl; further, preferably R 2 Any one selected from the group consisting of methyl, ethyl, cyclohexylethyl, cyclopropyl, cyclohexyl, phenyl, 2-methylphenyl, 2,4,6-trimethylphenyl and 2-thienyl.

[0011] Furthermore, the above R 12 , R 13 are each independently selected from substituted or unsubstituted C 1 ~C 10 Straight chain alkyl, substituted or unsubstituted C 3 ~C 10 Branched alkyl, substituted or unsubstituted C 2 ~C 10 Straight chain olefins, substituted or unsubstituted C 4 ~C 10 Branched olefins, substituted or unsubstituted C 3 ~C 10 Cycloalkyl, substituted or unsubstituted C 4 ~C 10 Cycloalkylalkyl, substituted or unsubstituted C 4 ~C 10 Any one of the alkylcycloalkyl groups; preferably R 12 , R 13are each independently selected from substituted or unsubstituted C 1 ~C 8 Straight chain alkyl, substituted or unsubstituted C 3 ~C 6 Branched alkyl, substituted or unsubstituted C 2 ~C 6 Straight chain olefins, substituted or unsubstituted C 4 ~C 8 Branched olefins, substituted or unsubstituted C 3 ~C 6 Cycloalkyl, substituted or unsubstituted C 4 ~C 6 Cycloalkylalkyl, substituted or unsubstituted C 4 ~C 6 Any one of the alkylcycloalkyl groups; preferably R 12 , R 13 Each is independently selected from any one of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, isopropyl, isobutyl, isopentyl, ethylene, propenyl, isopropenyl, isobutenyl, cyclopropyl, cyclobutanyl, cyclopentanyl, cyclohexanyl, cyclopropylmethyl, cyclopropylethyl, methylcyclopropyl, ethylcyclopropyl, and ethylcyclobutyl; preferably R 12 , R 13 Each is independently selected from any one of methyl, ethyl, butyl and octyl; further, preferably B is selected from -CH 2 -、-C((CH 2 ) 3 CH 3 ) 2 -、-NCH 3 -、-N(CH 2 ) 7 CH 3 -、-NCH 2 CH 3 Any one of -, -O-, and -S-.

[0012] Furthermore, the structural formula of the modified oxime ester compound is

[0013]

[0014] Any one of .

[0015] According to another aspect of the present invention, a method for preparing the aforementioned modified oxime ester compound is provided, the method comprising: step S1, subjecting compound 1 to a Suzuki coupling reaction or a Friedel-Crafts acylation reaction to obtain compound 2; step S2, subjecting compound 2 to an oximation reaction with compound 3 to generate an oxime compound; step S3, subjecting the oxime compound to an acylation agent to an esterification reaction to obtain a modified oxime ester compound; wherein compound 3 is selected from any one of nitrous acid, alkyl nitrite, and hydroxylamine hydrochloride, and compound 1 has any one of structural formula I, structural formula II, structural formula III, and structural formula IV:

[0016]

[0017] Compound 2 has structural formula V or structural formula VI:

[0018]

[0019] The oxime compound has any one of structural formula VII, structural formula VIII, structural formula IX, and structural formula X:

[0020]

[0021] A, B, Z, R 1 , m are the same as A, B, Z, R mentioned above 1 , m, X is a bromine or chlorine atom.

[0022] Furthermore, in the above step S1, when compound 1 has structural formula I or structural formula II, compound 1 undergoes Suzuki coupling reaction to obtain compound 2; when compound 1 has structural formula III or structural formula IV, compound 1 undergoes Friedel-Crafts acylation reaction to obtain compound 2.

[0023] Furthermore, the alkyl nitrite is selected from any one or more of methyl nitrite, ethyl nitrite, isopropyl nitrite, butyl nitrite and isoamyl nitrite.

[0024] Furthermore, in the above step S3, the temperature of the esterification reaction is -10 to 60°C, preferably 0 to 25°C, and the time of the esterification reaction is 1 to 5 hours; the acylating agent is selected from substituted or unsubstituted C 1 ~C 15 Alkanoyl chloride, substituted or unsubstituted C 6 ~C 20 Aroyl chloride, substituted or unsubstituted C 4 ~C 20 Heteroaroyl chloride, substituted or unsubstituted C 4 ~C 40 Any one of the anhydrides of; preferably the acylating agent is selected from substituted or unsubstituted C 1 ~C6 Alkanoyl chloride, substituted or unsubstituted C 6 ~C 12 Aroyl chloride, substituted or unsubstituted C 4 ~C 10 Any one of the heteroaromatic acid chlorides; preferably substituted or unsubstituted C 1 ~C 6 The alkanoyl chloride is selected from substituted or unsubstituted formyl chloride, substituted or unsubstituted acetyl chloride, substituted or unsubstituted propionyl chloride, substituted or unsubstituted butyryl chloride, substituted or unsubstituted valeryl chloride, substituted or unsubstituted hexanoyl chloride; preferably, the substituted or unsubstituted formyl chloride is selected from any one of ethylformyl chloride, propylformyl chloride and cyclohexanecarbonyl chloride; preferably, the substituted or unsubstituted acetyl chloride is selected from methoxyacetyl chloride, ethoxyacetyl chloride, butoxyacetyl chloride, (2-butoxyethoxy)acetyl chloride, phenoxyacetyl chloride, chlorophenoxyacetyl chloride, nitrophenoxyacetyl chloride, phenylacetyl chloride, chlorophenylacetyl chloride, nitrophenylacetyl chloride, thiophene-2- -acetyl chloride; preferably substituted or unsubstituted propionyl chloride is selected from any one of 3-chloropropionyl chloride, 3-(methylthio)propionyl chloride, phenoxypropionyl chloride, and phenylpropionyl chloride; preferably substituted or unsubstituted butyryl chloride is selected from any one of 4-phenylbutyryl chloride, 2-methylphenylbutyryl chloride, and phenoxybutyryl chloride; preferably substituted or unsubstituted valeryl chloride is selected from any one of 2-propylvaleryl chloride, 5-chlorovaleryl chloride, and 3-chloropivaloyl chloride; preferably substituted or unsubstituted hexanoyl chloride is selected from any one of 3,5,5-trimethylhexanoyl chloride, 6-bromohexanoyl chloride, and 6-phenylhexanoyl chloride; preferably substituted or unsubstituted C 6 ~C 12 The aromatic acid chloride is selected from any one of benzoyl chloride, 3,5-dimethylbenzoyl chloride, 4-methoxybenzoyl chloride, 4-cyanobenzoyl chloride, 4-nitrobenzoyl chloride, 4-phenylbenzoyl chloride, chlorobenzoyl chloride, naphthoyl chloride, 2-ethoxy-1-naphthoyl chloride and anthracene chloride; preferably substituted or unsubstituted C 4 ~C 10 The heteroaromatic acid chloride is selected from any one of 2-thenoyl chloride, 2-furoyl chloride, quinoline chloride and chloronicotinoyl chloride; preferably substituted or unsubstituted C 4 ~C 40 The acid anhydride is selected from any one of acetic anhydride, 4-methoxyphenylacetic anhydride, propionic anhydride, isobutyric anhydride, tert-valeric anhydride, capric anhydride and stearic anhydride.

