KR101814672B1 - Photosensitive resin layer, black column spacerusing the sameand color filter - Google Patents

Abstract

A first resin film formed by coating a first composition on a substrate and cured, and a second resin film formed by applying a second composition onto the first resin film and curing the first resin film, wherein the first composition comprises a cadmium binder resin, a reactive unsaturated compound, Wherein the second composition comprises an acrylic binder resin, a reactive unsaturated compound, a photopolymerization initiator and a solvent, wherein the weight average molecular weight of the acrylic binder resin in the second composition is 25000 g / mol to 29000 g / mol, a black column spacer manufactured by exposing and developing the photosensitive resin film, and a color filter including the black column spacer.

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin film, a black column spacer using the same, and a color filter using the same. BACKGROUND ART [0002]

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

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

Recently, 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.

However, conventionally, the photosensitive resin film is formed from a single photosensitive resin composition, so that the reliability is lowered, it is difficult to realize a desired level difference, and the improvement effect in terms of the developing margin is not shown. In addition, the conventional photosensitive resin film has a problem that the critical dimension (CD) is large and the taper angle of the color filter pattern produced therefrom is low.

Therefore, studies for developing a photosensitive resin film capable of overcoming the above problems are continuing.

One embodiment is for providing a photosensitive resin film comprising a first resin film and a second resin film, wherein the second resin film comprises an acrylic binder resin having a specific range of weight average molecular weight.

Another embodiment is to provide a black column spacer manufactured using the photosensitive resin film.

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

One embodiment includes a first resin film formed by applying a first composition onto a substrate and then curing the first composition, and a second resin film formed by applying a second composition onto the first resin film and curing the first resin film, wherein the first composition comprises a cadmium- Wherein the second composition comprises an acrylic binder resin, a reactive unsaturated compound, a photopolymerization initiator and a solvent, wherein the weight average molecular weight of the acrylic binder resin in the second composition is 25000 g / mol to 29000 g / mol.

The acrylic binder resin in the second composition may include a repeating unit represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

R ¹ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

R ² is a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

The acrylic binder resin in the second composition may further include a repeating unit represented by the following formula (2) and (3).

(2)

(3)

In the general formulas (2) and (3)

R ³ , R ⁵ and R ⁶ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

R ⁴ is a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

The repeating unit represented by the formula (1), the repeating unit represented by the formula (2) and the repeating unit represented by the formula (3) are preferably a repeating unit represented by the following formula (1): a repeating unit represented by the formula Repeating unit = 35 to 45:40 to 50:15 to 25 ".

The pigment may comprise a black pigment.

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

Wherein the first composition comprises a pigment dispersion comprising the pigment, wherein the first composition comprises from 1 wt% to 30 wt% of a cationic binder resin, from 1 wt% to 20 wt% of a reactive unsaturated compound, from 0.05 wt% 5 wt%, pigment dispersion 5 wt% to 60 wt%, and solvent balance.

The second composition may include 3 to 40% by weight of an acrylic binder resin, 2 to 20% by weight of a reactive unsaturated compound, 0.1 to 5% by weight of a photopolymerization initiator, and a remaining amount of a solvent.

The second composition may further comprise a pigment.

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 prepared by exposing and developing the photosensitive resin film.

The pattern in the black column spacer may have a taper angle of 20 degrees or greater.

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

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

The photosensitive resin film according to an embodiment includes a first resin film and a second resin film, and the second resin film includes an acrylic binder resin having a weight average molecular weight in a specific range, and the CD of the pattern is small and has a high taper angle A black column spacer and a color filter including the black column spacer are provided.

1 to 3 are scanning electron microscope (SEM) photographs of a pattern in a black column spacer manufactured by using the photosensitive resin film according to Example 1, Example 2 and Comparative Example 1. Fig.
4 to 6 are image photographs of the CD of the photosensitive resin film according to Example 1, Example 2, and Comparative Example 1 measured with a 3-D profiler.

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, unsaturated bonds include not only multiple bonds between carbon-carbon atoms, but also include other molecules such as carbonyl bonds, azo bonds, and the like.

In the present specification, the cadmium resin means a resin in which at least one functional group selected from the group consisting of the following formulas (4-1) to (4-11) is contained in the main backbone of the resin.

