JP6722742B2 - Colored dispersion liquid, colored photosensitive resin composition containing the same, pattern layer produced using the resin composition, color filter containing the pattern layer, and display device containing the color filter - Google Patents

Description

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

The color filter is widely used in various display devices such as an image sensor and a liquid crystal display device (LCD), and its application range is rapidly expanding. The color filter used in the image pickup device, the liquid crystal display device, or the like is formed of a coloring pattern of three colors of red, green, and blue, or yellow, magenta. , And cyan (Cyan).

The color pattern of each of the color filters is generally formed using a colored photosensitive resin composition containing a colorant such as a pigment or a dye, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. It Processing of the colored pattern using the colored photosensitive resin composition is usually performed in a lithographic process.

The colored photosensitive resin is an essential material for color filters, liquid crystal display materials, organic light emitting devices, displays and the like. For example, in the case of a color filter used in a liquid crystal display, a pixel including pixels of red (red), green (green), and blue (blue) is included to prevent color mixture of these pixels or to prevent electrodes from mixing. A black matrix is formed at the boundary between the colored layers of each color to hide the pattern. In addition, the black column spacer (Black Column Spacer, BCS) is required to have excellent solvent resistance and characteristics that no residue remains on the organic film at a portion that directly contacts the liquid crystal.

Patent Document 1 relates to a black column spacer in which a column spacer and a black matrix are integrated in one module, and satisfies all properties such as an elastic recovery rate required as a column spacer and a light blocking property required as a black matrix. The colored photosensitive resin composition and the black column spacer are disclosed. However, it is not sufficient in improving solvent resistance and storage stability.

Korean Patent Registration No. 10-1658374

The present invention has been made in order to solve the above-mentioned problems of the prior art, and an object of the present invention 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 made of a colored photosensitive resin composition, a color filter including the pattern layer, and a display device including the color filter.

To achieve the above objectives,
The present invention is a colored dispersion liquid containing a colorant, a dispersion resin, and a solvent,
The colorant includes an organic black pigment, a blue pigment, and a violet pigment,
The dispersion resin includes a copolymer represented by Chemical Formula 1 below, to provide a colored dispersion liquid.

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

The present invention also provides a colored photosensitive resin composition containing the colored dispersion of the present invention, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.

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

Furthermore, the present invention provides a color filter including the pattern layer of the present invention.

The present invention also provides a display device including the color filter of the present invention.

Since the colored dispersion liquid of the present invention contains the dispersion resin containing the copolymer of Chemical Formula 1, it has an excellent effect on the dispersibility and storage stability of the pigment.

Further, the colored photosensitive resin composition of the present invention is excellent in reliability such as solvent resistance and storage stability by including the colored dispersion liquid of the present invention, and when applied to a substrate, on a organic film. It has an effect that no residue is generated.

Further, the colored photosensitive resin composition of the present invention is used by mixing two or more kinds of copolymers having different epoxy equivalents, so that the coating film produced using the same has an excellent elastic recovery rate. Have the effect of having.

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

The present invention is a colored dispersion liquid containing a colorant, a dispersion resin, and a solvent,
The colorant includes an organic black pigment, a blue pigment, and a violet pigment,
The dispersion resin includes a colored dispersion liquid containing a copolymer represented by the following Chemical Formula 1.

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

The colored dispersion of the present invention can improve the dispersibility and storage stability of the pigment by using the dispersion resin containing the copolymer of Chemical Formula 1, and further, the colored photosensitive resin composition to which the dispersion is applied. The reliability such as solvent resistance and storage stability can be improved.

When the colored dispersion liquid is manufactured using the dispersion resin containing the copolymer of Chemical Formula 1, the colored dispersion liquid in which the surface of the pigment is uniformly coated with the dispersion resin can be obtained. Therefore, the colored photosensitive resin composition containing such a colored dispersion liquid contains the pigment particles coated with the dispersion resin, thereby improving the solvent resistance by preventing the pigment from being eluted in the solvent. The storage stability can be improved by suppressing the aggregation between pigment particles and preventing the viscosity of the colored photosensitive resin composition from increasing.

The colored dispersion of the present invention contains 65 to 75% by weight of a colorant and 7 to 12% by weight of a dispersion resin, based on the total weight of solids in the colored dispersion, and the total weight of the colored dispersion. And 70 to 80% by weight of the solvent. When the colorant, the dispersion resin, and the solvent satisfy the above ranges, it is possible to produce a colored dispersion having excellent pigment dispersibility and storage stability.

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

The present invention also relates to a colored photosensitive resin composition containing the colored dispersion liquid, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.

The colored photosensitive resin composition of the present invention can improve the optical density of the colored photosensitive resin composition by including an organic black pigment, a blue pigment, and a violet pigment as colorants.

Also, the colored photosensitive resin composition of the present invention may include the copolymer of Chemical Formula 1 as an alkali-soluble resin. Thereby, reliability such as solvent resistance and chemical resistance can be improved through the crosslinking reaction of the colored photosensitive resin composition.

Further, the colored photosensitive resin composition of the present invention is prepared by using an alkali-soluble resin containing two or more kinds of copolymers having different epoxy equivalents as the copolymer represented by the chemical formula 1. The elastic recovery rate of the coating film produced by the method can be improved.

Hereinafter, the colored dispersion liquid and the colored photosensitive resin composition of the present invention will be described in detail for each component.

Colorant In the present invention, a colorant having a property of shielding visible light is used, and the colorant of the present invention includes an organic black pigment, a violet pigment, and a blue pigment.

The organic black pigment contains at least one selected from the group consisting of lactam black, aniline black, and perylene black, and preferably contains lactam black. By including the organic black pigment, the dielectric constant and the transmittance can be improved without affecting the infrared region while improving the optical density.

