KR101768658B1 - Carbazole derivatives, photopolymerization initiator and photoresist composition containing the same - Google Patents

Abstract

The present invention relates to a novel carbazole derivative, a photopolymerization initiator comprising the same, and a photoresist composition. The carbazole derivative according to the present invention has oxime ester group and phosphonate group in one molecule at the same time, And a photoresist composition which can realize high sensitivity, heat resistance and chemical resistance, and which can realize an excellent residual film ratio, developability and strength, as well as a photopolymerization initiator composition and a photoresist composition.

Description

[0001] The present invention relates to a carbazole derivative, a photopolymerization initiator comprising the same, and a photoresist composition containing the photoresist composition.

The present invention relates to a carbazole derivative, a photopolymerization initiator and a photoresist composition containing the same, more specifically, to a carbazole derivative containing oxime ester group and phosphonate group at the same time, a photopolymerization initiator containing the same, To a resist composition.

The photopolymerization initiator can generate a radical active species by the irradiated light to cause a photopolymerization reaction of the polycondensation monomer, They can be selectively cured to form various patterns. Therefore, they are used in photocurable ink, photosensitive printing plate, various photoresists, and the like. As a photopolymerization initiator having such properties, various kinds of compounds such as acetophenone derivatives, oxime ester derivatives, triazine derivatives, benzophenone derivatives, bimidazole derivatives and acylphosphine oxide derivatives are known, and most of them are used Examples of the photopolymerization initiator include acetophenone derivatives, oxime ester derivatives, and triazine derivatives. Acetophenone derivatives have good color characteristics and good solubility and are relatively inexpensive. However, in order to obtain sufficient sensitivity, the residual film ratio is lowered, which may cause liquid crystal contamination, since 3% or more, or even 10% Concentration of the composition, particularly the black photosensitive composition, has a weak sensitivity, and there is a problem that desorption of the pattern is seriously occurred when the composition is used alone. The oxime ester derivative has low coloring and high transparency and is excellent in stability and compatibility in the composition but is not efficient in absorbing UV light source and has a problem that the process time is prolonged. When the concentration of the pigment is high or the thickness of the coating film is 2.5 It is still difficult to form a fine pattern because the curing degree of the thick film is not sufficiently satisfied, and the formed pattern can not satisfy the CD (critical dimension) and the mechanical strength required in the product (Patent Documents 1 and 2). Further, halomethyltriazine derivatives which are decomposed by light irradiation to generate halogen radicals in the triazine derivatives are known to have good sensitivity to a UV light source as compared with the above-mentioned photopolymerization initiators, but they have a high crystallinity, And tends to be rapidly crystallized in the film (Patent Document 3).

In order to solve the problems as described above, there is a demand for a new photopolymerization initiator which has characteristics such as higher sensitivity, excellent thermal stability and storage stability, and can meet cost reduction effect and industrial field demand.

Therefore, the applicant of the present invention has found that a carbazole derivative which can efficiently absorb a UV light source and realize a sufficient sensitivity to reduce a contamination source of a liquid crystal, improve a residual film ratio of pattern and increase the usable width of other raw materials, The present invention has been completed to provide a photopolymerization initiator and a photoresist composition containing the same.

(Patent Document 1) United States Patent No. 4590145 (Patent Document 2) United States Patent No. 4255513 (Patent Document 3) Japanese Laid-Open Patent Application No. 2013-531086

An object of the present invention is to provide a novel carbazole derivative which absorbs ultraviolet light effectively compared with conventional photopolymerization initiators and has remarkably improved sensitivity, heat resistance and chemical resistance.

Another object of the present invention is to provide a photopolymerization initiator composition and a photoresist composition comprising a novel carbazole derivative capable of realizing excellent physical properties such as residual film ratio, developability and strength even with a smaller amount of use .

The present invention provides a novel carbazole derivative represented by the following general formula (1).

[Chemical Formula 1]

In the formula (1)

L ₁ is a single bond, (C1-C20) alkylene, (C2-C20) alkenylene, -C (= O) -, -O-, -S-, -S (= O) -, -SO 2 - And -Se-;

R ₁ is (C1-C30) alkyl, (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C6-C30) aryl, (C3-C30) heteroaryl, nitro (-NO _2), a cyano (= O) R ₁₁ or -C (= O) OR ₁₂ wherein R ₁₁ and R ₁₂ are each independently selected from the group consisting of hydrogen, deuterium, (C 1 -C 30) C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C6-C30) aryl and (C3-C30) is selected from a heteroaryl, wherein the R ₁₁ and the cycloalkyl, heterocycloalkyl of R _12, aryl, and The heteroaryl may be further substituted with (C1-C30) alkyl or (C1-C30) alkoxy;

R ₂ and R ₃ are each independently selected from the group consisting of hydrogen, deuterium, (C 1 -C 30) alkyl, (C 3 -C 30) cycloalkyl, (C 3 -C 30) heterocycloalkyl, (C 6 -C 30) C30) heteroaryl;

R ₄ and R ₅ are each independently selected from the group consisting of (C 6 -C 30) aryl, (C 3 -C 30) heteroaryl, (C 2 -C 30) alkenyl, (C 2 -C 30) alkynyl, C2-C30) alkynyloxy or _{-L 2 -OC (= O) -R} 13 , and wherein R ₁₃ is (C2-C30) alkenyl, (C2-C30) and alkynyl, wherein R ₄ and R ₅ is And at least one of R ₄ and R ₅ necessarily contains an unsaturated group; L ₂ is (C 1 -C 30) alkylene;

n is an integer of 0 or 1;

The alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl of R _{1 and} the alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl of R ₂ and R ₃ and the alkenyl, alkynyl or heteroaryl of R ₄ and R ₅ , (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, halogen, cyano, cyano, _{nitro, -CR 24, -OR 21, -SR} 22, -NR 21 R 22, -C (= O) R 23, -C (= O) OR 23, -C (= O) NR 21 R 22 , and P (= O) (OR ₂₁ ) (OR ₂₂ ), and R ₂₁ To R ₂₃ are each independently selected from hydrogen, heavy hydrogen (deuterium), halogen, (C1-C30) alkyl, (C2-C30) alkenyl, (C3-C30) cycloalkyl (C1-C30) alkyl, (C3-C30) cycloalkyl, (C3-C30), and heterocycloalkyl, (C6-C30) aryl or (C3-C30) heteroaryl, wherein R ₂₄ is a halogen, wherein the heterocycloalkyl and heteroaryl are B, N, O, S , P (= O), Si and P.

The carbazole derivative according to an embodiment of the present invention may be represented by the following formula (2).

(2)

In the formula (2)

L ₁ are each independently a single bond or (C ₁ -C 20) alkylene;

R ₁ is (C1-C20) alkyl, (C3-C20) cycloalkyl, (C3-C20) heterocycloalkyl, (C6-C20) aryl, (C3-C20) heteroaryl, nitro (-NO _2), a cyano (= O) R ₁₁ or -C (= O) OR ₁₂ wherein R ₁₁ and R ₁₂ are each independently selected from the group consisting of (C 1 -C 20) alkyl, (C 3 -C 20) cycloalkyl, (C3-C20) heterocycloalkyl, (C6-C20) aryl or (C3-C20) heteroaryl;

R ₂ and R ₃ are each independently (C 1 -C 20) alkyl, (C 3 -C 20) cycloalkyl, (C 3 -C 20) heterocycloalkyl, (C 6 -C 20) aryl or (C 3 -C 20) heteroaryl;

R ₆ is (C2-C20) alkenyl or (C2-C20) alkynyl;

R ₅ is selected from the group consisting of (C 6 -C 20) aryl, (C 3 -C 20) heteroaryl, (C 2 -C 20) alkenyl, (C 2 -C 20) alkynyl, (C 2 -C 20) alkenyloxy, is oxy or _{-L 2 -OC (= O) -R} 13, wherein R ₁₃ is (C2-C20) alkenyl, (C2-C20) alkynyl is, form a ring is the R ₅ and R ₆ are connected to each other L < ₂ > is (C1-C7) alkylene;

n is an integer of 0 or 1;

The alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl of R _{1 and} the alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl of R ₂ and R ₃ and the alkenyl, alkynyl or heteroaryl of R ₅ and R ₆ , Each of the rings is independently selected from the group consisting of (C1-C20) alkyl, (C2-C20) alkenyl, (C2- C20) alkynyl, (C3- C20) cycloalkyl, (C3-C20) heterocycloalkyl, _{nitro, -CR 24, -OR 21, -SR} 22, -NR 21 R 22, -C (= O) R 23, -C (= O) OR 23, -C (= O) NR 21 R 22 , and P (= O) (OR ₂₁ ) (OR ₂₂ ), and R ₂₁ To R ₂₃ are each independently selected from hydrogen, heavy hydrogen (deuterium), halogen, (C1-C20) alkyl, (C2-C20) alkenyl, (C3-C20) cycloalkyl (C1-C20) alkyl, (C3-C20) cycloalkyl, (C3-C20), and heterocycloalkyl, (C6-C20) aryl or (C3-C20) heteroaryl, wherein R ₂₄ is a halogen, wherein the heterocycloalkyl and heteroaryl are B, N, O, S , P (= O), Si and P.

