KR102157142B1 - 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 includes (A) a colorant, (B) a binder resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator and a (E) solvent, wherein the colorant includes a black colorant, a purple colorant and a blue colorant, The binder resin includes a compound represented by the following formula (1), and the photopolymerizable compound contains at least 8 functional groups, and a black photosensitive resin composition and a column spacer, a black matrix, or a black column spacer prepared using the same A color filter including, and a display device including the color filter, are provided.
[Formula 1]

Description

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 TECHNICAL FIELD [A] A COLOR FILTER COMPRISING A BLACK METRICS AND/OR A COLUMN SPACER PREPARED BY USING THE COMPOSITION, AND A DISPLAY COMPRISING THE COLOR FILTER}

The present invention relates to a black photosensitive resin composition, a color filter including a black matrix and/or 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 a boundary between each color pixel and is black and does not substantially transmit visible light. A black matrix or black column spacer is a material that secures a space required for liquid crystal to move between two glass plates constituting an LCD and maintains LCD elasticity, and is formed of a black photosensitive resin composition.

When the 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 the boundary between the colored layers in order to enhance the contrast of red, green, and blue and the color development effect. In addition, recently, it is required to be positioned on an array substrate to perform various roles at once by forming a spacer for maintaining a cell gap as well as a role of a black matrix.

The black photosensitive resin composition is an essential material for not only color filters, but also liquid crystal display materials, organic light emitting devices, displays, etc., and studies on black photosensitive resin compositions with excellent elastic modulus and reliability as well as optical effects for basic light blocking have been conducted. It is actively progressing.

Korean Patent Registration No. 10-1658374 discloses a technology for improving the properties of a column spacer and a black matrix using a colored photosensitive resin composition, but does not disclose the improvement of adhesion between a column spacer and a black mattress through improved reflow properties. Has a problem.

Korean Patent Registration No. 10-1658374

An object of the present invention is to provide a black photosensitive resin composition that has been devised to solve the problems of the prior art, and improves reflow characteristics, thereby improving adhesion of a column spacer or a black mattress.

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

In order to achieve the above object, the present invention comprises (A) a colorant, (B) a binder resin, (C) a photopolymerizable compound (D) a photopolymerization initiator and (E) a solvent, and the colorant is a black colorant, a purple colorant And a blue colorant, wherein the binder resin includes a compound represented by the following formula (1), and the photopolymerizable compound provides a black photosensitive resin composition comprising at least 8 functional groups.

[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 positive integers.

In addition, the present invention provides a color filter including a column spacer, a black matrix, or a black column spacer manufactured using the black photosensitive resin composition.

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

The black photosensitive resin composition of the present invention includes a binder resin represented by Chemical Formula 1, thereby improving reflow characteristics and DOP characteristics, thereby providing an effect of improving adhesion of a column spacer or a black mattress.

In addition, the black photosensitive resin composition provides an effect of improving reliability by including a photopolymerizable compound containing 8 or more functional groups.

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

The present invention comprises (A) a colorant, (B) a binder resin, (C) a photopolymerizable compound (D) a photopolymerization initiator and a (E) solvent, wherein the colorant includes a black colorant, a purple colorant and a blue colorant, The binder resin includes a compound represented by the following formula (1), and the photopolymerizable compound provides a black photosensitive resin composition, characterized in that it contains at least 8 functional groups.

[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 positive integers.

Hereinafter, each component constituting the black photosensitive resin composition of the present invention will be described. However, the present invention is not limited by these components.

(A) colorant

The colorant is used to implement a black color, and imparts light blocking properties to all of 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 light leakage, and the spacer serves to prevent malfunction of the device due to external light.

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

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, etc., and CI in terms of light blocking It is preferable to include pigment violet 19, 23, 29, and C.I. It is more preferred 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 the like, and C.I. Pigment Blue 15:3, 15:6, 16, it is preferable to contain at least one selected from the group consisting of 60, C.I. It is more preferred to include Pigment Blue 60.

As the black colorant, it may be appropriately selected from inorganic or organic pigments. Black colorants that can be used include carbon black, atetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, titanium black, ramtam black, perylene black, organic black (OBP), and the like. Depending on the purpose, inorganic pigments and organic pigments may be used alone or in combination.

