Oxime ester photoinitiators with chalcone structure, and methods for producing and using the same

Abstract

The present invention provides an oxime ester photoinitiator having a chalcone structure, and a method for preparing and using the same. The initiator has the following structure. The oxime ester photoinitiator having a chalcone structure has a large conjugated structure, excellent sensitivity, is less likely to migrate after curing, and has excellent yellowing resistance. In addition, the photoinitiator is easy to synthesize, does not require the use of expensive catalysts in the synthesis process, and has excellent curing speed, so it can be widely used in the photocuring field. [Formula 1] TIFF2024523053000054.tif20170[where, Ar 1 , Ar 2 is a substituent containing an aromatic ring or a heteroaromatic ring, R 1 is C 1 ~C 20 A linear or branched alkyl group of C 3 ~C 20 Cycloalkyl groups of C 3 ~C 8 C substituted with cycloalkyl groups 1 ~C 10 Alkyl groups of C 1 ~C 20 C substituted with alkyl groups 3 ~C 8 Cycloalkyl groups of C 6 ~C 20 Aryl group, C 1 ~C 5 C substituted with alkyl groups 6 ~C 20 Aryl group, C 4 ~C 20 or C 1 ~C 5 C substituted with alkyl groups 6 ~C 20 is a heteroaryl group represented by the formula:

Description

[Technical Field]

[0001] This application claims priority from a Chinese application with CN Application No. 202110501130.3, filed on May 8, 2021, and the entire disclosure of that CN application is incorporated herein by reference.

[0002] The present invention relates to the field of organic chemistry, and specifically to an oxime ester photoinitiator having a chalcone structure and its preparation method and use. [Background technology]

[0003] Compounds having an oxime ester structure are widely used as photoinitiators in the photocuring field, and the design and synthesis of new oxime ester photoinitiators with better application performance have been the subject of active research in the photocuring field. Oxime ester photoinitiators have high sensitivity and can be used in photopolymerizable compositions containing colorants for applications such as color filters and black matrices used in color televisions, liquid crystal displays, solid-state imaging devices, and cameras. For example, patent documents such as CN99108598A, CN101508744A, CN10565472A, and CN103293855A disclose different carbazole oxime ester and ketoxime ester photoinitiators. These photoinitiators have good photosensitivity and storage stability and can meet, to varying degrees, the general requirements for use in photocuring applications such as conventional display panels and color filters. However, until now, they have not been able to balance sensitivity and yellowing resistance.

[0004] CN107344918A, CN110066352A, and CN110066225A each disclose different oxime ester photoinitiators containing polymerizable groups, but the synthesis processes are complicated, and the synthesis of such compounds requires the use of expensive palladium catalysts. In addition, the post-treatment processes are complicated, purification is very difficult, and the production costs are very high, which greatly limits their use.

[0005] Therefore, providing a novel oxime ester photoinitiator that is easy to synthesize and has excellent sensitivity and yellowing resistance is an urgent problem that must be solved in this field. Summary of the Invention

[0006] The main object of the present invention is to provide an oxime ester photoinitiator having a chalcone structure, and a method for producing and using the same, in order to solve the problem that the oxime ester photoinitiator of the prior art cannot have both excellent sensitivity and yellowing resistance and a simple synthesis scheme.

[0007] To achieve the above object, according to one aspect of the present invention, there is provided an oxime ester photoinitiator having a chalcone structure and having a structure represented by the following general formula I:

[0008] [ka] [In the formula, Ar1 and Ar2 are substituents containing an aromatic ring or a heteroaromatic ring, and R1 is a C1-C 20 Straight or branched alkyl groups, C3 to C 20 cycloalkyl groups of C1-C substituted with C3-C8 cycloalkyl groups 10 Alkyl groups, C1-C 20 C3-C8 cycloalkyl group substituted with an alkyl group of 20 C6-C substituted with aryl groups, C1-C5 alkyl groups 20 Aryl groups, C4-C 20 or a C6-C alkyl group substituted with a C1-C5 alkyl group. 20 is a heteroaryl group of the formula: According to another aspect of the present invention, there is provided a method for producing the chalcone-structured oxime ester photoinitiator, comprising the steps of: subjecting Ar1-H to a formylation reaction with phosphoryl trichloride to produce intermediate 1; [ka] and a step of obtaining intermediate 1. [ka] and condensation reaction to obtain intermediate 2 [ka] and a step of subjecting intermediate 2 to an oximation reaction with hydroxylamine hydrochloride to obtain intermediate 3. [ka] and reacting intermediate 3 with [ka] to obtain the chalcone-structured oxime ester photoinitiator, wherein Ar1, Ar2, and R1 are as defined above.

