KR101767079B1 - Black photosensitive resin composition and black matrix using the same - Google Patents

Abstract

(상기 화학식 14에서, 각 치환기는 명세서에 정의된 바와 같다.)(A) a cadmium-based binder resin; (B) a pigment dispersion containing silver and having a particle diameter of 100 nm or less; (C) a photopolymerization initiator; (D) a photopolymerizable monomer; And (E) a solvent, wherein the photopolymerization initiator comprises a compound represented by the following formula (14), a light-shielding layer using the same, and a color filter.
[Chemical Formula 14]

(In the above formula (14), each substituent is as defined in the specification.)

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a black photosensitive resin composition and a light-

The present invention relates to a black photosensitive resin composition, a light-shielding layer using the same, and a color filter.

The black photosensitive resin composition is an indispensable material for the production of display elements such as color filters, liquid crystal display materials, organic light emitting devices (EL) and display panel materials. For example, a color filter such as a color liquid crystal display requires a light shielding layer at a boundary portion between coloring layers such as red, green, and blue in order to enhance display contrast and coloring effect, The light-shielding layer is mainly formed of a black photosensitive resin composition.

Known patents related to the light-shielding layer material are well known. In Japanese Laid-Open Patent Application No. 2002-047423, cobalt oxide is applied as a black pigment in order to realize a black matrix having high black color and insulating properties. Further, in Japanese Laid-Open Patent Application No. 2007-071994, a black matrix material using a perylene compound is used.

In recent years, development trends of black matrix materials have progressed in the direction of decreasing the film thickness of black matrix by maximizing the optical density (OD). This is because the black matrix has a high film thickness, So as to secure the dropping margin of the liquid crystal.

Accordingly, studies on a light-shielding layer material capable of improving resolution through efficient patterning while increasing the optical density as much as possible have been continued.

One embodiment is to provide a black photosensitive resin composition having high optical density and excellent resolution.

Another embodiment is to provide a light-shielding layer made using the black photosensitive resin composition.

Another embodiment is to provide a color filter including the light shielding layer.

One embodiment includes (A) a cationic binder resin; (B) a pigment dispersion liquid containing a metal fine particle pigment having a particle diameter of 100 nm or less containing silver; (C) a photopolymerization initiator; (D) a photopolymerizable monomer; And (E) a solvent, wherein the photopolymerization initiator comprises a compound represented by the following formula (14).

[Chemical Formula 14]

(In the above formula (14)

R ¹ , R ³ , R ⁴ , R ⁶ and R ⁷ are each independently a hydrogen atom, a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 2 to C 20 alkenyl group, a substituted or unsubstituted C 2 to C 20 A substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C3 to C20 cycloalkynyl group, or A substituted or unsubstituted C6 to C30 aryl group,

R ² and R ⁵ are each independently -ROR '(wherein R is a substituted or unsubstituted C1 to C20 alkylene group and R' is a substituted or unsubstituted C1 to C20 alkyl group)

R ⁸ is a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C3 to C20 cycloalkynyl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, A substituted or unsubstituted C2 to C20 heterocycloalkenyl group, a substituted or unsubstituted C2 to C20 heterocycloalkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group ,

n ¹ and n ³ are each independently an integer of 0 to 3 and n ² is an integer of 0 to 4.)

The photopolymerization initiator may be at least one selected from the compounds represented by the following general formulas (15) to (18).

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

The metal fine particle pigment may further contain tin.

The weight ratio of silver to tin in the metal microparticle pigment may be from 6: 4 to 8: 2.

The pigment dispersion may further comprise carbon black.

The cadmium-based binder resin may include a compound represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

X ¹ and X ² each independently represents a single bond, a substituted or unsubstituted C1 to C10 alkylene group, -O-, -CO-, -COO-, -SO ₂ -, and a linking group represented by the following formulas , And one of the groups selected from the group consisting of

Y is an acid anhydride residue,

Z ¹ and Z ² are each independently an acid anhydride residue,

a1 to a8 each independently represent an integer of 0 to 10,

n is an integer of 0 to 20, m is an integer of 0 or 1, and n + m? 1.

[Chemical Formula 2] < EMI ID =

　　　　

　　　 　

　　　　

　　　 　

[Chemical Formula 5] < EMI ID =

　　　　　　 　

　　　　

　　　　　　 　

　　　　

[Chemical Formula 8]

　　　　　　　　　　

　　　　　 　

　

　　　　　　　　　　

　　　　　 　

[Chemical Formula 12] [Chemical Formula 13]

　　　　　　 　

　　　　　 　　

　

　　　　　　 　

　　　　　 　　

In Formula 6,

R _f is a hydrogen atom, an ethyl group, -C ₂ H ₄ Cl, -C ₂ H ₄ OH, -CH ₂ CH = CH ₂ , or a phenyl group.

Wherein the black photosensitive resin composition comprises (A) 5 to 50% by weight of the cationic binder resin; (B) 1 to 90% by weight of the pigment dispersion; (C) 0.1 to 10% by weight of the photopolymerization initiator; (D) 1 to 20% by weight of the photopolymerizable monomer; And (E) the solvent balance.

Another embodiment provides a light-shielding layer made using the black photosensitive resin composition.

The light-shielding layer may have an optical density of 5.3 or more at a film thickness of 1 mu m.

Another embodiment provides a color filter comprising the light shielding layer.

The details of other embodiments are included in the detailed description below.

Since a black photosensitive resin composition having high optical density and excellent resolution is provided, it can be effectively applied to a light-shielding layer used for a color filter or the like.

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

Unless otherwise specified herein, "substituted" means that at least one hydrogen atom is replaced by a halogen atom (F, Cl, Br, I), a hydroxy group, a C1 to C20 alkoxy group, a nitro group, a cyano group, A thio group, an ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, an amidino group, a hydrazino group, a hydrazino group, a carbonyl group, a carbamyl group, A cycloalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkenyl group having 3 to 20 carbon atoms, a cycloalkynyl group having 3 to 20 carbon atoms, Substituted with a substituent of a C2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkenyl group, a C2 to C20 heterocycloalkynyl group, a C3 to C30 heteroaryl group, or a combination thereof.

