KR101927875B1 - Xanthene dye compounds and photoresist composition containing the same - Google Patents

Abstract

The present invention relates to a xanthene-based dye compound and a photoresist composition containing the same. More specifically, the present invention relates to a xanthene-based dye compound having improved heat resistance And a photoresist composition containing the same.

Description

Xanthene dye compounds and photoresist compositions containing the same,

The present invention relates to a xanthene-based dye compound and a photoresist composition containing the same. More particularly, the present invention relates to a novel xanthene-based dye compound having improved solubility in solvents as well as excellent sensitivity, chemical resistance, Lt; / RTI >

The color filter can be embedded in a color photographing apparatus of an image sensor such as a complementary metal oxide semiconductor (CMOS) or a charge coupled device (CCD) to actually obtain a color image, (PDP), a liquid crystal display (LCD), a field emission display (FEL), and a light emitting display (LED), and its application range is rapidly expanding. Particularly in recent years, applications for LCDs having advantages such as light weight, low power, and low driving voltage have been expanded. Accordingly, color filters are recognized as one of the most important components in reproducing LCD color tone.

Such a color filter realizes a full-color image by doping using a light source whose light transmittance is controlled by a liquid crystal layer, and a desired coloring pattern can be formed using a photoresist composition containing a coloring material. Specifically, it can be manufactured by forming a coating layer made of a photoresist composition containing a coloring material on a substrate, forming a pattern on the formed coating layer, exposing and developing the coating layer, and heating and thermally curing the coating layer. At this time, the colorant included in the photoresist composition generally uses a pigment, but recently, attempts have been made to use a dye having high brightness and excellent heat resistance. The use of only a dye as a coloring material is preferable because it can realize all the excellent characteristics of a dye. However, the dye is not better than the pigment treated with the other components of the photoresist composition and has a large color change at a high temperature. . Due to such a problem, a method of using a hybrid type coloring material using both a pigment and a dye as coloring materials has been attempted, but up to now, the problem of using a coloring material containing a dye has not been completely solved.

As described above, when a color filter is produced using a photoresist composition containing a dye as a coloring material, discoloration or color change occurs at a post-process at a high temperature, and due to lack of compatibility with the material used, Foreign matter may be generated during formation. In addition, when a color filter is manufactured using the same, the developing speed is slow and the sensitivity is insufficient, so that problems such as frequent peeling of the pattern formed in the development process by the alkaline developer may occur. Accordingly, there is a demand for developing a photoresist composition suitable for a lithographic process, which contains a dye as a coloring material used in a photoresist composition or can solve the problems when a dye alone is used.

As a photoresist composition using a conventional dye, Patent Document 1 discloses a blue coloring composition for a color filter. Characterized in that the blue coloring composition for a color filter contains a binder resin and a coloring agent, the coloring agent comprises a blue pigment and a salt-forming product, and the salt-forming product is formed from a compound having a xanthene acid dye and a cationic group, There is a problem that satisfactory heat resistance can not be ensured when the color filter is formed. In addition, Patent Document 2 relates to a colored photosensitive resin composition and a color filter array and a solid-state imaging device using the same, wherein the colored photosensitive resin composition discloses a xanthene-based compound and a salt thereof. However, in the case of a color filter using the above-mentioned colored photosensitive resin composition, there is a problem that the voltage holding ratio is lowered.

Taking this into consideration, the Applicant has completed the present invention in order to solve the above-mentioned problems and to provide a novel xanthene dye compound and a photoresist composition containing the same which have higher solubility, sensitivity, chemical resistance and developability .

Korean Patent No. 1533669 Japanese Patent Laid-Open No. 2008-242311

An object of the present invention is to provide a xanthene-based dye compound in which solubility in a solvent is remarkably improved.

Another object of the present invention is to provide a photoresist composition comprising a novel xanthene dye compound having excellent compatibility with other components of a photoresist composition and having excellent process characteristics such as solubility, sensitivity, chemical resistance and developability .

It is still another object of the present invention to provide a high quality color filter and black matrix such as high luminance, high contrast ratio, and high definition.

The present invention provides a xanthene-based dye compound represented by the following formula (1).

[Chemical Formula 1]

In formula (1)

R ₁ and R ₃ are each independently hydrogen, (C1-C30) alkyl, (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C6-C30) aryl, (C3-C30) heteroaryl, (C1-C30) alkylamino, (C6-C30) arylamino, halogen, cyano, nitrile and amino;

R ₂ is a monovalent anion;

R ₄ and R ₅ are each independently selected from the group consisting of (C 2 -C 30) alkenyl, (C 2 -C 30) alkenyloxy, (C 2 -C 30) alkynyl, (C 2 -C 30) alkynyloxy, (C6-C30) aryloxy, (C3-C30) heteroaryl and (C3-C30) heteroaryloxy, or R ₄ and R ₅ may be connected to each other to form a ring;

R ₆ is hydrogen, (C1-C30) alkyl, (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C6-C30) aryl and (C3-C30) heteroaryl is selected from;

L ₁ is a direct bond, (C ₁ -C 30) alkylene or (C 1 -C 30) heteroalkylene;

n is an integer selected from 1 to 3;

The alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, alkylamino and arylamino of R ₁ and R _{3 and} the alkyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl of R ₆ are each independently (C6-C30) alkyl, halo (C1-C30) alkyl, halogen, cyano, nitrile, hydroxy, (C3- C30) cycloalkyl, (C3-C30) aryl, (C6-C30) aryl (C1-C30) alkyl, (C1-C30) ) Heteroaryl and (C3-C30) heteroaryl substituted with (C6-C30) aryl, said heterocycloalkyl, heteroaryl, heteroaryloxy and heteroalkylene Each independently comprise at least one heteroatom selected from B, N, O, S, P (= O), Si and P;

The xanthene dye compound according to one embodiment of the present invention may be represented by the following general formula (2), but is not limited thereto.