[0025] According to another aspect of the present invention, a photocurable composition is provided. The photocurable composition includes a photoinitiator, and the photoinitiator is the aforementioned modified oxime ester compound.

[0026] Furthermore, the photocurable composition is any one of a coating, an ink, and an adhesive.

[0027] By using the technical solution of the present invention, the oxime ester compound is used as a free radical photoinitiator to improve the photoreactivity of the effective molecules of the photoinitiator, thereby greatly promoting the efficiency of the photoinitiated polymerization reaction. The modified oxime ester compound of the present application has a large conjugated structure. Therefore, the photocurable composition including the modified oxime ester compound of the present application has a greatly reduced amount of small molecular fragments generated by the cleavage of the oxime ester bond under ultraviolet light irradiation while retaining the original good polymerization inhibition performance, thereby greatly reducing the probability of failure of the light-emitting device, and due to R 1 The substituent is an aromatic or heteroaryl substituent, so that it can be cured at a lower temperature, thereby better exerting the performance of the photoinitiator in accelerating the curing rate of ink and the like and improving the photosensitivity efficiency of the photoinitiator. At the same time, since the absorption wavelength of the modified oxime ester compound of the present application is further red-shifted, it can be cured at a longer ultraviolet wavelength, such as under a 365nm ultraviolet light source, further expanding the application of oxime ester photoinitiators. DETAILED DESCRIPTION

[0028] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present invention will be described in detail below in conjunction with the embodiments.

[0029] As analyzed in the background technology, the oxime ester photoinitiators in the prior art have the problem of difficulty in taking into account both a small amount of small molecule fragments and low-temperature curing. To solve this problem, the present invention provides a modified oxime ester compound and a preparation method thereof, and a photocurable composition.

[0030] In a typical embodiment of the present application, a modified oxime ester compound is provided, and the modified oxime ester compound has any one or more of the following general formula I, general formula II, general formula III, and general formula IV:

[0031]

[0032] R 1 For-R 11 or-COR 11 ; R 11 is selected from substituted or unsubstituted C 6 ~C 20 Aryl, substituted or unsubstituted C 3 ~C 20 Any one of the heteroaryl groups; R 2 is selected from substituted or unsubstituted C 1 ~C 20 Alkyl, substituted or unsubstituted C 3 ~C 20 Cycloalkyl, substituted or unsubstituted C 6 ~C20 Aryl, substituted or unsubstituted C 4 ~C 20 Heteroaryl, substituted or unsubstituted C 3 ~C 20 any one of the heterocycloalkyl groups; m is any integer from 0 to 2; A is empty, a single bond or C 1 ~C 5 An alkylene group; B is selected from -CR 12 R 13 -、-R 13 Any one of N-, -O-, -S-, where R 12 , R 13 are each independently selected from hydrogen, substituted or unsubstituted C 1 ~C 20 Straight chain alkyl, substituted or unsubstituted C 3 ~C 20 Branched alkyl, substituted or unsubstituted C 2 ~C 20 Straight chain olefins, substituted or unsubstituted C 4 ~C 20 Branched olefins, substituted or unsubstituted C 3 ~C 20 Cycloalkyl, substituted or unsubstituted C 4 ~C 20 Cycloalkylalkyl, substituted or unsubstituted C 4 ~C 20 Any one of the alkylcycloalkyl groups; Z is selected from -O-, -CH 2 - or a single key.

[0033] Oxime ester compounds, as free radical photoinitiators, can improve the photoreactivity of effective molecules of photoinitiators, thereby greatly promoting the efficiency of photoinitiated polymerization reactions. The modified oxime ester compounds of the present application have a large conjugated structure, so the photocurable composition including the modified oxime ester compounds of the present application, while retaining the original good polymerization inhibition performance, greatly reduces the amount of small molecular fragments generated by the oxime ester bond breakage under ultraviolet light irradiation, thereby greatly reducing the probability of light-emitting device failure, and due to R 1 The substituent is an aromatic or heteroaryl substituent, so that it can be cured at a lower temperature, thereby better exerting the performance of the photoinitiator in accelerating the curing rate of ink and the like and improving the photosensitivity efficiency of the photoinitiator. At the same time, since the absorption wavelength of the modified oxime ester compound of the present application is further red-shifted, it can be cured at a longer ultraviolet wavelength, such as under a 365nm ultraviolet light source, further expanding the application of oxime ester photoinitiators.

