KR20190044556A - A black photo sensitive resin composition, a color filter comprising a black metrics and/or a column spacer prepared by using the composition, and a display comprising the color filter - Google Patents

Abstract

The present invention relates to a black photosensitive resin composition comprising: (A) a colorant; (B) a binder resin; (C) a photopolymerizable compound; (D) a photopolymerization initiator, and (E) a solvent, wherein the colorant comprises a black colorant, a purple colorant and a blue colorant, the binder resin comprises a compound represented by chemical formula 1, and the photopolymerizable compound comprises 8 or more functional groups, to a color filter comprising a column spacer, a black matrix, or a black column spacer produced by using the same, and to a display device comprising the color filter.

Description

TECHNICAL FIELD [0001] The present invention relates to a black photosensitive resin composition, a color filter including a black matrix and / or a column spacer manufactured using the same, and a display device including the color filter. BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] A COLUMN SPACER PREPARED BY USING THE COMPOSITION, AND DISPLAY COMPRISING THE COLOR FILTER}

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

The color filter is composed of three primary color pixels of a red pixel, a green pixel, and a blue pixel, and a black matrix formed at the boundary of each color pixel and not transmitting visible light substantially as black. The black matrix or black column spacer is a material for securing the space required for moving the liquid crystal between the two glass plates constituting the LCD and maintaining the elasticity of the LCD, and is formed of a black photosensitive resin composition.

When a black photosensitive resin composition is used for a color filter of a liquid crystal display, a light shielding layer using a black photosensitive resin composition is formed at a boundary portion between coloring layers to enhance the contrast and coloring effect of red, green and blue. In recent years, it has been required to be positioned on an array substrate so as to not only serve as a black matrix but also form a spacer for holding a cell gap, thereby enabling various roles to be performed at one time.

The black photosensitive resin composition is not only a color filter but also an essential material for a liquid crystal display material, an organic light emitting element, a display and the like. In addition to optical effects for basic shading, research on a black photosensitive resin composition having excellent elasticity and reliability It is actively proceeding.

Korean Patent No. 10-1658374 discloses a technique for improving the properties of a column spacer and a black matrix by using a colored photosensitive resin composition but does not disclose the improvement of the adhesion between the column spacer and the black mattress by improving the reflow property There is a problem.

Korean Patent No. 10-1658374

SUMMARY OF THE INVENTION It is an object of the present invention to provide a black photosensitive resin composition which is improved in reflow characteristics and improves the adhesion of a column spacer or a black mattress.

It is another object of the present invention to provide a color filter including a column spacer, a black matrix or a black column spacer manufactured using the black photosensitive resin composition, and a display device including the color filter.

(B) a binder resin, (C) a photopolymerizable compound (D) a photopolymerization initiator, and (E) a solvent, wherein the colorant is a black colorant, a purple colorant And a blue colorant, wherein the binder resin comprises a compound represented by the following formula (1), and the photopolymerizable compound contains 8 or more functional groups.

[Chemical Formula 1]

In formula (1), the sum of mole% of x, y, z and w is 100, and x, y, z and w are each independently a positive integer.

The present invention also provides a color filter comprising a column spacer, a black matrix, or a black column spacer manufactured using the black photosensitive resin composition.

Further, the present invention provides a display device including the color filter.

The black photosensitive resin composition of the present invention includes the binder resin represented by the general formula (1), thereby improving the reflow property and the DOP property, thereby providing the effect of improving the adhesion of the column spacer or the black mattress.

Further, the black photosensitive resin composition contains a photopolymerizable compound containing 8 or more functional groups, thereby providing an effect of improving reliability.

In addition, a color filter including a column spacer, a black matrix, or a black column spacer manufactured using the black photosensitive resin composition, and a display device including the color filter provide excellent characteristics in terms of driving performance and durability.

The present invention provides a colorant composition comprising (A) a colorant, (B) a binder resin, (C) a photopolymerizable compound (D) a photopolymerization initiator, and (E) a solvent, wherein the colorant comprises a black colorant, a purple colorant, Wherein the binder resin comprises a compound represented by the following general formula (1), and the photopolymerizable compound contains 8 or more functional groups.

[Chemical Formula 1]

In formula (1), the sum of mole% of x, y, z and w is 100, and x, y, z and w are each independently a positive integer.

Each component constituting the black photosensitive resin composition of the present invention will be described below. However, the present invention is not limited to these components.

(A) Colorant

The colorant is used for black implementation and imparts light shielding to both the spacer, the black matrix and the black column spacer. The black column spacer means that the column spacer and the black matrix are integrally formed. That is, the black matrix serves to prevent the light leakage, and the spacer can prevent the malfunction of the device caused by the light generated from the outside.