(2)

In formula (2)

R _11, R ₁₂ and R ₁₆ is hydrogen, (C1-C20) alkyl, (C3-C20) cycloalkyl, (C3-C20) heterocycloalkyl, (C6-C20) aryl and (C3-C20), each independently (C3-C20) cycloalkyl, (C3-C20) heterocycloalkyl, (C6-C20) aryl and (C3-C20) heteroaryl, wherein said alkyl, heterocycloalkyl, aryl and heteroaryl are optionally substituted with -C20) heteroaryl, halogen, cyano, and nitrile;

R ₁₃ is a non-nucleophilic anion;

R ₁₄ and R ₁₅ are each independently selected from the group consisting of (C 2 -C 20) alkenyl, (C 2 -C 20) alkenyloxy, (C 2 -C 20) alkynyl, (C 2 -C 20) alkynyloxy, (C6-C20) aryloxy, (C3-C20) heteroaryl and (C3-C20), or selected from heteroaryloxy, wherein R ₁₄ and R ₁₅ are connected to each other may form a ring;

L ₂ is a direct bond, (C 1 -C 20) alkylene or (C 1 -C 20) heteroalkylene.

The xanthene dye compound according to one embodiment of the present invention may be represented by the following formula (3), but is not limited thereto.

(3)

In formula (3)

R ₁₆ is selected from hydrogen, (C 1 -C 20) alkyl, (C 3 -C 20) cycloalkyl, (C 3 -C 20) heterocycloalkyl, (C 6 -C 20) aryl and (C 3 -C 20) (C3-C20) heterocycloalkyl, (C6-C20) aryl and (C3-C20) heteroaryl, halogen, Nitrogen, and nitrile; and R < 1 >

R ₁₃ is a non-nucleophilic anion;

R ₁₄ and R ₁₅ are each independently selected from the group consisting of (C 2 -C 20) alkenyl, (C 2 -C 20) alkenyloxy, (C 2 -C 20) alkynyl, (C 2 -C 20) alkynyloxy, (C6-C20) aryloxy, (C3-C20) heteroaryl and (C3-C20), or selected from heteroaryloxy, wherein R ₁₄ and R ₁₅ are connected to each other may form a ring;

L ₂ is a direct bond, (C 1 -C 20) alkylene or (C 1 -C 20) heteroalkylene.

The present invention provides a photoresist composition comprising the xanthene-based dye compound represented by the above formula (1). The photoresist composition may further include at least one selected from a binder resin, a photopolymerizable compound, a photopolymerization initiator, a solvent, a colorant, and the like. In particular, the xanthene dye compound according to the present invention has remarkably improved solubility in solvents such as propylene glycol monomethyl ether acetate and the like, so that the compatibility with other components of the photoresist composition can be remarkably improved. Commercial use is expected.

Further, it was confirmed that the sensitivity and chemical resistance of the pattern were remarkably improved by the radical reaction by including the xanthene-based dye compound containing an unsaturated group. That is, by using the photoresist composition according to the present invention, it is possible to provide a high-quality color filter and black matrix having excellent sensitivity, chemical resistance, resistance to developing, and the like.

The xanthene-based dye compound according to the present invention shows not only excellent solubility but also a behavior of a dye having a narrow distribution of UV spectrum. Further, the xanthene dye compound according to the present invention may contain an unsaturated group to form a crosslinked structure by a radical reaction, thereby improving the degree of curing and significantly improving the etching resistance.

The photoresist composition according to the present invention is excellent in compatibility with the xanthene dye compound alone or in combination with other colorants and with a multifunctional monomer or binder resin used in a photoresist composition, It is possible to implement color. Further, it is excellent in heat resistance and chemical resistance and can minimize color change even at high temperature curing.

Accordingly, the color photosensitive material to which the xanthene-based dye compound according to the present invention is applied is advantageous not only for additional film forming processes such as column spacer, overcoat, passivation, etc., but also for high temperature process characteristics.

The present invention relates to a novel xanthene dye compound 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 the description of known functions and configurations which may unnecessarily obscure the gist of the present invention will be omitted in the following description.

Since the xanthene dye compound according to the present invention has a phosphonate group containing an unsaturated group, not only the solubility can be remarkably improved, but also it can be used independently or in combination with other colorants to realize a clear color and minimize color change at high temperature Which can be used as a dye for a color filter. In addition, the xanthene dye compound according to the present invention has both intramolecular and anionic ions, and is substantially electrically neutral in the composition, and can participate in the radical reaction and cure according to the desired combination of compositions .

Specifically, the xanthene dye compound according to the present invention can be represented by the following formula (1).

