KR20240005843A - Oxime ester photoinitiator with chalcone structure and manufacturing method and application thereof - Google Patents

Abstract

The present invention provides an oxime ester-based photoinitiator with a chalcone structure and a production method and application thereof. The initiator has a structure represented by the following general formula (I), Ar ₁ and Ar ₂ are substituents containing an aromatic ring or a heteroaromatic ring, and R ₁ is a C ₁ to C ₂₀ straight or branched alkyl group, C ₃ to C ₂₀ cycloalkyl group, C ₁ to C ₁₀ alkyl group substituted with C ₃ to _{C 8} cycloalkyl group, C ₃ to C ₈ cycloalkyl group substituted with C ₁ to C ₂₀ alkyl group, C ₆ to C ₂₀ aryl group, C It is a C ₆ to C ₂₀ aryl group substituted with _{a 1} to C ₅ alkyl group, a C ₄ to _{C 20} heteroaryl group, or a C ₆ to C ₂₀ heteroaryl group substituted with a C ₁ to C ₅ alkyl group. The oxime ester photoinitiator of the chalcone structure has a large conjugated structure, has excellent sensitivity, does not easily allow fragments to flow after curing, and has excellent yellowing resistance. In addition, the photoinitiator has other features such as simple synthesis, no need to use expensive catalysts in the synthesis process, and excellent curing speed, so it can be widely applied in the photocuring field.

Description

Oxime ester photoinitiator with chalcone structure and manufacturing method and application thereof

This application claims priority based on a Chinese application with a filing date of May 8, 2021 and CN application number 202110501130.3, and all content disclosed in the CN application is re-used in this application.

The present invention relates to the field of organic chemistry, and more specifically to an oxime ester-based photoinitiator with a chalcone structure and its preparation method and application.

Compounds with an oxime ester structure are used as photoinitiators for various purposes in the photocuring field, and designing and synthesizing new oxime ester photoinitiators with better application performance is always a topic of research in the photocuring field. Because oxime ester photoinitiators have high sensitivity, they can be used in photopolymerization compositions containing colorants for color filters and black matrices used in color TVs, liquid crystal displays, solid-state imaging devices, and cameras. For example, patent documents such as publication numbers CN99108598A, CN101508744A, CN10565472A and CN103293855A disclose various carbazole oxime ester and ketoxime ester photoinitiators, and these disclosed photoinitiators have excellent photosensitivity and storage stability and are used in display panels and color filters. Currently, the general application requirements in the photocuring field are met to various degrees, but the balance in sensitivity and yellowing performance has not been achieved.

CN107344918A, CN110066352A, and CN110066225A disclose various oxime ester photoinitiators each containing a polymerizable group, but their synthesis process is complicated, an expensive palladium catalyst must be used to synthesize such compounds, and the post-treatment process is complicated. It is difficult to purify and its high production cost greatly limits its application.

Therefore, providing a new oxime ester photoinitiator that is simple to synthesize and has excellent sensitivity and yellowing performance is a task that must be urgently solved in the relevant technical field.

The main purpose of the present invention is to provide an oxime ester-based photoinitiator with a chalcone structure, and a method for producing and applying the same, which solves the problem of not being able to combine excellent sensitivity, yellowing performance, and a simple synthetic route in the prior art.

In order to realize the above object, according to one aspect of the present invention, an oxime ester-based photoinitiator having a chalcone structure having a structure represented by the following general formula (I) is provided:

General formula (I)

Here, Ar ₁ and Ar ₂ are substituents containing an aromatic ring or a heteroaromatic ring, and R ₁ is a C ₁ ∼ C ₂₀ straight or branched chain alkyl group, a C ₃ ∼ _{C 20} cycloalkyl group, or a C ₃ ∼ C ₈ cycloalkyl group. Substituted C _{1∼C 10 alkyl} group, C _{3∼C 8} cycloalkyl group substituted with C _{1∼C 20} alkyl group, C _{6∼C 20} aryl group, C _{6∼C 20} aryl group substituted with C _{1∼C 5} alkyl group , a C ₄ to _{C 20} heteroaryl group or a C ₆ to C ₂₀ heteroaryl group substituted with a C ₁ to C ₅ alkyl group.

According to another aspect of the present invention, a method for producing the oxime ester photoinitiator of the chalcone structure is further provided, comprising the following steps: formylating Ar ₁ -H with phosphorus oxychloride; obtaining phosphorus intermediate 1; The intermediate 1 and condensation reaction obtaining phosphorus intermediate 2; The intermediate 2 was subjected to oximation reaction with hydroxylamine hydrochloride. Obtaining phosphorus intermediate 3; The intermediate 3 and Obtaining an oxime ester photoinitiator having the chalcone structure by esterifying an acid chloride or anhydride containing; Here, Ar ₁ , Ar ₂ , and R ₁ have the same definitions as above.

According to another aspect of the present invention, there is further provided a photocurable composition containing a photoinitiator, wherein the photoinitiator is an oxime ester photoinitiator having the chalcone structure.

The oxime ester photoinitiator of the chalcone structure provided by the present invention has a large conjugated structure, has superior sensitivity compared to conventional oxime ester initiators, does not easily allow fragments to flow after curing, and has excellent yellowing resistance. In addition, the photoinitiator has other features such as simple synthesis, no need to use expensive catalysts during the synthesis process, and excellent curing speed after use, so it can be widely applied in the photocuring field.

It should be noted that the embodiments and features of the embodiments of the present application can be combined with each other as long as there is no conflict. In the following, the present invention will be described in detail along with examples.