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

The photosensitive resin film according to an embodiment includes a first resin film and a second resin film. For example, the photosensitive resin film may consist of the first resin film and the second resin film. The first resin film is formed by applying a first composition onto a substrate and then curing, and the second resin film is formed by applying the second composition onto the first resin film and curing the same. Wherein the first composition comprises a cationic binder resin, a reactive unsaturated compound, a photopolymerization initiator, a pigment, and a solvent, wherein the second composition has a weight average molecular weight of 25000 g / mol to 29000 g / mol, , A photopolymerization initiator, and a solvent.

The optical density per 1 mu m of the first resin film may be larger than the optical density per 1 mu m of the second resin film by 0.4 or more, for example, 1.0 or more, such as 1.5 or more. In general, a photosensitive resin film for manufacturing a black column spacer is formed as a single layer, and therefore imperfect steps are required to be realized. However, since the photosensitive resin film according to one embodiment is composed of the first resin film including, for example, the first composition for obtaining the optical density and the second resin film including the spacer and the second composition for realizing the step difference , Sensitivity and developability can be easily controlled, so that a desired level difference can be obtained. Furthermore, since the surface of the first resin film can be hardened by the light transmitted through the second resin film, which may have optical density lower by 0.4 or more per 1 m than the first resin film at the intermediate position of the photosensitive resin film, A very improved result in terms of the developing margin can be obtained.

The photosensitive resin film including the first resin film and the second resin film provides a black column spacer through exposure, development, curing, or the like.

However, the double-layered photosensitive resin film tends to have a problem that the taper is low at the time of pattern formation or the acrylic binder resin is not dissolved in the solvent depending on the weight average molecular weight of the acrylic binder resin in the second resin film.

In order to solve the above problems, the photosensitive resin film according to one embodiment is characterized in that the weight average molecular weight of the acrylic binder resin in the second composition constituting the second resin film is limited to 25000 g / mol to 29000 g / mol, The resin was dissolved well in the solvent and at the same time had a high taper during pattern formation.

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

The first resin film is formed by applying a first composition on a substrate and then curing the first composition, wherein the first composition includes a cadmium binder resin, a reactive unsaturated compound, a photopolymerization initiator, a pigment, and a solvent.

Since the first resin film should have a high optical density, the pigment may include a black pigment. The black pigments include inorganic black pigments, organic black pigments, or combinations thereof, such as aniline black, perylene black, titanium black, cyanine black, lignin black, lactam-based organic black, RGB black, carbon black, can do. Specifically, the black pigment may include an inorganic black pigment and an organic black pigment, the inorganic black pigment may be carbon black, and the organic black pigment may be a lactam-based organic black represented by the following formula (A).

(A)

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

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

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

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

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

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

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

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

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

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

Specifically, the pigment may be used in the form of a pigment dispersion including the dispersant and a solvent described later, and the pigment dispersion may include a solid pigment, a dispersant, and a solvent. The pigment dispersion may be included in an amount of 5% by weight to 60% by weight, for example, 5% by weight to 50% by weight based on the total weight of the first composition. When the pigment dispersion is contained within the above range, the resolution and the linearity of the pattern are excellent.

The binder resin in the first composition may further comprise a cadmium-based binder resin or an acrylic-based binder resin.

When the binder resin in the first composition is a cadmium-based binder resin, the first composition containing the same is excellent in developability, sensitivity in photo-curing, and excellent in fine pattern formation. In addition, when a cadmium 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 (4).

[Chemical Formula 4]

In Formula 1,

R ¹¹ And R ¹² are each independently a hydrogen atom or a substituted or unsubstituted (meth) acryloyloxyalkyl group,

R ¹³ and R ¹⁴ 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) Is any one of the linking groups represented by the following formulas (4-1) to (4-11)

[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

[Formula 4-4]

[Formula 4-5]

(In the above Formula 4-5,

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.)

[Formula 4-6]

[Formula 4-7]

[Formula 4-8]

[Chemical Formula 4-9]

[Formula 4-10]

[Formula 4-11]

Z ² is an acid anhydride residue,

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

The cadmium-based binder resin may include a functional group represented by the following formula (5) in at least one of the two terminals.

[Chemical Formula 5]

In Formula 5,

Z ³ can be represented by the following formulas (5-1) to (5-7).

[Formula 5-1]

(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 5-2]

[Formula 5-3]

[Formula 5-4]

[Formula 5-5]

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 alkenylamine group.

[Formula 5-6]

[Formula 5-7]

Examples of the cationic binder resin include fluorene-containing compounds such as 9,9-bis (4-oxiranylmethoxyphenyl) fluorene; Benzene tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, cyclobutanetetracarboxylic dianhydride, perylenetetracarboxylic dianhydride , Tetrahydrofuran tetracarboxylic acid dianhydride, tetrahydrophthalic anhydride and the like; 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.