The violet pigment serves to reduce the transmittance in the region of 400 to 600 nm and improve the optical density (OD). Moreover, the content of the organic black pigment can be reduced by using the violet pigment, and the reliability of the colored photosensitive resin composition can be improved. The type of the violet pigment is not particularly limited, but C.I. I. Pigment Violet 19, 23, 29, 31, and 37 are preferably used, and one or more selected from the group consisting of C.I. I. Pigment Violet 29 is most preferably used.

The blue pigment is a compound containing no central metal, and the presence of the central metal may affect the driving of the liquid crystal. However, in the present invention, by using a compound containing no central metal as the blue pigment, A merit can be secured for 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. I. Pigment Blue 16, 60, 63, and 66 are preferably used, and at least one selected from the group consisting of C.I. I. Most preferably, Pigment Blue 60 is used.

Further, the colored photosensitive resin composition of the present invention may include a black pigment as an additional colorant. The black pigment is not particularly limited as long as it has a property of shielding visible light, but it is preferable to use one containing at least one selected from the group consisting of titanium black and carbon black. It is more preferable to use carbon black. The carbon black is not particularly limited as long as it is a pigment having a light-shielding property, 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 carbon black may be resin-coated, and the resin-coated carbon black has a lower conductivity than uncoated carbon black, and thus has excellent electrical properties when forming a black matrix or column spacers. Insulation can be imparted.

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

More specifically, the colorants include organic black pigments, violet pigments, blue pigments, and black pigments of 1:0.08 to 2.5:0.2 to 3.3:0.12 to 1.7. Can be mixed in a weight ratio of. Moreover, it is preferable to mix them in a weight ratio of 1:0.27 to 1:0.47 to 1.88:0.27 to 0.87. When the organic black pigment, violet pigment, blue pigment, and black pigment are contained in the above weight ratio, a colored photosensitive resin composition having excellent optical density and reliability can be obtained.

Dispersion resin The dispersion resin coats the pigment particles existing in the colored dispersion liquid with the dispersion resin to prevent the pigment particles from being dissolved in a solvent, and suppresses the aggregation between the pigment particles to thereby cause the aggregation between the pigment particles. It plays a role in preventing an increase in viscosity.

The dispersion resin of the present invention includes a copolymer represented by the following chemical formula 1.

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

In the present invention, solvent resistance, storage stability, and residual film rate can be improved by including the copolymer of Chemical Formula 1 containing an epoxy group as the dispersion resin.

The weight average molecular weight of the dispersion 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. Good.

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

The dispersion resin may be a copolymer of the copolymer represented by Chemical Formula 1 and another monomer copolymerizable with the copolymer.

Specific examples of the monomer copolymerizable with the chemical formula 1 of the dispersion resin include styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, Aromatic vinyl compounds such as o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether; methyl ( (Meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, sec-butyl (meth)acrylate, Alkyl (meth)acrylates such as t-butyl (meth)acrylate; cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.02,6]decane Alicyclic (meth)acrylates such as -8-yl (meth)acrylate, 2-dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate; phenyl (meth)acrylate, benzyl (meth)acrylate, etc. Aryl(meth)acrylates; hydroxyalkyl(meth)acrylates such as 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate; N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm-methylphenylmaleimide, Np-methylphenylmaleimide, N- N-substituted maleimide compounds such as o-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide and Np-methoxyphenylmaleimide; unsaturated amide compounds such as (meth)acrylamide and N,N-dimethyl(meth)acrylamide 3-(methacryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2 Unsaturated oxetane compounds such as phenyl oxetane, 2-(methacryloyloxymethyl)oxetane, and 2-(methacryloyloxymethyl)-4-trifluoromethyl oxetane.

The compounds exemplified above can be used alone or in combination of two or more kinds.

The dispersion resin of the present invention can be used by optionally mixing various other well-known alkali-soluble resins commonly used in the art.

The dispersion resin is contained in an amount of 1 to 20% by weight, preferably 7 to 12% by weight, based on the total weight of the solid content in the colored dispersion liquid. When the content of the dispersion resin is within the above range, the pigment particles are uniformly dispersed, aggregation between the pigment particles can be prevented, and solvent resistance and storage stability are improved, which is preferable.

Dispersant The dispersant is added for deagglomeration of the pigment and maintenance of stability. Specific examples of the dispersant include cationic, anionic, nonionic, polyester-based, Examples thereof include polyamine-based surfactants and the like, and these can be used alone or in combination of two or more kinds.

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

Specific examples of the anionic surfactant, higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, And alkylaryl sulfonates such as sodium dodecylnaphthalene sulfonate.

Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkylaryl ether, other polyoxyethylene derivatives, oxyethylene/oxypropylene block copolymer, sorbitan. Examples thereof include fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, and polyoxyethylene alkylamine.

In addition, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, polyethylene imines, and the like can be mentioned.

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

As the dispersant, a pigment dispersant of another resin type may be used in addition to the acrylate dispersant. As the other resin type dispersant, a known resin type dispersant, in particular, polyurethane, polycarboxylic acid ester represented by polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) Amine salts, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphate salts, esters of hydroxyl-containing polycarboxylic acids, and their modified products or free. ) Oily dispersants such as amides formed by the reaction of polyesters having carboxyl groups with poly(lower alkyleneimines) or salts thereof; (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth ) Water-soluble resins or water-soluble polymer compounds such as acrylate ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, or polyvinylpyrrolidone; polyesters; modified polyacrylates; ethylene oxide/propylene oxide addition products; and phosphate esters and the like. Can be mentioned.

In the commercial products of the other resin type dispersants, as the cationic resin dispersant, for example, trade names of BYK (Big) Chemie: 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 trade names: EFKA-44, EFKA-46, EFKA. -47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA-4330, EFKA-4400, EFKA-4406, EFKA-4510. EFKA-4800; Trade name of Lubirzol: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10; Trade name of Kawaken Fine Chemicals: HINOACT T-6000, HINOACT T-7000, HINOACT T-8000. Ajinomoto Co., Inc. product names: AJISPUR PB-821, AJISPER PB-822, AJISPER PB-823; Kyoeisha Chemical Co., Ltd. product names: FLORENE DOPA-17HF, Fluorene DOPA-15BHF, Fluorene DOPA-33, Floren DOPA-44 etc. are mentioned.