As the coloring agent, any coloring agent known in the art such as an organic pigment and a black pigment may be used as long as it is shielding from visible light, but it is preferable to include a purple coloring agent, a blue coloring agent and a black coloring agent.

As the purple colorant, C.I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32 , 37, 39, 42, 44, 47, 49, 50, and the like, Pigment Violet 19, 23, and 29, and it is preferable that C.I. It is more preferable to include Pigment Violet 29.

As the blue colorant, C.I. Pigment Blue 15: 3, 15: 4, 15: 6, 16, 21, 28, 60 and 76, and C.I. Pigment Blue 15: 3, 15: 6, 16 and 60, and C.I. It is more preferable to include Pigment Blue 60.

The black colorant may be appropriately selected from inorganic or organic pigments. Examples of the black colorant that can be used include carbon black, atteylene black, lamp black, black black, graphite, iron black, aniline black, cyanine black, titanium black, rhammet black, perylene black and organic black (OBP) Depending on the purpose, inorganic pigments and organic pigments may be used singly or in combination.

The carbon black may be resin-coated on its surface for electrical insulation. In addition, since the resin-coated carbon black has a lower conductivity than carbon black not coated with the resin, excellent electrical insulation can be imparted to the black matrix, the spacer, or the black column spacer (black matrix integrated spacer) . The carbon black may be channel black, furnace black, thermal black, lamp black, or the like.

The colorant may be contained in an amount of 15 to 55% by weight based on the total solid content of the black photosensitive resin composition, more preferably 28 to 50% by weight. When the content of the colorant is within the above range, it can exhibit a sufficient shielding property, that is, a high optical density (OD), which is preferable in that sufficient pattern formation is possible.

More specifically, carbon black, organic black, V29, B60 and the like may be used as the coloring agent. These may be used singly or in combination of two or more.

The content of the black colorant in the present invention is preferably 4 to 12% by weight, more preferably 5 to 9% by weight, based on the total solid content of the black photosensitive resin composition. When the content of the black colorant is less than 4% by weight, the optical density is low. When the content of the black colorant is more than 12% by weight, the transmittance and the permittivity can be deteriorated in the infrared region.

The content of the purple colorant may be 4 to 18% by weight of the total solid content of the black photosensitive resin composition. If the content of the purple colorant is less than 4% by weight, a great effect can not be expected. If the content is more than 18% by weight, the reliability of the product may be affected. When V29 is used as the purple coloring agent, the visible light transmittance in the range of 400 to 600 nm can be reduced and the optical density can be improved.

The content of the blue colorant may be 5 to 25% by weight based on the total solid content of the black photosensitive resin composition. If the amount of the blue colorant is less than 5% by weight, the effect is not significant, and if it is more than 25% by weight, it may affect the infrared region. When B60 is used as the blue colorant, there is no metal element, which is advantageous in driving the apparatus.

In the present invention, the total solid content of the black photosensitive resin composition means the sum of the components of the black photosensitive resin composition from which the solvent has been removed.

In addition, the colorant may further optionally include a color correcting agent. As the color correcting agent, condensation polycyclic pigments such as anthraquinone pigments or perylene pigments, phthalocyanine pigments, or organic pigments such as azo pigments can be used. Anthraquinone pigments or phthalocyanine pigments are preferred, and phthalocyanine pigments are more preferred . Examples of the phthalocyanine pigments may include C.I. Pigment Blue 15: 6, C.I. Pigment Blue 15: 4, and C.I. Pigment Blue 16. Examples of the anthraquinone type pigment include C.I. Pigment Blue 60. The phthalocyanine pigment may be C.I. Pigment Blue 15: 6.

In addition, it is preferable to use a pigment dispersion in which the particle diameter of the pigment is uniformly dispersed. Examples of a method for uniformly dispersing the particle diameter of the pigment include a method of dispersing the pigment dispersion (a1) by containing the pigment dispersant (a1), and a method of obtaining a pigment dispersion in which the pigment is uniformly dispersed in the solution have.

(a1) pigment dispersant

The pigment dispersant is added for deaggregation of the pigment and maintenance of stability. Specific examples of the pigment dispersant include a cationic surfactant, an anionic surfactant, a nonionic surfactant, a positive surfactant, a polyester surfactant, and a polyamine surfactant. , Which may be used alone or in combination of two or more.

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts.

Specific examples of the anionic surfactant include higher alcohol sulfuric acid ester salts such as sodium lauryl alcohol sulfate ester and sodium oleyl alcohol sulfate ester, alkylsulfates such as sodium laurylsulfate and ammonium laurylsulfate, sodium dodecylbenzenesulfonate, And alkylarylsulfonic acid salts such as sodium dodecylnaphthalenesulfonate.

Specific examples of the nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.

In addition, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines have.