As explained in the technical background of the invention, the oxime ester photoinitiator of the prior art has the problem of not being able to combine excellent sensitivity, yellowing performance, and a simple synthetic route.

In order to solve the above problem, the present invention provides an oxime ester-based photoinitiator with a chalcone structure having a structure represented by the following general formula (I):

General formula (I)

Here, Ar ₁ and Ar ₂ are substituents containing an aromatic ring or a heteroaromatic ring, and R ₁ is a C ₁ ∼ C ₂₀ straight or branched chain alkyl group, a C ₃ ∼ _{C 20} cycloalkyl group, or a C ₃ ∼ C ₈ cycloalkyl group. Substituted C _{1∼C 10 alkyl} group, C _{3∼C 8} cycloalkyl group substituted with C _{1∼C 20} alkyl group, C _{6∼C 20} aryl group, C _{6∼C 20} aryl group substituted with C _{1∼C 5} alkyl group , a C ₄ to _{C 20} heteroaryl group or a C ₆ to C ₂₀ heteroaryl group substituted with a C ₁ to C ₅ alkyl group.

Chalcones have been reported to be used as polymer monomers due to their highly conjugated structure and excellent light absorption and optical properties, but reports of their use as a photoinitiator parent group are rare. The present inventors surprisingly found that when the chalcone structure is applied to the preparation of oxime ester photoinitiator, the synthesis is simple, the obtained product has the property of absorbing long wavelengths, and when applied to color filters and black matrices, it has excellent sensitivity, and exists in the prior art. It was discovered that the problem of high yellowing could be further solved with high initiator sensitivity.

The oxime ester photoinitiator of the chalcone structure provided by the present invention has a large conjugated structure, has superior sensitivity compared to conventional oxime ester initiators, does not easily allow fragments to flow after curing, and has excellent yellowing resistance. In addition, the photoinitiator has other features such as simple synthesis, no need to use expensive catalysts during the synthesis process, and excellent curing speed after use, so it can be widely applied in the photocuring field.

In order to further improve the sensitivity of the photoinitiator, improve yellowing resistance after application, and at the same time ensure that the photoinitiator has better initiation efficiency, in a preferred embodiment, Ar ₁ and Ar ₂ are each independently

is selected from: optionally, -CH ₂ - in these functional groups may be substituted with -O- or -S-; R ₃ is H, nitro group, hydroxy group, C ₁ to _{C 20} straight or branched alkyl group, C ₃ to _{C 20} cycloalkyl group, C ₄ to _{C 20} alkylcycloalkyl group or cycloalkylalkyl group, C ₂ to C ₂₀ chain alkenyl group. , C ₅ to _{C 10} substituted or unsubstituted cyclic or heterocyclic alkenyl group, C ₆ to _{C 12} aryl group or heteroaryl group, C ₆ to _{C 12} aryl group or heteroaryl group substituted by C ₁ to _{C 4} is an alkyl group, and optionally, -CH ₂ - in these functional groups may be substituted with -O- or -C(=O)-; R ₄ represents H, C ₁ to C ₆ straight or branched alkyl group, C ₁ to _{C 6} chain alkenyl group, phenyl group or substituted phenyl group.

More preferably, Ar ₁ and Ar ₂ are each independently

is selected from The photoinitiator formed by selecting the above types of functional groups as the Ar ₁ and Ar ₂ functional groups can better perform the dual roles of the chalcone structure and the oxime ester structure, and can further improve the various performances of the photoinitiator.

"*" in the above functional groups indicates the connection position of the Ar ₁ and Ar ₂ functional groups.

In a preferred embodiment, R ₁ is a C ₁ to _{C 5} straight or branched alkyl group or a C ₆ to C ₁₂ aryl group.

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

According to another aspect of the present invention, a method for producing the oxime ester photoinitiator of the chalcone structure is further provided, comprising the following steps: formylating Ar ₁ -H with phosphorus oxychloride; obtaining phosphorus intermediate 1; The intermediate 1 and condensation reaction obtaining phosphorus intermediate 2; The intermediate 2 was subjected to oximation reaction with hydroxylamine hydrochloride. Obtaining phosphorus intermediate 3; The intermediate 3 and Obtaining an oxime ester photoinitiator having the chalcone structure by esterifying an acid chloride or anhydride containing; Here, Ar ₁ , Ar ₂ , R ₁ , and R ₂ have the same definitions as above.

Using the above production method, an oxime ester-based photoinitiator with a chalcone structure can be prepared by sequentially subjecting Ar ₁ -H to a formylation reaction, a condensation reaction with an acetylated aryl compound, an oxime reaction, and an esterification reaction. The above synthesis method has advantages in terms of both the synthesis route and the synthesis cost because the route is simple, the conditions for each step are mild, the operation is convenient, and there is no need to use raw materials such as expensive catalysts during the synthesis process. The prepared photoinitiator shows excellent performance in terms of sensitivity, yellowing resistance, and curing speed.

The Ar ₁ -H, It should be noted that acid chloride or anhydride, phosphorus oxychloride, hydroxylamine hydrochloride, etc. containing are all compounds known in the prior art and can be purchased commercially or manufactured in-house using conventional methods.

In the formylation reaction process, a formyl group is introduced into the substrate Ar ₁ -H to prepare for the subsequent reaction. In order to make the reaction process more stable and maximize reaction efficiency, in a preferred embodiment, during the formylation reaction, the reaction temperature is 60 to 120°C, preferably 100°C, and the reaction time is 1 to 5 hours. ego; More preferably, the formylation reaction is carried out in a first solvent, and the first solvent is DMF.