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

The dispersant is contained in an amount of more than 0 and 1 part by weight or less, preferably 0.05 to 0.5 part by weight, relative to 1 part by weight of the colorant. When the dispersant is contained in an amount of more than 0 and not more than 1 part by weight, a uniformly dispersed pigment can be obtained, which is preferable.

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 alkali developing solution used in the developing step. In the present invention, the alkali-soluble resin is not particularly limited, but is preferably a copolymer of a monomer having a carboxyl group and another monomer copolymerizable therewith.

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 acid and unsaturated dicarboxylic acid. 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 can be used alone or in combination of two or more kinds.

Specific examples of the other monomer include aromatic vinyl compounds, unsaturated carboxylate compounds, unsaturated aminoalkyl carboxylate compounds, unsaturated glycidyl carboxylate compounds, vinyl carboxylate compounds, vinyl cyanide compounds, and unsaturated oxetanes. A carboxylate compound etc. are mentioned.

Specific examples of the vinyl compound include styrene, α-methylstyrene, vinyltoluene and the like. Specific examples of the unsaturated carboxylate compound include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, and 2 -Phenylthioethyl acrylate and the like. Specific examples of the unsaturated aminoalkyl carboxylate compound include aminoethyl acrylate. Specific examples of the unsaturated glycidyl carboxylate compound include glycidyl methacrylate. 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-acryloxymethyl oxetane, 3-methyl-3-methacryloxymethyl oxetane, 3-ethyl-3-acryloxymethyl oxetane, 3-ethyl- 3-methacryloxymethyl oxetane, 3-methyl-3-acryloxyethyl oxetane, 3-methyl-3-methacryloxyethyl oxetane, 3-methyl-3-acryloxyethyl oxetane, and 3-methyl-3-methacryloxyethyl Examples include oxetane. The other monomers may be used alone or in combination of two or more.

The alkali-soluble resin may include the copolymer of the chemical formula 1, and the alkali-soluble resin may include the copolymer of the chemical formula 1 including an epoxy group to reduce solvent resistance and The storage stability can be improved.

Further, in the present invention, the alkali-soluble resin may be a mixture of two or more kinds of copolymers having different epoxy equivalents as the copolymer of the chemical formula 1, and the copolymer (b1) is preferable. And the copolymer (b2) can be mixed and used.

The copolymer (b1) may have an epoxy equivalent of 500 to 800, 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.

Further, the copolymers (b1) and (b2) are included in a weight ratio of 1:0.1-5, and preferably in a weight ratio of 1:0.25-3. When the copolymers (b1) and (b2) satisfy the ranges of the epoxy equivalent and the range of the weight ratio, they are preferable in that an excellent elastic recovery rate can be exhibited.

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. May be.

The alkali-soluble resin is contained in an amount of 5 to 60% by weight, preferably 20 to 50% by weight, based on the total weight of solids in the colored photosensitive resin composition. When the content of the alkali-soluble resin is within the range, pattern formation is easy and the resolution and the residual film rate are improved, which is preferable.

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 100 parts by weight of the total amount of the alkali-soluble resin and the photopolymerizable compound. When the alkali-soluble resin is mixed within the range, the solubility is sufficient and pattern formation is easy, film reduction of the pixel portion of the exposed portion during development is prevented, and good non-pixel portion dropout coloring is achieved. A photosensitive resin composition can be provided.

Photopolymerizable compound The photopolymerizable compound is a compound that contains an unsaturated bond and is capable of advancing a photoreaction with a photopolymerization initiator to form a colored photosensitive resin layer. It must be a compound that can be polymerized by action.

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

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

Specific examples of the trifunctional monomer among the polyfunctional monomers include trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, and propoxylated trimethylolpropane tri(meth)acrylate. Acrylate, pentaerythritol tri(meth)acrylate, and the like.

Specific examples of the tetrafunctional monomer among the polyfunctional monomers include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, ditrimethylolpropane tetraacrylate, ditrimethylolpropane tetramethacrylate, dipentaerythritol tetraacrylate, and tetrapentaerythritol tetraacrylate. Methylol methane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, glycerin tetraacrylate, glycerin tetramethacrylate and the like can be mentioned.

Specific examples of the pentafunctional monomer among the polyfunctional monomers include dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol monohydroxypentaacrylate and dipentaerythritol monohydroxypentamethacrylate. Are listed.

Specific examples of the hexafunctional monomer among the polyfunctional monomers include dipentaerythritol hexaacrylate and dipentaerythritol hexamethacrylate.

Specific examples of the 7 to 10 functional monomer among the polyfunctional monomers include tripentaerythritol octamethacrylate, tripentaerythritol octaacrylate, tetrapentaerythritol heptamethacrylate, and tetrapentaerythritol heptaacrylate. Are listed.

The photopolymerizable compound is contained in an amount of 5 to 50% by weight, preferably 7 to 45% by weight, based on the total weight of solids in the colored photosensitive resin composition of the present invention. The photopolymerizable compound can improve the strength and flatness of the pixel portion in the range of 5 to 50% by weight.

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

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-1-[4-(2 -Hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2 -Dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one, and 2-(4 -Methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one and the like.

Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoisobutyl ether.

Specific examples of the benzophenone compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3′,4,4′-tetra (Tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone and the like.

Specific examples of the triazine-based compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine and 2,4-bis(trichloromethyl). -6-(4-Methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-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(trichloromethyl)-6-[2-(3,4dimethoxyphenyl)ethenyl]-1,3,5-triazine.