Also, the pigment dispersant preferably includes an acrylate-based dispersant (hereinafter referred to as an acrylate-based dispersant) containing butyl methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA). Dispersing BYK-2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150 and the like may be used as the acrylate-based dispersing agent, The rate-based dispersing agents may be used alone or in combination of two or more.

As the pigment dispersant, other resin type pigment dispersants other than the acrylate dispersant may be used. The other resin type pigment dispersing agent may be a known resin type pigment dispersing agent, especially a polycarboxylic acid ester such as polyurethane, polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) Amine salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long chain polyaminoamide phosphate salts, esters of hydroxyl group-containing polycarboxylic acids and their modified products, or free ) Oil-based dispersants such as amides formed by reaction of a polyester having a carboxyl group with poly (lower alkyleneimine) or salts thereof; Soluble resin or water-soluble polymer compound such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinylpyrrolidone; Polyester; Modified polyacrylates; Adducts of ethylene oxide / propylene oxide; And phosphate esters.

DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, and DISPER BYK-160 available from BYK (Big) Chemie are examples of commercially available pigment dispersants of other resin types. BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; EFKA-4060, EFKA-4060, EFKA-4055, EFKA-4055, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA- 4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10 from Lubirzol; Hinoact T-6000, Hinoact T-7000, Hinoact T-8000; available from Kawaken Fine Chemicals; AJISPUR PB-821, Ajisper PB-822, Ajisper PB-823 manufactured by Ajinomoto; FLORENE DOPA-17HF, fluorene DOPA-15BHF, fluorene DOPA-33, and fluorene DOPA-44 are trade names of Kyoeisha Chemical Co.,

In addition to the acrylate-based dispersant, other resin-type pigment dispersants may be used alone or in admixture of two or more, and may be used in combination with an acrylate-based dispersant.

The pigment dispersant is contained in an amount of more than 0 to 1 part by weight, preferably 0.01 to 0.5 part by weight based on 1 part by weight of the colorant. When the pigment dispersant is contained in an amount exceeding 0 to 1 part by weight, the uniformly dispersed pigment can be obtained.

(B) binder resin

In the present invention, the binder resin usually makes the non-visible portion of the black photosensitive resin layer formed using the black photosensitive resin composition alkali-soluble, and may also function as a dispersion medium for the pigment.

The binder resin may be selected from a variety of polymers used in the relevant application fields, but may preferably include an epoxy group and may be a compound represented by the following formula (1).

[Chemical Formula 1]

The sum of mole% of x, y, z, and w in Formula 1 may be 100, and x, y, z, and w are independently positive integers.

Wherein x is from 35 to 85, y is from 3 to 15, z is from 10 to 40, and w is from 3 to 15. [

When the binder resin contains the compound represented by Formula 1, reflow characteristics are improved, taper angle can be easily controlled, flowability can be improved, and DOP characteristics can be improved.

The weight average molecular weight of the binder resin may be 3,000 to 20,000 g / mol, and preferably 5,000 to 15,000 g / mol. The acid value of the binder resin may be 50 to 200 mgKOH / g based on the total solid content of the black photosensitive resin composition. Thus, the developability against alkali development is improved, the residue generation is suppressed, and the adhesion of the pattern is improved .

The binder resin may further include a compound represented by the following formula (2). When the binder resin further contains a compound represented by the general formula (2), there is an advantage in terms of reliability.

(2)

In the general formula (2), the sum of the mole% of x and y is 100, x is an integer of 50 to 95, and y is an integer of 5 to 50.

In the formula (2), the monomer A is not particularly limited as long as it contains a carboxyl group. For example, when monomer A is -COOH, the repeating unit of y may be acrylic acid. For example, the repeating unit of y is preferably selected from acrylic acid, methacrylic acid, and 4-vinylbenzoic acid.

The binder resin may be contained in the total solid content of the black photosensitive resin composition in an amount of 15 to 50% by weight, more preferably 20 to 45% by weight. When the content of the binder resin is within the above range, the reflow property is improved and it is preferable that the taper angle value can be effectively controlled.

(C) Photopolymerizable compound

The photopolymerizable compound of the present invention contains an unsaturated bond and undergoes a photoreaction with the photopolymerization initiator to form a photosensitive resin layer. The photopolymerizable compound preferably contains 8 or more functional groups and contains 8 to 10 functional groups . When the photopolymerizable compound contains less than 8 functional groups, there is a problem in that reliability is deteriorated in view of the solvent resistance.

Specific examples of the 8 to 10 functional monomers among the polyfunctional monomers include compounds represented by the following formula (3).

(3)

In Formula 3, m is 2 or 3, and R is -H or -COCH = CH ₂ .

For example, when m is 2 and R is -COCH = CH ₂ in the above formula (3), m is 3 and R is -COCH = CH ₂ in formula (3-1) , It may be represented by the following formula (3-2).

