WO2022237644A1

WO2022237644A1 - Oxime ester photoinitiator of chalcone structure, preparation method therefor and application thereof

Info

Publication number: WO2022237644A1
Application number: PCT/CN2022/091212
Authority: WO
Inventors: 钱晓春
Original assignee: 常州强力先端电子材料有限公司; 常州强力电子新材料股份有限公司
Priority date: 2021-05-08
Filing date: 2022-05-06
Publication date: 2022-11-17
Also published as: JP2024523053A; CN115304511A; KR20240005843A

Abstract

The present invention provides an oxime ester photoinitiator of a chalcone structure, a preparation method therefor and an application thereof. The initiator has the following structure: Ar1, wherein Ar2 is a substituent containing an aromatic ring or a heteroaromatic ring, and R1 is C1-C20 linear or branched alkyl, C3-C20 cycloalkyl, C3-C8 cycloalkyl-substituted C1-C10 alkyl, C1-C20 alkyl-substituted C3-C8 cycloalkyl, C6-C20 aryl, C1-C5 alkyl-substituted C6-C20 aryl, C4-C20 heteroaryl, or C1-C5 alkyl-substituted C6-C20 heteroaryl. The oxime ester photoinitiator of the chalcone structure has a large conjugated structure and excellent sensitivity, is difficult to migrate after curing, and has excellent yellowing resistance. In addition, the photoinitiator also has the characteristics of simple synthesis, no need of expensive catalyst in the synthesis process, excellent curing speed and the like, and can be widely applied to the field of photocuring.

Description

Oxime ester photoinitiator with chalcone structure and its preparation method and application

This application is based on the Chinese application with CN application number 202110501130.3 and the application date is May 8, 2021, and claims its priority. The disclosure content of this CN application is incorporated into this application as a whole again.

technical field

The invention relates to the field of organic chemistry, in particular to an oxime ester photoinitiator with a chalcone structure and a preparation method and application thereof.

Background technique

Compounds with oxime ester structure are widely used as photoinitiators in the field of photocuring. Designing and synthesizing new oxime ester photoinitiators with better application performance has always been a research hotspot in the field of photocuring. Due to the high sensitivity of oxime ester photoinitiators, it can be used for color filters, black matrices, etc. used in color televisions, liquid crystal displays, solid-state imaging elements, cameras, etc. in the polymer composition. Patent documents such as publication numbers CN99108598A, CN101508744A, CN10565472A, and CN103293855A disclose different carbazole oxime esters and ketoxime ester photoinitiators. These disclosed photoinitiators have good photosensitivity and storage stability, and can be used in different To a certain extent, it meets the general application requirements in the field of light curing such as display panels and color filters, but it has not been able to balance the sensitivity and yellowing performance.

CN107344918A, CN110066352A, and CN110066225A disclose different oxime ester photoinitiators containing polymerizable groups respectively, but their synthesis process is complex, and the synthesis of this type of compound needs to use expensive palladium catalysts, and the post-treatment process is complicated, and purification is very difficult. The high cost of production greatly limits their applications.

Therefore, it is an urgent problem to be solved in this field to provide a new oxime ester photoinitiator, which is easy to synthesize and has excellent sensitivity and yellowing performance.

Contents of the invention

The main purpose of the present invention is to provide an oxime ester photoinitiator with a chalcone structure and its preparation method and application, to solve the problem that the oxime ester photoinitiator in the prior art cannot take into account the excellent sensitivity and yellowing performance, and the synthesis The problem with the simple route.

In order to achieve the above object, according to one aspect of the present invention, a kind of oxime ester photoinitiator of chalcone structure is provided, and it has the structure shown in following general formula I:

Among them, Ar ₁ and Ar ₂ are substituents containing an aromatic ring or a heteroaromatic ring, R ₁ is a C ₁ to C ₂₀ linear or branched chain alkyl group, a C ₃ to C ₂₀ cycloalkyl group, a C ₃ to C 20 ₈ cycloalkyl substituted C ₁ -C ₁₀ alkyl, C ₁ -C ₂₀ alkyl substituted C ₃ -C ₈ cycloalkyl, C ₆ -C ₂₀ aryl, C ₁ -C ₅ alkane C ₆ -C ₂₀ aryl substituted by radical, C ₄ -C ₂₀ heteroaryl or C ₆ -C ₂₀ heteroaryl substituted by C ₁ -C ₅ alkyl.

