KR20160002242A - Method of manufacturing black column spacer, black column spacer, and color filter - Google Patents

Abstract

Provided are a method for manufacturing a black column spacer, a black column spacer manufactured by the method, and a color filter including the black column spacer. The method for manufacturing a black column spacer includes the following steps: preparing a substrate; applying a first composition onto the substrate; forming a first organic film by vacuum-drying the applied first composition; applying a second composition onto the first organic film; forming a second organic film by heating the applied second composition; and exposing, developing, and hardening the first organic film and the second organic film.

Description

TECHNICAL FIELD The present invention relates to a black column spacer,

The present disclosure relates to a method of manufacturing a black column spacer, a black column spacer manufactured by the method, 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.

One embodiment is to provide a method of manufacturing a black column spacer having excellent developing margin, processability and solvent resistance.

Another embodiment is to provide a black column spacer produced by the above method.

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

One embodiment includes the steps of preparing a substrate; Applying a first composition on the substrate; Vacuum drying the coated first composition to form a first organic layer; Applying a second composition on the first organic layer; Heating the applied second composition to form a second organic film; And exposing, developing and curing the first organic film and the second organic film to form a black column spacer.

The manufacturing method further includes a step of vacuum drying the applied second composition between the step of applying the second composition on the first organic film and the step of heating the applied second composition to form the second organic film can do.

The vacuum drying may be performed at a pressure of 0.1 torr to 5 torr for 10 seconds to 60 seconds.

The first composition may include a binder resin, a reactive unsaturated compound, a photopolymerization initiator, a pigment, and a solvent.

The second composition may include a binder resin, a reactive unsaturated compound, a photopolymerization initiator, and a solvent.

The second composition may further comprise a pigment.

The pigment may comprise a black pigment, and the black pigment may be an organic black pigment and / or an inorganic 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.

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 pigment; And solvent balance.

The second composition comprises 3% to 70% by weight of a binder resin; 2% to 40% by weight of a reactive unsaturated compound; 0.1 to 5% by weight of a photopolymerization initiator; And solvent balance.

Wherein the first composition and the second composition are each independently selected from malonic acid; 3-amino-1,2-propanediol; Silane coupling agents; Leveling agents; Fluorine surfactants; A radical polymerization initiator; Or a combination thereof.

The second composition is heated to form the second organic film, and the heating may be carried out at a temperature of 70 ° C to 100 ° C for 1 minute to 10 minutes.

The post-exposure development and curing may be performed at a temperature of 150 ° C to 250 ° C for 10 minutes to 60 minutes.

Another embodiment provides a black column spacer made by the above process.

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

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

According to the manufacturing method according to one embodiment, it is possible to provide a black column spacer having excellent developing margin, processability, and solvent resistance, and further, cost reduction is also great due to excellent processability.

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a schematic view of a conventional method of manufacturing a black column spacer. FIG.
2 is a photograph of a black column spacer according to Example 1 measured by a scanning electron microscope (SEM).
3 is a photograph of a cross section of a black column spacer according to Example 1 measured by a scanning electron microscope (SEM).
4 is a schematic view illustrating a method of manufacturing a black column spacer according to one embodiment.
5 is a graph showing a developing margin of a black column spacer according to Example 1 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, 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.

A method of manufacturing a black column spacer according to an embodiment includes: preparing a substrate; Applying a first composition on the substrate; Vacuum drying the applied first composition to form a first organic layer (Layer 1); Applying a second composition on the first organic layer; Heating the applied second composition to form a second organic layer (Layer 2); And exposing, developing, and curing the first organic film and the second organic film.

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 manufacturing a black column spacer proceeds to a step of coating a black column spacer composition on a substrate at one time to expose, develop and cure the black column spacer composition. Since the black column spacer composition has a high optical density (OD) In the step of exposure (S2), light does not reach substantially to the lower portion of the black column spacer composition formed on the substrate, and hardening does not easily occur. Thus, after the halftone is substantially exposed at the time of exposure, the black spacer is cut away to about half, and a step is formed in a state where no hardening is progressed, and then the pattern is thermally cured in the post-baking step. 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 with a uniform thickness.