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 cadmium binder resin may be included in an amount of 1% by weight to 30% by weight, for example, 5% by weight to 30% by weight, for example, 1% by weight to 20% by weight based on the total amount of the first composition. When the cadmium 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 (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol monomethyl 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, doah Gosei cultivating the T (weeks)社Aronix M-101 ^®, the same M-111 ^®, the same M-114 ^®, and the like; KAYARAD TC-110S ^® and TC-120S ^{® from} Nihon Kayaku Co., Ltd.; Osaka yukki cultivate may be a T (weeks)社of ^{V-158 ®, V-2311} ® and the like. The (meth) transfer function of an example esters of acrylic acid are, doah Gosei cultivating the T (weeks)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 cultivating and the like T (weeks)社of ^{V-260 ®, V-312} ®, V-335 HP ®. Examples of the tri-functional ester of (meth) acrylic acid, doah Gosei the cultivating T (weeks)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 compound include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, pt Dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1 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) -Dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) (Trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) - 4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthol-1-yl) -Bis (trichloromethyl) -6- (4-methoxystyryl) -s-triazine, and the like. .

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

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

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

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

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

The solvent may be a pigment dispersion containing the pigment, 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 monomethyl ether and ethylene glycol monoethyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate and diethyl cellosolve acetate; Carbitols such as methylethylcarbitol, diethylcarbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl- ; Saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate and isobutyl acetate; Lactic acid esters such as methyl lactate and ethyl lactate; Oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate and butyl oxyacetate; Alkoxyacetic acid alkyl esters such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, and ethyl ethoxyacetate; 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate and propyl 2-oxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate and methyl 2-ethoxypropionate; 2-methylpropionic acid esters such as methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy- Monooximonocarboxylic acid alkyl esters of 2-alkoxy-2-methylpropionic acid alkyls such as ethyl methyl propionate; Esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate and methyl 2-hydroxy-3-methylbutanoate; Ketone acid esters such as ethyl pyruvate, and the like, and also include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide , N-methylpyrrolidone, dimethylsulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, And high boiling solvents such as ethyl acetate, diethyl oxalate, diethyl maleate,? -Butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.

Of these, glycol ethers such as ethylene glycol monoethyl ether and ethylene glycol diethyl ether are preferable in view of compatibility and reactivity; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as ethyl 2-hydroxypropionate; Carbitols such as diethylene glycol monomethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate can be used.

The solvent may be included in an amount of 30% by weight to 90% by weight based on the total amount of the first composition. When the solvent is included within the above range, the first composition has an appropriate viscosity, and thus the processability of the black column spacer is excellent.

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

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

Examples of the silane-based coupling agent include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatepropyltriethoxysilane,? -Glycine (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. 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; Mecha Pack F 142D ^® , Copper F 172 ^® , Copper F 173 ^® , Copper F 183 ^® , Copper F 554 ^® 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 fluorinated surfactant may be used in an amount of 0.001 part by weight to 5 parts by weight based on 100 parts by weight of the first composition. When the surfactant is contained within the above range, coating uniformity is ensured, no staining occurs, and wetting to an IZO substrate or a glass substrate is excellent.

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

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

The second resin film is formed by applying a second composition on the first resin film and curing the second resin film, and the second composition includes an acrylic binder resin, a reactive unsaturated compound, a photopolymerization initiator, and a solvent.

The weight average molecular weight of the acrylic binder resin in the second composition is 25000 g / mol to 29000 g / mol. When the weight average molecular weight of the acrylic binder resin in the second composition is less than 25000 g / mol, the taper of the pattern is lowered to less than 20 °. If the weight average molecular weight of the acrylic binder resin in the second composition is more than 29000 g / mol the solubility in the solvent of the second composition such as n-butyl acetate is significantly lowered, making the preparation of the second composition difficult.

The acrylic binder resin in the second composition is preferably a mixture of a first ethylenically unsaturated monomer 　 And a second ethylenically unsaturated monomer copolymerizable therewith, and may be a resin containing at least one acrylic repeating unit.

For example, the acrylic binder resin in the second composition may include a repeating unit represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

R ¹ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

R ² is a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

The acrylic binder resin in the second composition may further include a repeating unit represented by the following formula (2) and (3).

(2)

(3)

In the general formulas (2) and (3)

R ³ , R ⁵ and R ⁶ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,

R ⁴ is a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group.