[Chemical Formula 1]

In formula (1)

R ₁ and R ₃ are each independently hydrogen, (C1-C30) alkyl, (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C6-C30) aryl, (C3-C30) heteroaryl, (C1-C30) alkylamino, (C6-C30) arylamino, halogen, cyano, nitrile and amino;

R ₂ is a monovalent anion;

R ₄ and R ₅ are each independently selected from the group consisting of (C 2 -C 30) alkenyl, (C 2 -C 30) alkenyloxy, (C 2 -C 30) alkynyl, (C 2 -C 30) alkynyloxy, (C6-C30) aryloxy, (C3-C30) heteroaryl and (C3-C30) heteroaryloxy, or R ₄ and R ₅ may be connected to each other to form a ring;

R ₆ is hydrogen, (C1-C30) alkyl, (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C6-C30) aryl and (C3-C30) heteroaryl is selected from;

L ₁ is a direct bond, (C ₁ -C 30) alkylene or (C 1 -C 30) heteroalkylene;

n is an integer selected from 1 to 3;

The alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, alkylamino and arylamino of R ₁ and R _{3 and} the alkyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl of R ₆ are each independently (C6-C30) alkyl, halo (C1-C30) alkyl, halogen, cyano, nitrile, hydroxy, (C3- C30) cycloalkyl, (C3-C30) aryl, (C6-C30) aryl (C1-C30) alkyl, (C1-C30) ) Heteroaryl and (C3-C30) heteroaryl substituted with (C6-C30) aryl, said heterocycloalkyl, heteroaryl, heteroaryloxy and heteroalkylene Each independently comprise at least one heteroatom selected from B, N, O, S, P (= O), Si and P;

The substituents comprising " alkyl ", " alkoxy " and other " alkyl " moieties described in this invention encompass both linear and branched forms. The term " aryl " in the present invention means an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen, and may be a single or fused ring containing 4 to 7, preferably 5 or 6 ring atoms, A ring system, and a form in which a plurality of aryls are connected by a single bond. Specific examples thereof include phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylenyl, But are not limited thereto. &Quot; Heteroaryl " as defined in the present invention is an organic radical derived from aromatic hydrocarbons by the removal of one hydrogen. The term " heteroaryl " 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, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, Monocyclic heteroaryl such as triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl and the like; 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 are not limited thereto.

Furthermore, " cycloalkyl ", alone or as part of another group described in the present invention, refers to a fully saturated and partially unsaturated hydrocarbon ring of 3 to 9 carbon atoms, and when aryl or heteroaryl is fused Quot; heterocycloalkyl " as used herein includes 4 to 10 ring atoms containing one or more heteroatoms selected from B, N, O, S, P (= O), Si and P And may be a cyclic or polycyclic non-aromatic radical.

The term " alkenyl " of the present invention is a linear or branched hydrocarbon having one or more double bonds, and examples thereof include ethenyl, prop-1-en-1-yl, 2-yl, 2-methyl-prop-1-en-1-yl, 1-yl, but-2-en-1-yl, but-2-en-2-yl, But the present invention is not limited thereto. "Alkynyl" of the present invention is a linear or branched hydrocarbon having at least one triple bond such as ethynyl, prop-1-yn-1-yl, 1-yl, but-1-yn-3-yl or but-3-yn-1-yl, and the like.

The "alkylene" of the present invention is an organic radical derived by removing two hydrogens from a linear or branched hydrocarbon containing a certain number of carbon atoms, for example, methylene, ethylene, propylene, butylene, pentylene , Hexylene, heptylene and the like. The "heteroalkylene" of the present invention means that at least one of the carbon atoms of the alkylene is optionally substituted with -N (R ') -, -O- or -S-, May be replaced by an organic radical.

&Quot; Alkylamino " and " arylamino ", as used in the present invention, may be mono or dialkylamino, mono or diarylamino, at least one substituent is alkyl or aryl, and an amino group having a different substituent is also included in the scope of the present invention .

Furthermore, the "halogen" described in the present invention means fluoro, chloro, bromo or iodo.

The xanthene dye compound according to the present invention has an unsaturated group, and it is possible to realize improved heat resistance and chemical resistance by a radical reaction. In addition, the solubility in a solvent such as propylene glycol monomethyl ether acetate is remarkably improved to enable the expression of a clear color and excellent thermal stability, and it is particularly used for a color filter or a black matrix of a display device such as a liquid crystal display Lt; / RTI >

In addition, the xanthene dye compound according to one embodiment of the present invention is excellent in low-temperature storage stability and exhibits a VHR (voltage holding ratio). The xanthene dye compound represented by the following Chemical Formula 2 or Chemical Formula 3 But is not limited thereto.

(2)

(3)

In formulas (2) and (3)

R _11, R ₁₂ and R ₁₆ is hydrogen, (C1-C20) alkyl, (C3-C20) cycloalkyl, (C3-C20) heterocycloalkyl, (C6-C20) aryl and (C3-C20), each independently (C3-C20) cycloalkyl, (C3-C20) heterocycloalkyl, (C6-C20) aryl and (C3-C20) heteroaryl, wherein said alkyl, heterocycloalkyl, aryl and heteroaryl are optionally substituted with -C20) heteroaryl, halogen, cyano, and nitrile; < / RTI >

R ₁₃ is a non-nucleophilic anion;

R ₁₄ and R ₁₅ are each independently selected from the group consisting of (C 2 -C 20) alkenyl, (C 2 -C 20) alkenyloxy, (C 2 -C 20) alkynyl, (C 2 -C 20) alkynyloxy, (C6-C20) aryloxy, (C3-C20) heteroaryl and (C3-C20), or selected from heteroaryloxy, wherein R ₁₄ and R ₁₅ are connected to each other may form a ring;

L ₂ is a direct bond, (C 1 -C 20) alkylene or (C 1 -C 20) heteroalkylene.