According to another aspect of the present invention, there is provided a method for preparing the oxime ester photoinitiator of the above-mentioned chalcone structure, which includes the following steps: performing a formylation reaction with Ar ₁ -H and phosphorus oxychloride to obtain an intermediate 1

Combine intermediate 1 with

Condensation reaction was carried out to obtain intermediate 2

Intermediate 2 is oximated with hydroxylamine hydrochloride to obtain intermediate 3 as

Combine intermediate 3 with

The acid chloride or acid anhydride is esterified to obtain the oxime ester photoinitiator with the above-mentioned chalcone structure; wherein Ar ₁ , Ar ₂ , and R ₁ have the same definitions as those described above.

According to yet another aspect of the present invention, a photocurable composition is provided, including a photoinitiator, which is the above-mentioned oxime ester photoinitiator with a chalcone structure.

The oxime ester photoinitiator with a chalcone structure provided by the present invention has a large conjugated structure, and compared with the existing oxime ester photoinitiator, it has excellent sensitivity, hardened fragments are not easy to migrate, and has excellent anti-yellowing performance. In addition, the photoinitiator also has the characteristics of simple synthesis, no need to use expensive catalysts in the synthesis process, and excellent curing speed after use, and can be widely used in the field of photocuring.

Detailed ways

It should be noted that, in the case of no conflict, the embodiments in the present application and the features in the embodiments can be combined with each other. The present invention will be described in detail below in conjunction with examples.

As described in the background technology section, the photoinitiators of oxime esters in the prior art have the problems of not being able to balance the excellent sensitivity and yellowing performance, and the synthesis route is simple.

In order to solve the above problems, the invention provides a kind of oxime ester photoinitiator of chalcone structure, and it has the structure shown in following general formula I:

Chalcone is a structure with a high degree of conjugation, which has excellent light-absorbing properties and optical properties. There are reports of its use as a polymer monomer, but its use as a photoinitiator parent group has indeed been reported. The present inventors are surprised to find that applying the chalcone structure to the production of the oxime ester photoinitiator is simple to synthesize, and the obtained product has the characteristics of long-wavelength absorption, and is applied to color filters and black matrixes with excellent sensitivity, and The problem of high yellowing caused by high initiator sensitivity in the prior art can be further solved.

In order to further improve the sensitivity of the photoinitiator, improve the anti-yellowing performance after application, and at the same time make the photoinitiator have better initiation efficiency, in a preferred embodiment, Ar ₁ and Ar ₂ are each independently selected from

Optionally, -CH ₂ - in the above groups can be substituted by -O- or -S-; R ₃ is H, nitro, hydroxyl, C ₁ to C ₂₀ straight or branched chain alkyl, C ₃ ~C ₂₀ cycloalkyl, C ₄ ~C ₂₀ alkylcycloalkyl or cycloalkylalkyl, C ₂ ~C ₂₀ alkenyl, C ₅ ~C ₁₀ substituted or unsubstituted cyclic or Heterocyclic alkenyl, C ₆ to C ₁₂ aryl or heteroaryl, C ₆ to C ₁₂ aryl or C ₁ to C ₄ alkyl substituted by heteroaryl, optionally, among these groups -CH ₂ - can be substituted by -O- or -C(=O)-; R ₄ represents H, C ₁ to C ₆ straight chain or branched chain alkyl, C ₁ to C ₆ alkenyl, benzene group or substituted phenyl group.

More preferably, Ar ₁ and Ar ₂ are each independently selected from

By selecting the above types of groups as the Ar ₁ and Ar ₂ groups, the formed photoinitiator can better exert the dual functions of the chalcone structure and the oxime ester structure, and further improve various properties of the photoinitiator.

It should be noted that "*" in the above groups represents the connection positions of the Ar ₁ and Ar ₂ groups.