또는

의 고리를 형성할 수 있으며, 상기 R₃₁ 및 R₃₂ 는 각각 독립적으로 수소, (C2-C7)알케닐, (C2-C7)알키닐, (C3-C20)시클로알킬 또는 (C3-C20)헤테로시클로알킬이고, 상기 R₃₁ 및 R₃₂ 중 하나 이상은 불포화기를 포함하는 것을 특징으로 한다.Each of carbazole derivatives wherein R ₄ and R ₅ are, each independently, according to an embodiment of the invention (C6-C20) aryl, (C3-C20) heteroaryl, (C2-C7) alkenyl, (C2-C7) alkynyl, (C2-C7) alkenyloxy, (C2-C7) alkynyloxy or _{-L 2 -OC (= O) -R} 13 , and wherein L ₂ is (C1-C7) alkylene, wherein R ₁₃ is (C2-C7) alkenyl, (C2-C7) alkynyl, and R ₄ and R ₅ are connected to each other

or

A can form a ring, wherein R ₃₁ and R ₃₂ are each independently hydrogen, (C2-C7) alkenyl, (C2-C7) alkynyl, (C3-C20) cycloalkyl or (C3-C20) heteroaryl Cycloalkyl, and at least one of R ₃₁ and R ₃₂ includes an unsaturated group.

The present invention provides a photopolymerization initiator composition and a photoresist composition comprising the carbazole derivative represented by the general formula (1).

In addition, the present invention can provide a color filter or a black matrix that absorbs ultraviolet rays efficiently using the above-described carbazole derivative and has excellent sensitivity, excellent residual film ratio, mechanical strength, heat resistance, chemical resistance, Particularly, in the case of a black matrix using a high coloring agent to adjust the optical density, even a small amount of the black matrix exhibits high sensitivity compared to the same exposure amount, thereby realizing more improved physical characteristics.

Since the carbazole derivative according to the present invention has both intramolecular oxime ester group and phosphonate group in the molecule, it has superior sensitivity than conventional photopolymerization initiators and has improved solubility and improved commerciality with colorants, multi functional monomers or binder resins It is possible to minimize the defective rate by effectively suppressing the outgassing occurring in the exposure and postbake processes due to the high thermal stability.

The photoresist composition containing the carbazole derivative having high sensitivity according to the present invention can remarkably improve the polymerization and curing reaction rate of the polymerizable compound having unsaturated bonds by irradiation with light, The desired physical properties can be realized by appropriately controlling the polymerization and curing reaction rates, and addition reaction with the photosensitizer containing a thiol group, a silyl group and the like can be performed to realize more improved physical properties.

Further, since the photoresist composition according to the present invention can realize excellent reactivity even at a low exposure dose, even in the case of a black matrix in which a high colorant is to be used, the photoresist composition has remarkably improved residual film ratio, mechanical strength, heat resistance, And the like.

Accordingly, the carbazole derivative according to the present invention is advantageous not only in curing of a column spacer, an overcoat, a passivation material, etc. of a liquid crystal display element but also in a high temperature process characteristic.

The present invention relates to a novel carbazole derivative, a photopolymerization initiator and a photoresist composition containing the same, which will be described below. However, unless otherwise defined in technical terms and scientific terms used herein, And a description of known functions and configurations that may unnecessarily obscure the gist of the present invention will be omitted in the following description.

In order to accomplish the object of the present invention, the oxazole ester group and the phosphonate group may be simultaneously included to have a higher optical sensitivity, which may be a carbazole derivative represented by the following general formula (1).

[Chemical Formula 1]

In the formula (1)

L ₁ is a single bond, (C1-C20) alkylene, (C2-C20) alkenylene, -C (= O) -, -O-, -S-, -S (= O) -, -SO 2 - And -Se-;

R ₁ is (C1-C30) alkyl, (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C6-C30) aryl, (C3-C30) heteroaryl, nitro (-NO _2), a cyano (= O) R ₁₁ or -C (= O) OR ₁₂ wherein R ₁₁ and R ₁₂ are each independently selected from the group consisting of hydrogen, deuterium, (C 1 -C 30) C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C6-C30) aryl and (C3-C30) is selected from a heteroaryl, wherein the R ₁₁ and the cycloalkyl, heterocycloalkyl of R _12, aryl, and The heteroaryl may be further substituted with (C1-C30) alkyl or (C1-C30) alkoxy;

R ₂ and R ₃ are each independently selected from the group consisting of hydrogen, deuterium, (C 1 -C 30) alkyl, (C 3 -C 30) cycloalkyl, (C 3 -C 30) heterocycloalkyl, (C 6 -C 30) C30) heteroaryl;

R ₄ and R ₅ are each independently selected from the group consisting of (C 6 -C 30) aryl, (C 3 -C 30) heteroaryl, (C 2 -C 30) alkenyl, (C 2 -C 30) alkynyl, C2-C30) alkynyloxy or _{-L 2 -OC (= O) -R} 13 , and wherein R ₁₃ is (C2-C30) alkenyl, (C2-C30) and alkynyl, wherein R ₄ and R ₅ is And at least one of R ₄ and R ₅ necessarily contains an unsaturated group; L ₂ is (C 1 -C 30) alkylene;

n is an integer of 0 or 1;

The alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl of R _{1 and} the alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl of R ₂ and R ₃ and the alkenyl, alkynyl or heteroaryl of R ₄ and R ₅ , (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, halogen, cyano, cyano, _{nitro, -CR 24, -OR 21, -SR} 22, -NR 21 R 22, -C (= O) R 23, -C (= O) OR 23, -C (= O) NR 21 R 22 , and P (= O) (OR ₂₁ ) (OR ₂₂ ), and R ₂₁ To R ₂₃ are each independently selected from hydrogen, heavy hydrogen (deuterium), halogen, (C1-C30) alkyl, (C2-C30) alkenyl, (C3-C30) cycloalkyl (C1-C30) alkyl, (C3-C30) cycloalkyl, (C3-C30), and heterocycloalkyl, (C6-C30) aryl or (C3-C30) heteroaryl, wherein R ₂₄ is a halogen, wherein the heterocycloalkyl and heteroaryl are B, N, O, S , P (= O), Si and P.

The carbazole derivative according to the present invention is excellent in the efficiency of absorbing ultraviolet rays to produce radicals and acts as an effective initiator in the polymerization and curing reaction of polymerizable compounds having various unsaturated groups, so that the reaction rate and sensitivity can be appropriately controlled Mechanical strength, heat resistance, chemical resistance, and developability of the photosensitive material produced therefrom can be remarkably improved.

At this time, the photosensitive material is a photosensitive material for forming a black matrix such as a pigment dispersed type photosensitive material for TFT LCD color filter, a TFT LCD and an organic light emitting diode, a photosensitive material for forming an overcoat layer, a photosensitive material for a column spacer, A photosensitive material for a printing wiring board, and the like, but is not limited thereto.

The term " single bond "of the present invention means that N of the carbazole group and P of the phosphonate group are directly bonded to form a single bond, and the terms" alkyl ", " Quot; moiety " may < / RTI > refer to a hydrocarbon radical that includes both linear and branched forms. The alkyl may be preferably (C1-C20) alkyl, more preferably a short chain hydrocarbon radical selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and the like, but is not limited thereto.

In addition, the term "alkenyl" means an unsaturated hydrocarbon radical in the form of a straight chain or a branched chain containing at least one double bond, and specific examples thereof include ethenyl, prop-1-en-1-yl, 2-yl, prop-2-en-1-yl, 1-yl, but-2-en-1-yl, but-2-en-2-yl, buta- Di-2-yl, and the like, but is not limited thereto. The term "alkynyl" means an unsaturated hydrocarbon radical in the form of a straight or branched chain containing at least one triple bond, and specific examples thereof include ethynyl, prop-1-yn-1-yl, 1-yl, -but-1-yn-1-yl, but-1-yn-3-yl or but-3-yn-1-yl and the like.

The term "cycloalkyl ", as used herein, may refer to fully saturated and partially unsaturated hydrocarbon rings of from 3 to 9 carbon atoms, including those where aryl or heteroaryl is fused. The term "heterocycloalkyl" can also be a monocyclic or polycyclic non-aromatic radical comprising at least one heteroatom selected from B, N, O, S, P (= O), Si and P.