[0009] According to yet another aspect of the present invention, there is provided a photocurable composition comprising a photoinitiator, wherein the photoinitiator is an oxime ester photoinitiator having the above chalcone structure.

[0010] The chalcone-structured oxime ester photoinitiator provided by the present invention has a large conjugated structure, and is more sensitive than conventional oxime ester photoinitiators, and is less likely to migrate after curing, and has excellent yellowing resistance. In addition, the photoinitiator is simple to synthesize, does not require the use of expensive catalysts in the synthesis process, and has excellent curing speed after use, making it suitable for wide use in photocuring applications. DETAILED DESCRIPTION OF THE INVENTION

[0011] It should be noted that, unless there is a contradiction, the embodiments and features of the embodiments in the present application may be combined with each other. The present invention will be described in detail below in connection with the embodiments.

[0012] As explained in the Background Art section, the oxime ester photoinitiators of the prior art have a problem in that they cannot simultaneously achieve excellent sensitivity and yellowing resistance and a simple synthesis scheme.

[0013] In order to solve the above problems, the present invention provides an oxime ester photoinitiator having a chalcone structure, which has a structure represented by the following general formula I:

[0014] [ka] [In the formula, Ar1 and Ar2 are substituents containing an aromatic ring or a heteroaromatic ring, and R1 is a C1-C 20 Straight or branched alkyl groups, C3 to C 20 cycloalkyl groups of C1-C substituted with C3-C8 cycloalkyl groups 10 Alkyl groups, C1-C 20 C3-C8 cycloalkyl group substituted with an alkyl group of 20 C6-C substituted with aryl groups, C1-C5 alkyl groups 20 Aryl groups, C4-C 20 or a C6-C alkyl group substituted with a C1-C5 alkyl group. 20 is a heteroaryl group of the formula: Chalcones have a highly conjugated structure and excellent light absorption and optical properties. While their use as polymer monomers has been reported, their use as the parent group of photoinitiators has been rarely reported. The inventors surprisingly discovered that the use of chalcone structures in the preparation of oxime ester photoinitiators simplifies synthesis and results in products characterized by long wavelength absorption. When used in color filters and black matrices, these products offer excellent sensitivity and solve the problem of high yellowing due to the high sensitivity of initiators in the prior art.

[0015] The chalcone-structured oxime ester photoinitiator provided by the present invention has a large conjugated structure, and is more sensitive than conventional oxime ester photoinitiators, and is less likely to migrate after curing, and has excellent yellowing resistance. In addition, the photoinitiator is easy to synthesize, does not require the use of expensive catalysts in the synthesis process, and has excellent curing speed after use, making it suitable for wide use in photocuring applications.

[0016] In order to further improve the sensitivity of the photoinitiator and improve the yellowing resistance after use while making the photoinitiator have better initiation efficiency, in one preferred embodiment, Ar1 and Ar2 are each independently [ka] In the above groups, optionally, -CH2- may be replaced by -O- or -S-; R3 is selected from the group consisting of H, a nitro group, a hydroxyl group, a C1-C 20 Straight or branched alkyl groups, C3 to C 20 Cycloalkyl groups of C4 to C 20 alkylcycloalkyl group or cycloalkylalkyl group, C2-C 20 Chain alkenyl group, C5-C 10 substituted or unsubstituted cyclic or heterocyclic alkenyl groups, C6-C 12 aryl or heteroaryl groups, C6-C 12 and R4 represents H, a C1-C6 linear or branched alkyl group, a C1-C6 chain alkenyl group, a phenyl group, or a substituted phenyl group.