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'-tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole, 2,2-bis(2,6-dichlorophenyl)-4,4',5 , 5′-tetraphenyl-1,2′-biimidazole, or an imidazole compound in which the phenyl group at the 4,4′,5,5′ position is substituted with a carboalkoxy group.

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 the like can be mentioned.

Specific examples of the oxime compound include o-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one and the like, and commercially available products may be OXE01 and OXE02 manufactured by Basuf Company. ..

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

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

In the present invention, the photopolymerization initiator is contained in an amount of 0.1 to 20% by weight, preferably 1 to 10% by weight, based on the total weight of solids in the colored photosensitive resin composition.

Within the range of 0.1 to 20% by weight, the sensitivity of the colored photosensitive resin composition is increased, and the strength of the pixel portion formed using the colored photosensitive resin composition and the smoothness on the surface of the pixel portion are improved. Get better

Further, in the present invention, a photopolymerization initiation auxiliary agent can be additionally used as the photopolymerization initiator.

The photopolymerization initiation auxiliary agent is a compound used for promoting the polymerization of the photopolymerizable compound whose polymerization is initiated by the photopolymerization initiator, and the photopolymerization initiation auxiliary agent is, for example, an amine compound or Examples thereof include alkoxy anthracene compounds.

Specific examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and benzoic acid. Acid 2-dimethylaminoethyl, 2-dimethylhexyl 4-dimethylaminobenzoate, N,N-dimethylparatoluidine, 4,4′-bis(dimethylamino)benzphenone (commonly known as Michler's ketone), 4,4′-bis( Examples thereof include diethylamino)benzophenone and 4,4′-bis(ethylmethylamino)benzophenone. Among them, 4,4′-bis(diethylamino)benzophenone is preferable.

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

Further, a commercially available photopolymerization initiation auxiliary agent can be used, and examples of the commercially available photopolymerization initiation auxiliary agent include trade name “EAB-F” (manufacturer: Hodogaya Chemical Co., Ltd.).

When the photopolymerization initiator auxiliary agent is used, it is usually preferably used in an amount of more than 0 and 10 mol or less, or 0.01 to 5 mol, per 1 mol of the photopolymerization initiator. When the photopolymerization initiation auxiliary agent is used in the range of more than 0 and 10 mol or less, the sensitivity of the colored photosensitive resin composition is further increased, and the productivity of the color filter formed using the colored photosensitive resin composition is improved. it can.

Solvent: The solvent is a solvent used in a usual colored photosensitive resin composition, as long as it is effective in dissolving other components contained in the colored photosensitive resin composition and does not react. Can be used without particular limitation, and ethers, acetates, aromatic hydrocarbons, ketones, alcohols, esters and the like are particularly preferable.

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;
Examples thereof include 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 acetates include methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3-methoxybutyl acetate, 3-methyl-3-methoxy-1-. Butyl acetate, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, methyl 3-methoxypropionate, propylene glycol methyl ether acetate, 3-methoxy-1-butyl acetate, 1,2-propylene glycol diacetate, ethylene Glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, diethylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoacetate, diethylene glycol Examples thereof include diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate, and propylene carbonate.

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.

The solvents may be used alone or in admixture 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., for example, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxy. Examples include ethyl propionate and methyl 3-methoxypropionate.

The solvent is contained in an amount of 60 to 90% by weight, preferably 65 to 85% by weight, based on the total weight of the colored photosensitive resin composition. When the solvent is contained in the range of 60 to 90% by weight, when coated with a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (also referred to as a die coater), and an ink jet, Good coatability.

Additive The colored photosensitive resin composition of the present invention contains, in addition to the components described above, other additives as required by ordinary technicians as long as the object of the present invention is not impaired.

The additive specifically includes, for example, a filler, another polymer compound, a thermal initiator, a curing agent, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an agglomeration inhibitor. One or more additives selected from the group may be additionally included.

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

The thermal initiator serves to maximize the initiation efficiency by causing a curing reaction by heat. The thermal initiator may be a peroxide compound.

The specific type of the thermal initiator is not particularly limited, but includes tetramethylbutyl peroxyneodecanoate (ex. Perocta ND, NOF Co., Ltd.), bis(4-butylcyclohexyl) peroxydicarbonate (ex. Peroyl). TCP, NOF company (manufactured), di(2-ethylhexyl) peroxycarbonate, butylperoxy neodecanoate (ex.Perbutyl ND, NOF company manufactured), dipropylperoxydicarbonate (ex.Peroyl NPP, NOF company manufactured) (Manufactured), diisopropyl peroxydicarbonate (ex. Peroyl IPP, NOF (manufactured)), diethoxyethyl peroxydicarbonate (ex. Peroyl EEP, NOF manufactured (manufactured)), diethoxyhexyl peroxydicarbonate (ex. Peroyl OEP, NOF (manufactured), hexyl peroxydicarbonate (ex.Perhexyl ND, NOF manufactured (manufactured)), dimethoxybutyl peroxydicarbonate (ex.Peroyl MBP, NOF manufactured (manufactured)), bis(3-methoxy). -3-Methoxybutyl)peroxydicarbonate (ex. Peroyl SOP, NOF Co., Ltd.), dibutylperoxydicarbonate, dicetyl peroxydicarbonate, dimyristyl peroxydicarbonate, 1,1,3,3 -Tetramethylbutylperoxypivalate, hexylperoxypivalate (ex.Perhexyl PV, NOF (manufactured by NOF)), butylperoxypivalate (ex.Perbutyl, NOF, manufactured by), trimethylhexanoylperoxide (ex) Peroyl 355, NOF (manufactured by NOF), dimethylhydroxybutyl peroxy neodecanoate (ex.Luperox 610M75, Atofina (manufactured)), amylperoxy neodecanoate (ex.Luperox 546M75, Atofina (manufactured)), butylperoxy. Neodecanoate (ex.Luperox 10M75, Atofina (manufactured)), t-butylperoxyneoheptanoate, amylperoxypivalate (ex.Luperox 546M75, Alofina (manufactured)), t-butylperoxypivalate. , T-amyl peroxy-2- Ethyl hexanoate, t-butyl peroxy-2-ethyl hexanoate, lauryl peroxide, dilauroyl peroxide, didecanoyl 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-butylperoxy)-3,3,5-trimethylcyclohexane, tert-butylhydroperoxide, tert-butylperoxide, tert-butylperoxybenzoate, tert-butylperoxyisopropyl carbonate, cumene hydroxyperoxide, dimethyl 1 selected from the group consisting of mill peroxide, lauroyl peroxide, 2,4-pentanedione peroxide, tert-butyl peracetate, peracetic acid, and potassium persulfate. It may be more than one species.

