Oxime ester photoinitiator, method for producing the same, and use thereof

Abstract

The present application provides an oxime ester photoinitiator, a method for producing the same, and its use. 【Solution means】The oxime ester photoinitiator has a structure represented by the general formula (I). The oxime ester photoinitiator of the present application has a diketoxime ester structure and an asymmetric substituent, and further has a delocalized structure. Compared with conventional photoinitiators of the same type, it has significantly improved solubility. When applied to a photocurable composition, it can achieve both high sensitivity and low yellowing property, and has the potential for wide application. 【Chemical formula 1】 JPEG2025520737000096.jpg73131 [In the formula, R1 and R2 are each independently a substituted or unsubstituted C1-C 20 alkyl group, a substituted or unsubstituted C3-C 20 heteroalkyl group, a substituted or unsubstituted C6-C 20 aryl group, a substituted or unsubstituted C4-C 20 heteroaryl group, a substituted or unsubstituted C3-C 20 alicyclic heterocyclic group selected from the group consisting of. m is 1 or 0. n is 1 or 0. x is 1 or 0. y is 1 or 0. z is 1 or 0.]

Description

Technical Field

[0001] This application claims the priority of Chinese Patent Application No. 202210893632.X with an application date of July 27, 2022. This application incorporates the entire text of the above-mentioned Chinese patent application by reference.

[0002] This application relates to the field of organic chemical technologies, and specifically, to oxime ester photoinitiators, methods for producing the same, and their uses.

Background Art

[0003] Due to their relatively excellent performance, oxime ester photoinitiators are widely used in the production of various photoresists. Among them, oxime ester initiators based on carbazole as the parent group are an important type among oxime ester photoinitiators and have attracted wide attention from those skilled in the art because they have relatively high sensitivity. High-sensitivity oxime ester initiators have always been the goal pursued by engineers in the industry. Patents CN103833872A, CN103819583A, and CN110066225A respectively modified the molecular structure, redshifted the absorption wavelength to improve the sensitivity, and obtained initiators with high sensitivity under LED curing conditions.

[0004] However, due to the problem of yellowing, such initiators are difficult to apply to RGB color photoresists and transparent coating layers. Patents such as CN114369178A, CN104910053A, and Application No. 202111363587.9 have reduced the yellowing coefficient to a certain extent, but their photosensitivity is still not satisfactory. In addition, some structures are relatively complex and difficult to apply industrially. In order to improve the light transmittance of transparent photoresists and the color saturation of color photoresists, the photoinitiators used need to have low yellowing properties and high photosensitivity. Therefore, it is necessary to develop new photoinitiator products with higher sensitivity and lower yellowing properties.

Summary of the Invention

Problems to be Solved by the Invention

[0005] The main object of the present application is to provide an oxime ester photoinitiator, a method for producing the same, and its use, in order to solve the problem that the photoinitiators in the prior art cannot achieve both high sensitivity and low yellowing property.

Means for Solving the Problem

[0006] In order to achieve the above object, according to one aspect of the present application, an oxime ester photoinitiator having a structure represented by the general formula (I) is provided.

[0007]

Chemical Formula

[0008] [In the formula, R1 and R2 are each independently a substituted or unsubstituted C1-C 20 alkyl group, a substituted or unsubstituted C3-C 20 heteroalkyl group, a substituted or unsubstituted C6-C 20 aryl group, a substituted or unsubstituted C4-C 20 heteroaryl group, or a substituted or unsubstituted C3-C 20 alicyclic heterocyclic group, selected from the group consisting of. m is 1 or 0. n is 1 or 0. x is 1 or 0. y is 1 or 0. z is 1 or 0.] Furthermore, among the substituted C1-C 20 alkyl groups, the substituent is selected from C3-C 12 heteroalkyl groups; the substituted or unsubstituted C1-C 20 alkyl group may have at least one -CH2- substituted by -O- or -S-; among the substituted C3-C 20 heteroalkyl groups, the substituent is selected from C1-C 10 linear or branched alkyl groups; among the substituted C6-C 20 aryl groups, the substituent is a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkoxy group having 1 to C 10 linear or branched, C1-C10 It is one or more selected from the group consisting of a linear or branched alkylthio group, a linear or branched acyl group having 1 to 8 carbon atoms, a linear or branched acyloxy group having 1 to 8 carbon atoms, a halogen atom, a cyano group or a nitro group; Substituted C4-C 20 Among the heteroaryl groups, the substituent is selected from linear or branched alkyl groups having 1 to 8 carbon atoms; Substituted C3-C 20 Among the alicyclic heterocyclic groups, the substituent is selected from linear or branched alkyl groups having 1 to 6 carbon atoms.

[0009] Furthermore, R1 and R2 are each independently selected from an alkyl group having 1 to C 20 and an aryl group having 6 to C 20 Preferably, R1 and R2 are each independently selected from a methyl group, an ethyl group or a phenyl group.

[0010] Furthermore, the oxime ester photoinitiator has a structure represented by any of the structural formulas (1) to (13).

