TW201917177A - A pigment dispersion, a photo sensitive resin composition comprising the pigment dispersion, a pattern layer prepared by using the composition, a color filter comprising the pattern layer, and a display device comprising the color filter with the pigment dispersion containing a coloring agent, a dispersion resin and a solvent - Google Patents

Abstract

The present invention discloses a photo sensitive resin composition comprising the pigment dispersion, a pattern layer prepared by using the composition, a color filter comprising the pattern layer, and a display device comprising the color filter. The photo sensitive resin composition contains a pigment dispersion, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The pigment dispersion contains a coloring agent containing an organic black pigment, a blue pigment, a purple pigment, and carbon black, a dispersion resin, and a solvent. The dispersion resin contains a copolymer of the following Chemical Formula 1, in which R1 and R2 are each independently hydrogen or a methyl group, and the molar ratio of the a monomer and the b monomer is from 1:20 to 20:1.

Description

   Colored dispersion liquid, colored photosensitive resin composition containing the colored dispersion liquid, pattern layer manufactured using the composition, color filter including the pattern layer, and display device including the color filter   

The present invention relates to a colored dispersion, a colored photosensitive resin composition containing the colored dispersion, a pattern layer manufactured using the resin composition, a color filter including the pattern layer, and a color filter including the color filter. Display device.

Color filters are widely used in various display devices such as image pickup elements and liquid crystal display devices (LCD), and their applications are rapidly expanding. Color filters used in imaging devices, liquid crystal display devices, etc. are formed by color patterns of three colors: red, green, and blue, or yellow, magenta (Magenta) ) And cyan (Cyan) and other three colors.

Each coloring pattern of a color filter is generally formed using a coloring photosensitive resin composition containing a coloring agent containing a pigment or a dye, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The coloring pattern processing using the colored photosensitive resin composition is usually performed by a photolithography process.

The colored photosensitive resin is a material necessary for a color filter, a liquid crystal display material, an organic light emitting element, a display, and the like. For example, in the case of a color filter used in a liquid crystal display, pixels including pixels of red, green, and blue are included. In order to prevent such pixels, In order to hide the color of the electrode or to hide the electrode pattern, a black matrix is formed at the boundary portion between the colored layers. In addition, a black columnar spacer (Black Colum Spacer, BCS) is a part that is in direct contact with the liquid crystal, and requires excellent solvent resistance and a property that does not leave any residue on the organic film.

Korean Registered Patent No. 10-1658374 relates to a black columnar spacer in which a columnar spacer and a black matrix are integrated in one module. It has been disclosed that a colored photosensitive resin composition and a black columnar spacer satisfy all the following requirements. Object: characteristics such as the elastic recovery rate required as a columnar spacer and the light-shielding property required as a black matrix. However, it is still insufficient to improve solvent resistance and storage stability.

    Prior art literature         Patent literature    

Patent Document 1: Korean Registered Patent No. 10-1658374

The present invention has been made in order to solve the above-mentioned problems of the prior art, and an object thereof is to provide a colored dispersion liquid having excellent pigment dispersibility and storage stability.

Another object of the present invention is to provide a colored photosensitive resin composition containing a colored dispersion liquid, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.

Another object of the present invention is to provide a pattern layer produced from the colored photosensitive resin composition, a color filter including the pattern layer, and a display device including the color filter.

In order to achieve the above object, the present invention provides a colored dispersion liquid, which includes a coloring agent, a dispersing resin, and a solvent. The coloring agent includes an organic black pigment, a blue pigment, a purple pigment, and a black pigment. The dispersion resin contains the following Copolymer of Chemical Formula 1.

(In Chemical Formula 1, R ₁ and R ₂ are each independently hydrogen or methyl, and a and b are each independently an integer of 1 to 20.)

Moreover, this invention provides the coloring photosensitive resin composition containing the coloring dispersion liquid of this invention, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.

The present invention also provides a pattern layer produced from the colored photosensitive resin composition of the present invention.

The present invention also provides a color filter including the pattern layer of the present invention.

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

The colored dispersion liquid of the present invention has the effect of being excellent in pigment dispersibility and storage stability by permeating a dispersion resin containing a copolymer of Chemical Formula 1.

In addition, the colored photosensitive resin composition of the present invention has excellent reliability in terms of solvent resistance and storage stability by transmitting the colored dispersion liquid of the present invention, and does not cause residues on the organic film when applied to a substrate.

In addition, since the colored photosensitive resin composition of the present invention is used by mixing two or more copolymers having different epoxy equivalents from each other, the coating film produced by using the resin composition has excellent elastic recovery.

Hereinafter, the present invention will be described in more detail.

The present invention relates to a colored dispersion liquid, which comprises a colorant, a dispersing resin, and a solvent. The colorant includes an organic black pigment, a blue pigment, a purple pigment, and carbon black. The dispersion resin contains a copolymer of Chemical Formula 1 below. Thing.

(In Chemical Formula 1, R ₁ and R ₂ are each independently hydrogen or methyl, and the molar ratio of monomer a to monomer b is 1:20 to 20: 1.)

The use of the dispersion resin containing the copolymer of Chemical Formula 1 in the coloring dispersion liquid of the present invention can improve pigment dispersibility and storage stability, and can further improve the solvent resistance and storage stability of the coloring photosensitive resin composition using the dispersion resin. And other reliability.

In the case where a colored dispersion liquid is produced using a dispersion resin containing the above-mentioned copolymer of Chemical Formula 1, a colored dispersion liquid in which the pigment surface is uniformly coated with the above-mentioned dispersion resin can be obtained. Therefore, since the colored photosensitive resin composition containing the colored dispersion liquid contains pigment particles coated with the dispersed resin, the pigment is prevented from leaching out in the solvent, the solvent resistance can be improved, and aggregation between the pigment particles can be prevented to prevent The viscosity of the colored photosensitive resin composition is increased, so that storage stability can be improved.

The colored dispersion liquid of the present invention is characterized in that it contains 65 to 75% by weight of the colorant and 7 to 12% by weight of the dispersing resin with respect to the total weight of the solid content in the colored dispersion, and 70% of the solvent relative to the total weight of the colored dispersion Up to 80% by weight. When the colorant, the dispersion resin, and the solvent satisfy the above-mentioned ranges, a colored dispersion liquid having excellent pigment dispersibility and storage stability can be produced.

In addition, the coloring dispersion liquid may further include a dispersant. By adding a dispersant to a colored dispersion liquid and performing a dispersion treatment, a colored dispersion liquid in which a pigment is more uniformly dispersed in a solution can be obtained.

Moreover, this invention relates to the coloring photosensitive resin composition containing the said coloring dispersion liquid, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.

The colored photosensitive resin composition of the present invention contains an organic black pigment, a purple pigment, a blue pigment, and carbon black as a colorant, so that the optical density of the colored photosensitive resin composition can be increased.

Moreover, the coloring photosensitive resin composition of this invention may contain the copolymer of said chemical formula 1 as an alkali-soluble resin. Therefore, it is possible to improve reliability such as solvent resistance and chemical resistance through the crosslinking reaction of the colored photosensitive resin composition.

In addition, the colored photosensitive resin composition of the present invention can improve the coating film produced by using the resin composition by using two or more copolymers represented by the above Chemical Formula 1 and having different epoxy equivalents as the alkali-soluble resin. Flexible response rate.