In a preferred embodiment, the condensation reaction is carried out under the catalysis of a base of the first type, preferably the base of the first type is sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide and It is one or more types selected from potassium tert-butoxide. Using a base as a catalyst can effectively improve reaction efficiency, and more preferably, sodium hydroxide is used as a catalyst.

In order to further stabilize the reaction, preferably, during the condensation reaction, the reaction temperature is 20 to 60° C. and the reaction time is 2 to 6 hours; Preferably, the condensation reaction is performed in a second solvent, and the second solvent is at least one selected from methanol, ethanol, isopropanol, tert-butanol, tetrahydrofuran, DMF and DMSO, and more preferably methanol.

In a preferred embodiment, the reaction temperature of the oximation reaction is 60 to 90° C., and the reaction time is 10 to 16 hours; Preferably, the oximation reaction is performed in a third solvent, and the third solvent is at least one selected from methanol, ethanol, isopropanol, and tert-butanol, and more preferably ethanol.

In a preferred embodiment, the esterification reaction is carried out under the action of a second type base, preferably the second type base being selected from the group consisting of triethylamine, pyridine, diisopropylethylamine, potassium hydroxide, sodium hydroxide and sodium hydride. There is more than one type to be selected. Performing the esterification reaction by selecting a base as a catalyst is advantageous for efficiently increasing the esterification reaction. Preferably, the reaction temperature of the esterification reaction is -10 to 60°C, more preferably 0 to 25°C; Preferably, the condensation reaction is performed in a fourth solvent, and the fourth solvent is diethyl ether, acetonitrile, tert-butylmethyl ether, tetrahydrofuran, vinyl acetate, toluene, xylene, acetone, methyl ethyl ketone, dichloro It is one or more selected from methane, chloroform, chlorobenzene, dimethylacetamide, and dimethylformamide.

According to another aspect of the present invention, application of the photoinitiator in the field of photocuring is further provided. The photoinitiator has excellent sensitivity and yellowing resistance, making it very suitable for application to various photopolymerization compositions in the photocuring field.

According to another aspect of the present invention, there is further provided a photocurable composition containing a photoinitiator, wherein the photoinitiator is an oxime ester photoinitiator having the chalcone structure.

In addition, the chalcone oxime ester initiator is used as a paint for coating substrates such as plastic, metal, glass, ceramic, wood, walls, and optical fibers; Protective film materials such as hard coatings, anti-fouling films, anti-reflective films, and impact buffering films; Photocurable adhesives, adhesives, photodegradable paints, coating films, moldings; Optical recording media such as holographic imaging materials; Optical molding resins, such as ink (resin) for 3D printing, photoresist for manufacturing electronic circuits and semiconductors, photoresist for electronic materials such as color filters in displays, black matrix, dry film, etc.; Interlayer insulating film, light extraction film, brightness enhancement film, sealant; Printing ink for screen printing, offset printing, gravure printing, etc., photocuring ink for inkjet printing; Optical members such as lenses, lens arrays, optical waveguides, light guide plates, light diffusion plates, and diffraction elements; It can be applied to photo spacers, ribs, nanoimprinting materials, etc.

Below, the present application is described in more detail with reference to specific examples, but these examples should not be construed as limiting the scope of protection of the present application.

Example 1

Preparation of Compound 1

(1) Step, preparation of intermediate 1a

Add 150 mL of DMF to a 1 L three-necked flask, cool to 0°C in an ice bath, then slowly add 100 mL of POCl ₃ and stir for 30 minutes while maintaining the temperature; 55.7 g (0.2 mol) of dibutylfluorene was dissolved in 150 mL of DMF and then added to the reaction solution. The temperature was raised to 100°C and stirred for 2 hours while maintaining the temperature. When the raw materials are completely reacted, 500 g of ice water is added to quench the reaction, the reaction liquid is extracted with 500 mL of DCM, the organic phase is washed three times with 500 mL of water, and the concentrated solid is dissolved in 500 mL of n-hexane and cooled to room temperature. The mixture was stirred for 30 minutes and filtered to obtain 43.3 g of intermediate 1a, a white approaching solid with a yield of 70.6%.

(2) Step, preparation of intermediate 1b

Intermediate 1a (0.13 mol), 15.7 g (0.13 mol) of acetophenone, 5.7 g (0.14 mol) of sodium hydroxide, and 400 g of methanol were added to a 500 mL three-neck flask, and stirred at room temperature for 3 hours to completely react the raw materials. 400 mL of water was added to the reaction solution, extracted with 200 mL of DCM, and the organic phase was concentrated to obtain 36.4 g of intermediate 1b, an approaching white solid with a yield of 68.6%.

Step (3), preparation of intermediate 1c

Add 30 g (0.07 mol) of intermediate 1b, 15.3 g (0.21 mol) of hydroxylamine hydrochloride, 29.8 g (0.21 mol) of sodium sulfate, and 300 g of ethanol to a 500 mL three-necked flask, heat until reflux, and stir for 12 hours. Thus, the raw materials were completely reacted. 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 three times with 120 mL of water, and the organic phase was concentrated. The obtained solid was dissolved in 50 mL of acetone. It was cooled to 0-10°C in an ice bath, stirred for 2 hours, and filtered to obtain 25.9 g of intermediate 1c, a pale yellow solid with a yield of 87.4%.

