KR101754326B1 - Photosensitive resin composition layer, black column spacerusing the same, the method of black column spacerand color filter - Google Patents

Abstract

Wherein the first organic film is an organic film obtained by curing the first composition, the second organic film is an organic film obtained by curing the second composition, and a second organic film , Wherein the first composition comprises a binder resin, a reactive unsaturated compound, a photopolymerization initiator, a colorant including a silver halide and a solvent, and the second composition is a photosensitive resin composition comprising a binder resin, a reactive unsaturated compound, a photopolymerization initiator and a solvent Layer, a black column spacer manufactured using the same, a method of manufacturing the black column spacer, 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 manufactured using the same, a method of manufacturing a black column spacer, and a color filter,

The present invention relates to a photosensitive resin composition layer, a black column spacer manufactured using the same, a method of manufacturing a black column spacer, 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, solvent resistance and reliability.

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

Another embodiment is to provide a method for producing the black column spacer.

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

One embodiment includes a first organic film and a second organic film positioned on the first organic film, wherein the first organic film is an organic film that is a cured first composition, Wherein the first composition comprises a binder resin, a reactive unsaturated compound, a photopolymerization initiator, a colorant containing silver halide and a solvent, and the second composition includes a binder resin, a reactive unsaturated compound, a photopolymerization initiator, and a solvent Based on the weight of the photosensitive resin composition.

The colorant in the first composition may further comprise carbon black.

The colorant in the first composition may contain silver halide and carbon black in a weight ratio of 1: 1 to 9: 1.

Wherein the colorant in the first composition comprises a first pigment dispersion comprising the silver halide, the first dispersant and the first solvent; And a second pigment dispersion containing the carbon black, the second dispersant and the second solvent.

The colorant in the first composition may be obtained as a pigment dispersion comprising the carbon black, the silver halide, a dispersant and a solvent.

The second composition may further comprise a colorant.

The coloring agent may include silver halide.

Silver halide may be contained in an amount of 50 to 90% by weight based on 100% by weight of the colorant in the first composition, and silver halide may be included in an amount of 0.1 to 10% by weight based on 100% by weight of the second composition.

The binder resin may include a carcass binder resin, an acrylic binder resin, a polyimide binder resin, a polyurethane binder resin, or a combination thereof.

The cationic binder resin may have a weight average molecular weight of 1,000 g / mol to 50,000 g / mol, and the acrylic binder resin may have a weight average molecular weight of 3,000 g / mol to 150,000 g / mol.

The weight average molecular weight of the cationic binder resin may be from 1,000 g / mol to 50,000 g / mol.

The first composition comprises 0.5 to 20% by weight of binder resin, 1 to 20% by weight of a reactive unsaturated compound, 0.1 to 10% by weight of a photopolymerization initiator, 1 to 50% by weight of a colorant, can do.

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 each independently include malonic acid, 3-amino-1,2-propanediol, a silane coupling agent, a leveling agent, a fluorinated surfactant, a radical polymerization initiator, can do.

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

In another embodiment, there is provided a method of manufacturing a semiconductor device, comprising: preparing a substrate; applying a first composition on the substrate and then heating to form a first organic film; Applying a second composition on the first organic layer and then heating to form a second organic layer; Developing, and curing a substrate on which the first organic layer and the second organic layer are formed, wherein the first composition includes a binder resin, a reactive unsaturated compound, a photopolymerization initiator, a colorant including a silver halide, and a solvent , And the second composition comprises a binder resin, a reactive unsaturated compound, a photopolymerization initiator, and a solvent.

The colorant in the first composition may further comprise carbon black, and the silver halide and carbon black may be contained in a weight ratio of 1: 1 to 9: 1.

The second composition may further comprise silver halide.

Silver halide may be contained in an amount of 50 to 90% by weight based on 100% by weight of the colorant in the first composition, and silver halide may be included in an amount of 0.1 to 10% by weight based on 100% by weight of the second composition.

