Novel dialoylcarbazole compounds and their use as sensitizers

Abstract

The present invention provides novel diaroylcarbazole compounds that exhibit significant synergistic initiation when used in a photoresist composition together with a carbazolyl oxime ester photoinitiator, and that exhibit optimal sensitization effects when the molar ratio of the diaroylcarbazole compound to the carbazolyl oxime ester photoinitiator is 0.1 to 1.4.

Description

[Technical Field] 【0001】 The present invention belongs to the fields of organic chemistry and photocuring, and more specifically, relates to a novel dialoylcarbazole compound that exhibits high sensitivity when used in the production of photocurable compositions, particularly photoresists, by forming a photoinitiator composition with a carbazolyl oxime ester as a highly active sensitizer. [Background technology] 【0002】 Photocuring technology has been widely used since its development in the 1970s. For example, UV photocuring technology is commonly used in the manufacturing of paints, printing inks, and electronic devices. The components of photoinitiators and initiators used with photoinitiators, such as sensitizers, are factors that affect curing efficiency. Carbazolyl oxime esters are an important type of oxime ester photoinitiator and, due to their high sensitivity, are known, studied, and used by those skilled in the art. For example, patent applications with publication numbers CN1922142A (Mitsubishi Chemical), CN100528838C(02), CN101528694A(831), CN101528693A, CN101508744A(304), CN103153952A(03), CN103492948A, and CN107793502A disclose carbazolyl oxime ester compounds with various different substituents, which are used in materials and devices such as color filters, black matrices, photospacers, and liquid crystal splitting orientations. To enhance saturation or opacity, the pigment content in photocuring formulations is increasing. In particular, in black photoresists with high pigment content, the utilization rate of light energy decreases due to pigment absorption during the curing process. Therefore, the development of more sensitive photoinitiators or photoinitiator compositions is expected, and sensitization of conventional photoinitiators is one method of improving sensitivity. As sensitizers described in the prior art, for example, in patent CN100528838C, benzophenone and its derivatives, thioxanthone and its derivatives, anthraquinone and its derivatives, coumarin derivatives, camphorquinone, phenothiazine and its derivatives, 3-(aloylmethylene)thiazoline, rhodanine and its derivatives, eosin, rhodamine, acridine, anthocyanin, merocyanine dyes, and tertiary amine compounds are disclosed. Of these, benzophenone and its derivatives, thioxanthone and its derivatives, anthraquinone and its derivatives, and coumarin derivatives are preferred.Experiments have shown that when these sensitizers are used in combination with carbazolyl oxime esters, they do not exhibit a satisfactory sensitizing effect. For example, compounds such as eosin, anthocyanins, and phenothiazines contain phenolic hydroxyl groups or anilino groups, which leads to a decrease in the photocuring efficiency of the photocurable composition formulation. While the four preferred compounds themselves are photoinitiators, their photoinitiation efficiency is far lower compared to carbazolyl oxime ester compounds, and they do not exhibit a synergistic sensitizing effect when used in combination with carbazolyl oxime esters. For this reason, there were no suitable sensitizers in the prior art. 【0003】 However, engineers are focused on improving performance in areas such as exposure sensitivity, resolution, and thermal stability, and are constantly facing new challenges with conventional product and formulation technologies. [Overview of the Initiative] 【0004】 The inventors synthesized novel dialoylcarbazole compounds represented by formulas I and II, and surprisingly found that when used in combination with carbazolyl oxime esters, such as Irgacure® OXE 03, in specific proportions, they exhibit a remarkable sensitizing effect, with a sensitizing efficiency far higher than that of those compounds disclosed in the prior art. Based on this, the inventors propose the use of a photoinitiator composition containing the above-mentioned dialoylcarbazole compounds and carbazolyl oxime esters, and a photocurable composition, particularly in photoresists. 【0005】 In the first embodiment, a dialoylcarbazole compound whose structure is represented by formula I or formula II is provided. [ka] (In the formula, R1, R8, R 11 , R 18 These are, independently, H, halogen atom, C1-C8 alkyl group, C1-C8 alkoxy group, and CN. R2, R3, R4, R5, R6, R7, R 12 , R13 , R 14 , R 15 , R 16 , R 17 are each independently H, F, Cl, COOR 20 , a C1-C12 straight or branched alkyl group, a C1-C12 straight or branched alkoxy group, wherein the C1-C12 straight or branched alkyl group is unsubstituted or substituted with a phenyl group, a C3-C6 cycloalkyl group, a C3-C6 heterocyclic group, F, Cl, COOR 21 , OR 21 , SR 21 , PO(OC n H 2n+1 )2, Si(C n H 2n+1 )3, and is substituted with one or more groups thereof, and n is an integer from 1 to 4, provided that at