(4) Step, Preparation of Compound 1

20 g (0.05 mol) of intermediate 1c, 8.1 g (0.08 mol) of TEA, and 100 mL of dichloromethane were added to a 250 mL reaction flask, and stirred to dissolve clearly. 6.1 g (0.06 mol) of acetic anhydride was added dropwise, and after the dropwise addition was completed, it was stirred at room temperature for 2 hours. 100 mL of water was added to the reaction solution, stirred for 30 minutes, left to stand to separate the layers, the lower organic phase was separated and washed with neutral water, the organic phase was concentrated, and the obtained solid was dissolved in 100 mL of methanol. It was refluxed and stirred for an hour. It was cooled to room temperature and stirred for 1 hour, cooled again to 5-10°C in an ice bath, and stirred for 1 hour. Filtered and washed the filter cake with 100 mL methanol to obtain the crude product. The crude product was dissolved in 60 mL of acetone, added to 180 mL of methanol, crystallized by stirring, continued stirring in an ice bath for 1 hour, filtered, the filter cake was washed with 100 mL methanol, and the obtained solid was placed in a vacuum drying oven at 60°C. and dried for 24 hours to obtain 19.2 g of a white solid with a yield of 82.3% and a purity of 99.64%.

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

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).

Example 2

Preparation of Compound 2

The reaction pathway is as follows:

20 g (0.05 mol) of intermediate 1c, 8.1 g (0.08 mol) of TEA, and 100 mL of dichloromethane were added to a 250 mL reaction flask, and stirred to dissolve clearly. 8.4 g of benzoyl chloride (6.1 g (0.06 mol)) was added dropwise, and after the dropwise addition was completed, it was stirred at room temperature for 2 hours. 100 mL of water was added to the reaction solution, stirred for 30 minutes, left to stand to separate the layers, the lower organic phase was separated and washed with neutral water, the organic phase was concentrated, and the obtained solid was dissolved in 100 mL of methanol. It was refluxed and stirred for an hour. It was cooled to room temperature and stirred for 1 hour, cooled again to 5-10°C in an ice bath, and stirred for 1 hour. Filtered and washed the filter cake with 100 mL methanol to obtain the crude product. The crude product was dissolved in 60 mL of acetone, added to 180 mL of methanol, crystallized by stirring, continued stirring in an ice bath for 1 hour, filtered, the filter cake was washed with 100 mL methanol, and the obtained solid was placed in a vacuum drying oven at 60°C. and dried for 24 hours to obtain 19.5 g of a white solid with a yield of 73.9% and a purity of 98.72%.

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

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).

Example 3

In addition, as shown in Table 1, compounds with various structures can be obtained by selecting and using various raw materials and performing reactions under various reaction conditions, but are not limited to this.