[0017] More preferably, Ar1 and Ar2 are each independently [ka] [ka] The photoinitiator formed by selecting and using the above-mentioned groups as the Ar1 and Ar2 groups can better utilize the dual functions of the chalcone structure and the oxime ester structure, thereby further improving the performance of the photoinitiator.

[0018] In addition, the "*" in the above groups represents a bond between the Ar1 and Ar2 groups.

[0019] In one preferred embodiment, R1 is a C1 to C5 linear or branched alkyl group or a C6 to C 12 is an aryl group of the formula:

[0020] Illustratively, the photoinitiator is one or more of the following compounds:

[0021] [ka] [ka] [ka] [ka] [ka] [ka] According to another aspect of the present invention, there is provided a method for producing the chalcone-structured oxime ester photoinitiator, comprising the steps of: subjecting Ar1-H to a formylation reaction with phosphoryl trichloride to produce intermediate 1; [ka] and a step of obtaining intermediate 1. [ka] and condensation reaction to obtain intermediate 2 [ka] and a step of subjecting intermediate 2 to an oximation reaction with hydroxylamine hydrochloride to obtain intermediate 3. [ka] and reacting intermediate 3 with [ka] and an esterification reaction with an acid chloride or acid anhydride containing the formula:

[0022] Using this method, Ar1-H can be sequentially subjected to formylation, condensation with an acetylated aryl compound, oximation, and esterification to produce a chalcone-structured oxime ester photoinitiator. The synthesis scheme is simple, the conditions for each step are mild, the operation is convenient, and there is no need to use expensive raw materials such as catalysts during the synthesis process, offering advantages in terms of synthesis scheme and synthesis cost. The resulting photoinitiator has excellent sensitivity, yellowing resistance, and curing speed.

[0023] In addition, the above Ar1-H, [ka] The acid chlorides or acid anhydrides containing the compound (III), phosphoryl trichloride, hydroxylamine hydrochloride, etc. are all compounds known in the prior art and may be commercially available or may be prepared by conventional methods.

[0024] In the formylation reaction, an aldehyde group is introduced into the substrate Ar1-H, preparing it for the subsequent reaction. In order to stabilize the reaction and improve the reaction efficiency as much as possible, in one preferred embodiment, the reaction temperature is 60 to 120°C, preferably 100°C, and the reaction time is 1 to 5 hours. More preferably, the formylation reaction is carried out in a first solvent, and the first solvent is DMF.

[0025] In one preferred embodiment, the condensation reaction is carried out under the catalysis of a first alkali, and the first alkali is preferably one or more selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, and potassium tert-butoxide. The use of an alkali as a catalyst can effectively improve the reaction efficiency, and more preferably, sodium hydroxide is used as the catalyst.

[0026] To further stabilize the reaction, the reaction temperature in the condensation reaction process is preferably 20 to 60°C, the reaction time is preferably 2 to 6 hours, the condensation reaction is preferably carried out in a second solvent, and the second solvent is preferably one or more selected from the group consisting of methanol, ethanol, isopropanol, tert-butanol, tetrahydrofuran, DMF, and DMSO, more preferably methanol.

[0027] In one preferred embodiment, the reaction temperature of the oximation reaction is 60 to 90°C, and the reaction time is 10 to 16 h Preferably, the oxime-forming reaction is carried out in a third solvent, and the third solvent is one or more selected from the group consisting of methanol, ethanol, isopropanol, and tert-butanol, more preferably ethanol.

[0028] In one preferred embodiment, the esterification reaction is carried out under the action of a second alkali, and preferably, the second alkali is one or more selected from the group consisting of triethylamine, pyridine, diisopropylethylamine, potassium hydroxide, sodium hydroxide, and sodium hydride. Selecting an alkali as a catalyst for the esterification reaction is advantageous for efficient esterification. Preferably, the reaction temperature for the esterification reaction is −10 to 60° C., more preferably 0 to 25° C. Preferably, the esterification reaction is carried out in a fourth solvent, and the fourth solvent is one or more selected from the group consisting of diethyl ether, acetonitrile, tert-butyl methyl ether, tetrahydrofuran, vinyl acetate, toluene, xylene, propanone, methyl ethyl ketone, dichloromethane, chloroform, chlorobenzene, dimethylacetamide, and dimethylformamide.