The term "aryl " of the present invention is an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen, which may be monocyclic or polycyclic aromatic hydrocarbon radicals, suitably containing from 3 to 7, Includes a single or fused ring system containing 5 or 6 ring atoms and includes a form in which a plurality of aryls are connected by a single bond, and specific examples thereof include phenyl, naphthyl, biphenyl, terphenyl, anthryl, But are not limited to, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylenyl, crycenyl, naphthacenyl, fluoranthenyl and the like.

The term "heteroaryl ", as used herein, refers to an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen, such as 3, including at least one heteroatom selected from B, N, O, S, P To 8 ring atoms, and includes a single or fused ring system, suitably containing from 3 to 7, preferably 5 or 6, ring atoms in each ring And includes a form in which a plurality of heteroaryls are connected by a single bond. Specific examples include furyl, thiophenyl, pyrrolyl, pyranyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, Monocyclic heteroaryl such as isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl and pyridazinyl; And benzofuranyl, benzofuranyl, benzothiophenyl, isobenzofuranyl, benzoimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazole Polycyclic heteroaryl such as benzyl, tolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinolizinyl, quinoxalinyl, carbazolyl, phenanthridinyl, benzodioxolyl and the like; But the present invention is not limited thereto.

The term "alkylene" or "alkenylene" in the present invention means a residual divalent residue after removal of one hydrogen atom from (C1-C20) May have a carbon number of C2 to C7, but the present invention is not limited thereto.

The term "halogen" of the present invention means fluoro, chloro, bromo or iodo.

The carbazole derivative represented by Chemical Formula 1 according to an embodiment of the present invention may be a carbazole derivative represented by Chemical Formula 2 in view of high solubility in solvents and high sensitivity in a wide range of absorption spectra .

(2)

In the formula (2)

L ₁ are each independently a single bond or (C ₁ -C 20) alkylene;

R ₁ is (C1-C20) alkyl, (C3-C20) cycloalkyl, (C3-C20) heterocycloalkyl, (C6-C20) aryl, (C3-C20) heteroaryl, nitro (-NO _2), a cyano (= O) R ₁₁ or -C (= O) OR ₁₂ wherein R ₁₁ and R ₁₂ are each independently selected from the group consisting of (C 1 -C 20) alkyl, (C 3 -C 20) cycloalkyl, (C3-C20) heterocycloalkyl, (C6-C20) aryl or (C3-C20) heteroaryl;

R ₂ and R ₃ are each independently (C 1 -C 20) alkyl, (C 3 -C 20) cycloalkyl, (C 3 -C 20) heterocycloalkyl, (C 6 -C 20) aryl or (C 3 -C 20) heteroaryl;

R ₆ is (C2-C20) alkenyl or (C2-C20) alkynyl;

R ₅ is selected from the group consisting of (C 6 -C 20) aryl, (C 3 -C 20) heteroaryl, (C 2 -C 20) alkenyl, (C 2 -C 20) alkynyl, (C 2 -C 20) alkenyloxy, is oxy or _{-L 2 -OC (= O) -R} 13, wherein R ₁₃ is (C2-C20) alkenyl, (C2-C20) and alkynyl, wherein R ₄ and R ₅ are connected to each other to form a ring L < ₂ > is (C1-C7) alkylene;

n is an integer of 0 or 1;

The alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl of R _{1 and} the alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl of R ₂ and R ₃ and the alkenyl, alkynyl or heteroaryl of R ₅ and R ₆ , Each of the rings is independently selected from the group consisting of (C1-C20) alkyl, (C2-C20) alkenyl, (C2- C20) alkynyl, (C3- C20) cycloalkyl, (C3-C20) heterocycloalkyl, _{nitro, -CR 24, -OR 21, -SR} 22, -NR 21 R 22, -C (= O) R 23, -C (= O) OR 23, -C (= O) NR 21 R 22 , and P (= O) (OR ₂₁ ) (OR ₂₂ ), and R ₂₁ To R ₂₃ are each independently selected from hydrogen, heavy hydrogen (deuterium), halogen, (C1-C20) alkyl, (C2-C20) alkenyl, (C3-C20) cycloalkyl (C1-C20) alkyl, (C3-C20) cycloalkyl, (C3-C20), and heterocycloalkyl, (C6-C20) aryl or (C3-C20) heteroaryl, wherein R ₂₄ is a halogen, wherein the heterocycloalkyl and heteroaryl are B, N, O, S , P (= O), Si and P.

In addition, the carbazole derivative according to an embodiment of the present invention includes a substituent group containing an oxime ester group and a phosphonate group, and a phosphonate group having at least one unsaturated group at the R ₄ and R ₅ substituent group or a phosphinate group, it was confirmed that the sensitivity to ultraviolet rays and the heat resistance can be remarkably improved. Also, it can react with a photosensitizer containing a thiol group, a silyl group or the like to form a fine pattern with high adhesion to a substrate and high strength.

The substituents which can be substituted at the positions of R ₄ and R ₅ according to the present invention are not limited, but when used in combination with a photosensitizer containing a thiol group, a silyl group and the like, a high temperature postbake due to excellent sensitivity and thermal stability, Naphthyl, biphenyl, terphenyl, or the following structure, from the viewpoint of minimizing the occurrence of cracks and the like.

또는

의 고리를 형성할 수 있으며, 상기 R₃₁ 및 R₃₂ 는 각각 독립적으로 수소, (C2-C7)알케닐, (C2-C7)알키닐, (C3-C20)시클로알킬 또는 (C3-C20)헤테로시클로알킬인 것 일 수 있으며, 상기 R₃₁ 및 R₃₂ 중 하나 이상은 불포화기를 포함하는 것을 특징으로 한다.Each of carbazole derivatives wherein R ₄ and R ₅ are, each independently, according to an embodiment of the invention (C6-C20) aryl, (C3-C20) heteroaryl, (C2-C7) alkenyl, (C2-C7) alkynyl, (C2-C7) alkenyloxy, (C2-C7) alkynyloxy or _{-L 2 -OC (= O) -R} 13 , and wherein L ₂ is (C1-C7) alkylene, wherein R ₁₃ is (C2-C7) alkenyl, (C2-C7) alkynyl, and R ₄ and R ₅ are connected to each other

or

A can form a ring, wherein R ₃₁ and R ₃₂ are each independently hydrogen, (C2-C7) alkenyl, (C2-C7) alkynyl, (C3-C20) cycloalkyl or (C3-C20) heteroaryl Cycloalkyl, and at least one of R ₃₁ and R ₃₂ includes an unsaturated group.

The carbazole derivative according to an embodiment of the present invention can realize sufficient sensitivity as a photopolymerization initiator even in a small amount to minimize the contamination source of the liquid crystal to thereby improve the residual film ratio of the pattern and increase the usable width of other raw materials L ₁ may preferably be (C ₁ -C 7) alkylene, but is not limited thereto.

The carbazole derivative according to an embodiment of the present invention can more effectively absorb the UV light source even in a small amount of use and can be selected from the following structures in terms of sensitivity and high temperature process characteristics But is not limited thereto.

The carbazole derivative according to the present invention can be prepared by the method shown in the following Reaction Schemes 1 and 2, and can be prepared by various synthetic methods.

[Reaction Scheme 1]

[Reaction Scheme 2]

The carbazole derivative according to the present invention not only remarkably improves the UV light absorption rate but also can control the pattern properties of the composition of the photoresist according to the substituent change and control the physical properties of the thin film such as heat resistance and chemical resistance. That is, the composition of the photoresist according to the present invention can be applied to a black matrix, a color filter, a column spacer, an organic insulating film, a photoresist composition for an overcoat, and the like, and can be effectively applied to a black matrix requiring a high colorant.

The present invention provides a photopolymerization initiator composition comprising the carbazole derivative.

The present invention also provides a photoresist composition comprising the carbazole derivative.

The photoresist composition according to the present invention comprises a binder resin, a colorant, and a carbazole derivative according to the present invention, wherein the carbazole derivative is contained in an amount of 0.01 to 15% by weight based on 100% by weight of the total photoresist composition Preferably 0.01 to 10% by weight, more preferably 0.01 to 5% by weight, may minimize contamination by by-products decomposed after photoinitiation.