Also, unless otherwise specified herein, "hetero" means that at least one heteroatom of N, O, S, and P is included in the formula.

&Quot; (Meth) acrylic acid "refers to both" acrylic acid "and" methacrylic acid " "It means both are possible.

&Quot; Combination " as used herein, unless otherwise specified, means mixing or copolymerization.

Unless otherwise defined in the chemical formulas in this specification, when no chemical bond is drawn at the position where the chemical bond should be drawn, it means that the hydrogen atom is bonded at the above position.

In the chemical formulas described herein, " * " means the same or different atom or moiety connected to the chemical formula.

The black photosensitive resin composition according to one embodiment comprises (A) a carcass binder resin; (B) a pigment dispersion liquid containing a metal fine particle pigment having a particle diameter of 100 nm or less containing silver; (C) a photopolymerization initiator; (D) a photopolymerizable monomer; And (E) a solvent.

Since the black photosensitive resin composition contains a pigment dispersion liquid containing a metal fine particle pigment having a particle diameter of 100 nm or less containing silver, it is possible to manufacture a light shielding layer having a high optical density and a high resolution by improving blackness and light shielding property Do.

Each component will be described in detail below.

(B) Pigment dispersion

The black photosensitive resin composition according to one embodiment includes a pigment dispersion containing a metal fine particle pigment, wherein the metal fine particle pigment contains silver and has a particle diameter of 100 nm or less. The metal microparticulate pigment may have a particle size of, for example, 1 nm to 100 nm, for example, 3 nm to 95 nm, for example, 5 nm to 90 nm. When the particle size of the metal fine particle pigment is within the above range, it is possible to prevent the generation of fine impurities which may occur in the substrate during the process for forming a pattern.

The metal fine particle pigment may further contain tin. For example, the pigment may comprise a silver-tin alloy.

When the metal microparticle pigment comprises a silver-tin alloy, silver and tin may be included in a weight ratio of 6: 4 to 8: 2, such as 7: 3 to 7.5: 2.5. When the weight ratio of silver and tin is within the above range, a high optical density of 5.3 or more can be obtained, the light shielding property is excellent, the appropriate conductivity is obtained, and the dielectric constant is easily controlled.

The silver-tin alloy may be coated with a surface treated to be an insulating film, and the coating may be performed with a silica-based compound. The coated silver-tin alloy can be easily dispersed in a solvent and a high optical density of the light-shielding layer can be obtained.

The pigment dispersion may further comprise carbon black.

For example, the pigment dispersion may contain a metal microparticle pigment containing silver, or may contain a metallic microparticle pigment containing a silver-tin alloy, or may include a metallic microparticle pigment containing silver and carbon black, or a silver- And a carbon black.

When the pigment dispersion contains carbon black, the weight ratio of the carbon black to the metal fine particle pigment containing silver-tin alloy may be in the range of 1: 9 to 9: 1, such as 1: 1 to 1: 8. When a metal fine particle pigment containing carbon black and a silver-tin alloy is included in the above weight ratio, a high optical density can be obtained, and excellent processability such as patternability and resolution is excellent.

If desired, the pigment dispersion may further comprise the metallic microparticle pigment and additional inorganic pigments other than carbon black, organic pigments, or combinations thereof. Among these, an organic pigment and an additional inorganic pigment can be mixed and used for realizing a high optical density.

For example, the organic pigment may be a black organic pigment. The black organic pigment is insulating.

Examples of the black organic pigments include perylene black and cyanine black. These pigments can be used singly or in combination of two or more kinds.

The black organic pigment may be a mixture of two or more kinds of organic pigments and a black color. Any pigment can be used as long as it is a combination of pigments having a black color upon mixing in a color coordinate system. For example, any pigment can be used as long as it is a mixture of red pigment, blue pigment, And two or more kinds of pigments may be combined and blackened. For example, a red pigment, a blue pigment and a green pigment may be mixed and blackened, or a green pigment and a magenta pigment may be mixed and blackened.

Examples of the red pigments include perylene pigments, anthraquinone pigments, dianthraquinone pigments, azo pigments, diazo pigments, quinacridone pigments, and anthracene pigments. have. Specific examples of the red pigments include perylene pigments, quinacridone pigments, naphthol AS, siccone pigments, anthraquinone (sudan I, II, III, R), dianthraquinonyl, Vis azo, benzopyrrole, and the like.

Examples of the blue pigments include metal phthalocyanine pigments, indanthrone pigments, indophenol pigments, and the like. Specific examples of the blue pigments include phthalocyanine metal complexes such as copper phthalocyanine, chloroglyphthalocyanine, chloraluminophthalocyanine, titanyl phthalocyanine, vanadinic acid phthalocyanine, magnesium phthalocyanine, zinc phthalocyanine and cobalt phthalocyanine.

Examples of the green pigments include halogenated phthalocyanine pigments and the like. Examples thereof include polychloro-copper phthalocyanine and polychlorobromophthalocyanine.

Examples of the magenta-colored pigment include dioxazine violet, first violet B, methyl violet lake, and indanthrene brilliant violet.

Examples of the yellow pigments include tetrachloroisoindolinone pigments, hansa pigments, benzidine yellow pigments, and azo pigments. Examples of the yellow pigments include tetrachloroisoindolinone pigments, hansa pigments, benzidine yellow pigments, and azo pigments. For example, hansa yellow (10G, 5G, 3G, G, GR, A, RN, R), benzidine (G, GR), chrome yellow, permanent yellow FGL, H10G, HR).

Examples of the cyanine pigment include metal-free phthalocyanine, merocyanine, and the like.