[0034] In one embodiment of the present application, the above R11 is selected from substituted or unsubstituted C 6 ~C 10 Aryl, substituted or unsubstituted C 3 ~C 10 Any one of the heteroaryl groups; preferably R 11 is selected from any one of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted thiazolyl, substituted or unsubstituted thienyl; preferably R 11 Any one selected from phenyl, 4-methoxyphenyl, 4-nitrophenyl, 6-methoxy-2-naphthyl, 2-thiazolyl, 2-thienyl; further, preferably R 1 Any one selected from the group consisting of phenyl, 4-methoxyphenyl, 4-nitrophenyl, 6-methoxy-2-naphthyl, 2-thiazolyl, 2-thienyl and benzoyl.

[0035] The above R 1 The substituent has a conjugated effect with the benzene ring directly connected to it. 1 The substituent is beneficial to improving the stability of the modified oxime ester compounds.

[0036] The modified oxime ester compounds are effective free radical photoinitiators. After the NO bond is broken, the acyl group undergoes a decarboxylation reaction to produce carbon dioxide, which is helpful to alleviate the inhibition problem of the photopolymerization process caused by oxygen in the air. The above R 2 The substituted C 1 ~C 20 The substituents in the alkyl group are selected from C 3 ~C 12 Any one of cycloalkyl, halogen, cyano, and nitro; preferably substituted C 1 ~C 20 The substituents in the alkyl group are selected from C 3 ~C 6 Any of the cycloalkyl groups; preferably substituted C 1 ~C 20 The substituent in the alkyl group is cyclohexyl; preferably substituted C 1 ~C 20 Any one or more -CH 2 - is substituted by O- or -S-; preferably substituted by C 6 ~C 20 The substituents in the aryl group are selected from C 1 ~C 6 Alkyl, C 1 ~C 10 Alkoxy, C 1 ~C 10 Alkylthio, C 1 ~C 8 Acyl, C1 ~C 8 The acyloxy group, C 1 ~C 8 Any one of oxyacyl, halogen, cyano, and nitro; preferably substituted C 6 ~C 20 The substituents in the aryl group are selected from C 1 ~C 3 Alkyl, C 1 ~C 6 Alkoxy, C 1 ~C 6 Alkylthio, C 1 ~C 4 Acyl, C 1 ~C 4 The acyloxy group, C 1 ~C 4 Any of the oxygen acyl groups; preferably substituted C 6 ~C 20 The substituents in the aryl group are selected from any one of methyl, ethyl, propyl, methoxy, ethoxy, propoxy, methylthio, ethylthio, propylthio, formyl, acetyl, propionyl, formyloxy, acetoxy, propionyloxy, oxyformyl, oxyacetyl, and oxypropionyl; preferably substituted C 4 ~C 20 The substituents in the heteroaryl group are selected from C 1 ~C 8 A straight chain alkyl or C 3 ~C 8 Any one of the branched alkyl groups; preferably substituted C 4 ~C 20 The substituents in the heteroaryl group are selected from C 1 ~C 4 A straight chain alkyl or C 3 ~C 6 Any one of the branched alkyl groups; preferably substituted C 4 ~C 20 The substituents in the heteroaryl are selected from any one of methyl, ethyl, propyl, butyl, isopropyl, isobutyl and isopentyl; preferably substituted C 3 ~C 20 The substituents in the heterocycloalkyl group are selected from C 1 ~C 6 Straight chain alkyl, C 3 ~C 6 Any one of the branched alkyl groups; preferably substituted C 3 ~C 20 The substituents in the heterocycloalkyl are selected from any one of methyl, ethyl, propyl, butyl, isopropyl, isobutyl and isopentyl; preferably substituted C 3 ~C20 The substituents in the cycloalkyl group are selected from C 1 ~C 10 Straight chain alkyl, C 3 ~C 10 Any one of the branched alkyl groups; preferably substituted C 3 ~C 20 The substituents in the cycloalkyl group are selected from C 1 ~C 6 Straight chain alkyl, C 3 ~C 6 Any one of the branched alkyl groups; preferably substituted C 3 ~C 20 The substituents in the cycloalkyl group are selected from any one of methyl, ethyl, propyl, butyl, isopropyl, isobutyl and isopentyl.

[0037] In one embodiment of the present application, the above R 2 is selected from substituted or unsubstituted C 1 ~C 10 Alkyl, substituted or unsubstituted C 3 ~C 12 Cycloalkyl, substituted or unsubstituted C 6 ~C 10 Aryl, substituted or unsubstituted C 4 ~C 10 Heteroaryl, substituted or unsubstituted C 3 ~C 10 Any one of the heterocycloalkyl groups; preferably R 2 is selected from substituted or unsubstituted C 1 ~C 6 A straight chain alkyl or substituted or unsubstituted C 3 ~C 6 Branched alkyl, substituted or unsubstituted C 3 ~C 6 cycloalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted C 4 ~C 6 Heteroaryl, substituted or unsubstituted C 3 ~C 6 Any one of the heterocycloalkyl groups; preferably R 2 Any one selected from methyl, ethyl, cyclohexylethyl, propyl, butyl, isopropyl, isobutyl, isopentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, tolyl, trimethylphenyl, thienyl; further, preferably R 2 Any one selected from the group consisting of methyl, ethyl, cyclohexylethyl, cyclopropyl, cyclohexyl, phenyl, 2-methylphenyl, 2,4,6-trimethylphenyl and 2-thienyl.

[0038] Preferably, the above R2 This is beneficial to further alleviate the inhibition problem of the photopolymerization process caused by oxygen in the air.

