TWI682971B - Colored photosensitive resin composition, a pattern layer manufactured using the same, a color filter including the pattern layer, and a display device including the color filter - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition comprising a colorant containing a black pigment, a blue pigment and an orange pigment, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, a pattern layer produced using the colored photosensitive resin composition, a color filter including the pattern layer, and a display device including the color filter.

Description

Colored photosensitive resin composition, pattern layer manufactured using the same, Color filter including the pattern layer and display device including the color filter

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

Color filters are widely used in various display devices such as imaging elements and liquid crystal display (LCD) devices, and their application range is rapidly expanding. The color filters used in the above imaging elements, liquid crystal display devices, etc. are formed by coloring patterns of three colors of red (Red), green (Green), and blue (Blue), or by yellow (Yellow), magenta ( Magenta and Cyan coloring patterns are formed.

Each coloring pattern of the above color filter generally uses a colorant containing a pigment or dye, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent It is formed by coloring the photosensitive resin composition. The coloring pattern using the above-mentioned colored photosensitive resin composition is usually processed through a lithography process.

The colored photosensitive resin is an essential material for color filters, liquid crystal display materials, organic light-emitting elements, and displays. For example, in the case of a color filter used in a liquid crystal display, it includes pixels (Pixel) formed of each color of red (Red), green (Green), and blue (Blue). In order to prevent these pixels Color mixing, or hidden electrode patterns, will form a black matrix at the boundary between the colored layers of each color. In addition, the black columnar spacer (Black Colum Spacer, BCS) is a portion that directly contacts the liquid crystal, and requires excellent solvent resistance and no residue residue on the organic film.

In recent years, the proportion of LCDs in the field of flat panel displays is increasing, and as the screens are enlarged, bright backlights are used. As the backlight becomes brighter, the black matrix is also required to have higher light-shielding characteristics than before. However, in the case where the content of carbon black is increased in order to improve the light-shielding characteristics, the process characteristics continue to deteriorate and the defect rate becomes high, thereby causing a problem of a decrease in production yield.

Korean Published Patent No. 10-2014-0121824 relates to a coloring photosensitive composition, a black columnar spacer containing the colored photosensitive composition, and a color filter, and discloses that while maintaining light shielding properties and voltage retention of liquid crystals A coloring photosensitive composition and a black columnar spacer exhibiting high adhesion to the substrate. However, the improvement in solvent resistance and optical density is insufficient.

Existing technical literature Patent Literature

Patent Literature 1: Korean Published Patent No. 10-2014-0121824

The present invention has been made to solve the above-mentioned problems of the prior art, and its object is to provide a coloring photosensitive resin composition excellent in solvent resistance and optical density.

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

Provided is a coloring photosensitive resin composition, characterized in that it includes a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, and the colorant includes a black pigment, a blue pigment, and an orange pigment, and the blue The pigment is CI Pigment Blue 80 represented by Chemical Formula 1 below.

In addition, the invention provides a pattern layer produced from the above-mentioned coloring photosensitive resin composition of the present invention.

In addition, the present invention provides a color filter including the above-described pattern layer of the present invention.

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

The coloring photosensitive resin composition of the present invention can reduce the content of the coloring agent in the coloring photosensitive resin composition required to obtain the same optical density (OD/μm) by introducing CI Pigment Blue 80 with high coloring power (Pigment Weight Concentration; PWC), thereby improving reliability such as solvent resistance.

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

The present invention relates to a coloring photosensitive resin composition. The colored photosensitive resin composition includes a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The colorant includes a black pigment, a blue pigment, and an orange pigment The blue pigment is CI Pigment Blue 80 represented by the following Chemical Formula 1.

In the present invention, by including CI pigment blue 80 with high coloring power as a blue pigment, the content of the coloring agent (PWC) in the coloring photosensitive resin composition for obtaining the same optical density (OD/ μm ) can be reduced. When the content of the coloring agent in the coloring photosensitive resin composition is reduced in this way, the components other than the coloring agent are increased and the phenomenon that the coloring agent is eluted in the solvent can be reduced, thereby improving the solvent resistance of the coloring photosensitive resin composition Thus, reliability can be improved.

Hereinafter, each component of the coloring photosensitive resin composition of the present invention will be described in detail.

Colorant

In the present invention, a substance having a light-shielding property for visible light is used, and the coloring agent of the present invention contains a blue pigment and an orange pigment.

The above-mentioned blue pigment is a compound that does not contain a central metal. If the above-mentioned central metal is present, it will affect the liquid crystal driving. However, in the present invention, by using a compound that does not contain a central metal as a blue pigment, it can be beneficial to ensure equipment Drive. The present invention is characterized in that the blue pigment is CI Pigment Blue 80. When CI Pigment Blue 80 is included, a more excellent optical density (OD/ μm ) can be obtained, and the content of the coloring agent in the coloring photosensitive resin composition required to obtain the same optical density can be reduced ( PWC). When the content of the coloring agent in the colored photosensitive resin composition is reduced in this manner, the phenomenon of elution of the coloring agent in the solvent can be reduced, thereby improving the solvent resistance of the colored photosensitive resin composition and improving the reliability.