Examples of the magenta pigment include dimethyl quinacridone, thioindigo, and the like.

Examples of the additional inorganic pigment include chromium oxide, iron oxide, titanium black, titanium carbon and the like. These inorganic pigments exhibit resistance characteristics and can be used alone or in combination of two or more.

The organic pigment and the inorganic pigment may be used in a weight ratio of 1 to 10: 1, for example, 2 to 7: 1. When mixed in the weight ratio range, the processability is stabilized and a low dielectric constant can be secured.

The pigment dispersion may be prepared by mixing the metal fine particle pigment with carbon black or an additional pigment with a dispersant, a solvent or the like and use it in the black photosensitive resin composition. For example, a pigment dispersion may be prepared by mixing a metal fine particle pigment containing the silver-tin alloy and, if necessary, a further organic pigment or an inorganic pigment, etc. with a dispersant, a solvent and the like. Or a first pigment dispersion prepared by mixing a metal fine particle pigment containing the silver-tin alloy with a dispersant, a solvent and the like, and a second pigment dispersion prepared by mixing the carbon black and the additional pigments, a dispersant, After mixing the second pigment dispersions, the mixture of the dispersions may be used in the black photosensitive resin composition. Alternatively, a pigment dispersion liquid prepared by simultaneously mixing a metal fine particle pigment containing the silver-tin alloy and carbon black, a dispersant, and a solvent may be used in the black photosensitive resin composition.

The dispersant may help disperse the pigments uniformly in the solvent.

Examples of the dispersing agent include a nonionic compound, an anionic compound, a cationic compound or a combination thereof. Specific examples thereof include polyalkylene glycols and esters thereof, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adducts, An alcohol alkylene oxide adduct, a sulfonic acid ester, a sulfonic acid salt, a carboxylic acid ester, a carboxylate, an alkylamide alkylene oxide adduct, and an alkylamine.

DISPERBYK-161, DISPERBYK-160, DISPERBYK-161, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-160 and DISPERBYK-160 of BYK Co., -166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001 and the like; EFKA-47, EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400 and EFKA-450 of EFKA Chemical Co., Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000 from Zeneka; Or PB711 and PB821 from Ajinomoto.

The dispersant may be contained in an amount of 0.1 to 15% by weight based on the total weight of the black photosensitive resin composition. When the dispersing agent is contained within the above range, the dispersibility of the black photosensitive resin composition is excellent, and thus the stability, developability and patterning property of the light-shielding layer are excellent.

The solvent is as described below.

The pigment dispersion may be contained in an amount of 1 to 90% by weight, for example 5 to 90% by weight, based on the total weight of the black photosensitive resin composition. When the pigment dispersion is contained within the above range, it has excellent insulating properties in the production of a light-shielding layer, has high optical density, and is excellent in developability and processability.

(C) Light curing Initiator

The photopolymerization initiator is contained in the black photosensitive resin composition to form a radical at the time of exposure in the pattern formation step so that photopolymerization occurs.

The photopolymerization initiator may include a compound represented by the following general formula (14). When the compound represented by the following formula (14) is used as a photopolymerization initiator, the sensitivity to ultraviolet rays can be broadened and more ultraviolet rays can be used.

[Chemical Formula 14]

In Formula 14, R ¹ , R ³ , R ⁴ , R ^6, and R ⁷ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, A substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C3 to C20 cyclo An alkynyl group, or a substituted or unsubstituted C6 to C30 aryl group.

In Formula 14, R ² and R ⁵ are each independently -ROR '(wherein R is a substituted or unsubstituted C1 to C20 alkylene group and R' is a substituted or unsubstituted C1 to C20 alkyl group). For example, R may be a substituted or unsubstituted C1 to C10 alkylene group, and R 'may be a substituted or unsubstituted C1 to C10 alkyl group.

Wherein R ⁸ is a substituted or unsubstituted C 3 to C 20 cycloalkyl group, a substituted or unsubstituted C 3 to C 20 cycloalkenyl group, a substituted or unsubstituted C 3 to C 20 cycloalkynyl group, a substituted or unsubstituted C 2 to C 20 cycloalkenyl group, A substituted or unsubstituted C2 to C20 heterocycloalkenyl group, a substituted or unsubstituted C2 to C20 heterocycloalkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group, Or a heteroaryl group.

For example, in Formula 14, R ⁸ is a substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C2 to C20 heterocycloalkenyl group, a substituted or unsubstituted C2 to C20 heterocycloalkynyl group, A substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group.

In Formula 14, n ¹ and n ³ each independently may be an integer of 0 to 3, and n ² may be an integer of 0 to 4.

The photopolymerization initiator may be at least one selected from compounds represented by the following general formulas (15) to (18).

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

In addition to the photopolymerization initiator, an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, a triazine-based compound, or a combination thereof may also be used as a photopolymerization initiator.

Examples of the acetophenone-based compound include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropanone, p-butyldichloroacetophenone, 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one.

Examples of the benzophenone compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis (dimethylamino) benzophenone, '-Bis (diethylamino) benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 3,3'-dimethyl-2-methoxybenzophenone.

Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2- Chlorothioxanthone and the like.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal.

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) Bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) Bis (trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho 1-yl) -4,6 Bis (trichloromethyl) -s-triazine, 2,4- bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphtho- 6-piperonyl-s-triazine, 2,4-bis (trichloromethyl) -6- (4'-methoxystyryl) -s-triazine and the like.

Further, carbazole-based compounds, diketone-based compounds, sulfonium borate-based compounds, diazo-based compounds, and imidazole-based compounds can also be used as a photopolymerization initiator.

These photopolymerization initiators may be used alone or in combination of two or more.

The photopolymerization initiator may be used in combination with a photosensitizer that generates a chemical reaction by absorbing light to be in an excited state and transferring its energy .