least one substituent on the benzene ring of each benzoyl group is a group containing a fluorine atom or a fluoroalkyl group, and R9, R 19 are each independently a C1-C12 straight or branched alkyl group, a C2-C12 alkenyl group, a C3-C12 alkenylalkyl group, wherein the hydrogen on the carbon atom is unsubstituted or substituted with a phenyl group, a C3-C6 cycloalkyl group, a C3-C6 heterocyclic group, a halogen, COOR 20 , OR 20 , SR 20 , PO(OC n H 2n+1 )2, Si(C n H 2n+1 )3, and is substituted with one or more groups thereof, and n is an integer from 1 to 4, or the C3-C12 alkenylalkyl group is separated by one or more of O, S, SO, SO2, CO, COO, or, R9, R 19 are each independently a C3-C12 alkyl group, and the alkyl chain is separated by one or more of O, S, SO, SO2, CO, or, R9, R 19 are each independently a phenyl group, and the phenyl group is unsubstituted or substituted with a C1-C8 alkyl group, a halogen atom, OR 20 , SR 20 , COR 20Substituted with one or more of CN, COOH, or R9 may form a C4-C6 heterocyclic structure together with substituent R1 or substituent R8, or R 19 is substituent R 11 or substituent R 18 Together, they may form a C4-C6 heterocyclic structure. R 20 The group is a C1-C12 alkyl group or a phenyl group, and is either unsubstituted, or a phenyl group, a C3-C6 cycloalkyl group, a C3-C6 heterocyclic group, F, Cl, OR 21 , SR 21 Substituted with one or more of the following groups, R 21 (These are C1-C12 alkyl groups.) 【0006】 Preferably, the compound represented by formula I is selected from the compounds represented by formulas IA and IB, and the compound represented by formula II is selected from the compounds represented by II-A and II-B. [ka] (In the formula, R2, R3, R4, R5, R6, R7, R 12 , R 13 , R 14 , R 15 , R 16 , R 17 These are H, F, Cl, and COOR, respectively, independently. 20 The C1-C12 linear or branched alkyl group, or the C1-C12 linear or branched alkoxy group, where the C1-C12 linear or branched alkyl group is unsubstituted, or a phenyl group, a C3-C6 cycloalkyl group, a C3-C6 heterocyclic group, F, Cl, or COOR. 21 , OR 21 , SR 21 , PO(OCH 2n+1 )2, Si(C n H 2n+1 ) is substituted with one or more of the three elements, where n is an integer from 1 to 4. As a condition, at least one substituent on the benzene ring of each benzoyl group is a group containing a fluorine atom or a fluoroalkyl group. R9, R 19 The definition is as described above. Y1 and Y2 are independently C2-C8 linear or branched alkyl groups, and the chain is O, S, NR 21 Alternatively, a carbonyl group may be inserted, or the hydrogen atom on the carbon may be replaced with an OH group or a halogen atom. 【0007】 Preferably, examples of the dialoylcarbazole compounds represented by formulas IA and IB include the following: [ka] TIFF0007873963000004.tif110162 【0008】 In the second embodiment, a compound represented by formula III-A or formula III-B is used as a starting material and subjected to a one- or two-step Friedel-Crafts acylation reaction with a corresponding substituted alloyl chloride or acid anhydride to obtain a symmetric or asymmetric dialoyl compound. If any of the aryl groups contains a carboxyl group or a halogen atom having resubstitution activity, R 20 The present invention provides a method for producing a dialoylcarbazole compound represented by formula I or formula II, by esterification or etherification reaction with an OH alcohol compound. [ka] (In the formula, R1, R8, R9, R 11 , R 18 , R 19 It is defined as described above. 【0009】 In a third aspect, the present invention further provides a photoinitiator composition comprising at least one of the above-mentioned dialoylcarbazole compounds and at least one carbazolyloxime ester photoinitiator, wherein the carbazolyloxime ester photoinitiator comprises at least one oxime ester group TIFF0007873963000006.tif1972 is linked directly or via one carbonyl group to the parent structure of an N-substituted carbazole, where R 22 The C1-C12 alkyl group is unsubstituted, or contains a halogen atom, OR 24 , SR 24 , C3-C8 cycloalkyl groups, phenyl groups, C4-C20 heteroaryl groups, COOR 24 Substituted with one or more of the groups, or R 22 The C6-C20 aryl group or C4-C20 heteroaryl group is, respectively, unsubstituted, or a C1-C8 alkyl group, CN, OR substituted with a halogen atom, a C1-C20 alkyl group, or one or more fluorine atoms. 24 , SR 24 , NR 25 R 26 Substituted with one or more of the groups, or R 22 R is a C6-C20 alloyl group, a C4-C20 heteroaloyl group, 23 R is selected from C1-C12 alkyl groups, C6-C20 aryl groups, and C1-C4 alkoxy groups. 