The above-mentioned orange pigment serves to reduce the transmittance in the region of 400 to 550 nm and increase the optical density. Although the type of the above-mentioned orange pigment is not particularly limited, it is preferable to use one or more selected from the group consisting of C.I. Pigment Orange 59, 61, 64, 65, 68, and 70, and it is most preferable to use C.I. Pigment Orange 64.

In addition, the color-forming photosensitive resin composition of the present invention may further contain a black pigment as an additional color-forming agent. The black pigment is not particularly limited as long as it has light-shielding properties for visible light, but it is preferably used by including one or more selected from the group consisting of aniline black, perylene black, titanium black, and carbon black, and more preferably carbon black. use. on The 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 of the black pigment include channel black, furnace black, thermal black, lamp black, and the like. The above-mentioned carbon black may be covered with a resin, and the carbon black coated with the resin has lower conductivity than the uncoated carbon black, and thus 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, preferably 25 to 45% by weight relative to the total weight of the solid content in the colored photosensitive resin composition. If the content of the colorant is 13 to 60% by weight, the optical density and reliability are excellent.

More specifically, the black pigment, blue pigment, and orange pigment in the above-mentioned colorant may be mixed in a weight ratio of 1:1 to 2:1 to 1.5. In addition, it may be preferably mixed in a weight ratio of 1:1.5 to 1.7:1.2 to 1.4. If the above black pigment, blue pigment, and orange pigment are included in the above weight ratio, a color-sensitive photosensitive resin composition excellent in optical density and reliability can be obtained.

In addition, the content of the black pigment may be 3 to 10% by weight, preferably 4 to 7% by weight, relative to the total weight of the solid content in the colored photosensitive resin composition. The content of the above-mentioned C.I. Pigment Blue 80 may be 1 to 20% by weight, preferably 6 to 12% by weight relative to the total weight of the solid content in the colored photosensitive resin composition. The content of the orange pigment may be 1 to 15% by weight, preferably 5 to 12% by weight relative to the total weight of the solid content in the colored photosensitive resin composition. If the content of the black pigment, C.I. Pigment Blue 80, and orange pigment is within the above range, a color-sensitive photosensitive resin composition excellent in optical density and reliability can be obtained.

Furthermore, the coloring photosensitive resin composition of the present invention may further contain C.I. Pigment Blue 15:6 of a blue pigment as an additional coloring agent. If the above colorants are added Step C.I. Pigment Blue 15:6 containing blue pigments, the black pigment, blue pigment and orange pigment in the above colorant can be mixed in a weight ratio of 1:2.0~3.0:1.0~2.0. In addition, it may be preferably mixed in a weight ratio of 1:2.2 to 2.8:1.2 to 1.7. If the above black pigment, blue pigment, and orange pigment are included in the above weight ratio, a color-sensitive photosensitive resin composition excellent in optical density and reliability can be obtained.

The content of the above C.I. Pigment Blue 15:6 may be 5 to 15% by weight, preferably 7 to 12% by weight relative to the total weight of the solid content in the colored photosensitive resin composition. If the above-mentioned C.I. Pigment Blue 15:6 is included in the above-mentioned weight ratio, the absorbance at a long wavelength can be improved, and thus a color-sensitive photosensitive resin composition excellent in optical density can be obtained.

In the present invention, the solid content in the colored photosensitive resin composition means the total amount of components after removing the solvent.

In addition, as the colorant, it is preferable to use a pigment dispersion liquid in which the particle diameter of the pigment is uniformly dispersed. As an example of a method for uniformly dispersing the particle diameter of the pigment, a method of adding a dispersant to perform a dispersion treatment, etc., and a pigment dispersion liquid in a state where the pigment is uniformly dispersed in a solution can be obtained by the above method.

Dispersion resin

The above-mentioned dispersion resin functions to prevent the pigment particles present in the colored dispersion liquid from being dissolved in the solvent by coating with the dispersion resin, and to prevent the increase in viscosity caused by the aggregation of the pigment particles by suppressing the aggregation between the pigment particles.

The dispersion resin of the present invention contains the copolymer of Chemical Formula 2 below.

[Chemical Formula 2]

(In the above Chemical Formula 2, 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 epoxy group-containing copolymer of Chemical Formula 2 as a dispersion resin, solvent resistance, storage stability, and film retention 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 mgKOH/g based on the solid content, and when it is within 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 copolymerizable therewith.

Specific examples of the monomer copolymerizable with Chemical Formula 1 of the above-mentioned dispersion resin include styrene, vinyl toluene, α -methylstyrene, p-chlorostyrene, o-methoxystyrene, and m-methoxy Styrene, p-methoxystyrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl Aromatic vinyl compounds such as glycidyl ether, p-vinylbenzyl glycidyl ether; methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, (meth)acrylic acid Alkyl (meth)acrylates such as isopropyl ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate; Cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.02,6]decane-8-yl (methyl) Alicyclic (meth)acrylates such as acrylate, 2-dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate; phenyl (meth)acrylate, (meth) Aryl (meth)acrylates such as benzyl acrylate; hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; N-rings Hexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide , N-p-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, N-m-methylphenylmaleimide, N-p-methylphenylmaleimide N-substituted maleimides such as amines, N-o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide, N-p-methoxyphenylmaleimide, etc. Imine compounds; (meth)acrylamide, N,N-dimethyl (meth)acrylamide and other unsaturated amide compounds; 3-(methacryl oxymethyl) oxetane , 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-( Methacryloyloxymethyl)-2-phenyloxetane, 2-(methacryloyloxymethyl)oxetane, 2-(methacryloyloxymethyl)-4- Unsaturated oxetane compounds such as trifluoromethyloxetane, etc.