Hereinafter, the coloring dispersion liquid and the coloring photosensitive resin composition of this invention are demonstrated in detail for each component.

Colorant

In the present invention, a coloring agent having a light-shielding property against visible light is used. The coloring agent of the present invention includes an organic black pigment, a purple pigment, and a blue pigment.

The organic black pigment contains one or more selected from the group consisting of lactam black, nigrosine, and osmium black, and preferably includes lactam black. By including the organic black pigment, the optical density can be increased without affecting the infrared region, and the dielectric constant and light transmittance can be improved.

The purple pigment has a function of reducing the light transmittance and increasing the optical density (O.D.) in the region of 400 to 600 nanometers. In addition, since the content of the organic black pigment can be reduced by using the purple pigment, the reliability of the colored photosensitive resin composition can be improved. The type of purple pigment is not particularly limited, and one or more selected from the group consisting of C.I. Pigment Purple 19, 23, 29, 31, and 37 is preferably used, and C.I. Pigment Purple 29 is most preferably used.

The blue pigment is a compound containing no central metal. If a central metal is present, it may affect the liquid crystal drive. However, in the present invention, the use of a compound without a central metal as the blue pigment can facilitate device driving. . In the present invention, the type of the blue pigment is not particularly limited as long as it is a compound containing no central metal. It is preferable to use one or more members selected from the group consisting of CI Pigment Blue 16, 60, 63, and 66. CI is most preferably added. Pigment Blue 60 is used.

In addition, the colored photosensitive resin composition of the present invention may include a black pigment as an additional colorant. The type of the black pigment is not particularly limited as long as it has light-shielding properties in visible light, and it is preferred to use one or more selected from the group consisting of titanium black and carbon black, and more preferably to use carbon black. Carbon black is not particularly limited as long as it is a light-shielding pigment, and known carbon black can be used. Specific examples of the carbon black as the black pigment include channel black, furnace black, thermal black, and lamp black. The carbon black may be coated with a resin, and the carbon black covered with the resin has lower electrical conductivity than the uncoated carbon black, and can provide excellent electrical insulation when forming a black matrix or a columnar spacer.

In the present invention, the content of the colorant is 13 to 60% by weight, and preferably 25 to 45% by weight, based on the total weight of the solid content in the colored photosensitive resin composition. When the content of the colorant is 13 to 60% by weight, the optical density and reliability are excellent.

More specifically, the colorant may be prepared by mixing an organic black pigment, a purple pigment, a blue pigment, and a black pigment in a weight ratio of 1: 0.08 to 2.5: 0.2 to 3.3: 0.12 to 1.7. In addition, more preferably, it can be mixed according to a weight ratio of 1: 0.27 ~ 1: 0.47 ~ 1.88: 0.27 ~ 0.87. When the organic black pigment, the purple pigment, the blue pigment, and the black pigment are included in the above weight ratio, a colored photosensitive resin composition excellent in optical density and reliability can be obtained.

Dispersion resin

The dispersion resin functions to prevent dissolution in the solvent by coating the pigment particles in the colored dispersion liquid with the dispersion resin, and to prevent the increase in viscosity due to the aggregation between the pigment particles by suppressing the aggregation between the pigment particles.

The dispersion resin of the present invention contains a copolymer of the following Chemical Formula 1.

(In Chemical Formula 1, R ₁ and R ₂ are each independently hydrogen or methyl, and the molar ratio of monomer a to monomer b is 1:20 to 20: 1.)

In the present invention, by including the copolymer of the above-mentioned chemical formula 1 containing an epoxy group as a dispersion resin, solvent resistance, storage stability, and residual film rate can be improved.

The weight average molecular weight of the dispersion resin is not particularly limited, and may be 3,000 to 100,000, preferably 3,000 to 50,000, and more preferably 5,000 to 50,000.

The acid value of the dispersing resin is 50 to 200 mg KOH / g based on the solid content, and in the above range, the dispersion stability of the pigment can be improved.

The dispersion resin may be a copolymer of the copolymer represented by the above Chemical Formula 1 and another monomer capable of being copolymerized therewith.

Specific examples of the monomer copolymerizable with the copolymer represented by Chemical Formula 1 in the dispersion resin include styrene, vinyltoluene, α -methylstyrene, p-chlorostyrene, and o-methoxystyrene. , M-methoxystyrene, p-methoxystyrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether , Aromatic vinyl compounds such as m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, Isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, secondary butyl (meth) acrylate, tertiary butyl (meth) acrylate, etc. (methyl ) Alkyl acrylates; cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.02,6] dec-8 -Cycloaliphatic (meth) acrylates such as (meth) acrylate, 2-dicyclopentyloxyethyl (meth) acrylate, isoamyl (meth) acrylate, etc .; (Aryl) (meth) acrylic aryl esters such as phenyl acrylate and benzyl (meth) acrylate; (meth) acrylic acid such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate Hydroxyalkyl acrylates; N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-o-hydroxyphenylmaleimide, N -M-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, N-m-methylphenylmaleimide, N -P-methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide, N-p-methoxyphenylmaleimide N-substituted maleimide imide compounds such as fluorenimine; unsaturated fluorenamine compounds such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide; 3- (methacryl) Oxomethyl) oxetane, 3- (methacrylic oxomethyl) -3-ethyloxetane, 3- (methacrylic oxomethyl) -2-trifluoromethyl Oxetane, 3- (methacrylic acid oxomethyl) -2-phenyloxetane, 2- (methacrylic acid oxomethyl) oxetane, 2- (formyl Propylene oxide Yl) -4-trifluoromethyl oxetane unsaturated oxetane compound.

The compounds exemplified above may be used individually or in combination of two or more kinds.

The dispersion resin of the present invention can be further mixed with a variety of other alkali-soluble resins generally known in the art and used as necessary.

The content of the dispersed resin is 1 to 20% by weight, and preferably 7 to 12% by weight, with respect to the total weight of the solid content in the colored dispersion liquid. When the content of the dispersing resin is within the above range, pigment particles are uniformly dispersed, and aggregation between the pigment particles can be prevented to improve solvent resistance and storage stability.

Dispersant

The dispersant is added to decoagulate the pigment and maintain stability. Specific examples of the dispersant include cationic, anionic, nonionic, polyester, and polyamine surfactants. They are used individually or in combination of 2 or more types.

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 sulfate salts such as sodium lauryl sulfate and sodium oleyl sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, and twelve Alkyl aryl sulfonates such as sodium alkylbenzenesulfonate and sodium dodecylnaphthalenesulfonate.

Specific examples of the non-ionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkylaryl ether, other polyoxyethylene derivatives, and oxyethylene / oxypropylene copolymers. Block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerol fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines Wait.

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

The dispersant preferably contains an acrylate-based dispersant (hereinafter referred to as an acrylate-based dispersant) containing butyl methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA). . As the acrylate-based dispersant, a dispersant produced by an activity control method is preferably used. Examples of commercially available products include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, and DISPER BYK-2150. Each of the dispersants may be used alone or as a mixture of two or more.