[0029] According to yet another aspect of the present invention, there is further provided a use of the above-mentioned photoinitiator in the field of photocuring. The photoinitiator has excellent sensitivity and yellowing resistance, making it highly suitable for use in various photopolymerizable compositions in the field of photocuring.

[0030] According to yet another aspect of the present invention, there is further provided a photocurable composition comprising a photoinitiator, wherein the photoinitiator is the above-described oxime ester photoinitiator having a chalcone structure.

[0031] Furthermore, the chalcone oxime ester initiators can be used in coatings applied to substrates such as plastics, metals, glass, ceramics, wood, walls, and optical fibers; protective film materials such as hard coats, antifouling films, antireflection films, and buffer films; photocurable adhesives, pressure-sensitive adhesives, photodegradable coatings, coatings, and molded articles; optical recording media such as hologram materials; optical molding resins, for example, 3D printing inks (resins), photoresists for electronic circuit and semiconductor manufacturing, color filters in displays, black matrices, and photoresists for electronic materials such as dry films; interlayer insulating films, light extraction films, brightness enhancement films, and encapsulants; printing inks for screen printing, offset printing, gravure printing, and the like, and photocurable inks for inkjet printing; optical components such as lenses, lens arrays, optical waveguides, light guide plates, light diffusion plates, and diffraction elements; photospacers, ribs, and nanoimprint materials.

[0032] Example Hereinafter, the present application will be described in more detail in combination with specific examples, and it can be understood that these examples do not limit the scope of protection sought for by the present application.

[0033] Example 1 Preparation of Compound 1 [ka] Step (1) Preparation of Intermediate 1a [ka] A 1L three-neck flask was charged with 150mL of DMF and cooled to 0°C in an ice bath. 100mL of POCl3 was slowly added and stirred for 30 minutes while maintaining the temperature. 55.7g of dibutylfluorene (0.2mol) was dissolved in 150mL of DMF and then added to the reaction mixture. The temperature was raised to 100°C and the mixture was stirred for 2 hours while maintaining the temperature. Upon complete reaction of the starting materials, 500g of ice water was added to quench the reaction. The reaction mixture was extracted with 500mL of DCM. The organic phase was washed three times with 500mL of water and concentrated. The resulting solid was dissolved in 500mL of n-hexane, stirred at room temperature for 30 minutes, and filtered to obtain 43.3g of an off-white solid, i.e., Intermediate 1a, in a 70.6% yield.

[0034] Step (2) Preparation of Intermediate 1b [ka] A 500 mL three-neck flask was charged with 40 g of intermediate 1a (0.13 mol), 15.7 g of acetophenone (0.13 mol), 5.7 g of sodium hydroxide (0.14 mol), and 400 g of methanol, and the mixture was stirred at room temperature for 3 hours to allow the materials to react completely. 400 mL of water was added to the reaction mixture, which was then extracted with 200 mL of DCM. The organic phase was concentrated to give 36.4 g of an off-white solid, intermediate 1b, in a 68.6% yield.

[0035] Step (3) Preparation of Intermediate 1c [ka] A 500 mL three-neck flask was charged with 30 g of intermediate 1b (0.07 mol), 15.3 g of hydroxylamine hydrochloride (0.21 mol), 29.8 g of sodium sulfate (0.21 mol), and 300 g of ethanol. The mixture was heated to reflux and stirred for 12 h to allow the materials to react completely. The reaction mixture was cooled to room temperature, filtered, and the filtrate was concentrated. The resulting oil was dissolved in 120 mL of DCM and washed three times with 120 mL of water. The organic phase was concentrated, and the resulting solid was dissolved in 50 mL of propanone. The mixture was cooled to 0-10 °C in an ice bath, stirred for 2 h, and filtered to obtain 25.9 g of a pale yellow solid, i.e., intermediate 1c, in an 87.4% yield.