[0011]

Chemical formula

[0012]

Chemical formula

[0013]

Chemical formula

[0014]

Chemical formula

[0015]

Chemical formula

[0016] [Chemical]

[0017] [Chemical]

[0018] [Chemical]

[0019] [Chemical]

[0020] [Chemical]

[0021] [Chemical]

[0022] [Chemical]

[0023] [Chemical]

[0024] Furthermore, the oxime ester photoinitiator is [Chemical] , [Chemical] or [Chemical] is.

[0025] Furthermore, the manufacturing method is carbazole

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

Chem.

[0026] Furthermore, in Step S1, the substitution reaction is carried out under alkaline conditions, and the alkali is potassium hydroxide and / or sodium hydroxide, and / or in Step S2, the first Friedel-Crafts reaction is carried out under the condition of being catalyzed by aluminum chloride, and the solvent for the first Friedel-Crafts reaction is dichloromethane and / or dichloroethane, and / or in Step S3, the second Friedel-Crafts reaction is carried out under the condition of being catalyzed by aluminum chloride, and the solvent for the second Friedel-Crafts reaction is dichloromethane and / or dichloroethane, and / or in Step S4, the nitrite is sodium nitrite and / or potassium nitrite, the nitrous ester is one or more of ethyl nitrite, isopentyl nitrite, and isooctyl nitrite. Preferably, the oximation reaction is carried out under acidic conditions, the acid is concentrated hydrochloric acid and / or halogenated carboxylic acid, the halogenated carboxylic acid is chloroacetic acid or bromoacetic acid, and the solvent for the oximation reaction is one or more of ethyl acetate, tetrahydrofuran, and dichloromethane, and / or in Step S5, the acid anhydride is acetic anhydride and / or benzoic anhydride, the acid chloride is one or more of acetyl chloride, propionyl chloride, and benzoyl chloride. Preferably, the esterification reaction is carried out under alkaline conditions, and the alkali is one or more of triethylamine, diisopropylethylamine, and 4-dimethylaminopyridine.

[0027] Furthermore, in step S1, the molar ratio of raw material A to carbazole is (1 to 1.1):1. Preferably, the reaction temperature of the substitution reaction is 50 to 100°C, more preferably, the reaction temperature of the substitution reaction is 50 to 80°C, and / or in step S2, the molar ratio of raw material B to intermediate a is (1 to 1.1):1. Preferably, the reaction temperature of the first Friedel-Crafts reaction is -10 to 10°C, more preferably, the reaction temperature of the first Friedel-Crafts reaction is 0 to 5°C, and / or in step S3, the molar ratio of raw material C to intermediate b is (1 to 1.1):1. Preferably, the reaction temperature of the second Friedel-Crafts reaction is -10 to 10°C, more preferably, the reaction temperature of the second Friedel-Crafts reaction is 0 to 5°C, and / or in step S4, the molar ratio of nitrite and / or nitrous ester to intermediate c is (2 to 3.5):1. Preferably, the reaction temperature of the oximation reaction is 0 to 30°C, more preferably, the reaction temperature of the oximation reaction is 20 to 25°C, and / or in step S5, the molar ratio of acid anhydride and / or acid chloride to intermediate d is (2 to 2.8):1. Preferably, the reaction temperature of the esterification reaction is 0 to 30°C, more preferably, the reaction temperature of the esterification reaction is 20 to 25°C.

[0028] According to another aspect of the present application, there is provided the use of the oxime ester photoinitiator of the present application in a photoresist.

[0029] According to another aspect of the present application, there is provided a photocurable composition containing a photoinitiator, wherein the photoinitiator is the oxime ester photoinitiator of the present application. Preferably, by weight, the photocurable composition contains 800 to 1000 parts of a solvent, 100 to 300 parts of an acrylate copolymer, 50 to 150 parts of dipentaerythritol hexaacrylate, and 3 to 10 parts of the oxime ester photoinitiator.

Advantages of the Invention

[0030] The oxime ester photoinitiator of the present application has a diketoxime ester structure, with greatly improved sensitivity. By providing an asymmetric substituent to limit the type of specific groups, the dissolution performance is improved. Additionally, the delocalized structure it possesses can reduce the fluctuation of groups and improve the yellowing performance. Compared with conventional photoinitiators of the same type, the oxime ester photoinitiator of the present application has significantly improved solubility, excellent performance when used in photocurable compositions, and not only has the characteristic of low yellowing when used in photocurable compositions, but also has high sensitivity. Therefore, high sensitivity and low yellowing can be achieved simultaneously. Moreover, the oxime ester photoinitiator is easier to synthesize and has advantages such as low cost, and is expected to be widely applied in the field of photocuring.

Embodiments for Carrying Out the Invention

[0031] Unless there is a contradiction, the examples in the present application and the features in the examples may be combined with each other. Hereinafter, the present application will be described in detail with reference to the examples.

[0032] Explanation of terms: "Concentrated hydrochloric acid" is an aqueous hydrochloric acid solution with a mass concentration of 38% or more.

[0033] As described in the background art of the present application, there is a problem in the prior art that photoinitiators cannot achieve both high sensitivity and low yellowing. To solve the above problem, in one representative embodiment of the present application, an oxime ester photoinitiator having a structure represented by the general formula (I) is provided.