As the dispersant, a resin-based pigment dispersant other than the acrylate-based dispersant can be used. Examples of other resin-based dispersants include known resin-based dispersants, and in particular, polyurethanes, polycarboxylates represented by polyacrylates, unsaturated polyamines, polycarboxylic acids, polycarboxylic acid (Partial) amine salts of carboxylic acids, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminophosphonium phosphates, esters of hydroxy-containing polycarboxylic acids, and modifications thereof Oily dispersants, such as amidine or its salts, formed by the reaction of high-quality products or polyesters with free carboxyl groups with poly (lower alkyleneimine); (meth) acrylic acid-styrene copolymerization Compounds, (meth) acrylic acid- (meth) acrylate copolymers, styrene-maleic acid copolymers, water-soluble resins or water-soluble polymer compounds such as polyvinyl alcohol or polyvinylpyrrolidone; polyesters; modified Quality polyacrylates; ethylene oxide / propylene oxide addition products; and phosphate esters.

As commercially available products of other resin-based dispersants, for the cationic resin dispersant, for example, the following product names of BYK Chemical Company: 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, DISPER BYK-2000; BASF (BASF) company's following product name products: 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; Lubrizol's products with the following brand names: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204 / 10; Chuanyan Chemical Co., Ltd.'s following product names : HINOACT T-6000, HINOACT T-7000, HINOACT T-8000; Ajinomoto's products with the following brand names: AJISPUR PB-821, AJISPUR PB-822, AJISPUR PB-823; the following product names of Kyoeisha Chemical Co., Ltd. Products: FLORENE DOPA-17HF, FLORENE DOPA-15BHF, FLORENE DOPA-33, FLORENE DOPA-44, etc.

The resin-based dispersant other than the above-mentioned acrylate-based dispersant may be used alone or as a mixture of two or more kinds, or may be used in combination with the acrylate-based dispersant.

The content of the dispersant is more than 0 parts by weight and 1 part by weight or less, and preferably 0.05 to 0.5 parts by weight with respect to 1 part by weight of the colorant. If the content of the dispersant is more than 0 parts by weight and 1 part by weight or less, it is preferable to obtain a uniformly dispersed pigment.

Alkali-soluble resin

The alkali-soluble resin contained in the colored photosensitive resin composition of the present invention is a component that imparts solubility to an alkaline developing solution used in a developing process. In the present invention, the alkali-soluble resin is not particularly limited, but a copolymer of a monomer having a carboxyl group and another monomer capable of being copolymerized therewith is preferred.

Examples of the monomer having a carboxyl group include unsaturated carboxylic acids having one or more carboxyl groups in the molecule, such as unsaturated monocarboxylic acids and unsaturated dicarboxylic acids. Specific examples thereof include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid. The monomer having a carboxyl group is a compound having a carbon-carbon unsaturated bond, and each of them may be used alone or in combination of two or more.

Specific examples of the other monomers include aromatic vinyl compounds, unsaturated carboxylic acid ester compounds, unsaturated amino alkyl carboxylic acid ester compounds, unsaturated glycidyl carboxylic acid ester compounds, and vinyl carboxylic acid esters. Compounds, vinyl cyanide compounds, unsaturated oxetane carboxylate compounds, and the like.

Specific examples of the vinyl compound include styrene, α-methylstyrene, vinyl toluene, and the like. Specific examples of the unsaturated carboxylic acid ester compound include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, and 2-hydroxyethyl acrylate. , 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, and 2-phenylthioethyl acrylate. Specific examples of the unsaturated aminoalkyl carboxylic acid ester compound include aminoethyl acrylate and the like. Specific examples of the unsaturated glycidyl carboxylate compound include glycidyl methacrylate and the like. Specific examples of the vinyl carboxylate compound include vinyl acetate and vinyl propionate. Specific examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and azobisdimethylvaleronitrile. Specific examples of the unsaturated oxetane carboxylic acid ester compound include 3-methyl-3-methacryloxymethyloxetane, and 3-ethyl-3-propenyloxy Methyloxetane, 3-ethyl-3-methacryloxymethyloxetane, 3-methyl-3-propenyloxyethyloxetane, 3 -Methyl-3-methacryloxyethyloxetane, 3-methyl-3-propenyloxyethyloxetane, and 3-methyl-3-methacryl Oxyethyloxetane and the like. These other monomers may be used alone or in combination of two or more.

In addition, the alkali-soluble resin may be characterized by including the copolymer of the above-mentioned chemical formula 1, and the alkali-soluble resin may improve the solvent resistance and storage stability by transmitting the copolymer of the above-mentioned chemical formula 1 containing an epoxy group.

In the present invention, as the alkali-soluble resin, as the copolymer of Chemical Formula 1, two or more copolymers having different epoxy equivalents can be mixed and used. It is preferable that the copolymer (b1) and the copolymer (b2) )Mixed use.

The epoxy equivalent of the copolymer (b1) may be 500 to 800, and preferably 600 to 700. The epoxy equivalent of the copolymer (b2) may be 1,000 to 1,300, and preferably 1,100 to 1,200.

In addition, the copolymers (b1) and (b2) may be included in a weight ratio of 1: 0.1 to 5 and preferably the copolymers (b1) and (b2) are included in a weight ratio of 1: 0.25 to 3. In the case where the copolymers (b1) and (b2) satisfy the above-mentioned range of epoxy equivalents and weight ratios, they can exhibit excellent elastic recovery rates, and are therefore preferred.

The weight-average molecular weight of the alkali-soluble resin is not particularly limited, but may be 3,000 to 100,000, preferably 3,000 to 50,000, and more preferably 5,000 to 50,000.

The content of the alkali-soluble resin is 5 to 60% by weight, and preferably 20 to 50% by weight based on the total weight of the solid content in the colored photosensitive resin composition. If the content of the alkali-soluble resin is within the above-mentioned range, it is easy to form a pattern, and the resolution and the residual film rate are improved, which is preferable.

In addition, the alkali-soluble resin of the present invention is mixed in an amount of 30 to 95 parts by weight, preferably 40 to 85 parts by weight, based on a total of 100 parts by weight of the alkali-soluble resin and the photopolymerizable compound. When the alkali-soluble resin is mixed in the above range, it is possible to provide a colored photosensitive resin composition that has sufficient solubility and is easy to form a pattern, and that the film portion of the pixel portion of the exposed portion is reduced during development and the peeling property of the pixel portion is excellent.

Photopolymerizable compound

The photopolymerizable compound should contain an unsaturated bond and react with a photopolymerization initiator to form a colored photosensitive resin layer, that is, a compound capable of polymerizing through the action of a photopolymerization initiator described below.

In the present invention, the functional group of the photopolymerizable compound may be a (meth) acrylate generally used.

The photopolymerizable compound contains 3 to 10 functional groups, and preferably contains 4 to 8 functional groups.

Specific examples of the trifunctional monomer in the polyfunctional monomer include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, and propoxylate. Trimethylolpropane tri (meth) acrylate, neopentaerythritol tri (meth) acrylate, and the like.

Specific examples of the tetrafunctional monomer in the polyfunctional monomer include neopentaerythritol tetraacrylate, neopentaerythritol tetramethacrylate, ditrimethylolpropane tetraacrylate, and ditrimethylol. Propane tetramethacrylate, dinepentaerythritol tetraacrylate, tetramethylolmethane tetraacrylate, ethoxylated neopentaerythritol tetraacrylate, glycerol tetraacrylate, glycerol tetramethacrylate, etc. .

