KR101776264B1 - Photosensitive resin composition layer, black column spacer using the same, and color filter - Google Patents

Abstract

A first layer formed by coating a first composition on a substrate and then dried; and a second layer formed by applying and drying a second composition on the first layer, wherein the first composition comprises a binder resin, a reactive unsaturated compound, Wherein the second composition comprises a binder resin, a reactive unsaturated compound, a photopolymerization initiator, and a solvent, wherein the optical density per 1 μm of the first layer and the optical density of the first layer There is provided a photosensitive resin composition layer having an optical density difference of 0.4 or more per 1 mu m of the two layers, a black column spacer manufactured by exposing and developing the photosensitive resin composition layer, and a color filter including the black column spacer.

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition layer, a black column spacer using the same, and a color filter,

The present invention relates to a photosensitive resin composition layer, a black column spacer manufactured using the same, and a color filter including the black column spacer.

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

In recent years, efforts have been made to use the black matrix material as a column spacer supporting between two TFTs and a C / F substrate existing between the liquid crystal layers, and the column spacer is referred to as a black column spacer.

In order to realize the function of the black column spacer, basic characteristics such as compression displacement, elastic recovery rate and breaking strength are required, and steps of a black column spacer pattern must be realized by adjusting the exposure amount using a mask. Further, since the black column spacer is present on the uppermost layer, liquid crystal contamination problems may occur, so reliability and solvent resistance (chemical resistance to solvent) must be realized at the same time.

Therefore, studies for developing a photosensitive resin composition layer capable of realizing the above characteristics are continuing.

One embodiment is to provide a photosensitive resin composition layer excellent in developing margin and solvent resistance.

Another embodiment is to provide a black column spacer manufactured using the above photosensitive resin composition layer.

Another embodiment is to provide a color filter comprising the black column spacer.

One embodiment includes a first layer formed by applying a first composition on a substrate followed by drying, and a second layer formed by applying a second composition on the first layer and drying the first composition. The first composition includes a binder resin, a reactive unsaturated compound, Wherein the second composition comprises a binder resin, a reactive unsaturated compound, a photopolymerization initiator, and a solvent, wherein the optical density per 1 μm of the first layer and the optical density of the first layer And the optical density of the second layer differs by 0.4 or more per 1 mu m.

The optical density per 1 mu m of the first layer may be 0.4 or more larger than the optical density per 1 mu m of the second layer.

The second composition may further comprise a pigment dispersion comprising a pigment.

The pigment may comprise a black pigment.

The black pigment may include aniline black, perylene black, titanium black, cyanine black, lignin black, lactam-based organic black, RGB black, carbon black, or a combination thereof.

The binder resin may include a cadmium binder resin, an acrylic binder resin, or a combination thereof.

Wherein the first composition comprises 1 to 30% by weight of a binder resin, 1 to 20% by weight of a reactive unsaturated compound, 0.05 to 5% by weight of a photopolymerization initiator, 1 to 30% by weight of a pigment dispersion comprising a pigment, And solvent balance.

The second composition may comprise from 3 wt% to 70 wt% of the binder resin, from 2 wt% to 40 wt% of the reactive unsaturated compound, from 0.1 wt% to 5 wt% of the photopolymerization initiator, and the balance of the solvent.

The first composition and the second composition may each independently include an additive of malonic acid, 3-amino-1,2-propanediol, a silane coupling agent, a leveling agent, a fluorine surfactant, a radical polymerization initiator, .

Another embodiment provides a black column spacer prepared by exposing and developing the photosensitive resin composition layer.

Another embodiment provides a color filter comprising the black column spacer.

Other aspects of the present invention are included in the following detailed description.

There is provided a photosensitive resin composition layer excellent in developing margin and solvent resistance and further provided with a black column spacer prepared by exposing and developing the photosensitive resin composition layer and a color filter comprising the black column spacer.

1 is a scanning electron microscope (SEM) photograph of a black column spacer prepared by exposing and developing the photosensitive resin composition layer according to Example 1. Fig.
2 is a scanning electron microscope (SEM) photograph of a cross section of a black column spacer prepared by exposing and developing the photosensitive resin composition layer according to Example 1. Fig.
3 is a graph showing the developing margins of the black column spacer according to Example 1 and Comparative Example 2. FIG.

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, "alkyl group" means a C1 to C20 alkyl group, "alkenyl group" means a C2 to C20 alkenyl group, "cycloalkenyl group" means a C3 to C20 cycloalkenyl group Quot; means a C3 to C20 heterocycloalkenyl group, "an aryl group" means a C6 to C20 aryl group, an "arylalkyl group" means a C6 to C20 arylalkyl group, Refers to a C 1 to C 20 alkylene group, "arylene group" refers to a C6 to C20 arylene group, "alkylarylene group" refers to a C6 to C20 alkylarylene group, "heteroarylene group" refers to a C3 to C20 hetero Quot; means an arylene group, and the "alkoxysilylene group" means a C1 to C20 alkoxysilylene group.