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

The dispersion resin of the present invention may be further mixed with a variety of other alkali-soluble resins generally used in the art, as needed.

The content of the above-mentioned dispersion resin is 1 to 20% by weight, preferably 2 to 10% by weight relative to the total weight of the solid content in the colored dispersion liquid. If the content of the above-mentioned dispersing resin is within this range, the pigment particles are uniformly dispersed, the aggregation between the pigment particles can be prevented, and the solvent resistance and storage stability can be improved, which is preferable.

Dispersant

The dispersant is added for the purpose of deagglomerating and maintaining stability of the pigment. Specific examples of the dispersant include cationic, anionic, nonionic, polyester, polyamine, and other surfactants. These You may use each individually or in combination of 2 or more types.

Specific examples of the cationic surfactants include amine salts such as stearylamine hydrochloride and lauryl trimethylammonium chloride, and quaternary ammonium salts.

Specific examples of the above-mentioned anionic surfactants include higher alcohol sulfate salts such as sodium lauryl sulfate sodium and oleyl sulfate sodium, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, and Alkyl aryl sulfonates such as sodium dialkyl benzene sulfonate and sodium dodecyl naphthalene sulfonate.

Specific examples of the nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, and ethylene oxide/ Propylene oxide block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester and polyoxyethylene alkyl Amine and so on.

In addition, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethane And polyethyleneimines.

In addition, 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). The acrylate-based dispersant is preferably a dispersant produced through an activity control method, and as a commercially available product, DISPER can be mentioned. For BYK-2000, DISPER BYK-2001, DISPER BYK-2070, or DISPER BYK-2150, etc., the above acrylate dispersants may be used alone or in combination of two or more.

As the dispersant, resin-type pigment dispersants other than acrylate-based dispersants may be used. Examples of the above-mentioned other resin-type dispersants include known resin-type dispersants, especially polyurethanes, polycarboxylates represented by polyacrylates, unsaturated polyamides, polycarboxylic acids, and polycarboxylic acids. (Part) Ammonium salts, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphates, esters of hydroxyl-containing polycarboxylic acids and their modified products , Or an oily dispersant of amide or its salt formed by the reaction of polyester with free carboxyl group and poly(lower alkyleneimine); (meth)acrylic acid-styrene copolymer, (Meth)acrylic acid-(meth)acrylate copolymer, styrene-maleic acid copolymer, water-soluble resin or water-soluble polymer compound of polyvinyl alcohol or polyvinylpyrrolidone; polyester; modified polyacrylate ; Addition products of ethylene oxide/propylene oxide; and phosphate esters.

As a commercially available product of the above resin-type dispersant, examples of the cationic resin dispersant include the trade names of BYK (Bike) 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; the trade name of BASF (BASF) company: 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 (Lubrizol) company's trade name: SOLSPERS-24000, SOLSPERS-32550, NB Z -4204/10; Trade name of Chuanken Refinery: HINOACT T-6000, HINOACT T-7000, HINOACT T-8000; Trade name of Ajinomoto: AJISPUR PB-821, AJISPUR PB-822, AJISPUR PB- 823; Trade names of Kyoeisha Chemical Company: FLORENE DOPA-17HF, FLORENE DOPA-15BHF, FLORENE DOPA-33, FLORENE DOPA-44, etc.

The resin-type dispersants other than the acrylate-based dispersants may be used alone or in combination of two or more, or may be used in combination with an acrylic dispersant.

The content of the dispersant is more than 0 and less than 1 part by weight relative to 1 part by weight of the colorant, preferably 0.05 to 0.5 parts by weight. If the content of the dispersant exceeds 0 and is 1 part by weight or less, the pigment can be uniformly dispersed, which is preferable.

Alkali soluble resin

The alkali-soluble resin contained in the coloring photosensitive resin composition of the present invention is a component that imparts solubility to the alkali developer used in the development process. In the present invention, although the above-mentioned alkali-soluble resin is not particularly limited, it is preferably a copolymer of a monomer having a carboxyl group and another monomer copolymerizable with the monomer.

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 of these monomers include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, and the like. The monomer having a carboxyl group is a compound having a carbon-carbon unsaturated bond, and each may be used alone or in combination of two or more.

Specific examples of the above other monomers include aromatic vinyl compounds, unsaturated carboxylic acid ester compounds, unsaturated aminoalkyl carboxylic acid ester compounds, unsaturated glycidyl carboxylic acid ester compounds, and vinyl carboxylic acid ester compounds. , Vinyl cyanide compounds and unsaturated oxetane carboxylate compounds, etc.