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 dissolution possibility of metal ions and pigments in the spacer pattern by the solvent is higher than that of carbon black which is an inorganic black pigment. As a result, the reliability of the black column spacer contacting the liquid crystal is deteriorated. In addition, the lower layer portion of the black column spacer is not cured at all, hardened only by the thermosetting resin, and the degree of curing is not high, so that the required chemical resistance can not be sufficiently obtained.

A method of manufacturing a black column spacer according to an embodiment of the present invention includes forming a first organic film on a substrate to obtain an optical density, further forming a second organic film on the first organic film, By conducting the exposure, development and curing processes in one process, the sensitivity and developability of the first organic film and the second organic film can be controlled. Thus, not only the development process can be stopped at a desired step in the development process, but also the second organic (organic) layer having a lower optical density (OD) than the first organic layer Since the surface of the first organic film can be cured by the light transmitted through the film, a black column spacer with greatly improved reliability and developing margin can be manufactured. Furthermore, in the step of drying the solvent in the first composition to form the first organic film, the solvent is dried by a vacuum drying method instead of prebaking by heat, thereby improving the processability and reducing the cost.

Hereinafter, each step of the manufacturing method will be described in detail with reference to FIG.

(A) preparing a substrate

A substrate for forming a black column spacer is prepared. The substrate may be an IZO substrate, a glass substrate, or the like, but is not limited thereto. Any material can be used as long as it is necessary to form a black column spacer and form a black column spacer.

(B) applying the first composition

In order to form a first organic film on the substrate, a first composition is first applied on the substrate. The application of the first composition onto the substrate can be carried out by a known method such as a spin or slit coat method, a roll coating method, a screen printing method or an applicator method to a desired thickness, for example, a thickness of 2 to 25 탆 The first composition may be applied.

(C) vacuum drying the first composition to form the first Organic membrane  Forming step

The applied first composition is vacuum dried to form a first organic layer (Layer 1). The vacuum drying is a process of removing all or part of the solvent in the first composition, and the solvent may be removed in a chamber including a vacuum pump. For example, the solvent in the first composition may be completely or partially removed by allowing the first composition to remain in the chamber (0.1 torr to 5 torr) containing the vacuum pump for 10 seconds to 60 seconds.

The first composition may include a binder resin, a reactive unsaturated compound, a photopolymerization initiator, a pigment, and a solvent.

Since the first organic film obtained by vacuum drying the first composition has high optical density, the pigment in the first composition may include a black pigment. The black pigment may include an inorganic black pigment, an organic black pigment, or a combination thereof. For example, 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. 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 organic film 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 dispersant 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.

The pigment may be included 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. When the pigment is included 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. For example, 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 dianhydride, benzene tetracarboxylic acid dianhydride, naphthalene tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, benzophenone tetracarboxylic 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, 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 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% by weight to 30% by weight, for example, 2% by weight to 20% by weight based on the total amount 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, excellent 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% based on the total amount of the first organic film 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 material that has compatibility with the pigment, the binder resin, the reactive unsaturated compound, and the photopolymerization initiator but does not react.

Examples of the solvent include alcohols such as methanol and ethanol; Ethers such as dichloroethyl ether, n-butyl ether, diisobutyl ether, methylphenyl ether and tetrahydrofuran; Glycol ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether and propylene glycol methyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate and diethyl cellosolve acetate; Carbitols such as methylethylcarbitol, diethylcarbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether and diethylene glycol diethyl ether; 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 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.

On the other hand, the first composition may include malonic acid; 3-amino-1,2-propanediol; Silane coupling agents; Leveling agents; Fluorine surfactants; 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.

(D) applying the second composition

In order to form a second organic film on the substrate, a second composition is applied on the first organic film. The application of the second composition can be carried out by a known method such as a spin or slit coat method, a roll coating method, a screen printing method, an applicator method or the like to a desired thickness, for example, a thickness of 2 탆 to 25 탆, The composition can be applied.

