KR101691045B1 - PHOTOSENSITIVE RESIN COMPOSITION, BLACK Column SPACER PREPARED BY USING THE COMPOSITION, AND COLOR FILTER HAVING THE BLACK Column SPACER - Google Patents

Abstract

(A) a colorant comprising an organic black pigment containing a lactam-based compound and a phthalocyanine-based pigment containing a center metal; (B) a binder resin; (C) a photopolymerizable monomer; (D) a photopolymerization initiator; And (E) a solvent, a black column spacer using the black photosensitive resin composition, and a color filter.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition, a black column spacer using the same, and a color filter including the black column spacer. BACKGROUND ART [0002]

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

A liquid crystal display device includes a lower substrate on which a color filter including a light shielding layer and an ITO pixel electrode are formed; An active circuit composed of a liquid crystal layer, a thin film transistor, and a capacitor capacitor layer; And an upper substrate on which ITO pixel electrodes are formed.

The light-shielding layer serves to cut off light which is transmitted through the substrate other than the transparent pixel electrode in order to prevent the contrast caused by the light transmitted through the thin film transistor from deteriorating, and the colored layers of red, green, The main role is to transmit light of a specific wavelength to express color.

Recently, development trends of light shielding layer are all focused on functional materials. One of the above development trends is to have two functions simultaneously in one process. For example, in one process, a black matrix and a column spacer are simultaneously realized as a single material, and the thus formed portion is called a BLACK column spacer (BCS).

The black column spacer may be formed as a pattern of a black matrix and a column spacer. At this time, pattern formation is required to use a half tone mask or a slit mask in the pattern formation process so that a difference in film thickness appears between the exposed part and the less exposed part.

Further, since the black column spacer is located immediately below the alignment film in contact with the liquid crystal, it can react with impurities in the solvent used for the liquid crystal and the alignment film, and therefore excellent chemical resistance to a solvent is required.

However, the conventional black column spacer has poor chemical resistance and has a problem of lowering the transmittance of the color filter including the black column spacer.

An embodiment of the present invention is to provide a black photosensitive resin composition excellent in pattern forming property, developability, and chemical resistance.

Another embodiment of the present invention is to provide a black column spacer manufactured using the black photosensitive resin composition.

Another embodiment of the present invention is to provide a color filter comprising a black column spacer manufactured using the black photosensitive resin composition.

One embodiment of the present invention relates to a colorant comprising (A) an organic black pigment containing a lactam-based compound and a phthalocyanine-based pigment containing a center metal; (B) a binder resin; (C) a photopolymerizable monomer; (D) a photopolymerization initiator; And (E) a solvent.

The colorant may be an organic black pigment containing the lactam compound and a phthalocyanine pigment containing the center metal in a weight ratio of 60:40 to 90:10.

The colorant may include an organic black pigment containing the lactam-based compound and a phthalocyanine-based pigment containing the center metal and covalently dispersing the mixture.

The phthalocyanine-based pigment containing the center metal may be a blue pigment.

The colorant may further include an inorganic black pigment.

The inorganic black pigment may be included in an amount of 5 to 15 parts by weight based on 100 parts by weight of the colorant.

The inorganic black pigment may be carbon black.

The black photosensitive resin composition comprises 1 to 80% by weight of a colorant comprising an organic black pigment containing the lactam-based compound (A) and a phthalocyanine-based pigment containing a center metal; 0.1 to 30% by weight of the binder resin (B); 1 to 20% by weight of the (C) photopolymerizable monomer; 0.01 to 5% by weight of the photopolymerization initiator (D); And (E) the solvent balance.

The black photosensitive resin composition may include malonic acid; 3-amino-1,2-propanediol; A silane-based coupling agent comprising a vinyl group or (meth) acryloxy group; Leveling agents; Surfactants; A radical polymerization initiator; Or a combination thereof.

Another embodiment provides a black column spacer produced using the black photosensitive resin composition.

Another embodiment provides a color filter comprising the black spacer.