Specific examples of the aromatic vinyl compound include styrene, α -methylstyrene, and vinyl toluene. 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 Ester, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, 2-phenylthioethyl acrylate, etc. Specific examples of the unsaturated aminoalkyl carboxylate 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 carboxylate compound include 3-methyl-3-propenyloxymethyloxetane and 3-methyl-3-methacryl Oxymethyloxetane, 3-ethyl-3-propenyloxymethyloxetane, 3-ethyl-3-methacryloxymethyloxetane, 3-methyl-3-propenyl oxyethyl oxetane, 3-methyl-3-methyl propenyl oxyethyl oxetane, 3-ethyl-3-propenyl oxetane Ethyl oxetane and 3-ethyl-3-methacryl oxyethyl oxetane etc. The other monomers described above may be used alone or in two or more kinds.

In addition, the alkali-soluble resin may be characterized by a copolymer containing the above Chemical Formula 2, and if the alkali-soluble resin contains the copolymer of the above Chemical Formula 2 containing an epoxy group, solvent resistance and storage stability can be improved.

The weight average molecular weight of the alkali-soluble 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 content of the alkali-soluble resin is 5 to 60% by weight, preferably 20 to 50% by weight, relative to the total weight of the solid content in the colored photosensitive resin composition. If the content of the alkali-soluble resin is within this range, it is easy to form a pattern and the resolution and film retention 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 with respect to a total of 100 parts by weight of the alkali-soluble resin and the photopolymerizable compound. If the above-mentioned alkali-soluble resin is mixed within this range, it is possible to provide a color-sensitive photosensitive resin composition with sufficient solubility and easy pattern formation, preventing the film of the pixel portion of the exposed portion during development from being reduced, and the non-pixel portion having good peelability.

Photopolymerizable compound

The above-mentioned photopolymerizable compound should contain an unsaturated bond and undergo a photoreaction with a photopolymerization initiator to form a colored photosensitive resin layer, that is, a compound that can be polymerized under the action of a photopolymerization initiator described later.

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

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

Specific examples of the trifunctional monomer among the above-mentioned multifunctional monomers include trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, and propylene. Oxylated trimethylolpropane tri(meth)acrylate and pentaerythritol tri(meth)acrylate etc.

Specific examples of the tetrafunctional monomer among the above-mentioned multifunctional monomers include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, ditrimethylolpropane tetraacrylate, and ditrimethylolpropane tetramethyl. Acrylic ester, dipentaerythritol tetraacrylic acid Ester, tetramethylolmethane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, glycerol tetraacrylate, glycerol tetramethacrylate, etc.

Specific examples of pentafunctional monomers among the above-mentioned polyfunctional monomers include dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol monohydroxypentaacrylate, and dipentaerythritol monohydroxypentamethacrylate. Wait.

Specific examples of the hexafunctional monomer among the above-mentioned multifunctional monomers include dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the like.

Specific examples of the seven to ten functional monomers among the above-mentioned multifunctional monomers include tripentaerythritol octamethacrylate, tripentaerythritol octaacrylate, pentaerythritol heptamethacrylate, and pentaerythritol heptaacrylate.

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

Photopolymerization initiator

The photopolymerization initiator can be used without limitation as long as it polymerizes the photopolymerizable compound, but it is preferably selected from the group consisting of acetophenone-based compounds, considering polymerization characteristics, initiation efficiency, absorption wavelength, availability, price, and the like. One or more compounds in the group consisting of benzoin-based compounds, benzophenone-based compounds, triazine-based compounds, biimidazole-based compounds, oxime-based compounds, and thioxanthone-based compounds.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, and benzoyl dimethyl acetal. Ketone, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-( 4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-di Methylamino-1-(4-morpholinophenyl)butane-1-one, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane-1 -Ketone and 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butane-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. .

Specific examples of the benzophenone-based compound include benzophenone, methyl phthaloyl benzoate, 4-phenylbenzophenone, and 4-benzoyl-4'- Methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc.

As the triazine-based compound, specifically, for example, 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 Styryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethylene]-1, 3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethylene]-1,3,5-triazine, 2,4-bis (Trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethylene]-1,3,5-triazine and 2,4-bis(trichloromethyl Group)-6-[2-(3,4-dimethoxyphenyl)ethylene]-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 4,4',5,5' position Oxycarbonyl substituted imidazole compounds, etc.

More preferably, 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 so on.

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

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

The above photopolymerization initiators can be used alone or in combination of two or more.

In the present invention, the content of the photopolymerization initiator is 0.1 to 40% by weight, preferably 1 to 30% by weight relative to the total weight of the solid content in the colored photosensitive resin composition.

Within the range of 0.1 to 40% by weight, the colored photosensitive resin composition is increased in sensitivity, and the strength of the pixel portion formed using the colored photosensitive resin composition and the smoothness of the surface of the pixel portion become good .

In addition, in the present invention, a photopolymerization initiator may be further used as a photopolymerization initiator.

The photopolymerization initiation aid is a compound used to promote the polymerization of a photopolymerizable compound that initiates polymerization by the photopolymerization initiator. Examples of the photopolymerization initiation aid include amine compounds and alkoxyanthracene compounds. Wait.