[0034]

Chemical formula

[0035] [In the formula, R1 and R2 are each independently a substituted or unsubstituted C1-C 20 alkyl group, a substituted or unsubstituted C3-C 20 heteroalkyl group, a substituted or unsubstituted C6-C 20 aryl group, a substituted or unsubstituted C4-C 20selected from the group consisting of a heteroaryl group, a substituted or unsubstituted C3-C 20 alicyclic heterocyclic group. m is 1 or 0. n is 1 or 0. x is 1 or 0. y is 1 or 0. z is 1 or 0.]

[0036] The oxime ester photoinitiator of the present application has a diketoxime ester structure, greatly improving the sensitivity. Also, by providing an asymmetric substituent to limit the type of specific groups, the dissolution performance is improved. Moreover, the delocalized structure it has can reduce the wave motion of the groups and improve the yellowing performance. Compared with the conventional photoinitiators of the same type, the oxime ester photoinitiator of the present application has significantly improved solubility, excellent performance when used in a photocurable composition, and not only has the characteristic of low yellowing when used in a photocurable composition, but also has high sensitivity, thus enabling both high sensitivity and low yellowing property. In addition, the oxime ester photoinitiator has advantages such as being easier to synthesize and having low cost, and is expected to be widely applied in the field of photocuring.

[0037] Specifically, in one preferred embodiment, among the substituted C1-C 20 alkyl groups, the substituent is selected from C3-C 12 heteroalkyl groups; the substituted or unsubstituted C1-C 20 alkyl groups may have at least one -CH2- substituted by -O- or -S-; Among the substituted C3-C 20 heteroalkyl groups, the substituent is selected from C1-C 10 linear or branched alkyl groups; Among the substituted C6-C 20 aryl groups, the substituent is one or more selected from the group consisting of a C1-C6 linear or branched alkyl group, a C1-C 10 linear or branched alkoxy group, a C1-C 10 linear or branched alkylthio group, a C1-C8 linear or branched acyl group, a C1-C8 linear or branched acyloxy group, a halogen atom, a cyano group or a nitro group; substituted C4-C20 Among the heteroaryl groups, the substituent is selected from linear or branched alkyl groups having 1 to 8 carbon atoms; Substituted C3-C 20 Among the alicyclic heterocyclic groups, the substituent is selected from linear or branched alkyl groups having 1 to 6 carbon atoms; The oxime ester photoinitiator having the above substituent has better dissolution performance.

[0038] In one preferred embodiment, R1 and R2 are each independently selected from alkyl groups having 1 to C 20 carbon atoms or aryl groups having 6 to C 20 carbon atoms, and preferably, R1 and R2 are each independently selected from a methyl group, an ethyl group or a phenyl group. The oxime ester photoinitiator having the above substituent has higher sensitivity and lower yellowing property.

[0039] Preferably, the oxime ester photoinitiator has a structure represented by any one of structural formulas (1) to (13) and has better comprehensive performance.

[0040]

Chemical formula

[0041]

Chemical formula

[0042]

Chemical formula

[0043]

Chemical formula

[0044]

Chemical formula

[0045] [Chemistry]

[0046] [Chemistry]

[0047] [Chemistry]

[0048] [Chemistry]

[0049] [Chemistry]

[0050] [Chemistry]

[0051] [Chemistry]

[0052] [Chemistry]

[0053] More preferably, the oxime ester photoinitiator is [Chemistry] , [Chemistry] or [Chemistry] , most preferably, the oxime ester photoinitiator is [Chemical formula] . The oxime ester photoinitiator with the above structure has a much improved sensitivity, better dissolution performance, and due to the substituents and delocalized structure, it reduces the fluctuation of the group, has a better yellowing performance improvement effect, further improved solubility, can better balance high sensitivity and low yellowing property, and is easier to synthesize and has a lower cost.

[0054] In another representative embodiment of the present application, a method for manufacturing the oxime ester photoinitiator of the present application is further provided. This manufacturing method includes carbazole [Chemical formula] as raw material A [Chemical formula] to carry out a substitution reaction to obtain intermediate a [Chemical formula] in step S1, and using intermediate a as raw material B [Chemical formula] to carry out the first Friedel-Crafts reaction to obtain intermediate b [Chemical formula] in step S2, and using intermediate b as raw material C [Chemical formula] to carry out the second Friedel-Crafts reaction to obtain intermediate c [Chemical formula] Step S3 of obtaining reacting intermediate c with nitrite and / or nitrous ester for oxime reaction to obtain intermediate d [Chemical formula] Step S4 of obtaining reacting intermediate d with acid anhydride and / or acid chloride for esterification reaction to obtain oxime ester photoinitiator [Chemical formula] [However, X is F, Cl, Br or I, m is 1 or 0, n is 1 or 0, x is 1 or 0, y is 1 or 0, and z is 1 or 0.] Step S5 of obtaining includes

[0055] In the present application, first, carbazole is subjected to a substitution reaction with raw material A to realize the substitution of N-H of carbazole and obtain intermediate a. Then, intermediate a is subjected to the first Friedel-Crafts reaction with raw material B to connect raw material B to the carbazole benzene ring and obtain intermediate b. Subsequently, intermediate b is subjected to the second Friedel-Crafts reaction with raw material C to connect raw material C to another carbazole benzene ring and obtain intermediate c. Then, intermediate c is subjected to an oxime reaction with nitrite and / or nitrous ester to form an aldoxime structure and obtain intermediate d. Finally, intermediate d is subjected to an esterification reaction with acid anhydride and / or acid chloride to form an oxime ester structure and obtain the oxime ester photoinitiator of the present application.