The binder resin is not limited if it is known in the art, but it has an average molecular weight of 2,000 to 300, 000 g / mol and a dispersion degree of 1.0 to 10.0 in terms of high compatibility with the carbazole derivative according to the present invention Acrylic polymer, novolak resin, and the like. The acrylic polymer may be a copolymer of monomers containing the following monomers. Specific examples of the monomer include, but not limited to, methyl (meth) acrylate, ethyl (meth) acrylate, (Meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (Meth) acrylate, dodecyl (meth) acrylate, isooctyl (meth) acrylate, isooctyl (meth) acrylate, (Meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (Meth) acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic acid anhydride, maleic acid monoalkyl ester, monoalkyl itaconate, monoalkyl fumarate, glycidyl acrylate (Meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, (Meth) acrylate, styrene,? -Methylstyrene, acetoxystyrene, N-methylmaleimide, N-ethylmaleimide, (Meth) acrylamide, N-methyl (meth) acrylamide, etc. These monomers may be used alone or in combination of two or more kinds thereof. The novolak resin is a phenolic compound and an aldehyde compound The phenolic compound is not particularly limited, and specific examples thereof include phenol, o-, m-, and p-cresol, 2,5-xylenol, 3,4- Butylphenol, 4-t-butylphenol, 2-ethylphenol, 3-ethylphenol, 3-t- Butylphenol, 4-methyl-2-t-butylphenol, 2-naphthol, 1,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1 And 7-dihydroxynaphthalene. These may be one or a mixture of two or more of them. The aldehyde compound is not particularly limited, and specific examples thereof include formaldehyde, p-formaldehyde, acetaldehyde Propyl aldehyde,? - and? -Phenyl propyl aldehyde, benzaldehyde, o-, m- and p-hydroxybenzaldehyde, o- and p-methylbenzaldehyde, glutaraldehyde, , Glycidyl, and the like can be mentioned the oxalate, these may be that the mixture of at least one or two, preferably benzyl (meth) acrylate and meth preferably a copolymer of acrylic acid.

The coloring material is not limited as long as it is known in the art, and specific examples thereof include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, Anthanthrone pigments, indanthrone pigments, pravanthrone pigments, pyranthrone pigments, anthraquinone pigments, anthraquinone pigments, anthanthrone pigments, anthanthrone pigments, anthanthrone pigments, indanthrone pigments, Pigments, diketopyrrolo pyrrole pigments, and the like. Specific examples of the inorganic pigment include oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc and antimony, Oxide, carbon black and the like. Particularly, the organic pigments and inorganic pigments can be compounds classified as pigments in the color index (published by The Society of Dyers and Colourists), and more specific examples include CI Pigment Yellow 13, 20, 24, 31, 53 , 83, 86, 93, 94, 109, 110, 117, 125, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180 and 185; CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 and 71; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 208, 215, 216, 224, 242, 254, 255 and 264; CI Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37 and 38; CI Pigment Blue 15 (15: 3, 15: 4, 15: 6, etc.), 21, 28, 60, 64 and 76; CI Pigment Green 7, 10, 15, 25, 36, 47 and 58; CI Pigment Brown 28; CI Pigment Black 1 and 7, Lactam Black, and Pigments of Color Index (CI) number. The coloring material may be used in the form of a dispersion. Examples of the solvent for forming the coloring material dispersion include ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl Ether, propylene glycol monomethyl ether acetate, propylene glycol methyl ether propionate, and the like. The colorant dispersion may be prepared by mixing 0.1 to 30% by weight of the solid content colorant based on 100% by weight of the total weight of the colorant dispersion.

The photoresist composition according to the present invention may further comprise a photosensitizer. At this time, it is preferable that the photosensitizer has a reactive substituent such as a thiol group and a silyl group, and the photosensitizer containing the photosensitizer reacts rapidly with the carbazole derivative according to the present invention to realize sensitivity to the remarkably enhanced light And the residual film ratio and developability of a color filter, a black matrix and the like manufactured using the same can be significantly improved.

The photo-sensitizer having high reactivity with the carbazole derivative according to the present invention is not limited as long as it includes a thiol group, a silyl group, and the like. As a non-limiting example, pentaerythritol tetrakis thioglycolate, A photosensitizer containing a thiol group such as pentaerythritol tetrakis thiopropionate and pentaerythritol tetrakis (3-mercapto butylate); ≪ / RTI > In addition, the carbazole derivative according to the present invention may be produced by reacting a reactive substituent such as a thiol group or a silyl group with a hydrosilylation reaction, a thiol-olefin addition reaction, a thiol-acetylene addition reaction, Reaction and the like.

In addition, when the photoresist composition is mixed in an amount of 0.01 to 10% by weight based on 100% by weight of the photoresist composition, optimal sensitivity can be achieved due to reaction with the carbazole derivative according to the present invention.

In addition, the photoresist composition according to the present invention may further contain a solvent other than the photosensitizer containing the colorant, the carbazole derivative, the binder resin and the reactive group (thiol group, silyl group, etc.), an adhesion aid, Antifoaming agents, and the like.

As the solvent, ethyl acetate, butyl acetate, diethylene glycol dimethyl ether, diethylene glycol dimethyl ethyl ether, methyl methoxy propionate, ethyl (meth) acrylate and the like are added in consideration of compatibility with the binder resin, the photopolymerization initiator according to the present invention, Propylene glycol monomethyl ether acetate (PGMEA), propylene glycol methyl ether propionate (PGMEP), propylene glycol methyl ether, propylene glycol propyl ether, methyl cellosolve acetate, ethyl lactate, ethyl lactate, Diethyleneglycol ethyl acetate, acetone, methyl isobutyl ketone, cyclohexanone, dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methyl (NMP),? -Butyrolactone, diethyl ether, ethylene glycol dimethyl ether, Diglyme, The solvent is selected from the group consisting of tetrahydrofuran (THF), methanol, ethanol, propanol, iso-propanol, methyl cellosolve, ethyl cellosolve, diethylene glycol methyl ether, diethylene glycol ethyl ether, dipropylene glycol methyl ether, toluene, , Heptane, and octane may be used alone or in combination of two or more, but the present invention is not limited thereto.

The adhesion promoter may be a silicone compound having an epoxy group or an amine group, but is not limited thereto. Specific examples thereof include (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, (3-glycidoxypropyl) dimethyldimethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, (3-glycidoxypropyl) dimethylmethoxysilane, , 3,4-epoxybutyltrimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl ) Ethyltriethoxysilane, 2-methacryloxypropyltrimethoxysilane, and aminopropyltrimethoxysilane, which may be used alone or in combination of two or more.

Further, as additional additives commonly used in the art, hydroquinone, hydroquinone having a substituent such as an alkyl ether, catechol having a substituent such as an alkyl ether such as butyl catechol, pyrogallol, 2,2,6, A radical chelating agent such as 6-tetramethyl-1-piperidinyloxy radical, at least one heat polymerization inhibitor selected from thiophenols,? -Naphthyl amines and? -Naphthols; BM-1000 and BM-1100 from BM Chemie. Mechac-packs F 142D, F 172, F 173, and F 183 manufactured by Dainippon Ink & Chemicals Incorporated. Prorad FC-135, FC-170C, FC-430, FC-431 of Sumitomo Heavy Industries, S-112, S-113, S-131, S-141 and S-145 of Saffron copper of Asahi Glass Co., SH-28PA, Dong-190, Dong-93, SZ-6032 and SF-8428 of Toray Silicone Co., A leveling agent of a commercially available product, etc. may be further mixed and used, but the present invention is not limited thereto.

Hereinafter, the present invention will be described in more detail based on the following examples. However, the following examples are illustrative of the present invention but are not limited thereto. All of the following compound examples were run in an inert argon or nitrogen atmosphere using a glove box or Schlenk line and the product was analyzed using ¹ H Nuclear Magnetic Resonance (NMR).