[Formula 3-1]

[Formula 3-2]

The photopolymerizable compounds exemplified above may be used alone or in combination of two or more thereof

The photopolymerizable compound may be contained in an amount of 10 to 20% by weight based on the total solid content of the black photosensitive resin composition, more preferably 12 to 18% by weight. When the content of the photopolymerizable compound is within the above range, the pattern characteristics and the efficiency of the developing process can be improved.

(D) a photopolymerization initiator

The photopolymerization initiator is a compound for initiating the polymerization of the photopolymerizable compound and is not particularly limited in the present invention. However, the photopolymerization initiator is not particularly limited in the present invention, and may be, for example, an acetophenone, benzophenone, triazine, thioxanthone, oxime, benzoin, And imidazole-based compounds. These may be used alone or in combination of two or more.

Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- hydroxy- 1- [4- 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2- Oligomers of benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one and 2-hydroxy-2- methyl [4- (1-methylvinyl) phenyl] propan- Among them, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one can be preferably used.

Examples of the benzophenone compound include benzophenone, benzoyl benzoic acid, benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis (dimethylamino) benzophenone, Bis (diethylamino) benzophenone, and the like.

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

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone and 1-chloro-4-propanecioxanthone. have.

Examples of the oxime-based compound include o-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one and the like. Commercially available products include Irgacure OXE01 and Irgacure OXE02 manufactured by BASF.

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

Examples of the anthraquinone-based compounds include 2-ethyl anthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, and 2,3-diphenylanthraquinone.

Examples of the nonimidazole-based compounds include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'- ) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, a phenyl group in the 4,4', 5,5 'position is bonded to a carboalkoxy group And an imidazole compound substituted by a halogen atom.

The photopolymerization initiator may be contained in an amount of 0.5 to 6% by weight based on the total solid content of the black photosensitive resin composition, more preferably 1.5 to 4.5% by weight. Such a content range takes into consideration the photopolymerization rate of the photopolymerizable compound and the physical properties of the resultant coating film. If the amount is less than the above range, the polymerization rate is low and the overall process time may be prolonged. On the other hand, The physical properties of the coating film may be lowered. When the photopolymerization initiator is used within the above content range, the intensity of the pixel portion and the linearity of the pattern can be improved.

The photopolymerization initiator may be used in combination with a photopolymerization initiator. When the photopolymerization initiator is used in combination with the photopolymerization initiator, the black photosensitive resin composition containing the photopolymerization initiator becomes more sensitive, and productivity is improved when the supporting spacer for holding the cell gap is formed.

The photopolymerization initiation auxiliary may be used for increasing the polymerization efficiency, and at least one compound selected from the group consisting of an amine compound, an alkoxyanthracene compound, a thioxanthone compound, a carbamic acid and a sulfonic acid compound may be used, May be selected from the group consisting of a carboxylic acid and a sulfonic acid compound.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid isoamyl, benzoic acid- (Dimethylamino) benzophenone (collectively, Michler's ketone), 4,4'-bis (diethylamino) benzoate, 2-ethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, Phenanone, 4,4'-bis (ethylmethylamino) benzophenone, and the like, among which 4,4'-bis (diethylamino) benzophenone is preferable.

Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, .

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- And the like.

Specific examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichloro And aromatic heteroacetic acids such as phenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

The photopolymerization initiator may be produced directly or commercially available.

The photopolymerization initiator is preferably used in an amount of usually not more than 10 mol, preferably 0.01 to 5 mol per mol of the photopolymerization initiator. When the photopolymerization initiator is used within the above range, the polymerization efficiency can be increased and the productivity improvement effect can be expected.

(E) Solvent

As the above-mentioned solvent, it is possible to use any one that has compatibility with the components of the black photosensitive resin composition and does not react so as to dissolve or disperse the above-mentioned composition. In the present invention, And is not particularly limited. Preferably, an organic solvent having a boiling point of 100 to 200 DEG C in terms of coatability and dryness may be used, or a plurality of organic solvents having different boiling points may be mixed and used.

Representative examples of usable solvents include alkylene glycol monoalkyl ethers, alkylene glycol alkyl ether acetates, aromatic hydrocarbons, ketones, lower and higher alcohols, and cyclic esters. More specifically, alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; Alkylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate Ryu; Aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin; Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; and cyclic esters such as? -butyrolactone.

Among the above solvents, alkylene glycol alkyl ether acetates, ketones, esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate may be preferably used, and propylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and the like can be used. These solvents may be used singly or in combination of two or more.