Specific examples of the amine-based compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-Dimethylaminobenzoic acid isoamyl ester, benzoic acid 2-dimethylamino Ethyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, N,N-dimethyl-p-toluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as rice Chestone), 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (ethylmethylamino) benzophenone, etc., of which 4,4'-bis (Diethylamino) benzophenone.

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, etc.

In addition, as a photopolymerization initiation aid, a commercially available product can be used, and as a commercially available photopolymerization initiation aid, a trade name "EAB-F" (manufacturer: Hodogaya Chemical Industry Co., Ltd.) and the like can be mentioned.

In the case of using the above-mentioned photopolymerization initiation aid, the amount of the photopolymerization initiation aid used is usually more than 0 and 10 moles or less, preferably 0.01 to 5 moles, relative to 1 mole of the photopolymerization initiator. If the photopolymerization initiation aid is used in the above range of more than 0 and 10 moles or less, the sensitivity of the colored photosensitive resin composition is further increased, and the color filter formed using the colored photosensitive resin composition can be improved productivity.

Solvent

As long as the above solvent is effective and does not react when dissolving other components contained in the colored photosensitive resin composition, the solvent used in the ordinary coloring photosensitive resin composition can be used without particular limitation. In particular, ethers, acetates, aromatic hydrocarbons, ketones, alcohols or esters are preferred.

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

Examples of the aforementioned acetates include methyl cellosolve acetate, ethyl cellosolve 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 acetate 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, etc.

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, glycerin, 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 alone or in combination of two or more.

From the viewpoint 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 thereof include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and cyclohexanone. Ethyl 3-ethoxypropionate and methyl 3-methoxypropionate.

The content of the solvent is 60 to 90% by weight, preferably 65 to 85% by weight, relative to the total weight of the colored photosensitive resin composition. If the content of the above-mentioned solvent is in the range of 60 to 90% by weight, when using a roll coater, spin coater, slit-type spin coater, slit coater (sometimes referred to as die coater) and sprayer When coating is performed by a coating device, the coating performance is improved.

additive

The color-forming photosensitive resin composition of the present invention contains, in addition to the above-mentioned components, other additives in accordance with the needs of a person of ordinary skill within the range that does not impair the object of the present invention.

Specifically, the above additives may further include one or more selected from the group consisting of, for example, other polymer compounds, thermal initiators, curing agents, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, and anticoagulants Additives.

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

The above thermal initiator functions to cause the curing reaction by heat to maximize the efficiency of initiation. The thermal initiator may be a peroxide-based compound.

The specific type of the above thermal initiator is not particularly limited, and may be selected from tetramethylbutyl neodecanoate peroxide (for example, Perocta ND, manufactured by NOF Corporation), bis(4-butylcyclohexyl) peroxydicarbonate Ester (eg Peroyl TCP, manufactured by NOF Corporation), bis(2-ethylhexyl) peroxycarbonate, butyl neodecanoate (eg Perbutyl ND, manufactured by NOF Corporation), diperoxydicarbonate Propyl ester (eg Peroyl NPP, manufactured by NOF Corporation), diisopropyl peroxydicarbonate (eg Peroyl IPP, manufactured by NOF Corporation), dicarbon peroxide Diethoxyethyl acid (eg Peroyl EEP, manufactured by NOF Corporation), diethoxyhexyl peroxydicarbonate (eg Peroyl OEP, manufactured by NOF Corporation), hexyl peroxydicarbonate (eg Perhexyl) ND, NOF (manufactured)), dimethoxybutyl peroxydicarbonate (eg Peroyl MBP, NOF (manufactured)), bis(3-methoxy-3-methoxybutyl peroxydicarbonate) ) Ester (for example, Peroyl SOP, manufactured by NOF Corporation), dibutyl peroxydicarbonate, dihexadecyl peroxydicarbonate (dicetyl), dimyristyl peroxydicarbonate (dimyristyl) ester, 1 , 1,3,3-tetramethylbutyl peroxypivalate, peroxypivalate (eg Perhexyl PV, manufactured by NOF Corporation), butyl peroxypivalate (eg Perbutyl (manufactured by NOF), trimethylhexyl peroxide (eg Peroyl355, manufactured by NOF), dimethylhydroxybutyl neodecanoate (eg Luperox 610M75, manufactured by Atofina), Amyl peroxyneodecanoate (eg Luperox 546M75, manufactured by Atofina), butyl peroxyneodecanoate (eg Luperox 10M75, manufactured by Atofina), tert-butyl neoheptanoate, pivalic acid peroxy Amyl ester (e.g. Luperox 546M75, Alofina (manufactured)), tert-butyl peroxypivalate, tert-amyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, lauryl Peroxide, dilauroyl peroxide (dilauroyl), didecyl peroxide, benzoyl peroxide, dibenzoyl peroxide, 2,2-bis(tert-butylperoxy)butane, 1,1 -Bis(tert-butylperoxy)cyclohexane, 2,5-bis(butylperoxy)-2,5-dimethylhexane, 2,5-bis(tert-butylperoxy)-1- Methylethyl)benzene, 1,1-bis(tert-butyl peroxide)-3,3,5-trimethylcyclohexane, tert-butyl hydroperoxide, tert-butyl peroxide, benzene peroxide Tert-butyl formate, tert-butyl peroxyisopropyl carbonate, cumene hydroperoxide, dicumyl peroxide, lauryl peroxide, 2,4-pentanedione peroxide, tert-butyl peracetate ( Tert-butyl peracetate), peracetic acid (peracetic acid) and potassium persulfate (potassium persulfate).