Wherein according to one embodiment of the invention R ₁₃ is remarkably low reflected the ability to cause a nuclear reaction with the parent monovalent anion-nucleophilic, -CO ₂ as a non-limiting example ^-, -SO ₄ ^- or -SO ₃ ^-, SO ₂ N ^- SO ₂ CF ₃ , and the like, and it may be -SO ₃ ^- in view of solubility in a more improved solvent, but is not limited thereto.

The xanthene dye compound according to an embodiment of the present invention is excellent in compatibility with another colorant, a multi-functional monomer or a binder resin used in a photoresist composition and has improved heat resistance and chemical resistance , L < ₂ > may be a direct bond, (C1-C7) alkylene or (C1-C7) heteroalkylene, but is not limited thereto.

In addition, the xanthene dye compound according to an embodiment of the present invention has a phosphonate group containing an unsaturated group, so that a radical reaction can be performed even under a low energy, long wavelength-output exposure light source, and a thiol group, It is possible to form a fine pattern having high adhesion to a substrate and high strength with a remarkably improved sensitivity by reacting with a photosensitizer having a reactive substituent.

The R ₄ and R ₅ or R ₁₄ and R ₁₅ according to the present invention can be used in a color filter or a black matrix in which a high content of a dye and a coloring material should be used in view of realizing properties such as excellent sensitivity, , Preferably phenyl, naphthyl, biphenyl, terphenyl or the following structures.

The xanthene-based dye compound according to an embodiment of the present invention may be selected from the following structures, but is not limited thereto.

The xanthene-based dye compound according to the present invention shows a behavior of a dye having excellent solubility and can have a narrow UV spectrum. In addition, the xanthene dye compound according to the present invention includes a phosphate group having an unsaturated group, and can control the pattern characteristics of the composition of the photoresist and the physical properties such as heat resistance and chemical resistance easily according to various substituent changes.

That is, the composition of the photoresist according to the present invention can be applied to a black matrix, a color filter, a colored column spacer, a colored organic insulating film, and the like, and can be effectively applied particularly to a black matrix and a colored photosensitive material requiring a high- .

The present invention provides a photoresist composition comprising the xanthene-based dye compound. At this time, the photoresist composition may further contain at least one selected from a binder resin, a photopolymerizable compound, a photopolymerization initiator, a solvent and a coloring material.

Hereinafter, the photoresist composition according to the present invention will be described in detail.

The photoresist composition according to the present invention comprises at least one selected from the group consisting of a binder resin, a photopolymerizable compound, a photopolymerization initiator, a solvent and a coloring material, together with a xanthene-based dye compound. The xanthene- May be contained in an amount of 0.01 to 30% by weight, preferably 0.1 to 20% by weight, based on the total weight of the composition (100% by weight).

The binder resin according to one embodiment of the present invention is not limited as long as it is known in the art, but it has an average molecular weight of 2,000 to 300, 000 g / mol, a degree of dispersion of 1.0 to 10.0, a novolak resin, a cado resin, or the like can be used. 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, may be mixed to them more than one or two. At this time, the binder resin may be mixed in an amount of 1 to 20% by weight based on the total weight of the photoresist composition (100% by weight), but is not limited thereto.

The photopolymerizable compound and the photopolymerization initiator according to an embodiment of the present invention are not limited as long as they are well known in the art, but a non-limiting example is a thioxanthone compound, an acetophenone compound, , A triazine compound, an O-acyloxime compound, an onium salt compound, a benzoin compound, a benzophenone compound, an? -Diketone compound, a polynuclear quinone compound, a diazo compound, an imidosulfonate compound, Alone, or a mixture thereof, but are not limited thereto. At this time, when the photopolymerizable compound and the photopolymerization initiator are mixed at 0.01 to 10 wt% with respect to the total weight (100 wt%) of the entire photoresist composition, optimum sensitivity may be realized.

The solvent may be ethyl acetate, butyl acetate, diethyleneglycol dimethyl ether, diethyleneglycol dimethylethylether, methylmethoxypropionate, ethylethoxypropionate (EEP), ethyl Propylene glycol monomethyl ether acetate (PGMEA), propylene glycol methyl ether propionate (PGMEP), propylene glycol methyl ether, propylene glycol propyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol methyl (DMF), N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), N, N'-dicyclohexylcarbodiimide, ? -Butyrolactone, diethyl ether, ethylene glycol dimethyl ether, diglyme, tetrahydrofuran (THF), methanol, ethanol, propanol, Propylene glycol ethers such as isopropyl alcohol, isopropanol, ethylene glycol acetate, methyl cellosolve, ethyl cellosolve, diethylene glycol methyl ether, diethylene glycol ethyl ether, dipropylene glycol methyl ether, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, Xylene, hexane, heptane, and octane may be used alone or in combination of two or more, but the present invention is not limited thereto. In this case, the solvent may be mixed in an amount of 30 to 90% by weight based on the total weight of the photoresist composition (100% by weight), but is not limited thereto.