(C) heating the second composition to produce a second Organic membrane  Forming step

The applied second composition is heated to form a second organic layer (Layer 2). The heating is a process of removing all or part of the solvent in the second composition. For example, after the application of the second composition, the solvent is heat-treated at a temperature of 70 ° C to 110 ° C for 1 minute to 10 minutes, Or partly removed.

Since the second composition is for realizing a step difference and does not necessarily require a high optical density (OD), the pigment of the constituents of the first composition may not necessarily be contained in the second composition. That is, the second composition may include a binder resin, a reactive unsaturated compound, a photopolymerization initiator, and a solvent, or may optionally further include a pigment as the second composition. In addition, the second composition may further include the above-mentioned additives.

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 (OD) after curing of the first composition and the second composition may be different.

Accordingly, the components constituting the binder resin, the reactive unsaturated compound, the photopolymerization initiator, the solvent and / or the pigment constituting the second composition are the same as those described for the first composition.

The optical density (OD) of the second organic film may be lower than the optical density (OD) of the first organic film. In this case, since the reliability of the black column spacer can be ensured, the second composition for forming the second organic film is preferably a binder resin which contains less cadmium binder resin than other cadmium binder resins, 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 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 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, since the second composition is applied after drying the first composition, the solvent of the second composition may be less soluble 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, EDM, 3-MBA, n-butyl acetate, n-pentyl acetate, Acetate, and the like, but is not limited thereto.

(D) exposure, developing and curing step

After the first organic film and the second organic film are formed on the substrate, the substrate on which the first organic film and the second organic film are formed is exposed on the front side. The term " front exposure " is a term opposite to back exposure, which means exposure of the entire surface of the substrate, that is, the surface on which the first organic film and the second organic film are formed, not the back surface of the substrate. That is, the step of exposing may mean the step of performing only the front exposure.

The step of performing the front exposure can be performed using a single halftone mask, so that the black matrix and the column spacer can be patterned in one process. The halftone mask refers to a mask including a full-tone portion that completely transmits light and a halftone portion that transmits only a part of the light. The single halftone mask may include a region that transmits 100% of light during exposure and a region that transmits light during exposure of less than 100%. The region for transmitting light at the time of exposure under the condition of 100% or less is, for example, 20% to 70%, that is, 21% to 70%, 22% to 70%, 23% to 70%, 24% 70%, 26% to 70%, 27% to 70%, 28% to 70%, 29% to 70%, 30% to 70%, 31% to 70%, 32% to 70% %, 33% -70%, 34% -70%, 35% -70%, 36% -70%, 37% -70%, 38% -70%, 39% -70%, 40% 45% to 70%, 46% to 70%, 47% to 70%, 48% to 70%, 49% to 70%, 42% to 70%, 43% to 70%, 44% To 70%, 50% to 70%, 51% to 70%, 52% to 70%, 53% to 70%, 54% to 70% 60% to 70%, 62% to 70%, 63% to 70%, 64% to 70%, 65% to 70%, 60% to 70% , 66% to 70%, 67% to 70%, 68% to 70%, or 69% to 70%

After the exposure, the optical density of the first organic film and the optical density of the second organic film may differ by 1.0 or more by development and curing. For example, the optical density of the first organic film may be 1.0 to 5.0.

The curing temperature may be 150 to 250 ° C, and the curing time may be 10 to 60 minutes. By such heat treatment, it is possible to induce full curing of the portion that is not photo-cured, thereby improving reliability and pattern stability.

Another embodiment provides a black column spacer made using the black column spacer manufacturing method described above.

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 )

(Preparation of first composition and second composition)

Manufacturing example  1 to Manufacturing example  3

The organic film composition according to each of Production Examples 1 to 3 was prepared with the compositions shown in Tables 1 to 3 below using the following components.