[0056] The manufacturing method of the present application is simple in process, generates no contaminated waste, has high product purity, high yield, is suitable for industrial production, and the manufactured oxime ester photoinitiator can achieve both high sensitivity and low yellowing property. In the process of manufacturing the above oxime ester compounds, all the reaction reagents used are compounds known in the prior art and can be conveniently obtained by commercial purchase or conventional synthesis methods.

[0057] Based on the synthetic concept disclosed in the present application, the specific reaction conditions can be easily determined by those skilled in the art. In one preferred embodiment, for the purpose of improving the yield, the nitrite is sodium nitrite and / or potassium nitrite, the nitrite ester is one or more of ethyl nitrite, isopentyl nitrite and isooctyl nitrite, and / or the acid anhydride is acetic anhydride and / or benzoic anhydride, and the acid chloride is one or more of acetyl chloride, propionyl chloride and benzoyl chloride.

[0058] The above reaction is carried out in an organic solvent. The type of the organic solvent is not particularly limited as long as it can dissolve the raw materials and does not have an adverse effect on the reaction. Further, in order to further improve the reaction rate, in one preferred embodiment, in step S1, the substitution reaction is carried out under alkaline conditions, and the alkali is potassium hydroxide and / or sodium hydroxide, and / or in step S2, the first Friedel-Crafts reaction is carried out under the condition catalyzed by aluminum chloride, and the solvent for the first Friedel-Crafts reaction is dichloromethane and / or dichloroethane, and / or in step S3, the second Friedel-Crafts reaction is carried out under the condition catalyzed by aluminum chloride, and the solvent for the second Friedel-Crafts reaction is dichloromethane and / or dichloroethane, and / or in step S4, the oxime formation reaction is carried out under acidic conditions, and the acid is concentrated hydrochloric acid and / or a halogenated carboxylic acid, the halogenated carboxylic acid is chloroacetic acid or bromoacetic acid, and the solvent for the oxime formation reaction is one or more of ethyl acetate, tetrahydrofuran and dichloromethane, and / or in step S5, the esterification reaction is carried out under alkaline conditions, and the alkali is one or more of triethylamine (TEA), diisopropylethylamine and 4-dimethylaminopyridine.

[0059] In the reaction process, if the reactant added later is made slightly in excess of the stoichiometric ratio in the reaction formula, a more sufficient reaction can be obtained. The reaction temperature varies slightly depending on the type of raw material. In one preferred embodiment, in step S1, the molar ratio of raw material A to carbazole is (1 to 1.1):1. Preferably, the reaction temperature of the substitution reaction is 50 to 100°C, more preferably, the reaction temperature of the substitution reaction is 50 to 80°C, and / or in step S2, the molar ratio of raw material B to intermediate a is (1 to 1.1):1. Preferably, the reaction temperature of the first Friedel-Crafts reaction is -10 to 10°C, more preferably, the reaction temperature of the first Friedel-Crafts reaction is 0 to 5°C, and / or in step S3, the molar ratio of raw material C to intermediate b is (1 to 1.1):1. Preferably, the reaction temperature of the second Friedel-Crafts reaction is -10 to 10°C, more preferably, the reaction temperature of the second Friedel-Crafts reaction is 0 to 5°C, and / or in step S4, the molar ratio of nitrite and / or nitrite ester to intermediate c is (2 to 3.5):1. Preferably, the reaction temperature of the oximation reaction is 0 to 30°C, more preferably, the reaction temperature of the oximation reaction is 20 to 25°C, and / or in step S5, the molar ratio of acid anhydride and / or acid chloride to intermediate d is (2 to 2.8):1. Preferably, the reaction temperature of the esterification reaction is 0 to 30°C, more preferably, the reaction temperature of the esterification reaction is 20 to 25°C. In this way, the optimal reaction effect can be obtained, and the yield of the product will be higher.

[0060] In yet another representative embodiment of the present application, the use of the oxime ester photoinitiator of the present application in a photoresist is further provided. In particular, it is suitable for a UV-LED photocuring system, especially suitable for initiation by the action of a 365 nm light source, has excellent sensitivity after use, and has the characteristics of low yellowing and high solubility.