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 C3 to C20 cycloalkenyl group, a C3 to C20 cycloalkynyl group, a C2 to C20 alkynyl group, a C6 to C20 aryl group, a C3 to C20 cycloalkyl group, a C3 to C20 cycloalkenyl group, 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 C20 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.

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

Unless otherwise specified herein, an unsaturated bond includes not only multiple bonds between carbon-carbon atoms but also other molecules such as carbonyl bonds, azo bonds, and the like.

As used herein, the cadmium resin means a resin in which at least one functional group selected from the group consisting of the following formulas (1-1) to (1-11) is contained in the main backbone of the resin.

Also, unless otherwise specified herein, "*" means the same or different atom or moiety connected to the formula.

The photosensitive resin composition layer according to one embodiment is composed of a first layer and a second layer. The first layer is formed by applying a first composition on a substrate and drying the second layer, and the second layer is formed by applying a second composition on the first layer and then drying. The first composition includes a pigment dispersion including a binder resin, a reactive unsaturated compound, a photopolymerization initiator, a solvent, and a pigment, and the second composition includes a binder resin, a reactive unsaturated compound, a photopolymerization initiator, and a solvent.

The optical density per 1 mu m of the first layer and the optical density per 1 mu m of the second layer differ by 0.4 or more. For example, the optical density per 1 mu m of the first layer may be 0.4 or more, for example, 1.0 or more, such as 1.5 or more, than the optical density per 1 mu m of the second layer. In general, the photosensitive resin composition layer for manufacturing a black column spacer has a single layer, which results in incomplete steps and has a problem of low reliability. However, since the photosensitive resin composition layer according to one embodiment is composed of, for example, a first layer comprising a first composition for obtaining optical density and a second layer comprising a spacer and a second composition for realizing a step difference , Sensitivity and developability can be easily controlled, so that a desired level difference can be obtained. Furthermore, since the surface of the first layer can be hardened by the light transmitted through the second layer, which may have an optical density lower by 0.4 or more per 1 탆 than the first layer at the intermediate position of the photosensitive resin composition layer, And a very high improvement in terms of the developing margin can be obtained.

Hereinafter, the first layer will be described in detail.

The first layer is formed by applying a first composition on a substrate and drying the first composition, and the first composition includes a pigment dispersion including a binder resin, a reactive unsaturated compound, a photopolymerization initiator, a solvent, and a pigment.

Since the first layer should have a high optical density, the pigment may comprise a black pigment. The black pigment may be an inorganic black pigment, an organic black pigment or a combination thereof such as aniline black, perylene black, titanium black, cyanine black, lignin black, lactam-based organic black, RGB black, carbon black, . ≪ / RTI > Specifically, the black pigment may include an inorganic black pigment and an organic black pigment, the inorganic black pigment may be carbon black, and the organic black pigment may be a lactam-based organic black represented by the following formula (A).

(A)

The RGB black refers to a pigment in which at least two or more kinds of colored pigments such as a red pigment, a green pigment, a blue pigment, a violet pigment, a yellow pigment, and a purple pigment are mixed to form a black color.

When the black pigment contains carbon black, it is excellent in light shielding property, surface smoothness, dispersion stability, compatibility with the binder resin, and the like. On the other hand, when the black pigment is used, it may be used in combination with a color correcting agent such as an anthraquinone pigment, a perylene pigment, a phthalocyanine pigment or an azo pigment.

A dispersing agent may be used together to disperse the pigment. Specifically, the pigment may be surface-treated in advance with a dispersant, or a dispersant may be added together with the pigment when the first composition is prepared.

As the dispersing agent, a nonionic dispersing agent, an anionic dispersing agent, a cationic dispersing agent and the like can be used. Specific examples of the dispersing agent include polyalkylene glycols and esters thereof, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adduct, alcohol alkylene oxide adduct, sulfonic acid ester, sulfonic acid salt, carboxylic acid ester, carboxylic acid Salts, alkylamide alkylene oxide adducts, and alkylamines. These may be used singly or in combination of two or more.

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 Ajinomoto's PB711 and PB821.

The dispersant may be included in an amount of 0.1 to 15% by weight based on the total weight of the first composition. When the dispersing agent is contained within the above range, the dispersibility of the first composition is excellent, and thus the stability, developability and patternability of the black column spacer are excellent.