The solvent may be contained in a balance such that the black photosensitive resin composition satisfies 100% by weight, and may be contained in an amount of 60 to 90% by weight based on the total weight% of the black photosensitive resin composition, and is included in the range of 70 to 85% desirable. When the content of the solvent is within the above-mentioned range, the dispersion stability of the black photosensitive resin composition and the easiness of process in the production process (for example, coatability) can be improved. In other words, the black photosensitive resin composition according to the present invention can produce a black matrix, a spacer or a black column spacer (black matrix integrated spacer) by a wet coating method, wherein the wet coating method is a roll coater, a spin coater, A coating apparatus such as a coater, a slit coater (which may be referred to as a die coater), an ink jet or the like may be used.

(F) Additive

The black photosensitive resin composition of the present invention may further contain additives according to needs of those skilled in the art as long as the objects of the present invention are not impaired, in addition to the above-mentioned components.

The additive may include at least one selected from the group consisting of, for example, fillers, other high molecular compounds, curing agents, leveling agents and adhesion promoters.

Specific examples of the filler include glass, silica, and alumina.

Specific examples of the other polymer compound include a curable resin such as an epoxy resin and a maleimide resin; And thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester and polyurethane.

The curing agent is used for increasing the curing depth and mechanical strength, and specific examples thereof include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound and an oxetane compound.

Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolak epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin Alicyclic or aromatic epoxy compounds, butadiene (co) polymeric epoxides and isoprene (co) polymers other than the brominated derivatives, epoxy resins and brominated derivatives of these epoxy resins, glycidyl ester resins, glycidyl amine resins, (Co) polymer epoxides, glycidyl (meth) acrylate (co) polymers, and triglycidyl isocyanurate.

Specific examples of the oxetane compound in the curing agent include carbonates bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexanedicarboxylic acid bisoxetane, and the like.

The curing agent may be used together with a curing assistant compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound together with the curing agent. The curing assistant compound includes, for example, polyvalent carboxylic acids, polyvalent carboxylic anhydrides, and acid generators. The polyvalent carboxylic acid anhydrides may be those commercially available as an epoxy resin curing agent. Specific examples of the above-mentioned epoxy resin curing agents include commercial products such as ADEKA HARDONA EH-700 (ADEKA INDUSTRIAL CO., LTD.), Trade name (RICACIDO HH) (manufactured by New Japan Chemical Co., Ltd.) Manufactured by Shin-Etsu Chemical Co., Ltd.). The curing agents exemplified above may be used alone or in combination of two or more.

As the leveling agent, a commercially available surfactant may be used for further improving the film-forming property of the black photosensitive resin composition. For example, a silicone, fluorine, ester, cationic, anionic, nonionic, And surfactants. These may be used alone or in combination of two or more.

Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, (Manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), F-top (manufactured by TOKEM PRODUCTS CO., LTD.), Megapak (manufactured by Dainippon Ink Chemical Industry Co., (Manufactured by Sumitomo 3M Ltd.), Asahi Guard Co., Ltd., Sapron (manufactured by Asahi Glass Co., Ltd.), Sorpsas (manufactured by Zeneca), EFKA (manufactured by EFKACHEMICALS) ), PB821 (manufactured by Ajinomoto Co., Ltd.), and the like.

The adhesion promoter is an additive which is used for improving coatability and adhesion to a substrate, and is a silane coupling agent containing a reactive substituent selected from the group consisting of a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, . Specific examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxy Silane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- glycidoxypropylmethyldimethoxysilane , 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, -Mercaptopropyltrimethoxysilane, and the like.

The additive can be suitably added and used by those skilled in the art within a range not hindering the effect of the present invention. For example, the additive may be used in an amount of 0.05 to 10 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the entire black photosensitive resin composition.

For example, a coloring agent may be added to a solvent, and then the remaining composition and other additives may be added thereto, followed by stirring. At this time, the colorant may be added in the form of a mill base in which a pigment or the like is dissolved or dispersed in advance in a solvent or an alkali-soluble resin. The additive, if in solution form, may be added in advance to the solvent along with the colorant.

Color filters and liquid crystal displays

The method of producing the black photosensitive resin composition of the present invention is not particularly limited and follows the known production method of the black photosensitive resin composition.

For example, a coloring agent may be added to a solvent, and then the remaining composition and other additives may be added thereto, followed by stirring. At this time, the colorant may be added in the form of a mill base in which a pigment or the like is dissolved or dispersed in advance in a solvent or an alkali-soluble resin. The additive, if in solution form, may be added in advance to the solvent along with the colorant.

The thus-prepared black photosensitive resin composition can be preferably used for the production of a display device, preferably a black matrix of a liquid crystal display device, a spacer for holding a cell gap, or a black column spacer (black matrix integrated spacer).

In particular, the black photosensitive resin composition of the present invention can be preferably used for producing a black column spacer (black matrix integrated spacer), and the black column spacer (black matrix integrated spacer) does not form a black matrix and a spacer, It is formed in a structure that can perform both a black matrix and a spacer in one pattern.

The present invention also relates to a color filter comprising a color filter comprising a black matrix or a black column spacer made using the black photosensitive resin composition.