For example, the repeating unit represented by the formula (1), the repeating unit represented by the formula (2), and the repeating unit represented by the formula (3) are preferably a repeating unit represented by the following formula (1) May be included in the weight ratio of the repeating units shown = 35 to 45:40 to 50:15 to 25 ". When the weight ratio of the repeating unit represented by the formula (1), the repeating unit represented by the formula (2) and the repeating unit represented by the formula (3) is within the above range, a high taper of 20 ° or more can be maintained.

The acid value of the acrylic binder resin in the second composition 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.

Since the second composition is intended to realize spacers and steps and does not necessarily require a high optical density, the pigment (particularly the pigment dispersion containing the pigment) of the constituents of the first composition is not necessarily contained in the composition . That is, the second composition contains an acrylic binder resin, a reactive unsaturated compound, a photopolymerization initiator and a solvent, or if necessary, the second composition also contains a pigment (specifically, a pigment dispersion containing a pigment) such as a black pigment You may. In addition, the second composition may further comprise additives described for the first composition.

The second composition may contain the same constituents as those of the first composition except for the acrylic binder resin. However, in this case, the content of each component of the first composition and the second composition may be different, so that the optical density per 1 μm of the first composition and the second composition may be different.

Therefore, the acrylic binder resin, the reactive unsaturated compound, the photopolymerization initiator, the pigment (specifically, the pigment dispersion containing the pigment) and the solvent constituting the second composition for forming the second resin film can be used as the first resin film for forming the first resin film May be the same as described for the composition.

The acrylic binder resin contained in the second composition may be included in an amount of 3% by weight to 40% by weight, for example, 5% by weight to 30% by weight based on the total amount of the second composition. When the binder resin is contained within the above range, excellent sensitivity, developability, resolution, and straightness of the pattern can be obtained.

The reactive unsaturated compound contained in the second composition may be included in an amount of 2% by weight to 20% by weight, for example, 3% by weight to 10% 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, 0.1 wt% to 3 wt% with respect to the total amount of the second composition. When the photopolymerization initiator is contained within the above range, it is possible to obtain sufficient reliability due to sufficient curing during exposure in the pattern formation step, to have excellent heat resistance, light resistance and chemical resistance, excellent resolution and adhesion, It is possible to prevent the transmittance from being lowered.

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

Another embodiment provides a black column spacer prepared by exposing and developing the above-mentioned photosensitive resin film, for example, exposure, development and curing.

The pattern in the black column spacer may have a taper angle of 20 DEG or more, for example, 20 DEG or more and 60 DEG or less.

The black column spacer manufacturing method is as follows.

(1) Coating and Film Formation Step

The first composition is coated on a substrate such as a glass substrate or an IZO substrate subjected to a predetermined pretreatment to a desired thickness using a spin, slit coat method, roll coating method, screen printing method, applicator method, And then heated at 70 ° C to 100 ° C for 1 minute to 10 minutes to remove the solvent to form a first resin film. Thereafter, the second composition is applied and cured on the first resin film in the same manner. Thereby, the photosensitive resin film according to one embodiment is formed.

(2) Exposure step

In order to form a pattern necessary for the obtained photosensitive resin 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 film  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 was coated on a substrate such as a glass substrate or an IZO substrate to a thickness of 2.0 탆 and dried by a VCD process for 1 minute to 10 minutes to cure the second composition. And then cured for 1 minute to 10 minutes to prepare a photosensitive resin film 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. Then, the other additives were added to the obtained solution, stirred for about 10 minutes, and then the pigment dispersion was added thereto 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, respectively.

(Unit: g) ingredient content Binder resin Cadmium binder resin (V259ME, Nippon Steel Corporation) 6.363 The reactive unsaturated compound Dipentaerythritol hexaacrylate (Nippon Catalyst Co., Ltd.) 1.522 Photopolymerization initiator OXE01 (BASF) 0.660 menstruum PGMEA 26.116 EDM 16.700 Pigment dispersion Lactam-based organic black (BASF) Mill base (Mikuni, PWC 15%) 41.253 Carbon black included Mill base (Tokushiki, PWC 25%) 6.286 additive Fluorine-based surfactant (F-554, DIC) 1.100

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

(A)

)

)

(Unit: g) ingredient content Binder resin Acrylic binder resin (100S-12, SMS company) 27.734 The reactive unsaturated compound Dipentaerythritol hexaacrylate (Nippon Catalyst Co., Ltd.) 5.066 Photopolymerization initiator OXE01 (BASF) 0.130 menstruum PGMEA 4.170 n-butyl acetate 60.900 additive Fluorine-based surfactant (F-554, DIC) 2.000

Example  2

A photosensitive resin film according to Example 2 was prepared in the same manner as in Example 1, except that the second composition was prepared using the following components as shown in Table 3 below.