The pigment may be used by pretreatment using a water-soluble inorganic salt and a wetting agent. When the pigment is used by the pretreatment, the average particle diameter of the pigment can be made smaller.

The pretreatment may be performed by kneading the pigment with a water-soluble inorganic salt and a wetting agent, and filtering and washing the pigment obtained in the kneading step.

The kneading may be carried out at a temperature of 40 to 100 DEG C, and the filtration and washing may be performed by washing the inorganic salt with water, etc., followed by filtration.

Examples of the water-soluble inorganic salt include, but are not limited to, sodium chloride and potassium chloride. The wetting agent acts as a medium through which the pigment and the water-soluble inorganic salt are uniformly mixed to easily pulverize the pigment. Examples of the wetting agent include ethylene glycol monoethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether and the like Alkylene glycol monoalkyl ethers; And alcohols such as ethanol, isopropanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, polyethylene glycol, glycerin polyethylene glycol and the like. These may be used singly or in combination of two or more thereof.

Specifically, the pigment may be used in the form of a pigment dispersion including the dispersant and a solvent described later, and the pigment dispersion may be used in an amount of 1 to 30 wt%, for example, 2 to 20 wt% %. ≪ / RTI > When the pigment dispersion is contained within the above range, the resolution and the linearity of the pattern are excellent.

The binder resin may include a cadmium binder resin, an acrylic binder resin, or a combination thereof.

The binder resin may be a cadmium-based binder resin. When the binder resin is a cadmium-based binder resin, the first composition containing the binder resin is excellent in developability, has good sensitivity upon photo-curing, and is excellent in fine pattern formation. In particular, when a cadmium-based binder resin is used, the reliability of the black column spacer can be secured.

The cadmium binder resin may include a repeating unit represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

R ¹ And R ² are each independently a hydrogen atom or a substituted or unsubstituted (meth) acryloyloxyalkyl group,

R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

Z ¹ is a single bond, O, CO, SO ₂ , CR ⁷ R ⁸ , SiR ⁹ R ¹⁰ (wherein R ⁷ to R ¹⁰ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group) Or a linking group represented by any of the following formulas (1-1) to (1-11)

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

(In the formula (1-5)

R ^a 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.

[Chemical Formula 1-6]

[Chemical Formula 1-7]

[Chemical Formula 1-8]

[Chemical Formula 1-9]

[Chemical Formula 1-10]

[Formula 1-11]

Z ² is an acid anhydride residue,

m1 and m2 are each independently an integer of 0 to 4,

n is an integer of 1 to 30;

The cadmium-based binder resin may include a functional group represented by the following formula (2) on at least one of both terminals.

(2)

In Formula 2,

Z ³ may be represented by the following general formulas (2-1) to (2-7).

[Formula 2-1]

(Wherein R ^b and R ^c are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, an ester group, or an ether group).

[Formula 2-2]

[Formula 2-3]

[Chemical Formula 2-4]

[Chemical Formula 2-5]

Wherein R ^d is O, S, NH, a substituted or unsubstituted C1 to C20 alkylene group, a C1 to C20 alkylamine group, or a C2 to C20 allylamine group.

[Chemical Formula 2-6]

[Chemical Formula 2-7]

Examples of the cationic binder resin include fluorene-containing compounds such as 9,9-bis (4-oxiranylmethoxyphenyl) fluorene; Benzene tetracarboxylic acid dianhydride, naphthalene tetracarboxylic acid dianhydride, biphenyl tetracarboxylic dianhydride, benzophenonetetracarboxylic dianhydride, pyromellitic dianhydride, cyclobutanetetracarboxylic dianhydride, Anhydride compounds such as lyrenetetracarboxylic acid dianhydride, tetrahydrofuran tetracarboxylic acid dianhydride, and tetrahydrophthalic anhydride; Glycol compounds such as ethylene glycol, propylene glycol, and polyethylene glycol; Alcohol compounds such as methanol, ethanol, propanol, n-butanol, cyclohexanol and benzyl alcohol; Propylene glycol methyl ethyl acetate, and N-methyl pyrrolidone; Phosphorus compounds such as triphenylphosphine; And an amine or an ammonium salt compound such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, benzyltriethylammonium chloride, or the like.

The weight average molecular weight of the cationic binder resin may be from 500 g / mol to 50,000 g / mol, such as from 1,000 g / mol to 30,000 g / mol. When the weight average molecular weight of the cadmium binder resin is within the above range, the pattern can be formed well without residue during the production of the black column spacer, a good pattern can be obtained without loss of film thickness during development.

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, and combinations thereof.