compound ^1H NMR (500 MHz, Chloroform- d ) 8.22 (dd, J = 7.5, 1.6 Hz, 1H), 8.07 (d, J = 1.5 Hz, 1H), 7.88 (d, J = 7.5 Hz, 1H), 7.69 (d, J = 7.4 Hz, 1H), 7.55 - 7.50 (m, 2H), 7.49 - 7.45 (m, 1H), 7.45 - 7.38 (m, 3H), 7.35 (d, J = 1.5 Hz, 1H), 7.29 - 7.22 (m, 1H), 7.15 ( d, J = 15.2 Hz, 1H), 2.15 (s, 3H), 2.09 (dt, J = 12.4, 7.0 Hz, 2H), 1.84 (dt, J = 12.4, 7.0 Hz, 2H), 1.55 - 1.43 (m , 4H), 1.43 - 1.32 (m, 4H), 0.88 (t, J = 7.9 Hz, 6H). 7.83 (d, J = 7.5 Hz, 1H), 7.80 - 7.75 (m, 3H), 7.75 - 7.66 (m, 2H), 7.57 - 7.48 (m, 5H), 7.47 (s, 1H), 7.47 - 7.37 ( m, 5H), 7.28 - 7.21 (m, 1H), 7.09 (d, J = 15.2 Hz, 1H), 2.15 (s, 3H), 1.94 (dt, J = 12.3, 7.0 Hz, 2H), 1.84 (dt) , J = 12.4, 7.0 Hz, 2H), 1.60 - 1.44 (m, 4H), 1.42 - 1.31 (m, 4H), 0.88 (t, J = 8.0 Hz, 6H). 8.10 (dd, J = 7.5, 1.5 Hz, 1H), 8.04 (d, J = 1.4 Hz, 1H), 7.86 (dd, J = 7.5, 1.6 Hz, 1H), 7.82 (d, J = 7.5 Hz, 1H) ), 7.77 (dd, J = 7.5, 1.5 Hz, 1H), 7.73 (d, J = 7.5 Hz, 1H), 7.51 (ddd, J = 9.3, 7.4, 1.7 Hz, 3H), 7.48 - 7.37 (m, 4H), 7.28 - 7.22 (m, 1H), 7.21 (t, J = 7.5 Hz, 1H), 7.09 (d, J = 15.2 Hz, 1H), 2.15 (s, 3H), 1.94 (dt, J = 12.3 , 7.1 Hz, 2H), 1.84 (dt, J = 12.4, 7.0 Hz, 2H), 1.60 - 1.44 (m, 4H), 1.42 - 1.31 (m, 4H), 0.88 (t, J = 8.0 Hz, 6H) . 7.59 - 7.49 (m, 8H), 7.49 - 7.41 (m, 5H), 7.41 - 7.34 (m, 1H), 7.27 (d, J = 15.1 Hz, 1H), 7.19 (d, J = 15.1 Hz, 1H) , 2.14 (s, 3H). 8.37 - 8.31 (m, 2H), 7.83 - 7.77 (m, 2H), 7.59 - 7.53 (m, 4H), 7.53 - 7.49 (m, 2H), 7.48 - 7.38 (m, 3H), 7.31 - 7.24 (m) , 1H), 7.19 (d, J = 15.1 Hz, 1H), 2.13 (s, 3H). 7.84 - 7.78 (m, 2H), 7.75 (dd, J = 7.5, 1.3 Hz, 1H), 7.71 - 7.66 (m, 2H), 7.60 - 7.54 (m, 4H), 7.54 - 7.50 (m, 2H), 7.48 - 7.38 (m, 4H), 7.33 - 7.23 (m, 3H), 7.15 (d, J = 15.1 Hz, 1H), 2.42 (d, J = 0.6 Hz, 3H), 2.15 (s, 3H). 7.59 - 7.51 (m, 2H), 7.49 - 7.39 (m, 5H), 7.39 - 7.33 (m, 2H), 7.31 - 7.24 (m, 1H), 7.20 - 7.07 (m, 2H), 7.04 - 6.98 (m , 2H), 6.92 - 6.87 (m, 2H), 2.14 (s, 3H). 7.58 - 7.51 (m, 2H), 7.48 - 7.39 (m, 5H), 7.39 - 7.33 (m, 2H), 7.31 - 7.24 (m, 1H), 7.20 - 7.08 (m, 2H), 7.04 - 6.98 (m , 2H), 6.92 - 6.86 (m, 2H), 2.51 (q, J = 8.0 Hz, 2H), 1.14 (t, J = 8.0 Hz, 3H). 8.07 (dd, J = 7.5, 1.5 Hz, 1H), 8.00 - 7.94 (m, 2H), 7.76 (dd, J = 7.5, 1.5 Hz, 1H), 7.60 - 7.53 (m, 2H), 7.48 - 7.37 ( m, 5H), 7.30 - 7.23 (m, 1H), 7.21 (t, J = 7.5 Hz, 1H), 7.16 - 7.07 (m, 3H), 6.94 - 6.88 (m, 2H), 2.15 (s, 3H) . 7.86 - 7.80 (m, 2H), 7.75 (dd, J = 7.4, 1.3 Hz, 1H), 7.60 - 7.53 (m, 2H), 7.48 - 7.37 (m, 6H), 7.33 - 7.23 (m, 3H), 7.16 - 7.07 (m, 3H), 6.94 - 6.88 (m, 2H), 2.41 (d, J = 0.7 Hz, 3H), 2.15 (s, 3H). 7.59 - 7.51 (m, 2H), 7.47 - 7.42 (m, 3H), 7.39 - 7.34 (m, 6H), 7.33 - 7.28 (m, 2H), 7.28 - 7.16 (m, 3H), 2.14 (s, 3H) ). 8.18 - 8.12 (m, 2H), 7.58 - 7.51 (m, 2H), 7.48 - 7.34 (m, 7H), 7.33 - 7.25 (m, 3H), 7.17 (d, J = 15.0 Hz, 1H), 2.13 ( s, 3H). 7.58 - 7.51 (m, 2H), 7.47 - 7.34 (m, 9H), 7.32 - 7.21 (m, 4H), 7.19 (d, J = 15.1 Hz, 1H), 2.50 (q, J = 8.0 Hz, 2H) , 1.14 (t, J = 8.0 Hz, 3H). 7.77 - 7.71 (m, 2H), 7.55 - 7.48 (m, 2H), 7.48 - 7.36 (m, 7H), 7.33 - 7.24 (m, 3H), 7.11 - 7.01 (m, 3H), 2.38 (s, 6H) ), 2.29 (s, 3H), 2.15 (s, 3H). 