Regarding the content of the thermal initiator, it is preferably contained in an amount of 1 to 10% by weight, more preferably 1 to 5% by weight, based on the total weight of solids in the colored photosensitive resin composition. When it is contained in the content, it is preferable due to processability and undercut.

The curing agent is used to enhance deep-curing and mechanical strength, and specific examples thereof include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound.

Specific examples of the epoxy compound in the curing agent include bisphenol A-based epoxy resin, hydrogenated bisphenol A-based epoxy resin, bisphenol F-based epoxy resin, hydrogenated bisphenol F-based epoxy resin, novolac type epoxy resin, and other aromatic-based compounds. Epoxy resin, alicyclic epoxy resin, glycidyl ester resin, glycidyl amine resin, or brominated derivative of such epoxy resin, epoxy resin and aliphatic, alicyclic or aromatic epoxy other than the brominated derivative thereof Examples thereof include compounds, butadiene (co)polymer epoxidized products, isoprene (co)polymer epoxidized products, glycidyl (meth)acrylate (co)polymers, and triglycidyl isocyanurate.

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

As the curing agent, a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound can be used together with the curing agent. Examples of the curing auxiliary compound include polyvalent carboxylic acids, polycarboxylic acid 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, as commercially available products, trade name (ADEKA HARDNER EH-700) (manufactured by ADEKA KOGYO CO., LTD.), trade name (RIKACID HH) (manufactured by Shin Nippon Rika Co., Ltd.), and product. Name (MH-700) (manufactured by New Japan Rika Co., Ltd.) and the like. The curing agents exemplified above can be used alone or in combination of two or more.

The surfactant can be used to further improve the film forming property of the photosensitive resin composition, and examples thereof include silicone-based, fluorine-based, ester-based, cationic-based, anionic-based, nonionic-based, Further, a surfactant such as an amphoteric system can be used, and a silicone-based surfactant or a fluorine-based surfactant can be preferably used.

Examples of the silicone-based surfactants include commercially available products such as DC3PA, DC7PA, SH11PA, SH21PA, and SH-8400 manufactured by Dow Corning Toray Silicone Co., Ltd., and TSF-4440, TSF-4300, TSF-4445 manufactured by GE Toshiba Silicone Co., Ltd. , TSF-4446, TSF-4460, TSF-4452, and the like. The fluorosurfactant is, for example, as a commercially available product, Megapiece F554, F-470, F-471, F-475, F-482, and F-489 (Dainippon Ink and Chemicals, Inc.), BM-1000, BM-1100 (BM Chemie company), Florard FC-135/FC-170C/FC-430 (Sumitomo 3M Ltd.), etc. are mentioned.

Other examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes, polyethyleneimines. In addition to the above, as commercial products, KP (Shin-Etsu Chemical Co., Ltd.), Polyflow (Kyoei Chemical Co., Ltd.), F-Top (Tochem Products Co., Ltd.), Megafac (Dainippon Ink and Chemicals Co., Ltd.), Florard (Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (above Asahi Glass Co., Ltd.), Sols Perth (Zeneca Co., Ltd.), EFKA (EFKACHEMICALS), PB821 (Ajinomoto Co., Inc.) and the like.

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

The adhesion promoter is an additive used for promoting coating properties and adhesion with a substrate, and is a reaction selected from the group consisting of a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, and a combination thereof. A silane coupling agent containing a reactive substituent can be included. The silane coupling agent is specifically, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N. -(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4 -Epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, trimethoxysilylbenzoic acid, vinyltri Examples thereof include acetoxysilane and γ-isocyanatopropyltriethoxysilane.

Specific examples of the antioxidant include 2,2'-thiobis(4-methyl-6-t-butylphenol) and 2,6-di-t-butyl-4-methylphenol.

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

Specific examples of the aggregation preventing agent include sodium polyacrylate and the like.

The additive may be included in an amount of 0.01 to 10% by weight, preferably 0.05 to 2% by weight, based on the total weight of solids in the colored photosensitive resin composition.
The colored photosensitive resin composition thus produced can be preferably used for producing a black matrix of a display device, preferably a liquid crystal display device, a column spacer for maintaining a cell gap, or a black column spacer.

The column spacer, the black matrix, and/or the black column spacer according to the present invention have advantages of high optical density, excellent reliability, and excellent shielding property.

In particular, the colored photosensitive resin composition of the present invention can be preferably used for producing a black column spacer (black matrix integrated spacer), and the black column spacer does not form a black matrix and a column spacer, respectively. It means that the black matrix and the column spacer are integrally formed in one pattern.

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

The color filter according to 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.

The substrate may be the substrate itself of the color filter or a portion 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 (SiO _x ), or a polymer substrate, and the polymer substrate may be polyethersulfone (PES) or polycarbonate (polycarbonate, PC). ) Or the like.

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

The pattern layer may be a layer formed by applying the colored photosensitive resin composition described above and exposing, developing and thermosetting in a predetermined pattern, and the pattern layer is commonly known in the art. It can be formed by performing the method described above.