Specific examples of the pentafunctional monomer in the polyfunctional monomer include dipentaerythritol pentaacrylate, dinepentaerythritol pentamethacrylate, dinepentaerythritol monohydroxy pentaacrylate, Pentaerythritol monohydroxy pentamethacrylate and the like.

Specific examples of the hexafunctional monomer in the polyfunctional monomer include dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the like.

Specific examples of the seven to ten functional monomers in the polyfunctional monomer include trinepentaerythritol octamethacrylate, trinepentaerythritol octaacrylate, and tetranepentaerythritol methacrylate , And tetranepentaerythritol heptaacrylate.

The content of the photopolymerizable compound is 5 to 50% by weight, and preferably 7 to 45% by weight, based on the total weight of the solid content in the colored photosensitive resin composition of the present invention. When the photopolymerizable compound is in a range of 5 to 50% by weight, the strength or flatness of the pixel portion can be improved.

Photopolymerization initiator

The photopolymerization initiator can be used without limitation as long as it can polymerize the photopolymerizable compound. Preferably, the photopolymerization initiator may be selected from the group consisting of phenylethyl ether in consideration of polymerization characteristics, starting efficiency, absorption wavelength, availability, and price. One or more compounds selected from the group consisting of a ketone compound, a benzoin compound, a benzophenone compound, a triazine compound, a biimidazole compound, an oxime compound, and a thioxanthone compound.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and benzophenone dimethyl ketal. Ketone, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- ( 4-methylthiophenyl) -2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) but-1- Ketones, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one, and 2- (4-methylbenzyl) -2- (dimethyl Amino) -1- (4-morpholinylphenyl) butan-1-one and the like.

Specific examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Wait.

Specific examples of the benzophenone-based compound include benzophenone, methyl orthobenzoylbenzoate, 4-phenylbenzophenone, and 4-benzophenyl-4 ' -Methyldiphenyl sulfide, 3,3 ', 4,4'-tetrakis (tertiary butylperoxycarbonyl) benzophenone, and 2,4,6-trimethylbenzophenone, etc. .

Specific examples of the triazine-based compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxy Phenylstyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1, 3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (Trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, and 2,4-bis (tri Chloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.

Specific examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5 ' -Tetrakis (alkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (trialkoxyphenyl) biimidazole, 2, 2-bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, or phenyl at 4,4', 5,5 'position A biimidazole compound substituted with an alkoxycarbonyl group and the like.

More preferred examples include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) ) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2-bis (2,6-dichlorophenyl) -4,4', 5,5'-tetraphenyl-1, 2'-biimidazole and the like.

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

Specific examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro- 4-propoxythioxanthone and the like.

The photopolymerization initiators may be used alone or as a mixture of two or more of them.

In the present invention, the content of the photopolymerization initiator is 0.1 to 20% by weight, and preferably 1 to 10% by weight, based on the total weight of the solid content in the colored photosensitive resin composition.

In the range of 0.1 to 20% by weight, since the colored photosensitive resin composition is highly photosensitized, the strength of the pixel portion formed using the colored photosensitive resin composition and the smoothness of the surface of the pixel portion can be improved.

Further, in the present invention, a photopolymerization initiator may be additionally used in the photopolymerization initiator.

The photopolymerization initiation aid is a compound used to promote the polymerization of a photopolymerizable compound that is polymerized by the photopolymerization initiator. Examples of the photopolymerization initiation aid include amine compounds and alkoxy groups. Anthracene-based compounds and the like.

Specific examples of the amine-based compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, and ethyl 4-dimethylaminobenzoate. Ester, 4-dimethylaminobenzoic acid isoamyl ester, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethyl P-toluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michelin), 4,4'-bis (diethylamino) benzophenone, and 4 , 4'-bis (ethylmethylamino) benzophenone, etc. Among them, 4,4'-bis (diethylamino) benzophenone is preferred.

Specific examples of the alkoxyanthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, and 9,10-diethoxy Anthracene and 2-ethyl-9,10-diethoxyanthracene.

As the photopolymerization initiation aid, a commercially available photopolymerization initiation aid may be used. As the commercially available photopolymerization initiation aid, a product "EAB-F" (manufacturer: Hodogaya Chemicals) Industrial Corporation) and so on.

In the case of using the above-mentioned photopolymerization initiation aid, the photopolymerization initiation aid is usually used in an amount of more than 0 mol to 10 mol, preferably 0.01 to 5 mol relative to 1 mol of the photopolymerization starter. Agent. When the photopolymerization initiation aid is used in a range of more than 0 mol to 10 mol, the sensitivity of the colored photosensitive resin composition can be further improved, and the color filter formed by using the colored photosensitive resin composition can be improved. Light sheet productivity.

Solvent

As long as the solvent is effective in dissolving other components contained in the colored photosensitive resin composition and does not react, the solvent used in the general colored photosensitive resin composition is not particularly limited, and particularly preferred are ethers and acetic acid. Esters, aromatic hydrocarbons, ketones, alcohols, or esters.

Examples of the ethers include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether. ; Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dialkyl ethers such as diethylene glycol dibutyl ether.

Examples of the acetates include methyl cyperidine acetate, ethyl cyperidine acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, and butyl lactate. Ester, 3-methoxybutyl acetate, 3-methyl-3-methoxy-1-butyl acetate, methoxypentyl acetate, ethylene glycol monoacetate, ethyl Glycol diacetate, methyl 3-methoxypropionate, propylene glycol methyl ether acetate, 3-methoxy-1-butyl acetate, 1,2-propanediol diacetate, ethyl Glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butanediol diacetate, diethylene glycol monobutyl Ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoacetate, diethylene glycol diacetate, diethylene glycol mono Butyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate, propylene carbonate, and the like.

Examples of the aromatic hydrocarbons include benzene, toluene, xylene, and mesitylene.

Examples of the ketones include methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone.

Examples of the alcohols include ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol, and 4-hydroxy-4-methyl-2-pentanone.

Examples of the esters include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and γ-butyrolactone.

These solvents can be used individually or in mixture of 2 or more types.

In terms of coating properties and drying properties, it is preferable to use an organic solvent having a boiling point of 100 ° C to 200 ° C. Examples include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and cyclohexyl Ketones, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate.

The content of the solvent is 60 to 90% by weight, and preferably 65 to 85% by weight, based on the total weight of the colored photosensitive resin composition. If the content of the solvent is in the range of 60 to 90% by weight, when using a roll coater, a spin coater, a slit-type spin coater, a slit coater (also sometimes referred to as a die coater), a sprayer, etc. When the coating device performs coating, the coatability can be improved.

additive

In the colored photosensitive resin composition of the present invention, in addition to the above components, other additives may be included in accordance with the needs of a person of ordinary skill, as long as the purpose of the present invention is not impaired.

Specifically, it may additionally be selected from the group consisting of, for example, fillers, other polymer compounds, thermal initiators, curing agents, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, and anticoagulants. More than one additive.