The photoresist composition according to an embodiment of the present invention may further include a colorant, and the colorant is not limited as long as it is well known in the art, and examples thereof include water-soluble azo pigments, insoluble azo pigments, Anthanthrone pigments, anthanthrone pigments, anthanthrone pigments, anthanthrone pigments, anthanthrone pigments, anthanthrone pigments, anthanthrone pigments, anthanthrone pigments, ) Pigments, indanthrone pigments, pravantron pigments, pyranthrone pigments, diketopyrrolopyrrole 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 mixed in an amount of 0.1 to 30% by weight based on the total weight of the photoresist composition (100% by weight).

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 may react sensitively with the photoactive compound according to the present invention, 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 photosensitizer having high reactivity with the photoactive compound according to the present invention is not limited as long as it contains a thiol group, a silyl group, and the like. Nonlimiting examples thereof include pentaerythritol tetrakis thioglycolate, pentaerythritol tetrakis thioglycolate, A photosensitizer containing a thiol group such as pentaerythritol tetrakis thiopropionate and pentaerythritol tetrakis (3-mercapto butylate); A photosensitizer containing a silyl group; ≪ / RTI > In addition, the photoactive compound 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 And the like. At this time, when the photosensitizer is mixed at 0.01 to 10 wt% with respect to the total weight of the entire photoresist composition (100 wt%), the photosensitizer may exhibit optimal sensitivity due to high reactivity with the photopolymerization compound and the photopolymerization initiator .

In addition, the photoresist composition according to the present invention may further contain a solvent other than the photosensitizer containing the colorant, the photoactive compound, the binder resin and the reactive group (thiol group, silyl group, etc.), the adhesion aid, ≪ / RTI > 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.

The present invention provides a color filter or black matrix using a photoresist composition containing the xanthene-based dye compound. In particular, even when the content of the organic black pigment is high, the photoresist composition according to the present invention has tradeoffs in various reliability properties such as the content of the black spacer, ion elution property, and VHR (Voltage Holding Ratio) It is possible to remarkably inhibit the phenomenon of failure.

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).

The physical properties of the dye compound prepared or used in Examples and Comparative Examples according to the present invention and the physical properties of the resist film formed using the photoresist composition containing the same were measured by the following methods.

1. Evaluation of solubility

The solubilities of the xanthene-based dye compounds prepared in Examples 2 to 5 and the dyes used in Comparative Example 1 were measured using propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether (PGME), ethyl lactate (EL) Dimethylacetamide (DMAc) and cyclohexanone (CHN) were each used as a solvent, and the solubility thereof was measured.

2. Sensitivity evaluation

The photoresist composition according to the present invention was spin-coated on a glass substrate at 100 ° C. for 90 seconds, exposed to light 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.

3. Chemical resistance evaluation

The photoresist composition according to the present invention was spin-coated on a glass substrate and subjected to a heat treatment at 100 for 90 seconds, exposed at 365 nm, post-baked at 220 for 30 minutes, 60 for 10 minutes to observe the appearance change of the resist film. 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 evaluation

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 1)

Step 1. b Preparation of compounds

a compound (30.0 g, 74.02 mmol), 2,6-dimethylaniline (44.85 g, 370.14 mmol) and N-methylpyridone (175 g) were mixed in a nitrogen atmosphere. The mixture was slowly cooled to room temperature (23 ° C.), and then 1000 g of 2% aqueous hydrochloric acid solution was slowly added thereto. The mixture was stirred for 1 hour, and the resulting crystals were filtered through reduced pressure filtration. The filtered crystals were washed with a mixed rinse solution of tetrahydrofuran: distilled water (1: 4) ratio and dried under reduced pressure at 60 ° C for 15 hours to obtain b compound (25.52 g, yield 60%).

^{1 H-NMR (δ ppm:} CDCl 3): 1.68-2.29 (12H, m), 5.72-6.56 (2H, d), 7.01-7.78 (13H, m), 7.87-8.12 (1H, d), 9.85- 10.12 (2H, s)

Step 2. Preparation of Compound c

20.0 g (37.80 mmol) of the compound b prepared in the above Step 1, 57.71 g (417.61 mmol) of potassium carbonate and 110 g of N-methylpyridone were mixed and stirred under a nitrogen atmosphere. The mixture was heated to 80 DEG C and 27.39 g (174.0 mmol) of 1-bromo-3-chloropropane was slowly added dropwise to the mixture, followed by stirring for 8 hours. The reaction mixture was cooled to room temperature, concentrated by distillation under reduced pressure, and slowly added to distilled water. After stirring for 1 hour, the precipitated crystals were filtered by reduced pressure filtration, washed with a mixed washing solution of methanol: distilled water (1: 5) mixed ratio, and dried at 60 ° C for 15 hours under reduced pressure to obtain c compound (18.23 g, yield 72 %).