The content of the thermal initiator is preferably 1 to 10% by weight, and more preferably 1 to 5% by weight relative to the total weight of the solid content in the colored photosensitive resin composition. When it is contained at this content, it is more preferable in terms of processability and under cut.

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

Among the above curing agents, specific examples of the epoxy compound include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, Novolac epoxy resins, other aromatic epoxy resins, alicyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, or brominated derivatives of these epoxy resins, epoxy resins and Aliphatic, alicyclic or aromatic epoxy compounds other than brominated derivatives, butadiene (co)polymer epoxide, isoprene (co)polymer epoxide, (meth)acrylic acid Glycidyl ester (co)polymer, triglycidyl isocyanurate, etc.

Specific examples of the oxetane compound in the curing agent include carbonate dioxetane, xylene dioxetane, adipate dioxetane, and p-benzene Dioxetane dioxetane, cyclohexane dicarboxylic acid dioxetane, etc.

The above curing agent may be used together with a curing aid compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound together with the curing agent. Examples of the above curing auxiliary compound include polycarboxylic acids, polycarboxylic acid anhydrides, and acid generators. Commercially available epoxy resin curing agents can be used for the above polycarboxylic acid anhydrides. Specific examples of the above epoxy resin curing agent include ADEKA HARDENER EH-700 (trade name, manufactured by ADEKA Industries, Ltd.) as a commercially available product, RIKACID HH (trade name, manufactured by Nippon Rico Chemical Co., Ltd.), MH-700 (trade name, manufactured by Nippon Rico Chemical Co., Ltd.), etc. The curing agents exemplified above may be used alone or in combination of two or more.

The above-mentioned surfactants can be used to further improve the film-forming properties of the colored photosensitive resin composition, and for example, silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, and amphoteric surfactants can be used Preferably, a silicone-based surfactant or a fluorine-based surfactant can be used.

Regarding the above-mentioned silicone-based surfactants, for example, as commercial products, DC3PA, DC7PA, SH11PA, SH21PA, and SH-8400 of Dow Corning Toray Silicone Corporation, TSF-4440, TSF of GE Toshiba Silicone Corporation, etc. may be mentioned. -4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452, etc. Regarding the above-mentioned fluorine-based surfactant, for example, as a commercially available product, Megafac F554, F-470, F-471, F-475, F-482, and F-489 (Dainippon Ink Chemical Industry Co., Ltd.), BM -1000, BM-1100 (BM Chemie), Fluorad FC-135/FC-170C/FC-430 (Sumitomo 3M Co., Ltd.), etc.

As other examples of the above surfactants, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters may be mentioned. Types, tertiary amine modified polyurethanes, polyethyleneimines, etc., as well as KP (Shin-Etsu Chemical Co., Ltd.), POLYFLOW (Kyoei Chemical Co., Ltd.), EFTop (TOHKEM PRODUCTS), Megafac (Dainippon Ink Chemical Industry Co., Ltd.), Fluorad (Sumitomo 3M Co., Ltd.), AsahiGuard, Surflon (above Asahi Glass Co., Ltd.), Solsperse (Zeneca Co., Ltd.), EFKA (EFKACHEMICALS Co., Ltd.), PB821 (Ajino Prime (strain) etc.

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

The adhesion promoter is an additive used to promote the coating and adhesion to the substrate, and may contain an additive selected from the group consisting of a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, and a combination thereof Silane coupling agent with reactive substituents. Specific examples of the silane coupling agent include vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tri(2-methoxyethoxy) silane, and N-(2-amino Ethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- Glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3- Chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, trimethoxymethoxy Silyl benzoic acid, vinyl triethoxysilane, γ-isocyanate propyl triethoxysilane, etc.

Specific examples of the above-mentioned antioxidants include 2,2'-thiobis(4-methyl-6-tert-butylphenol) and 2,6-di-tert-butyl-4-methylphenol.

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

Specific examples of the anticoagulant include sodium polyacrylate.

The content of the above-mentioned additives may be 0.01 to 10% by weight, preferably 0.05 to 2% by weight relative to the total weight of the solid content in the colored photosensitive resin composition.

The color-forming photosensitive resin composition produced in this way can be preferably used for the production of a display device, preferably a black matrix of a liquid crystal display device, a column spacer for maintaining a cell gap (Cell Gap), or a black column spacer.

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

In particular, the color-forming photosensitive resin composition of the present invention can be preferably used for the production of black columnar spacers (black matrix integrated spacers). The above-mentioned black columnar spacers mean that the black matrix and the columnar spacer The pattern is formed integrally, instead of separately forming a black matrix and a column spacer.