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

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

A black column spacer manufactured using the photosensitive resin composition layer, a method of manufacturing the black column spacer, and a color filter including the same.

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a schematic view of a conventional method of manufacturing a black column spacer. FIG.
FIG. 2 is a scanning electron microscope (SEM) photograph of a black column spacer produced using the photosensitive resin composition layer according to Example 1. FIG.
3 is a scanning electron microscope (SEM) photograph of a cross section of a black column spacer prepared using the photosensitive resin composition layer according to Example 1. Fig.
4 is a graph showing the developing margins of black column spacers according to Example 1, Example 2 and Comparative Example 1. 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, 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, a C1-C10 alkyl group, a C1- A C2 to C20 alkenyl 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, a C3 to C20 cycloalkynyl group, a C2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkyl group, To C20 heterocycloalkenyl groups, C2 to C20 heterocycloalkynyl groups, C3 to C20 heteroaryl groups, or combinations 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.

In the present specification, the cadmium binder resin means a resin in which at least one functional group selected from the group consisting of the following formulas (2) to (12) 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 an embodiment includes a first organic film and a second organic film disposed on the first organic film. The first organic layer may be obtained by applying a first composition on a substrate and then curing the first composition. The second organic layer may be obtained by applying a second composition on the first organic layer and then curing the second composition. The first composition includes a binder resin, a reactive unsaturated compound, a photopolymerization initiator, a colorant including a silver halide and a solvent, and the second composition includes a binder resin, a reactive unsaturated compound, a photopolymerization initiator, and a solvent.

A conventional method of manufacturing a black column spacer is as shown in FIG. Referring to FIG. 1, a substrate is prepared (S1), a black column spacer composition is coated on the substrate, exposure is performed using a halftone mask (S2), the substrate is developed (S3) And thermosetting (S4).

That is, the conventional method of producing a black column spacer proceeds to a step of applying a black column spacer composition on a substrate at one time to expose, develop and cure the black column spacer composition, which comprises an organic black pigment and has a high optical density (OD) Light does not reach to the lower portion of the black column spacer composition formed on the substrate in the step of exposure (S2), so that only the surface hardens and the hardening does not easily occur to the inside. Thus, after the exposure, the portion where hardening is not performed at all is thermally cured in the post-baking step to perform patterning. In this case, the step forming margin of the black column spacer becomes very narrow, and it becomes difficult to realize a process of maintaining a step of uniform thickness on the entire surface of the substrate.

Further, even after the patterning of the black column spacer, the necessity of recognizing the align key of the panel substrate makes it necessary to recognize the align key of the panel substrate in the Near-IR wavelength band (800 nm to 1000 nm) Transmittance should be shown. Therefore, the organic black pigment used in the production of the black column spacer uses, for example, an organic black pigment whose transmittance at? = 950 nm is maintained at 20% or more. However, in the case of such an organic black pigment, there is a problem that the possibility of elution of metal ions and pigments in the spacer pattern by the solvent is high. As a result, the reliability of the black column spacer contacting the liquid crystal is deteriorated. Further, the interior of the black column spacer is not cured at all, but is cured only by the thermosetting resin, so that the degree of curing is not high, and the required chemical resistance is not sufficiently obtained.

However, the photosensitive resin composition layer according to one embodiment uses a coloring agent containing silver halide instead of the organic black pigment to cause photocuring up to the interior of the black column spacer, thereby lowering the developing margin, reliability, and chemical resistance Can be solved. Further, silver halide is colorless before exposure, and discoloration occurs to black after exposure, so that reliability can be further improved as compared with the case of using an organic black pigment which is black before exposure.

Hereinafter, the first organic film will be described in detail.

1st Organic film

The first organic film is an organic film obtained by curing the first composition, and the first composition includes a binder resin, a reactive unsaturated compound, a photopolymerization initiator, a colorant including a silver halide, and a solvent.

The first composition may be a black composition.