[0036] Step (4) Preparation of Compound 1 [ka] A 250 mL reaction flask was charged with 20 g of intermediate 1c (0.05 mol), 8.1 g of TEA (0.08 mol), and 100 mL of dichloromethane, and the mixture was stirred until a clear solution was obtained. 6.1 g of acetic anhydride (0.06 mol) was added dropwise, and the mixture was stirred at room temperature for 2 h. 100 mL of water was added to the reaction mixture, and the mixture was stirred for 30 minutes. The mixture was then allowed to stand for phase separation. The lower organic phase was isolated and washed with water until neutral. The organic phase was concentrated, and the resulting solid was dissolved in 100 mL of methanol and stirred under reflux for 1 h. The mixture was cooled to room temperature, stirred for 1 h, and then cooled to 5-10 °C in an ice bath and stirred for 1 h. The mixture was filtered, and the filter cake was washed with 100 mL of methanol to obtain the crude product. The crude product was dissolved in 60 mL of propanone and added to 180 mL of methanol. The mixture was stirred to precipitate crystals, and the mixture was stirred in an ice bath for 1 hour. The mixture was then filtered, and the filter cake was washed with 100 mL of methanol. The resulting solid was dried in a vacuum drying cabinet at 60°C for 24 hours to obtain 19.2 g of an off-white solid with a yield of 82.3% and a purity of 99.64%.

[0037] The structure of Compound 1 was confirmed by the following nuclear magnetic data.

[0038] 1H NMR (500 MHz, Chloroform-d) δ 7.69 (d, J = 7.3 Hz, 1H), 7.56 (ddd, J = 7.8, 4.3, 2.2 Hz, 3H), 7.50 - 7.44 (m, 1H), 7.44 - 7.37 (m, 5H), 7.33 - 7.26 (m, 2H), 7.24 (dd, J = 15.2, 0.6 Hz, 1H), 7.17 (d, J = 15.0 Hz, 1H), 2.15 (s, 3H), 2.04 - 1.95 (m, 2H), 1.93 (d, J = 7.1 Hz, 1H), 1.91 (d, J = 7.0 Hz, 1H), 1.60 - 1.44 (m, 4H), 1.37 (dtd, J = 15.0, 8.0, 7.0 Hz, 4H), 0.88 (t, J = 7.9 Hz, 6H).

[0039] Example 2 Preparation of Compound 2 [ka] The reaction scheme is as follows:

[0040] [ka] A 250 mL reaction flask was charged with 20 g of intermediate 1c (0.05 mol), 8.1 g of TEA (0.08 mol), and 100 mL of dichloromethane, and the mixture was stirred until the solution became clear. 8.4 g of benzoyl chloride (0.06 mol) was added dropwise, and the mixture was stirred at room temperature for 2 h. 100 mL of water was added to the reaction mixture, and the mixture was stirred for 30 minutes. The mixture was then allowed to stand for phase separation. The lower organic phase was isolated and washed with water until neutral. The organic phase was concentrated, and the resulting solid was dissolved in 100 mL of methanol and stirred under reflux for 1 h. The mixture was cooled to room temperature, stirred for 1 h, and then cooled to 5-10 °C in an ice bath and stirred for 1 h. The mixture was filtered, and the filter cake was washed with 100 mL of methanol to obtain the crude product. The crude product was dissolved in 60 mL of propanone and added to 180 mL of methanol. Crystals were precipitated with stirring, and the mixture was stirred in an ice bath for 1 hour. The mixture was then filtered, and the filter cake was washed with 100 mL of methanol. The resulting solid was dried in a vacuum drying box at 60°C for 24 hours to obtain 19.5 g of an off-white solid with a yield of 73.9% and a purity of 98.72%.

[0041] The structure of Compound 2 was confirmed by the following nuclear magnetic data.

[0042] 1H NMR (500 MHz, Chloroform-d) δ 8.17 - 8.10 (m, 2H), 7.69 (d, J = 7.5 Hz, 1H), 7.63 - 7.57 (m, 1H), 7.57 - 7.52 (m, 3H), 7.52 - 7.37 (m, 8H), 7.36 - 7.22 (m, 3H), 7.09 (d, J = 15.0 Hz, 1H), 2.08 (dt, J = 12.3, 7.1 Hz, 2H), 1.98 (dt, J = 12.4, 7.0 Hz, 2H), 1.60 - 1.44 (m, 4H), 1.43 - 1.31 (m, 4H), 0.88 (t, J = 8.0 Hz, 6H).