(Example 1) 1- (9- (3-allyl propyl phosphonate) -6-naphthoyl -9 H-carbazole-3-yl) ethanone oxime acetate -O- (1) Preparation

Step 1. 9- (3-chloropropyl) -9 H - carbazol-prepared

To a solution of 50.0 g (299.03 mmol) of carbazole and 1.92 g (5.98 mmol) of tetrabutylammonium bromide in 200 ml of toluene, 400 ml of 50% sodium hydroxide aqueous solution was slowly added. After the temperature of the mixture was raised to 40 占 폚, 70.61 g (448.54 mmol) of 1-bromo-3-chloropropane was diluted in 80 ml of toluene and slowly added dropwise to the mixture. The mixture was stirred at 40 < 0 > C for 5 hours. After 300 ml of ice distilled water was poured slowly, the reaction was terminated, and the organic layer was separated and washed with water twice. The organic layer was dried over anhydrous magnesium sulfate, and anhydrous magnesium sulfate was filtered off. The filtrate was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain the product (solvent: ethyl Oh glyphosate acid: n-hexane = 1: 8) to give 9- (3-chloropropyl) -9 H - carbazol 66.32g (Yield 91%) was obtained

^{1 H-NMR (δ ppm:} CDCl 3): 2.23-2.29 (2H, m), 3.45 (2H, t), 4.47 (2H, t), 7.22 (2H, t), 7.40-7.45 (4H, m) , 8.06 (2H, d)

Step 2. Preparation of (9- (3-chloropropyl) -9 H - carbazol-3-yl) naphthalen-1-yl methanone prepared

Of 9- (3-chloropropyl) prepared in Step 1 -9 H - carbazol 20.0g (80.73mmol), naphthoyl chloride was dissolved 18.47g (96.88mmol) in 200ml dichloromethane and aluminum chloride 10.87g (96.88mmol ) Was slowly added at 0 < 0 > C. After further stirring at 0 ° C for 2 hours, stirring was further continued at room temperature for 12 hours. The reaction mixture was slowly poured into 400 ml of ice distilled water. After completion of the reaction, the organic layer was separated and washed with water twice. The organic layer was dried over anhydrous magnesium sulfate, and anhydrous magnesium sulfate was filtered off. The filtrate was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain the product (solvent: ethyl Oh glyphosate acid: n-hexane = 1: 4) to give (9- (3-chloropropyl) -9 H - carbazol-3 23.77 g (yield: 74%) of naphthalen-1-ylmethanone was obtained

^{1 H-NMR (δ ppm:} CDCl 3): 2.25-2.30 (2H, m), 3.44 (2H, t), 4.46 (2H, t), 7.27 (1H, t), 7.35-7.52 (6H, m) , 7.92-8.02 (2H, m), 8.10-8.23 (5H, m)

Step 3. 1 - (9- (3-chloropropyl) -6-naphthoyl -9 H-carbazole-3-yl) -ethane-1-one

Prepared in Step 2 (Synthesis of 9- (3-chloropropyl) -9 H - carbazol-3-yl) naphthalen-1-yl -methanone 10.0g (25.13mmol), acetyl chloride 2.36g (30.16mmol) dichloro Methane, and 3.38 g (30.16 mmol) of aluminum chloride was slowly added thereto at 0 ° C. After further stirring at 0 ° C for 2 hours, stirring was further continued at room temperature for 12 hours. The reaction mixture was slowly poured into 200 ml of ice-distilled water. After completion of the reaction, the organic layer was separated and washed with water twice. The organic layer was dried over anhydrous magnesium sulfate, and anhydrous magnesium sulfate was filtered off. The filtrate was concentrated under reduced pressure, and the obtained product was purified by silica gel column chromatography (solvent: ethyl acetate: n-hexane = 1: 4) to obtain 1- (9- (3-chloropropyl) -6- H -carbazol-3-yl) -ethan-1-one (yield 78%)

^{1 H-NMR (δ ppm:} CDCl 3): 2.21-2.37 (5H, m), 3.42 (2H, t), 4.48 (2H, t), 7.41-7.52 (5H, m), 7.82-7.99 (2H, m), 8.04-8.20 (6 H, m)

Step 4. 1 - (9- (3-diallyl-propyl phosphonate) -6-naphthoyl -9 H-carbazole-3-yl) -ethane-1-one

(86.38 mmol) of allyl alcohol and 8.74 g (86.38 mmol) of triethylamine were dissolved in 90 ml of dichloromethane under nitrogen atmosphere, and the temperature was maintained at 0 ° C. Then, 3.75 g (27.28 mmol) of phosphorus trichloride was diluted in 10 ml of dichloromethane And the mixture was stirred at room temperature for 1 hour. The reaction product is separated into a precipitate and a filtrate using a filter paper. The filtrate was diluted with ethyl acetate and washed with distilled water. The organic layer was dried over anhydrous magnesium sulfate, and anhydrous magnesium sulfate was filtered off. The filtrate was concentrated under reduced pressure The obtained product was dissolved in 20ml dimethyl acetamide was prepared as described in Step 3 1 - (9- (3-chloropropyl) -6-naphthoyl -9 H - carbazol-3-yl) -Ethan-1-one (10.0 g, 22.73 mmol). The reaction was heated to 110 ° C and refluxed and stirred for 12 hours. After pouring slowly into 100 ml of distilled water, the reaction was terminated and the product was extracted with 200 ml of dichloromethane. The organic layer was separated and washed with water twice. The organic layer was dried over anhydrous magnesium sulfate, and anhydrous magnesium sulfate was filtered off. The filtrate was concentrated under reduced pressure, and the obtained product was purified by silica gel column chromatography (solvent: ethyl acetate: n-hexane = 1: 2) to obtain 1- (9- (3-diallylpropylphosphonate) naphthoyl -9 H-carbazole-3-yl) ethane-1-one was obtained 6.94g (54% yield)

^{1 H-NMR (δ ppm:} CDCl 3): 1.65-1.85 (2H, m), 2.27-2.46 (5H, m), 4.22-4.40 (4H, m), 4.52 (2, t), 5.10-5.15 ( (2H, d), 5.24-5.32 (2H, d), 5.92-6.08 (2H, m), 7.44-7.57 (5H, m), 7.88-8.04

Step 5. 1- (9- (3-allyl propyl phosphonate) -6-naphthoyl -9 H-carbazole-3-yl) ethanone oxime prepared

Ethane-1-one 10.0g (17.68mmol) - 1-a prepared in the above Step 4 (9- (3-allyl propyl phosphonate) -6-naphthoyl -9 H - carbazol-3-yl) Was dissolved in 70 ml of dimethylacetamide under nitrogen atmosphere and 1.84 g (26.52 mmol) of hydroxyamine hydrochloride was added dropwise. The reaction product was heated, stirred at 70 ° C for 2 hours, and cooled to room temperature. The reaction was poured slowly into 200 ml of distilled water and the reaction was terminated. The solid precipitate was filtered off, methanol: distilled water (3: 1) and washed with a mixed solution and dried to obtain 1 - (9- (3-allyl propyl phosphonate) -6-naphthoyl -9 H - carbazol-3-yl) -Ethanone oxime (72%).

¹ H-NMR (? Ppm: CDCl ₃ ): 1.52-1.80 (2H, m), 2.20-2.41 (5H, m), 4.20-4.37 (4H, m), 4.50 2H, d), 5.24-5.34 (2H, d), 5.95-6.11 (2H, m), 7.56-7.67 (5H, m), 7.95-8.12 (2H, m), 8.31-8.48 11.02 (1 H, s)

Step 6. 1 - (9- (3-allyl propyl phosphonate) -6-naphthoyl -9 H-carbazole-3-yl) -ethanone oxime-O-acetate prepared

The 1-prepared in Step 5 (9- (3-allyl propyl phosphonate) -6-naphthoyl -9 H-carbazole-3-yl) -ethyl the ethanone oxime 5.0g (8.61mmol) ethyl , And 1.32 g (12.928 mmol) of acetic anhydride was added thereto. The reaction mixture was heated to 80 DEG C for 2 hours, and then cooled to room temperature. The reaction was slowly added dropwise to 50 ml of hexane. After filtered off the solid needle cheonmul produced by drying 1 - (9- (3-diallyl-propyl phosphonate) -6-naphthoyl -9 H-carbazole-3-yl) -ethanone oxime-O-acetate 4.02 g (75%) of the title compound was obtained

¹ H-NMR (? Ppm: CDCl ₃ ): 1.60-1.82 (2H, m), 2.25-2.47 (8H, m), 4.22-4.38 (4H, m), 4.52 (2H, t), 5.10-5.19 (2H, d), 5.22-5.32 (2H, d), 5.94-6.05 (2H, m), 7.47-7.58 (5H, m), 7.85-8.05

(Example 2) 1- (9- (2-yl-hexyl phosphonate pin 6-deep) -9-nitro-6 H - carbazol-3-yl) phenyl methanone oxime - O - acetate (2 )

Step 1. 9- (6-Bromo-hexyl) -9 H - carbazol-prepared

300 ml of 50% sodium hydroxide aqueous solution was slowly added to a solution of 30.0 g (179.42 mmol) of carbazole and 1.16 g (3.59 mmol) of tetrabutylammonium bromide in 400 ml of toluene. After the temperature of the mixture was raised to 40 占 폚, 87.54 g (358.83 mmol) of 1,6-dibromohexane was diluted in 80 ml of toluene and slowly added dropwise to the mixture. The mixture was stirred at 40 < 0 > C for 5 hours. After 300 ml of ice distilled water was poured slowly, the reaction was terminated, and the organic layer was separated and washed with water twice. The organic layer was dried over anhydrous magnesium sulfate, and anhydrous magnesium sulfate was filtered off. The filtrate was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain the product Photography (solvent: ethyl Oh glyphosate acid: n-hexane = 1: 8) to yield 9- (6-Bromo-hexyl) -9 H in - carbazol 36.14g ( Yield: 61%).