Specifically, after dissolving a photopolymerization initiator in a solvent, the mixture is sufficiently stirred at room temperature for 30 minutes or more, and then a binder resin and a reactive unsaturated compound are added thereto, followed by stirring at room temperature for about 1 hour. Subsequently, other additives are added to the obtained solution, stirred for about 10 minutes, and then the pigment is added thereto and stirred at room temperature for 2 hours or more (in the case of Production Example 2, no pigment is added). Subsequently, the product is filtered three times to remove impurities, thereby preparing an organic film composition.

Manufacturing example  1: 1st Organic film  Produce

(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 Pigment 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)

Manufacturing example  2: 2nd Organic film  Produce

(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

Manufacturing example  3: 2nd Organic film  Produce

(Unit: g) ingredient content Binder resin Cadmium binder resin (V259ME, Nippon Steel Corporation) 18.200 The reactive unsaturated compound Dipentaerythritol hexaacrylate (Nippon Catalyst Co., Ltd.) 4.368 Photopolymerization initiator OXE01 (BASF) 1.303 menstruum n-butyl acetate 75.504 Pigment Lactam-based organic black (BASF) Mill base (Mikuni, PWC 18%) 1.958 Carbon black included Mill base (Tokushiki, PWC 25%) 0.337 additive γ-glycidoxypropyltrimethoxysilane (S-510, Chisso) 0.330

(In Table 3, the lactam-based organic black is represented by the following formula (A).

(A)

)

)

(black column Spacer  Produce)

Example  One

(1) application of the first composition and formation of the first organic film

The first composition of Production Example 1 was coated on an IZO substrate subjected to a predetermined pretreatment to a thickness of 1.5 탆 by a spin or slit coating method, a roll coating method, a screen printing method, an applicator method or the like, And vacuum-dried at a pressure of 0.1 torr to 5 torr for 10 seconds to 60 seconds to remove the solvent to form a first organic film.

 (2) Application of the second composition and formation of the second organic film

The second composition of Production Example 2 was coated on the IZO substrate having the first organic film formed thereon to a thickness of 1.5 탆 by a spin, slit coat method, roll coating method, screen printing method, applicator method or the like, Vacuum drying is performed at a pressure of 0.1 torr to 5 torr using a chamber for 10 seconds to 60 seconds and then heat is applied at 70 to 100 DEG C for 1 to 10 minutes using a hot plate to be dried Thereby forming a second organic film.

(3) Exposure step

In order to form a pattern necessary for the first organic film and the second organic film, a halftone portion (light is transmitted through 20% to 70% light) for implementing a black matrix pattern and a Fulton portion (light is transmitted through 100%) for implementing a column spacer pattern A mixed-structured mask is placed on the second organic film and exposed to an active line of 200 nm to 500 nm using an exposure machine (Ushio, HB-50110AA) to perform front exposure. 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 is 500 mJ / cm ² (according to the 365 nm sensor) or less when a high-pressure mercury lamp is used, though it depends on the kind of the components in the composition, the blending amount, and the film thickness upon drying.

(4) Development step

Following the above exposure step, an unnecessary portion is dissolved and removed with a 0.2 wt% aqueous solution of potassium hydroxide (KOH) using a developing device (SVS, SSP-200) to leave only the exposed portion to form a pattern.

(5) Post-treatment (curing) step

There is a post-heating process for obtaining a pattern excellent in terms of heat resistance, light resistance, adhesion, crack resistance, chemical resistance, high strength and storage stability of the image pattern obtained by the above development. Specifically, the image pattern obtained by the above-mentioned development was heated in an oven at 230 캜 for 30 minutes to prepare a black column spacer specimen.

Example  2

A black column spacer was prepared in the same manner as in Example 1 except that the second composition of Production Example 3 was used instead of the second composition of Production Example 2.

Comparative Example  One

A black column spacer was prepared in the same manner as in Example 1 except that the first composition of Production Example 1 was applied to a thickness of 3.0 탆 without using the second composition of Production Example 2.