The photopolymerization initiator may be contained in an amount of 1 to 40 parts by mass based on 100 parts by mass of the total amount of the photopolymerizable monomer and the photopolymerization initiator described later.

The photopolymerization initiator may be included in an amount of 0.1 to 10% by weight, for example, 0.5 to 7% by weight based on the total amount of the black photosensitive resin composition. When the photopolymerization initiator is contained within the above range, photopolymerization sufficiently occurs upon exposure in the pattern formation step, and the decrease of the transmittance due to the unreacted initiator can be prevented.

(A) Carometer  Binder resin

As a cadmium-based binder resin, a compound represented by the following formula (1) may be used.

[Chemical Formula 1]

In Formula 1, X ¹ and X ² each independently represents a single bond, a substituted or unsubstituted C1 to C10 alkylene group, -O-, -CO-, -COO-, -SO ₂ - , And a linking group represented by the following formula (13).

[Chemical Formula 2] < EMI ID =

　　　　

　　　 　

　　　　

　　　 　

[Chemical Formula 5] < EMI ID =

　　　　　　 　

　　　　

　　　　　　 　

　　　　

[Chemical Formula 8]

　　　　　　　　　　

　　　　　 　

　

　　　　　　　　　　

　　　　　 　

[Chemical Formula 12] [Chemical Formula 13]

　　　　　 　　

　　　　　 　　

　　　　　 　　

　　　　　 　　

In Formula 6, R _f may be a hydrogen atom, an ethyl group, -C ₂ H ₄ Cl, -C ₂ H ₄ OH, -CH ₂ CH = CH ₂ , or a phenyl group.

When the cation resin is used, the heat resistance, chemical resistance and adhesion of the photosensitive resin composition can be improved.

In Formula 1, Y may be an acid dianhydride residue.

In Formula 1, Z ¹ and Z ² may each independently be an anhydride residue.

In Formula 1, a1 to a8 may each independently be an integer of 0 to 10.

In Formula 1, n may be an integer of 0 to 20, for example, an integer of 4 to 7, and m may be an integer of 0 or 1, where n + m? 1. When m or n is 0, the formula (1) has no form of one of the repeating units represented by m or n, and the cross-linking between the repeating units represented by m and n may be a hydrolyzed form have. That is, when m is 0, the compound of Formula 1 may be represented by Formula 1-1 and when n is 0, the compound of Formula 1 may be represented by Formula 1-2.

[Formula 1-1]

[Formula 1-2]

X ¹ , X ² , Y, Z ¹ , Z ² , a ¹ to a8 and n are as defined in the above formula (1).

The weight average molecular weight of the cation resin as measured by gel permeation chromatography (GPC) may be from 1,000 to 15,000 g / mol, and specifically from 1,500 to 7,000 g / mol. When the weight average molecular weight of the cadene resin is within the above range, excellent patterning property and developability can be obtained in the production of the light-shielding layer.

The cationic binder resin may be used together with an acrylic binder resin.

The acrylic binder resin may contain a first ethylenic unsaturated monomer 　 And a second ethylenically unsaturated monomer copolymerizable therewith, and is a resin comprising at least one acrylic repeating unit.

The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least one carboxyl group, and specific examples thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or a combination thereof.

The first ethylenically unsaturated monomer may be contained in an amount of 5 to 50% by weight, for example, 10 to 40% by weight based on the total amount of the acrylic resin.

The second ethylenically unsaturated monomer may be an aromatic vinyl compound such as styrene,? -Methylstyrene, vinyltoluene, or vinylbenzyl methyl ether; (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, Unsaturated carboxylic acid ester compounds such as cyclohexyl (meth) acrylate and phenyl (meth) acrylate; Unsaturated carboxylic acid aminoalkyl ester compounds such as 2-aminoethyl (meth) acrylate and 2-dimethylaminoethyl (meth) acrylate; Carboxylic acid vinyl ester compounds such as vinyl acetate and vinyl benzoate; Unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth) acrylate; A vinyl cyanide compound such as (meth) acrylonitrile; Unsaturated amide compounds such as (meth) acrylamide; These may be used singly or in combination of two or more.

Specific examples of the acrylic binder resin include methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymer Methacrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, but are not limited thereto, and they may be used alone or in combination of two or more.

The weight average molecular weight of the acrylic binder resin may be 3,000 to 150,000 g / mol, specifically 5,000 to 50,000 g / mol, and more specifically 2,000 to 30,000 g / mol. 　　 When the weight average molecular weight of the acrylic binder resin is within the above range, the black photosensitive resin composition is excellent in physical and chemical properties, has an appropriate viscosity, and is excellent in adhesion to a substrate when the light-shielding layer is produced.

The acid value of the solid content of the acrylic binder resin may be 50 to 150 mgKOH / g, and more specifically 70 to 120 mgKOH / g. When the acid value of the acrylic binder resin is within the above range, the resolution of the pixel pattern is excellent.

The binder resin may be contained in an amount of 5 to 50% by weight, for example, 5 to 30% by weight based on the total amount of the black photosensitive resin composition. When the binder resin is contained within the above range, the viscosity is appropriately maintained, and the patterning property, the processability, and the developing property are excellent when the light-shielding layer is produced.

(D) Photopolymerization  Monomer

The photopolymerizable monomer is a compound which undergoes photopolymerization by the photopolymerization initiator described above.

The photopolymerizable monomer may be a monofunctional or polyfunctional ester of (meth) acrylic acid having at least one ethylenically unsaturated double bond. The photopolymerizable monomer is a compound having two or more ethylenically unsaturated double bonds, and may have an acryloyl group or a methacryloyl group.

Since the photopolymerizable monomer has the ethylenically unsaturated double bond, sufficient polymerization is caused during exposure in the pattern formation step, whereby a pattern having excellent heat resistance, light resistance and chemical resistance can be formed.