¹ H-NMR (? Ppm: CDCl ₃ ): 1.37-1.44 (2H, m), 1.48-1.55 (2H, m), 1.77-1.85 2H), 4.34 (2H, t), 7.23 (2H, t), 7.39-7.45 (4H, m), 8.08

Step 2. Preparation of (9- (6-Bromo-hexyl) -9 H - carbazol-3-yl) phenyl methanone prepared

Prepared in Step 1 of 9- (6-Bromo-hexyl) -9 H - carbazol 20.0g (60.56mmol), benzoyl chloride was dissolved 10.22g (72.67mmol) in 200ml dichloromethane, aluminum chloride, 8.15g (72.67mmol ) Was slowly added at 0 < 0 > C. After further stirring at 0 ° C for 2 hours, stirring was further continued at room temperature for 12 hours. The reaction mixture was slowly poured into 400 ml of ice distilled water. After completion of the reaction, the organic layer was separated and washed with water twice. The organic layer was dried over anhydrous magnesium sulfate, and anhydrous magnesium sulfate was filtered off. The filtrate was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain the product (solvent: ethyl Oh glyphosate acid: n-hexane = 1: 4) to give (9- (6-Bromo-hexyl) -9 H - carbazol -3 - yl) phenylmethanone (yield: 68%) was obtained

¹ H-NMR (? Ppm: CDCl ₃ ): 1.37-1.42 (2H, m), 1.44-1.52 (2H, m), 1.77-1.85 (2H, m), 1.87-1.94 (2H, t), 4.32-4.35 (2H, t), 7.30-7.44 (4H, m), 7.50-7.59 (3H, m), 8.10-8.25

Step 3. 1 - (9- (6-Bromo-hexyl) -9-nitro-6 H - carbazol-3-yl) phenyl-methanone

30 ml of acetic acid and 60 ml of acetic anhydride were mixed, and 5.62 g (24.17 mmol) of copper nitrate hydrate was added thereto, followed by stirring at room temperature for 10 minutes. 10.0 g (23.02 mmol) of the (9- (6-bromohexyl) -9 H -carbazol-3-yl) phenylmethanone prepared in the above step 2 was dissolved in 20 ml of acetic acid and then slowly added dropwise. After stirring for 2 hours at room temperature and dried by filtration gave slowly then the precipitated solid was poured into ice distilled water 100ml 1- (9- (6- bromohexyl) -9-nitro-6 H - carbazol-3-yl ) Phenyl methanone (88%).

¹ H-NMR (? Ppm: CDCl ₃ ): 1.38-1.45 (2H, m), 1.46-1.53 (2H, m), 1.79-1.87 (2H, t), 4.38-4.41 (2H, t), 7.35-7.57 (5H, m), 8.13-8.22 (3H, m), 8.34 d)

Step 4. Preparation of 1- (9- (6-deep-2-yl-hexyl phosphonate pin) -9-nitro-6 H - carbazol-3-yl) phenyl methanone prepared

(79.27 mmol) of propyl alcohol and 8.02 g (79.27 mmol) of triethylamine were dissolved in 70 ml of dichloromethane and maintained at 0 ° C. Then, 3.44 g (25.03 mmol) of phosphorus trichloride was diluted with 10 ml of dichloromethane And the mixture was stirred at room temperature for 1 hour. The reaction product is separated into a precipitate and a filtrate using a filter paper. The filtrate was diluted with ethyl acetate and washed with distilled water. The organic layer was dried over anhydrous magnesium sulfate, and anhydrous magnesium sulfate was filtered off. The filtrate was concentrated under reduced pressure The obtained product was dissolved in 20ml dimethyl acetamide was prepared as described in Step 3 1- (9- (6-Bromo-hexyl) -9-nitro-6 H - carbazol-3-yl) Phenylmethanone (10.0 g, 20.86 mmol) was added thereto. The reaction was heated to 110 ° C and refluxed and stirred for 12 hours. After pouring slowly into 100 ml of distilled water, the reaction was terminated and the product was extracted with 200 ml of dichloromethane. The organic layer was separated and washed with water twice. The organic layer was dried over anhydrous magnesium sulfate, and anhydrous magnesium sulfate was filtered off. The filtrate was concentrated under reduced pressure, and the obtained product was purified by silica gel column chromatography (solvent: ethyl acetate: n-hexane = 1: 2) to obtain 1- (9- (6-dipropyn- carbonate) -9-nitro-6 H - carbazol-3-yl) phenyl methanone was obtained 8.59g (74% yield)

¹ H-NMR (? Ppm: CDCl ₃ ): 1.35-1.42 (2H, m), 1.47-1.55 (2H, m), 1.77-1.85 (2H, t), 2.40-2.47 (2H, m), 4.14-4.28 (4H, m), 4.40 (2H, t), 7.38-7.59 (5H, m), 8.15-8.25 8.34 (1H, d), 8.72 (1H, d), 9.02 (1H, d)

Step 5. 1- (9- (6-deep-2-yl-hexyl phosphonate pin) -9-nitro-6 H - carbazol-3-yl) phenyl methanone oxime - O - acetate prepared

The 1 prepared in Step 4 (as 9- (6-dipped pin-2-yl-hexyl phosphonate) -9-nitro-6 H - carbazol-3-yl) but using phenyl-methanone by performing step 5 to step 6 in example 1 in the same manner as 1- (9- (2-yl-hexyl phosphonate pin 6-deep) -9-nitro-6 H - carbazol-3-yl ) Phenylmethanone oxime- O -acetate (4.24 g, 79%).

¹ H-NMR (? Ppm: CDCl ₃ ): 1.32-1.42 (2H, m), 1.46-1.58 (2H, m), 1.76-1.87 (2H, t), 2.38-2.46 (2H, m), 3.72 (3H, s), 4.18-4.30 (4H, m), 4.42 8.30 (1H, d), 9.09 (1H, s)

(Example 3) 1 - (9- (3-allyl-phenyl-propyl phosphinate) -9-nitro-6 H - carbazol-3-yl) -1,2-propane-dione-2-oxime - O - acetate (5)

Step 1. 1 - (9- (3-chloropropyl) -6-nitro -9 H - carbazol-3-yl) -1-propanone prepared

Of 9- (3-chloropropyl) -9 H prepared in Step 1 of Example 1 using the carbazole in Step 2 of Example 1 in the same manner except for the use of propionyl chloride (9 - (3-chloro-propyl) -9 H-carbazole-3-yl) -1-propanone was prepared in the same manner as in step 3 of example 2 1- (9- (3-chloropropyl) - 6-nitro -9 H - carbazol-3-yl) -1-propanone was obtained 18.86g (82% yield).

^{1 H-NMR (δ ppm:} CDCl 3): 1.24 (3H, t), 2.23-2.34 (4H, m), 3.47 (2H, t), 4.48 (2H, t), 7.46-7.51 (2H, m) 8.20-8.24 (1H, d), 8.40-8.44 (1H, d), 8.75 (1H, s), 9.04

Step 2. 1 - (9- (3-allyl-phenyl-propyl phosphinate) -9-nitro-6 H - carbazol-3-yl) -1-propanone prepared

The 1 prepared in Step 1 (Synthesis of 9- (3-chloropropyl) -6-nitro -9 H - carbazol-3-yl) -1-dichlorophenyl phosphine in Step 4 of Example 1 by using propanone the same method, except for using the pin as 1- (9- (3-allyl-phenyl-propyl phosphinate) -9-nitro-6 H - carbazol-3-yl) -1-propanone 7.82g (yield: 55%).

^{1 H-NMR (δ ppm:} CDCl 3): 1.27 (3H, t), 1.65-1.82 (2H, m), 2.26-2.38 (4H, m), 4.17-4.21 (2H, m), 4.54 (2H, m), 7.80-7.88 (2H, m), 8.22-7.58 (1H, m) 8.27 (1H, d), 8.42-8.45 (1H, d), 8.77 (1H, s), 9.02

Step 3. 1 - (9- (3-allyl-phenyl-propyl phosphinate) -9-nitro-6 H - carbazol-3-yl) -1,2-propane-dione-2-oxime prepared

Prepared in Step 2 1- (9- (3-allyl-phenyl-propyl phosphinate) -9-nitro-6 H - carbazol-3-yl) propane-1-on-10.0g (20.39mmol) nitrogen , 20 ml of 4N hydrogen chloride (1,4-dioxane) and 2.87 g (24.47 mmol) of isopentyl nitrite were added thereto, followed by stirring at room temperature for 4 hours. The reaction was poured slowly into 150 ml of distilled water and the reaction was terminated. The solid precipitate was filtered, dissolved in ethyl acetate, and washed sequentially with saturated sodium hydrogencarbonate and distilled water. The organic layer was dried over anhydrous magnesium sulfate, and anhydrous magnesium sulfate was filtered off. The filtrate was concentrated under reduced pressure 1 - (9- (3-allyl-phenyl-propyl phosphinate) -9-nitro-6 H - carbazol-3-yl) -1,2-propane-dione-2-oxime 7.31g ( Yield 69%).