(Colorant in the first composition)

The colorant in the first composition includes silver halide, and the silver halide may be specifically fluorinated, silver chloride, silver bromide, silver iodide, or a combination thereof.

The colorant in the first composition may further comprise carbon black. The carbon black is not particularly limited, and examples thereof include graphitized carbon, furnace black, acetylene black, and ketjen black.

The colorant in the first composition may include silver halide and carbon black in a weight ratio of 1: 1 to 9: 1, such as 4: 1 to 8: 1. When the colorant is used in the form of a pigment dispersion as described below, the weight ratio is based on the solid content of each of the carbon black and the silver halide present in each pigment dispersion. When it is contained in the above weight ratio range, it is easy to obtain a black column spacer which can form a fine pattern and is excellent in chemical resistance.

The colorant may be used in the photosensitive resin composition, for example, in the first composition, in the form of a pigment dispersion by mixing together silver halide, carbon black, a dispersant, a solvent and the like. Specifically, the colorant in the first composition may be a first pigment dispersion comprising the silver halide, the first dispersant and the first solvent; And a second pigment dispersion containing the carbon black, the second dispersant and the second solvent. Further, the colorant in the first composition may be obtained as a pigment dispersion comprising the carbon black, the silver halide, the dispersant and the solvent. The thus obtained coloring agent in the form of a pigment dispersion can be used in the photosensitive resin composition, for example, the first composition.

The first dispersant may help to uniformly disperse the silver halide in the first solvent and the second dispersant may help to uniformly disperse the carbon black in the second solvent, The carbon black can be uniformly dispersed in the solvent at the same time.

Examples of the dispersant, the first dispersant and the second dispersant include a nonionic compound, an anionic compound, a cationic compound or a combination thereof. Specific examples thereof include polyalkylene glycols and esters thereof, polyoxyalkylene , A polyhydric alcohol ester alkylene oxide adduct, an alcohol alkylene oxide adduct, a sulfonic acid ester, a sulfonic acid salt, a carboxylic acid ester, a carboxylic acid salt, an alkylamide alkylene oxide adduct, and an alkylamine.

DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, and DISPERBYK-163 manufactured by BYK Corporation are commercially available products of the dispersant, the first dispersant and the second dispersant. , DISPERBYK-164, DISPERBYK-165, DISPERBYK-166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK- 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, the first dispersant, and the second dispersant may each be contained in the photosensitive resin composition, for example, 0.1% to 15% by weight based on the total amount of the first composition. When it is contained within the above-mentioned range, a black column spacer having excellent stability, developability and patternability can be produced because of excellent dispersibility of the first composition as a photosensitive resin composition.

The solvent, the first solvent and the second solvent are the same as the types of the solvent described below.

The silver halide may be contained in an amount of 50 to 90% by weight, for example, 55 to 90% by weight and 60 to 90% by weight, based on 100% by weight of the colorant in the first composition. In this case, the first organic film may have a high optical density.

(Binder resin in the first composition)

The binder resin in the first composition may include a cadmium-based binder resin, an acrylic-based binder resin, a polyimide-based binder resin, a polyurethane-based binder resin, or a combination thereof.

The weight average molecular weight of the binder resin may be from 1,000 g / mol to 150,000 g / mol.

Among the above-mentioned kinds of binder resins, the cadmium-based binder resin and the acrylic-based binder resin can be preferably used. In this case, the heat resistance and chemical resistance of the first composition may be improved.

The weight average molecular weight of the cationic binder resin may be from 1,000 g / mol to 50,000 g / mol, such as from 3,000 g / mol to 35,000 g / mol. When the weight average molecular weight of the cationic binder resin is within the above range, excellent patterning and developability can be obtained in the production of a black column spacer.