[0039] In one embodiment of the present application, the above R 12 , R 13 are each independently selected from substituted or unsubstituted C 1 ~C 10 Straight chain alkyl, substituted or unsubstituted C 3 ~C 10 Branched alkyl, substituted or unsubstituted C 2 ~C 10 Straight chain olefins, substituted or unsubstituted C 4 ~C 10 Branched olefins, substituted or unsubstituted C 3 ~C 10 Cycloalkyl, substituted or unsubstituted C 4 ~C 10 Cycloalkylalkyl, substituted or unsubstituted C 4 ~C 10 Any one of the alkylcycloalkyl groups; preferably R 12 , R 13 are each independently selected from substituted or unsubstituted C 1 ~C 8 Straight chain alkyl, substituted or unsubstituted C 3 ~C 6 Branched alkyl, substituted or unsubstituted C 2 ~C 6 Straight chain olefins, substituted or unsubstituted C 4 ~C 8 Branched olefins, substituted or unsubstituted C 3 ~C 6 Cycloalkyl, substituted or unsubstituted C 4 ~C 6 Cycloalkylalkyl, substituted or unsubstituted C 4 ~C 6 Any one of the alkylcycloalkyl groups; preferably R 12 , R 13 Each is independently selected from any one of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, isopropyl, isobutyl, isopentyl, ethylene, propenyl, isopropenyl, isobutenyl, cyclopropyl, cyclobutanyl, cyclopentanyl, cyclohexanyl, cyclopropylmethyl, cyclopropylethyl, methylcyclopropyl, ethylcyclopropyl, and ethylcyclobutyl; preferably R 12 , R 13 Each is independently selected from any one of methyl, ethyl, butyl and octyl; further, preferably B is selected from -CH 2 -、-C((CH2 ) 3 CH 3 ) 2 -、-NCH 3 -、-N(CH 2 ) 7 CH 3 -、-NCH 2 CH 3 Any one of -, -O-, and -S-.

[0040] Preferably, the above R 13 , R 14 This allows B to simultaneously form p-П conjugation with the benzene ring and with the carbon-carbon double bond on the unsaturated hydrocarbon ring, thereby improving the stability of the overall modified oxime ester compound structure, which in turn helps reduce the amount of oxime ester bonds that break and produce small molecular fragments.

[0041] In one embodiment of the present application, the structural formula of the modified oxime ester compound is

[0042]

[0043] Any one of .

[0044] The modified oxime ester compounds of the above structure have a relatively stable ring core structure and combine the electronic effect and steric hindrance effect of each substituent, so that when the modified oxime ester compounds are used as free radical photoinitiators, they can take into account a small amount of small molecular fragments and curing at low temperature.

[0045] In another typical embodiment of the present application, a method for preparing the above-mentioned modified oxime ester compound is provided, and the preparation method comprises: step S1, subjecting compound 1 to a Suzuki coupling reaction or a Friedel-Crafts acylation reaction to obtain compound 2; step S2, subjecting compound 2 to an oximation reaction with compound 3 to generate an oxime compound; step S3, subjecting the oxime compound to an acylation agent to an esterification reaction to obtain a modified oxime ester compound; wherein compound 3 is selected from any one of nitrous acid, alkyl nitrite, and hydroxylamine hydrochloride, and compound 1 has any one of structural formula I, structural formula II, structural formula III, and structural formula IV:

[0046]

[0047] Compound 2 has structural formula V or structural formula VI:

[0048]

[0049] The oxime compound has any one of structural formula VII, structural formula VIII, structural formula IX, and structural formula X:

[0050]

[0051]

[0052] A, B, Z, R 1 , m are the same as A, B, Z, R mentioned above 1 , m, X is a bromine or chlorine atom.

[0053] By optimizing the structure of compound 1, the above preparation method can obtain modified oxime ester compounds with excellent comprehensive performance through simple oximation reaction and esterification reaction. It is used as a free radical photoinitiator to improve the efficiency of the polymerization reaction of the photocurable composition. On the basis of retaining the original good polymerization inhibition performance, the amount of small molecule fragments generated by the oxime ester bond breakage under ultraviolet light irradiation of the photocurable composition is greatly reduced, thereby greatly reducing the probability of failure of the light-emitting device, and can be cured at a lower temperature, thereby better exerting the performance of the photoinitiator in accelerating the curing rate of ink and the like and improving the photosensitivity efficiency of the photoinitiator.

[0054] In addition, when the compound 2 has a structural formula V, the compound 2 reacts with nitrous acid or an alkyl nitrite to obtain an oxime compound of structural formula VIII, and the compound 2 reacts with hydroxylamine hydrochloride to obtain an oxime compound of structural formula VII. When the compound 2 has a structural formula VI, the compound 2 reacts with nitrous acid or an alkyl nitrite to obtain an oxime compound of structural formula IX, and the compound 2 reacts with hydroxylamine hydrochloride to obtain an oxime compound of structural formula X.

[0055] In order to obtain a compound with a structure shown in Compound 2, in the above step S1, when Compound 1 has Structural Formula I or Structural Formula II, Compound 1 undergoes a Suzuki coupling reaction to obtain Compound 2; when Compound 1 has Structural Formula III or Structural Formula IV, Compound 1 undergoes a Friedel-Crafts acylation reaction to obtain Compound 2.

[0056] When the above structure is an oxime ester structure (i.e., structural formula VII, structural formula X), in order to improve the efficiency of the above oximation reaction, the solvent used can be a mixed solvent of alcohol and water, preferably a mixed solvent of ethanol and water; the reaction is carried out under heating reflux.

[0057] When the above structure is a ketoxime ester structure (i.e., structural formula VIII, structural formula IX), in order to improve the efficiency of the above oximation reaction, the temperature of the above oximation reaction is preferably -15 to 50° C., preferably 0 to 25° C., and the time of the oximation reaction is 1 to 5 hours. Preferably, the alkyl nitrite is selected from any one or more of methyl nitrite, ethyl nitrite, isopropyl nitrite, butyl nitrite, and isoamyl nitrite. Of course, those skilled in the art can also select other suitable alkyl nitrites according to actual conditions, which will not be repeated here.