24 R is a C1-C8 alkyl group which may be substituted with one or more of H, C1-C8 alkyl groups, C3-C8 heterocyclic groups, F, or acetoxy groups, phenyl groups, or C1-C20 alkylphenyl groups, 25 , R 26 These are C1-C4 alkyl groups, OR 24 A C2-C4 alkyl group substituted with, or NR 25 R 26 It has a ring structure It is TIFF0007873963000007.tif1893, The carbazole parent structure is selected from carbazole, benzocarbazole, and dibenzocarbazole. The hydrogen atoms on the parent structure, in addition to the oxime ester group or the carbonyl substituent linked to the oxime ester group, include a C1-C20 alkyl group, halogen, NO2, CN, OR 27 、a C6-C20 aroyl group, a C4-C20 heteroaroyl group, and may be substituted with one or more groups among 4,5-diphenylimidazol-2-yl. When the substituents on the parent structure are spatially adjacent, they form a new 5- to 7-membered cyclic structure. Here, the C1-C20 alkyl group is unsubstituted or substituted with halogen, a C3-C8 cycloalkyl group, a C3-C8 heterocyclic group, a phenyl group, COOR 27 、OR 27 、PO(OC n H 2n+1 )2, Si(C n H 2n+1 )3, and is substituted with one or more groups among them. n is an integer from 1 to 4. Or, when the number of carbon atoms is greater than 3, one or more oxygen atoms are inserted. R 27 is a C1-C8 alkyl group or a C1-C8 alkyl group substituted with a C3-C8 heterocycloalkyl group Based Yes, C6-C20 alloyl groups, The aryl group or heteroaryl group in the C4-C20 heteroaroyl group is unsubstituted or substituted with a halogen atom, CN, TIFF0007873963000008.tif2070R 24 ’, OR 24 ’, SR 24 ’, NR 25 ’R 26 ’, COOR 24 ’, R 24 ’SO2, and is substituted with one or more groups among them. The definitions of R 22 ’, R 23 ’, R 24 ’, NR 25 ’R 26 ’ are the same as the corresponding R 22 、R 23 、R 24 、NR 25 R 26 . 【0010】 Preferably, the carbazolyl oxime ester photoinitiator is selected from the following compounds or any mixture thereof. [ka] TIFF0007873963000010.tif218164 TIFF0007873963000011.tif94164 【0011】 One method for producing carbazolyl oxime esters involves using a corresponding acylcarbazole parent compound as a raw material and obtaining the carbazolyl oxime ester through oximing and esterification. Many prior arts relating to this can be referenced, such as CN103153952A. 【0012】 Preferably, the method for producing the photoinitiator composition includes the step of uniformly mixing 0.1 molar amounts of a sensitizer compound, for example, a compound of formula I-1, and 0.1 molar amounts of a carbazolyl oxime ester, for example, a compound of formula IV-22, to obtain the photoinitiator composition. Alternatively, in the production of the photocurable composition, one or more types of sensitizer compounds and one or more types of carbazolyl oxime esters are directly mixed with other components, but the ratio of the total molar amount of the sensitizer to the total molar amount of the carbazolyl oxime ester is 2:1 or less, preferably 0.1:1 to 1.4:1, and more preferably 0.22:1 to 1.16:1. 【0013】 In a fourth aspect, the present invention further provides a photocurable composition, and this photocurable composition, a. A photoinitiator composition comprising at least one sensitizer represented by formula I, formula IIA, and IIB, and at least one carbazolyl oxime ester compound represented by formula IV1-IV37, wherein selectively, the mass ratio of component a to the total mass of the solids of the formulation is 1 to 10%, preferably 1 to 8%, and b. Selectively, at least one free radical polymerizable compound selected from acrylate compounds, methacrylate compounds, resins containing acrylate groups or methacrylate groups, or any mixture thereof, It contains. 【0014】 Examples of low molecular weight compounds among free radical polymerizable compounds include alkyl acrylates, cycloalkyl acrylates, hydroxyalkyl acrylates, dialkylaminoalkyl acrylates, alkyl methacrylates, cycloalkyl methacrylates, hydroxyalkyl methacrylates, dialkylaminoalkyl methacrylates, such as methyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, ethyl methacrylate, and polysiloxane acrylate. Other examples include acrylonitrile, vinyl acetate, vinyl ether, styrene, and N-vinylpyrrolidone. Examples of compounds containing two or more double bonds include ethylene glycol, polyethylene glycol, propylene glycol, neopentyl glycol, 1,6-hexanediol diacrylate, trihydroxymethane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, vinyl acrylate, and triallyl isocyanurate. Examples of relatively high molecular weight double bond compounds include substances commonly known as oligomers, such as acrylic epoxy resins, acrylic polyester resins, unsaturated polyester resins, acrylic polyether resins, and acrylic polyurethane resins, which generally have molecular weights of 500 to 3000. 【0015】 In a fifth aspect, the present invention further provides an ink or coating in which, in addition to the above-mentioned photocurable composition, other necessary components may be added depending on performance requirements such as ink color and printing application. The ink or coating can be applied to pattern printing, 3D printing, PCB solder masks, liquid or dry film resist materials, substrate protective coatings, and the like. 【0016】 In a fifth aspect, the present invention further provides a binder to which, in addition to the above-mentioned photocurable composition, other necessary components may be added depending on the performance requirements of the binder. The binder can be applied to the adhesion of glass, plastic, metal parts, and the like. 【0017】 In addition to the examples herein, those skilled in the art may readily add other necessary components, such as stabilizers, surfactants, leveling agents, and dispersants, depending on the prior art and the intended use of the photocurable composition. 