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

[Chemical Formula 1]

(In the formula 1,

R ₂₄ to R ₂₇ are each independently a hydrogen atom, a halogen atom, or a substituted or unsubstituted C1 to C20 alkyl group,

R ₂₈ and R ₂₉ each independently represent a hydrogen atom or CH ₂ OR _a (R _a is a vinyl group, an acrylate group or a methacrylate group)

R ₃₀ is a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, an acrylate group or a methacrylate group,

Z ¹ is a single bond, O, CO, SO ₂ , CR _b R _c , SiR _d R _e (wherein R _b to R _e are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group) , Or a compound represented by any one of the following formulas (2) to (12)

Z ₂ is an acid anhydride residue.)

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(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.

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

The cadmium binder resin can be specifically obtained by reacting a compound represented by the following formula (13) with a tetracarboxylic acid dianhydride.

[Chemical Formula 13]

The tetracarboxylic acid dianhydride may be an aromatic tetracarboxylic acid anhydride. Examples of the aromatic tetracarboxylic acid dianhydride include pyromellic acid dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4-biphenyltetracarboxylic acid dianhydride, 2 ', 3,3'-biphenyltetracarboxylic acid dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenylether tetracarboxylic acid dianhydride, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 2,3 , 6,7-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 2,3,5,6-pyridine tetracarboxylic acid dianhydride, 3,4,9,10-perylenetetra Carboxylic acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride and the like, but are not limited thereto.

The acrylic binder resin is a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable with the first ethylenically unsaturated monomer, and is a resin containing 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 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 binder 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 and from 2,000 g / mol 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 acrylic binder resin may be from 15 mgKOH / g to 60 mgKOH / g, such as from 20 mgKOH / g to 50 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 included in an amount of 0.5% by weight to 20% by weight, for example, 1% by weight to 10% by weight based on the total weight of the first 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 in the production of the black column spacer.

(Reactive unsaturated compound in the first composition)

The reactive unsaturated compound may be a monofunctional or polyfunctional ester of (meth) acrylic acid having at least one ethylenically unsaturated double bond as a monomer or oligomer generally used in a photosensitive resin composition.

Specific examples of the reactive unsaturated compound include ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, 1,6-hexanediol Diacrylate, 1,6-hexanediol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, bisphenol A epoxy acrylate , Ethylene glycol monomethyl ether acrylate, trimethylolpropane triacrylate, trisacryloyloxyethyl phosphate, and the like.

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 included in an amount of 1 wt% to 20 wt%, for example, 1 wt% to 15 wt% based on the total amount of the first composition. When the reactive unsaturated compound is contained within the above range, compatibility with the binder resin is improved, and patterning property in the production of a black column spacer and sensitivity in the presence of oxygen are excellent, and a smooth surface film can be obtained.

(Photopolymerization initiator in the first composition)

The photopolymerization initiator may be, for example, an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, or a triazine-based compound as a photopolymerization initiator generally used in a photosensitive resin composition.

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

The photopolymerization initiator may be a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo 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.

The photopolymerization initiator may be included in an amount of 0.1 wt% to 10 wt%, for example, 0.1 wt% to 3 wt% with respect to the total amount of the first composition. When the photopolymerization initiator is contained within the above range, the sensitivity of the radical is good, the color concentration of the first composition solution is appropriately maintained, and the decrease of the transmittance due to the unreacted initiator can be prevented.

(Solvent in the first composition)

The solvent in the first composition may be a colorant containing the silver halide, a binder resin, a 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 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; alkyl acetates such as n-butyl acetate, n-pentyl acetate, n-hexyl acetate and isobutyl acetate; 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 , N-methylpyrrolidone, dimethylsulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, Ethyl, 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, from 50% by weight to 80% by weight based on the total amount of the first composition. When the solvent is contained within the above range, the first composition has an appropriate viscosity, and therefore, the black column spacer is excellent in the fairness in manufacturing the black column spacer.

(Other additives in the first composition)

The first composition may further comprise additives such as malonic acid, 3-amino-1,2-propanediol, a silane coupling agent, a leveling agent, a fluorinated surfactant, a radical polymerization initiator or a combination thereof.

The first composition may further include a silane-based coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, or an epoxy group in order to improve adhesion with a substrate.