[0058] In order to improve the efficiency of the above esterification reaction, it is preferred that in the above step S3, the temperature of the esterification reaction is -10 to 60°C, preferably 0 to 25°C, and the time of the esterification reaction is 1 to 5 hours; the acylating agent is selected from substituted or unsubstituted C 1 ~C 15 Alkanoyl chloride, substituted or unsubstituted C 6 ~C 20 Aroyl chloride, substituted or unsubstituted C 4 ~C 20 Heteroaroyl chloride, substituted or unsubstituted C 4 ~C 40 Any one of the anhydrides of; preferably the acylating agent is selected from substituted or unsubstituted C 1 ~C 6 Alkanoyl chloride, substituted or unsubstituted C 6 ~C 12 Aroyl chloride, substituted or unsubstituted C 4 ~C 10 Any one of the heteroaromatic acid chlorides; preferably substituted or unsubstituted C 1 ~C 6 The alkanoyl chloride is selected from substituted or unsubstituted formyl chloride, substituted or unsubstituted acetyl chloride, substituted or unsubstituted propionyl chloride, substituted or unsubstituted butyryl chloride, substituted or unsubstituted valeryl chloride, substituted or unsubstituted hexanoyl chloride; preferably, the substituted or unsubstituted formyl chloride is selected from any one of ethylformyl chloride, propylformyl chloride and cyclohexanecarbonyl chloride; preferably, the substituted or unsubstituted acetyl chloride is selected from methoxyacetyl chloride, ethoxyacetyl chloride, butoxyacetyl chloride, (2-butoxyethoxy)acetyl chloride, phenoxyacetyl chloride, chlorophenoxyacetyl chloride, nitrophenoxyacetyl chloride, phenylacetyl chloride, chlorophenylacetyl chloride, nitrophenylacetyl chloride, thiophene-2- -acetyl chloride; preferably substituted or unsubstituted propionyl chloride is selected from any one of 3-chloropropionyl chloride, 3-(methylthio)propionyl chloride, phenoxypropionyl chloride, and phenylpropionyl chloride; preferably substituted or unsubstituted butyryl chloride is selected from any one of 4-phenylbutyryl chloride, 2-methylphenylbutyryl chloride, and phenoxybutyryl chloride; preferably substituted or unsubstituted valeryl chloride is selected from any one of 2-propylvaleryl chloride, 5-chlorovaleryl chloride, and 3-chloropivaloyl chloride; preferably substituted or unsubstituted hexanoyl chloride is selected from any one of 3,5,5-trimethylhexanoyl chloride, 6-bromohexanoyl chloride, and 6-phenylhexanoyl chloride; preferably substituted or unsubstituted C 6 ~C 12 The aromatic acid chloride is selected from any one of benzoyl chloride, 3,5-dimethylbenzoyl chloride, 4-methoxybenzoyl chloride, 4-cyanobenzoyl chloride, 4-nitrobenzoyl chloride, 4-phenylbenzoyl chloride, chlorobenzoyl chloride, naphthoyl chloride, 2-ethoxy-1-naphthoyl chloride and anthracene chloride; preferably substituted or unsubstituted C 4 ~C10 The heteroaromatic acid chloride is selected from any one of 2-thenoyl chloride, 2-furoyl chloride, quinoline chloride and chloronicotinoyl chloride; preferably substituted or unsubstituted C 4 ~C 40 The acid anhydride is selected from any one of acetic anhydride, 4-methoxyphenylacetic anhydride, propionic anhydride, isobutyric anhydride, tert-valeric anhydride, capric anhydride and stearic anhydride. The preferred acylating agent helps to decarboxylate the acyloxy bond of the formed modified oxime ester compound to produce as much carbon dioxide as possible.

[0059] In addition, in order to further improve the efficiency of the esterification reaction, the esterification reaction is preferably carried out in an alkaline reagent and a solvent. The alkaline reagent is preferably selected from any one or more of triethylamine, pyridine, diisopropylethylamine, potassium hydroxide, sodium hydroxide, and sodium hydride; the solvent is preferably selected from any one or more of diethyl ether, acetonitrile, tert-butyl methyl ether, tetrahydrofuran, vinyl acetate, toluene, xylene, acetone, methyl ethyl ketone, dichloromethane, chloroform, chlorobenzene, dimethylacetamide, and dimethylformamide.

[0060] In another typical embodiment of the present application, a photocurable composition is provided. The photocurable composition includes a photoinitiator, and the photoinitiator is the above-mentioned modified oxime ester compound.

[0061] Modified oxime ester compounds as free radical photoinitiators can improve the photoreaction activity of effective molecules of photoinitiators, thereby greatly promoting the efficiency of photoinitiated polymerization reactions of photocurable compositions including the modified oxime ester compounds. On the basis of retaining the original good polymerization inhibition performance, the amount of small molecule fragments produced by the breakage of oxime ester bonds under ultraviolet light irradiation is greatly reduced, thereby greatly reducing the probability of failure of light-emitting equipment, and can be cured at lower temperatures, thereby better exerting the performance of photoinitiators in accelerating the curing rate of inks and the like and improving the photosensitivity of photoinitiators, further expanding the application of oxime ester photoinitiators.

[0062] In one embodiment of the present application, the photocurable composition is any one of a coating, an ink, and an adhesive.

[0063] The photocurable composition of the present application, as any one of coatings, inks, and adhesives, not only has excellent photoinitiating properties, but also has the properties of a small amount of small molecule fragments and low-temperature curing, so that the photoinitiator can better play the role of accelerating the curing rate of inks and the like and improving the photosensitivity efficiency of the photoinitiator.

[0064] The beneficial effects of the present application will be described below in conjunction with specific embodiments.