The present invention also relates to a liquid crystal display device including the color filter.

A typical patterning process for forming a black matrix, spacer or black column spacer (black matrix integrated spacer) according to the photolithography method comprises the following steps:

a) applying a black photosensitive resin composition to a substrate;

b) prebaking step of drying the solvent;

c) applying a photomask onto the obtained film to irradiate an actinic ray to cure the exposed portion;

d) performing a developing step of dissolving the unexposed portion using an aqueous alkali solution; And

e) Dry and post-baking steps.

A glass substrate or a polymer plate is used as the substrate. As the glass substrate, in particular, soda lime glass, barium or strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass or quartz can be preferably used. Examples of the polymer plate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone.

The coating may be performed by a wet coating method using a coating apparatus such as a roll coater, a spin coater, a slit and spin coater, a slit coater (which may be referred to as a die coater), an ink jet or the like so as to obtain a desired thickness.

Prebaking is performed by heating with an oven, a hot plate or the like. At this time, the heating temperature and the heating time in the pre-baking are appropriately selected depending on the solvent to be used, for example, at a temperature of 80 to 150 ° C for 1 to 30 minutes.

The exposure performed after the pre-baking is performed by an exposure machine, and exposed through a photomask to expose only the portion corresponding to the pattern. The light to be irradiated may be, for example, visible light, ultraviolet light, X-ray, electron beam, or the like.

Alkali development after exposure is carried out for the purpose of removing the photosensitive resin composition in the portion where the non-exposed portion is not removed, and a desired pattern is formed by this development. As the developer suitable for the alkali development, for example, an aqueous solution of a carbonate of an alkali metal or an alkaline earth metal may be used. Particularly, a weakly alkaline aqueous solution containing 1 to 3% by weight of a carbonate such as sodium carbonate, potassium carbonate or lithium carbonate is used at a temperature of 10 to 50 캜, preferably 20 to 40 캜, using a developing machine or an ultrasonic cleaner .

The post bake is performed to increase the adhesion between the patterned film and the substrate, and is performed by heat treatment at 80 to 250 ° C for 10 to 120 minutes. Post-baking Pre-baking is carried out using an oven, hot plate or the like.

At this time, the thickness of the black matrix is preferably 0.2 to 10.0 m, more preferably 0.5 to 7 m, and particularly preferably 1.0 to 5.0 m.

The film thickness of the column spacer and the black column spacer (black matrix integrated spacer) is preferably 0.5 m to 8 m, more preferably 0.1 m to 6 m, and particularly preferably 0.1 m to 4 m.

The black matrix, the spacer, or the black column spacer (black matrix integrated spacer) made of the black photosensitive resin composition of the present invention has an effect of improving the adhesion of the black matrix or the black column spacer to the substrate to improve the dynamic and durability And the like.

Further, the present invention provides a liquid crystal display device including the color filter described above.

Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are intended to further illustrate the present invention, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.

Production Example 1: Preparation of Binder Resin (BP1)

In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was allowed to flow at 0.02 L / min to make a nitrogen atmosphere, and 150 g of diethylene glycol methyl ethyl ether was added and heated to 70 캜 with stirring. Then, 0.45 mol of EDCPA, 0.09 mol of AA, 0.35 mol of VT and 0.11 mol of HEMA are dissolved in 150 g of diethyl glycol methyl ethyl ether to prepare a solution such that the total of EDCPA, AA, VT and HEMA is 1 mol. The prepared solution was dropped into a flask using a dropping funnel, 27.9 g (0.11 mol) of polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved in 200 g of diethylene glycol methyl ethyl ether Was added dropwise to the flask over 4 hours using a separate dropping funnel. After the dropping of the solution of the polymerization initiator was completed, the solution was maintained at 70 DEG C for 4 hours and then cooled to room temperature to prepare the binder resin (BP1).

Production Example 2: Preparation of a binder resin (BP2)

In the same manner as in Preparation Example 1 except that 0.9 mol of EDCPA and 0.1 mol of AA were dissolved in 150 g of diethyl glycol methyl ethyl ether to prepare a solution so that the total amount of EDCPA and AA was 1 mol in Preparation Example 1, (BP2).