【0018】 In the seventh aspect, the present invention is a. At least one of the above photoinitiator compositions, wherein selectively, the mass ratio of the photoinitiator composition to the total mass of the solids of the formulation is 0.2 to 10%, preferably 1 to 8%, and b. At least one free radical polymerizable compound, for example, a polyfunctional acrylate monomer, c. Alkali-soluble resin and, d. Pigments and, e. Solvent and, Further providing of photoresists containing the above. 【0019】 Examples of polyfunctional acrylates in component b include dipentaerythritol hexaacrylate and pentaerythritol acrylate. Examples of alkali-soluble resins in component c include copolymers obtained by copolymerizing polyacrylates having carboxylic acid groups, such as methacrylic acid, itaconic acid, and maleic acid, with common monomers in the required proportions. Common monomers include methyl acrylate, butyl methacrylate, benzyl acrylate, hydroxyethyl acrylate, styrene, butadiene, and maleic anhydride. Preferred examples of copolymers are copolymers of methyl methacrylate and methacrylic acid, copolymers of benzyl methacrylate and methacrylic acid, copolymers of methyl methacrylate and butyl methacrylate, and copolymers of methacrylic acid and styrene. 【0020】 Examples of pigments in component d include, for example, CI Pigment Red 177, CI Pigment Green 7, CI Pigment Blue 15:6, Solvent Blue 25, Carbon Black, Titanium Black, and CI Pigment Black 1. 【0021】 There are many prior art documents concerning components b, c, d, and e, such as CN103153952A, which a person skilled in the art may select as needed. 【0022】 In addition to using component a as a photoinitiator, other conventional photoinitiators or initiators, such as Omnirad BDK, Omnirad369, Omnirad379, Omnirad389, Omnirad TPO, Omnirad819, Omnirad ITX, Omnirad DETX, and Omnirad784, may be added to other conventional commercial products or prior art, provided that they are advantageous to the performance of the photocurable composition, especially the photoresist. Omnirad is a product of IGM Resins. 【0023】 In addition to the above components, other resins that can be added include polyalkyl methacrylate, ethylcellulose, carboxymethylcellulose, novolac resin, polyvinyl butyral, polyvinyl acetate, polyester, and polyimide. 【0024】 In the eighth aspect, a black photoresist is provided, and if the pigment in the photoresist is a well-dispersed black pigment, such as carbon black or titanium black, a black photoresist is obtained. The black photoresist can be used in the manufacture of black matrices, cell gap spacers, and microlenses. 【0025】 In the ninth aspect, a color filter device, which is an important component of a color display, is obtained by using the photoresist and / or black photoresist of the present invention as raw materials and going through a color filter processing process. 【0026】 By using any material containing the photoinitiator composition of the present invention, such as an ink, paint, binder, photoresist, or black photoresist, as a raw material and processing it in the necessary steps, any article, such as a color filter or a color display, can be obtained. [Modes for carrying out the invention] 【0027】 The following examples and comparative examples can illustrate the present invention in more detail. 【0028】 light source equipment 365nm LED surface light source, manufactured by Blue Tian Light Development Co., Ltd.; Test Equipment Stereomicroscope, COVS-50G, manufactured by Guangzhou Mingmei Optoelectronic Technology Co., Ltd., line width in μm. Experimental materials Formula I-1 compound: derived from Compound Preparation Example 1; Formula II-2 compound: derived from Compound Preparation Example 2; Omnirad DETX: A photoinitiator product manufactured by IGM Resin Corporation; Esacure3644: A photoinitiator product manufactured by IGM Resin Corporation; Omnirad EMK: A photoinitiator product manufactured by IGM Resin Corporation; OXE 02: Formula IV-1 compound, a photoinitiator product manufactured by BASF Corporation; OXE 03: Formula IV-22 compound, a photoinitiator product manufactured by BASF Corporation; NCI 831: Formula IV-9 compound, product of ADEKA Corporation Japan; PBG 304: Formula IV-2 compound, product of Changzhou Strong Electronic New Materials Co., Ltd.; Photomer 6010: Aliphatic polyurethane triacrylate, product of IGM Resin Co., Ltd. DPHA: Dipentaerythritol V, Hexaacrylate, a product of Tianjin Tianjiao Chemical Co., Ltd. HPMA: Polymaleic acid, a product of Aladdin Industries, Inc., USA. 