The carbon black may be coated with a resin on its surface for electrical insulation. Incidentally, since carbon black coated with resin has a lower conductivity than carbon black not coated with resin, it can provide excellent electrical insulation when forming a black matrix, spacer or 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 included 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 included within the above range, sufficient shielding properties, that is, high optical density (O.D.) can be exhibited, and sufficient pattern formation is possible.

More specifically, the colorant may be carbon black, organic black, V29, B60, or the like. These may be used alone or in combination of two or more.

The content of the black colorant in the present invention is preferably 4 to 12% by weight, and 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 lowered, and when it exceeds 12% by weight, it may be disadvantageous in terms of controlling transmittance and dielectric constant in the infrared region.

The content of the purple colorant may be included in 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, great effects cannot be expected, and if it exceeds 18% by weight, the reliability of the product may be affected. When V29 is used as the purple colorant, optical density may be improved by reducing visible light transmittance in the range of 400 to 600 nm.

The content of the blue colorant may be included in 5 to 25% by weight based on the total solid content of the black photosensitive resin composition. In the case of the blue colorant, when it is included in an amount of less than 5% by weight, the effect is not so great, and when it is more than 25% by weight, it may affect the infrared region. In the case of using B60 as the blue colorant, there is no metal element, so there is an advantage in driving the equipment.

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

In addition, the colorant may optionally further contain a color correcting agent as needed. As the color correcting agent, organic pigments such as condensed polycyclic pigments such as anthraquinone pigments or perylene pigments, phthalocyanine pigments or azo pigments may be used, and anthraquinone pigments or phthalocyanine pigments are preferable, and phthalocyanine pigments are more preferable. . Examples of the phthalocyanine pigment may include C.I pigment blue 15:6, C.I pigment blue 15:4, and C.I pigment blue 16, and examples of the anthraquinone pigment include C.I pigment blue 60. As the phthalocyanine pigment, C.I Pigment Blue 15:6 may be preferable.

In addition, the colorant is preferably a pigment dispersion in which the particle diameter of the pigment is uniformly dispersed. An example of a method for uniformly dispersing the particle diameter of the pigment may include a method of dispersing by containing a pigment dispersant (a1). According to the method, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained. have.

(a1) Pigment dispersant

The pigment dispersant is added for deagglomeration and stability of the pigment. Specific examples of the pigment dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, and polyamine. And these may be used alone or in combination of two or more.

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

Specific examples of the anionic surfactant include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, and Alkyl aryl sulfonates, such as sodium dodecyl naphthalene sulfonate, etc. are mentioned.

Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene/oxypropylene block copolymers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, and polyoxyethylene alkylamine.

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 are listed. have.

In addition, the pigment dispersant preferably includes an acrylate-based dispersant (hereinafter, an acrylate-based dispersant) including butyl methacrylate (BMA) or N,N-dimethylaminoethyl methacrylate (DMAEMA). It is preferable to use the acrylate-based dispersant manufactured by the living control method, and commercially available products include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070 or DISPER BYK-2150, and the acrylic Each of the rate-based dispersants may be used alone or in combination of two or more.

In addition to the acrylate-based dispersant, the pigment dispersant may use other resin type pigment dispersants. The other resin type pigment dispersants include known resin type pigment dispersants, especially polycarboxylic acid esters typified by polyurethanes and polyacrylates, unsaturated polyamides, polycarboxylic acids, and (partial) of polycarboxylic acids. Amine salts, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long chain polyaminoamide phosphate salts, esters of hydroxyl group-containing polycarboxylic acids and modified products thereof, or free ) An oily dispersant such as an amide formed by the reaction of a polyester having a carboxyl group with a poly(lower alkyleneimine) or a salt thereof; Water-soluble resins or water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinyl pyrrolidone; Polyester; Modified polyacrylate; Adducts of ethylene oxide/propylene oxide; And phosphate esters.

