Oxime ester compound and preparation method thereof, and photocurable composition

Abstract

The present invention provides an oxime ester compound and a preparation method thereof, and a photocurable composition. The oxime ester compound has any one of the following general formulas I, II, III, and IV: The oxime ester compound of the present application has a large planar conjugated structure, so the photocurable composition including the oxime ester compound of the present application, while retaining the original good polymerization inhibition performance, greatly reduces the amount of small molecule fragments generated by the oxime ester bond breakage under ultraviolet light irradiation, thereby greatly reducing the probability of light-emitting equipment failure, 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, further expanding the application of the oxime ester photoinitiator.

Description

Technical Field

[0001] The invention relates to the technical field of oxime ester photoinitiator synthesis, and in particular to an 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 an 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, an oxime ester compound is provided, and the oxime ester compound has any one of the following general formula I, general formula II, general formula III, and general formula IV:

[0005]

[0006]

[0007] R 1 is selected from H, halogen atoms, nitro, cyano, hydroxyl, carboxyl, formyl, sulfonyl, -R 11 、-OR 11 、-SR 11 、-NR 11 R 12 、-COR 11 、-SOR 11 、-SO 2 R11 、-CONR 11 R 12 Any one of the following; R 11 , R 12 are each independently selected from substituted or unsubstituted C 1 ~C 20 Hydrocarbon, substituted or unsubstituted C 2 ~C 20 Heterocycloalkyl, substituted or unsubstituted C 3 ~C 20 any one of a cycloalkyl group, a nitrile group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, an acryloyl group, a vinyl group, a vinyl methyl ether group, a mercapto group, and an isocyanate group; R 2 is selected from hydrogen atom, halogen atom, nitro group, cyano group, substituted or unsubstituted C 1 ~C 20 Alkyl, substituted or unsubstituted C 2 ~C 20 Heterocycloalkyl, substituted or unsubstituted C 3 ~C 20 Cycloalkyl, substituted or unsubstituted C 1 ~C 20 Alkoxy, substituted or unsubstituted C 6 ~C 20 any one of the aromatic groups; n is any integer from 0 to 4; m is 1 or 0; A is empty, a single bond or C 1 ~C 5 An alkylene group; B is selected from -C(R 13 R 14 )-、-R 14 Any one of N-, -O-, -S-, where R 13 , R 14 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-, -CH2 - or a single key.

[0008] Furthermore, the above R 11 , R 12 Substituted or unsubstituted C 1 ~C 20 Hydrocarbon, substituted or unsubstituted C 2 ~C 20 containing heterocyclic alkyl, substituted or unsubstituted C 3 ~C 20 Any one or more methylene groups in the cycloalkyl group are replaced by -O-, -CO-, -COO-, -OCO-, -NR 15 -、-NR 15 CO-, -S-, -SO 2 -, -SCO- or -COS-, R 15 is selected from hydrogen atom, substituted or unsubstituted C 1 ~C 20 Any of the hydrocarbon groups, preferably R 15 is selected from hydrogen atom, substituted or unsubstituted C 1 ~C 10 Any of the hydrocarbon groups, preferably R 15 is selected from hydrogen atom, substituted or unsubstituted C 1 ~C 6 Any of the hydrocarbon groups, preferably R 15 Any one selected from hydrogen, methyl, ethyl, and propyl; preferably R 11 , R 12 are each independently selected from substituted or unsubstituted C 1 ~C 10 Hydrocarbon, substituted or unsubstituted C 2 ~C 10 Heterocycloalkyl, substituted or unsubstituted C 3 ~C 10 Any one of the cycloalkyl groups; preferably R 11 , R 12 are each independently selected from substituted or unsubstituted C 1 ~C 6 Hydrocarbon, substituted or unsubstituted C 2 ~C 6 Heterocycloalkyl, substituted or unsubstituted C 3 ~C 6 Any one of the cycloalkyl groups; preferably R 11 , R 12 Each is independently selected from any one of methyl, ethyl, propyl, butyl, pentyl, hexyl, ethylene oxide, butylene oxide, cyclopentyl, cyclopropane, cyclobutane, cyclopentane, and cyclobutane; further, preferably R1 Any one selected from H, nitro, cyano, formyl and methyl.