Examples of the photopolymerizable monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A di (meth) acrylate, pentaerythritol di (meth) acrylate, (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol monomethyl (Meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, novolak epoxy (meth) acrylate, and caroepoxy diacrylate.

A commercially available product of the photopolymerizable monomer is exemplified as follows. The (meth) acrylic acid is one example of a polyfunctional ester, such as doah Gosei Kagaku Kogyo's (primary)社Aronix M-101 ^®, the same M-111 ^®, the same M-114 ^®; KAYARAD TC-110S ^® and TC-120S ^{® from} Nihon Kayaku Co., Ltd.; Osaka yukki the like Kagaku Kogyo (main)社of ^{V-158 ®, V-2311} ®. The (meth) transfer function of an example esters of acrylic acid are, doah Gosei Kagaku Kogyo (Note)社of Aronix M-210 ^®, copper or the like M-240 ^®, the same M-6200 ^®; KAYARAD HDDA ^® , HX-220 ^® and R-604 ^{® from} Nihon Kayaku Corporation; Osaka yukki the like Kagaku Kogyo Co., Ltd. of ^{社V-260 ®, V-} 312 ®, V-335 HP ®. Examples of the tri-functional ester of (meth) acrylic acid, doah Gosei Kagaku Kogyo (Note)社of Aronix M-309 ^®, the same M-400 ^®, the same M-405 ^®, the same M-450 ^®, Dong M -7100 ^® , copper M-8030 ^® , copper M-8060 ^® and the like; Nippon Kayaku (Note)社of KAYARAD TMPTA ^®, copper DPCA-20 ^{®, ®} copper -30, -60 ^® copper, copper ^® -120 and the like; Osaka yukki Kayaku high (primary)社of V-295 ^®, copper ^® -300, -360 ^® copper, copper -GPT ^®, copper -3PA ^®, and the like copper -400 ^®. These products may be used alone or in combination of two or more.

The photopolymerizable monomer may be treated with an acid anhydride to give better developing properties.

The photopolymerizable monomer may be contained in an amount of 1 to 20% by weight, for example, 1 to 15% by weight based on the total amount of the black photosensitive resin composition. When the photopolymerizable monomer is contained within the above range, the photopolymerizable monomer sufficiently cures upon exposure in the pattern formation step, is excellent in sensitivity in the presence of oxygen, and is excellent in compatibility with the binder resin.

(E) Solvent

The solvent may be a material that is compatible with the binder resin, the pigment dispersion, the photopolymerization initiator, and the photopolymerizable monomer but does not react.

Examples of the solvent include alcohols such as methanol and ethanol; Ethers such as dichloroethyl ether, n-butyl ether, diisobutyl ether, methylphenyl ether and tetrahydrofuran; Glycol ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether and propylene glycol methyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate and diethyl cellosolve acetate; Carbitols such as methylethylcarbitol, diethylcarbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl- ; Saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate and isobutyl acetate; Lactic acid alkyl esters such as methyl lactate and ethyl lactate; Hydroxyacetic acid alkyl esters such as methylhydroxyacetate, ethylhydroxyacetate and butylhydroxyacetate; Alkoxyalkyl esters such as methoxy methyl acetate, methoxy ethyl acetate, methoxy butyl acetate, ethoxy methyl acetate, and ethoxy ethyl acetate; 3-hydroxypropionic acid alkyl esters such as methyl 3-hydroxypropionate and ethyl 3-hydroxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate; 2-hydroxypropionic acid alkyl esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate and propyl 2-hydroxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate and methyl 2-ethoxypropionate; 2-hydroxy-2-methylpropionic acid alkyl esters such as methyl 2-hydroxy-2-methylpropionate and ethyl 2-hydroxy-2-methylpropionate; 2-alkoxy-2-methylpropionic acid alkyl esters such as methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate; Esters such as 2-hydroxyethyl propionate, 2-hydroxy-2-methyl ethyl propionate, hydroxy ethyl acetate and methyl 2-hydroxy-3-methyl butanoate; Or ethyl pyruvate. Examples of the ketone acid esters include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide Benzyl alcohol, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, Ethyl benzoate, diethyl oxalate, diethyl maleate,? -Butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc. These may be used alone or in combination of two or more.

In view of the miscibility and reactivity of the solvent, glycol ethers such as ethylene glycol monoethyl ether and the like; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as 2-hydroxyethyl propionate; Diethylene glycol such as diethylene glycol monomethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate can be used.

The solvent may be contained in a residual amount, for example, 40 to 90% by weight based on the total solid content of the black photosensitive resin composition. When the solvent is contained within the above range, the black photosensitive resin composition has an appropriate viscosity, so that the processability of the light-shielding layer is excellent.

(F) Other additives

The black photosensitive resin composition may contain at least one selected from the group consisting of malonic acid, malonic acid, and malonic acid to prevent spots or spots upon application, improve leveling performance, 3-amino-1,2-propanediol; A silane-based coupling agent comprising a vinyl group or (meth) acryloxy group; Leveling agents; Fluorine surfactants; And other additives such as a radical polymerization initiator.

Examples of the silane coupling agent include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatopropyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane, and? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane. These may be used singly or in combination of two or more.

Examples of the fluorine-based surfactant, BM Chemie Corporation ^{BM-1000 ®, BM-1100} ® , and the like; Mecha Pack F 142D ^® , Copper F 172 ^® , Copper F 173 ^® , Copper F 183 ^® and the like manufactured by Dainippon Ink & Chemicals Incorporated; M. Sumitomo Co., Inc. Pro rod FC-135 ^®, the same FC-170C ^®, copper FC-430 ^®, the same FC-431 ^®, and the like; Asahi Grass Co., Inc. Saffron S-112 ^®, the same S-113 ^®, the same S-131 ^®, the same S-141 ^®, the same S-145 ^®, and the like; Toray Silicone Co., Ltd.'s SH-28PA ^{®, ®} -190 copper, may be a commercially available product such as copper ^{-193 ®, SZ-6032 ®,} SF-8428 ®.