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

When the above photosensitive resin composition is used, a black column spacer having excellent pattern forming properties, developability and chemical resistance can be realized.

1 is a mask photograph used in the exposure step of a coating film.
2 is a scanning electron microscope (SEM) photograph showing a pattern of a coating film according to Example 1. Fig.
3 is a scanning electron microscope (SEM) photograph showing a pattern of a coating film according to Comparative Example 4. 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, "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 C30 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 C30 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 ring group.

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

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

One embodiment includes (A) a colorant comprising an organic black pigment comprising a lactam-based compound and a phthalocyanine-based pigment comprising a central metal; (B) a binder resin; (C) a photopolymerizable monomer; (D) a photopolymerization initiator; And (E) a solvent.

The above black photosensitive resin composition can be used for producing a black column spacer.

The black column spacer has a structure in which the functions of the light shielding layer and the column spacer are combined into one, and can be manufactured through one pattern forming process. In the case of a black column spacer, it is common to prepare a black column spacer using an organic black pigment since high optical density (OD) and transmittance must be realized. However, in the case of the organic black pigment, the metal ion and the pigment of the spacer pattern are liable to be eluted by a solvent such as N-methyl-2-pyrrolidone (NMP) used for a liquid crystal or an orientation film compared with an inorganic pigment such as carbon black, There is a problem that the pattern forming property, developability, and chemical resistance become poor.

Accordingly, in one embodiment, there is provided a black photosensitive resin composition which can have a transmittance and an optical density (OD) of a specific range or more as required in a black column spacer and is excellent in pattern forming property, developability and chemical resistance This was achieved by a black photosensitive resin composition comprising an organic black pigment and a phthalocyanine-based pigment containing a center metal as in the above embodiment.

Hereinafter, each component of the resin composition will be described in detail.

(A) Colorant

The black photosensitive resin composition according to one embodiment may contain, as an essential component, an organic black pigment and a phthalocyanine-based pigment containing a center metal as a colorant component. When a mixture of an organic black pigment and a phthalocyanine pigment containing a central metal is used, a high optical density can be realized and the pattern formability, developability and chemical resistance can be improved.

The organic black pigment may be contained in an amount of 60 to 90% by weight based on 100% by weight of the colorant. For example, the mixing weight ratio of the organic black pigment and the phthalocyanine pigment containing the center metal may be 60:40 to 90:10. When the content of the organic black pigment is less than 60% by weight with respect to 100% by weight of the colorant, the optical density is lowered and the light shielding property is deteriorated. When the content is more than 90% by weight,

The organic black pigment is a lactam-based organic black pigment containing a lactam-based compound and exhibits an insulating property.

The organic black pigment containing the lactam compound and the phthalocyanine pigment containing the center metal may be mixed with each other and incorporated into the colorant in a form covalently bonded to a solvent. When the organic black pigment and the phthalocyanine pigment containing a center metal are dispersed and mixed without covariance, the chemical resistance is poor.

The phthalocyanine-based pigment containing the center metal may be a blue pigment. Examples of the blue phthalocyanine pigments include phthalocyanine metal complexes such as copper phthalocyanine such as Blue 15: 6, chlorotungphthalocyanine, chloraluminophthalocyanine, titanyl phthalocyanine, vanadinic phthalocyanine, magnesium phthalocyanine, zinc phthalocyanine, iron phthalocyanine, cobalt phthalocyanine And the like.

The colorant may further comprise an inorganic black pigment in an amount of 5 to 15 parts by weight based on 100 parts by weight of the colorant. Examples of the inorganic black pigment include carbon black, chromium oxide, iron oxide, titanium black, titanium carbon and aniline black. These inorganic black pigments exhibit high resistance characteristics, and they can be used singly or in combination of two or more kinds.

As the solvent, ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, or 3-methoxy-1-butanol, Among these, propylene glycol methyl ether acetate can be preferably used.

A dispersant may be used together with the organic black pigment and the phthalocyanine pigment containing the center metal to covalently covalently bond the pigment to the solvent.