[0043] Example 3 Furthermore, as shown in Table 1, compounds with different structures can be obtained by selecting different raw materials and carrying out the reaction under different reaction conditions, but this is not limited to these.

[0044] [Table 1(1)] [Table 1(2)] [Table 1(3)] [Table 1(4)] [Table 1(5)] [Table 1(6)] Performance evaluation Typical photocurable resin compositions were prepared to evaluate the curing speed, migration, solubility, migration, and other performance characteristics of the photoinitiator represented by formula (I) of the present invention. The specific steps are as follows:

[0045] (1) A photocurable resin composition having the following composition is prepared: Acrylate copolymer 200 parts by mass [Benzyl methacrylate / methacrylic acid / hydroxyethyl methacrylate (molar ratio 70 / 10 / 20) copolymer (Mv: 10,000)] Dipentaerythritol hexaacrylate 100 parts by mass Photoinitiator 5 parts by mass Butanone (solvent) 900 parts by mass In the above compositions, the photoinitiator is a compound of formula (I) of the present invention or a photoinitiator known in the prior art (for comparison).

[0046] (2) Curing speed The composition was stirred under a yellow light lamp, and then taken and applied to a PET plate using a roll coater to form a film. The film was dried at 90°C for 2 minutes to obtain a coating film with a dry film thickness of 2 μm. The film was then cooled to room temperature and exposed to light using an LED lamp (light source wavelength: 385 nm, exposure machine model number: RW.LED-YT200sg1, exposure dose per exposure: 50 mJ / cm). 2 ) The coating film is exposed to radiation and hardened to form a film.

[0047] The coating was evaluated based on the number of times it passed through a crawler exposure machine until it cured and became a cured film, and the more times it passed, the worse the curing rate.

[0048] (3) Migration The cured film was cut into pieces, and 0.5 g of the cured film sample was weighed and placed in a 50 mL beaker. 4.5 mL of methanol was added and the sample was dissolved ultrasonically for 30 min. The resulting methanol solution was transferred to a 10 mL measuring flask. The sample was then washed twice with methanol (2 mL x 2) and placed in a measuring flask. 0.1 mL of toluene was pipetted as an internal standard substance, and methanol was added to the solution to make the volume constant. The sample was then shaken evenly and allowed to stand.

[0049] A Shimadzu LC-20A liquid chromatograph (Shim Pack column, 150 x 6.0 mm, SPD-20A detector, detection limit 20 ppm, detection wavelength 254 nm) was used to observe whether the presence of photoinitiators could be detected under the conditions of 25°C, flow rate 1.0 mL / min, and mobile phase (methanol / water = 90 / 10). Evaluation was based on the peak area percentage of the liquid phase relative to toluene, and it was shown that the higher the initiator content in the liquid phase, the greater the migration tendency.

[0050] (4) Yellowing degree The composition was applied to tinplate using a wire bar to form a 20 μm coating film, which was then exposed to light using a crawler exposure machine at 1000 mJ / cm 2 After receiving the energy and curing is complete, the product is left in an oven and baked at 230°C for 30 minutes, and yellowing is measured using an X-Rite colorimeter. The degree of yellowing is determined based on the b value; the higher the value, the more obvious the yellowing.

[0051] The characterization results are shown in Table 3.

[0052] [Table 2] [Table 3] In Tables 2 and 3, photoinitiator A is 1-(7-nitro-9,9-diallylfluoren-2-yl)-1-(2-methylphenyl)ketone-oxime acetate, photoinitiator B is 1-(6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl)-3-cyclohexyl-propan-1-one-oxime acetate, and photoinitiator C is 1-(9-(2-norbornene)methyl-9-methyl-9H-fluoren-2-yl)-1,2-propanedione-2-oxime-O-acetate.