The content of the additive can be easily adjusted according to desired properties.

The black photosensitive resin composition may further include an epoxy compound to improve adhesion with the substrate.

Examples of the epoxy compound include a phenol novolak epoxy compound, a tetramethylbiphenyl epoxy compound, a bisphenol A type epoxy compound, an alicyclic epoxy compound, or a combination thereof.

The epoxy compound may be included in an amount of about 0.01 to 5 parts by weight based on 100 parts by weight of the black photosensitive resin composition, and specifically about 0.1 to 5 parts by weight. When the epoxy compound is contained within the above range, the adhesive property, heat resistance, and chemical resistance are excellent.

Another embodiment provides a light-shielding layer made using the above-mentioned black photosensitive resin composition.

The method of manufacturing the light-shielding layer is as follows.

(1) Coating and Film Formation Step

The above-mentioned photosensitive resin composition is coated on a predetermined pretreated substrate by a spin, slit coat method, roll coating method, screen printing method, applicator method or the like to a desired thickness, for example, 0.5 to 25 탆 thickness, And the solvent is removed by heating at 110 DEG C for 1 minute to 10 minutes to form a coating film.

(2) Exposure step

In order to form a pattern necessary for the thus obtained coating film, a mask of a predetermined type is interposed, and then an active line of 190 nm to 500 nm is irradiated. As the light source used for the irradiation, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, an argon gas laser, or the like can be used.

The exposure dose varies depending on the kind of the photosensitive resin composition, the blending amount, and the dried film thickness, but in the case of using a high-pressure mercury lamp, the exposure dose is 500 mJ / cm ² or less (at 365 nm sensor).

(3) Development step

After the exposure step, an unnecessary portion is dissolved and removed by using an alkaline aqueous solution as a developer to leave an exposed portion to form an image pattern.

(4) Post-treatment step

The image pattern obtained by the above development can be cured by further heating or irradiation with actinic rays because it is possible to obtain an excellent pattern in terms of heat resistance, light resistance, adhesion, crack resistance, chemical resistance, high strength and storage stability .

By using the above-mentioned black photosensitive resin composition, excellent optical density and resolution required for the light-shielding layer can be obtained.

The light-shielding layer may have an optical density of 5.3 or more at a film thickness of 1 mu m.

Another embodiment provides a color filter including the light-shielding layer described above.

Hereinafter, preferred embodiments of the present invention will be described. However, the following examples are only a preferred embodiment of the present invention, and the present invention is not limited by the following examples.

( Light curing Initiator  Produce)

Manufacturing example  One

15 g of phenylcarbazole and 11.75 g of o-naphthoyl chloride were dissolved in 100 ml of dichloromethane, cooled to 2 캜 in ice bath, and 10.5 g of AlCl ₃ was added after stirring. After further stirring at room temperature for 3 hours, 16.8 g of 1-ethoxypropionyl chloride was added to 75 ml of dichloromethane solution, and 15 g of AlCl ₃ was added, followed by further stirring for 1 hour and 30 minutes. The reaction mixture was ice-cooled, 700 ml of dichloromethane was added, and the organic layer was separated. The recovered organic layer was dried with magnesium sulfate and evaporated to obtain 30 g of a white solid.

6.5 g of the white solid, 1.6 g of NH ₂ OH-HCl and 2 g of sodium acetate were mixed with 60 ml of isopropanol and refluxed for 3 hours. The whole was evaporated, and 120 ml of ethyl acetate was added thereto, followed by washing with 200 ml of saturated brine, drying with magnesium sulfate, and evaporation to obtain 6 g of a solid. This was purified by a carboxyl group column chromatography to obtain 4 g of crystals.

The crystals, 4 g of oxime and 4 g of acetyl chloride were dissolved in 80 g of dichloromethane and cooled. Then, 5.2 g of triethylamine was added, followed by reaction at room temperature for 4 hours. After confirming disappearance of the raw materials by thin layer chromatography, water was added, and 120 g of dichloromethane was added to separate the organic layer. It was then washed twice with aqueous NH ₄ Cl solution, three times with 5% Na ₂ CO ₃ solution, twice with saturated brine, dried over sodium sulfate and evaporated. The residue was purified by column of ethyl acetate / nucleic acid = 2/1 to obtain 1.5 g of yellow crystals, thereby preparing a compound represented by the following formula (15).

[Chemical Formula 15]

Manufacturing example  2

Compound No. 16 was prepared in the same manner as in Preparation Example 1 except that 2-thiophenylacetyl chloride was used in place of o-naphthoyl chloride in Preparation Example 1.

[Chemical Formula 16]

Manufacturing example  3

In the same manner as in Preparation Example 1 except that 9-carbazolylbenzoyl chloride was used in place of o-naphthoyl chloride in Production Example 1, a compound represented by the following Formula 17 was prepared.

[Chemical Formula 17]

Manufacturing example  4

Production Example 1 was repeated except that 9-carbazolylbenzoyl chloride was used in place of o-naphthoyl chloride and hexanoyl chloride was used in place of 1-ethoxypropionyl chloride. To prepare a compound represented by the following formula (18).