【0029】 Examples of compound production: Production of dialoylcarbazole compounds Manufacturing Example 1: Preparation of 9-ethyl-3,6-di[4-(2,2,3,3-tetrafluoropropoxy)benzoyl]carbazole (formula I-1 compound) 1a. Preparation of 9-ethyl-3,6-di(4-fluorobenzoyl)carbazole 19.5 g of N-ethylcarbazole was dissolved in 250 ml of dichloroethane, then 34 g of aluminum trichloride was added. While maintaining the temperature at 0 to -5°C, 40 g of p-fluorobenzoyl chloride was added dropwise to the solution, and the reaction was allowed to proceed for 15 hours while maintaining the temperature at 0 to 5°C. The reaction solution was added in batches to 100 ml of 10% HCl solution at 0°C, and after the addition was complete, the mixture was stirred for 30 minutes. After standing for 30 minutes, the mixture was separated, and the dichloroethane phase was washed with 50 ml of 2% sodium hydroxide solution for 30 minutes to separate the dichloroethane phase. The dichloroethane solution was recovered by vacuum distillation, and 80 ml of ethyl acetate crystals was added to the residue to obtain 30.5 g of product. The content of the white powder was 98.5%, and the yield was 69.5%. Preparation of 1b.9-ethyl-3,6-di[4-(2,2,3,3-tetrafluoropropoxy)benzoyl]carbazole 30 g of 9-ethyl-3,6-di(4-fluorobenzoyl)carbazole, 25 g of 2,2,3,3-tetrafluoropropanol, and 8 g of sodium hydroxide prepared in Step 1a were dissolved in 200 ml of pyridine and reacted at 70°C for 18 hours. Pyridine and excess 2,2,3,3-tetrafluoropropanol were removed by vacuum distillation. 100 ml of water and 250 ml of dichloroethane were added to the residue and stirred for 1 hour. The aqueous phase was separated and the dichloroethane solution was washed twice with 100 ml of water. Dichloroethane was recovered by vacuum distillation, 150 ml of ethyl acetate and 2 g of activated carbon were added to the residue, and the mixture was heated under reflux for 1 hour. The activated carbon was filtered, and the filtrate was vacuum distilled to remove approximately 100 ml of ethyl acetate. After cooling, crystallization occurred, and after filtration, the filtered cake was dried to obtain 27.8 g of a light yellow powder. The content was 98.5% and the yield was 61.4%. 1The structure was confirmed by 1H-NMR (CDCl3), and the δ[ppm] values ​​were 1.512 (t, 3H), 4.425-4.483 (m, 6H), 5.949-6.277 (m, 2H), 7.016-7.045 (m, 4H), 7.496-7.517 (d, 2H), 7.844-7.868 (d, 4H), 7.990-8.011 (d, 2H), and 8.534 (s, 2H). 【0030】 Manufacturing Example 2: Preparation of 11-(2-ethylhexyl)-5,8-di[4-(2,2,3,3-tetrafluoropropoxy)benzoyl]-11H-benzo[a]carbazole (formula II-2 compound) 2a. Preparation of 11-(2-ethylhexyl)-5,8-di(4-fluorobenzoyl)-11H-benzo[a]carbazole 2.0 g of B03D and 20 ml of dichloroethane were added to a 50 ml single-necked flask and dissolved. 0.2 g of zinc chloride and 2.3 g of 2-fluorobenzoyl chloride were added, and the mixture was reacted at 80°C with stirring for 10 hours. After cooling, the reaction mixture was washed twice with 20 ml of water, and the dichloroethane solution was concentrated under reduced pressure to dryness to obtain 4.0 g of a brownish, viscous substance, which was used in reaction 2b without purification. 2b. Preparation of 11-(2-ethylhexyl)-5,8-di[4-(2,2,3,3-tetrafluoropropoxy)benzoyl]-11H-benzo[a]carbazole 4.0 g of 11-(2-ethylhexyl)-5,8-di(4-fluorobenzoyl)-11H-benzo[a]carbazole, the product of step 2a, was dissolved in 20 ml of pyridine and placed in a 50 ml single-necked flask. Then, 2.2 g of tetrafluoropropanol and 1.2 g of sodium hydroxide were added, and the mixture was heated to 80°C and stirred for 5 hours. The reaction mixture was added dropwise to 100 ml of water, and then stirred with 100 ml of dichloroethane for 1 hour, after which it was allowed to stand and separate into layers. The separated dichloroethane solution was concentrated under reduced pressure to dryness to obtain 4.7 g of a brown solid. This solid was dissolved by heating in a mixed solvent of 20 ml of ethyl acetate and 20 ml of ethanol, 0.25 g of activated carbon was added, and the mixture was refluxed for 1 hour. After thermal filtration, the filtrate was cooled, and yellow crystals precipitated. After drying, 2.5 g was weighed, and the overall yield of the two-step reaction was 51.3%, with a content of 98.51%. 1 This structure was confirmed by 1H-NMR (CDCl3), and the following values ​​were observed: δ[ppm]: 0.754-0.789 (m, 6H), 1.126-1.328 (m, 8H), 2.113 (s, 1H), 4.369-4.452 (t, 2H), 4.513-4.599 (t, 2H), 4.928 (m, 2H), 4.994-5.342 (m, 1H), 5.537-5.885 (m, 1H), 7.251-7.272 (m, 4H), 7.430-7.455 (d, 1H), 7.566-7.811 (m, 6H), 7.950-7.979 (d, 1H), 8.430 (s, The results were 1H), 8.571 (s, 1H), 8.668-8.695 (d, 1H), and 8.736-8.764 (d, 1H). 【0031】 Manufacturing of photoinitiator compositions Composition production example 1: 12 g of the compound represented by formula II-2 and 28 g of OXE-02 were placed in a mortar, ground, and mixed to obtain 40 g of a composition in which the molar ratio of the acylcarbazole compound to the carbazolyl oxime ester photoinitiator was 0.22. 【0032】 Composition production example 2: 12 g of the compound represented by formula I-1 and 28 g of OXE-02 were placed in a mortar, ground, and mixed to obtain 40 g of a composition in which the molar ratio of the acylcarbazole compound to the carbazolyl oxime ester photoinitiator was 0.27. 【0033】 Composition production example 3: 12 g of the compound represented by formula I-1 and 12 g of OXE-03 were placed in a mortar, ground, and mixed to obtain 24 g of a composition in which the molar ratio of the acylcarbazole compound to the carbazolyl oxime ester photoinitiator was 1.16. 【0034】 Composition production example 4: 12 g of the compound represented by formula II-2 and 28 g of OXE-03 were placed in a mortar, ground, and mixed to obtain 40 g of a composition in which the molar ratio of the acylcarbazole compound to the carbazolyl oxime ester photoinitiator was 0.41. 