Commercially available products of the above other resin type pigment dispersants include cationic resin dispersants, for example, BYK (BIC) Chemie's brand names: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; BASF's brand names: EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA- 4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; Trade names of Lubirzol: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10; Kawaken Fine Chemical's trade names: Hinoact T-6000, Hinoact T-7000, Hinoact T-8000; Ajinomoto's brand names: AJISPUR PB-821, Ajisper PB-822, Ajisper PB-823; Kyoeisha Chemical Co., Ltd. trade names: FLORENE DOPA-17HF, Florene DOPA-15BHF, Floren DOPA-33, Florene DOPA-44, and the like.

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

The pigment dispersant is included in an amount greater than 0 and 1 part by weight or less, and preferably 0.01 to 0.5 parts by weight, based on 1 part by weight of the colorant. When the pigment dispersant is contained in an amount of more than 0 and 1 part by weight or less of the above, it is preferable because a uniformly dispersed pigment can be obtained.

(B) binder resin

In the present invention, the binder resin generally makes the non-exposed 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 various polymers used in the applicable technical field, but preferably, may contain an epoxy group, and may be a compound represented by the following formula (1).

[Formula 1]

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

In Formula 1, x may be 35 to 85, y may be 3 to 15, z may be 10 to 40, and w may be 3 to 15.

When the binder resin includes the compound represented by Chemical Formula 1, reflow characteristics are improved so that taper angle adjustment is facilitated, and flow characteristics are improved, so that DOP characteristics may 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, thereby improving developability against alkali development, suppressing the occurrence of residue, and improving the adhesion of the pattern. I can.

The binder resin may further include a compound represented by Formula 2 below. When the binder resin further includes a compound represented by Formula 2, there is an advantage in terms of reliability.

[Formula 2]

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

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

(C) photopolymerizable compound

The photopolymerizable compound of the present invention contains an unsaturated bond and undergoes a photoreaction with a photopolymerization initiator to form a photosensitive resin layer, and the photopolymerizable compound preferably contains at least 8 functional groups, and includes 8 to 10 functional groups. It is more preferable to do it. When the photopolymerizable compound contains less than 8 functional groups, there is a problem in that it is disadvantageous in terms of solvent resistance and reliability is lowered.

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

[Formula 3]

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

For example, when m is 2 in Formula 3, and R is -COCH=CH ₂ , it may be represented by the following Formula 3-1, in Formula 3, m is 3, and R is -COCH=CH ₂ In the case of, it may be represented by the following Formula 3-2.

[Formula 3-1]

[Chemical Formula 3-2]

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

The photopolymerizable compound may be included in an amount of 10 to 20% by weight in 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 included within the above range, pattern characteristics and efficiency of a developing process may be improved.

(D) photopolymerization initiator

The photopolymerization initiator is a compound for initiating polymerization of the photopolymerizable compound, and is not particularly limited in the present invention, but acetophenone system, benzophenone system, triazine system, thioxanthone system, oxime system, benzoin system, anthraquinone system, And biimidazole-based compounds may be used, and these may be used alone or in combination of two or more.

Examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, and 2-hydroxy-1-[4-(2-hydroxye). Oxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2- Oligomer of benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl[4-(1-methylvinyl)phenyl]propan-1-one, etc. Among them, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one may be preferably used.

Examples of the benzophenone-based compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'- Bis(diethylamino)benzophenone, etc. are mentioned.

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dime Toxic styryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxy naphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2 -(p-methoxy phenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-triazine)-4,6-bis(trichloromethyl)-s-triazine, 2 -Biphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho 1-yl)-4,6 -Bis(trichloromethyl)-s-triazine, 2-(4-methoxy naphtho 1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl (Piperonyl)-6-triazine, 2,4-trichloromethyl (4'-methoxy styryl)-6-triazine, etc. are mentioned.

Examples of the thioxanthone compounds include 2-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, and 1-chloro-4-propoxy thioxanthone. have.

Examples of the oxime compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, and commercially available products include BASF's Irgacure OXE01 and Irgacure OXE02.

As the benzoin-based compound, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, and the like can be used.

Examples of the anthraquinone-based compound include 2-ethyl anthraquinone, octamethyl anthraquinone, 1,2-benz anthraquinone, and 2,3-diphenyl anthraquinone.