^{1 H-NMR (δ ppm:} CDCl 3): 1.65-1.92 (4H, m), 2.06-2.31 (12H, m), 2.33-2.48 (4H, m), 3.74-3.95 (4H, m), 5.88- 6.20 (2H, m), 7.10-7.75 (13H, m), 8.04-8.26 (1H, m)

Step 3. Preparation of compound 1

1.82 g (31.33 mmol) of allyl alcohol and 3.17 g (31.33 mmol) of triethylamine were dissolved in 20 ml of dichloromethane under nitrogen atmosphere, and the solution was kept at 0 ° C. Then, 1.41 g (10.3 mmol) of trichloride was diluted with 10 ml of dichloromethane And the mixture was stirred at room temperature for 1 hour. The reaction product was 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, and the obtained product was dissolved in 20 ml of dimethylacetamide, and 3.0 g (4.12 mmol) of the compound c prepared in the above step 2 was added thereto. The reaction was heated to 110 ° C and refluxed and stirred for 12 hours. After pouring slowly into 50 ml of distilled water, the reaction was terminated and the product was extracted with 30 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: 1) to obtain compound 1 (2.3 g, yield 57%).

^{1 H-NMR (δ ppm:} CDCl 3): 1.61-1.94 (4H, m), 2.01-2.29 (12H, m), 2.31-2.51 (4H, m), 3.81-4.04 (4H, m), 4.10- (1H, m), 4.77 (8H, m), 5.02-5.67 (8H, m), 5.88-6.34 (6H, m), 7.07-7.77 (13H, m), 8.01-8.22

(Example 2) Preparation of Compound 2

1.22 g (21.03 mmol) of allyl alcohol and 2.13 g (21.03 mmol) of triethylamine were dissolved in 20 ml of dichloromethane under nitrogen atmosphere, and the temperature was maintained at 0 캜. Then, 1.85 g (10.31 mmol) of dichlorophenylphosphine was dissolved in dichloromethane 10 ml, slowly added dropwise, and then stirred at room temperature for 1 hour. The reaction product was 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, and the obtained product was dissolved in 20 ml of dimethylacetamide, and 3.0 g (4.12 mmol) of the compound c prepared in Step 2 of Example 1 was added thereto. The reaction was heated to 110 ° C and refluxed and stirred for 12 hours. After pouring slowly into 50 ml of distilled water, the reaction was terminated and the product was extracted with 30 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 = 3: 2) to obtain Compound 2 (2.06 g, yield 49%).

¹ H-NMR (? Ppm: CDCl ₃ ): 1.64-1.89 (4H, m), 2.04-2.35 (12H, m), 2.28-2.49 M), 8.05-8.24 (1 H, m), 5.08-5.51 (4H, m), 5.85-6.17 (4H, t), 7.05-8.01

(Example 3) Preparation of Compound 3

1.76 g (31.35 mmol) of propargyl alcohol and 3.17 g (31.35 mmol) of triethylamine were dissolved in 20 ml of dichloromethane under nitrogen atmosphere, and the mixture was maintained at 0 캜. Then, 1.41 g (10.31 mmol) Diluted in 10 ml of dichloromethane, slowly added dropwise, and then stirred at room temperature for 1 hour. The reaction product was 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, and the obtained product was dissolved in 20 ml of dimethylacetamide, and 3.0 g (4.12 mmol) of the compound c prepared in Step 2 of Example 1 was added thereto. The reaction was heated to 110 ° C and refluxed and stirred for 12 hours. After pouring slowly into 50 ml of distilled water, the reaction was terminated and the product was extracted with 30 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: 1) to obtain Compound 3 (2.48 g, yield 62%).

^{1 H-NMR (δ ppm:} CDCl 3): 1.62-1.88 (4H, m), 2.02-2.38 (12H, m), 2.25-2.48 (4H, m), 2.52-2.75 (4H, s), 3.80- (2H, m), 7.07-7.72 (13H, m), 8.01-8.18 (1H, m), 4.02 (4H, m), 4.12-4.68

(Example 4) Preparation of Compound 4

Step 1. Preparation of d compound

10.0 g (17.40 mmol) of the compound b prepared in the step 1 of Example 1, 14.43 g (104.4 mmol) of potassium carbonate and 50 g of N-methylpyridone were mixed and stirred under nitrogen atmosphere. The mixture was heated to 80 DEG C, and 3.01 g (19.14 mmol) of 1-bromo-3-chloropropane was slowly added dropwise to the mixture, followed by stirring for 8 hours. The reaction mixture was cooled to room temperature, concentrated by distillation under reduced pressure, and slowly added to distilled water. After stirring for 1 hour, the precipitated crystals were filtered by vacuum filtration, washed with a mixed washing solution of methanol: distilled water (1: 5), and dried at 60 ° C under reduced pressure for 2 hours. The dried crystals were purified by silica gel column chromatography (solvent: ethyl acetate: n-hexane = 2: 1) to obtain d compound (3.62 g, yield 32%).

^{1 H-NMR (δ ppm:} CDCl 3): 1.61-1.79 (2H, m), 2.04-2.28 (12H, m), 2.30-2.45 (2H, m), 3.70-3.85 (2H, m), 5.85- (1H, s), 6.18 (2H, m), 7.12-7.70 (13H, m), 8.05-8.22

Step 2. Preparation of compound 4

2.46 g (15.80 mmol) of 2,2-diallylpropane-1,3-diol and 1.67 g (16.55 mmol) of triethylamine were added to a solution of 20 ml of dichloromethane , And the mixture was maintained at 0 占 폚. Then, 2.0 g (15.05 mmol) of methyldichlorophosphite was diluted in 10 ml of dichloromethane, and the mixture was slowly added dropwise, followed by stirring at room temperature for 1 hour. The reaction product was 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, and the obtained product was dissolved in 20 ml of dimethylacetamide, and 3.0 g (4.60 mmol) of the compound d prepared in the above step 1 was added thereto. The reaction was heated to 120 DEG C and refluxed and stirred for 12 hours. After pouring slowly into 50 ml of distilled water, the reaction was terminated and the product was extracted with 30 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 = 3: 2) to obtain Compound 4 (1.46 g, yield 39%).