The color filter including the substrate and the pattern layer may include barrier ribs formed between the patterns or a black matrix, but is not limited thereto.

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

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

When the liquid crystal display device includes the color filter including the pattern layer according to the present invention, it has an advantage of excellent shielding property and reliability.

A general patterning process for forming a black matrix, a column spacer, or a black column spacer by a photolithography method is
a) applying a colored photosensitive resin composition to the substrate,
b) a pre-bake step of drying the solvent,
c) a step of applying a photomask on the obtained coating and irradiating it with an actinic ray to cure the exposed portion,
d) a step of performing a developing step of dissolving the unexposed portion using an alkaline aqueous solution,
e) comprises the steps of performing drying and post-baking.

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

At this time, the coating is performed by a wet method using a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (also referred to as a die coater), or an inkjet so that a desired thickness can be obtained. It is carried out by the coating method.

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

Further, the exposure performed after the pre-baking is performed by an exposure device and is exposed through a photomask, so that only a portion corresponding to the pattern is exposed. At this time, the irradiation light can be, for example, visible light, ultraviolet rays, X-rays, electron beams, or the like.

Alkali development after exposure This is carried out for the purpose of removing the colored photosensitive resin composition in the unremoved portion of the unexposed portion, and a desired pattern is formed by this development. As a developing solution suitable for this alkaline development, for example, an aqueous solution of an alkali metal or alkaline earth metal carbonate or the like can be used. Particularly, using an alkaline aqueous solution containing 1 to 3% by weight of a carbonate such as sodium carbonate, potassium carbonate or lithium carbonate, a developing device or ultrasonic cleaning is performed at a temperature of 10 to 50°C, preferably 20 to 40°C. Using a machine.

Post-baking is performed to enhance 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. Post bake is performed using an oven, a hot plate, or the like, as in pre bake.

At this time, the 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.

The thickness of the column spacer and the black column 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, the column spacer, or the black column spacer produced by the colored photosensitive resin composition of the present invention is excellent in physical properties such as optical density, adhesiveness, electrical insulation, and light-shielding property, as well as heat resistance and resistance. The reliability of the liquid crystal display device can be improved by being excellent in solvent property and the like.

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are for more specifically explaining the present invention, and the scope of the present invention is not limited by the following examples. The following embodiments can be appropriately modified and changed by a person skilled in the art within the scope of the present invention.

Production Example 1. Manufacture of Dispersion Resin A1 277 g of methoxybutylacetate was charged into a separable flask having an internal volume of 1 L equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube, and heated to 80°C. Next, 3,4-epoxytricyclo[5.2.1.0,2,6]decane-9-yl acrylate and 3,4-epoxytricyclo[5.2.1.0,2,6]. A mixed solution was prepared by dissolving 301 g of a mixture of decan-8-yl acrylate in a molar ratio of 50:50, 49 g of methacrylic acid, and 23 g of azobisdimethylvaleronitrile in 350 g of methoxybutyl acetate. The mixed solution was dropped into the flask using a dropping funnel over 5 hours, and then the reaction was allowed to proceed for 3 hours to produce a dispersion resin A1 [solid content (NV) 35.0% by weight]. The acid value (dry) of the produced dispersion resin A1 is 69.8 KOHmg/g, the weight average molecular weight (Mw) is 12,300, the dispersity (Mw/Mn) is 2.1, and the epoxy equivalent is 1,130. there were.

Production example 2. Production of Dispersion Resin A2 A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube was prepared. As a monomer dropping funnel, acrylic acid 14.4 parts by weight (0.2 mol), benzyl methacrylate 140.8 parts by weight (0.8 mol), t-butylperoxy-2-ethylhexanoate 2.0 parts by weight, It was prepared by mixing 40.0 parts by weight of propylene glycol monomethyl ether acetate (PGMEA). A chain transfer agent dropping tank was prepared by mixing 3.0 parts by weight of n-dodecanethiol and 24.0 parts by weight of PGMEA. Then, 395 parts by weight of PGMEA was added to the flask, the atmosphere in the flask was changed from air to 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 dropping was continued for 4 hours while maintaining 70° C., and after 1 hour, the temperature was raised to 90° C. and the reaction was allowed to proceed for 8 hours to produce dispersion resin A2 [solid content (NV) 35.0 wt %]. The acid value (dry) of the produced dispersion resin A2 was 80.0 KOHmg/g, the weight average molecular weight (Mw) was 45,200, and the dispersity (Mw/Mn) was 2.8.

Production example 3. Production of Dispersion Resin A3 A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introducing tube was prepared. As a monomer dropping funnel, 2-phenylthioethyl acrylate 52.1 parts by weight (0.25 mol), benzyl methacrylate 44.0 parts by weight (0.25 mol), methacrylic acid 12.9 parts by weight (0.15 mol) , 41.3 parts by weight (0.35 mol) of vinyltoluene, 4.0 parts by weight of t-butylperoxy-2-ethylhexanoate, and 40.0 parts by weight of PGMEA were mixed and prepared. A chain transfer agent dropping tank was prepared by mixing 6.0 parts by weight of n-dodecanethiol and 24.0 parts by weight of PGMEA. Then, 395 parts by weight of PGMEA was added to the flask, the atmosphere in the flask was changed from air to 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 dropping was continued for 2 hours while maintaining 90° C., and after 1 hour, the temperature was raised to 110° C. and the reaction was allowed to proceed for 8 hours to produce dispersion resin A3 [solid content (NV) 35.0 wt %]. The acid value (dry) of the produced dispersion resin A3 was 70.0 KOHmg/g, the weight average molecular weight (Mw) was 23,000, and the dispersity (Mw/Mn) was 2.4.