[0061] Although not limited, the oxime ester photoinitiator of the present application may be applied to paints, coatings, inks, molding materials, etc. Specifically, paints applied to substrates such as plastics, metals, glass, ceramics, wood, and walls; protective film materials such as hard coat agents, anti-fouling films, anti-reflection films, and shock buffer films; photocurable adhesives, adhesives, photodegradable paints, coatings, molded articles; optical recording media such as holographic imaging materials; optical molding resins such as photo resists for 3D printing inks (resins), electronic circuits, and semiconductor manufacturing, color filters, black matrices, dry films, etc. in displays; interlayer insulating films, light extraction films, brightness enhancement films, encapsulating materials; printing inks such as screen printing, offset printing, gravure printing, etc., and photocurable inks for inkjet printing; optical components such as lenses, lens arrays, optical waveguides, light guide plates, light diffusing plates, diffraction elements, etc.; photo spacers, rib walls, materials for nanoimprinting, quantum dots, OLEDs, etc. It may also be applied to the production of these.

[0062] In another representative embodiment of the present application, there is provided a photocurable composition containing a photoinitiator, wherein the photoinitiator is the oxime ester photoinitiator of the present application. Preferably, by weight part, the photocurable composition further contains 800 to 1000 parts of a solvent, 100 to 300 parts of an acrylate copolymer, 50 to 150 parts of dipentaerythritol hexaacrylate, and 3 to 10 parts of the oxime ester photoinitiator.

[0063] The type of the solvent of the above composition is not particularly limited as long as it can dissolve the raw materials and does not have an adverse effect on the reaction, and it may be one or more of butanone, ethyl acetate, tetrahydrofuran, and dichloromethane. The acrylate copolymer is preferably a copolymer with a molar ratio of benzyl methacrylate: methacrylic acid: hydroxyethyl methacrylate of 70:10:20 and Mw = 10000. The photocurable composition not only has the characteristic of low yellowing but also has high sensitivity, and can achieve both high sensitivity and low yellowing property. In addition, the term "part by weight" in the present application has the same dimension, for example, it represents 1 g or 1 kg, etc.

Example

[0064] The present application will be further described in detail with reference to specific examples below, and these examples are not understood to limit the scope claimed by the present application.

[0065] Example 1

Chemical formula

[0066] (1) Preparation of Intermediate 1a

Chemical formula

[0067] 20 g of carbazole (0.12 mol), 16.70 g of cyclohexylmethyl chloride (0.13 mol), 5.76 g of sodium hydroxide (0.14 mol) and 100 mL of DMF were added to a 250 mL three-necked flask, heated to 80 °C for a substitution reaction, stirred for 4 h, and it was confirmed by TLC that the raw materials had completely reacted. The reaction solution was cooled to room temperature, filtered through diatomaceous earth, 100 mL of dichloromethane was added to the filtrate, and then washed with water (200 mL × 3 times). The organic phase was concentrated, the obtained residue was dissolved in n-hexane, cooled to 5 - 10 °C, stirred for 2 h for crystallization, filtered, the solid was collected, and dried in an oven at 40 °C to obtain 24.81 g of a white solid, that is, Intermediate 1a, with a yield of 78.5%.

[0068] (2) Preparation of Intermediate 1c

Chemical formula

Chemical formula

[0069] 24 g of intermediate 1a (0.090 mol) and 12.60 g of aluminum chloride (0.095 mol) were dissolved in 100 mL of dichloromethane, and the temperature was lowered to 0 - 5°C. 15.88 g of cyclohexanepropanoic acid chloride (0.091 mol) was dissolved in 20 mL of dichloromethane, added dropwise to the reaction solution, and the temperature was controlled at 0 - 5°C to carry out the first Friedel - Crafts reaction. After the addition was complete, stirring was continued for 1 h to completely react the raw materials and obtain intermediate 1b.

[0070] The temperature was further lowered to 0 - 5°C. Then, 12.60 g of aluminum chloride (0.095 mol) was added. Further, 14.64 g of n - octanoyl chloride (0.095 mol) was added to 20 mL of dichloromethane and added to the reaction solution. The temperature was controlled at 0 - 5°C to carry out the second Friedel - Crafts reaction. After the addition was complete, stirring was continued for 1 h, and the completion of the reaction was confirmed by TLC. The reaction solution was gradually added to 500 mL of ice - water, stirred well, left standing for 30 min, and the organic phase was further washed with water (100 mL × 3 times). The organic phase was concentrated, the obtained solid was further dissolved in 200 mL of methanol, the temperature was lowered to 5 - 10°C, and crystallization was carried out by stirring for 2 h. After filtration, the obtained solid was dried in an oven at 60°C to obtain 40.19 g of a white solid, namely intermediate 1c, with a yield of 84.6%.

[0071] (3) Preparation of compound 1d

Chemical formula

[0072] 45 g of intermediate 1c (0.085 mol) and 270 mL of ethyl acetate were added to a 500 L round-bottom flask, 25.5 mL of concentrated hydrochloric acid was added, and 29.97 g of isopentyl nitrite (0.256 mol) was added dropwise at room temperature under a nitrogen gas atmosphere. After the addition was complete, an oxime reaction was continued for 2 h. 200 mL of an aqueous sodium chloride solution was added to the reaction solution, the organic phase was separated, and the organic phase was further washed with water (200 mL × 3). The organic phase was concentrated, the resulting residue was stirred with 200 mL of methanol for crystallization, filtered, and dried in an oven at 60 °C to obtain 33.91 g of a pale yellow solid, namely, intermediate 1d, with a yield of 68.1%.