Specific examples of the silane-based coupling agent include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. These may be used alone or in combination of two or more.

The silane coupling agent 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 binder resin.

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

Examples of the surfactants include, 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, copper -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 binder resin. When the surfactant is contained within the above range, coating uniformity is ensured, no staining occurs, and wetting of the glass substrate is excellent.

A certain amount of other additives such as antioxidants and stabilizers may be added to the first composition within a range that does not impair physical properties.

Hereinafter, the second organic film will be described in detail.

Second Organic film

The second organic film is an organic film obtained by curing the second composition, and the second composition includes a binder resin, a reactive unsaturated compound, a photopolymerization initiator, and a solvent.

(Colorant in the second composition)

The second composition may further comprise a colorant, such as silver halide. In this case, the silver halide may be contained in an amount of 0.1 to 10% by weight, for example, 0.5 to 5% by weight based on 100% by weight of the second composition. In this case, light curing can smoothly occur to the inside of the photosensitive resin composition layer.

The content of the coloring agent in the second composition is the same as that described above, except for the content-related portion described above.

(Binder resin in the second composition)

The binder resin in the second composition may include a cadmium-based binder resin, an acrylic-based binder resin, a polyimide-based binder resin, a polyurethane-based binder resin or a combination thereof. And the content of the acrylic binder resin may be greater than the content of the cadmium binder resin. When the binder resin in the second composition contains more acrylic binder resin than the caustic binder resin, the physical properties of the black column spacer, such as solvent resistance and developing margin, can be further optimized.

The binder resin in the second composition may be included in an amount of 3 wt% to 70 wt%, for example, 3 wt% to 60 wt% with respect to 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 content of the binder resin in the second composition is the same as that described above, except for the content-related portion described above.

(Reactive unsaturated compound in the second composition)

The reactive unsaturated compound in the second composition may be included in an amount of 2 wt% to 40 wt%, for example, 3 wt% to 30 wt% with respect to 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 content of the reactive unsaturated compound in the second composition is the same as that described above, except for the content-related portion described above.

(Photopolymerization initiator in the second composition)

The photopolymerization initiator 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 content of the photopolymerization initiator in the second composition is the same as that described above, except for the content-related portion described above.

(Solvent in the second composition)

The solvent in the second composition may be contained in an amount of from about 40% by weight to about 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.

The solvent of the second composition may be less soluble than the solvent of the first composition. The solvent of the second composition may be PGMEA, 3-MBA, n-butyl acetate, n-pentyl acetate, n-hexyl Acetate, and the like, but is not limited thereto.

The content of the solvent in the second composition is the same as that described above, except for the content-related portion described above.

(Other additives in the second composition)

The second composition may further comprise additives such as malonic acid, 3-amino-1,2-propanediol, a silane-based coupling agent, a leveling agent, a fluorinated surfactant, a radical polymerization initiator or a combination thereof.

The content of the other additives in the second composition is the same as described above.

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

In another embodiment, there is provided a method of manufacturing a semiconductor device, comprising: preparing a substrate; applying a first composition on the substrate and then heating to form a first organic film; Applying a second composition on the first organic layer and then heating to form a second organic layer; Developing, and curing a substrate on which the first organic layer and the second organic layer are formed, wherein the first composition includes a binder resin, a reactive unsaturated compound, a photopolymerization initiator, a colorant including a silver halide, and a solvent , And the second composition comprises a binder resin, a reactive unsaturated compound, a photopolymerization initiator, and a solvent.

The contents of the first organic film, the second organic film, the first composition, the second composition, and the like are the same as those described above.

Specifically, the black column spacer manufacturing method may be as follows.