As the dispersing agent, nonionic, anionic or cationic dispersing agents can be used. Examples thereof include polyalkylene glycols and esters thereof, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adducts, alcohol alkylene oxide adducts , A sulfonic acid ester, a sulfonic acid salt, a carboxylic acid ester, a carboxylate, an alkylamide alkylene oxide adduct, and an alkylamine. These dispersants may be used singly or in combination of two or more.

The total content of the coloring agent may be 10 to 60% by weight, for example 20 to 50% by weight, based on the total weight of the black photosensitive resin composition. When a colorant is used within the above range, the black column spacer to be produced may have an optical density of 1.0 / 1.0 占 퐉 or more.

(B) binder resin

The binder resin is contained in the above-mentioned black photosensitive resin composition, and imparts adhesion, developability and the like to the photosensitive resin composition.

The binder resin may be a carded resin, or a mixture of carded resin and acrylic resin. When the cation resin or a mixture of cation resin and acrylic resin is used, the heat resistance, chemical resistance and adhesion of the photosensitive resin composition can be improved.

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

[Chemical Formula 1]

(In the formula 1,

R ₂₄ to R ₂₇ are the same or different and each represents a hydrogen atom, a halogen atom, or a substituted or unsubstituted C1 to C20 alkyl group,

R ₂₈ And R ₂₉ are the same as or different from each other, and represent a hydrogen atom or -CH ₂ OR _a (R _a is a vinyl group, an acrylate group or a methacrylate group)

R ₃₀ are the same or different from each other and each represent a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, an acrylate group or a methacrylate group,

Z ¹ is the same as or different from each other, a single _{bond, -O-, -CO-, -SO 2 -} , -CR b R c -, -SiR d R e - ( wherein, R _b And R _e are the same or different and each is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group), or a linking group represented by the following general formulas (2) to (12)

Z ² are the same or different from each other, and the acid dianhydride residue.

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(6)

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

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

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

[Chemical Formula 13]

The tetracarboxylic dianhydride may be an aromatic tetracarboxylic dianhydride. Examples of the aromatic tetracarboxylic acid dianhydride include pyromellic acid dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4-biphenyltetracarboxylic dianhydride, 2 , 2 ', 3,3'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyl ether tetracarboxylic acid dianhydride , 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2, 3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridine tetracarboxylic dianhydride, 3,4,9,10-perylene Tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, and the like, but the present invention is not limited thereto.

The weight average molecular weight of the cardade resin may be from 1,000 to 20,000 g / mol, such as from 3,000 to 10,000 g / mol. When the cadmium resin has a weight average molecular weight within the above range, excellent patterning property and developability can be obtained in the production of the light-shielding layer and the black column spacer.

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

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

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

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

Specific examples of the acrylic 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 acrylic resin may have a weight average molecular weight of 3,000 to 150,000 g / mol, such as 5,000 to 50,000 g / mol, or 7,000 to 30,000 g / mol. 　　 When the weight average molecular weight of the acrylic resin is within the above range, the black photosensitive resin composition is excellent in physical and chemical properties, has a suitable viscosity, and has excellent adhesion with a substrate in the production of a black column spacer.

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

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

If the content of the acrylic binder resin exceeds the content of the cadmium-based binder resin, the chemical resistance and the reliability may be deteriorated.

The binder resin may be contained in an amount of 1 to 30% by weight, for example, 5 to 20% by weight based on the total amount of the black photosensitive resin composition. When the binder resin is contained within the above range, the patterning property, the processability, and the developing property are excellent in the production of the black column spacer.

(C) Photopolymerization  Monomer

The photopolymerizable monomer means a monomer of a compound which is photopolymerized by a photopolymerization initiator described later.

The photopolymerizable compound may be a monofunctional or polyfunctional ester of (meth) acrylic acid having at least one ethylenically unsaturated double bond.

By having the above-mentioned ethylenically unsaturated double bond, the photopolymerizable 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.