[0073] (4) Preparation of Compound 1

Chemical Structure

[0074] 48 g of intermediate 1d (0.082 mol), 8.70 g of TEA (0.172 mol), and 240 mL of dichloromethane were added to a 500 mL reaction flask, and the mixture was stirred until the solution became clear. 8.78 g of acetic anhydride (0.172 mol) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 2 h for an esterification reaction. 200 mL of water was added to the reaction solution, and the mixture was stirred for 10 min, allowed to stand for layer separation, and the lower organic phase was separated. The organic phase was washed with water until it became neutral, concentrated, and the resulting solid was dissolved in 200 mL of methanol, refluxed, and stirred for 1 h. The mixture was cooled to room temperature, stirred for 1 h, further placed in an ice bath, cooled to 5 - 10 °C, and stirred for 1 h. It was filtered, and the filter cake was washed with 200 mL of methanol to obtain a crude product. The crude product was dissolved in 150 mL of propanone, added to 300 mL of methanol, stirred for crystallization, continuously stirred in an ice bath for 1 h, filtered, and the filter cake was rinsed with 200 mL of methanol. The resulting solid was dried in a vacuum drying oven at 60 °C for 24 h to obtain 34.39 g of a pale yellow solid, namely, Compound 1, with a yield of 62.6% and a purity of 99.12%.

[0075] The structure of Compound 1 was confirmed by the following nuclear magnetic data.

[0076] 1H NMR (500 MHz, Chloroform-d) δ 8.61~8.57 (m, 1H), 8.57~8.53 (m, 1H), 7.97 (dd, J = 7.5, 1.5 Hz, 1H), 7.92 (dd, J = 7.5, 1.5 Hz, 1H), 7.80 (d, J = 7.5 Hz, 1H), 7.58 (d, J = 7.5 Hz, 1H), 4.12 (d, J = 7.1 Hz, 2H), 2.91 (d, J = 7.0 Hz, 2H), 2.76 (t, J = 7.1 Hz, 2H), 2.15 (s, 6H), 2.04 (dq, J = 13.9, 7.0 Hz, 1H), 1.95 (hept, J = 7.0 Hz, 1H), 1.65 (p, J = 7.1 Hz, 2H), 1.59~1.50 (m, 5H), 1.54~1.38 (m, 16H), 1.37~1.23 (m, 5H), 0.93~0.85 (m, 3H).

[0077] Examples 2 - 13 According to the method of Example 1, the corresponding raw materials were changed to prepare the following Compounds 2 - 13, and their structures and corresponding nuclear magnetic property evaluation data are shown in Table 1 below.

[0078] [Table 1]

[0079] JPEG2025520737000062.jpg216162

[0080] JPEG2025520737000063.jpg185162

[0081] JPEG2025520737000064.jpg208162

[0082] Examples 14 - 19 Examples 14 - 19 are different from Example 1 in that the molar ratios of the reactants in each reaction are different, as shown in detail in Table 2.

[0083]

Table 2

[0084] Examples 20 - 25 Examples 20 - 25 are different from Example 1 in that the reaction temperatures are different, and are specifically shown in Table 3.

[0085]

Table 3

[0086] In the manufacturing process of the same compound product, by changing different reaction conditions, the yields and purities of Compound 1 in Example 1 and Examples 14 - 25 are shown in Table 4.

[0087]

Table 4

[0088] As is clear from Tables 2 - 4, when the production molar ratios in each step of the examples are all within the preferred range of the present application, the yield and purity of the oxime ester photoinitiator are the highest. However, if it is too low, the reaction will be insufficient. If it exceeds the scope of the present application, the improvement of the yield and purity is not obvious. On the contrary, it will cause waste of reagents and raw materials, and ultimately lead to the occurrence of side reactions and affect the purity of the product. When the reaction temperatures in each step of the examples are all within the preferred range of the present application, the yield and purity of the oxime ester photoinitiator are the highest. However, if the temperature is too low, the reaction will be incomplete and the reaction rate will be slow. If the temperature is too high and exceeds the scope of the present application, the improvement of the yield and purity is not obvious. On the contrary, it will cause an increase in cost. Therefore, it is preferable that the production molar ratio and the reaction temperature are within the preferred range of the present application.

[0089] Performance Evaluation In addition, the photocurable compositions employed when performing photosensitivity measurement in Examples 1 to 13 and Comparative Examples 1 to 4 of the present application are prepared at the compounding ratios shown in Table 5. For example, by weight, the photocurable composition of Example 1 contains 200 parts of an acrylate copolymer, 100 parts of dipentaerythritol hexaacrylate, 5 parts of a photoinitiator, 900 parts of butanone (solvent), and 5 parts of Pigment Blue 15 (CAS: 147-14-8). And the above acrylate copolymer (manufacturer: Changzhou Qiangli Electronic New Materials Co., Ltd.) is a benzyl methacrylate / methacrylic acid / hydroxyethyl methacrylate (molar ratio 70:10:20) copolymer with Mw = 10,000. In the above photocurable composition, the photoinitiator is an oxime ester compound represented by the general formula (I) in the foregoing content of the present application or the same type of photoinitiator known in the prior art for comparison.