[0009] Furthermore, the above R 2 Substituted or unsubstituted C 1 ~C 20 Alkyl, substituted or unsubstituted C 2 ~C 20 Heterocycloalkyl, substituted or unsubstituted C 3 ~C 20 Cycloalkyl, substituted or unsubstituted C 1 ~C 20 Any one or more hydrogen atoms in the alkoxy group of is substituted by a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl group, a vinyl ether group, a mercapto group, or an isocyanate group; optionally, R 2 Substituted or unsubstituted C 1 ~C 20 Alkyl, substituted or unsubstituted C 2 ~C 20 Heterocycloalkyl, substituted or unsubstituted C 3 ~C 20 Cycloalkyl, substituted or unsubstituted C 1 ~C 20 The methylene group in the alkoxy group is replaced by -O-, -CO-, -COO-, -OCO-, -NR 16 -、-NR 16 CO-, -S-, -SO 2 -, -SCO- or -COS-, R 16 is selected from hydrogen atom, substituted or unsubstituted C 1 ~C 20 Any of the alkyl groups, preferably R 16 is selected from hydrogen atom, substituted or unsubstituted C 1 ~C 10 Any of the hydrocarbon groups, preferably R 16 is selected from hydrogen atom, substituted or unsubstituted C 1 ~C 6 Any of the hydrocarbon groups, preferably R 16 Any one selected from hydrogen, methyl, ethyl, and propyl; preferably R 2 is selected from substituted or unsubstituted C 1 ~C 10 Alkyl, substituted or unsubstituted C 2 ~C 10 Heterocycloalkyl, substituted or unsubstituted C 3 ~C 10 Cycloalkyl, substituted or unsubstituted C 1~C 10 Alkoxy, substituted or unsubstituted C 6 ~C 12 Any one of the aromatic groups; preferably R 2 is selected from substituted or unsubstituted C 1 ~C 6 Alkyl, substituted or unsubstituted C 2 ~C 6 Heterocycloalkyl, substituted or unsubstituted C 3 ~C 6 Cycloalkyl, substituted or unsubstituted C 1 ~C 6 Alkoxy, substituted or unsubstituted C 6 ~C 10 Any one of the aromatic groups; preferably R 2 is selected from substituted or unsubstituted C 1 ~C 6 Alkyl, substituted or unsubstituted C 2 ~C 6 Heterocycloalkyl, substituted or unsubstituted C 3 ~C 6 Cycloalkyl, substituted or unsubstituted C 1 ~C 6 Alkoxy, substituted or unsubstituted C 6 ~C 10 Any one of the aromatic groups; preferably R 2 is selected from any one of methyl, ethyl, propyl, ethylene oxide, butylene oxide, pentyl oxide, cyclopropyl, cyclobutyl, cyclopentyl, cyclobutyl, methoxy, ethoxy, propoxy, phenyl, 2-methylphenyl, and 2,4,6-trimethylphenyl; further, preferably R 2 Any one selected from the group consisting of methyl, ethyl, phenyl, 2-methylphenyl, and 2,4,6-trimethylphenyl.

[0010] Furthermore, the above R 13 , R 14 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 10Cycloalkylalkyl, substituted or unsubstituted C 4 ~C 10 Any one of the alkylcycloalkyl groups; preferably R 13 , R 14 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 13 , R 14 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 13 , R 14 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-.

[0011] Furthermore, the structural formula of the above-mentioned oxime ester compound is

[0012]

[0013] Any one of .

[0014] According to another aspect of the present invention, a method for preparing the aforementioned oxime ester compound is provided, the method comprising: step S1, subjecting compound 1 to an oximation reaction with compound 2 to generate an oxime compound; step S2, subjecting the oxime compound to an acylation agent to an esterification reaction to obtain an oxime ester compound; wherein compound 2 is selected from any one of nitrous acid, alkyl nitrite, and hydroxylamine hydrochloride, and compound 1 has structural formula I or structural formula II:

[0015]

[0016] The oxime compound has any one of the structural formulas III, IV, V and VI:

[0017]

[0018] A, B, Z, R 1 , m, n are the same as A, B, Z, R above 1 , m, n.