Production Example 4. Manufacture of alkali-soluble resin A4 277 g of methoxybutyl acetate was charged into a separable flask having an internal volume of 1 L equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube, and heated to 80°C. .. Next, 3,4-epoxytricyclo[5.2.1.0,2,6]decane-9-yl acrylate and 3,4-epoxytricyclo[5.2.1.0,2,6]. A mixed solution was prepared by dissolving 321 g of a mixture of decan-8-yl acrylate in a molar ratio of 50:50, 32 g of methacrylic acid, and 20 g of azobisdimethylvaleronitrile in 350 g of methoxybutyl acetate. The mixed solution was dropped into the flask over 5 hours using a dropping funnel, and then the reaction was allowed to proceed for 3 hours to produce a dispersion resin A4 [solid content (NV) 35.0% by weight]. The acid value (dry) of the produced alkali-soluble resin A4 was 59.8 KOHmg/g, the weight average molecular weight (Mw) was 9,300, the dispersity (Mw/Mn) was 1.9, and the epoxy equivalent was 665. It was

Example 1 and Comparative Examples 1-2
A mixture was prepared by mixing the dispersion resin, the colorant, the dispersant, and the solvent. Next, zirconia beads (average particle size: 0.1 mm) were mixed with the mixture at a weight ratio of 50:50, and dispersed for 6 hours using a bead mill. After the dispersion was completed, the dispersion was filtered to produce a colored dispersion, the content of which is shown in Table 1 below.

Colorant V29: C.I. I. Pigment Violet 29
OBP: organic black pigment B60: C.I. I. Pigment Blue 60
CB: Carbon black dispersion resin A1: Dispersion resin produced in Production Example 1 A2: Dispersion resin produced in Production Example 2 A3: Dispersion resin produced in Production Example 3 Dispersant: DisperBYK-2000 (BYK)
Solvent: Propylene glycol monomethyl ether acetate (PGMEA)

Examples 2-7 and Comparative Examples 3-8
A colored photosensitive resin composition was produced by mixing the colored dispersion liquid with an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, an additive, and a solvent, and the content thereof is shown in Table 2 below.

Colored dispersion B1: Colored dispersion B2 produced in Example 1: Colored dispersion B3 produced in Comparative Example 1: Colored dispersion produced in Comparative Example 2 Alkali-soluble resin A1: Resin A2 produced in Production Example 1: Resin A3 produced in Production Example 2: Resin A4 produced in Production Example 3: Resin produced in Production Example 4 Photopolymerizable compound: dipentaerythritol hexaacrylate (DPHA) (Nippon Kayaku Co., Ltd.)
Photopolymerization initiator: 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one (Irgacure369: Ciba)
Additive: Disper BYK-163 (BYK)
Solvent: Propylene glycol monomethyl ether acetate (PGMEA)

Experimental example 1. Measurement of physical properties of colored dispersion 1-1. Evaluation of Dispersibility of Pigment The dispersion characteristics of the colored dispersion liquids produced in Example 1 and Comparative Examples 1 and 2 were measured using a particle size analyzer (ELSZ-2000, Otsuka Co.), and the results (average particle size) are shown below. The results are shown in Table 3.

1-2. Storage stability evaluation The storage stability of the colored dispersions prepared in Example 1 and Comparative Examples 1 and 2 was measured by measuring the rate of change in viscosity (viscosity after 1 week at 40° C./initial viscosity×100). Is shown in Table 3 below.

The evaluation criteria are shown below.
<Evaluation criteria>
◯: Viscosity change rate of less than 105% Δ: Viscosity change rate of 105% or more, less than 110% ×: Viscosity change rate of 110% or more

Example 1, which is the colored dispersion liquid according to the present invention, showed excellent results in terms of pigment dispersibility and storage stability.

The colored dispersions of Comparative Examples 1 and 2 containing "dispersion resin A2" and "dispersion resin A2 and A3", respectively, as the dispersion resin, showed a result that the average particle size was measured to be relatively large and the dispersibility of the pigment was insufficient. The results showed that the viscosity change rate was increased and the storage stability was also poor.

Experimental example 2. Measurement of physical properties of colored photosensitive resin composition 2-1. Evaluation of Solvent Resistance of Coating Film After drying a 5 cm×5 cm glass substrate (Corning Co.) washed with a neutral detergent and water, the colored photosensitive resin produced in Examples 2 to 7 and Comparative Examples 3 to 8 above. Each composition was spin coated to a final film thickness of 3.0 μm. Then, this was placed on a heating plate and dried at a temperature of 80 to 120° C. for 1 to 2 minutes to remove the solvent. Next, exposure was performed at an exposure dose of 25 to 35 mJ/cm ² and baking was performed at 200 to 250° C. for 10 to 30 minutes to manufacture a colored substrate on which the colored photosensitive resin composition was applied to the entire surface without patterning.

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

2-2. Storage stability evaluation Storage stability was measured by measuring the rate of change in viscosity (viscosity after 3 months at 5° C./initial viscosity×100) of the colored photosensitive resin compositions produced in Examples 2 to 7 and Comparative Examples 3 to 8 above. The sex was evaluated.

The evaluation criteria are as follows, and the measurement results are shown in Table 4 below.
<Evaluation criteria>
◎: Viscosity change rate less than 105% ○: Viscosity change rate 105% or more, less than 110% △: Viscosity change rate 110% or more, less than 115% ×: Viscosity change rate 115% or more

2-3. Evaluation of residual film rate The residual film rate of the colored photosensitive resin compositions produced in Examples 2 to 7 and Comparative Examples 3 to 8 was measured, and the measurement results are shown in Table 4 below.