Specific examples of the photopolymerizable compound include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol Acrylate such as di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A di (meth) acrylate, pentaerythritol di (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol di Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol There may be mentioned furnace methyl ether (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, novolak epoxy (meth) acrylate, and the like.

Examples of commercially available products of the photopolymerizable compound 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; V-260 ^® V-312 ^® and V-335 HP ^{® from} Osaka Kikogaku Kogyo Co., Ltd., and the like. Examples of the tri-functional ester of (meth) acrylic acid, doah Gosei Kagaku Kogyo (Note)社of Aronix M-309 ^®, the same M-400 ^®, the same M-405 ^®, the same M-450 ^®, Dong M -7100 ^® , copper M-8030 ^® , copper M-8060 ^® and the like; Nippon Kayaku (Note)社of KAYARAD TMPTA ^®, copper DPCA-20 ^{®, ®} copper -30, -60 ^® copper, copper ^® -120 and the like; Osaka yukki Kayaku high (primary)社of V-295 ^®, copper ^® -300, -360 ^® copper, copper -GPT ^®, copper -3PA ^®, and the like copper -400 ^®. These products may be used alone or in combination of two or more.

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

The photopolymerizable compound may be contained in an amount of 0.1 to 10% by weight, for example, 1 to 5% by weight based on the total amount of the black photosensitive resin composition. When the photopolymerizable compound is contained within the above range, the pattern formation process sufficiently cures upon exposure to light, good patterning property, and favorable chemical resistance.

(D) Light curing Initiator

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

The photopolymerization initiator may be an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, a triazine-based compound, or an oxime-based compound.

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-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisobutyl Propyl thioxanthone and the like.

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

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

Examples of the oxime compounds include 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (o- Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone.

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 included in an amount of 0.01 to 5% by weight, for example, 0.1 to 2% by weight based on the total weight of the black photosensitive resin composition. When the photopolymerization initiator is included within the above range, photopolymerization sufficiently occurs upon exposure in the pattern formation step, and a suitable black column spacer pattern can be formed.

(E) Solvent

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

In view of miscibility and reactivity in the solvent, glycol ethers such as ethylene glycol monoethyl ether and ethylene glycol dimethyl ether are preferred; 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 contain the balance, specifically 20 to 90% by weight, such as 30 to 70% by weight of the black photosensitive resin composition. When the solvent is contained within the above range, the black photosensitive resin composition has appropriate storage stability, and thus the processability is good.

(F) Other additives

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

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

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

The additive can be easily adjusted according to desired properties.

Another embodiment provides a black column spacer prepared using the above-mentioned black photosensitive resin composition. The black column spacer has a structure in which the functions of the light shielding layer and the column spacer are combined and can be obtained through one pattern forming process. 　

A method of manufacturing the black column spacer is as follows.

(1) Coating and Film Formation Step

The above-mentioned black photosensitive resin composition is coated on a predetermined pretreated substrate by a method such as spin or slit coat method, roll coating method, screen printing method or applicator method to a desired thickness, for example, a thickness of 2 to 25 탆 Followed by primary heating (also referred to as "pre-bake") at 70 ° C. to 100 ° C. for 1 minute to 10 minutes to remove the solvent to form a coating film. 　

(2) Exposure step

In order to form a pattern necessary for the obtained coating film, a mask composed of a half tone part for implementing a light shielding layer pattern and a full tone part for implementing a column spacer pattern is interposed, and then a 200 nm to 500 nm active Inspect the line. 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 varies depending on the kind of each component constituting the photosensitive resin composition, the blending amount, and the dried film thickness. For example, when using a high-pressure mercury lamp, the exposure dose may be 500 mJ / cm ² (365 nm sensor) or less.

(3) Development step

After the above-described exposure step, an unnecessary portion is dissolved and removed by using an alkaline aqueous solution as a developer to leave only the exposed portion to form a pattern. The formed pattern is formed with a film step between an embodied portion of the light shielding layer pattern and an embodied portion of the column spacer pattern. 　