[0019] Furthermore, in the above step S1, the alkyl nitrite is selected from any one or more of methyl nitrite, ethyl nitrite, isopropyl nitrite, butyl nitrite, and isoamyl nitrite.

[0020] Furthermore, in the above step S2, 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 6The 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.

[0021] Furthermore, the above esterification reaction is carried out in an alkaline reagent and a solvent, preferably the alkaline reagent is selected from any one or more of triethylamine, pyridine, diisopropylethylamine, potassium hydroxide, sodium hydroxide, and sodium hydride; preferably the solvent is 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.

[0022] According to another aspect of the present invention, a photocurable composition is provided. The photocurable composition includes a photoinitiator, and the photoinitiator is the above-mentioned oxime ester compound.

[0023] Furthermore, the photocurable composition is any one of a coating, an ink, and an adhesive.

[0024] By applying the technical solution of the present invention, oxime ester compounds are used as free radical photoinitiators to improve the photoreactivity of effective molecules of photoinitiators, thereby promoting the efficiency of photoinitiated polymerization reactions to a great extent. The oxime ester compounds of the present application have a large planar conjugated structure, so the photocurable composition including the oxime ester compounds of the present application has a greatly reduced amount of small molecule fragments generated by the oxime ester bond breakage 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 being able to cure at a lower temperature, thereby better exerting the performance of the photoinitiator in accelerating the curing rate of inks and the like and improving the photosensitivity efficiency of the photoinitiator, further expanding the application of oxime ester photoinitiators. DETAILED DESCRIPTION

[0025] 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.

[0026] 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 an oxime ester compound and a preparation method thereof, and a photocurable composition.

[0027] In a typical embodiment of the present application, an oxime ester compound is provided, and the oxime ester compound has any one of the following general formula I, general formula II, general formula III, and general formula IV:

[0028]

[0029]

[0030] R 1 is selected from H, halogen atoms, nitro, cyano, hydroxyl, carboxyl, formyl, sulfonyl, -R 11 、-OR 11 、-SR 11 、-NR 11 R 12 、-COR 11 、-SOR 11 、-SO 2 R 11 、-CONR 11 R 12 Any one of the following; R 11 , R 12 are each independently selected from substituted or unsubstituted C 1 ~C 20Hydrocarbon, substituted or unsubstituted C 2 ~C 20 Heterocycloalkyl, substituted or unsubstituted C 3 ~C 20 any one of a cycloalkyl group, a nitrile group, a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, an acryloyl group, a vinyl group, a vinyl methyl ether group, a mercapto group, and an isocyanate group; R 2 is selected from hydrogen atom, halogen atom, nitro group, cyano group, substituted or unsubstituted C 1 ~C 20 Alkyl, substituted or unsubstituted C 2 ~C 20 Heterocycloalkyl, substituted or unsubstituted C 3 ~C 20 Cycloalkyl, substituted or unsubstituted C 1 ~C 20 Alkoxy, substituted or unsubstituted C 6 ~C 20 any one of the aromatic groups; n is any integer from 0 to 4; m is 1 or 0; A is empty, a single bond or C 1 ~C 5 An alkylene group; B is selected from -C(R 13 R 14 )-、-R 14 Any one of N-, -O-, -S-, where R 13 , R 14 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.

[0031] Oxime ester compounds, as free radical photoinitiators, can improve the photoreactivity of effective molecules of photoinitiators, thereby promoting the efficiency of photoinitiated polymerization reactions to a great extent. The oxime ester compounds of the present application have a large planar conjugated structure, so the photocurable composition including the oxime ester compounds of the present application, while retaining the original good polymerization inhibition performance, has a greatly reduced amount of small molecule fragments produced by the oxime ester bond breakage under ultraviolet light irradiation, 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 inks and the like and improving the photosensitivity efficiency of the photoinitiator, further expanding the application of oxime ester photoinitiators.