Production Example 3: Preparation of binder resin (BP3)

Except that the solution was prepared by dissolving 0.84 mol of EDCPA, 0.1 mol of AA, 0.03 mol of VT and 0.03 mol of HEMA in 150 g of diethyl glycol methyl ethyl ether so that the total amount of EDCPA, AA, VT and HEMA was 1 mol in Preparation Example 1 , A binder resin (BP3) was prepared in the same manner as in Preparation Example 1,

Production Example 4: Preparation of a binder resin (BP4)

Except that the solution was prepared by dissolving 0.26 mol of EDCPA, 0.11 mol of AA, 0.52 mol of VT and 0.11 mol of HEMA in 150 g of diethyl glycol methyl ethyl ether so that the total amount of EDCPA, AA, VT and HEMA was 1 mol in Production Example 1 , A binder resin (BP4) was prepared in the same manner as in Preparation Example 1. [

Production Example 5: Preparation of a binder resin (BP5)

Except that the solution was prepared by dissolving 0.45 mol of EDCPA, 0.09 mol of AA, 0.35 mol of VT, and 0.11 mol of MMA in 150 g of diethyl glycol methyl ethyl ether so that the total amount of EDCPA, AA, VT and MMA was 1 mol in Production Example 1 , A binder resin (BP5) was prepared in the same manner as in Preparation Example 1,

The binder resins represented by the above formula (1) prepared according to Production Examples 1 to 5 are summarized in Table 1 below.

division The mole% of each monomer in the binder resin EDCPA (x) AA (y) VT (z) HEMA (w) MMA BP1 45 9 35 11 - BP2 90 10 - - - BP3 84 10 3 3 - BP4 26 11 52 11 - BP5 45 9 35 - 11

EDCPA: 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-9-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate were mixed at a molar ratio of 50:50 compound

AA: acrylic acid

VT: vinyl toluene

HEMA: (hydroxyethyl) methacrylate

MMA: methyl methacrylate

Preparation of Black Photosensitive Resin Composition According to Examples and Comparative Examples

The black photosensitive resin compositions of Examples 1 to 4 were prepared with the compositions shown in Table 2 below, and the black photosensitive resin compositions of Comparative Examples 1 to 4 were prepared with the compositions shown in Table 3 below.

(Unit: g) division Example 1 Example 2 Example 3 Example 4 coloring agent V29 14.67 14.67 14.67 9.33 B60 21.33 21.33 21.33 13.33 CB 6.67 6.67 6.67 10.67 OBP - - - 6.67 B16 - - - - R179 - - - - Binder resin BP1 23.71 13.55 13.55 14.32 BP2 - 8.59 8.59 9.08 BP3 - - - - BP4 - - - - Photopolymerization
compound C1 3.42 3.42 2.28 3.57 C2 - - 1.14 - Photopolymerization initiator 0.44 0.46 0.46 0.46 additive 0.28 0.20 0.20 0.20 solvent 80.0 29.55 31.12 31.12

(Unit: g) division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 coloring agent V29 14.67 14.67 - - - 14.67 14.67 14.67 B60 21.33 21.33 - 20.67 25.33 21.33 21.33 21.33 CB 6.67 6.67 6.67 6.67 6.67 6.67 6.67 6.67 OBP - - - - - - - - B16 - - 33.33 - 26.67 - - - R179 - - 33.33 20 - - - - Binder resin BP1 - 13.55 4.62 12.19 8.89 - - - BP2 20.05 8.59 2.93 7.73 5.64 8.59 8.59 - BP3 - - - - - 13.32 - - BP4 - - - - - - 12.94 - BP5 - - - - - - - 21.90 Photopolymerizable compound C1 3.42 1.73 3.16 2.54 3.42 3.42 3.65 C2 - 3.42 - - - - - - Photopolymerization initiator 0.46 0.46 0.23 0.42 0.34 0.46 0.46 0.46 additive 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 solvent 33.21 31.12 16.95 28.96 23.72 31.34 31.73 31.13

V29: C.I. Pigment Violet 29B60: C.I. Pigment Blue 60

CB: carbon black

OBP: Organic Black

B16: C.I. Pigment Blue 16

R179: C.I. Pigment Red 179

Binder resin: Refer to manufacturing example

Photopolymerizable compound C1: tripentaerythritol octaacrylate (8-functional group, # V802, Osaka Organic Chemical Co., Ltd.)

Photopolymerizable compound C2: dipentaerythritol hexaacrylate (6-functional group, DPHA, Nippon Kayaku Co., Ltd.)

Photopolymerization initiator: PBG-327 (Tron)

Additive: F554 (DIC)

Solvent: Propylene glycol monomethyl ether acetate (PGMEA)

Test Example: Property Evaluation of Black Photosensitive Resin Composition

(1) Substrate fabrication

A 5 cm x 5 cm glass substrate (Corning) was cleaned with a neutral detergent and water and dried. Each of the black photosensitive resin compositions of the examples and comparative examples was spin-coated on the glass substrate to a final film thickness of 3.0 (+/- 0.2) 占 퐉, prebaked at 80 to 120 占 폚 and dried for 1 to 2 minutes to prepare a solvent To form a pre-cured film. Thereafter, a pattern was formed through exposure with an exposure amount of 25 to 35 mJ / cm ² via a photomask, and an unexposed area was removed using an aqueous alkali solution. Followed by baking at 200 to 250 DEG C for 10 to 30 minutes to prepare a colored substrate.