[0090]

Table 5

[0091] 1. Measurement of dissolution performance The solubility of the oxime ester photoinitiator in propylene glycol methyl ether acetate (PGMEA) indicates its dissolution performance and is one of the index parameters for evaluating the application performance of the photoinitiator. Compounds having the structure represented by the general formula (I) were selected, and the solubilities of Compounds 1 to 13 and Compounds A, B, C, and D in PGMEA at 25 °C were measured respectively, and the measurement results are as shown in Table 6.

[0092] 2. Measurement of photosensitivity performance (1) Measurement of photosensitivity The compositions of Examples 1 to 13 and Comparative Examples 1 to 4 were stirred in the dark and coated on a 21-step gray scale with a #6 wire bar to form a coating film with a film thickness of about 15 μm. The coating film was exposed with an LED lamp (385 nm) and irradiated with an energy of 191 mJ / cm 2 (100% light intensity, 8 m / min × 2 times), developed with a 2% NaOH aqueous solution for 2 min after curing, then washed with tap water for 1 min, and the measurement results of the gray scale were observed and shown in Table 6. (2) Measurement of yellowing resistance performance After sufficiently stirring the photocurable compositions of Examples 1 to 13 and Comparative Examples 1 to 4 in a yellow light chamber, the compositions were applied to a tin plate with a #15 wire bar to prepare a coating film with a wet film thickness of 10 μm. Exposure was carried out with a 365 nm-LED light source, and the energy of 2000 mJ / cm 2 was received to cure it sufficiently and completely. A Xrite color difference meter was used to measure yellowing, and the yellowing resistance performance of the photocurable resin was judged based on the Δb value. The higher the Δb value, the more obvious the yellowing, indicating poor yellowing resistance performance. The measurement results of the yellowing resistance performance of Examples 1 to 13 and Comparative Examples 1 to 4 are shown in Table 6.

[0093]

Table 6

[0094] From the above, compared with the conventional photoinitiators, the oxime ester initiator represented by formula (I) disclosed in the present application has excellent solubility in organic solvents, has the characteristics of high sensitivity and low yellowing after application, is easy to synthesize, has low cost, and has the potential to be widely applied in the field of photocuring.

[0095] The above are only preferred embodiments of the present application and are not intended to limit the present application. For those skilled in the art, the present application may have various changes and modifications. Any corrections, equivalent substitutions, improvements, etc. made within the spirit and principle of the present application are all included in the protection scope of the present application.

Claims

1. An oxime ester photoinitiator characterized by having a structure represented by the general formula (I). 【Chemical 1】 [Wherein, R １ , R ２ are each independently a substituted or unsubstituted C １ -C ２０ alkyl group, a substituted or unsubstituted C ３ -C ２０ heteroalkyl group, a substituted or unsubstituted C ６ -C ２０ aryl group, a substituted or unsubstituted C ４ -C ２０ heteroaryl group, a substituted or unsubstituted C ３ -C ２０ alicyclic heterocyclic group selected from the group consisting of. m is 1 or 0. n is 1 or 0. x is 1 or 0. y is 1 or 0. z is 1 or 0.]

2. The C before substitution １ ~C ２０ Among the alkyl groups of, the substituent is selected from C ３ ~C １２ The heteroalkyl group of, and the substituted or unsubstituted C １ ~C ２０ The alkyl group of may have at least one -CH ２ - being substituted by -O- or -S-, Said C before substitution ３ ~C ２０ Among the heteroalkyl groups of, the substituent is C １ ~C １０ Selected from linear or branched alkyl groups of, The C before substitution ６ - C ２０ Among the aryl groups of, the substituent is C １ - C ６ A linear or branched alkyl group of C １ - C １０ A linear or branched alkoxy group of C １ - C １０ A linear or branched alkylthio group of C １ - C ８ A linear or branched acyl group of C １ - C ８ One or more selected from the group consisting of a linear or branched acyloxy group, a halogen atom, a cyano group, or a nitro group Said C before substitution ４ ~C ２０ Among the heteroaryl groups of, the substituent is C １ ~C ８ Selected from linear or branched alkyl groups of, Said C before substitution ３ ~C ２０ Among the alicyclic heterocyclic groups of, the substituent is C １ ~C ６ The oxime ester photoinitiator according to claim 1, characterized in that it is selected from linear or branched alkyl groups of C

3. R １ 、R ２ each independently represents a C １ -C ２０ alkyl group or a C ６ -C ２０ aryl group, and preferably, R １ and R ２ each independently is selected from a methyl group, an ethyl group or a phenyl group. The oxime ester photoinitiator according to claim 1 or 2, characterized in that.