(1) Coating and Film Formation Step

In order to form the first organic film, 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 DEG C to 100 DEG C for 1 minute to 10 minutes to form a coating film. Thereafter, in order to form the second organic film, 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 at 80 ° C for 1 minute to 10 minutes using a hot plate to form a first organic film, 2 composition was applied and dried at 80 캜 for 1 minute to 10 minutes using a hot plate to form a second organic film (thickness: 1.5 탆) on the first organic film (thickness: 1.5 탆) To prepare a photosensitive resin composition layer according to Example 1 composed of two layers.

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, other additives were added to the obtained solution, stirred for about 10 minutes, then added with a coloring agent and stirred 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) 4.82 Acrylic binder resin (BX-04, manufactured by Nippon Shokubai Co., Ltd.) 4.82 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 coloring agent Mill base with AgBr 6.397 Carbon black included Mill base (Tokushiki, PWC25%) 1.438 additive γ-glycidoxypropyltrimethoxysilane (S-510, Chisso) 0.941

The Mill base containing AgBr in Table 1 was prepared as follows.

300 g of 0.5 mm zirconium oxide beads are placed in a 1 L basket mill equipped with a stirrer and a cooling jacket, and 300 g of AgBr and 380 g of PGMEA are introduced. Subsequently, 26 g of Disperbyk 161 dispersant BYK, 18 g of a cadmium polymer having a molecular weight of 3,000 g / mol, 4 g of 4,4 '- (9-fluorenylidene) diphenol glycidyl ether and 4 g of hexadecyl 4 g of trimethylammonium bromide was added and dispersed at 15 DEG C and 1000 rpm for 4 hours to obtain a dispersion.

(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.) 8.727 Photopolymerization initiator OXE01 (BASF) 0.489 menstruum PGMEA 48.64 EDM 16.40 additive γ-glycidoxypropyltrimethoxysilane (S-510, Chisso) 1.570

Example 2

The photosensitive resin composition layer according to Example 2 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 3 by using the following components.

(Unit: g) ingredient content Binder resin Cadmium binder resin (V259ME, Nippon Steel Corporation) 4.54 Acrylic binder resin (BX-04, manufactured by Nippon Shokubai Co., Ltd.) 18.71 The reactive unsaturated compound Dipentaerythritol hexaacrylate (Nippon Catalyst Co., Ltd.) 8.392 Photopolymerization initiator OXE01 (BASF) 0.470 menstruum PGMEA 46.14 EDM 16.40 coloring agent Mill base with AgBr 3.84 additive γ-glycidoxypropyltrimethoxysilane (S-510, Chisso) 1.508

Comparative Example  One

A photosensitive resin composition layer (thickness: 3.0) according to Comparative Example 1 composed of a single layer was prepared in the same manner as in Example 1 except that the photosensitive resin composition was prepared in the composition shown in Table 4 below using the following components Mu m).

(Unit: g) ingredient content Binder resin Cadmium binder resin (V259ME, Nippon Steel Corporation) 4.82 Acrylic binder resin (BX-04, Nippon Catalysts Co., Ltd.) 4.82 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 coloring agent 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 4, the lactam-based organic black is represented by the following formula (A).

(A)

)

)

Evaluation 1: Evaluation of developing margin

The photosensitive resin composition layers of Examples 1 and 2 and Comparative Example 1 were exposed to 100 mJ using a photomask with an exposure machine (Ushio, HB-50110AA). 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. The thickness and the step height of the specimen were measured with a contact thickness meter (Tencor, α-stepper) or a non-contact thickness meter (3-D profiler) to evaluate the development margin. The results are shown in FIG.

4, it can be seen that Examples 1 and 2 have a small thickness reduction with the elapse of the developing time and are excellent in the developing margin, whereas Comparative Example 1 shows a large decrease in thickness with the elapse of the developing time and a poor developing margin have.

Evaluation 2: Solvent resistance  evaluation

The specimen prepared in the above evaluation 1 was cut into a size of 1 cm * 1 cm and placed in a glass bottle containing 5 ml of NMP. The specimen was left in an oven at 100 ° C for 60 minutes to observe whether there was any discoloration, and the results are shown in Table 5 below.