【0035】 Manufacturing of alkali-soluble resins 18 g of benzyl methacrylate, 6 g of methacrylic acid, 6 g of hydroxyethyl methacrylate, 1.5 g of azobisisobutyronitrile, 0.6 g of dodecyl mercaptan, and 200 ml of toluene were placed in a 1 L constant-pressure dropping funnel. 100 ml of toluene was then added to a 500 ml four-necked flask, and the mixture was purged with nitrogen gas. The temperature was raised to 80°C, and the solution from the funnel was added dropwise. After a reaction of 6 hours, the temperature was lowered and the mixture was filtered to obtain 24 g of a white alkali-soluble resin. 【0036】 Examples and Comparative Examples of Photoresist Compositions Each example and comparative example was prepared using the components listed in Tables 1-4. The initiator and sensitizer can be the compositions from the production examples of the compositions, or a mixture of these in the proportions shown in the table, dissolved in PMA, and then mixed with a black slurry in a predetermined proportion. After uniformly mixing each component, the mixture was applied to a glass slide using a 10 μm wire rod, baked in a 90°C oven for 5 minutes, cured using a 365 nm light source in combination with a 120 μm mask, developed at 25°C with a 1% NaOH solution, washed by immersion in pure water for 10 seconds, baked in a 90°C oven for 30 minutes, and then the line width of the developed image was measured, with the unit of line width being μm. 【0037】 [Table 1] 【0038】 [Table 2] 【0039】 [Table 3] 【0040】 [Table 4] 【0041】 In the examples and comparative examples shown in Tables 1, 2, and 4, coating, curing, development, and measurement were performed, and the data are shown in Tables 5, 6, 7, and 8. As is clear from the results, in the examples where I-1 was used as a sensitizer in combination with several different carbazolyl oxime esters, and the usage ratio was within the range according to the present invention, the development effect was clearly superior to the comparative examples where no sensitizer was used, only a sensitizer was used, or the amount of sensitizer used was outside the range of the value according to the present invention. In particular, as is clear from the results of Comparative Example 2, the compound represented by formula I-1 could not form a development pattern on its own and had almost no polymerization initiation effect. Comparing the formulations in Table 4 with the data in Table 8, when I-1 was used as a sensitizer, its sensitizing effect was clearly superior to that of thioxanthone, coumarin, and 4,4'-bis(diethylamino)benzophenone, and in the latter three cases, the development linewidth was shown to be less than that of the formulation in Comparative Example 1, which used an oxime ester alone. 【0042】 In the examples and comparative examples in Table 3, coating, curing, development, and measurement were performed, and the data is shown in Table 7. As is clear from the results, in the examples where II-2 was used as a sensitizer in combination with several different carbazolyl oxime esters, and the usage ratio was within the range of the present invention, the development effect was clearly superior to the comparative examples where no sensitizer was used, the sensitizer was used alone, or the amount of sensitizer used was outside the range of the value according to the present invention. In particular, as is clear from the results of Comparative Example 9, the compound represented by formula II-2, when used alone, could not form a development pattern and had almost no polymerization initiation effect. Comparing the formulations in Table 4 with the data in Table 8, it was shown that when II-2 was used as a sensitizer, the sensitizing effect was clearly superior to that of thioxanthone, coumarin, and 4,4'-bis(diethylamino)benzophenone. 【0043】 [Table 5] 【0044】 [Table 6] 【0045】 [Table 7] 【0046】 [Table 8] 【0047】 Binder example Each example and comparative example was prepared using the components shown in Table 9. After uniformly mixing the components, the mixture was applied to a glass slide using a 50 μm wire rod. The mixture was cured using a 365 nm light source in combination with a mask. After curing, the weight of the film was measured. Subsequently, the film was immersed in acetone at room temperature for 36 hours, and the weight of the film was measured again to calculate the gel conversion rate. 【0048】 [Table 9] 【0049】 Table 10 shows the test data for the comparative examples and examples in Table 9. As can be seen from the data, in Examples 10 and 11, the binder of the photocurable composition according to the present invention was used, and when irradiated with light, the double bond gel conversion rate was higher than in Comparative Example 13, which used the oxime ester photoinitiator alone. 【0050】 [Table 10] 【0051】 As described above, the novel dialoylcarbazole compound according to the present invention exhibits a remarkable sensitizing effect when used in a photoresist composition or binder together with a carbazolyl oxime ester photoinitiator, and shows the optimal sensitizing effect when the molar ratio of the dialoylcarbazole compound to the carbazolyl oxime ester photoinitiator is 0.1 to 1.4.