^{1 H-NMR (δ ppm:} CDCl 3): 1.64-1.83 (2H, m), 2.24 (3H, s), 2.27-2.34 (2H, t), 4.16-4.21 (2H, m), 4.52 (2H, m), 7.82-7.92 (2H, m), 8.24-7.60 (1H, m) S), 9.05 (1H, s), 10.59 (1H, s), 8.25 (1H,

Step 4. 1 - (9- (3-allyl-phenyl-propyl phosphinate) -9-nitro-6 H - carbazol-3-yl) -1,2-propane-dione-2-oxime - O - acetate prepared

Prepared in the step 3, 1- (9- (3-allyl-phenyl-propyl phosphinate) -9-nitro-6 H - carbazol-3-yl) -1,2-propane-dione-2-oxime using the 1 and is to perform the step 6 of example 1 in the same way except that (9- (3-allyl-phenyl-propyl phosphinate) -9-nitro-6 H - carbazol-3-yl) 1,2 -Propanedione-2-oxime- O -acetate (yield: 70%).

^{1 H-NMR (δ ppm:} CDCl 3): 1.63-1.82 (2H, m), 2.22 (3H, s), 2.25-2.35 (2H, t), 3.36 (3H, s), 4.15-4.21 (2H, m), 4.50 (2H, t), 5.12-5.16 (IH, d), 5.24-5.30 (IH, d), 5.92-6.0 (IH, m), 7.42-7.58 (5H, m), 7.82-7.90 (2H, m), 8.26-8.29 (1H, d), 8.44-8.46

(Example 4) 1- (9- (3 - (- 5-norbornene-2,2-dimethyl) propyl phosphonate) - 6-toluoyl -9 H-carbazole-3-yl) ethane On oxime- O -acetate (6)

Step 1. 1 - (9- (3-chloropropyl) -6-toluoyl -9 H-carbazole-3-yl) ethane-1-one prepared

In the same manner except for using the carbazole the use of 2-methylbenzoyl chloride in step 2 of Example 1 to the Example 1 9- (3-chloropropyl) -9 H prepared in Step 1 of (9- (3-chloropropyl) -9H-carbazol-3-yl) -O-tolylmethanone was prepared in the same manner as in step 3 of Example 1, propyl) -6-toluoyl -9 H-carbazole-3-yl) ethane-1-one was obtained 18.98g (85% yield).

^{1 H-NMR (δ ppm:} CDCl 3): 2.20-2.35 (5H, m), 2.37 (3H, s), 3.44 (2H, t), 4.45 (2H, t), 7.34-7.42 (2H, m) , 7.48-7.60 (3H, m), 8.16-8.28 (3H, m), 8.76-8.84 (2H, m)

Step 2. 1 - (9- (3 - (- 5-norbornene-2,2-dimethyl) propyl phosphonate) - 6-toluoyl -9 H-carbazole-3-yl) -ethane -1 - on manufacturing

9.75 g (63.20 mmol) of 5-norbornene-2,2-dimethanol and 6.70 g (66.21 mmol) of triethylamine were dissolved in 100 ml of dichloromethane under a nitrogen atmosphere, and the mixture was maintained at 0 캜. Then, methyldichlorophosphite g (60.19 mmol) was diluted in 20 ml of dichloromethane, and the mixture was slowly added dropwise, followed by stirring at room temperature for 1 hour. The reaction product is separated into a precipitate and a filtrate using a filter paper. The filtrate was diluted with ethyl acetate and washed with distilled water. The organic layer was dried over anhydrous magnesium sulfate, and anhydrous magnesium sulfate was filtered off. The filtrate was concentrated under reduced pressure The obtained product was dissolved in 20ml dimethyl acetamide was prepared as described in Step 1, 1- (9- (3-chloropropyl) -6-toluoyl -9 H - carbazol-3-yl) -Ethan-1-one (10.0 g, 24.76 mmol). The reaction was heated to 120 DEG C and refluxed and stirred for 12 hours. After pouring slowly into 100 ml of distilled water, the reaction was terminated and the product was extracted with 200 ml of dichloromethane. The organic layer was separated and washed with water twice. The organic layer was dried over anhydrous magnesium sulfate, and anhydrous magnesium sulfate was filtered off. The filtrate was concentrated under reduced pressure, and the obtained product was purified by silica gel column chromatography (solvent: ethyl acetate: n-hexane = 1: 2) to obtain 1- (9- (3- (5- 2-dimethyl) propyl phosphonate) - 6-toluoyl -9 H-carbazole-3-yl) ethane-1-one was obtained 6.89g (yield: 49%)

^{1 H-NMR (δ ppm:} CDCl 3): 1.42-1.65 (4H, m), 1.72-1.85 (2H, m), 2.25-2.57 (10H, m) 4.02-4.17 (4H, m), 4.50 (2H m), 8.17-8.30 (3H, m), 8.75-8.86 (2H, m), 7.31-7.45 (2H, m)

Step 3. 1 - (9- (3 - (- 5-norbornene-2,2-dimethyl) propyl phosphonate) - 6-toluoyl -9 H-carbazole-3-yl) -ethanone oxime-O- acetate

Prepared in Step 2 1- (9- (3 - (- 5-norbornene-2,2-dimethyl) propyl phosphonate) - 6-toluoyl -9 H-carbazole-3-yl) - Ethan-1-one was used to carry out steps 5 to 6 of Example 1 in the same manner to give 1- (9- (3- (5-norbornene-2,2-dimethyl) phosphonate) - 6-toluoyl -9 H-carbazole-3-yl) -ethanone oxime-O-acetate to obtain the 3.75g (yield 70%).

^{1 H-NMR (δ ppm:} CDCl 3): 1.42-1.63 (4H, m), 1.73-1.86 (2H, m), 2.22-2.61 (13H, m), 4.0-4.15 (4H, m), 4.52 ( M), 8.38-8.85 (2H, m), 7.50-7.65 (3H, m), 8.18-8.32

(Example 5) Preparation of photoresist composition

9.8 g of an alkali soluble binder resin as a copolymer of benzyl methacrylate / methacrylic acid (molar ratio 70/30, molecular weight 20,000 g / mol, acid value 100 KOH mg / g), green pigment dispersion (CI Pigment Green 7, 20 wt% in PGMEA) , 10 g of dipentaerythritol hexaacrylate, 0.5 g of the carbazole derivative prepared in Example 1, 0.1 g of pentaerythritol tetrakis 3-mercaptobutyrate, 0.1 g of 2-methacryloxypropyltrimethoxysilane, And 49.5 g of propylene glycol monomethyl ether acetate (PGMEA) were successively mixed and stirred at room temperature for 3 hours to prepare a photoresist composition.

Evaluation of the photoresist composition prepared by the above method was performed on a glass substrate, and the performances such as sensitivity, residual film ratio, chemical resistance and developability of the photoresist composition were measured and the results are shown in Table 1 below.

1. Sensitivity

The above photoresist composition was spin-coated on a glass substrate and subjected to a heat treatment at 100 for 90 seconds, exposed using a step mask, and developed in a 0.04% KOH aqueous solution. The exposure amount at which the step mask pattern was maintained at 80% thickness with respect to the initial thickness was evaluated as sensitivity.

2. Residual film rate

After the photoresist composition was spin-coated on the substrate, it was subjected to a heat treatment at 100 for 90 seconds, followed by exposure at 365 nm, post-baking (post-baking) at 220 for 30 minutes, ) Were measured.

3. Chemical resistance

After the photoresist composition was spin-coated on the substrate, the resist film formed by the preheating treatment, the exposure treatment, the post-heat treatment, and the like was immersed in the NMP solution for 60 minutes for 10 minutes, and then the appearance change of the resist film was observed.

At this time, it was indicated that the appearance change was not good (O), that slight change of state was detected (Δ), the appearance was peeled or the solvent color was changed, and the defect (X) was indicated.