In a preferred embodiment, R ₁ is a C ₁ -C ₅ linear or branched alkyl group or a C ₆ -C ₁₂ aryl group.

Exemplarily, the photoinitiator is one or more of the following compounds:

According to another aspect of the present invention, also provide a kind of preparation method of the oxime ester photoinitiator of above-mentioned chalcone structure, it comprises the following steps: carry out formylation reaction with Ar ₁ -H and phosphorus oxychloride, Intermediate 1 is obtained, which is

Combine intermediate 1 with

Carry out condensation reaction, obtain intermediate 2, intermediate 2 is

Intermediate 2 is oximated with hydroxylamine hydrochloride to obtain intermediate 3, and intermediate 3 is

Combine intermediate 3 with

The acid chloride or acid anhydride undergoes esterification reaction to obtain an oxime ester photoinitiator with a chalcone structure; wherein Ar ₁ , Ar ₂ , R ₁ , and R ₂ have the same definitions as described above.

Using this preparation method, the oxime ester photoinitiator with chalcone structure can be prepared by sequentially passing Ar ₁ -H through formylation reaction, condensation reaction with acetylated aryl compound, oximation reaction and esterification reaction . The synthesis method has a simple route, mild conditions in each step, convenient operation, no need to use expensive catalysts and other raw materials in the synthesis process, and has advantages in synthesis route and synthesis cost. The prepared photoinitiator has excellent performance in sensitivity, anti-yellowing performance, curing speed and the like.

It should be noted that the above Ar ₁ -H, containing

Acyl chlorides or acid anhydrides, phosphorus oxychloride, hydroxylamine hydrochloride, etc. are all known compounds in the prior art, which can be purchased commercially or can be made by existing methods.

During the above formylation reaction, formyl groups are introduced into the substrate Ar ₁ -H to prepare for subsequent reactions. In order to make the reaction process more stable and improve the reaction efficiency as much as possible, in a preferred embodiment, during the formylation reaction, the reaction temperature is 60-120°C, preferably 100°C, and the reaction time is 1-5h ; More preferably, the formylation reaction is carried out in the first solvent, and the first solvent is DMF.

In a preferred embodiment, the condensation reaction is carried out under the catalysis of the first type of base, preferably the first type of base is selected from sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, sodium tert-butoxide and tert-butyl One or more of potassium alkoxides. Using alkali as a catalyst can effectively improve the reaction efficiency, more preferably using sodium hydroxide as a catalyst.

In order to make the reaction more stable, preferably, the reaction temperature during the condensation reaction is 20-60°C, and the reaction time is 2-6h; preferably, the condensation reaction is carried out in a second solvent, and the second solvent is selected from methanol, ethanol, One or more of isopropanol, tert-butanol, tetrahydrofuran, DMF and DMSO, more preferably methanol.

In a preferred embodiment, the reaction temperature of the oximation reaction is 60-90°C, and the reaction time is 10-16°C; preferably, the oximation reaction is carried out in a third solvent, and the third solvent is selected from methanol, ethanol , one or more of isopropanol and tert-butanol, more preferably ethanol.

In a preferred embodiment, the esterification reaction is carried out under the action of a second type of base, preferably the second type of base is selected from triethylamine, pyridine, diisopropylethylamine, potassium hydroxide, sodium hydroxide and one or more of sodium hydride. The use of base-catalyzed esterification reaction is beneficial to the efficient progress of the esterification reaction. Preferably, the reaction temperature of 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 selected from diethyl ether, acetonitrile, tertiary One or more of butyl methyl ether, tetrahydrofuran, vinyl acetate, toluene, xylene, acetone, methyl ethyl ketone, methylene chloride, chloroform, chlorobenzene, dimethylacetamide and dimethylformamide.

According to yet another aspect of the present invention, application of the above photoinitiator in the field of photocuring is also provided. Due to the excellent sensitivity and anti-yellowing performance of the photoinitiator, it is very suitable for various photopolymerizable compositions applied in the field of photocuring.

According to yet another aspect of the present invention, there is also provided a photocurable composition, including a photoinitiator, which is the above-mentioned oxime ester photoinitiator with a chalcone structure.