[Chemical Formula 18]

( Carometer  Binder resin)

Manufacturing example  5

462 g of bisphenol fluorene epoxy resin (epoxy equivalent 231 g / eq), 900 mg of triethylbenzylammonium chloride, 200 mg of 2,6-diisobutylphenyl and 144 g of acrylic acid were placed in a 1000 ml four-necked flask, and air Lt; RTI ID = 0.0 > 90 C < / RTI > Thereafter, the solution was gradually elevated to a cloudy state and heated to 120 DEG C to be completely dissolved. Thereafter, the acid value was measured and the heating and stirring were continued until it was less than 2.0 mgKOH / g. It took 8 hours until the acid value reached 0.8 mg KOH / g. Thereafter, the mixture was cooled to room temperature to obtain bisphenol fluorene epoxy acrylate which is colorless transparent and solid. After propylene glycol monomethyl ether acetate was dissolved in 152 g of the bisphenol fluorene epoxy acrylate, 19 g of 1,2,3,6-tetrahydrophthalic anhydride, 36.8 g of biphenyltetracarboxylic dianhydride and 36 g of bromotetraethyl Ammonium, and the mixture was slowly heated to react at 110 to 115 ° C for 2 hours to prepare a carcass binder resin represented by the following Chemical Formula 19.

[Chemical Formula 19]

(Wherein X ³ and X ⁴ are each a linking group represented by the following general formula (2), Y ¹ is a biphenyl group, Z ³ and Z ⁴ are each a linking group represented by the following general formula (20), m 1> 0 and n 1 > 0.)

The cation resin represented by the above formula (19) had a weight average molecular weight of 4300 g / mol as measured by GPC and a solid content of 100 mgKOH / g.

[Chemical Formula 2]

　　　　　　　

　

　　　　　　　

　

Manufacturing example  6

Production Example 5 was repeated except that benzophenonetetracarboxylic acid dianhydride was used in place of biphenyltetracarboxylic dianhydride to prepare a carcass binder resin represented by the following Chemical Formula 21 Respectively.

[Chemical Formula 21]

(Wherein, in the formula (21), X ⁵ and X ⁶ are each a linking group represented by the formula (2), Y ² is a benzophenone group, Z ⁵ and Z ⁶ are each a linking group represented by the formula (20) n2 > 0).

The cation binder resin represented by Formula 21 had a weight average molecular weight of 4,800 g / mol and a solid content of 110 mgKOH / g.

Manufacturing example  7

Was prepared in the same manner as in Production Example 5, except that 298 g of the biphenyl epoxy resin represented by the following formula (22) (epoxy equivalent: 149 g / eq) was used instead of 462 g of the bisphenol fluorene epoxy resin in Production Example 5, To produce a cardboard binder resin to be displayed.

[Chemical Formula 22]

(23)

(Wherein, in the formula (23), Y ³ is a biphenyl group, Z ⁷ and Z ⁸ are each a linking group represented by the formula (20) 　 m3 > 0 and n3 > 0).

The cation binder resin represented by the above formula (23) had a weight average molecular weight of 3,800 g / mol and a solid content of 110 mgKOH / g.

(Preparation of Pigment Dispersion)

Manufacturing example  8

Soluble colloids of silver and tin as metals were mixed at a ratio of 75:25, and the solvent was replaced with PGMEA by an evaporator. Then, Lurvisc K90 (BASF) was added as a dispersant, and dispersed with a bead type disperser NanoGren Mill (Asada Iron Works) And dispersed for about 4 hours using 0.2 mm beads until the dispersed particle diameter became 100 nm or less to prepare a pigment dispersion. The pigment dispersion was measured with a particle size analyzer FPAR-1000 (Otsuka Electronics Co., Ltd.), and the average particle diameter was 88 nm. The composition of the components used in the preparation of the pigment dispersion is shown in Table 1 below.

ingredient Composition (% by weight) The metal component (silver: tin = 75: 25) 15 Dispersant (LVISCOL K90) 1.5 Solvent (PGMEA) 83.5

(Preparation of Black Photosensitive Resin Composition)

The specifications of the components used in the production of the black photosensitive resin composition are as follows.

(A) Carometer  Binder resin

(A-1) A cadmium-based binder resin prepared in Production Example 5 was used.

(A-2) The cationic binder resin prepared in Production Example 6 was used.

(A-3) Cathode binder resin prepared in Production Example 7 was used.

(B) Pigment dispersion

(B-1) The pigment dispersion prepared in Production Example 8 was used.

(B-2) A carbon black dispersion of BK3877 (Tokushiki) was used.

(C) Light curing Initiator

(C-1) The compound prepared in Preparative Example 1 was used.

(C-2) The compound prepared in Production Example 2 was used.

(C-3) The compound prepared in Preparative Example 3 was used.

(C-4) The compound prepared in Production Example 4 was used.

(C-5) OXE02 from BASF was used.

(D) Photopolymerization  Monomer

Dipentaerythritol hexaacrylate (DPHA) was used.

(E) Solvent

Propylene glycol monomethyl ether acetate (PGMEA) was used.

(F) Other additives

300 ppm of a leveling agent (MCF-350SF, DIC) was used.

Example  1 to 6 and Comparative Example  1, 2

Each component was mixed with the composition shown in Table 2 below to prepare a black photosensitive resin composition. Specifically, the photopolymerization initiator was dissolved in the solvent, followed by sufficient stirring at room temperature for about 30 minutes. To this, a cationic binder resin and a photopolymerizable monomer were added and stirred for 1 hour. Thereafter, the pigment dispersion and other additives were added, and the entire composition was finally stirred for about 2 hours and filtered three times to remove impurities to prepare a black photosensitive resin composition.