[0065] Example 1

[0066]

[0067] 27.8 g of raw material 1a (0.1 mol) was added to a 500 mL reaction bottle, and 1% equivalent of palladium acetate (Pd(OAc) 2 ), 2% equivalent of 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (s-phos), 2 equivalents of potassium phosphate, 3 equivalents of 2-thienylboronic acid, and 250 mL of tetrahydrofuran to obtain a reaction solution, the reaction solution was stirred and reacted under reflux conditions for 4 hours, and after the reaction was detected to be complete, it was cooled to room temperature, 6 mol / L hydrochloric acid was added to the reaction solution to adjust the pH to 4-5, and stirred at room temperature for 1 hour, water and ethyl acetate were added for extraction, the organic phase was dried and concentrated, and purified to obtain intermediate 1b with a yield of 75.0%.

[0068]

[0069] Add intermediate 1b (28.1 g, 0.1 mol), 600 mL of dichloromethane, isoamyl nitrite (45.6 g, 0.39 mol) and 37% concentrated hydrochloric acid (41.1 g, 0.42 mol) to a 1000 mL reaction bottle, stir at room temperature (20-25°C) for 3 h, stop the reaction, add 200 mL of water, continue stirring for 20 min, let stand for stratification, separate the lower organic phase, wash the organic phase with water until neutral and concentrate. Add 200 mL of methanol to the concentrate, stir well at room temperature for 10-12 h, precipitate solid, rinse the filter cake obtained by filtration with methanol, and dry the obtained solid in a 60°C forced air oven for 5 h to obtain 18.6 g of intermediate 1c, with a yield of 60.0% and a purity of 96.5%.

[0070]

[0071] To a 250 mL reaction bottle, 15.5 g of intermediate 1c (0.05 mol), 100 mL of dichloromethane, and 10.2 g of acetic anhydride (0.1 mol) were added, and the mixture was stirred at room temperature to dissolve. The reaction progress was monitored by TLC. After the reaction, a product system was obtained. After dichloromethane was removed from the product system, slurry was made with a mixture of acetone and methanol in a volume ratio of 1:1 to obtain 16.8 g of modified oxime ester compound 1, with a yield of 95.6% and a purity of 95.8%.

[0072] Example 2

[0073]

[0074] 19.9 g of raw material 2a (0.1 mol), 200 mL of dichloromethane and 25.7 g of aluminum chloride were added to a 500 mL four-necked flask. Under nitrogen protection, 27.7 g of benzoyl chloride was added dropwise to the four-necked flask at a temperature of 0-10 ° C. The reaction progress was monitored by TLC. After the reaction was completed, the reaction solution was slowly added to a dilute hydrochloric acid solution to quench, and the organic layer was separated. The organic layer was washed with water, desolventized, and purified to obtain 21.2 g of intermediate 2b with a yield of 70.0% and a purity of 99.0%.

[0075]

[0076] Add intermediate 2b (15.2 g, 0.05 mol), 200 mL of dichloromethane, isoamyl nitrite (22.8 g, 0.20 mol) and 37% concentrated hydrochloric acid (20.6 g, 0.21 mol) to a 500 mL reaction bottle, stir at room temperature (20-25°C) for 4 h, then stop the reaction to obtain the product system, add 100 mL of water to the product system, continue stirring for 20 min, let stand for stratification, separate the lower organic phase, wash the organic phase with water until neutral and concentrate. Add 100 mL of methanol to the concentrate, stir well at room temperature for 6-8 h, precipitate solid, rinse the filter cake obtained by filtration with methanol, and dry the obtained solid in a 60°C forced air oven for 5 h to obtain 10.4 g of intermediate 2c, with a yield of 62.7% and a purity of 95.5%.

[0077]

[0078] To a 250 mL reaction bottle, 10.4 g of intermediate 2c (0.03 mol), 100 mL of dichloromethane, and 6.1 g of acetic anhydride (0.06 mol) were added, and the mixture was stirred at room temperature to dissolve. The reaction progress was monitored by TLC. After the reaction was completed, a reaction solution was obtained, and dichloromethane was removed from the reaction solution and the solution was slurried with a mixture of acetone and methanol in a volume ratio of 1:1 to obtain 10.7 g of modified oxime ester compound 2, with a yield of 95.4% and a purity of 95.8%.

[0079] According to the reaction steps similar to those of Examples 1 and 2, the substrates were replaced and the reaction conditions were adjusted to obtain the corresponding modified oxime ester compounds. The intermediates and oxime compounds in all the examples are listed in Table 1, and the corresponding modified oxime ester compounds prepared in all the examples are listed in Table 2.

[0080] The raw materials and their sources used in the following experiments:

[0081] The intermediates can be purchased commercially or synthesized by known synthesis methods, and the oxime compounds are prepared by subjecting the corresponding intermediates to oximation reaction.

[0082] Table 1

[0083]

[0084]

[0085]

[0086] Table 2

[0087]

[0088]

[0089]

[0090] Preparation of photosensitive resin composition

[0091]

[0092] In the above-mentioned photosensitive resin composition, the photoinitiator is the oxime ester compounds 1 to 12 of the present invention, the compound A and the compound B in the prior art, and accordingly, test examples 1 to 12, test comparative example 1 and test comparative example 2 are obtained, wherein the structural formulas of compound A and compound B are as follows:

[0093] Compound A: Compound B:

[0094] Photosensitivity test

[0095] (1) Sensitivity

[0096] The above-mentioned photocurable compositions were stirred in the dark and coated on a PET film using a 6# wire rod to form a coating film with a thickness of about 3 μm. The coating film was exposed to light using a mercury lamp (RW-LED-YT200gl) and a 365nm LED light source, giving 100 mj / cm 2 The energy was measured and the curing film was observed. The evaluation was conducted by finger touch method. The evaluation criteria were as follows:

[0097] 1: Oil, not solid;

[0098] 2: Surface oil, bottom layer solidified;

[0099] 3: The surface is sticky and the fingerprints are heavy after touching it;

[0100] 4: Basically dry, slightly astringent to the touch, with light fingerprints;

[0101] 5: Completely cured, smooth surface, no fingerprints after touch, test results are shown in Table 3.