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

The thermal initiator has a function of initiating a curing reaction caused by heat to maximize the starting efficiency. The thermal initiator may be a peroxide-based compound.

The specific type of the thermal initiator is not particularly limited, and may be selected from the group consisting of tetramethyl neodecanoate peroxide (for example, Perocta ND, manufactured by NOF Corporation), and bis (4-butylcyclohexyl peroxide neodecanoate). ) Esters (such as Peroyl TCP, manufactured by NOF Corporation), bis (2-ethylhexyl) peroxide, butyl peroxyneodecanoate (such as Perbutyl ND, manufactured by NOF Corporation), dicarbonate peroxide Dipropyl ester (such as Peroyl NPP, manufactured by NOF Corporation), diisopropyl peroxide dicarbonate (such as Peroyl IPP, NOF Corporation (manufactured)), diethoxyethyl peroxide dicarbonate (such as Peroyl EEP, NOF company (manufactured)), diethoxyhexyl peroxydicarbonate (for example, Peroyl OEP, NOF company (manufactured)), hexyl peroxydicarbonate (for example, Perhexyl ND, NOF company (manufactured)), diperoxy peroxide Dimethoxybutyl carbonate (for example, Peroyl MBP, manufactured by NOF Corporation), and bis (3-methoxy-3-methoxybutyl) peroxydicarbonate (for example, Peroyl SOP, manufactured by NOF Corporation) ), Dibutyl peroxydicarbonate, dicetyl peroxydicarbonate, dimyristyl peroxydicarbonate, divaleric acid 1,1,3,3-tetramethylene Methyl butyl ester, Hexyl pivalate (e.g. Perhexyl PV, manufactured by NOF Corporation), butyl peroxy pivalate (e.g. Perbutyl, manufactured by NOF Corporation), trimethylhexyl peroxide (e.g. Peroyl 355, NOF company (manufactured)), dimethyl hydroxybutyl peroxy neodecanoate (for example, Luperox 610M75, Atofina (manufactured)), amyl peroxy neodecanoate (for example, Luperox 546M75, Atofina (manufactured)), peroxin Butyl caprate (e.g. Luperox 10M75, Atofina (manufactured)), tertiary butyl perpeptanoate, amyl peroxypivalate (e.g. Luperox 546M75, Alofina (manufactured)), tertiary Butyl ester, tert-amyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, lauryl peroxide, dilauroyl peroxide, didecyl peroxide Hydrazone, benzamidine peroxide, dibenzosulfonium peroxide, 2,2-bis (tertiary butyl peroxide) butane, 1,1-bis (tertiary butyl peroxide) cyclohexane, 2, 5-bis (butyl peroxy) -2,5-dimethylhexane, 2,5-bis (tertiary butyl peroxide) -1-methylethyl) benzene, 1,1-bis (tri Butyl peroxide) -3,3,5-trimethylcyclohexane, hydrogen peroxide tributyl, tertiary Base peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, cumene hydroperoxide, dicumyl peroxide, lauryl peroxide, 2,4-pentanedioxide One or more members of the group consisting of ketone peroxide, tert-butyl peracetate, peracetic acid, and potassium persulfate.

The content of the thermal initiator is preferably 1 to 10% by weight, and more preferably 1 to 5% by weight based on the total weight of the solid content in the colored photosensitive resin composition. In the case of the content mentioned above, the processability and the undercut are better.

The curing agent is used for deep curing and improving mechanical strength. Specific examples include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, and oxetane compounds.

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, and phenolic resin. Varnish-type epoxy resins, other aromatic epoxy resins, alicyclic epoxy resins, glycidyl ester resins, glycidylamine resins, or brominated derivatives of these epoxy resins, epoxy resins, and Aliphatic, alicyclic or aromatic epoxy compounds other than its brominated derivatives, epoxy of butadiene (co) polymer, epoxy of isoprene (co) polymer, (methyl) Glycidyl acrylate (co) polymer, triglycidyl isocyanurate, and the like.

Specific examples of the oxetane compound in the curing agent include carbonate dioxetane, xylene dioxetane, adipate dioxetane, and terephthalic acid. Formate dioxetane, cyclohexanedicarboxylic acid dioxetane, and the like.

The above curing agent can be used in combination with a curing assistant compound, which together with the curing agent can ring-open polymerize the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound. Examples of the auxiliary curing compound include polycarboxylic acids, polycarboxylic anhydrides, and acid generators. As the polycarboxylic acid anhydride, a commercially available epoxy resin curing agent can be used. Specific examples of the epoxy resin curing agent include ADEKA HARDENER EH-700 (trade name, manufactured by ADEKA Industrial Co., Ltd.), RIKACID HH (trade name, manufactured by Nippon Rika Chemical Co., Ltd.), and MH-700 (trade name, (Manufactured by Nippon Physico Chemical Co., Ltd.). The curing agent exemplified above may be used alone or as a mixture of two or more kinds.

The surfactant can be used in order to further improve the film-forming property of the photosensitive resin composition. For example, a surface active agent such as a silicone-based, fluorine-based, ester-based, cationic, anionic, non-ionic, or amphoteric-based can be used. As the agent, a silicone-based surfactant or a fluorine-based surfactant can be preferably used.

Examples of the silicone-based surfactants include commercially available DC3PA, DC7PA, SH11PA, SH21PA, and SH8400 from Dow Corning Toray Silicone, and TSF-4440, TSF-4300, and TSF-4445 from GE Toshiba Silicone. , TSF-4446, TSF-4460 and TSF-4452. Examples of the fluorine-based surfactant include Megafac F-554, F-470, F-471, F-475, F-482, and F-489 (Dai Nihon Ink Chemical Industry Co., Ltd.) and BM-1000 as commercially available products. , BM-1100 (BMChemie), Fluorad FC-135 / FC-170C / FC-430 (Sumitomo 3M Co., Ltd.), etc.

Other examples of surfactants are polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, and fatty acid modified polyesters. In addition to polyurethanes, tertiary amines modified polyurethanes, polyethyleneimines, etc., KP (Shin-Etsu Chemical Industry Co., Ltd.), Polyflow (Kyoeisha Chemical Co., Ltd.) as commercially available products, EFTOP (Tohkem Products), Megafac (Danish Ink Chemical Industry Co., Ltd.), Fluoride (Sumitomo 3M Co., Ltd.), Asahi guard, Surflon (above, Asahi Glass Co., Ltd.), Solsperse (Zeneca Co., Ltd.), EFKA (EFKACHEMICALS) ), PB821 (Ajinomoto Corporation), etc.

The surfactants exemplified above can be used individually or in combination of two or more kinds.

The adhesion promoter is an additive used to enhance the coatability and adhesion to the substrate, and may include a silane coupling containing a reactive substituent selected from a carboxyl group, a methacryl group, an isocyanate group, an epoxy group, and a combination thereof. Agent. Specific examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (2-methoxyethoxy) silane, and N- (2-aminoethyl) ) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane , 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy Silane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-trimethoxysilylpropylsulfide Alcohols, trimethoxysilylbenzoic acid, vinyltriethoxysilane, γ-isocyanatepropyltriethoxysilane, and the like.

Specific examples of the antioxidant include 2,2'-thiobis (4-methyl-6-tert-butylphenol), 2,6-ditert-butyl-4-methylphenol, and the like .