[0032] In one embodiment of the present application, the above R 11 , R 12 Substituted or unsubstituted C 1 ~C 20 Hydrocarbon, substituted or unsubstituted C 2 ~C 20 containing heterocyclic alkyl, substituted or unsubstituted C 3 ~C 20 Any one or more methylene groups in the cycloalkyl group are replaced by -O-, -CO-, -COO-, -OCO-, -NR 15 -、-NR 15 CO-, -S-, -SO 2 -, -SCO- or -COS-, R 15 is selected from hydrogen atom, substituted or unsubstituted C 1 ~C 20 Any of the hydrocarbon groups, preferably R 15 is selected from hydrogen atom, substituted or unsubstituted C 1 ~C 10 Any of the hydrocarbon groups, preferably R 15 is selected from hydrogen atom, substituted or unsubstituted C 1 ~C 6 Any of the hydrocarbon groups, preferably R 15 Any one selected from hydrogen, methyl, ethyl, and propyl; preferably R 11 , R 12 are each independently selected from substituted or unsubstituted C 1 ~C 10 Hydrocarbon, substituted or unsubstituted C 2 ~C 10 Heterocycloalkyl, substituted or unsubstituted C 3 ~C 10 Any one of the cycloalkyl groups; preferably R 11 , R 12 are each independently selected from substituted or unsubstituted C 1 ~C6 Hydrocarbon, substituted or unsubstituted C 2 ~C 6 Heterocycloalkyl, substituted or unsubstituted C 3 ~C 6 Any one of the cycloalkyl groups; preferably R 11 , R 12 Each is independently selected from any one of methyl, ethyl, propyl, butyl, pentyl, hexyl, ethylene oxide, butylene oxide, cyclopentyl, cyclopropane, cyclobutane, cyclopentane, and cyclobutane; further, preferably R 1 Any one selected from H, nitro, cyano, formyl and methyl.

[0033] The above R 1 The substituent has a certain influence on the electronic effect and steric effect of the benzene ring directly connected to it through electronic effect and steric effect. The preferred R 1 The substituents are beneficial to improving the stability of oxime ester compounds.

[0034] 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 helps to alleviate the inhibition problem of the photopolymerization process caused by oxygen in the air. The above R 2 Substituted or unsubstituted C 1 ~C 20 Alkyl, substituted or unsubstituted C 2 ~C 20 Heterocycloalkyl, substituted or unsubstituted C 3 ~C 20 Cycloalkyl, substituted or unsubstituted C 1 ~C 20 Any one or more hydrogen atoms in the alkoxy group of is substituted by a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl group, a vinyl ether group, a mercapto group, or an isocyanate group; optionally, R 2 Substituted or unsubstituted C 1 ~C 20 Alkyl, substituted or unsubstituted C 2 ~C 20 Heterocycloalkyl, substituted or unsubstituted C 3 ~C 20 Cycloalkyl, substituted or unsubstituted C 1 ~C 20 The methylene group in the alkoxy group is replaced by -O-, -CO-, -COO-, -OCO-, -NR 16 -、-NR 16 CO-, -S-, -SO 2-, -SCO- or -COS-, R 16 is selected from hydrogen atom, substituted or unsubstituted C 1 ~C 20 Any of the alkyl groups, preferably R 16 is selected from hydrogen atom, substituted or unsubstituted C 1 ~C 10 Any of the hydrocarbon groups, preferably R 16 is selected from hydrogen atom, substituted or unsubstituted C 1 ~C 6 Any of the hydrocarbon groups, preferably R 16 Any one selected from hydrogen, methyl, ethyl, and propyl; preferably R 2 is selected from substituted or unsubstituted C 1 ~C 10 Alkyl, substituted or unsubstituted C 2 ~C 10 Heterocycloalkyl, substituted or unsubstituted C 3 ~C 10 Cycloalkyl, substituted or unsubstituted C 1 ~C 10 Alkoxy, substituted or unsubstituted C 6 ~C 12 Any one of the aromatic groups; preferably R 2 is selected from substituted or unsubstituted C 1 ~C 6 Alkyl, substituted or unsubstituted C 2 ~C 6 Heterocycloalkyl, substituted or unsubstituted C 3 ~C 6 Cycloalkyl, substituted or unsubstituted C 1 ~C 6 Alkoxy, substituted or unsubstituted C 6 ~C 10 Any one of the aromatic groups; preferably R 2 is selected from substituted or unsubstituted C 1 ~C 6 Alkyl, substituted or unsubstituted C 2 ~C 6 Heterocycloalkyl, substituted or unsubstituted C 3 ~C 6 Cycloalkyl, substituted or unsubstituted C 1 ~C 6 Alkoxy, substituted or unsubstituted C 6 ~C 10 Any one of the aromatic groups; preferably R 2is selected from any one of methyl, ethyl, propyl, ethylene oxide, butylene oxide, pentyl oxide, cyclopropyl, cyclobutyl, cyclopentyl, cyclobutyl, methoxy, ethoxy, propoxy, phenyl, 2-methylphenyl, and 2,4,6-trimethylphenyl; further, preferably R 2 The acyl group is selected from any one of methyl, ethyl, phenyl, 2-methylphenyl and 2,4,6-trimethylphenyl, so as to facilitate the decarboxylation reaction of the acyloxy group.