[0102] Table 3

[0103]

[0104] (2) Film-forming performance evaluation

[0105] After the above-mentioned photosensitive resin compositions were stirred sufficiently in a yellow light room, the compositions were coated on tinplate using a 15# wire rod to form a coating film of 10 μm, and an exposure machine (exposure machine model: EXECURE 4000, 365 nm LED light source, receiving 2000 mJ / cm 2 The coating film was exposed to light with a light source (with a light source of 100 μm) to cure the film. A light-transmitting portion (pattern) of a regular quadrilateral with a side length of 10 μm was used, and the interval between the regular quadrilaterals was 100 μm. After light irradiation, the coating film was immersed in an aqueous developer containing 0.12% non-ionic surfactant and 0.04% KOH for 100 seconds at 25°C for development, and then washed. After that, the coating film was dried in an oven at 220°C / 180°C / 160°C for 20 minutes, and the hardness (GB T 6739-1996) of the film-formed product was tested, as shown in Table 4.

[0106] Table 4

[0107]

[0108]

[0109] (3) outgas

[0110] Using the GC-MS test method, 5 g of the sample film obtained in the above film performance evaluation stage was taken, cut into appropriate sizes, and placed in a headspace bottle for standby use. Headspace injection was used to observe whether there was outgas output (except carbon dioxide and self-contained solvent peaks). The test results are shown in Table 5.

[0111] The equipment and test conditions used are as follows:

[0112] Agilent 7890B gas chromatograph, chromatographic column: Agilent HP-5ms column; vaporization temperature: 280°C; program temperature rise: 60°C for 3 min, 20°C / min heating rate, 280°C for 10 min;

[0113] Agilent 7697A headspace sampler, headspace conditions: heating box: 110°C; quantitative loop: 120°C; transfer line: 140°C; equilibrium time: 30 min;

[0114] Agilent 7010B mass spectrometer, mass spectrometry conditions: ion source temperature: 280°C; electron energy: 70 eV; scanning range (m / z): 30-400.

[0115] Table 5

[0116]

[0117] From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:

[0118] (1) As can be seen from Table 3, Test Examples 1 to 12 all have excellent sensitivity under Hg lamp and 365 nm, while Test Comparative Examples 1 and 2 have poor sensitivity under 365 nm.

[0119] (2) As can be seen from Table 4, Test Examples 1 to 12 can be cured into films at a lower temperature (160°C) and have excellent hardness, while Test Comparative Examples 1 and 2 are cured into films at a lower temperature (160°C or 180°C) and their hardness is worse than that of Test Examples 1 to 12.

[0120] (3) From the test results in Table 5, it can be seen that small molecule fragments were produced in the test comparative example 1, while Examples 1 to 12 did not produce small molecule fragments.

[0121] In summary, the oxime ester compounds of the present invention can be used as photoinitiators for conventional ultraviolet light curing systems, and can be well cured under mercury lamp light sources and 365nm light sources. Compared with the current initiators with better photosensitivity, the photosensitivity is better, the photocuring temperature is lower, and it also has the characteristics of low outgas.

[0122] From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:

[0123] Oxime ester compounds, as free radical photoinitiators, can improve the photoreactivity of effective molecules of photoinitiators, thereby greatly promoting the efficiency of photoinitiated polymerization reactions. The modified oxime ester compounds of the present application have a large conjugated structure, so the photocurable composition including the modified oxime ester compounds of the present application, while retaining the original good polymerization inhibition performance, greatly reduces the amount of small molecular fragments generated by the oxime ester bond breakage under ultraviolet light irradiation, thereby greatly reducing the probability of light-emitting device failure, and due to R 1 The substituent is an aromatic or heteroaryl substituent, so that it can be cured at a lower temperature, thereby better exerting the performance of the photoinitiator in accelerating the curing rate of ink and the like and improving the photosensitivity efficiency of the photoinitiator. At the same time, since the absorption wavelength of the modified oxime ester compound of the present application is further red-shifted, it can be cured at a longer ultraviolet wavelength, such as under a 365nm ultraviolet light source, further expanding the application of oxime ester photoinitiators.

[0124] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A modified oxime ester compound, It is characterized in that The modified oxime ester compound has any one or more of the following general formula I, general formula II, general formula III, and general formula IV: R 1 For-R 11 or-COR 11 ; R 11 Any one selected from phenyl, 4-methoxyphenyl, 4-nitrophenyl, 6-methoxy-2-naphthyl, 2-thiazolyl, and 2-thienyl; The R 2 Any one selected from methyl, ethyl, cyclohexylethyl, propyl, butyl, isopropyl, isobutyl, isopentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, tolyl, trimethylphenyl, and thienyl; m is any integer from 0 to 2; A is a single bond; B is selected from -CR 12 R 13 -、-R 13 Any one of N-, -O-, -S-, where R 12 , R 13 Each is independently selected from any one of methyl, ethyl, butyl and octyl; Z is a single bond.

2. The modified oxime ester compound according to claim 1, It is characterized in that The R 1 Any one selected from the group consisting of phenyl, 4-methoxyphenyl, 4-nitrophenyl, 6-methoxy-2-naphthyl, 2-thiazolyl, 2-thienyl and benzoyl.

3. The modified oxime ester compound according to claim 1, It is characterized in that The R 2 Any one selected from the group consisting of methyl, ethyl, cyclohexylethyl, cyclopropyl, cyclohexyl, phenyl, 2-methylphenyl, 2,4,6-trimethylphenyl and 2-thienyl.

4. The modified oxime ester compound according to claim 1, It is characterized in that The B is selected from -C((CH 2 ) 3 CH 3 ) 2 -、-N(CH 3 )-、-N((CH 2 ) 7 CH 3 )-、-N(CH 2 CH 3 )-, -O-, -S-.

5. The modified oxime ester compound according to any one of claims 1 to 3, It is characterized in that The structural formula of the modified oxime ester compound is Any one of .