[0053] As can be seen from the measurement results in Tables 2 and 3, the chalcone oxime ester photoinitiator represented by general formula (I) of the present invention has high initiator efficiency when used for photocuring, a fast curing speed, no migration, and little yellowing, and has excellent overall performance.

[0054] The yellowing index of Compound 3 is slightly lower than that of the other compounds of the present invention because its molecular structure contains a nitro group. Similarly, the yellowing index of Compound 3 is significantly improved when using Photoinitiators A and C, which also contain a nitro group. This also explains the beneficial effects achieved by the photoinitiators having a chalcone oxime ester structure provided by the present invention.

[0055] The above is merely a preferred embodiment of the present invention, and is not intended to limit the present invention. Those skilled in the art may make various modifications and changes to the present invention. All modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention are included within the protection scope of the present invention.

Claims

1. An oxime ester photoinitiator having a chalcone structure, characterized by having a structure represented by the following general formula I: 【Chemical 1】 [In the formula, Ar ２ is a substituent containing an aromatic ring or a heteroaromatic ring, and R １ is C １ ~C ２０ a linear or branched alkyl group of C ３ ~C ２０ a cycloalkyl group of C ３ ~C ８ C substituted with a cycloalkyl group of １ ~C １０ alkyl group of C １ ~C ２０ C substituted with an alkyl group ３ ~C ８ a cycloalkyl group of C ６ ~C ２０ an aryl group of C １ ~C ５ C substituted with an alkyl group ６ ~C ２０ an aryl group of C ４ ~C ２０ a heteroaryl group of the formula C １ ~C ５ C substituted with an alkyl group of ６ ~C ２０ is a heteroaryl group of the formula Ar 1 is 【Chemistry 2】 selected from the group consisting of Optionally, the —CH 2 — in the group may be replaced by —O— or —S—; R 3 is H, a nitro group, a hydroxyl group, a C 1 to C 20 linear or branched alkyl group, a C 3 to C 20 cycloalkyl group, a C 4 to C 20 alkylcycloalkyl or cycloalkylalkyl group, a C 2 to C 20 chain alkenyl group, a C 5 to C 10 substituted or unsubstituted cyclic or heterocyclic alkenyl group, a C 6 to C 12 aryl or heteroaryl group, or a C 1 to C 4 alkyl group substituted with a C 6 to C 12 aryl or heteroaryl group, and optionally, —CH 2 — in these groups may be replaced by —O— or —C(═O)—; R 4 represents H, a C 1 to C 6 linear or branched alkyl group, a C 1 to C 6 chain alkenyl group, a phenyl group, or a substituted phenyl group.]

2. Ar ２ teeth, 【Chemistry 3】 selected from the group consisting of Optionally, the —CH ２ - may be substituted with -O- or -S-, R ３ is H, nitro group, hydroxyl group, C １ ~C ２０ a linear or branched alkyl group of C ３ ~C ２０ a cycloalkyl group of C ４ ~C ２０ an alkylcycloalkyl group or a cycloalkylalkyl group of C ２ ~C ２０ a chain alkenyl group of C ５ ~C １０ a substituted or unsubstituted cyclic or heterocyclic alkenyl group represented by the formula C ６ ~C １２ an aryl or heteroaryl group of C ６ ~C １２ C substituted with an aryl or heteroaryl group １ ~C ４ and optionally, -CH ２ - may be substituted by -O- or -C(=O)-, R ４ is H, C １ ~C ６ a linear or branched alkyl group of C １ ~C ６ 2. The oxime ester photoinitiator having a chalcone structure according to claim 1, wherein the oxime ester photoinitiator is a chain alkenyl group, a phenyl group, or a substituted phenyl group represented by the formula:

3. Ar １ teeth, 【Chemistry 4】 【Chemistry 5】 selected from the group consisting of Ar ２ teeth, 【Chemistry 6】 【Chemistry 7】 The oxime ester photoinitiator having a chalcone structure according to claim 1, characterized in that it is selected from the group consisting of:

4. R １ is C １ ~C ５ or a linear or branched alkyl group of C ６ ~C １２ The oxime ester photoinitiator having a chalcone structure according to claim 1, characterized in that the aryl group is