(Unit: wt%) Example Comparative Example One 2 3 4 5 6 One 2 (A) Cathode binder resin (A-1) 7.2 (3.6) 7.2 (3.6) 7.2 (3.6) 7.2 (3.6) - - 7.2 (3.6) 7.2 (3.6) (A-2) - - - - 7.2 (3.6) - - - (A-3) - - - - - 7.2 (3.6) - - (B) Pigment dispersion (B-1) 86.6 (13) 86.6 (13) 86.6 (13) 65 (9.7) 86.6 (13) 86.6 (13) 86.6 (13) - (B-2) - - - 16.3 (3.3) - - - 65 (13) (C) a photopolymerization initiator (C-1) 1.0 - - - 1.0 1.0 - 1.0 (C-2) - 1.0 - - - - - - (C-3) - - 1.0 - - - - - (C-4) - - - 1.0 - - - - (C-5) - - - - - - 1.0 - (D) a photopolymerizable monomer DPHA 2.4 2.4 2.4 2.4 2.4 2.4 2.4 2.4 (E) Solvent PGMEA 2.8 2.8 2.8 8.1 2.8 2.8 2.8 24.4

(In Table 2, the numbers in parentheses indicate the solid content, and the sum of the solid content of each Example and Comparative Example is 20% by weight based on 100% by weight of the composition)

Evaluation 1: Optical density ( Optical Density , OD )

The black photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 and 2 were respectively coated on a cleaned glass substrate using a spin coater and dried on a hot plate at 90 DEG C for 2 minutes to obtain a solution 1.0 占 퐉 thick coating films were obtained, respectively. The optical density of each coating film was measured using a 310TR optical density meter (X-ray Co.). The results are shown in Table 3 below.

Rating 2: Resolution

In each of the coating films according to Examples 1 to 6 and Comparative Examples 1 and 2 obtained in Evaluation 1, a UV filter for blocking a wavelength of 350 nm or less was installed in a Proximity Exposure Meter manufactured by USHIO, and a matrix having an exposure dose of 40 mJ and a line width of 10 탆 As a mask pattern. A 0.04% KOH aqueous solution was stabilized at 23 캜 and spray-developed at a spray pressure of 1.0 kg / cm ² for 60 seconds to form a light-shielding layer pattern, and the pattern was observed for the minimum line width of the pattern using an optical microscope. The results are shown in Table 3 below.

Example Comparative Example One 2 3 4 5 6 One 2 Optical density 5.5 5.5 5.5 5.4 5.5 5.5 5.5 5.2 Resolution (탆) 5.0 5.0 5.0 5.5 6.0 6.0 11 20

It can be seen from Table 3 that Examples 1 to 6 using the pigment dispersion according to one embodiment and the photopolymerization initiator have high optical density and excellent resolution as compared with Comparative Examples 1 and 2.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (11)

(A) a cadmium-based binder resin;
(B) a pigment dispersion comprising a metal fine particle pigment having a particle diameter of 1 nm to 100 nm and containing silver;
(C) a photopolymerization initiator;
(D) a photopolymerizable monomer; And
(E) Solvent
Lt; / RTI >
Wherein the photopolymerization initiator is a black photosensitive resin composition comprising a compound represented by the following formula (14): < EMI ID =
[Chemical Formula 14]

(In the above formula (14)
R ¹ , R ³ , R ⁴ , R ⁶ and R ⁷ are each independently a hydrogen atom, a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 2 to C 20 alkenyl group, a substituted or unsubstituted C 2 to C 20 A substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C3 to C20 cycloalkynyl group, or A substituted or unsubstituted C6 to C30 aryl group,
R ² and R ⁵ are each independently -ROR '(wherein R is a substituted or unsubstituted C1 to C20 alkylene group and R' is a substituted or unsubstituted C1 to C20 alkyl group)
R ⁸ is a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C3 to C20 cycloalkynyl group, a substituted or unsubstituted C2 to C20 heterocycloalkyl group, A substituted or unsubstituted C2 to C20 heterocycloalkenyl group, a substituted or unsubstituted C2 to C20 heterocycloalkynyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group ,
n ¹ and n ³ are each independently an integer of 0 to 3 and n ² is an integer of 0 to 4.)
The method according to claim 1,
Wherein the cationic binder resin comprises a compound represented by the following formula (1): < EMI ID =
[Chemical Formula 1]

(In the formula 1,
X ¹ and X ² each independently represents a single bond, a substituted or unsubstituted C1 to C10 alkylene group, -O-, -CO-, -COO-, -SO ₂ -, and a linking group represented by the following formulas , And one of the groups selected from the group consisting of
Y is an acid anhydride residue,
Z ¹ and Z ² are each independently an acid anhydride residue,
a ¹ to a ⁸ each independently represents an integer of 0 to 10,
n is an integer of 0 to 20, m is an integer of 0 or 1, and n + m?
[Chemical Formula 2] < EMI ID =

[Chemical Formula 5] < EMI ID =

[Chemical Formula 8]

[Chemical Formula 12] [Chemical Formula 13]

(6)
R _f is a hydrogen atom, an ethyl group, -C ₂ H ₄ Cl, -C ₂ H ₄ OH, -CH ₂ CH = CH ₂ ,
The method according to claim 1,
Wherein R ⁸ is a substituted or unsubstituted C2 to C20 heterocycloalkyl group, a substituted or unsubstituted C2 to C20 heterocycloalkenyl group, a substituted or unsubstituted C2 to C20 heterocycloalkynyl group, a substituted or unsubstituted A C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group.
The method according to claim 1,
Wherein the photopolymerization initiator is at least one selected from compounds represented by the following general formulas (15) to (18).
[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

The method according to claim 1,
Wherein the metal fine particle pigment further comprises tin.
6. The method of claim 5,
Wherein silver and tin in said fine metal particle pigment are contained in a mass ratio of 6: 4 to 8: 2.
The method according to claim 1,
Wherein the pigment dispersion further comprises carbon black.
The method according to claim 1,
The black photosensitive resin composition
(A) 5 to 50% by weight of the cationic binder resin;
(B) 1 to 90% by weight of the pigment dispersion;
(C) 0.1 to 10% by weight of the photopolymerization initiator;
(D) 1 to 20% by weight of the photopolymerizable monomer; And
(E) the solvent remaining amount
Wherein the black photosensitive resin composition comprises:
A light-shielding layer produced by using the black photosensitive resin composition of any one of claims 1 to 8.
10. The method of claim 9,
Wherein the light-shielding layer has an optical density of 5.3 to 5.5 at a film thickness of 1 m.
A color filter comprising the light-shielding layer of claim 9.