The first ethylenically unsaturated monomer may be included in an amount of 5% by weight to 50% by weight, for example, 10% by weight 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 from 3,000 g / mol to 150,000 g / mol, such as from 5,000 g / mol to 50,000 g / mol, such as from 7,000 g / mol to 30,000 g / mol. 　　 When the weight average molecular weight of the acrylic binder resin is within the above range, physical and chemical properties of the first composition are excellent, viscosity is appropriate, and adhesion to the substrate is excellent when the black column spacer is produced.

The acid value of the acrylic binder resin may be from 15 mgKOH / g to 150 mgKOH / g, such as from 80 mgKOH / g to 130 mgKOH / g. When the acid value of the acrylic binder resin is within the above range, the resolution of the pixel pattern is excellent.

When the cationic binder resin and the acrylic binder resin are mixed and used, the content (weight) ratio between the cationic binder resin and the acrylic binder resin in the first composition may be 99: 1 to 50:50.

If the content of the acrylic binder resin in the first composition exceeds the content of the cadmium binder resin, the chemical resistance and the reliability may be deteriorated.

The binder resin may be contained in an amount of 1 to 30% by weight, for example, 2 to 20% by weight based on the total weight of the first composition. Specifically, the cation binder resin may be contained in an amount of 1 to 20% by weight based on the total amount of the first composition, and the acrylic binder resin may be included in an amount of 1 to 20% by weight based on the total weight of the first composition . When the binder resin is contained within the above range, superior sensitivity, developability, resolution, and straightness of the pattern can be obtained.

The reactive unsaturated compound may be monomers or oligomers, and monofunctional or polyfunctional esters of (meth) acrylic acid having at least one ethylenically unsaturated double bond may be used.

By having the ethylenically unsaturated double bond, the reactive unsaturated compound can form a pattern having excellent heat resistance, light resistance and chemical resistance by causing sufficient polymerization during exposure in the pattern formation step.

The reactive unsaturated compound may be, for example, at least one selected from the group consisting of 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, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri , Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol mono It may be a butyl ether (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, novolak epoxy (meth) acrylate, or a combination thereof.

Examples of commercially available products of the above reactive unsaturated compounds are 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 reactive unsaturated compound may be treated with an acid anhydride so as to give better developing properties.

The reactive unsaturated compound may be included in an amount of 1 wt% to 20 wt%, for example, 1 wt% to 10 wt% based on the total amount of the first composition. When the reactive unsaturated compound is contained within the above range, the pattern formation process sufficiently cures upon exposure to light, thereby providing excellent reliability, excellent heat resistance, light resistance and chemical resistance of the pattern, and excellent resolution and adhesion.

As the photopolymerization initiator, an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, a triazine-based compound, an oxime-based compound, or a combination thereof may be used.

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- Bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphtho-1-yl) (Trichloromethyl) -6- (4-methoxystyryl) -s-triazine, and the like.

Examples of the oxime compounds include O-acyloxime compounds, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, O-ethoxycarbonyl-a-oxyamino-1-phenylpropan- Can be used. Specific examples of the O-acyloxime-based compound include 1,2-octanedione, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin- 2-oxime-O-benzoate, 1- (4-phenylsulfanylphenyl) -octane-1,2-dione -1-one oxime-O-acetate, 1- (4-phenylsulfanylphenyl) -butan-1-one oxime- O-acetate and the like can be used.

The photopolymerization initiator may be a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, an imidazole compound, or a nonimidazole compound in addition to the above compounds.

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.

Examples of the photosensitizer include tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate and the like .

The photopolymerization initiator may be included in an amount of 0.05 wt% to 5 wt%, for example, 0.1 wt% to 5 wt% with respect to the total amount of the first composition. When the photopolymerization initiator is contained within the above range, it is possible to obtain sufficient reliability due to sufficient curing during exposure in the pattern formation step, to have excellent heat resistance, light resistance and chemical resistance, excellent resolution and adhesion, It is possible to prevent the transmittance from being lowered.

The solvent may be a pigment dispersion containing the pigment, the binder resin, the reactive unsaturated compound, and a material having compatibility with the photopolymerization initiator but not reacting with the binder resin.

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 monomethyl ether and ethylene glycol monoethyl 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 esters such as methyl lactate and ethyl lactate; Oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate and butyl oxyacetate; Alkoxyacetic acid alkyl esters such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, and ethyl ethoxyacetate; 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate and propyl 2-oxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate and methyl 2-ethoxypropionate; 2-methylpropionic acid esters such as methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy- Monooximonocarboxylic acid alkyl esters of 2-alkoxy-2-methylpropionic acid alkyls such as ethyl methyl propionate; Esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate and methyl 2-hydroxy-3-methylbutanoate; Ketone acid esters such as ethyl pyruvate, and the like, and also include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide , N-methylpyrrolidone, dimethylsulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, And high boiling solvents such as ethyl acetate, diethyl oxalate, diethyl maleate,? -Butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.