(4) Post-treatment step

In order to obtain a pattern excellent in heat resistance, light fastness, adhesion, crack resistance, chemical resistance, high strength and storage stability, the image pattern obtained in the above development step is subjected to secondary heating (at 200 캜 to 250 캜 for 15 minutes to 40 minutes (Also referred to as a " post-bake ").

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.

(Preparation of Black Photosensitive Resin Composition)

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

(A) Colorant

 (Irgaphor (R) Black S 0100 CF, BASF Co.) and (Blue 15: 6) were mixed at a ratio of 65:35 and covariance was obtained.

 (Irgaphor (R) Black S 0100 CF, BASF Co.) and (Blue 15: 6) were mixed at a ratio of 75:25 and covariance was performed.

 (A-3) lactam-based organic black pigment (Irgaphor®Black S 0100 CF, BASF) and Blue 15: 6 were mixed at a ratio of 85:15 and covariance was performed.

 (Irgaphor (R) Black S 0100 CF, BASF Co.): Blue 15: 6: carbon black were mixed at a ratio of 70:20:10 and covariance was carried out.

 (A-5) lactam-based organic black pigment (Irgaphor (R) Black S 0100 CF, BASF) was dispersed singly.

 (A-6) lactam-based organic black pigment (Irgaphor (R) Black S 0100 CF, BASF) and Blue 15: 6 in a ratio of 50:50.

 (A-7) lactam-based organic black pigment (Irgaphor®Black S 0100 CF, BASF) and Blue 15: 6 were mixed at a ratio of 95: 5 and covaried.

 (A-8) lactam-based organic black pigment (Irgaphor (R) Black S 0100 CF, BASF) and Blue 60 in a ratio of 75:25.

(B) binder resin

V259ME from Shinil Chemical Co., Ltd., having a solid content of 55% by weight, was used.

(C) Photopolymerization  Monomer

Dipentaerythritol hexaacrylate was used.

(D) Light curing Initiator

 (D-1) BASF's OXE01 was used.

 (D-2) BASF's IGR369 was used.

(E) Solvent

Propylene glycol monomethyl ether acetate was used.

(F) Additive

As the surfactant, F-475 from DIC was used.

Example  1 to 4 and Comparative Example  1 to 4: Preparation of black photosensitive resin composition

Each component was mixed with the composition shown in Table 1 below to prepare a black photosensitive resin composition. Specifically, the photopolymerization initiator was dissolved in the solvent, followed by sufficient stirring at room temperature for about 30 minutes. The binder resin and the photopolymerizable monomer were added thereto, followed by stirring for 1 hour. The additive was added thereto, a colorant was added, and the mixture was stirred for about 2 hours. The solution was filtered three times to remove impurities, thereby preparing a black photosensitive resin composition.

Example Comparative Example One 2 3 4 One 2 3 4 (A)
coloring agent (A-1) (g) 42 (A-2) (g) 42 (A-3) (g) 42 (A-4) (g) 42 (A-5) (g) 42 (A-6) (g) 42 (A-7) (g) 42 (A-8) (g) 42 (B) Binder resin (g) 11.5 11.5 11.5 11.5 11.5 11.5 11.5 11.5 (C) a photopolymerizable monomer (g) 2.2 2.2 2.2 2.2 2.2 2.2 2.2 2.2 (D)
Photopolymerization initiator (D-1) (g) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 (D-2) (g) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 (E) Solvent (g) 43 43 43 43 43 43 43 43 (F) Additive (g) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5

Rating 1: Pattern Formability  And Developability  evaluation

The black photosensitive resin compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 4 were coated on a glass substrate and dried to form a coating film. Each coating was irradiated with 70 mJ / cm ² of light having a wavelength of 365 nm by using a mask as shown in Fig. Developed in an aqueous solution diluted with 1% by weight of potassium hydroxide at 23 DEG C for 1 minute, then rinsed with pure water for 1 minute. The pattern obtained by this method was cured by heating in an oven at 220 캜 for 30 minutes, and then the shape of the pattern was visually observed using an optical microscope. The results are shown in Table 2, Fig. 2 and Fig.