7.96 - 7.90 (m, 1H), 7.77 (d, J = 7.5 Hz, 1H), 7.58 - 7.51 (m, 2H), 7.47 - 7.34 (m, 7H), 7.29 - 7.19 (m, 3H), 4.46 ( q, J = 8.0 Hz, 2H), 2.13 (s, 3H), 1.39 (t, J = 8.0 Hz, 3H). 8.26 - 8.20 (m, 2H), 8.11 (d, J = 7.3 Hz, 1H), 7.80 (d, J = 7.6 Hz, 1H), 7.58 - 7.52 (m, 2H), 7.49 - 7.42 (m, 3H) , 7.42 - 7.34 (m, 2H), 7.24 (d, J = 1.9 Hz, 2H), 4.25 (q, J = 8.0 Hz, 2H), 2.14 (s, 3H), 1.39 (t, J = 8.0 Hz, 3H). 7.99 (d, J = 7.5 Hz, 1H), 7.87 (d, J = 1.4 Hz, 1H), 7.85 - 7.79 (m, 2H), 7.76 - 7.70 (m, 2H), 7.57 - 7.38 (m, 10H) , 7.22 (s, 2H), 4.25 (q, J = 8.0 Hz, 2H), 2.15 (s, 3H), 1.41 - 1.34 (m, 3H). 7.98 - 7.93 (m, 1H), 7.77 (d, J = 7.3 Hz, 1H), 7.58 - 7.51 (m, 2H), 7.48 - 7.33 (m, 7H), 7.26 - 7.19 (m, 3H), 4.46 ( q, J = 8.0 Hz, 2H), 2.46 (q, J = 8.0 Hz, 2H), 1.39 (t, J = 8.0 Hz, 3H), 1.13 (t, J = 8.0 Hz, 3H). 8.06 (d, J = 7.2 Hz, 1H), 7.85 (d, J = 1.4 Hz, 1H), 7.81 (dt, J = 7.5, 1.3 Hz, 2H), 7.68 (dd, J = 7.5, 1.5 Hz, 1H) ), 7.60 - 7.52 (m, 2H), 7.51 (d, J = 1.6 Hz, 1H), 7.48 - 7.38 (m, 4H), 7.24 - 7.16 (m, 3H), 6.88 (t, J = 7.5 Hz, 1H), 4.25 (q, J = 8.0 Hz, 2H), 2.15 (s, 3H), 1.39 (t, J = 8.0 Hz, 3H). 8.01 (d, J = 7.5 Hz, 1H), 7.87 (d, J = 1.5 Hz, 1H), 7.85 - 7.78 (m, 2H), 7.75 (dd, J = 7.5, 1.4 Hz, 1H), 7.58 - 7.50 (m, 3H), 7.48 - 7.38 (m, 5H), 7.33 - 7.24 (m, 2H), 7.22 (s, 2H), 4.25 (q, J = 8.0 Hz, 2H), 2.41 (d, J = 0.6 Hz, 3H), 2.15 (s, 3H), 1.41 - 1.34 (m, 3H). 8.03 (dd, J = 7.5, 1.4 Hz, 1H), 7.73 (d, J = 7.5 Hz, 1H), 7.56 (ddt, J = 7.4, 2.9, 1.3 Hz, 4H), 7.51 - 7.41 (m, 5H) , 7.40 - 7.33 (m, 1H), 7.31 (d, J = 0.7 Hz, 1H), 7.22 (d, J = 15.2 Hz, 1H), 2.14 (s, 3H). 7.88 - 7.82 (m, 2H), 7.80 - 7.73 (m, 3H), 7.70 (d, J = 7.5 Hz, 1H), 7.60 - 7.37 (m, 10H), 7.15 (d, J = 15.0 Hz, 1H) , 6.86 (dd, J = 15.2, 0.7 Hz, 1H), 2.15 (s, 3H). 7.86 (dd, J = 7.4, 1.6 Hz, 1H), 7.82 (d, J = 1.4 Hz, 1H), 7.79 - 7.72 (m, 2H), 7.71 (d, J = 7.4 Hz, 1H), 7.60 - 7.51 (m, 4H), 7.48 - 7.37 (m, 4H), 7.34 - 7.25 (m, 2H), 7.15 (d, J = 15.0 Hz, 1H), 6.86 - 6.79 (m, 1H), 2.41 (d, J) = 0.6 Hz, 3H), 2.15 (s, 3H). 8.03 (dd, J = 7.5, 1.5 Hz, 1H), 7.88 - 7.81 (m, 3H), 7.81 - 7.75 (m, 1H), 7.70 (d, J = 7.5 Hz, 1H), 7.60 - 7.51 (m, 4H), 7.48 - 7.37 (m, 3H), 7.24 - 7.14 (m, 2H), 6.86 - 6.79 (m, 1H), 2.15 (s, 3H). 8.36 (d, J = 1.6 Hz, 1H), 8.14 (dd, J = 7.5, 1.5 Hz, 1H), 8.00 (d, J = 7.5 Hz, 1H), 7.69 (d, J = 7.5 Hz, 1H), 7.58 - 7.49 (m, 3H), 7.48 - 7.39 (m, 4H), 7.36 - 7.29 (m, 1H), 7.22 (d, J = 15.0 Hz, 1H), 2.13 (s, 3H). 8.33 - 8.28 (m, 1H), 7.98 (d, J = 1.5 Hz, 1H), 7.91 (d, J = 7.5 Hz, 1H), 7.74 (dd, J = 7.6, 1.5 Hz, 1H), 7.59 - 7.51 (m, 2H), 7.47 (dd, J = 7.5, 1.5 Hz, 1H), 7.46 - 7.39 (m, 4H), 7.39 - 7.29 (m, 2H), 7.22 (d, J = 15.2 Hz, 1H), 2.14 (s, 3H). 8.22 (d, J = 1.6 Hz, 1H), 8.08 (d, J = 1.5 Hz, 1H), 7.99 (d, J = 7.7 Hz, 1H), 7.94 (d, J = 7.5 Hz, 1H), 7.78 ( dd, J = 7.5, 1.5 Hz, 1H), 7.55 - 7.48 (m, 2H), 7.48 - 7.39 (m, 4H), 7.30 (dd, J = 15.1, 0.6 Hz, 1H), 7.12 (d, J = 15.0 Hz, 1H), 7.02 (s, 2H), 2.38 (s, 6H), 2.30 (s, 3H), 2.15 (s, 3H).