Among them, glycol ethers such as ethylene glycol monoethyl ether and the like are preferably used in consideration of compatibility and reactivity; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as ethyl 2-hydroxypropionate; Carbitols such as diethylene glycol monomethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate can be used.

The solvent may be included in an amount of from about 40% by weight to about 90% by weight based on the total amount of the first composition. When the solvent is included within the above range, the first composition has an appropriate viscosity, and thus the processability of the black column spacer is excellent.

Meanwhile, the first composition may further include additives such as malonic acid, 3-amino-1,2-propanediol, a silane coupling agent, a leveling agent, a fluorine-based surfactant, a radical polymerization initiator, or a combination thereof.

The silane-based coupling agent may have a reactive substituent such as a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group, or an epoxy group in order to improve adhesion with a substrate.

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.

The silane coupling agent may be included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the first composition. When the silane coupling agent is included in the above range, the adhesion and storage stability are excellent.

The first composition may further contain a surfactant, for example, a fluorine-based surfactant, in order to improve coatability and prevent defect formation, if necessary.

The fluorine is a surfactant, the ^{BM Chemie社BM-1000 ®,} BM-1100 ® , and the like; Mechacup F 142D ^® , copper F 172 ^® , copper F 173 ^® , copper F 183 ^® and the like manufactured by Dainippon Ink & Chemicals Incorporated; Sumitomo M. (Note)社Pro rod FC-135 ^®, the same FC-170C ^®, copper FC-430 ^®, the same FC-431 ^®, and the like; Asahi Grass Co., Saffron S-112 ^® of社, such S-113 ^®, the same S-131 ^®, the same S-141 ^®, the same S-145 ^®, and the like; Toray Silicone ^® (Note)社SH-28PA, the same -190 ^®, may be used a fluorine-containing surfactants commercially available under the name such as copper ^{-193 ®, SZ-6032 ®,} SF-8428 ®.

The surfactant may be used in an amount of 0.001 part by weight to 5 parts by weight based on 100 parts by weight of the first composition. When the surfactant is contained within the above range, coating uniformity is ensured, no staining occurs, and wetting to an IZO substrate or a glass substrate is excellent.

In addition, the first composition may contain a certain amount of other additives such as an antioxidant, a stabilizer and the like within a range that does not impair the physical properties.

Hereinafter, the second layer will be described in detail.

The second layer is formed by applying a second composition on the first layer and then drying the second composition, wherein the second composition includes a binder resin, a reactive unsaturated compound, a photopolymerization initiator, and a solvent.

Since the second composition is for realizing spacers and steps and does not necessarily require high optical density, the pigment dispersion containing the pigment among the constituents of the first composition may not necessarily be contained in the second composition. That is, the second composition may further comprise a pigment dispersion containing a binder resin, a reactive unsaturated compound, a photopolymerization initiator, and a solvent, or if necessary, the second composition may also include a pigment. In addition, the second composition may further comprise additives described for the first composition.

The second composition may comprise the same constituents as the constituents of the first composition. However, in this case, the content of each component of the first composition and the second composition may be different, whereby the optical density per 1 μm of the first composition and the second composition may be different.

Therefore, the binder resin, the reactive unsaturated compound, the photopolymerization initiator, the pigment dispersion including the pigment constituting the second composition for forming the second layer, and the respective components constituting the solvent are dispersed in the first layer for forming the first layer May be the same as described for the composition.

The optical density per 1 mu m of the second layer may be lower than the optical density per 1 mu m of the first layer by 0.4 or more, for example, 1.0 or more, such as 1.5 or more. In this case, since the reliability of the black column spacer can be ensured, the second composition for forming the second layer is preferably a binder resin containing less cadmium binder resin, and other binder resin other than cadmium binder resin, A binder resin, and the like. When the binder resin in the second composition contains more acrylic binder resin than the cation resin, the physical properties of the black column spacer, such as solvent resistance and developing margin, can be further optimized.

The binder resin contained in the second composition may be included in an amount of 3% by weight to 70% by weight, for example, 3% by weight to 60% by weight based on the total amount of the second composition. When the binder resin is contained within the above range, excellent sensitivity, developability, resolution, and straightness of the pattern can be obtained.

The reactive unsaturated compound contained in the second composition may be included in an amount of 2% by weight to 40% by weight, for example, 3% by weight to 30% by weight, based on the total amount of the second composition. When the reactive unsaturated compound is contained within the above range, the pattern formation process sufficiently cures upon exposure to light, thereby providing excellent reliability, excellent heat resistance, light resistance and chemical resistance of the pattern, and excellent resolution and adhesion.