Further, the above-mentioned chalcone oxime ester initiator can be applied to coatings coated on substrates such as plastics, metals, glass, ceramics, wood, walls, optical fibers; hard coating agents, antifouling films , anti-reflection film, impact buffer film and other protective film materials; photocurable adhesives, adhesives, photodegradable coatings, coating films, moldings; optical recording media such as holographic materials; optical molding resins, for example, for 3D printing Ink (resin), photoresist for electronic circuit and semiconductor manufacturing, photoresist for electronic materials such as color filter, black matrix, dry film in display, etc.; interlayer insulating film, light extraction film, brightness enhancement film, sealing Materials; printing inks such as screen printing, offset printing, and gravure printing; light-curing inks for inkjet printing; optical components such as lenses, lens arrays, optical waveguides, light guide plates, light diffusion plates, and diffraction elements; optical spacers, Rib walls, materials for nanoimprinting, etc.

The present application will be described in further detail below in conjunction with specific examples, and these examples should not be construed as limiting the scope of protection claimed in the present application.

Example 1

Preparation of Compound 1

Step (1) Preparation of Intermediate 1a

Add 150mL DMF to a 1L three-necked flask, put it in an ice bath, cool down to 0°C, slowly add 100mL POCl ₃ , keep stirring for half an hour; dissolve 55.7g dibutylfluorene (0.2mol) in 150mL DMF, and then add it to the reaction solution middle. Raise the temperature to 100°C and keep stirring for 2h. The reaction of the raw materials was complete, adding 500g of ice water to quench the reaction, the reaction solution was extracted with 500mL of DCM, the organic phase was washed 3 times with 500mL of water, concentrated, the obtained solid was dissolved in 500mL of n-hexane, stirred at room temperature for half an hour, and filtered to obtain 43.3g of off-white Solid, intermediate 1a, yield 70.6%.

Step (2) Preparation of Intermediate 1b

Add 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 into a 500 mL three-necked flask, stir at room temperature for 3 h, and the reaction of the raw materials is complete. 400mL of water was added to the reaction solution, extracted with 200mL of DCM, and the organic phase was concentrated to obtain 36.4g of off-white solid, i.e. intermediate 1b, with a yield of 68.6%.

Step (3) Preparation of Intermediate 1c

Add 30g of intermediate 1b (0.07mol), 15.3g of hydroxylamine hydrochloride (0.21mol), 29.8g of sodium sulfate (0.21mol) and 300g of ethanol into a 500mL three-neck flask, heat to reflux, stir for 12h, and the reaction of the raw materials is complete. The reaction solution was cooled to room temperature, filtered, and the filtrate was concentrated. The obtained oil was dissolved in 120 mL of DCM, washed 3 times with 120 mL of water, and the organic phase was concentrated. The obtained solid was dissolved in 50 mL of acetone, cooled to 0-10 ° C, stirred for 2 hours, and filtered. , to obtain 25.9 g of light yellow solid, ie intermediate 1c, with a yield of 87.4%.

Step (4) Preparation of Compound 1

Add 20g of intermediate 1c (0.05mol), 8.1g of TEA (0.08mol) and 100mL of dichloromethane into a 250mL reaction flask, stir to dissolve. 6.1 g of acetic anhydride (0.06 mol) was added dropwise, and the mixture was stirred at room temperature for 2 h after the drop was completed. Add 100 mL of water to the reaction solution, stir for half an hour, let stand to separate layers, separate the lower organic phase, wash with water until neutral, concentrate the organic phase, dissolve the obtained solid in 100 mL of methanol, and stir at reflux for 1 h. Cool to room temperature, stir for 1 h, then ice-bath, cool to 5-10°C, and stir for 1 h. Filter, and wash the filter cake with 100 mL of methanol to obtain a crude product. The crude product was dissolved in 60mL of acetone, added to 180mL of methanol, stirred and crystallized, continued to stir in an ice bath for 1h, filtered, the filter cake was rinsed with 100mL of methanol, and the obtained solid was dried in a vacuum oven at 60°C for 24h to obtain 19.2g of White solid, yield 82.3%, purity 99.64%.