Specific examples of the ultraviolet absorber include 2- (3-tertiarybutyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, and alkoxybenzophenone. .

Specific examples of the anticoagulant include sodium polyacrylate and the like.

The content of the additive may be 0.01 to 10% by weight, and preferably 0.05 to 2% by weight, with respect to the total weight of the solid content in the colored photosensitive resin composition.

The colored photosensitive resin composition produced in this manner is preferably used for a display device, and is preferably used for producing a black matrix of a liquid crystal display device, a columnar spacer for maintaining a cell gap, or a black columnar spacer.

The columnar spacer, the black matrix, and / or the black columnar spacer of the present invention have advantages such as high optical density, excellent reliability, and excellent shielding properties.

In particular, the colored photosensitive resin composition of the present invention is preferably used for the production of a black columnar spacer (a black matrix and a spacer formed in one piece). Instead of forming a black matrix and a columnar spacer separately, the objects are formed as a pattern.

The present invention also relates to a color filter using a black matrix, a columnar spacer, or a black columnar spacer produced using the colored photosensitive resin composition.

The color filter of the present invention has the advantages of high optical density, excellent reliability, and excellent shielding properties. The color filter includes a substrate and a pattern layer formed on the substrate.

As far as the substrate is concerned, the color filter itself may be a substrate, or may be a portion where the color filter is located in a display device or the like, which is not particularly limited. The substrate may be glass, silicon (Si), silicon oxide (SiO _x ), or a polymer substrate. The polymer substrate may be polyethersulfone (PES) or polycarbonate (PC).

The pattern layer is a layer containing a cured product of the colored photosensitive resin composition of the present invention, and may include a columnar spacer, a black matrix, and / or a black columnar spacer.

The pattern layer may be a layer formed by applying the colored curable resin composition and exposing, developing, and thermal curing in a predetermined pattern, and the pattern layer may be formed by a method generally known in the art.

The color filter including the substrate and the pattern layer as described above may further include a partition wall formed between the patterns, and may further include a black matrix, but is not limited thereto.

The present invention also relates to a display device including the above color filter. For example, the liquid crystal display device of the present invention may include a color filter including a cured product pattern layer containing the colored photosensitive resin composition.

The color filter of the present invention can be applied not only to general liquid crystal display devices, but also to various image display devices such as electroluminescence display devices, plasma display devices, and field emission display devices.

When the liquid crystal display device includes a color filter provided with the pattern layer of the present invention, there is an advantage that shielding properties and reliability are improved.

A general patterning process using a photolithography method to form a black matrix, a columnar spacer, or a black columnar spacer includes: a) a step of coating a colored photosensitive resin composition on a substrate; and b) drying before solvent drying Step; c) placing a photomask on the obtained film to irradiate active light to cure the exposed portion; d) performing a development process of dissolving the non-exposed portion using an alkaline aqueous solution; and e) performing drying and post-baking A step of.

The substrate is a glass substrate or a polymer plate. As the glass substrate, soda-lime glass, glass containing barium or strontium, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, quartz, or the like is particularly preferably used. Examples of the polymer plate include polycarbonate, polyacrylate, polyethylene terephthalate, polyether fluorene, and polyfluorene.

In this case, the coating can be performed by a wet coating method using a coating device such as a roll coater, a spin coater, a slit spin coater, a slit coater (also sometimes referred to as a die coater), or a sprayer. So that the desired thickness can be obtained.

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

In addition, the exposure performed after the pre-baking is performed using an exposure machine, and exposure is performed through a photomask, so that only a corresponding portion of the pattern is photosensitive. At this time, the irradiated light may be, for example, visible light, ultraviolet light, X-rays, and electron rays.

The alkali development after the exposure is performed in order to remove the colored photosensitive resin composition of the non-exposed portion of the non-exposed portion, and a desired pattern is formed by the development. As a developing solution suitable for alkali development, for example, an aqueous carbonate solution of an alkali metal or an alkaline earth metal can be used. In particular, it is carried out using a carbonate alkali aqueous solution containing 1 to 3% by weight of sodium carbonate, potassium carbonate, lithium carbonate and the like at a temperature of 10 to 50 ° C, preferably 20 to 40 ° C, using a developing machine or an ultrasonic cleaner.

Post-baking is performed in order to improve the adhesion between the patterned film and the substrate, and is achieved by heat treatment under conditions of 80 to 220 ° C for 10 to 120 minutes. Post-baking is performed using an oven, a hot plate, and the like, as in front-baking.

At this time, the film thickness of the black matrix is preferably 0.2 μm to 20 μm, more preferably 0.5 μm to 10 μm, and particularly preferably 0.8 μm to 5 μm.

In addition, the film thickness of the columnar spacer and the black columnar spacer is preferably 0.1 micrometer to 8 micrometers, more preferably 0.1 micrometer to 6 micrometers, and particularly preferably 0.1 micrometer to 4 micrometers.

The black matrix, the columnar spacer, or the black columnar spacer manufactured from the colored photosensitive resin composition of the present invention is not only excellent in physical properties such as optical density, adhesion, electrical insulation, light-shielding properties, but also excellent in heat resistance and solvent resistance Therefore, the reliability of the liquid crystal display device can be improved.

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are only used to explain the present invention more specifically, and the scope of the present invention is not limited by the following examples. Those skilled in the art can appropriately modify and change the following embodiments within the scope of the present invention.

Production Example 1. Production of Dispersion Resin A1

A 1-liter separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube was charged with 277 g of methoxybutyl acetate and heated to 80 ° C. Next, 3,4-epoxytricyclo [5.2.1.0,2,6] dec-9-yl acrylate and 3,4-epoxytricyclo [5.2.1.0,2,6] dec-8 -A mixture of 301 g of acrylates at a molar ratio of 50:50, 49 g of methacrylic acid, and 23 g of azobisdimethylvaleronitrile dissolved in 350 g of methoxybutyl acetate Prepare a mixed solution. The above-mentioned mixed solution was dropped into a flask over a period of 5 hours using a dropping funnel, and then reacted for 3 hours to produce a dispersion resin A1 [solid content (NV) 35.0% by weight]. The acid value (dry) of the dispersion resin A1 obtained above was 69.8 mg KOH / g, the weight average molecular weight (Mw) was 12,300, and the degree of dispersion (Mw / Mn) was 2.1.

Production Example 2. Production of Dispersion Resin A2

Prepare a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube. As a monomer dropping funnel, 14.4 parts by weight of acrylic acid (0.2 mol), 140.8 parts by weight of benzyl methacrylate (0.8 mol), 2.0 parts by weight of tert-butyl peroxide-2-ethylhexanoate, and propylene glycol Monomethyl ether acetate (PGMEA) was prepared by mixing 40.0 parts by weight. As a chain transfer agent, a dropwise addition tank was prepared by mixing 3.0 parts by weight of n-dodecanethiol and 24.0 parts by weight of PGMEA. Thereafter, 395 parts by weight of PGMEA was added to the flask, and the atmosphere in the flask was replaced with air from nitrogen, and then the temperature of the flask was raised to 90 ° C. while stirring. Next, the monomer and the chain transfer agent were dropped from the dropping funnel. The dropwise addition was performed for 4 hours while maintaining 70 ° C, and after 1 hour, the temperature was raised to 90 ° C, and the reaction was performed for 8 hours to produce a dispersion resin A2 [solid content (NV) 35.0% by weight]. The acid value (dry) of the dispersion resin A2 obtained above was 80.0 mgKOH / g, the weight average molecular weight (Mw) was 45,200, and the degree of dispersion (Mw / Mn) was 2.8.