The present invention also relates to a color filter including a black matrix, a column spacer, or a black column spacer manufactured using the above-mentioned 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 for the substrate, the color filter itself may be a substrate, or may be a location where the color filter is located in a display device or the like, and is not particularly limited. The substrate may be glass, silicon (Si), silicon oxide (SiOx), or a polymer substrate. The polymer substrate may be polyethersulfone (PES), polycarbonate (PC), or the like.

The above-mentioned pattern layer is a layer containing the cured product of the coloring photosensitive resin composition of the present invention, and may include columnar spacers, black matrixes, and/or black columnar spacers.

The pattern layer may be a layer formed by coating the colored photosensitive resin composition and exposing, developing, and thermally curing in a predetermined pattern. The pattern layer may be formed by performing a method generally known in the art.

The color filter including the substrate and the pattern layer as described above may further include partitions formed between the patterns, or may further include a black matrix, but it 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 pattern layer including the cured product of 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, field emission display devices, and the like.

When the liquid crystal display device described above includes a color filter containing the pattern layer of the present invention, it has the advantage of excellent shielding properties and reliability.

A common patterning process for forming a black matrix, columnar spacers, or black columnar spacers using the lithography method includes: a) the step of coating the colored photosensitive resin composition on the substrate, b) pre-baking after drying the solvent Steps, c) Step of placing a photomask on the resulting film and irradiating active light to cure the exposed part, d) Step of performing a development process of dissolving the unexposed part using an alkaline aqueous solution, and e) Drying and post-baking step.

As the substrate, a glass substrate or a polymer plate can be used. As the glass substrate, it is particularly preferable to use soda lime glass, glass containing barium or strontium, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, quartz, or the like. In addition, as a polymer Examples of the board include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone.

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-type spin coater, a slit coater (sometimes referred to as a die coater), and a spray coater. In order to be able to obtain the desired thickness.

The pre-baking can be performed by heating using an oven, 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 used, and may be performed at a temperature of 80 to 150° C. for 1 to 30 minutes, for example.

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

The alkali development after exposure is performed to remove the colored photosensitive resin composition that is the unremoved portion of the non-exposed portion, and the desired pattern is formed through the 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 an alkaline aqueous solution containing 1 to 3% by weight of carbonates such as sodium carbonate, potassium carbonate, lithium carbonate, etc., using a developing machine or an ultrasonic cleaner at a temperature of 10 to 50°C, preferably 20 to 40°C. get on.

The post-baking is performed to improve the adhesion between the patterned film and the substrate, and is performed by heat treatment at 80 to 220° C. for 10 to 120 minutes. The post-baking is performed in the same manner as the front-baking using an oven, hot plate, or the like.

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 μm to 8 μm , more preferably 0.1 μm to 6 μm , and particularly preferably 0.1 μm to 4 μm .

The black matrix, columnar spacer, or black columnar spacer produced from the color-forming photosensitive resin composition of the present invention not only has excellent physical properties such as optical density, adhesion, electrical insulation, light-shielding properties, but also heat resistance and solvent resistance. Excellent, so that 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 used to more specifically illustrate the present invention, and the scope of the present invention is not limited by the following examples. For the following embodiments, those skilled in the art can make appropriate modifications and changes within the scope of the present invention.

Synthesis example. Synthesis of dispersion resin

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

Production Examples 1-7. Production of colored dispersions

A mixture in which the above dispersion resin is mixed with a coloring agent, a dispersing agent, and a solvent is prepared. Next, zirconium dioxide beads (average particle diameter 0.1 mm) and the above mixture were mixed in a weight ratio of 50:50, and subjected to dispersion treatment for 4 to 6 hours using a bead mill. After the dispersion was completed, it was filtered to produce a colored dispersion liquid, the content of which is shown in Table 1 below.

[Table 1]

Colorant

O64: C.I. Pigment Orange 64

B15: 6: C.I. Pigment Blue 15: 6

CB: Carbon black

B80: C.I. Pigment Blue 80

B60: C.I. Pigment Blue 60

V29: C.I. Pigment Violet 29

V23: C.I. Pigment Violet 23

Dispersion resin: The dispersion resin synthesized in the synthesis example

Dispersant: Disper BYK-2000 (Bike)

Solvent: Propylene glycol monomethyl ether acetate (PGMEA)

Examples 1 to 7 and Comparative Examples 1 to 2

The above-mentioned 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, and the content thereof is shown in Table 2 below.

Coloring dispersion

A1: Coloring dispersion liquid produced in Production Example 1

A2: Coloring dispersion liquid produced in Production Example 2

A3: The coloring dispersion liquid produced in Production Example 3

A4: Coloring dispersion liquid produced in Production Example 4

A5: Coloring dispersion liquid produced in Production Example 5

A6: Coloring dispersion liquid produced in Production Example 6

A7: Coloring dispersion liquid produced in Production Example 7

Alkali-soluble resin: the dispersion resin produced in the synthesis example

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

Photopolymerization initiator: 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one (Irgacure369: Ciba)

Additive: Disper BYK-163 (Bike)

Solvent: Propylene glycol monomethyl ether acetate (PGMEA)

Experimental example

1. Solvent resistance evaluation

A 5 cm × 5 cm glass substrate (Corning Corporation) washed with a neutral detergent and water was dried, and then spin-coated in the above Examples 1 to 7 and Comparative Examples 1 to 2 so that the final film thickness was 3.0 μm Each colored photosensitive resin composition. After that, 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, it is exposed at an exposure amount of 25 to 35 mJ/cm ² and fired at 200 to 250° C. for 10 to 30 minutes to manufacture a colored substrate coated with a colored photosensitive resin composition on its entire surface without a pattern.