6. A method for preparing the modified oxime ester compound according to any one of claims 1 to 5, It is characterized in that The preparation method comprises: Step S1, subjecting compound 1 to a Suzuki coupling reaction or a Friedel-Crafts acylation reaction to obtain compound 2; Step S2, the compound 2 and the compound 3 are subjected to an oximation reaction to generate an oxime compound; Step S3, subjecting the oxime compound to an acylating agent for esterification reaction to obtain the modified oxime ester compound; Wherein, the compound 3 is selected from any one of nitrous acid, alkyl nitrite, and hydroxylamine hydrochloride, and the compound 1 has any one of structural formula I, structural formula II, structural formula III, and structural formula IV: The compound 2 has structural formula V or structural formula VI: The oxime compound has any one of structural formula VII, structural formula VIII, structural formula IX, and structural formula X: A, B, Z, R 1 , m are the same as A, B, Z, R as described in any one of claims 1 to 5 1 , m, X is a bromine or chlorine atom.

7. The preparation method according to claim 6, It is characterized in that In the step S1, When the compound 1 has structural formula I or structural formula II, The compound 1 is subjected to the Suzuki coupling reaction to obtain the compound 2; When the compound 1 has the structural formula III or the structural formula IV, The compound 1 is subjected to the Friedel-Crafts acylation reaction to obtain the compound 2.

8. The preparation method according to claim 6, It is characterized in that The alkyl nitrite is selected from any one or more of methyl nitrite, ethyl nitrite, isopropyl nitrite, butyl nitrite and isoamyl nitrite.

9. The preparation method according to claim 6, It is characterized in that In step S3, the temperature of the esterification reaction is -10 to 60°C, and the time of the esterification reaction is 1 to 5 hours; The acylating agent is selected from substituted or unsubstituted C 1 ~C 15 Alkanoyl chloride, substituted or unsubstituted C 6 ~C 20 Aroyl chloride, substituted or unsubstituted C 4 ~C 20 Heteroaroyl chloride, substituted or unsubstituted C 4 ~C 40 Any one of the anhydrides.

10. The preparation method according to claim 9, It is characterized in that The temperature of the esterification reaction is 0-25°C.

11. The preparation method according to claim 9, It is characterized in that The acylating agent is selected from substituted or unsubstituted C 1 ~C 6 Alkanoyl chloride, substituted or unsubstituted C 6 ~C 12 Aroyl chloride, substituted or unsubstituted C 4 ~C 10 Any one of the heteroaromatic acid chlorides.

12. The preparation method according to claim 9, It is characterized in that The substituted or unsubstituted C 1 ~C 6 The alkanoyl chloride is selected from substituted or unsubstituted formyl chloride, substituted or unsubstituted acetyl chloride, substituted or unsubstituted propionyl chloride, substituted or unsubstituted butyryl chloride, substituted or unsubstituted valeryl chloride, substituted or unsubstituted hexanoyl chloride.

13. The preparation method according to claim 12, It is characterized in that The substituted or unsubstituted formyl chloride is selected from any one of ethyl formyl chloride, propyl formyl chloride and cyclohexaneformyl chloride.

14. The preparation method according to claim 12, It is characterized in that The substituted or unsubstituted acetyl chloride is selected from any one of methoxyacetyl chloride, ethoxyacetyl chloride, butoxyacetyl chloride, (2-butoxyethoxy)acetyl chloride, phenoxyacetyl chloride, chlorophenoxyacetyl chloride, nitrophenoxyacetyl chloride, phenylacetyl chloride, chlorophenylacetyl chloride, nitrophenylacetyl chloride and thiophene-2-acetyl chloride.

15. The preparation method according to claim 12, It is characterized in that The substituted or unsubstituted propionyl chloride is selected from any one of 3-chloropropionyl chloride, 3-(methylthio)propionyl chloride, phenoxypropionyl chloride and phenylpropionyl chloride.

16. The preparation method according to claim 12, It is characterized in that The substituted or unsubstituted butyryl chloride is selected from any one of 4-phenylbutyryl chloride, 2-methylphenylbutyryl chloride and phenoxybutyryl chloride.

17. The preparation method according to claim 12, It is characterized in that The substituted or unsubstituted valeryl chloride is selected from any one of 2-propyl valeryl chloride, 5-chlorovaleryl chloride and 3-chloropivaloyl chloride.

18. The preparation method according to claim 12, It is characterized in that The substituted or unsubstituted hexanoyl chloride is selected from any one of 3,5,5-trimethylhexanoyl chloride, 6-bromohexanoyl chloride and 6-phenylhexanoyl chloride.

19. The preparation method according to claim 11, It is characterized in that The substituted or unsubstituted C 6 ~C 12 The aromatic acid chloride is selected from any one of benzoyl chloride, 3,5-dimethylbenzoyl chloride, 4-methoxybenzoyl chloride, 4-cyanobenzoyl chloride, 4-nitrobenzoyl chloride, 4-phenylbenzoyl chloride, chlorobenzoyl chloride, naphthoyl chloride and 2-ethoxy-1-naphthoyl chloride.

20. The preparation method according to claim 11, It is characterized in that The substituted or unsubstituted C 4 ~C 10 The heteroaromatic acid chloride is selected from any one of 2-thenoyl chloride, 2-furoyl chloride, quinolinecarbonyl chloride and chloronicotinoyl chloride.

21. The preparation method according to claim 9, It is characterized in that The substituted or unsubstituted C 4 ~C 40 The acid anhydride is selected from any one of acetic anhydride, 4-methoxyphenylacetic anhydride, propionic anhydride, isobutyric anhydride, tert-valeric anhydride, capric anhydride and stearic anhydride.

22. A photocurable composition comprising a photoinitiator, It is characterized in that The photoinitiator is the modified oxime ester compound according to any one of claims 1 to 5.

23. The photocurable composition according to claim 22, It is characterized in that The photocurable composition is any one of a coating, an ink and an adhesive.

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