Performance evaluation

A representative photocurable resin composition was prepared to evaluate the application performance of the photoinitiator represented by the formula (I) of the present invention, such as curing speed, fluidity, solubility, and fluidity, and the specific steps are as follows:

(1) Prepare a photocurable resin composition of the following composition:

In the composition, the photoinitiator is a compound of formula (I) of the invention or a photoinitiator known from the prior art (for comparison).

(2) Curing speed

The composition was stirred under a yellow light lamp, taken out on a PET template, formed into a film by roll coating, dried at 90°C for 2 minutes to obtain a coating film with a dry film thickness of 2 μm, and then cooled to room temperature and applied with an LED lamp (light source wavelength: The coating film was exposed to light at 385 nm, exposure machine model number: RW.LED-YT200sg1, single exposure amount of 50 mJ/cm ² ), and cured to form a film.

When the coating film was cured into a cured film, it was evaluated by the number of times it passed through the crawler exposure belt, and a higher number of passes indicates a non-ideal curing speed.

(3) Liquidity

Cut the cured film into pieces, weigh 0.5 g of the cured film sample, put it in a 50 mL beaker, add 4.5 mL of methanol and dissolve it by ultrasonication for 30 minutes, transfer the obtained methanol solution to a 10 mL volumetric flask, and then wash the sample twice with methanol. It was washed (2mLХ2) and poured into a volumetric flask, and 0.1mL of toluene was taken out using a pipette and used as an internal standard. Methanol was added to make a constant volume, shaken evenly, and allowed to stand.

Using a Japanese Shimadzu LC-20A liquid chromatograph (Simpak column, 150Х6.0nm, detector SPD-20A, detection limit 20ppm, detection wavelength 254nm), flow rate 1.0mL/min at 25°C, mobile phase (methanol/water = 90/10) was observed to determine whether the presence of a photoinitiator was detected. It was evaluated as a percentage of the peak area of the liquid phase of toluene, which explains that the higher the initiator content in the liquid phase, the greater the fluidity.

(4) yellowing

Apply the composition on a tin plate using a wire bar to form a 20μm coating film, expose with a crawler exposure machine, complete curing by receiving 1000mJ/cm ² of energy, place in an oven, bake at 230°C for 30 minutes, and X-Rite A yellowing test was performed using a colorimeter. The state of yellowing was judged based on the b value, and the higher the value, the clearer the yellowing.

The characterization results are shown in Table 3.

photoinitiator Curing speed liquidity Example Compound 1 One Not detected compound 2 One Not detected Compound 3 One Not detected Compound 8 One Not detected Compound 9 One Not detected Compound 10 One Not detected Compound 11 One Not detected Compound 12 One Not detected Compound 14 One Not detected Compound 15 One Not detected Comparative example Photoinitiator A One Not detected Photoinitiator B 2 2.26 Photoinitiator C 3 Not detected

Example Gyeonghwajeon
b value After curing
b value Baking 30 minutes
b value After hardening - Before hardening
Δb1 After baking - before curing
Δb2 Compound 1 -0.03 0.98 0.99 1.01 1.02 Compound 2 -0.01 0.71 0.83 0.72 0.84 Compound 3 1.02 2.95 3.19 1.93 2.17 Compound 8 0.31 2.63 3.24 2.32 2.93 Compound 9 -0.03 1.86 3.27 1.89 3.3 Compound 10 0.12 2.71 3.5 2.59 3.38 Compound 11 -0.02 1.33 2.11 1.35 2.13 Compound 12 -0.02 2.66 2.82 2.68 2.84 Compound 14 -0.03 2.02 3.25 2.05 3.28 Compound 15 -0.02 2.31 3.29 2.33 3.31 Photoinitiator A 0.4 3.55 4.13 3.15 3.73 Photoinitiator B 0.93 2.86 3.27 1.93 2.34 Photoinitiator C 2.38 5.6 6.25 3.22 3.87

In Tables 2 and 3, photoinitiator A is 1-(7-nitro-9,9-diallylfluoren-2-yl)-1-(2-methylphenyl)methanone-oxime acetate (1-(7-nitro- 9,9-diallylfluoren-2-yl)-1-(2-methylphenyl)methanone-oxime acetate), and photoinitiator B is 1-(6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl) -3-cyclopentyl-propan-1-one-oxime acetate (1-(6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl)-3-cyclopentyl-propan-1-one-oxime acetate) Photoinitiator C is 1-(9-(2-norbornene)methyl-9-methyl-9H-fluoren-2-yl)-1,2-propanedione-2-oxime-O-acetate (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 in Tables 2 and 3, the chalcone oxime ester photoinitiator represented by general formula (I) of the present invention has high initiator efficiency, fast curing speed, no flow, and low yellowing in photocuring applications. Overall performance was excellent.

Noteworthy is that the yellowing performance of Compound 3 was slightly lower than that of other compounds of the present invention, because it has a nitro group in its molecular structure. In the case of photoinitiators A and C containing the same nitro group, the yellowing performance of compound 3 was significantly improved. This is also sufficient to explain the beneficial effects obtained by the photoinitiator of the chalcone oxime ester-based structure provided by the present invention.

The above-described details are only preferred embodiments of the present invention and are not intended to limit the present invention. The present invention may be modified and changed in various ways by those skilled in the art. All modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention are included within the protection scope of the present invention.

Claims (12)

Oxime ester photoinitiator having a chalcone structure having a structure represented by the following general formula (I):