(2) Evaluation of optical characteristics (optical density, O.D.)

The optical characteristics were evaluated with a substrate manufactured so that a black photosensitive resin was applied on the entire surface without a pattern in accordance with the above production standards. O.D. The OD was measured using X-rite equipment. The film thickness was measured using Dektak equipment and evaluated according to the evaluation criteria shown in Table 4 below. Table 5 shows the results.

(3) Reliability (solvent resistance) evaluation

A substrate is manufactured so that a black photosensitive resin is applied to the entire surface without a pattern, on the basis of the above-described production standards. It is cut into a size of 3 x 3 cm, immersed in NMP solvent, and heated at 100 캜 for 60 minutes. Thereafter, only the NMP solvent was extracted, the degree of elution in the NMP solvent was measured, and the absorbance was measured using a UV-vis spectrometer to measure the solvent resistance. The results are shown in Table 5 below.

(4) Evaluation of reflow characteristics

A substrate was fabricated using a line pattern mask on the basis of the above-described fabrication standards. The line pattern of the substrate was cut, the cross section was confirmed by SEM, the taper angle of the wiring was measured, and the result was evaluated according to the evaluation criteria shown in Table 4 below.

(5) Evaluation of Degree of Planarization (DOP)

A substrate is manufactured according to the same manufacturing standards as described above, and a CS pattern substrate is manufactured. After the size of the CS pattern on the CS pattern substrate is measured, a substrate is manufactured so that the black photosensitive resin composition is applied on the entire surface of the CS pattern substrate without a pattern. The manufactured substrate was measured for the level difference between the CS portion and the BM portion of the substrate using the SNU equipment to confirm the DOP and evaluated according to the evaluation criteria shown in Table 4. The results are shown in Table 5 below.

Optical property 550 nm unit OD. Excellent ⊚ = 1.3 or more / good ◯ = less than 1.3 to 1.2 or more
Insufficient △ = less than 1.2 ~ 1.1 or more / worse X = 1.0 or less responsibility 400 to 700 nm Abs. Excellent ⊚ = 1.0 or less / Good ◯ = over 1.0 to 2.0 or less Insufficient △ = 2.0 to less than 3.0 / worsening X = 3.0 or more Reflow characteristics Taper Angle Excellent ◎ = more than 25 ° to less than 35 ° / good ○ = more than 35 ° to less than 40 °
△ = over 40˚ to less than 45˚ / worsening X = 45˚ or more DOP CS / BM step
1.0 μm standard Excellent ◎ = Within ± 0.5um / Good ○ = Over ± 0.5 ~ Within ± 1.0um
Insufficient △ = Over ± 1.0 ~ Within ± 1.5um / Aging X = Over ± 1.5um

division Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Optical property ◎ ◎ ◎ ◎ ◎ ◎ X ◎ ◎ ◎ ◎ ◎ responsibility ○ ◎ ○ ◎ ◎ △ X △ X ◎ △ △ Reflow characteristics ◎ ◎ ◎ ◎ △ ○ X △ X △ ◎ X DOP ◎ ◎ ◎ ◎ △ ○ X △ X △ △ X

Claims (8)

(A) a colorant, (B) a binder resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, and (E)
Wherein the colorant comprises a black colorant, a purple colorant and a blue colorant,
Wherein the binder resin comprises a compound represented by the following formula (1)
Wherein the photopolymerizable compound comprises 8 or more functional groups.
[Chemical Formula 1]

In formula (1), the sum of mole% of x, y, z and w is 100, and x, y, z and w are each independently a positive integer.
The method according to claim 1,
Wherein x is an integer of 35 to 85, y is an integer of 3 to 15, z is an integer of 10 to 40, and w is an integer of 3 to 15. The black photosensitive resin composition of claim 1,
The method according to claim 1,
Wherein the binder resin further comprises a compound represented by the following general formula (2), and in the general formula (2), the monomer A comprises a carboxyl group.
(2)

In formula (2), the sum of mole% of x and y is 100, x is an integer of 50 to 95, and y is an integer of 5 to 50.
The method according to claim 1,
Wherein the photopolymerizable compound comprises 8 to 10 functional groups.
The method according to claim 1,
Wherein the black photosensitive resin composition further comprises (F) an additive.
The method according to claim 1,
(A) 15 to 55% by weight of a colorant, (B) 15 to 50% by weight of a binder resin, (C) 10 to 20% by weight of a photopolymerizable compound, To 6% by weight of the black photosensitive resin composition and (E) 60 to 90% by weight of the solvent based on the total content of the black photosensitive resin composition.
A color filter comprising a column spacer, a black matrix, or a black column spacer manufactured using the black photosensitive resin composition of any one of claims 1 to 6.
A display device comprising the color filter of claim 7.