As the biimidazole-based compound, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl) )-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole, the phenyl group at the 4,4',5,5' position to the carboalkoxy group And imidazole compounds substituted by.

The photopolymerization initiator may be included 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. This content range is in consideration of the photopolymerization rate of the photopolymerizable compound and the physical properties of the final coating film.If it is less than the above range, the polymerization rate is low, and the overall process time may be lengthened.Conversely, if it exceeds the above range, the crosslinking reaction is caused by excessive reaction. In the past, the physical properties of the coating film may rather deteriorate. When the photopolymerization initiator is used within the above content range, the intensity of the pixel portion and the straightness of the pattern may be improved.

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

The photopolymerization initiation aid may be used to increase polymerization efficiency, and at least one compound selected from the group consisting of an amine compound, an alkoxyanthracene compound, a thioxanthone compound, a carboxylic acid and a sulfonic acid compound may be used, preferably Preferably, it may be selected from the group consisting of carboxylic acid and sulfonic acid compounds.

Examples of the amine compound include triethanolamine, methyl diethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, benzoic acid-2-dimethylaminoethyl, 4 -Dimethylaminobenzoic acid 2-ethylhexyl, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzphenone (common name, Michler's ketone), 4,4'-bis(diethylamino)benzo Phenone, 4,4'-bis(ethylmethylamino)benzophenone, etc. are mentioned. Among these, 4,4'-bis(diethylamino)benzophenone is preferable.

Examples of the alkoxyanthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. I can.

Examples of the thioxanthone-based compound include 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, and 1-chloro-4-pro Foxittioxanthone, etc. are mentioned.

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 initiation aid may be prepared directly or purchased commercially.

It is preferable to use the photopolymerization initiator auxiliary agent in the range of usually 10 moles or less, preferably 0.01 to 5 moles per 1 mole of the photopolymerization initiator. When the photopolymerization initiation aid is used within the above range, it is possible to increase the polymerization efficiency and improve productivity.

(E) solvent

The solvent has compatibility with the constituents of the black photosensitive resin composition so that the above-mentioned composition can be dissolved or dispersed, but any one that does not react can be used. It does not specifically limit. Preferably, an organic solvent having a boiling point of 100 to 200° C. may be used in terms of coatability and drying properties, and a plurality of organic solvents having different boiling points may be mixed and used.

Representatively, examples of the solvent that can be used 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; Cyclic esters, such as γ-butyrolactone, etc. are mentioned.

Among the solvents, preferably alkylene glycol alkyl ether acetates, ketones, esters such as ethyl 3-ethoxypropionate or methyl 3-methoxypropionate may be used, and more preferably 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 alone or in combination of two or more.

The solvent may be included in the remaining amount so that the black photosensitive resin composition satisfies 100% by weight, may be included in 60 to 90% by weight, based on the total weight% of the black photosensitive resin composition, and included in 70 to 85% by weight. desirable. When the content of the solvent is within the above-described range, the dispersion stability of the black photosensitive resin composition and the ease of processing in the manufacturing process (eg, coating property) can be improved. In other words, the black photosensitive resin composition according to the present invention can prepare a black matrix, a spacer, or a black column spacer (a black matrix integrated spacer) by wet coating, and at this time, a roll coater, a spin coater, a slit and spin A coating device such as a coater, a slit coater (sometimes referred to as a die coater), an ink jet, or the like can be used.

(F) additive

In addition to the above components, the black photosensitive resin composition of the present invention may further contain additives as needed by those skilled in the art within a range that does not impair the object of the present invention.

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

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

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

The curing agent is used to increase deep curing 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, noblock epoxy resin, other aromatic epoxy resins, alicyclic epoxy resins , Glycidyl ester resins, glycidylamine resins, or brominated derivatives of these epoxy resins, aliphatic, alicyclic or aromatic epoxy compounds other than the epoxy resins and brominated derivatives thereof, butadiene (co)polymer epoxides, isoprene ( Co) polymer epoxidation product, glycidyl (meth)acrylate (co)polymer, triglycidyl isocyanurate, etc. are mentioned.