(Unit: g) ingredient content Binder resin Acrylic binder resin (100S-13, SMS) 27.533 The reactive unsaturated compound Dipentaerythritol hexaacrylate (Nippon Catalyst Co., Ltd.) 5.066 Photopolymerization initiator OXE01 (BASF) 0.130 menstruum PGMEA 4.371 n-butyl acetate 60.900 additive Fluorine-based surfactant (F-554, DIC) 2.000

Comparative Example  One

A photosensitive resin film according to Comparative Example 1 was prepared in the same manner as in Example 1 except that the second composition was prepared using the following components in the compositions shown in Table 4 below.

(Unit: g) ingredient content Binder resin Acrylic binder resin (100S-11, SMS company) 28.041 The reactive unsaturated compound Dipentaerythritol hexaacrylate (Nippon Catalyst Co., Ltd.) 5.066 Photopolymerization initiator OXE01 (BASF) 0.130 menstruum PGMEA 3.863 n-butyl acetate 60.900 additive Fluorine-based surfactant (F-554, DIC) 2.000

Comparative Example  2

A photosensitive resin film according to Comparative Example 2 was prepared in the same manner as in Example 1, except that the second composition was prepared in the composition shown in Table 5 below using the following components.

(Unit: g) ingredient content Binder resin Acrylic binder resin (100S-7, SMS) 28.041 The reactive unsaturated compound Dipentaerythritol hexaacrylate (Nippon Catalyst Co., Ltd.) 5.066 Photopolymerization initiator OXE01 (BASF) 0.130 menstruum PGMEA 3.863 n-butyl acetate 60.900 additive Fluorine-based surfactant (F-554, DIC) 2.000

The weight average molecular weight of the acrylic binder resin used in Example 1, Example 2, Comparative Example 1 and Comparative Example 2, the repeating unit represented by the following Formula 1-1 constituting the acrylic binder resin, And the weight ratio between repeating units represented by the formula (3-1) are shown in Table 6 below.

The acrylic binder resin of Example 1 The acrylic binder resin of Example 2 The acrylic binder resin of Comparative Example 1 The acrylic binder resin of Comparative Example 2 Weight average molecular weight
(g / mol) 26000 29000 24000 27000 Formula 1-1: Formula 2-1: Formula 3-1 38: 44: 18 38: 44: 18 38: 44: 18 33: 53: 14

[Formula 1-1]

[Formula 2-1]

[Formula 3-1]

Evaluation 1: Evaluation of solubility

The acrylic binder resin used in Example 1, Example 2, Comparative Example 1, and Comparative Example 2, the repeating unit represented by Formula 1-1, the repeating unit represented by Formula 2-1, and the repeating unit represented by Formula 3-1 (30 ° C) of the acrylic binder resin having a weight-average molecular weight of 30000 g / mol and containing 100% by weight of the monomer unit and measuring the solubility thereof in 100 g of n-butyl acetate.

Solubility evaluation criteria

O: Solubility of 5 or more

X: Solubility less than 5

(Unit: g) The acrylic binder resin of Example 1 The acrylic binder resin of Example 2 The acrylic binder resin of Comparative Example 1 The acrylic binder resin of Comparative Example 2 An acrylic binder resin (100S-9, SMS Company) having a weight average molecular weight of 30000 g / mol, Solubility assessment ○ ○ ○ ○ X

From Table 7, it can be seen that when the weight average molecular weight of the acrylic binder resin in the second composition exceeds 29000 g / mol, the solubility in an organic solvent such as n-butyl acetate is lowered and the preparation of the second composition is difficult .

Evaluation 2: CD  Measure

The photosensitive resin film prepared in Example 1, Example 2, Comparative Example 1 and Comparative Example 2 was exposed at 50 mJ using an exposure apparatus (Ushio, HB-50110AA) and a photomask. 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. A CD of a 10 탆 pattern among the column spacer patterns of the patterned sample was measured with a non-contact thickness meter (3-D profiler), and the results are shown in Table 8 and Figs. 4 to 6.