The photopolymerization initiator contained in the second composition may be included in an amount of 0.1 wt% to 5 wt%, for example, 0.2 wt% to 5 wt% with respect to the total amount of the second composition. When the photopolymerization initiator is contained within the above range, it is possible to obtain sufficient reliability due to sufficient curing during exposure in the pattern formation step, to have excellent heat resistance, light resistance and chemical resistance, excellent resolution and adhesion, It is possible to prevent the transmittance from being lowered.

The solvent contained in the second composition may be included in a residual amount, for example, 40% to 90% by weight based on the total amount of the second composition. When the solvent is contained within the above range, the second composition has an appropriate viscosity, and therefore, the black column spacer is excellent in the fairness in manufacturing the black column spacer. However, the solvent of the second composition may be lower in solubility (lower) than the solvent of the first composition. For example, the solvent of the first composition may be PGMEA, PGME, EDM, 3-MBA, EEP, and the solvent of the second composition may be PGMEA, 3-MBA, n-butyl acetate, n-pentyl acetate, But is not limited thereto.

Another embodiment provides a black column spacer manufactured using the photosensitive resin composition layer described above.

The method of preparing the black column spacer is as follows.

(1) Coating and Film Formation Step

In order to form the first layer, the first composition is coated on a substrate such as a glass substrate or an IZO substrate subjected to a predetermined pretreatment by a spin or slit coat method, a roll coating method, a screen printing method, an applicator method or the like And then the solvent is removed by heating at 70 to 100 DEG C for 1 to 10 minutes to form a coating film. Thereafter, in order to form the second layer, the second composition is applied and heated in the same manner on the coating film. Thus, the photosensitive resin composition layer according to one embodiment is formed.

(2) Exposure step

In order to form a pattern necessary for the obtained coating film, a mixed mask consisting of a half tone portion for implementing a black matrix pattern and a full tone portion for implementing a column spacer pattern is interposed, and then an active line of 200 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, and the like can be used.

The exposure dose differs depending on the kind of each component of the composition, the blending amount, and the dried film thickness, but is 500 mJ / cm ² (according to the 365 nm sensor) or less when high pressure mercury lamp is used.

(3) Development step

As a developing method, an unnecessary portion is dissolved and removed by using an alkaline aqueous solution as a developing solution following the above-described exposure step, so that only the exposed portion is left to form a pattern.

(4) Post-treatment step

There is a post-heating process for obtaining an image pattern obtained by development in the above process, in terms of heat resistance, light resistance, adhesion, crack resistance, chemical resistance, high strength and storage stability.

Another embodiment provides a color filter comprising the black column spacer.

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.

( Example )

(Photosensitive resin Composition layer  Produce)

Example  One

The following compositions were used to prepare the first composition in the composition shown in Table 1 below and the second composition in the composition shown in Table 2 below. The first composition is coated on a substrate such as a glass substrate or an IZO substrate and then dried for 1 minute to 10 minutes, and then the second composition is coated on the first composition and dried for 1 minute to 10 minutes to form two layers To prepare a photosensitive resin composition layer according to Example 1.

Specific methods of preparing the first composition and the second composition are as follows. After dissolving the photopolymerization initiator in the solvent, the mixture was thoroughly stirred at room temperature for 30 minutes or more, and then binder resin and reactive unsaturated compound were added thereto, followed by stirring at room temperature for about 1 hour. Subsequently, the other additives were added to the resulting mixture, stirred for about 10 minutes, and then the pigment dispersion was added thereto, followed by stirring at room temperature for 2 hours or more. The product was then filtered three times to remove impurities, thereby preparing the first composition and the second composition.

(Unit: g) ingredient content Binder resin Cadmium binder resin (V259ME, Nippon Steel Corporation) 9.64 The reactive unsaturated compound Dipentaerythritol hexaacrylate (Nippon Catalyst Co., Ltd.) 2.566 Photopolymerization initiator OXE01 (BASF) 0.464 menstruum PGMEA 63.211 EDM 15.343 Pigment dispersion Lactam-based organic black (BASF) Mill base (Mikuni, PWC 18%) 6.397 Carbon black included Mill base (Tokushiki, PWC 25%) 1.438 additive γ-glycidoxypropyltrimethoxysilane (S-510, Chisso) 0.941

(In Table 1, the lactam-based organic black is represented by the following formula (A).