^{1 H-NMR (δ ppm:} CDCl 3): 1.63-1.80 (2H, m), 2.04-2.47 (20H, m), 3.76-3.95 (2H, m), 4.15-4.38 (4H, m), 5.07- (2H, m), 7.05-7.70 (13H, m), 8.0-8.15 (1H, m)

(Example 5) Preparation of Compound 5

1.83 g (11.85 mmol) of 5-norbornene-2,2-dimethanol and 1.26 g (12.41 mmol) of triethylamine were dissolved in 20 ml of dichloromethane under a nitrogen atmosphere, and the mixture was maintained at 0 캜. Then, methyldichlorophosphite 1.50 g (11.28 mmol) was diluted in 10 ml of dichloromethane, slowly added dropwise, and then stirred at room temperature for 1 hour. The reaction product was 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, and the obtained product was dissolved in 20 ml of dimethylacetamide and 3.0 g (4.60 mmol) of the compound d prepared in Step 1 of Example 4 was added thereto. The reaction was heated to 120 DEG C and refluxed and stirred for 12 hours. After pouring slowly into 50 ml of distilled water, the reaction was terminated and the product was extracted with 30 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 = 3: 2) to obtain Compound 4 (1.80 g, yield 48%).

^{1 H-NMR (δ ppm:} CDCl 3): 1.42-1.62 (4H, m), 1.70-1.89 (2H, m), 2.01-2.62 (18H, m), 3.78-3.98 (2H, m), 4.17- (1H, s), 4.91 (4H, s), 5.91-6.19 (4H, m), 7.04-7.70 (13H, m), 8.02-8.15

 (Example 6) Preparation of photoresist composition

10 g of an alkali-soluble binder resin as a copolymer of benzyl methacrylate / methacrylic acid (molar ratio 70/30, molecular weight 15,000 g / mol, acid value 100 KOH mg / g), a blue pigment dispersion (CI Pigment Blue 15: 6, 20 wt% in PGMEA ), 1 g of the xanthene dye (compound 1) prepared in Example 1, 1 g of the photopolymerization initiator OXE-01 (BASF, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -Imine), 10 g of pentaerythritol hexaacrylate, 0.1 g of 2-methacryloxypropyltrimethoxysilane, and 47.4 g of propylene glycol monomethyl ether acetate (PGMEA) as a solvent were sequentially mixed, and the mixture was stirred at room temperature for 3 hours Followed by stirring to prepare a photoresist composition. The photoresist composition thus prepared was measured for its performance such as sensitivity, chemical resistance and developability by the above-mentioned method, and the results are shown in Table 2 below.

(Example 7) Preparation of photoresist composition

A photoresist composition was prepared in the same manner as in Example 6 except that the xanthene dye (Compound 2) prepared in Example 2 was used in place of the xanthene dye (Compound 1) prepared in Example 1, The performance of the photoresist composition, such as sensitivity, chemical resistance, and developability, was measured by the above-described method, and the results are shown in Table 2 below.

(Example 8) Preparation of photoresist composition

A photoresist composition was prepared in the same manner as in Example 6 except that the xanthene dye (Compound 3) prepared in Example 3 was used in place of the xanthene dye (Compound 1) prepared in Example 1, The performance of the photoresist composition, such as sensitivity, chemical resistance, and developability, was measured by the above-described method, and the results are shown in Table 2 below.

 (Example 9) Preparation of photoresist composition

A photoresist composition was prepared in the same manner as in Example 6 except that the xanthene dye (Compound 4) prepared in Example 4 was used in place of the xanthene dye (Compound 1) prepared in Example 1, The performance of the photoresist composition, such as sensitivity, chemical resistance, and developability, was measured by the above-described method, and the results are shown in Table 2 below.

 (Example 10) Preparation of photoresist composition

A photoresist composition was prepared in the same manner as in Example 6, except that the xanthene dye (Compound 5) prepared in Example 5 was used in place of the xanthene dye (Compound 1) prepared in Example 1, The performance of the photoresist composition, such as sensitivity, chemical resistance, and developability, was measured by the above-described method, and the results are shown in Table 2 below.

(Comparative Example 1)

A photoresist composition was prepared in the same manner as in Example 6 except that the dye compound having the following structure was used in place of the xanthene dye (Compound 1) prepared in Example 1, The performance of the composition, such as sensitivity, chemical resistance and developability, was measured and the results are shown in Table 2 below.

The solubilities of the xanthene-based dye compounds prepared in Examples 1 to 5 and the dye compounds used in Comparative Example 1 were measured by the above-described methods and are shown in Table 1 below. When the solubility is 3 wt% or more, it is indicated by o, when 1 wt% or more is less than 3 wt%,? And when less than 1 wt% is indicated by X,

As shown in Tables 1 and 2, the xanthene dyes according to the present invention have remarkably improved solubility as compared with conventional dyes, and the resist films prepared using the dyes have excellent sensitivity, chemical resistance, and developability And it was found. That is, if a photoresist composition containing a xanthene dye compound according to the present invention is used, it is possible to provide a high-quality color filter, a black matrix, a colored column spacer, a colored organic insulating film, For example, a liquid crystal display, an organic EL device, an electronic paper, and the like) and a solid-state image pickup device.