CD (탆) Example 1 18.4 Example 2 17.5 Comparative Example 1 21.2 Comparative Example 2 24.5

Through Table 8 and FIGS. 4 to 6, the weight average molecular weight of the acrylic binder resin in the second composition is 25000 g / mol to 29000 g / mol, and the weight ratio of the monomers constituting the acrylic binder resin falls within a specific range It is confirmed that the occurrence of tails at the rim portion of the column spacer pattern is minimized in Examples 1 and 2 as compared with Comparative Example 1 and Comparative Example 2. [

Rating 3: Taper  Angle rating

The taper angle of the 10 탆 pattern in the column spacer pattern of the patterned specimen manufactured in the above Evaluation 1 was measured using a scanning electron microscope (SEM), and the results are shown in Table 9 and Figs. 1 to 3 Respectively.

Taper angle (°) Example 1 20.5 Example 2 22.1 Comparative Example 1 18.3 Comparative Example 2 15.2

Through Table 9 and FIGS. 1 to 3, the weight average molecular weight of the acrylic binder resin in the second composition is 25000 g / mol to 29000 g / mol, and the weight ratio of the monomers constituting the acrylic binder resin falls within a specific range It is confirmed that the taper angles of 20 DEG or more are maintained in Examples 1 and 2 as compared with Comparative Examples 1 and 2, and the generation of tails at the rim portion of the column spacer pattern is minimized.

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 (13)

A first resin film formed by coating a first composition on a substrate and cured, and a second resin film formed by coating a second composition on the first resin film and curing the first resin film,
The first composition includes a cationic binder resin, a reactive unsaturated compound, a photopolymerization initiator, a pigment, and a solvent, wherein the first composition comprises a repeating unit represented by the following formula (4), and the second composition comprises an acrylic binder resin, a reactive unsaturated compound, And a solvent,
Wherein the weight average molecular weight of the acrylic binder resin in the second composition is 25000 g / mol to 29000 g / mol.
[Chemical Formula 4]

(In the formula 1,
R ¹¹ and R ¹² are each independently a hydrogen atom or a substituted or unsubstituted (meth) acryloyloxyalkyl group,
R ¹³ and R ¹⁴ 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) Is any one of the linking groups represented by the following formulas (4-1) to (4-11)
[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

[Formula 4-4]

[Formula 4-5]

(In the above Formula 4-5,
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)
[Formula 4-6]

[Formula 4-7]

[Formula 4-8]

[Chemical Formula 4-9]

[Formula 4-10]

[Formula 4-11]

Z ² is an acid anhydride residue,
m1 and m2 are each independently an integer of 0 to 4)
The method according to claim 1,
Wherein the acrylic binder resin in the second composition is a photosensitive resin film comprising a repeating unit represented by the following formula (1)
[Chemical Formula 1]

In Formula 1,
R ¹ is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,
R ² is a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group.
3. The method of claim 2,
Wherein the acrylic binder resin in the second composition further comprises a repeating unit represented by the following general formula (2) and (3)
(2)

(3)

In the general formulas (2) and (3)
R ³ , R ⁵ and R ⁶ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,
R ⁴ is a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C10 cycloalkyl group, or a substituted or unsubstituted C6 to C20 aryl group.
The method of claim 3,
The repeating unit represented by the formula (1), the repeating unit represented by the formula (2), and the repeating unit represented by the formula (3)
"A photosensitive resin film comprising a repeating unit represented by the following formula (1): repeating unit represented by the following formula (2): repeating unit represented by the following formula (3) = 35 to 45:40 to 50:15 to 25"
The method according to claim 1,
Wherein the pigment comprises a black pigment.
6. The method of claim 5,
The black pigment includes aniline black, perylene black, titanium black, cyanine black, lignin black, lactam-based organic black, RGB black, carbon black or a combination thereof.
The method according to claim 1,
Wherein the first composition comprises a pigment dispersion comprising the pigment,
The first composition comprises 1 to 30% by weight of a cadmium binder resin, 1 to 20% by weight of a reactive unsaturated compound, 0.05 to 5% by weight of a photopolymerization initiator, 5 to 60% by weight of a pigment dispersion, A photosensitive resin film containing an amount.
The method according to claim 1,
Wherein the second composition comprises 3 wt% to 40 wt% of an acrylic binder resin, 2 wt% to 20 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 second composition further comprises a pigment.
The method according to claim 1,
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, .
A black column spacer produced by exposing and developing the photosensitive resin film of any one of claims 1 to 10.
12. The method of claim 11,
Wherein the pattern in the black column spacer has a taper angle of greater than or equal to 20 degrees and less than or equal to 60 degrees.
A color filter comprising the black column spacer of claim 11.

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