Color separation  How to display measurement result

X: No color separation when observed with naked eyes

O: When the sample is observed with the naked eye, color dropout is very high

Example 1 Example 2 Comparative Example 1 Missing color X X ○

It can be seen from Table 5 that Examples 1 and 2 are excellent in solvent resistance as compared with Comparative Example 1 because there is no discoloration.

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 (19)

A first organic film and a second organic film located on the first organic film,
Wherein the first organic film is an organic film obtained by curing the first composition,
The second organic film is an organic film obtained by curing the second composition,
Wherein the first composition comprises a binder resin, a reactive unsaturated compound, a photopolymerization initiator, a colorant comprising silver halide and a solvent,
Wherein the second composition comprises a binder resin, a reactive unsaturated compound, a photopolymerization initiator, and a solvent.
The method according to claim 1,
Wherein the colorant in the first composition further comprises carbon black.
3. The method of claim 2,
Wherein the colorant in the first composition comprises silver halide and carbon black in a weight ratio of 1: 1 to 9: 1.
3. The method of claim 2,
Wherein the colorant in the first composition comprises a first pigment dispersion comprising the silver halide, the first dispersant and the first solvent; And a second pigment dispersion liquid containing carbon black, a second dispersant and a second solvent.
3. The method of claim 2,
Wherein the colorant in the first composition is obtained from a pigment dispersion comprising the carbon black, the silver halide, a dispersant and a solvent.
The method according to claim 1,
Wherein the second composition further comprises a coloring agent.
The method according to claim 6,
Wherein the coloring agent comprises silver halide.
8. The method of claim 7,
Silver halide is contained in an amount of 50% by weight to 90% by weight based on 100% by weight of the colorant in the first composition,
Wherein the silver halide is contained in an amount of 0.1 to 10% by weight based on 100% by weight of the total of the second composition.
The method according to claim 1,
Wherein the binder resin in the first composition and the binder resin in the second composition each independently comprise a cationic binder resin, an acrylic binder resin, a polyimide binder resin, a polyurethane binder resin or a combination thereof.
10. The method of claim 9,
The cationic binder resin has a weight average molecular weight of 1,000 g / mol to 50,000 g / mol,
Wherein the acrylic binder resin has a weight average molecular weight of 3,000 g / mol to 150,000 g / mol.
The method according to claim 1,
The first composition comprises 0.5 to 20% by weight of binder resin, 1 to 20% by weight of a reactive unsaturated compound, 0.1 to 10% by weight of a photopolymerization initiator, 1 to 50% by weight of a colorant, And a photosensitive resin composition layer.
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,
Wherein the first composition and the second composition each independently comprise a photosensitive resin composition further comprising an additive of malonic acid, 3-amino-1,2-propanediol, a silane coupling agent, a leveling agent, a fluorine surfactant, layer.
A black column spacer produced by using the photosensitive resin composition layer according to any one of claims 1 to 13.
A substrate is prepared,
Applying a first composition on the substrate and heating the first composition to form a first organic layer;
Applying a second composition on the first organic layer and then heating to form a second organic layer;
Developing, and curing the substrate on which the first organic film and the second organic film are formed,
Wherein the first composition comprises a binder resin, a reactive unsaturated compound, a photopolymerization initiator, a colorant comprising silver halide and a solvent,
Wherein the second composition comprises a binder resin, a reactive unsaturated compound, a photopolymerization initiator, and a solvent.
16. The method of claim 15,
The colorant in the first composition further comprises carbon black,
Wherein the silver halide and the carbon black are contained in a weight ratio of 1: 1 to 9: 1.

16. The method of claim 15,
Wherein the second composition further comprises silver halide. 18. The method of claim 17,
Silver halide is contained in an amount of 50% by weight to 90% by weight based on 100% by weight of the colorant in the first composition,
And the silver halide is contained in an amount of 0.1 to 10 wt% based on 100 wt% of the total of the second composition.
A color filter comprising the black column spacer of claim 14.

Images