General formula (I)
Here, Ar ₁ and Ar ₂ are substituents containing an aromatic ring or a heteroaromatic ring, and R ₁ is a C ₁ ∼ C ₂₀ straight or branched chain alkyl group, a C ₃ ∼ _{C 20} cycloalkyl group, or a C ₃ ∼ C ₈ cycloalkyl group. Substituted C _{1∼C 10 alkyl} group, C _{3∼C 8} cycloalkyl group substituted with C _{1∼C 20} alkyl group, C _{6∼C 20} aryl group, C _{6∼C 20} aryl group substituted with C _{1∼C 5} alkyl group , a C ₄ to _{C 20} heteroaryl group or a C ₆ to C ₂₀ heteroaryl group substituted with a C ₁ to C ₅ alkyl group.
According to clause 1,
Ar ₁ and Ar ₂ are each independently

is selected from: optionally, -CH ₂ - in the functional group may be substituted with -O- or -S-;
R ₃ is H, nitro group, hydroxy group, C ₁ to _{C 20} straight or branched alkyl group, C ₃ to _{C 20} cycloalkyl group, C ₄ to _{C 20} alkylcycloalkyl group or cycloalkylalkyl group, C ₂ to C ₂₀ chain alkenyl group. , C ₅ to _{C 10} substituted or unsubstituted cyclic or heterocyclic alkenyl group, C ₆ to _{C 12} aryl group or heteroaryl group, C ₆ to _{C 12} aryl group or heteroaryl group substituted by C ₁ to _{C 4} is an alkyl group, and optionally, -CH ₂ - in these functional groups may be substituted with -O- or -C(=O)-;
R ₄ represents H, a C ₁ to C ₆ straight-chain or branched alkyl group, a C ₁ to _{C 6} chain alkenyl group, a phenyl group, or a substituted phenyl group,
Oxime ester photoinitiator with chalcone structure.
According to clause 1,
Ar ₁ and Ar ₂ are each independently


An oxime ester-based photoinitiator with a chalcone structure selected from:
According to any one of claims 1 to 3,
R ₁ is a chalcone-structured oxime ester photoinitiator wherein R 1 is a C ₁ to C ₅ straight or branched alkyl group or a C ₆ to C ₁₂ aryl group.
According to clause 1,
The photoinitiator is an oxime ester photoinitiator with a chalcone structure, which is one or more of the following compounds:






Ar ₁ -H is formylated with phosphorus oxychloride obtaining phosphorus intermediate 1;
The intermediate 1 and condensation reaction obtaining phosphorus intermediate 2;
The intermediate 2 was subjected to oximation reaction with hydroxylamine hydrochloride. Obtaining phosphorus intermediate 3;
The intermediate 3 and Obtaining an oxime ester photoinitiator having the chalcone structure by esterifying an acid chloride or anhydride containing; Including,
Here, Ar ₁ , Ar ₂ , and R ₁ have the same definition as any one of claims 1 to 5,
A method for producing the oxime ester-based photoinitiator having a chalcone structure according to any one of claims 1 to 5.
According to clause 6,
During the formylation reaction, the reaction temperature is 60 to 120°C, preferably 100°C, and the reaction time is 1 to 5 hours;
Preferably, the formylation reaction is performed in a first solvent, and the first solvent is DMF,
Method for producing an oxime ester-based photoinitiator with a chalcone structure.
According to clause 6,
The condensation reaction is carried out under the catalysis of a first type base, preferably the first type base is sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide and potassium tert-butoxide. at least one selected from among, more preferably sodium hydroxide;
Preferably, during the condensation reaction, the reaction temperature is 20 to 60° C. and the reaction time is 2 to 6 hours;
Preferably, the condensation reaction is performed in a second solvent, and the second solvent is at least one selected from methanol, ethanol, isopropanol, tert-butanol, tetrahydrofuran, DMF, and DMSO, and more preferably methanol. person,
Method for producing an oxime ester-based photoinitiator with a chalcone structure.
According to clause 6,
The reaction temperature of the oximation reaction is 60 to 90° C., and the reaction time is 10 to 16 hours;
Preferably, the oximation reaction is performed in a third solvent, and the third solvent is at least one selected from methanol, ethanol, isopropanol, and tert-butanol, more preferably ethanol.
Method for producing an oxime ester-based photoinitiator with a chalcone structure.
According to clause 6,
The esterification reaction is carried out under the action of a second type base, preferably the second type base is at least one selected from triethylamine, pyridine, diisopropylethylamine, potassium hydroxide, sodium hydroxide and sodium hydride. ego;
Preferably, the reaction temperature of the esterification reaction is -10 to 60°C, more preferably 0 to 25°C;
Preferably, the condensation reaction is performed in a fourth solvent, and the fourth solvent is diethyl ether, acetonitrile, tert-butylmethyl ether, tetrahydrofuran, vinyl acetate, toluene, xylene, acetone, and methyl ethyl ketone. , dichloromethane, chloroform, chlorobenzene, dimethylacetamide and dimethylformamide,
Method for producing an oxime ester-based photoinitiator with a chalcone structure.
A photocurable composition containing a photoinitiator,
The photoinitiator is an oxime ester photoinitiator having a chalcone structure according to any one of claims 1 to 5, a photocurable composition.
According to claim 11,
The photocurable composition may be used as a paint for coating a plastic, metal, glass, ceramic, wood, wall, or optical fiber substrate; Hard coating, anti-fouling film, anti-reflective film, or impact-absorbing film materials; Photocurable adhesives, adhesives, photodegradable paints, coating films, moldings; optical recording media; Optical molding resin; Interlayer insulating film, light extraction film, brightness enhancement film, sealant; Printing ink, photocurable ink for inkjet printing; optical member; Applies to photo spacers, ribs, and materials for nanoimprinting;
Preferably, the optical molding resin is an ink or resin for 3D printing, a photoresist for manufacturing electronic circuits and semiconductors, or a photoresist for electronic materials,
Preferably, the printing ink is an ink for screen printing, offset printing, or gravure printing;
Preferably, the optical member is a lens, lens array, optical waveguide, light guide plate, light diffuser plate, or diffractive element;
Preferably, the optical recording medium is a holographic imaging material.