Production example 3. Production of dispersion resin A3

Prepare a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube. As a monomer dropping funnel, 52.1 parts by weight (0.25 mol) of 2-phenylthioethyl acrylate, 44.0 parts by weight (0.25 mol) of benzyl methacrylate, and 12.9 parts by weight (0.15 mol) of methacrylic acid ), 41.3 parts by weight (0.35 moles) of vinyl toluene, 4.0 parts by weight of tert-butyl peroxy-2-ethylhexanoate, and 40.0 parts by weight of PGMEA were prepared by mixing. As a chain transfer agent, a dropwise addition tank was prepared by mixing 6.0 parts by weight of n-dodecanethiol and 24.0 parts by weight of PGMEA. Thereafter, 39 parts by weight of PGMEA was added to the flask, and the atmosphere in the flask was replaced with nitrogen from air, and then the temperature of the flask was raised to 90 ° C. while stirring. Next, the monomer and the chain transfer agent were dropped from the dropping funnel. The dropwise addition was performed for 2 hours while maintaining 90 ° C, and after 1 hour, the temperature was raised to 110 ° C, and the reaction was performed for 8 hours to produce a dispersion resin A3 [solid content (NV) 35.0% by weight]. The acid value (dry) of the dispersion resin A3 obtained above was 70.0 mgKOH / g, the weight average molecular weight (Mw) was 23,000, and the degree of dispersion (Mw / Mn) was 2.4.

Production example 4. Production of alkali-soluble resin A4

A 1-liter separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube was charged with 277 g of methoxybutyl acetate and heated to 80 ° C. Next, 3,4-epoxytricyclo [5.2.1.0,2,6] dec-9-yl acrylate and 3,4-epoxytricyclo [5.2.1.0,2,6] dec-8 -A mixture of 321 g of acrylates at a molar ratio of 50:50, 32 g of methacrylic acid, and 20 g of azobisdimethylvaleronitrile, dissolved in 350 g of methoxybutyl acetate, and Prepare a mixed solution. The above-mentioned mixed solution was dropped into a flask over a period of 5 hours using a dropping funnel, and then reacted for 3 hours to produce a dispersion resin A4 [solid content (NV) 35.0% by weight]. The acid value (dry) of the alkali-soluble resin A4 obtained above was 59.8 mg KOH / g, the weight average molecular weight (Mw) was 9,300, the dispersion (Mw / Mn) was 1.9, and the epoxy equivalent was 665.

Example 1 and Comparative Examples 1 to 2

The dispersion resin is mixed with a colorant, a dispersant, and a solvent to prepare a mixture. Next, zirconia beads (average particle diameter: 0.1 mm) and the mixture were mixed at a weight ratio of 50:50, and dispersion treatment was performed for 6 hours using a bead mill. After the dispersion was completed, a colored dispersion was prepared by filtration, and the contents are shown in Table 1 below.

Colorant

V29: C.I. Pigment Violet 29

OBP: Organic Black Pigment

B60: C.I. Pigment Blue 60

CB: carbon black

Dispersion resin

A1: The dispersion resin produced in Production Example 1

A2: The dispersion resin produced in Production Example 2

A3: The dispersion resin produced in Production Example 3

Dispersant: Disper BYK-2000 (Beike)

Solvent: propylene glycol monomethyl ether acetate (PGMEA)

Examples 2 to 4 and Comparative Examples 3 to 8

The colored dispersion liquid was mixed with an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, an additive, and a solvent to produce a colored photosensitive resin composition. The contents are shown in Table 2 below.

Color dispersion

B1: Colored dispersion liquid produced in Example 1

B2: Colored dispersion liquid produced in Comparative Example 1

B3: Colored dispersion liquid produced in Comparative Example 2

Alkali-soluble resin

A1: Resin produced in Production Example 1

A2: Resin produced in Production Example 2

A3: Resin produced in Production Example 3

A4: Resin produced in Production Example 4

Photopolymerizable compound: diglyceryl hexaacrylate (DPHA) (Nippon Kayaku Co., Ltd.)

Photopolymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) butan-1-one (Irgacure 369: Ciba)

Additive: Disper BYK-163 (Becker)

Solvent: propylene glycol monomethyl ether acetate (PGMEA)

Experimental example 1. Measurement of physical properties of colored dispersion

1-1. Evaluation of pigment dispersibility

The dispersion characteristics of the colored dispersion liquids produced in the above-mentioned Example 1 and Comparative Examples 1 to 2 were measured with a particle size analyzer (ELSZ-2000, Otsuka Corporation). The results (average particle size) are shown below. In Table 3.

1-2. Evaluation of storage stability

Regarding the storage stability of the colored dispersion liquids produced in the above Example 1 and Comparative Examples 1 to 2, the viscosity change rate (viscosity after standing at 40 ° C for 1 week / initial viscosity × 100) was measured. in.

The evaluation criteria are described below.

<Evaluation Criteria>

○: The viscosity change rate is less than 105%

△: The viscosity change rate is more than 105% and less than 110%

×: Viscosity change rate is 110% or more

Example 1 as the colored dispersion liquid of the present invention showed results excellent in both pigment dispersibility and storage stability.

The average particle diameters of the colored dispersions of Comparative Examples 1 and 2 which contained "dispersion resins A2 and A3" instead of "dispersion resin A1" as the dispersion resin were larger, showing the result of insufficient pigment dispersibility, and viscosity The rate of change increased, showing results with poor storage stability.

Experimental example 2. Measurement of physical properties of colored photosensitive resin composition

2-1. Evaluation of Solvent Resistance of Coating

After drying a 5 cm × 5 cm glass substrate (Corning) after washing with a neutral detergent and water, the colored photosensitive resin compositions produced in the above Examples 2 to 4 and Comparative Examples 3 to 8 were separately processed. Spin-coated so that the final film thickness was 3.0 microns. Then, it is placed on a hot plate and dried at a temperature of 80 to 120 ° C for 1 to 2 minutes to remove the solvent. Next, exposure is performed at an exposure amount of 25 to 35 mJ / cm 2 and heat treatment is performed at 200 to 250 ° C. for 10 to 30 minutes to produce a patternless colored substrate coated with a colored photosensitive resin composition on the entire surface.

The substrate was cut into a size of 3 cm × 3 cm, and immersed in an N-methylpyrrolidone (NMP) solvent at 100 ° C. for 60 minutes. Then, after only extracting the NMP solvent, the absorbance at the wavelength of visible light was measured with a UV-vis spectrometer (UV-2600, Shimadzu Corporation), and the solvent resistance was evaluated. The measurement results of the absorbance are shown in Table 4 below.

2-2. Evaluation of storage stability

The viscosity change rate (viscosity after standing at 5 ° C for 3 months / initial viscosity × 100) of the colored photosensitive resin composition produced in the above Examples 2 to 4 and Comparative Examples 3 to 8 was measured, and the storage stability was evaluated.