(A)

)

)

(Unit: g) ingredient content Binder resin Cadmium binder resin (V259ME, Nippon Steel Corporation) 4.718 Acrylic binder resin (BX-04, manufactured by Nippon Shokubai Co., Ltd.) 19.456 The reactive unsaturated compound Dipentaerythritol hexaacrylate (Nippon Catalyst Co., Ltd.) 8.728 Photopolymerization initiator OXE01 (BASF) 0.489 menstruum n-butyl acetate 65.039 additive γ-glycidoxypropyltrimethoxysilane (S-510, Chisso) 1.570

Example  2

Using the following components, a first composition was prepared according to the composition shown in the following Table 3, and a second composition was prepared according to the composition shown in Table 4 below. In the same manner as in Example 1, To prepare a photosensitive resin composition layer.

(Unit: g) ingredient content Binder resin Cadmium binder resin (V259ME, Nippon Steel Corporation) 9.64 The reactive unsaturated compound Dipentaerythritol hexaacrylate (Nippon Catalyst Co., Ltd.) 2.566 Photopolymerization initiator OXE01 (BASF) 0.464 menstruum PGMEA 63.211 EDM 15.343 Pigment dispersion Lactam-based organic black (BASF) Mill base (Mikuni, PWC 18%) 6.397 Carbon black included Mill base (Tokushiki, PWC 25%) 1.438 additive γ-glycidoxypropyltrimethoxysilane (S-510, Chisso) 0.941

(Unit: g) ingredient content Binder resin Cadmium binder resin (V259ME, Nippon Steel Corporation) 11.24 The reactive unsaturated compound Dipentaerythritol hexaacrylate (Nippon Catalyst Co., Ltd.) 2.916 Photopolymerization initiator OXE01 (BASF) 0.464 menstruum n-butyl acetate 78.554 Pigment dispersion Lactam-based organic black (BASF) Mill base (Mikuni, PWC 18%) 4.797 Carbon black included Mill base (Tokushiki, PWC 25%) 1.088 additive γ-glycidoxypropyltrimethoxysilane (S-510, Chisso) 0.941

Example  3

The following compositions were used to prepare the first composition in the composition shown in the following Table 5 and the second composition was prepared in the composition shown in the following Table 6, To prepare a photosensitive resin composition layer.

(Unit: g) ingredient content Binder resin Cadmium binder resin (V259ME, Nippon Steel Corporation) 9.64 The reactive unsaturated compound Dipentaerythritol hexaacrylate (Nippon Catalyst Co., Ltd.) 2.566 Photopolymerization initiator OXE01 (BASF) 0.464 menstruum PGMEA 63.211 EDM 15.343 Pigment dispersion Lactam-based organic black (BASF) Mill base (Mikuni, PWC 18%) 6.397 Carbon black included Mill base (Tokushiki, PWC 25%) 1.438 additive γ-glycidoxypropyltrimethoxysilane (S-510, Chisso) 0.941

(Unit: g) ingredient content Binder resin Cadmium binder resin (V259ME, Nippon Steel Corporation) 12.84 The reactive unsaturated compound Dipentaerythritol hexaacrylate (Nippon Catalyst Co., Ltd.) 3.266 Photopolymerization initiator OXE01 (BASF) 0.464 menstruum PGMEA 63.211 EDM 15.343 Pigment dispersion Lactam-based organic black (BASF) Mill base (Mikuni, PWC 18%) 3.197 Carbon black included Mill base (Tokushiki, PWC 25%) 0.738 additive γ-glycidoxypropyltrimethoxysilane (S-510, Chisso) 0.941

Comparative Example  One

The photosensitive resin composition layer according to Comparative Example 1 was prepared in the same manner as in Example 1, except that the second composition was prepared in the composition shown in the following Table 7 using the following components.

(Unit: g) ingredient content Binder resin Cadmium binder resin (V259ME, Nippon Steel Corporation) 9.64 The reactive unsaturated compound Dipentaerythritol hexaacrylate (Nippon Catalyst Co., Ltd.) 2.566 Photopolymerization initiator OXE01 (BASF) 0.464 menstruum n-butyl acetate 78.554 Pigment dispersion Lactam-based organic black (BASF) Mill base (Mikuni, PWC 18%) 6.397 Carbon black included Mill base (Tokushiki, PWC 25%) 1.438 additive γ-glycidoxypropyltrimethoxysilane (S-510, Chisso) 0.941

(In Table 7, the lactam-based organic black is represented by the following formula (A).

(A)

)

)

Comparative Example  2

A composition was prepared with the compositions shown in Table 1 above. The composition was coated on a substrate such as a glass substrate or an IZO substrate and then dried for 1 minute to 10 minutes to prepare a photosensitive resin composition layer according to Comparative Example 2 composed of a single layer. The composition was prepared in the same manner as in Example 1.