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

The curing agent may be used in combination with a curing agent and a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound. Examples of the curing auxiliary compound include polyvalent carboxylic acids, polyvalent carboxylic anhydrides, and acid generators. The polyhydric carboxylic anhydrides may be commercially available as an epoxy resin curing agent. Specific examples of the epoxy resin curing agent are commercial products such as a brand name (Adeka Hadona EH-700) (manufactured by Adeka Industries, Ltd.), a brand name (Rika Shiddo HH) (manufactured by Shin Nippon Ewha Corporation), and a brand name (MH-700) ( Shin Nippon Ewha Co., Ltd.) and the like. The curing agent exemplified above may be used alone or in combination of two or more.

As the leveling agent, a commercially available surfactant may be used to further improve the film-forming property of the black photosensitive resin composition. For example, silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, amphoteric, etc. Surfactants and the like are mentioned, and these may be used alone or in combination of two or more.

Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, In addition to polyethyleneimines, under brand names, KP (manufactured by Shin-Etsu Chemical Industries, Ltd.), Polyflow (manufactured by Kyei Chemical Corporation), Ftop (manufactured by Tochem Products), Megapak (manufactured by Tochem Products), Megapak (manufactured by Dai Nippon Ink Chemical Industries, Ltd.) Co., Ltd.), Florade (manufactured by Sumitomo 3M Co., Ltd.), Asahigard, Saffron (above, manufactured by Asahi Glass Co., Ltd.), Sor Spas (manufactured by Geneva Co., Ltd.), EFKA (manufactured by EFKACHEMICALS) ), PB821 (manufactured by Ajinomoto Co., Ltd.), and the like.

The adhesion promoter is an additive used to improve the coating property and adhesion with the substrate, and includes a silane coupling agent including a reactive substituent selected from the group consisting of a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, and combinations thereof. Can include. The silane coupling agent is specifically, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxy Silane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane , 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3 -Mercaptopropyl trimethoxysilane, etc. are mentioned.

The above additives may be appropriately added and used by a person skilled in the art within a range that does not impair the effects 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 total black photosensitive resin composition, but is not limited thereto.

For example, after adding a colorant to a solvent, the remaining composition and other additives may be added and obtained through 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 a solvent or an alkali-soluble resin in advance. When the additive is in the form of a solution, it may be added in advance to the solvent together with the colorant.

Color filter and liquid crystal display

The method for producing the black photosensitive resin composition of the present invention is not particularly limited, and a known method for producing a black photosensitive resin composition is followed.

For example, after adding a colorant to a solvent, the remaining composition and other additives may be added and obtained through 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 a solvent or an alkali-soluble resin in advance. In the case of a solution form, the additive may be added in advance to the solvent together with the colorant.

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

In particular, the black photosensitive resin composition of the present invention can be preferably used in the manufacture of 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, respectively, It is formed in a structure that can serve as both a black matrix and a spacer in one pattern.

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

It also relates to a liquid crystal display device including the color filter.

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

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

b) a prebaking step of drying the solvent;

c) placing a photo mask on the obtained film and irradiating active light to cure the exposed portion;

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

e) Drying and post-baking steps.

As the substrate, a glass substrate or a polymer plate is used. 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. Moreover, polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, polysulfone, etc. are mentioned as a polymer plate.

In this case, the coating may be performed by a wet coating method using a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (also referred to as a die coater), or an inkjet 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 heating time in the pre-baking are appropriately selected according to the solvent to be used, and are performed at, for example, 80 to 150°C for 1 to 30 minutes.

Further, the exposure performed after the prebaking is performed by an exposure machine and exposed through a photo mask, thereby sensitizing only the portion corresponding to the pattern. The light to be irradiated at this time may be, for example, visible light, ultraviolet light, X-ray, and electron beam.

Alkali development after exposure It is performed for the purpose of removing the photosensitive resin composition in the part which is not removed from the non-exposed part, and a desired pattern is formed by this development. As a developer suitable for this alkali development, for example, an aqueous solution of an alkali metal or alkaline earth metal carbonate can be used. In particular, using a less alkaline aqueous solution containing 1 to 3% by weight of carbonates such as sodium carbonate, potassium carbonate, and lithium carbonate, and using a developer or ultrasonic cleaner at a temperature of 10 to 50°C, preferably 20 to 40°C. To do it.