Claims (11)

A xanthene dye compound represented by the following formula (1);
[Chemical Formula 1]

In formula (1)
R ₁ and R ₃ are each independently hydrogen, (C1-C30) alkyl, (C3-C30) cycloalkyl, (C3-C30) heterocycloalkyl, (C6-C30) aryl, (C3-C30) heteroaryl, (C1-C30) alkylamino, (C6-C30) arylamino and amino;
R ₂ is ^{_{* -CO 2 -, * -SO 4}} -, * -SO 3 - and -SO ₂ N ^- SO ₂ CF ₃ anions selected from monovalent and;
One of R ₄ and R ₅ is selected from (C 2 -C 30) alkenyl, (C 2 -C 30) alkenyloxy, (C 2 -C 30) alkynyl and (C 2 -C 30) alkynyloxy, (C3-C30) alkenyl, (C2-C30) alkenyloxy, (C2-C30) alkynyl, C30) heteroaryl and (C3-C30) heteroaryloxy, or R < ₄ > and R < ₅ > may be linked together to form a ring comprising an unsaturated group;
R < ₆ > is selected from (C6-C30) aryl and (C3-C30) heteroaryl;
L ₁ is a direct bond, (C ₁ -C 30) alkylene or (C 1 -C 30) heteroalkylene;
n is an integer selected from 1 to 3;
Wherein R ₁ and R ₃ an alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, alkylamino, and aryl and heteroaryl of said R ₆ and arylamino are each independently (C1-C30) alkyl and (C3-C30 Heteroaryl, heteroaryloxy and heteroalkylene are each independently selected from the group consisting of B, N, O, S, P (= O) , Si and < RTI ID = 0.0 > P. < / RTI > The method according to claim 1,
A xanthene dye compound represented by the following formula (2);
(2)

In formula (2)
Wherein R ₁₁ and R ₁₂ are each independently selected from hydrogen, (C 1 -C 20) alkyl and (C 6 -C 20) aryl, wherein said alkyl and aryl are each independently selected from the group consisting of (C 1 -C 20) alkyl and (C 3 -C 20) ≪ RTI ID = 0.0 > and / or < / RTI >
Wherein R ₁₆ is selected from (C 6 -C 30) aryl and (C 3 -C 30) heteroaryl, wherein said aryl and heteroaryl are each independently selected from the group consisting of (C 1 -C 20) alkyl and (C 3 -C 20) Which may be further substituted by one or more;
R ₁₃ is ^{_{* -CO 2 -, * -SO 4}} -, * -SO 3 - or -SO ₂ N ^- SO ₂ CF ₃ and;
R ₁₄ and R ₁₅ is selected from (C 2 -C 20) alkenyl, (C 2 -C 20) alkenyloxy, (C 2 -C 20) alkynyl and (C 2 -C 20) alkynyloxy, (C2-C20) alkenyl, (C2-C20) alkenyloxy, (C2-C20) alkynyl, C20) or selected from heteroaryl and (C3-C20) heteroaryloxy, wherein R ₁₄ and R ₁₅ are connected to each other to form a ring containing an unsaturated group, and;
L ₂ is a direct bond, (C 1 -C 20) alkylene or (C 1 -C 20) heteroalkylene. The method according to claim 1,
A xanthene dye compound represented by the following formula (3);
(3)

In formula (3)
R ₁₆ is a least one selected from (C6-C20) aryl and (C3-C20) is selected from heteroaryl, and the aryl and heteroaryl (C1-C20) alkyl and (C3-C20) cycloalkyl group consisting of alkyl Further substituted;
R ₁₃ is ^{_{* -CO 2 -, * -SO 4}} -, * -SO 3 - or -SO ₂ N ^- SO ₂ CF ₃ and;
R ₁₄ and R ₁₅ is selected from (C 2 -C 20) alkenyl, (C 2 -C 20) alkenyloxy, (C 2 -C 20) alkynyl and (C 2 -C 20) alkynyloxy, (C2-C20) alkenyl, (C2-C20) alkenyloxy, (C2-C20) alkynyl, C20) or selected from heteroaryl and (C3-C20) heteroaryloxy, wherein R ₁₄ and R ₁₅ are connected to each other to form a ring containing an unsaturated group, and;
L ₂ is a direct bond, (C 1 -C 20) alkylene or (C 1 -C 20) heteroalkylene. The method according to claim 2 or 3,
Wherein L ₂ is a direct bond, (C1-C7) alkylene or (C1-C7) heteroalkylene. delete The method according to claim 1,
A xanthene dye compound selected from the following structures.

A photoresist composition containing the xanthene-based dye compound according to claim 1. 8. The method of claim 7,
Wherein the photoresist composition further comprises at least one selected from a binder resin, a photopolymerizable compound, a photopolymerization initiator, a solvent and a colorant. 9. The method according to claim 7 or 8,
Wherein the photoresist composition further comprises at least one selected from a photosensitizer containing a thiol group and a silyl group. A color filter comprising the photoresist composition according to claim 7. A black matrix comprising the photoresist composition according to claim 7.