5. The oxime ester photoinitiator having a chalcone structure according to claim 1, wherein the photoinitiator is one or more of the following compounds: 【Chemistry 8】 【Chemistry 9】 【Chemistry 10】 【Chemistry 11】 【Chemistry 12】 【Chemistry 13】

6. A method for producing the oxime ester photoinitiator having a chalcone structure according to any one of claims 1 to 5, comprising the steps of: Ar １ -H and phosphoryl trichloride to form intermediate 1 【Chemistry 14】 and The intermediate 1 【Chemistry 15】 to form intermediate 2 【Chemistry 16】 and The intermediate 2 is subjected to an oximation reaction with hydroxylamine hydrochloride to obtain intermediate 3. 【Chemistry 17】 and The intermediate 3 【Chemistry 18】 and an acid chloride or acid anhydride containing the compound (I) to obtain an oxime ester photoinitiator having a chalcone structure. Including, However, Ar １ , Ar ２ , R １ A method for producing an oxime ester photoinitiator having a chalcone structure, characterized in that the oxime ester photoinitiator is as defined in any one of claims 1 to 5.

7. In the formylation reaction, the reaction temperature is 60 to 120°C, and the reaction time is 1 to 5 hours; 7. The method for producing an oxime ester photoinitiator having a chalcone structure according to claim 6, wherein the formylation reaction is carried out in a first solvent, and the first solvent is DMF.

8. the condensation reaction is carried out under the catalytic action of a first alkali, and the first alkali is one or more selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, and potassium tert-butoxide; The reaction temperature during the condensation reaction is 20 to 60°C, and the reaction time is 2 to 6 hours; The method for producing an oxime ester photoinitiator having a chalcone structure according to claim 6, characterized in that the condensation reaction is carried out in a second solvent, and the second solvent is one or more selected from the group consisting of methanol, ethanol, isopropanol, tert-butanol, tetrahydrofuran, DMF, and DMSO.

9. the reaction temperature of the oximation reaction is 60 to 90°C, and the reaction time is 10 to 16 hours; The method for producing an oxime ester photoinitiator having a chalcone structure according to claim 6, characterized in that the oxime-forming reaction is carried out in a third solvent, and the third solvent is one or more selected from the group consisting of methanol, ethanol, isopropanol, and tert-butanol.

10. the esterification reaction is carried out under the action of a second alkali, and the second alkali is one or more selected from the group consisting of triethylamine, pyridine, diisopropylethylamine, potassium hydroxide, sodium hydroxide, and sodium hydride; the reaction temperature of the esterification reaction is −10 to 60° C., The method for producing an oxime ester photoinitiator having a chalcone structure according to claim 6, wherein the esterification reaction is carried out in a fourth solvent, and the fourth solvent is one or more solvents selected from the group consisting of diethyl ether, acetonitrile, tert-butyl methyl ether, tetrahydrofuran, vinyl acetate, toluene, xylene, propanone, methyl ethyl ketone, dichloromethane, chloroform, chlorobenzene, dimethylacetamide, and dimethylformamide.

11. A photocurable composition comprising a photoinitiator, wherein the photoinitiator is an oxime ester photoinitiator having a chalcone structure according to any one of claims 1 to 5.

12. The photocurable composition is used in the fields of: paints to be applied to plastics, metals, glass, ceramics, wood, walls, or optical fiber substrates; hard coating agents, antifouling films, antireflection films, or buffer film materials; photocurable adhesives, pressure-sensitive adhesives, photodegradable paints, coating films, and molded articles; optical recording media; optical molding resins; interlayer insulating films, light extraction films, brightness improving films, and sealants; printing inks and photocurable inks for inkjet printing; optical components; photospacers, ribs, and nanoimprint materials. The optical molding resin is an ink or resin for 3D printing, a photoresist for electronic circuit and semiconductor manufacturing, or a photoresist for electronic materials; the printing ink is an ink for screen printing, offset printing or gravure printing, the optical member is a lens, a lens array, an optical waveguide, a light guide plate, a light diffusion plate, or a diffraction element, 12. The photocurable composition according to claim 11, wherein the optical recording medium is a holographic material.

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