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

At this time, the thickness of the black matrix is preferably 0.2 µm to 10.0 µm, more preferably 0.5 µm to 7.0 µm, and particularly preferably 1.0 µm to 5.0 µm.

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

The black matrix, spacer, or black column spacer (black matrix integrated spacer) made of the black photosensitive resin composition of the present invention has the effect of improving the adhesion of the black matrix or the black column spacer to the substrate, thereby improving drivability and durability of a liquid crystal display. It can have excellent properties in the back.

In addition, 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 through examples. However, the following examples are for explaining the present invention more specifically, 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.

Preparation 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 flowed at 0.02 L/min to obtain a nitrogen atmosphere, and 150 g of diethylene glycol methyl ethyl ether was added and heated to 70° C. while stirring. Subsequently, 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 methylethyl ether so that the total of EDCPA, AA, VT, and HEMA is 1 mol, to prepare a solution. After dropping the prepared solution into the flask using a dropping funnel, 27.9 g (0.11 mol) of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was added to 200 g of diethylene glycol methylethyl ether. The solution dissolved in was added dropwise into the flask over 4 hours using a separate dropping funnel. After the dropping of the polymerization initiator solution was completed, the solution was maintained at 70° C. for 4 hours, and then cooled to room temperature to prepare the binder resin (BP1).

Preparation Example 2: Preparation of binder resin (BP2)

Binder resin 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 methylethyl ether so that the total of EDCPA and AA in Preparation Example 1 was 1 mol. (BP2) was prepared.

Preparation Example 3: Preparation of binder resin (BP3)

Except for preparing a solution by dissolving EDCPA 0.84 mol, AA 0.1 mol, VT 0.03 mol, and HEMA 0.03 mol in 150 g of diethyl glycol methylethyl ether so that the total of EDCPA, AA, VT, and HEMA is 1 mol in Preparation Example 1 Then, a binder resin (BP3) was prepared in the same manner as in Preparation Example 1.

Preparation Example 4: Preparation of binder resin (BP4)

Except for preparing a solution 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 methylethyl ether so that the total of EDCPA, AA, VT, and HEMA in Preparation Example 1 is 1 mol. Then, a binder resin (BP4) was prepared in the same manner as in Preparation Example 1.

Preparation Example 5: Preparation of binder resin (BP5)

Except for preparing a solution by dissolving EDCPA 0.45 mol, AA 0.09 mol, VT 0.35 mol, and MMA 0.11 mol in 150 g of diethyl glycol methylethyl ether so that the total of EDCPA, AA, VT, and MMA is 1 mol in Preparation Example 1 Then, a binder resin (BP5) was prepared in the same manner as in Preparation Example 1.

The binder resins represented by Formula 1, prepared according to Preparation Examples 1 to 5, are summarized in Table 1 below.

division 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-eopxytricyclo[5.2.1.0 ^2,6 ]decane-9-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8-yl acrylate are 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

Black photosensitive resin compositions according to Examples 1 to 4 were prepared with the composition of Table 2 below, and black photosensitive resin compositions according to Comparative Examples 1 to 4 were prepared with the composition of 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: See Manufacturing Example

Photopolymerizable compound C1: tripentaerythritol octaacrylate (8 functional group, #V802, Osaka Organic Chemicals)

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

Photopolymerization initiator: PBG-327 (Tronley)

Additive: F554 (DIC company)

Solvent: Propylene glycol monomethyl ether acetate (PGMEA)

Test Example: Evaluation of physical properties of black photosensitive resin composition

(1) board fabrication

A 5cmX5cm glass substrate (Corning) was washed with a neutral detergent and water, and then dried. Each of the black photosensitive resin compositions according to Examples and Comparative Examples was spin-coated on the glass substrate so that the final film thickness was 3.0 (±0.2) µm, pre-baked at 80 to 120°C, and dried for 1 to 2 minutes. Was removed to form a precured film. Thereafter, a pattern was formed by exposing through a photomask at an exposure amount of 25 to 35 mJ/cm ² , and an aqueous alkali solution was used to remove the unexposed part. Then, after firing at 200 to 250°C for 10 to 30 minutes, a colored substrate was prepared.