The structure of compound 1 was confirmed by the following NMR data:

1H NMR (500MHz, Chloroform-d) δ7.69 (d, J＝7.3Hz, 1H), 7.56 (ddd, J＝7.8, 4.3, 2.2Hz, 3H), 7.50–7.44 (m, 1H), 7.44– 7.37(m,5H),7.33–7.26(m,2H),7.24(dd,J=15.2,0.6Hz,1H),7.17(d,J=15.0Hz,1H),2.15(s,3H),2.04 –1.95(m,2H),1.93(d,J=7.1Hz,1H),1.91(d,J=7.0Hz,1H),1.60–1.44(m,4H),1.37(dtd,J=15.0,8.0 ,7.0Hz,4H),0.88(t,J=7.9Hz,6H).

Example 2

Preparation of Compound 2

The reaction scheme is as follows:

Add 20g of intermediate 1c (0.05mol), 8.1g of TEA (0.08mol) and 100mL of dichloromethane into a 250mL reaction flask, stir to dissolve. 8.4 g of benzoyl chloride (0.06 mol) was added dropwise, and the mixture was stirred at room temperature for 2 h after the drop was completed. Add 100 mL of water to the reaction solution, stir for half an hour, let stand to separate layers, separate the lower organic phase, wash with water until neutral, concentrate the organic phase, dissolve the obtained solid in 100 mL of methanol, and stir at reflux for 1 h. Cool to room temperature, stir for 1 h, then ice-bath, cool to 5-10°C, and stir for 1 h. Filter, and wash the filter cake with 100 mL of methanol to obtain a crude product. The crude product was dissolved in 60mL of acetone, added to 180mL of methanol, stirred and crystallized, continued to stir in an ice bath for 1h, filtered, the filter cake was washed with 100mL of methanol, and the obtained solid was dried in a vacuum oven at 60°C for 24h to obtain 19.5g of White solid, yield 73.9%, purity 98.72%.

The structure of compound 2 was confirmed by the following NMR data:

1H NMR (500MHz, Chloroform-d) δ8.17–8.10(m,2H),7.69(d,J＝7.5Hz,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＝15.0Hz,1H),2.08(dt,J＝12.3,7.1Hz,2H),1.98(dt,J＝ 12.4,7.0Hz,2H),1.60–1.44(m,4H),1.43–1.31(m,4H),0.88(t,J＝8.0Hz,6H).

Example 3

Further, different raw materials can be selected for the reaction and different reaction conditions to obtain compounds with different structures, but not limited thereto, see Table 1.

Table 1

performance evaluation

By preparing a representative photocurable resin composition, the curing speed, mobility, solubility, mobility and other application properties of the photoinitiator shown in the formula (I) of the present invention are evaluated, and the specific steps are as follows:

(1) prepare the photocurable resin composition of following composition:

Acrylate copolymer 200 parts by mass

[Benzyl methacrylate/methacrylic acid/hydroxyethyl methacrylate (molar ratio 70/10/20) copolymer (Mv:10000)]

Dipentaerythritol hexaacrylate 100 parts by mass

Photoinitiator 5 parts by mass

Butanone (solvent) 900 parts by mass

In the above composition, the photoinitiator is the compound of formula (I) of the present invention or a known photoinitiator in the prior art (as a comparison).

(2) Curing speed

Stir the above composition under a yellow light, take the material and roll-coat it on a PET template to form a film, dry it at 90°C for 2 minutes to obtain a coating film with a dry film thickness of 2 μm, then cool it to room temperature, and use an LED lamp (wavelength of light source: 385nm, exposure machine model: RW.LED-YT200sg1, single exposure dose 50mJ/cm ² ) to expose the coating film to cure it to form a film.

It is evaluated by the number of times that the coating film is cured into a cured film and passes through the crawler exposure belt. The more the number of passes, the less ideal the curing speed is.

(3) Migration

Cut the cured film into pieces, weigh 0.5g of the cured film sample and place it in a 50mL beaker, add 4.5mL of methanol, and dissolve it with ultrasonic waves for 30min, transfer the resulting methanol solution to a 10mL volumetric flask, and continue to wash the sample twice with methanol ( 2mL×2), pour it into a volumetric flask, use a pipette to pipette 0.1mL toluene as the internal standard, add methanol to determine the solution, shake evenly, and let stand.