Claims

[Claim 1] A dialoylcarbazole compound whose structure is represented by formula I or formula II. 【Chemistry 1】 (In the formula, R 1 , R 8 , R 11 , R 18 These are, independently, H, halogen atom, C1-C8 alkyl group, C1-C8 alkoxy group, and CN. R in Formula I 2 R 3 R 4 R 5 R 6 R 7 is, independently of one another, H, F, Cl, COOR 20 , a C1-C12 straight-chain or branched alkyl group, a C1-C12 straight-chain or branched alkoxy group, a C1-C12 straight-chain or branched fluoroalkoxy group, with the proviso that at least one substituent on the benzene ring of each benzoyl group is a C1-C12 straight-chain or branched fluoroalkoxy group, where the C1-C12 straight-chain or branched alkyl group is unsubstituted or substituted with one or more groups selected from phenyl group, a C3-C6 cycloalkyl group, F, Cl, COOR 21 , OR 21 , SR 21 , PO(OCH 2n+1 ) 2 , Si(C n H 2n+1 ) 3 and n is an integer from 1 to 4 R in Equation II 12 , R 13 , R 14 , R 15 , R 16 , R 17 These are H, F, Cl, and COOR, each independently. 20 The C1-C12 linear or branched alkyl group, the C1-C12 linear or branched alkoxy group, and the C1-C12 linear or branched fluoroalkoxy group, wherein at least one substituent on the benzene ring of each benzoyl group is a C1-C12 linear or branched fluoroalkoxy group, and the C1-C12 linear or branched alkyl group is unsubstituted, or a phenyl group, a C3-C6 cycloalkyl group, F, Cl, COOR 21 , OR 21 , SR 21 , PO(OCH 2n+1 ) 2 , Si(C n H 2n+1 ) 3 It is substituted with one or more of the following elements, where n is an integer from 1 to 4. R 9 , R 19 These are, independently, a C1-C12 linear or branched alkyl group, a C2-C12 alkenyl group, and a C3-C12 alkenylalkyl group, where the hydrogen atoms on the carbon atoms are unsubstituted, or a phenyl group, a C5-C6 cycloalkyl group, a C3-C6 heterocyclic group, a halogen, or COOR. 20 , OR 20 , SR 20 , PO(OC n H 2n+1 ) 2 , Si(C n H 2n+1 ) 3 Substituted with one or more of the following groups, where n is an integer from 1 to 4, or the C3-C12 alkenylalkyl group is O, S, SO, SO 2 Separated by one or more of CO, COO, or R 9 , R 19 Each of these is independently a C3-C12 alkyl group, and its alkyl chain consists of O, S, SO, SO 2 , separated by one or more of the COs, R 20 is a C1-C12 alkyl group or phenyl group, unsubstituted, or phenyl group, C3-C6 cycloalkyl group, F, Cl, OR 21 , SR 21 Substituted with one or more of the following groups, R 21 (These are C1-C12 alkyl groups.) [Claim 2] The dialoylcarbazole compound according to claim 1, wherein the compound represented by formula I is selected from the compounds represented by formula I-A, and the compound represented by formula II is selected from the compounds represented by formula II-A. 【Chemistry 2】 (In the formula, R in equation I-A 2 , R 3 , R 4 , R 5 , R 6 , R 7 These are H, F, Cl, and COOR, each independently. 20 The C1-C12 linear or branched alkyl group, the C1-C12 linear or branched alkoxy group, and the C1-C12 linear or branched fluoroalkoxy group, wherein at least one substituent on the benzene ring of each benzoyl group is a C1-C12 linear or branched fluoroalkoxy group, and the C1-C12 linear or branched alkyl group is unsubstituted, or a phenyl group, a C3-C6 cycloalkyl group, F, Cl, COOR 21 , OR 21 , SR 21 , PO(OCH 2n+1 ) 2 , Si(C n H 2n+1 ) 3 It is substituted with one or more of the following elements, where n is an integer from 1 to 4. R in equation II-A 12 , R 13 , R 14 , R 15 , R 16 , R 17 These are H, F, Cl, and COOR, each independently. 20 The C1-C12 linear or branched alkyl group, the C1-C12 linear or branched alkoxy group, and the C1-C12 linear or branched fluoroalkoxy group, wherein at least one substituent on the benzene ring of each benzoyl group is a C1-C12 linear or branched fluoroalkoxy group, and the C1-C12 linear or branched alkyl group is unsubstituted, or a phenyl group, a C3-C6 cycloalkyl group, F, Cl, COOR 21 , OR 21 , SR 21 , PO(OCH 2n+1 ) 2 , Si(C n H 2n+1 ) 3 It is substituted with one or more of the following elements, where n is an integer from 1 to 4. R 9 and R 19 are each independently a C1-C12 linear or branched alkyl group, a C2-C12 alkenyl group, or a C3-C12 alkenylalkyl group, where the hydrogen on the carbon atom here is unsubstituted or substituted with one or more groups selected from a phenyl group, a C5-C6 cycloalkyl group, a C3-C6 heterocyclic group, a halogen, COOR 20 OR 20 SR 20 PO(OC n H 2n+1 ), 2 Si(C n H 2n+1 ), 3 n is an integer from 1 to 4, or the C3-C12 alkenylalkyl group is separated by one or more of O, S, SO, SO 2 CO, COO, or R 9 and R 19 are each independently a C3-C12 alkyl group, the alkyl chain of which is separated by one or more of O, S, SO, SO 2 , CO R 20 is a C1-C12 alkyl group, unsubstituted, or a phenyl group, C3-C6 cycloalkyl group, F, Cl, OR 21 , SR 21 Substituted with one or more of the following groups, R 21 (These are C1-C12 alkyl groups.) [Claim 3] The dialoylcarbazole compound according to claim 1, which is one selected from the following compounds or any mixture thereof. 【Transformation 3】 [Claim 4] Using a compound represented by formula III-A or formula III-B as a starting material, a one- or two-step Friedel-Crafts acylation reaction is carried out with the corresponding substituted alloyl chloride or acid anhydride to obtain a symmetric or asymmetric dialoyl compound. If any of the aryl groups contains a carboxyl group or a halogen atom, R 20 A method for producing a dialoylcarbazole compound according to claim 1, characterized by obtaining a dialoylcarbazole compound represented by formula I or formula II by esterification or etherification with an OH alcohol compound. 