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

Based on the above manufacturing criteria, optical properties were evaluated with a substrate prepared such that a black photosensitive resin was applied on the entire surface without a pattern. O.D. And the film thickness was measured to calculate OD/um, and OD was measured using X-rite's equipment, and the film thickness was measured using Dektak's equipment, and evaluated according to the evaluation criteria in Table 4 below. Table 5 shows the results.

(3) Reliability (solvent resistance) evaluation

Based on the above manufacturing standards, a substrate is manufactured such that a black photosensitive resin is applied on the entire surface without a pattern. It is cut into a size of 3x3 cm, immersed in an NMP solvent, and then heated at 100°C for 60 minutes. Thereafter, only the NMP solvent was extracted, the degree of elution in the NMP solvent was measured, the absorbance was measured using a UV-vis spectrometer, and the solvent resistance was measured, and the evaluation was performed according to the evaluation criteria in Table 4 below, and the results are shown in Table 5 below.

(4) Reflow characteristic evaluation

A substrate was fabricated using a line pattern mask based on the fabrication standard as described above. The line pattern of the substrate was cut, the cross-section was confirmed with SEM, the taper angle of the wiring was measured, and evaluated according to the evaluation criteria in Table 4 below, and the results are shown in Table 5 below.

(5) DOP (Degree of planarization) characteristic evaluation

A substrate is manufactured according to the same manufacturing standard, but a CS pattern substrate is manufactured. After measuring the size of the CS pattern on the CS pattern substrate, a substrate is prepared so that the black photosensitive resin composition is applied on the entire surface without a pattern on the CS pattern substrate. The fabricated substrate was evaluated according to the evaluation criteria in Table 4 below by measuring the step difference between the CS portion and the BM portion of the substrate using SNU equipment, and then evaluated according to the evaluation criteria in Table 4 below, and the results are shown in Table 5 below.

Optical properties 550nm unit O.D. Excellent◎ = 1.3 or more / Good ○ = Less than 1.3 ~ 1.2 or more
Insufficient △ = less than 1.2-more than 1.1 / worse X = less than 1.0 responsibility 400~700nm Abs. Excellent◎ = Less than 1.0 / Good ○ = More than 1.0 to less than 2.0 Lack △ = More than 2.0 to less than 3.0 / Deterioration X = more than 3.0 Reflow characteristics Taper Angle Excellent◎ = Above 25˚ ~ Below 35˚ / Good ○ = Above 35˚ ~ Below 40˚
Lower foot△ = more than 40˚ ~ less than 45˚ / worse X = more than 45˚ DOP CS/BM step
1.0㎛ standard Excellent◎ = within ±0.5um / Good ○ = greater than ±0.5 to within ±1.0um
Insufficient△ = exceeding ±1.0 to within ±1.5um / worse X = exceeding ±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 properties ◎ ◎ ◎ ◎ ◎ ◎ 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 photoinitiator and (E) a solvent,
The colorant includes a black colorant, a purple colorant and a blue colorant,
The binder resin includes a compound represented by the following Chemical Formula 1 and Chemical Formula 2, and the monomer A in the following Chemical Formula 2 contains a carboxyl group,
The photopolymerizable compound is a black photosensitive resin composition, characterized in that it contains at least 8 functional groups:
[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 positive integers.

[Formula 2]

In 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.
The method according to claim 1,
In Formula 1, 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, characterized in that the black photosensitive resin composition.
delete The method according to claim 1,
The photopolymerizable compound is characterized in that it contains 8 to 10 functional groups, black photosensitive resin composition.
The method according to claim 1,
The black photosensitive resin composition further comprises (F) an additive, a black photosensitive resin composition.
The method according to claim 1,
Based on the total solid content in the black photosensitive resin composition (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, (D) 0.5 to a photopolymerization initiator To 6% by weight and (E), based on the total content of the black photosensitive resin composition, containing 60 to 90% by weight of the solvent, black photosensitive resin composition.
A color filter comprising a column spacer, a black matrix, or a black column spacer prepared by using the black photosensitive resin composition of any one of claims 1, 2 and 4 to 6.
A display device comprising the color filter of claim 7.