Rating 1: Optical density ( Optical Density ; OD ) evaluation

The organic film compositions prepared in Preparation Examples 1 to 3 were coated on IZO substrates of 10 cm x 10 cm each using a spin coater (Mikasa, Opticoat MS-A150) to a thickness of 1.5 탆, hot- (Soft-baking or pre-baking) at 80 DEG C for 150 seconds and exposed at 50 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. Optical densities of the specimens were measured and are shown in Table 4 below.

Production Example 1 Production Example 2 Production Example 3 Optical density (OD) 2.2 0 0.3

Evaluation 2: Evaluation of developing margin

The thickness and level difference of the black column spacer specimens according to Examples 1 and 2 and Comparative Example 1 were measured with a contact thickness meter (Tencor,? -Stepper) or a non-contact thickness meter (3-D profiler) The results are shown in FIG.

5, in Example 1 and Example 2, the thickness reduction with the elapse of the developing time was small and the developing margin was excellent, whereas in Comparative Example 1, the thickness reduction with the elapse of the developing time was large (0.414 mu m / 10 sec) It can be seen that it is bad.

Rating 3: Solvent resistance  evaluation

The black column spacer specimens according to Example 1, Example 2 and Comparative Example 1 were cut into a size of 1 cm * 1 cm, placed in a glass bottle having 5 mL of NMP and allowed to stand in an oven at 100 ° C. for 15 minutes, 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 O

From Table 5, it can be confirmed 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 (17)

Preparing a substrate;
Applying a first composition on the substrate;
Vacuum drying the coated first composition to form a first organic layer;
Applying a second composition on the first organic layer;
Heating the applied second composition to form a second organic film; And
Exposing, developing and curing the first organic film and the second organic film
≪ / RTI >
The method according to claim 1,
Further comprising vacuum drying the applied second composition between the step of applying the second composition on the first organic layer and the step of forming the second organic layer by heating the applied second composition, Spacer.
3. The method according to claim 1 or 2,
Wherein the vacuum drying is performed at a pressure of 0.1 torr to 5 torr for 10 seconds to 60 seconds.
The method according to claim 1,
Wherein the first composition comprises a binder resin, a reactive unsaturated compound, a photopolymerization initiator, a pigment, and a solvent.
The method according to claim 1,
Wherein the second composition comprises a binder resin, a reactive unsaturated compound, a photopolymerization initiator, and a solvent.
6. The method of claim 5,
Wherein the second composition further comprises a pigment.
The method according to claim 4 or 6,
Wherein the pigment comprises a black pigment.
8. The method of claim 7,
Wherein the black pigment comprises aniline black, perylene black, titanium black, cyanine black, lignin black, lactam-based organic black, RGB black, carbon black or a combination thereof.
7. The method according to any one of claims 4 to 6,
Wherein the binder resin comprises a cadmium-based binder resin, an acrylic-based binder resin, or a combination thereof.
5. The method of claim 4,
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; From 1% to 30% by weight of pigment, and a balance of solvent.
6. The method of claim 5,
The second composition comprises 3% to 70% by weight of a binder resin; 2% to 40% by weight of a reactive unsaturated compound; 0.1 to 5% by weight of a photopolymerization initiator; And a solvent remaining amount.
5. The method of claim 4,
The first composition comprises malonic acid; 3-amino-1,2-propanediol; Silane coupling agents; Leveling agents; Fluorine surfactants; A radical polymerization initiator; Or a combination thereof. ≪ / RTI >
The method according to claim 5 or 6,
The second composition comprises malonic acid; 3-amino-1,2-propanediol; Silane coupling agents; Leveling agents; Fluorine surfactants; A radical polymerization initiator; Or a combination thereof. ≪ / RTI >
The method according to claim 1,
Wherein the heating is carried out at a temperature of 70 DEG C to 100 DEG C for 1 minute to 10 minutes.
The method according to claim 1,
Wherein the curing is carried out at a temperature of 150 ° C to 250 ° C for 10 minutes to 60 minutes.
A black column spacer produced by the method of claim 1.
A color filter comprising the black column spacer of claim 16.

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