Adopt Shimadzu LC-20A liquid chromatography (shim pack column, 150 × 6.0nm, detector SPD-20A, detection limit 20ppm, detection wavelength 254nm), use at 25 ℃, flow rate 1.0mL/min, mobile phase ( Methanol/water=90/10), observe whether the existence of photoinitiator can be detected. Based on the percentage of the peak area ratio of the liquid phase relative to toluene, the higher the initiator content in the liquid phase, the greater the mobility.

(4) Yellowing

Use a wire rod to coat the composition on the tinplate to form a 20μm coating film, expose it with a crawler exposure machine, receive an energy of 1000mJ/ ^cm2 , put it in an oven at 230°C and bake for 30min after curing, and use X-Rite color difference The yellowing test is carried out by the instrument, and the yellowing is judged according to the b value. The higher the value, the more obvious the yellowing.

The characterization results are shown in Table 3.

Table 2

table 3

In Tables 2 and 3, photoinitiator A is 1-(7-nitro-9,9-diallylfluoren-2-yl)-1-(2-methylphenyl)methanone-acetate oxime ester , Photoinitiator B is 1-(6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl)-3-cyclopentyl-propane-1-one-acetate oxime ester, light Initiator C is 1-(9-(2-norbornene)methyl-9-methyl-9H-fluoren-2-yl)-1,2-propanedione-2-oxime-O-acetate .

As can be seen from the test results of tables 2 and 3, the chalcone oxime ester photoinitiator shown in the general formula (I) of the present invention has high initiator efficiency, fast curing speed and no migration in photocuring applications. , less yellowing, excellent overall performance.

It should be pointed out that the yellowing performance of compound 3 is slightly worse than other compounds of the present invention, because it has carried a nitro group in its molecular structure, and for photoinitiators A and C that also contain nitro, the yellowing performance of compound 3 Obvious significantly improved, which is also sufficient to illustrate the beneficial effect of the photoinitiator provided by the present invention with the structure of chalcone oxime esters.

The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims

A kind of oxime ester photoinitiator of chalcone structure, it is characterized in that, described photoinitiator has structure shown in following general formula I:

Among them, Ar 1 and Ar 2 are substituents containing an aromatic ring or a heteroaromatic ring, R 1 is a C 1 to C 20 linear or branched chain alkyl group, a C 3 to C 20 cycloalkyl group, a C 3 to C 20 8 cycloalkyl substituted C 1 -C 10 alkyl, C 1 -C 20 alkyl substituted C 3 -C 8 cycloalkyl, C 6 -C 20 aryl, C 1 -C 5 alkane C 6 -C 20 aryl substituted by radical, C 4 -C 20 heteroaryl or C 6 -C 20 heteroaryl substituted by C 1 -C 5 alkyl.
The oxime ester photoinitiator of chalcone structure according to claim 1, is characterized in that, Ar 1 , Ar 2 are each independently selected from

Optionally, -CH 2 - in the group can be replaced by -O- or -S-;

R 3 is H, nitro, hydroxyl, C 1 to C 20 straight chain or branched chain alkyl, C 3 to C 20 cycloalkyl, C 4 to C 20 alkyl cycloalkyl or cycloalkyl alkane C 2 -C 20 alkenyl, C 5 -C 10 substituted or unsubstituted cyclic or heterocyclic alkenyl, C 6 -C 12 aryl or heteroaryl, C 6 -C 12 C 1 -C 4 alkyl substituted by aryl or heteroaryl, optionally, -CH 2 - in these groups may be substituted by -O- or -C(=O)-;

R 4 represents H, C 1 -C 6 linear or branched alkyl, C 1 -C 6 alkenyl, phenyl or substituted phenyl.
The oxime ester photoinitiator of chalcone structure according to claim 1, is characterized in that, Ar 1 , Ar 2 are each independently selected from
The oxime ester photoinitiator with a chalcone structure according to any one of claims 1 to 3, characterized in that R 1 is a C 1 to C 5 linear or branched alkyl group or a C 6 to C Aryl of 12 .
The oxime ester photoinitiator of chalcone structure according to claim 1, is characterized in that, described photoinitiator is one or more in the following compounds:
A preparation method for the oxime ester photoinitiator of the chalcone structure described in any one of claims 1 to 5, is characterized in that, comprises the following steps:

Ar 1 -H and phosphorus oxychloride are subjected to a formylation reaction to obtain intermediate 1, which is

The intermediate 1 and
Carry out condensation reaction, obtain intermediate 2, described intermediate 2 is

The intermediate 2 is oximated with hydroxylamine hydrochloride to obtain the intermediate 3, and the intermediate 3 is

Said intermediate 3 was mixed with
The acid chloride or acid anhydride is esterified to obtain the oxime ester photoinitiator of the chalcone structure;

Wherein Ar 1 , Ar 2 , and R 1 have the same definitions as in any one of claims 1 to 5.
The preparation method of the oxime ester photoinitiator of chalcone structure according to claim 6, is characterized in that, in the process of described formylation reaction, reaction temperature is 60～120 ℃, preferably 100 ℃, reaction The time is 1~5h;

Preferably, the formylation reaction is carried out in a first solvent, and the first solvent is DMF.
The preparation method of the oxime ester photoinitiator of chalcone structure according to claim 6, is characterized in that, described condensation reaction is carried out under the catalysis of first class base, and preferably described first class base is selected from One or more of sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide and potassium tert-butoxide, more preferably sodium hydroxide;

Preferably, the reaction temperature during the condensation reaction is 20-60° C., and the reaction time is 2-6 hours;

Preferably, the condensation reaction is carried out in a second solvent, the second solvent is selected from one or more of methanol, ethanol, isopropanol, tert-butanol, tetrahydrofuran, DMF and DMSO, more preferably methanol .
The preparation method of oxime ester photoinitiator with chalcone structure according to claim 6, characterized in that, the reaction temperature of the oximation reaction is 60-90°C, and the reaction time is 10-16°C;

Preferably, the oximation reaction is carried out in a third solvent, and the third solvent is selected from one or more of methanol, ethanol, isopropanol and tert-butanol, more preferably ethanol.
The preparation method of the oxime ester photoinitiator of chalcone structure according to claim 6, is characterized in that, described esterification is carried out under the effect of second class alkali, and preferably described second class alkali is selected from One or more of triethylamine, pyridine, diisopropylethylamine, potassium hydroxide, sodium hydroxide and sodium hydride;

Preferably, the reaction temperature of the esterification reaction is -10-60°C, more preferably 0-25°C;

Preferably, the esterification reaction is carried out in a fourth solvent selected from diethyl ether, acetonitrile, tert-butyl methyl ether, tetrahydrofuran, vinyl acetate, toluene, xylene, acetone, methyl ethyl ketone, di One or more of methyl chloride, chloroform, chlorobenzene, dimethylacetamide and dimethylformamide.
A photocurable composition, comprising a photoinitiator, characterized in that the photoinitiator is the oxime ester photoinitiator of the chalcone structure described in any one of claims 1 to 5.
The photocurable composition according to claim 11, wherein the photocurable composition is used in the following fields: coatings coated on plastics, metals, glass, ceramics, wood, walls or optical fiber substrates ; Hard coating agent, anti-fouling film, anti-reflection film or impact buffer film material; photocurable adhesive, adhesive, photodegradable coating, coating film, molding; optical recording medium; optical molding resin; interlayer insulating film , light extraction film, brightness enhancement film, sealing material; printing ink, photocurable ink for inkjet printing; optical components; optical spacers, rib walls, materials for nanoimprinting;

Preferably, the optical molding resin is ink or resin for 3D printing, photoresist for electronic circuit and semiconductor manufacturing, photoresist for electronic material;

Preferably, the printing ink is an ink for screen printing, offset printing or gravure printing;

Preferably, the optical component is a lens, a lens array, an optical waveguide, a light guide plate, a light diffusion plate or a diffraction element;

Preferably, the optical recording medium is a holographic image material.