The evaluation criteria are as follows, and the measurement results are shown in Table 4 below.

<Evaluation Criteria>

◎: Viscosity change rate is less than 105%

○: The viscosity change rate is 105% or more and less than 110%

△: The viscosity change rate is 110% or more and less than 115%

×: Viscosity change rate is 115% or more

2-3. Evaluation of residual film rate

The residual film ratio of the colored photosensitive resin composition produced in the above-mentioned Examples 2 to 4 and Comparative Examples 3 to 8 was measured, and the measurement results are shown in Table 4 below.

After drying a 5 cm × 5 cm glass substrate (Corning) after washing with a neutral detergent and water, the colored photosensitive resin compositions produced in the above Examples 2 to 4 and Comparative Examples 3 to 8 were separately processed. Spin-coated so that the final film thickness was 3.0 microns. Then, it is placed on a hot plate and dried at a temperature of 80 to 120 ° C for 1 to 2 minutes to remove the solvent. Next, the film was exposed at an exposure amount of 25 to 35 mJ / cm 2 to measure the film thickness (film thickness 1). After that, the substrates were individually developed in a developing solution of KOH 0.04% concentration, and heat-treated at 200 to 250 ° C. for 10 to 30 minutes, thereby manufacturing a colored substrate. The film thickness (film thickness 2) of the produced colored substrate was measured, and the residual film ratio (film thickness 2 / film thickness 1 × 100) was confirmed.

2-4. Evaluation of elastic response rate

After drying a 5 cm × 5 cm glass substrate (Corning) after washing with a neutral detergent and water, the colored photosensitive resin compositions produced in the above-mentioned Examples 1 to 3 and Comparative Examples 1 to 9 were separately processed. Spin-coated so that the final film thickness was 3.0 microns. Then, it is placed on a hot plate and dried at a temperature of 80 to 120 ° C for 1 to 2 minutes to remove the solvent. Next, exposure is performed at an exposure amount of 25 to 35 mJ / cm 2 to form a pattern, and a non-exposed portion is removed using an alkaline aqueous solution. Next, heat treatment is performed at 200 to 250 ° C. for 10 to 30 minutes to produce a colored substrate coated with a colored photosensitive resin composition.

The produced substrate was passed through a three-dimensional surface shape measuring device (SIS-2000, SNU) to measure the thickness and height of the pattern in a reference state. After that, it was pressed with a hardness tester (Nano-indenter HM500, Fisher) until the pattern was deformed by 1 micron. The hardness tester uses a flat indenter to press at a rate of 2 millinewtons / second. Hold at the position where the 1 micron deformation occurs for 5 seconds. Then, the thickness and height of the pattern were measured using a three-dimensional surface shape measuring device (SIS-2000, SNU), and the elastic recovery rate was measured by the change in thickness of the pattern before and after. Using Comparative Example 3 as a reference (STD), the relative elastic recovery rate was evaluated, and the results are shown in Table 4.

Examples 2 to 4 as the colored photosensitive resin composition of the present invention showed results that were excellent in solvent resistance, storage stability, and residual film rate. In particular, the colored photosensitive resin compositions of Examples 5 to 7 containing both the alkali-soluble resins A1 and A4 exhibited excellent solvent resistance, storage stability, and residual film ratio, and showed the same properties as those of Example 2. The result of the evaluation of the elastic recovery rate was more excellent than 4 to 4.

The colored photosensitive resin compositions of Comparative Examples 3 to 8 excluding the colored dispersion liquid of the present invention had relatively high absorbance measurements and showed results of insufficient solvent resistance, and the viscosity change rate after 3 months also showed significantly poor results. Results, and the residual film rate also showed lower results.

Claims (20)

A coloring dispersion liquid, comprising a colorant, a dispersing resin, and a solvent, the colorant including an organic black pigment, a blue pigment, and a purple pigment, and the dispersing resin containing a copolymer of the following Chemical Formula 1, In Chemical Formula 1, R ₁ and R ₂ are each independently hydrogen or methyl, and the molar ratio of the a monomer to the b monomer is 1:20 to 20: 1.     The coloring dispersion liquid according to claim 1, wherein the organic black pigment contains one or more members selected from the group consisting of lactam black, nigrosine, and perylene black.         The coloring dispersion liquid according to claim 1, wherein the organic black pigment comprises melamine black.         The colored dispersion liquid according to claim 1, wherein the blue pigment does not include a center metal.         The colored dispersion liquid according to claim 4, wherein the blue pigment contains one or more members selected from the group consisting of C.I. Pigment Blue 16, 60, 63, and 66.         The coloring dispersion liquid according to claim 1, wherein the purple pigment comprises one or more members selected from the group consisting of C.I. Pigment Violet 19, 23, 29, 31, and 37.         The colored dispersion liquid according to claim 1, wherein the colored photosensitive resin composition further contains a black pigment as an additional colorant.         The coloring dispersion liquid according to claim 7, wherein the black pigment contains one or more members selected from the group consisting of titanium black and carbon black.         The coloring dispersion liquid according to claim 7, wherein in the colorant, the organic black pigment, blue pigment, purple pigment, and black pigment are mixed in a weight ratio of 1: 0.08 to 2.5: 0.2 to 3.3: 0.12 to 1.7. .         The colored dispersion liquid according to claim 1, wherein the weight average molecular weight of the dispersion resin is 3,000 to 100,000.         The colored dispersion liquid according to claim 1, wherein the colored dispersion liquid contains 65 to 75% by weight of a colorant and 7 to 12% by weight of a dispersion resin with respect to the total weight of the solid content in the colored dispersion liquid, and is relative to The total weight of the colored dispersion liquid includes 70 to 80% by weight of the solvent.         A colored photosensitive resin composition comprising the colored dispersion liquid according to claim 1, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.     The colored photosensitive resin composition according to claim 12, wherein the alkali-soluble resin contains a copolymer of the following Chemical Formula 1, In Chemical Formula 1, R ₁ and R ₂ are each independently hydrogen or methyl. In Chemical Formula 1, the molar ratio of monomer a to monomer b is 1:20 to 20: 1.     The colored photosensitive resin composition according to claim 12, comprising 13 to 60% by weight of a colorant, 5 to 60% by weight of an alkali-soluble resin, and the total weight of the solid content in the colored photosensitive resin composition. The photopolymerizable compound is 5 to 50% by weight and the photopolymerization initiator is 0.1 to 20% by weight, and contains 60 to 90% by weight of the solvent based on the total weight of the colored photosensitive resin composition.         The colored photosensitive resin composition according to claim 12, wherein the colored photosensitive resin composition further comprises a material selected from the group consisting of fillers, other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, and ultraviolet rays. One or more additives in the group consisting of an absorbent and an anticoagulant.         The coloring photosensitive resin composition according to claim 13, wherein the alkali-soluble resin contains two or more copolymers having different epoxy equivalents.         A pattern layer produced from the colored photosensitive resin composition according to claim 12.         The pattern layer according to claim 17, wherein the pattern layer is one or more selected from the group consisting of a columnar spacer, a black matrix, and a black columnar spacer.         A color filter comprising the pattern layer according to claim 17.         A display device includes the color filter according to claim 19.