A 5 cm×5 cm glass substrate (Corning Co.) washed with a neutral detergent and water was post-dried, and then each of the colored photosensitive resin compositions prepared in Examples 2 to 7 and Comparative Examples 3 to 8 had a final film thickness. Was spin-coated so that the thickness was 3.0 μm. Then, this was placed on a heating plate and dried at a temperature of 80 to 120° C. for 1 to 2 minutes to remove the solvent. Next, exposure was performed at an exposure dose of 25 to 35 mJ/cm ² , and the film thickness (film thickness 1) was measured. Then, each of the substrates was developed in a developer having a concentration of 0.04% KOH and baked at 200 to 250° C. for 10 to 30 minutes to manufacture a colored substrate. The film thickness (film thickness 2) of the manufactured colored substrate was measured to confirm the residual film ratio (film thickness 2/film thickness 1×100).

2-4. Evaluation of Elastic Recovery Rate A 5 cm×5 cm glass substrate (Corning Co.) washed with a neutral detergent and water was post-dried, and then each of the colored photosensitive resin compositions prepared in Examples 2 to 7 and Comparative Examples 3 to 8 was used. Was spin-coated so that the final film thickness was 3.0 μm. Then, this was placed on a heating plate and dried at a temperature of 80 to 120° C. for 1 to 2 minutes to remove the solvent. Next, a pattern was formed by exposing at an exposure dose of 25 to 35 mJ/cm ² , and the non-exposed portion was removed using an alkaline aqueous solution. Next, it was baked at 200 to 250° C. for 10 to 30 minutes to produce a colored substrate coated with the colored photosensitive resin composition.

The thickness and height of the pattern in the standard state of the manufactured substrate are measured by a three-dimensional surface shape measuring device (SIS-2000, SNU). After that, a hardness meter (Nano-indenter HM500, Fisher) is used to push to a point where the pattern is deformed by 1 μm. A flatness indenter is used as the hardness meter, and it is pressed at a speed of 2 mN/sec. It has a holding time for 5 seconds at a point of 1 μm deformation. After that, 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 the thickness of the pattern before and after. The relative elastic recovery rate was evaluated using Comparative Example 3 as a standard (STD), and the results are shown in Table 4.

Examples 2 to 7, which are the colored photosensitive resin compositions of the present invention, showed excellent results in terms of solvent resistance, storage stability and residual film rate. In particular, the colored photosensitive resin compositions of Examples 5 to 7 containing all of the alkali-soluble resins A1 and A4 showed excellent solvent resistance, storage stability and residual film rate, and, at the same time, compared to Examples 2 to 4. The results of the evaluation of the elastic recovery rate are better.

The colored photosensitive resin compositions of Comparative Examples 3 to 8 which did not contain the colored dispersion of the present invention showed a result that the absorbance was measured to be relatively high and the solvent resistance was insufficient, and the viscosity change rate after 3 months was also high. The result was extremely poor, and the residual film rate was also relatively low.

Claims (17)

A colored photosensitive resin composition containing a colored dispersion liquid, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent,
The colored dispersion of the coloring agent, see containing a dispersion resin, and a solvent containing a copolymer of the following Formula 1,
The colorant includes an organic black pigment, a blue pigment, and a violet pigment,
The colored photosensitive resin composition, wherein the alkali-soluble resin includes a copolymer represented by the following chemical formula 1 and two or more copolymers having different epoxy equivalents.

(In Chemical Formula 1, R ₁ and R ₂ are each independently hydrogen or a methyl group, and the molar ratio of the a monomer and the b monomer is 1:20 to 20:1.) The colored photosensitive resin composition according to claim 1, wherein the organic black pigment includes at least one selected from the group consisting of lactam black, aniline black, and perylene black. The colored photosensitive resin composition according to claim 1, wherein the organic black pigment contains lactam black. The colored photosensitive resin composition according to claim 1, wherein the blue pigment does not contain a central metal. The blue pigment is C.I. I. Pigment Blue 16, 60, 63, and 66, and one or more kinds selected from the group consisting of, The colored photosensitive resin composition of Claim 4 characterized by the above-mentioned. The violet pigment is C.I. I. Pigment Violet 19, 23, 29, 31, and 37, 1 or more types selected from the group consisting of, The colored photosensitive resin composition of Claim 1 characterized by the above-mentioned. The colored photosensitive resin composition according to claim 1, further comprising a black pigment as an additional colorant. 8. The colored photosensitive resin composition according to claim 7, wherein the black pigment includes at least one selected from the group consisting of titanium black and carbon black. The organic black pigment, violet pigment, blue pigment, and black pigment in the colorant are used in a weight ratio of 1:0.08 to 2.5:0.2 to 3.3:0.12 to 1.7. The colored photosensitive resin composition according to claim 7, which is mixed. The colored photosensitive resin composition according to claim 1, wherein the dispersion resin has a weight average molecular weight of 3,000 to 100,000. The colored dispersion liquid contains 65 to 75% by weight of a colorant and 7 to 12% by weight of a dispersion resin based on the total weight of the solid content in the colored dispersion liquid, and 70% by weight of the solvent is added to the total weight of the colored dispersion liquid. The colored photosensitive resin composition according to claim 1, wherein the colored photosensitive resin composition comprises 80% by weight to 80% by weight. Colorant 13 to 60% by weight, alkali-soluble resin 5 to 60% by weight, photopolymerizable compound 5 to 50% by weight, and photopolymerization initiator, based on the total weight of the solid content in the colored photosensitive resin composition. it contains 0.1 to 20% by weight, relative to the total weight of the colored photosensitive resin composition, characterized in that it comprises 60 to 90 wt% solvent, colored photosensitive resin composition according to claim 1 .. The colored photosensitive resin composition is one selected from the group consisting of a filler, another polymer compound, a curing agent, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an agglomeration inhibitor. The colored photosensitive resin composition according to claim 1 , further comprising the above additives. A pattern layer produced from the colored photosensitive resin composition according to claim 1 . The pattern layer according to claim 14 , wherein the pattern layer is one or more selected from the group consisting of a column spacer, a black matrix, and a black column spacer. A color filter comprising the pattern layer according to claim 14 . A display device including the color filter according to claim 16 .