FIG. 2 is a scanning electron microscope (SEM) photograph showing a pattern of a coating film according to Example 1, and FIG. 3 is a scanning electron microscope (SEM) photograph showing a pattern of a coating film according to Comparative Example 4. FIG.

<Evaluation Criteria of Pattern Formability>

Good: 10 mu m pattern was formed, pattern straightness was good

DELTA: A 10 mu m pattern was formed, and the pattern straightness defect

×: No formation of 10 μm pattern

&Lt; Development evaluation standard &

○: The coating gradually develops

X: Developed as if the coating was torn

Evaluation 2: Chemical resistance evaluation

Each of the pattern samples according to Examples 1 to 4 and Comparative Examples 1 to 4 obtained in Evaluation 1 was cut into a size of 1 cm x 1 cm and 8 pieces were put into a 20 ml vial and 3 g of N-methylpyrrolidone Respectively. After standing for 10 minutes in a 100 ° C oven, the N-methylpyrrolidone eluate was measured by UV-Vis spectrometer. The results are shown in Table 2 below.

<Evaluation criteria for chemical resistance>

?: Transmittance of 90 to 100% (based on 550 nm)

?: Transmittance of 80 to 89% (based on 550 nm)

X: transmittance less than 80% (based on 550 nm)

Pattern forming property Developability Chemical resistance Example 1 ○ ○ ○ Example 2 ○ ○ ○ Example 3 ○ ○ ○ Example 4 ○ ○ ○ Comparative Example 1 ○ ○ × Comparative Example 2 ○ ○ △ Comparative Example 3 ○ ○ △ Comparative Example 4 △ × ×

It can be seen from Table 2 that the pattern formability, developability, and chemical resistance are both superior to those of Comparative Examples 1 to 4 in Examples 1 to 4 using the coloring agent according to one embodiment.

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

Claims (11)

(A) an organic black pigment comprising a lactam-based compound and a phthalocyanine-based pigment containing a center metal in a weight ratio of 60:40 to 90:10;
(B) a binder resin;
(C) a photopolymerizable monomer;
(D) a photopolymerization initiator; And
(E) Solvent
And the black photosensitive resin composition.
delete The method according to claim 1,
Wherein the colorant comprises a mixture of an organic black pigment containing the lactam-based compound and a phthalocyanine-based pigment containing the center metal, and covalently dissolving the black pigment.
The method according to claim 1,
The phthalocyanine-based pigment containing the center metal is a blue pigment.
The method according to claim 1,
Wherein the colorant further comprises an inorganic black pigment.
6. The method of claim 5,
Wherein the inorganic black pigment is contained in an amount of 5 to 15 parts by weight based on 100 parts by weight of the colorant.
6. The method of claim 5,
Wherein the inorganic black pigment is carbon black.
The method according to claim 1,
The above-mentioned black photosensitive resin composition,
10 to 60% by weight of a colorant mixed with an organic black pigment containing the lactam compound (A) and a phthalocyanine pigment containing a center metal at a weight ratio of 60:40 to 90:10;
1 to 30% by weight of the binder resin (B);
0.1 to 10% by weight of the (C) photopolymerizable monomer;
0.01 to 5% by weight of the photopolymerization initiator (D); And
The amount of the solvent (E)
Wherein the black photosensitive resin composition comprises:
The method according to claim 1,
The black photosensitive resin composition may include malonic acid; 3-amino-1,2-propanediol; A silane-based coupling agent comprising a vinyl group or (meth) acryloxy group; Leveling agents; Surfactants; A radical polymerization initiator; Or a combination thereof. &Lt; RTI ID = 0.0 &gt; 5. &lt; / RTI &gt;
A black column spacer produced by using the black photosensitive resin composition of any one of claims 1 to 9.
A color filter comprising the black column spacer of claim 10.

Images