4. Developability

Developability was evaluated by observing the development process when the exposed substrate was developed with a 0.04% KOH aqueous solution for 60 seconds. When the development was clean and the pattern after development was well formed, the development was good, but the development time was long A case in which the straightness of the pattern is not good, a case in which the pattern is not formed clearly and the straightness is also inferior due to poor developability is indicated by X. [

(Example 6) Preparation of photoresist composition

A photoresist composition was prepared in the same manner as in Example 5 except that 0.5 g of the carbazole derivative prepared in Example 2 was used instead of the carbazole derivative prepared in Example 1, The photoresist composition was prepared in the same manner as in Example 1, and its sensitivity, residual film ratio, chemical resistance and developability were measured. The results are shown in Table 1 below.

(Example 7) Preparation of photoresist composition

A photoresist composition was prepared in the same manner as in Example 5 except that 0.5 g of the carbazole derivative prepared in Example 3 was used instead of the carbazole derivative prepared in Example 1, The photoresist composition was prepared in the same manner as in Example 1, and its sensitivity, residual film ratio, chemical resistance and developability were measured. The results are shown in Table 1 below.

(Example 8) Preparation of photoresist composition

A photoresist composition was prepared in the same manner as in Example 5 except that 0.5 g of the carbazole derivative prepared in Example 4 was used instead of the carbazole derivative prepared in Example 1, The photoresist composition was prepared in the same manner as in Example 1, and its sensitivity, residual film ratio, chemical resistance and developability were measured. The results are shown in Table 1 below.

 (Comparative Example 1) Preparation of photoresist composition

A photoresist composition was prepared in the same manner as in Example 5 except that 0.5 g of OXE-02 (product of BASF, refer to the following structure) was used in place of the carbazole derivative prepared in Example 1, The properties of the photoresist composition such as sensitivity, residual film ratio, chemical resistance and developability were measured by the method of Example 5, and the results are shown in Table 1 below.

(OXE-02 structure)

As shown in Table 1, the photoresist composition containing the carbazole derivative according to the present invention is superior in sensitivity to the photoresist composition of the comparative example, and has excellent physical properties such as residual film ratio, chemical resistance and developability have.

Claims (9)

A carbazole derivative represented by the following formula (1);
[Chemical Formula 1]

In the formula (1)
L ₁ is a single bond, (C1-C20) alkylene, (C2-C20) alkenylene, -C (= O) -, -O-, -S-, -S (= O) -, -SO 2 - And -Se-;
R ₁ is (C1-C30) alkyl, (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C6-C30) aryl, (C3-C30) heteroaryl, nitro (-NO _2), a cyano (= O) R ₁₁ or -C (= O) OR ₁₂ wherein R ₁₁ and R ₁₂ are each independently selected from the group consisting of hydrogen, deuterium, (C 1 -C 30) C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C6-C30) aryl and (C3-C30) is selected from a heteroaryl, wherein the R ₁₁ and the cycloalkyl, heterocycloalkyl of R _12, aryl, and The heteroaryl may be further substituted with (C1-C30) alkyl or (C1-C30) alkoxy;
R ₂ and R ₃ are each independently selected from the group consisting of hydrogen, deuterium, (C 1 -C 30) alkyl, (C 3 -C 30) cycloalkyl, (C 3 -C 30) heterocycloalkyl, (C 6 -C 30) C30) heteroaryl;
R ₄ and R ₅ are each independently selected from the group consisting of (C 6 -C 30) aryl, (C 3 -C 30) heteroaryl, (C 2 -C 30) alkenyl, (C 2 -C 30) alkynyl, C2-C30) alkynyloxy or _{-L 2 -OC (= O) -R} 13 , and wherein R ₁₃ is (C2-C30) alkenyl, (C2-C30) and alkynyl, wherein R ₄ and R ₅ is And at least one of R ₄ and R ₅ necessarily contains an unsaturated group; L ₂ is (C 1 -C 30) alkylene;
n is an integer of 0 or 1;
The alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl of R _{1 and} the alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl of R ₂ and R ₃ and the alkenyl, alkynyl or heteroaryl of R ₄ and R ₅ , (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, halogen, cyano, cyano, (= O) OR ₂₃ , -C (= O) NR ₂₁ R _22, and P (= O) R ₂₃ , -NR ₂₁ , -SR ₂₂ , -NR ₂₁ R ₂₂ , (OR < ₂₁ >) (OR < ₂₂ >), and R < _{21 &} To R ₂₃ are each independently selected from hydrogen, heavy hydrogen (deuterium), halogen, (C1-C30) alkyl, (C2-C30) alkenyl, (C3-C30) cycloalkyl (C1-C30) alkyl, (C3-C30) (C3-C30) heterocycloalkyl, (C6-C30) aryl or (C3-C30) heteroaryl, said heterocycloalkyl and heteroaryl being optionally substituted with B, N, O, S, P Si and < RTI ID = 0.0 > P. ≪ / RTI > The method according to claim 1,
A carbazole derivative represented by the following formula (2);
(2)

In the formula (2)
L ₁ are each independently a single bond or (C ₁ -C 20) alkylene;
R ₁ is (C1-C20) alkyl, (C3-C20) cycloalkyl, (C3-C20) heterocycloalkyl, (C6-C20) aryl, (C3-C20) heteroaryl, nitro (-NO _2), a cyano (= O) R ₁₁ or -C (= O) OR ₁₂ wherein R ₁₁ and R ₁₂ are each independently selected from the group consisting of (C 1 -C 20) alkyl, (C 3 -C 20) cycloalkyl, (C3-C20) heterocycloalkyl, (C6-C20) aryl or (C3-C20) heteroaryl;
R ₂ and R ₃ are each independently (C 1 -C 20) alkyl, (C 3 -C 20) cycloalkyl, (C 3 -C 20) heterocycloalkyl, (C 6 -C 20) aryl or (C 3 -C 20) heteroaryl;
R ₆ is (C2-C20) alkenyl or (C2-C20) alkynyl;
R ₅ is selected from the group consisting of (C 6 -C 20) aryl, (C 3 -C 20) heteroaryl, (C 2 -C 20) alkenyl, (C 2 -C 20) alkynyl, (C 2 -C 20) alkenyloxy, is oxy or _{-L 2 -OC (= O) -R} 13, wherein R ₁₃ is (C2-C20) alkenyl, (C2-C20) and alkynyl, wherein R ₄ and R ₅ are connected to each other to form a ring L < ₂ > is (C1-C7) alkylene;
n is an integer of 0 or 1;
The alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl of R _{1 and} the alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl of R ₂ and R ₃ and the alkenyl, alkynyl or heteroaryl of R ₅ and R ₆ , Each of the rings is independently selected from the group consisting of (C1-C20) alkyl, (C2-C20) alkenyl, (C2- C20) alkynyl, (C3- C20) cycloalkyl, (C3-C20) heterocycloalkyl, (= O) OR ₂₃ , -C (= O) NR ₂₁ R _22, and P (= O) R ₂₃ , -NR ₂₁ , -SR ₂₂ , -NR ₂₁ R ₂₂ , (OR < ₂₁ >) (OR < ₂₂ >), and R < _{21 &} To R ₂₃ are each independently selected from hydrogen, heavy hydrogen (deuterium), halogen, (C1-C20) alkyl, (C2-C20) alkenyl, (C3-C20) cycloalkyl (C1-C20) alkyl, (C3-C20) O, S, P (= O), or (C3-C20) heteroaryl, wherein said heterocycloalkyl and said heteroaryl are optionally substituted with one or more substituents selected from the group consisting of H, alkyl, cycloalkyl, (C3-C20) heterocycloalkyl, Si and < RTI ID = 0.0 > P. ≪ / RTI > The method according to claim 1,
R ₄ and R ₅ are each independently selected from the group consisting of (C 6 -C 20) aryl, (C 3 -C 20) heteroaryl, (C 2 -C 7) alkenyl, (C 2 -C 7) alkynyl, C2-C7) alkynyloxy or _{-L 2 -OC (= O) -R} 13 , and wherein L ₂ is alkylene (C1-C7), wherein R ₁₃ is (C2-C7) alkenyl, (C2- C7) alkynyl, and R < ₄ > and R < ₅ &

or

A can form a ring, wherein R ₃₁ and R ₃₂ are each independently hydrogen, (C2-C7) alkenyl, (C2-C7) alkynyl, (C3-C20) cycloalkyl or (C3-C20) heteroaryl Carbazole derivatives which are cycloalkyl. The method according to claim 1,
A carbazole derivative selected from the following structures;

A photopolymerization initiator composition comprising a carbazole derivative according to claim 1. A photoresist composition comprising a carbazole derivative and a colorant according to claim 1. The method according to claim 6,
Wherein the photoresist composition further comprises a photosensitizer comprising a thiol group or a silyl group. A color filter comprising the photoresist composition according to claim 6. A black matrix comprising the photoresist composition according to claim 6.