The above substrate was cut to a size of 3 cm×3 cm, and immersed in an N-methylpyrrolidone (NMP) solvent at 100° C. for 60 minutes. After that, only the NMP solvent was extracted, and the degree of dissolution in the NMP solvent was measured using an ultraviolet-visible spectrometer (UV-vis spectrometer, UV-2600, Shimadzu Corporation) to measure the absorbance at a visible light wavelength to evaluate the solvent resistance. The measurement results of absorbance are shown in Table 3 below.

2. Optical density evaluation

The substrate was manufactured in the same manner as the method of manufacturing the substrate manufactured in the above solvent resistance evaluation.

The absorbance (OD) was measured using a photometer (X-rite), and the film thickness was measured using a film thickness measuring device (Dektak). The optical density (OD/ μm ) was calculated using the above measurement results, and the results are shown in Table 3 below.

3. Long wavelength absorbance evaluation

The substrate was manufactured in the same manner as the method of manufacturing the substrate manufactured in the above solvent resistance evaluation.

Using an ultraviolet-visible spectrometer (UV-vis spectrometer, UV-2600, Shimadzu Corporation), the absorbance at a visible light wavelength was measured, and the results are shown in Table 3 below.

The measured absorbances of Examples 1 to 7 as the coloring photosensitive resin composition of the present invention are low, and show the results of excellent solvent resistance, even at low PWC In this case, the optical density characteristics are more suitable. In particular, in the case of Example 1 containing C.I. Pigment Blue 80, the results showed the most excellent solvent resistance and very excellent optical density. In addition, in the case of Examples 2 to 7 further including C.I. Pigment Blue 15:6, the results show that the absorbance of the substrate, that is, the absorbance at a long wavelength is significantly improved.

The measured absorbance of the NMP solvent of the color-forming photosensitive resin compositions of Comparative Examples 1 to 2 having the same or more pigment content as compared to the color-sensitive photosensitive resin compositions of Examples 1 to 7 containing CI Pigment Blue 80 Higher, showing the result of insufficient solvent resistance.

In summary, although the present invention has been disclosed as above with examples, it is not intended to limit the present invention. Those with ordinary knowledge in the technical field to which the present invention belongs can make various modifications and retouching without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention shall be deemed as defined by the scope of the attached patent application.

Claims (11)

A coloring photosensitive resin composition, including a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, the colorant includes a blue pigment and an orange pigment, the blue pigment Is CI Pigment Blue 80 represented by the following Chemical Formula 1,

Wherein the colored photosensitive resin composition further comprises a black pigment as the additional colorant, wherein the black pigment, the blue pigment and the orange pigment in the colorant have a weight of 1:1.0~2.0:1.0~1.5 Than mixing. The coloring photosensitive resin composition as described in item 1 of the patent application range, wherein the black pigment contains one or more selected from the group consisting of aniline black, perylene black, titanium black, and carbon black. The coloring photosensitive resin composition as described in item 1 of the patent application range, wherein the orange pigment contains one or more selected from the group consisting of C.I. Pigment Orange 59, 61, 64, 65, 68, and 70. The coloring photosensitive resin composition as described in item 1 of the patent application range, wherein the coloring agent contains 13 to 60% by weight of the total weight of the solid content in the colored photosensitive resin composition and the alkali-soluble resin is 5 to 60 Wt%, photopolymerization The active compound is 5 to 50% by weight and the photopolymerization initiator is 0.1 to 40% by weight, and the solvent contains 60 to 90% by weight based on the total weight of the colored photosensitive resin composition. The coloring photosensitive resin composition as described in item 1 of the patent application range, wherein the colored photosensitive resin composition further contains C.I. Pigment Blue 15:6 as the blue pigment. The coloring photosensitive resin composition as described in item 5 of the patent application range, wherein the black pigment, the blue pigment and the orange pigment in the colorant are mixed in a weight ratio of 1:2.0~3.0:1.0~2.0. The coloring photosensitive resin composition as described in item 1 of the patent application range, wherein the colored photosensitive resin composition further comprises a polymer selected from the group consisting of other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, and ultraviolet rays One or more additives in the group consisting of absorbent and anticoagulant. A pattern layer made of the color-sensitive photosensitive resin composition as described in any one of claims 1 to 7. The pattern layer as described in item 8 of the patent application range, wherein the pattern layer is one or more selected from the group consisting of columnar spacers, black matrix, and black columnar spacers. A color filter including the pattern layer as described in item 8 of the patent application. A display device including the color filter as described in item 10 of the patent application scope.