[0035] In one embodiment of the present application, the above R 13 , R 14 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 13 , R 14 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 13 , R 14Each 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 13 , R 14 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-.

[0036] 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 oxime ester compound structure, which in turn helps reduce the amount of oxime ester bonds that break and produce small molecular fragments.

[0037] In one embodiment of the present application, the structural formula of the above-mentioned oxime ester compound is

[0038]

[0039]

[0040] Any one of .

[0041] The 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 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 temperatures.

[0042] In another typical embodiment of the present application, a method for preparing the above-mentioned oxime ester compound is provided, and the preparation method comprises: step S1, performing an oximation reaction on compound 1 and compound 2 to generate an oxime compound; step S2, performing an esterification reaction on the oxime compound and an acylating agent to obtain an oxime ester compound; wherein compound 2 is selected from any one of nitrous acid, alkyl nitrite, and hydroxylamine hydrochloride, and compound 1 has structural formula I or structural formula II:

[0043]

[0044] The oxime compound has any one of the structural formulas III, IV, V and VI:

[0045]

[0046]

[0047] A, B, Z, R 1 , m, n are the same as A, B, Z, R above 1 , m, n.

[0048] By optimizing the structure of compound 1, the above preparation method can obtain 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.

[0049] In addition, when the compound 1 has a structural formula I, the compound 1 reacts with nitrous acid or an alkyl nitrite to obtain an oxime compound of structural formula IV, and the compound 1 reacts with hydroxylamine hydrochloride to obtain an oxime compound of structural formula III. When the compound 1 has a structural formula II, the compound 1 reacts with nitrous acid or an alkyl nitrite to obtain an oxime compound of structural formula V, and the compound 1 reacts with hydroxylamine hydrochloride to obtain an oxime compound of structural formula VI.

[0050] When the above structure is an oxime ester structure (i.e., structural formula III, structural formula IV), 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.

[0051] When the above structure is a ketoxime ester structure (i.e., structural formula V, structural formula VI), 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 oximation reaction time 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.

[0052] In order to improve the efficiency of the above esterification reaction, it is preferred that in the above step S2, 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 ~C 10The 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 oxime compound to produce as much carbon dioxide as possible.

[0053] 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.

[0054] The esterification reaction process will produce acidic small molecules. 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, so as to help the solubility of each reactant in the solvent, thereby facilitating the improvement of the reaction efficiency.

[0055] 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 oxime ester compound.

[0056] 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 oxime ester compounds. On the basis of retaining the original good polymerization inhibition properties, 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.

[0057] In one embodiment of the present application, the photocurable composition is any one of a coating, an ink, and an adhesive.

[0058] 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.

[0059] The beneficial effects of the present application will be described below in conjunction with specific embodiments.