【Chemistry 4】 (In the formula, R 1 , R 8 , R 9 , R 11 , R 18 , R 19 The definition is the same as in claim 1. [Claim 5] The product comprises at least one dialoylcarbazole compound according to claim 1 and at least one carbazolyloxime ester photoinitiator, wherein the carbazolyloxime ester photoinitiator has at least one oxime ester group R is linked directly or via one carbonyl group to the parent structure of the N-substituted carbazole, in which R 22 is a C1-C12 alkyl group, which is unsubstituted or contains a halogen atom, OR 24 , SR 24 , C3-C8 cycloalkyl groups, phenyl groups, C4-C20 heteroaryl groups, COOR 24 Substituted with one or more of the groups, or R 22 The C6-C20 aryl group or C4-C20 heteroaryl group is a C6-C20 aryl group or a C4-C20 heteroaryl group, and the C6-C20 aryl group or C4-C20 heteroaryl group is unsubstituted or substituted with a halogen atom, a C1-C20 alkyl group, one or more fluorine atoms, a C1-C8 alkyl group, CN, OR 24 , SR 24 , NR 25 R 26 Substituted with one or more of the groups, or R 22 R is a C6-C20 alloyl group, a C4-C20 heteroaloyl group, 23 R is selected from C1-C12 alkyl groups, C6-C20 aryl groups, and C1-C4 alkoxy groups. 24 is a C1-C8 alkyl group which may be substituted with one or more of H, C1-C8 alkyl groups, C3-C8 heterocyclic groups, F, or acetoxy groups; a phenyl group; or a C1-C20 alkylphenyl group, and R 25 , R 26 These are C1-C4 alkyl groups, OR 24 A C2-C4 alkyl group substituted with, or NR 25 R 26 It has a ring structure And, The carbazole matrix structure is selected from carbazole, benzocarbazole, and dibenzocarbazole, and the hydrogen atoms on the matrix structure are C1-C20 alkyl groups, halogens, NOs, in addition to the oxime ester group or carbonyl substituents linked to the oxime ester group. 2 , CN, OR 27 The substituents may be substituted with one or more groups from among C6-C20 alloyl groups, C4-C20 heteroaloyl groups, and 4,5-diphenylimidazole-2yl, and when the substituents on the parent structure are spatially adjacent, they form a new 5-membered to 7-membered cyclic structure, where the C1-C20 alkyl group is unsubstituted, or a halogen, a C3-C8 cycloalkyl group, a C3-C8 heterocyclic group, a phenyl group, or COOR 27 , OR 27 , PO(OC n H 2n+1 ) 2 , Si(C n H 2n+1 ) 3 Substituted by one or more of the groups, where n is an integer from 1 to 4, or if the number of carbon atoms is greater than 3, one or more oxygen atoms are inserted, R 27 The C1-C8 alkyl group is substituted with a C1-C8 alkyl group or a C3-C8 heterocycloalkyl group, and the aryl group or heteroaryl group in the C6-C20 alloyl group or C4-C20 heteroaloyl group is unsubstituted, or a halogen atom, CN, R 24 ', OR 24 ', SR 24 ', NR 25 'R 26 ', COOR 24 ', R 24 'SO 2 Substituted with one or more of the groups, R 22 ', R 23 ', R 24 ', NR 25 'R 26 The definition of ' corresponds to R 22 , R 23 , R 24 , NR 25 R 26 A photoinitiator composition that is the same as the above. [Claim 6] The photoinitiator composition according to claim 5, wherein the carbazolyl oxime ester photoinitiator is selected from the following compounds or any mixture thereof. 【Transformation 5】 【change】 【change】 [Claim 7] The photoinitiator composition according to claim 5, wherein the molar ratio of the dialoylcarbazole compound of claim 1 to the carbazolyloxime ester photoinitiator is 0.1:1 to 1.4:

1. [Claim 8] The photoinitiator composition according to claim 5, wherein the molar ratio of the dialoylcarbazole compound of claim 1 to the carbazolyloxime ester photoinitiator is 0.22:1 to 1.16:

1. [Claim 9] a. At least one photoinitiator composition according to claim 5, b. A photocurable composition containing at least one free radical polymerizable compound. [Claim 10] The photocurable composition according to claim 9, wherein the free radical polymerizable compound is selected from acrylate compounds, methacrylate compounds, resins containing acrylate or methacrylate groups, or any mixture thereof. [Claim 11] The photocurable composition according to claim 9, wherein the mass ratio of component a in the total solid content is 1 to 10%. [Claim 12] An ink containing the photocurable composition according to any one of claims 9 to 11. [Claim 13] A paint containing the photocurable composition according to any one of claims 9 to 11. [Claim 14] A binder containing the photocurable composition according to any one of claims 9 to 11. [Claim 15] a. At least one photoinitiator composition according to claim 5, b. Polyfunctional acrylate monomers, c. Alkali-soluble resins, d. Pigments, e. A photoresist containing a solvent. [Claim 16] A black photoresist, which is a photoresist according to claim 15, wherein the pigment is a well-dispersed carbon black or titanium black. [Claim 17] A black matrix characterized by being manufactured using the black photoresist described in claim 16. [Claim 18] A photospacer characterized by being manufactured using the black photoresist described in claim 16. [Claim 19] A color filter device obtained by processing a filter using the photoresist described in claim 15 and the black photoresist described in claim 16 as raw materials for the photoresist.

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