Evaluation 1: Per 1 m Optical density ( Optical Depth : OD ) evaluation

The photosensitive resin compositions prepared in Examples 1 to 3, Comparative Examples 1 and 2 were coated on a 10 cm * 10 cm IZO substrate using a spin coater (Mikasa, Opticoat MS-A150) The second layer formed by applying the second composition on the first layer and then drying was coated so as to have a thickness of 1.5 탆 (in the case of Comparative Example 2, the thickness of the single composition layer Baking or pre-baking at 80 ° C for 150 seconds using a hot plate, exposure was carried out using an exposure device (HB-50110A, Ushio, Inc.) and a photo And exposed at 50 mJ using a mask. Subsequently, the substrate was developed with a 0.2 wt% aqueous solution of potassium hydroxide (KOH) for 150 seconds using a developing machine (SVS, SSP-200) and hard-baked or post-baked in an oven at 230 캜 for 30 minutes. And the patterned specimen was obtained. Optical densities of the specimens were measured and are shown in Table 8 below.

Example 1
(Double layer) Example 2
(Double layer) Example 3
(Double layer) Comparative Example 1
(Double layer) Comparative Example 2
(Single layer) The first layer Second layer The first layer Second layer The first layer Second layer The first layer Second layer Optical density per 1 탆 1.5 0 1.5 1.0 1.5 0.5 1.5 1.5 1.5

Evaluation 2: Evaluation of developing margin

The thickness and the step height of the specimen prepared in the evaluation 1 were measured with a contact thickness meter (Tencor, alpha-stepper) or a non-contact thickness meter (3-D profiler) to evaluate the developing margin. .

3, it can be seen that Example 1 has a small thickness decrease with the elapse of the developing time and is excellent in the developing margin, whereas Comparative Example 2 shows that the developing margin is poor (0.414 占 퐉 / 10 sec) .

Rating 3: Solvent resistance  evaluation

The specimen prepared in the above evaluation 1 was cut into a size of 1 cm * 1 cm, placed in a glass bottle containing 5 ml of NMP, allowed to stand in an oven at 100 ° C for 15 minutes, and the resultant color was observed.

Color separation  How to display measurement result

X: No color separation when observed with naked eyes

?: When color was observed with the naked eye, color discoloration was slightly observed

○: When observing with the naked eye, color discoloration is very high

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Missing color × △ × ○ ○

From Table 9, it can be confirmed that Examples 1 to 3 are excellent in the solvent resistance as compared with Comparative Example 1 and Comparative Example 2 because there is little color dropout.

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 first layer formed by applying a first composition on a substrate and dried, and a second layer formed by applying a second composition on the first layer and drying the first composition,
Wherein the first composition comprises a pigment dispersion comprising a binder resin, a reactive unsaturated compound, a photopolymerization initiator, a solvent, and a pigment, wherein the second composition comprises a binder resin, a reactive unsaturated compound, a photopolymerization initiator,
The solvent in the first composition is higher in solubility than the solvent in the second composition,
The optical density per 1 mu m of the first layer and the optical density per 1 mu m of the second layer differ by 0.4 or more.
The method according to claim 1,
Wherein the optical density per 1 mu m of the first layer is 0.4 or more larger than the optical density per 1 mu m of the second layer.
The method according to claim 1,
Wherein the second composition further comprises a pigment dispersion liquid containing a pigment.
The method according to claim 1 or 3,
Wherein the pigment comprises a black pigment.
5. The method of claim 4,
Wherein the black pigment includes aniline black, perylene black, titanium black, cyanine black, lignin black, lactam-based organic black, RGB black, carbon black, or a combination thereof.
The method according to claim 1,
The binder resin includes a cadmium binder resin, an acrylic binder resin, or a combination thereof.
The method according to claim 1,
Wherein the first composition comprises 1 to 30% by weight of a binder resin, 1 to 20% by weight of a reactive unsaturated compound, 0.05 to 5% by weight of a photopolymerization initiator, 1 to 30% by weight of a pigment dispersion comprising a pigment, And a residual solvent amount.
The method according to claim 1,
Wherein the second composition comprises 3 wt% to 70 wt% of a binder resin, 2 wt% to 40 wt% of a reactive unsaturated compound, 0.1 wt% to 5 wt% of a photopolymerization initiator, and a remaining amount of a solvent.
The method according to claim 1,
The first composition and the second composition may each independently include an additive of malonic acid, 3-amino-1,2-propanediol, a silane coupling agent, a leveling agent, a fluorine surfactant, a radical polymerization initiator, Based on the total weight of the photosensitive resin composition layer.
A black column spacer produced by exposing and developing the photosensitive resin composition layer of claim 1.
A color filter comprising the black column spacer of claim 10.

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