[0060] Example 1

[0061]

[0062] 20.1 g of raw material 1a (0.1 mol), 50 mL of ethanol, 50 mL of water, 8.3 g of hydroxylamine hydrochloride and 9.8 g of sodium acetate were added to a 250 mL reaction bottle. The reaction was stopped after stirring and refluxing for 5 h under heating, and the temperature was cooled to room temperature. Then 100 mL of water was added to the reaction bottle, and the mixture was allowed to stand for stratification after continued stirring for half an hour. The lower organic phase was separated, and the organic phase was washed with water until neutral. The organic phase after washing was concentrated, and the obtained viscous material was dissolved in 100 mL of methanol. After being fully stirred at room temperature for 4 to 6 h, a white solid was precipitated, and 17.4 g of a white solid, namely, intermediate 1b, was obtained by suction filtration, with a yield of 77% and a purity of 98.79%.

[0063]

[0064] Add 10.8g of intermediate 1b (0.05mol), 7.5g of triethylamine (TEA) and 500mL of dichloromethane to a 250mL reaction bottle and stir to dissolve. Slowly drop 5.2g of acetic anhydride at room temperature; after the drop is complete, stir at room temperature for 3h to obtain a reaction solution. Add 100g of water to the reaction solution, stir for half an hour and then stand to separate the organic phase of the lower layer, wash the organic phase with water until neutral, concentrate the organic phase, dissolve the obtained solid with 100mL of methanol, stir for 1h and gradually precipitate the solid; cool to 5-10℃ in an ice bath, stir for 2h and filter, wash the filter cake with 100mL of methanol to obtain a crude product. The crude product was dissolved in 50 mL of acetone, added to 50 mL of methanol, stirred for crystallization, and continued to stir for 1 h under ice bath, then filtered. The filter cake was rinsed with 50 mL of methanol and collected to obtain 12.3 g of light yellow solid, namely, oxime ester compound 1, with a yield of 95.4% and a purity of 99.48%.

[0065] According to the reaction steps similar to Example 1, the substrate is replaced and the reaction conditions are adjusted to obtain the corresponding oxime ester compounds. The substrate compound 1 and the intermediate oxime compounds in all the examples are listed in Table 1, and the corresponding oxime ester compounds prepared in all the examples are listed in Table 2.

[0066] The raw materials and their sources used in the following experiments:

[0067] Compound 1 can be purchased commercially or synthesized by a known synthesis method. The intermediate oxime compound is prepared by subjecting the corresponding compound 1 to an oximation reaction.

[0068] Table 1

[0069]

[0070]

[0071]

[0072] Table 2

[0073]

[0074]

[0075]

[0076] Preparation of photosensitive resin composition

[0077]

[0078]

[0079] 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:

[0080] Compound A: Compound B:

[0081] Photosensitivity test

[0082] (1) Sensitivity

[0083] 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) at 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:

[0084] 1: Oil, not solid;

[0085] 2: Surface oil, bottom layer solidified;

[0086] 3: The surface is sticky and the fingerprints are heavy after touching it;

[0087] 4: Basically dry, slightly astringent to the touch, with light fingerprints;

[0088] 5: Completely cured, smooth surface, no fingerprints after touch, test results are shown in Table 3.

[0089] Table 3

[0090]

[0091] (2) Film-forming performance evaluation

[0092] 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, so that it is fully cured) to form a 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, and then dried in an oven at 220°C / 180°C for 20 minutes, and the hardness of the film-formed product was tested (GB T 6739-1996), as shown in Table 4.

[0093] Table 4

[0094]

[0095] (3) outgas

[0096] 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.

[0097] The equipment and test conditions used are as follows:

[0098] 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;

[0099] Agilent 7697A headspace sampler, headspace conditions: heating box: 110°C; quantitative loop: 120°C; transfer line: 140°C; equilibrium time: 30 min;

[0100] Agilent 7010B mass spectrometer, mass spectrometry conditions: ion source temperature: 280°C; electron energy: 70 eV; scanning range (m / z): 30-400.