4. The oxime ester photoinitiator according to any one of Claims 1 to 3, characterized in that the oxime ester photoinitiator has a structure represented by any one of the structural formulas (1) to (13). 【Chemical 2】 【Chemical 3】 【Chemical 4】 [Chemical Formula 5] 【Chemical Formula 6】 【Chemical Formula 7】 【Chemical 8】 【Chemical Formula 9】 【Chemical Formula 10】 【Chemical 11】 【Chemical 12】 【Chemical 13】 【Chemical 14】

5. The oxime ester photoinitiator is 【Chemical Formula 15】 、 【Chemical 16】 or 【Chemical 17】 The oxime ester photoinitiator according to any one of Claims 1 to 4, characterized in that it is as described above.

6. carbazole 【Chemical Formula 18】 as raw material A 【Chemical Formula 19】 is subjected to a substitution reaction to obtain intermediate a 【Chemical 20】 in step S1; said intermediate a is subjected to a first Friedel-Crafts reaction with raw material B 【Chemical 21】 to obtain intermediate b 【Chemical 22】 in step S2; said intermediate b is subjected to a second Friedel-Crafts reaction with raw material C 【Chemical 23】 to obtain intermediate c 【Chemical 24】 in step S3; said intermediate c is subjected to an oximation reaction with nitrite and / or nitrite ester to obtain intermediate d 【Chemical 25】 in step S4; said intermediate d is subjected to an esterification reaction with acid anhydride and / or acid chloride to obtain the oxime ester photoinitiator 【Chemical 26】 [However, X is F, Cl, Br or I, m is 1 or 0. n is 1 or 0. x is 1 or 0. y is 1 or 0. z is 1 or 0.] in step S5; A method for producing an oxime ester photoinitiator according to any one of Claims 1 to 5, characterized by comprising the above steps.

7. In step S1, the substitution reaction is carried out under alkaline conditions, and the alkali is potassium hydroxide and / or sodium hydroxide, and / or In step S2, the first Friedel-Crafts reaction is carried out under the condition of being catalyzed by aluminum chloride, and the solvent for the first Friedel-Crafts reaction is dichloromethane and / or dichloroethane, and / or In step S3, the second Friedel-Crafts reaction is carried out under the condition of being catalyzed by aluminum chloride, and the solvent for the second Friedel-Crafts reaction is dichloromethane and / or dichloroethane, and / or In the step S4, the nitrite is sodium nitrite and / or potassium nitrite, the nitrite ester is one or more of ethyl nitrite, isopentyl nitrite, and isooctyl nitrite. Preferably, the oximation reaction is carried out under acidic conditions, the acid is concentrated hydrochloric acid and / or a halogenated carboxylic acid, the halogenated carboxylic acid is chloroacetic acid or bromoacetic acid, the solvent for the oximation reaction is one or more of ethyl acetate, tetrahydrofuran, and dichloromethane, and / or In the step S5, the acid anhydride is acetic anhydride and / or benzoic anhydride, the acid chloride is one or more of acetyl chloride, propionyl chloride, and benzoyl chloride. Preferably, the esterification reaction is carried out under alkaline conditions, and the alkali is one or more of triethylamine, diisopropylethylamine, and 4-dimethylaminopyridine. The manufacturing method according to claim 6 is characterized by this.

8. In the step S1, the molar ratio of the raw material A to the carbazole is (1 to 1.1):

1. Preferably, the reaction temperature of the substitution reaction is 50 to 100°C, more preferably, the reaction temperature of the substitution reaction is 50 to 80°C, and / or In the step S2, the molar ratio of the raw material B to the intermediate a is (1 to 1.1):

1. Preferably, the reaction temperature of the first Friedel-Crafts reaction is -10 to 10°C, more preferably, the reaction temperature of the first Friedel-Crafts reaction is 0 to 5°C, and / or In the step S3, the molar ratio of the raw material C to the intermediate b is (1 to 1.1):

1. Preferably, the reaction temperature of the second Friedel-Crafts reaction is -10 to 10°C, more preferably, the reaction temperature of the second Friedel-Crafts reaction is 0 to 5°C, and / or In the step S4, the molar ratio of the nitrite and / or nitrite ester to the intermediate c is (2 to 3.5):

1. Preferably, the reaction temperature of the oximation reaction is 0 to 30°C, more preferably, the reaction temperature of the oximation reaction is 20 to 25°C, and / or In the step S5, the molar ratio of the acid anhydride and / or acid chloride to the intermediate d is (2 to 2.8):

1. Preferably, the reaction temperature of the esterification reaction is 0 to 30°C, and more preferably, the reaction temperature of the esterification reaction is 20 to 25°C. The manufacturing method according to claim 6 or 7, characterized by the above.

9. Use of the oxime ester photoinitiator according to any one of claims 1 to 5 in a photoresist.

10. A photocurable composition containing a photoinitiator, wherein the photoinitiator is the oxime ester photoinitiator according to any one of claims 1 to 5. Preferably, by weight, the photocurable composition contains 800 to 1000 parts of a solvent, 100 to 300 parts of an acrylate copolymer, 50 to 150 parts of dipentaerythritol hexaacrylate, and 3 to 10 parts of the oxime ester photoinitiator. A photocurable composition characterized by the above.

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