[0101] Table 5

[0102]

[0103] (1) As can be seen from Table 4, Test Examples 1 to 12 can be cured at a lower temperature to form a film and have excellent hardness, while Test Comparative Examples 1 and 2 are cured at a lower temperature to form a film and their hardness is worse than that of Test Examples 1 to 12.

[0104] (2) 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.

[0105] In summary, the oxime ester compounds of the present invention can be used as photoinitiators in conventional ultraviolet light curing systems, can be cured well under mercury lamp light sources, have better photosensitivity than existing initiators with better photosensitivity, have lower photocuring temperatures, and also have the characteristics of low outgas.

[0106] From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:

[0107] Oxime ester compounds, as free radical photoinitiators, can improve the photoreactivity of effective molecules of photoinitiators, thereby promoting the efficiency of photoinitiated polymerization reactions to a great extent. The oxime ester compounds of the present application have a large planar conjugated structure, so the photocurable composition including the oxime ester compounds of the present application, while retaining the original good polymerization inhibition performance, has a greatly reduced amount of small molecule fragments produced by the oxime ester bond breakage under ultraviolet light irradiation, 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 inks and the like and improving the photosensitivity efficiency of the photoinitiator, further expanding the application of oxime ester photoinitiators.

[0108] 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. An oxime ester compound, It is characterized in that The oxime ester compound has any one of the following general formula I and general formula III: R 1 Any one selected from H, nitro, cyano, formyl, and methyl; R 2 Any one selected from methyl, ethyl, phenyl, 2-methylphenyl, 2,4,6-trimethylphenyl; n is any integer from 0 to 4; m is 1 or 0; A is a single bond; B is selected from -CH 2 -、-C((CH 2 ) 3 CH 3 ) 2 -、-N(CH 3 )-、-N((CH 2 ) 7 CH 3 )-、-N(CH 2 CH 3 )-, -O-, -S-; Z is selected from -O-, -CH 2 - or a single key.

2. The oxime ester compound according to claim 1, It is characterized in that The structural formula of the oxime ester compound is Any one of .

3. A method for preparing the oxime ester compound according to claim 1 or 2, It is characterized in that The preparation method comprises: Step S1, subjecting compound 1 and compound 2 to an oxime reaction to generate an oxime compound; Step S2, subjecting the oxime compound to an acylating agent for esterification reaction to obtain the oxime ester compound; Wherein, the compound 2 is selected from any one of nitrous acid, alkyl nitrite, and hydroxylamine hydrochloride, The compound 1 has a structural formula I: The oxime compound has the structural formula III: A, B, Z, R 1 , m, n are the same as A, B, Z, R in claim 1 1 , m, n.

4. The preparation method according to claim 3, It is characterized in that In the step S1, the alkyl nitrite is selected from any one or more of methyl nitrite, ethyl nitrite, isopropyl nitrite, butyl nitrite, and isoamyl nitrite.

5. The preparation method according to claim 3, It is characterized in that In step S2, 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.

6. The preparation method according to claim 5, 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.

7. The preparation method according to claim 5 or 6, It is characterized in that The temperature of the esterification reaction is 0-25°C.

8. The preparation method according to claim 5 or 6, 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.

9. The preparation method according to claim 7, 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.

10. The preparation method according to claim 9, 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.

11. The preparation method according to claim 9, 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.

12. The preparation method according to claim 9, 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.

13. The preparation method according to claim 9, 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.

14. The preparation method according to claim 9, 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.

15. The preparation method according to claim 9, 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.

16. The preparation method according to claim 8, 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.

17. The preparation method according to claim 8, 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.

18. The preparation method according to claim 5 or 6, 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.

19. The preparation method according to claim 3, It is characterized in that The esterification reaction is carried out in an alkaline reagent and a solvent.

20. The preparation method according to claim 19, It is characterized in that The alkaline agent is selected from any one or more of triethylamine, pyridine, diisopropylethylamine, potassium hydroxide, sodium hydroxide, and sodium hydride.

21. The preparation method according to claim 19, It is characterized in that The solvent is 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.

22. A photocurable composition comprising a photoinitiator, It is characterized in that The photoinitiator is the oxime ester compound according to claim 1 or 2.

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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