JP2019079048A - Coloring dispersion liquid, coloring 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

Abstract

The present invention provides 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 present invention provides a colorant containing an organic black pigment, a blue pigment, a violet pigment, and a carbon black, a dispersing resin containing an epoxy group, and a coloring dispersion containing a solvent, the coloring dispersion, an alkali-soluble resin, A photopolymerizable compound, a photopolymerization initiator, and a colored photosensitive resin composition containing a solvent, a pattern layer manufactured using the colored photosensitive resin composition, a color filter containing the pattern layer, and the color filter. And a display device including the same. [Selection diagram] None

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.

Color filters are widely used in various display devices such as imaging devices and liquid crystal displays (LCDs), and their application range is rapidly expanding. The color filters used in the image pickup device, liquid crystal display device, etc., consist of colored patterns of three colors of red (Red), green (Green) and blue (Blue), yellow (Yellow), and magenta (Magenta) , And cyan (Cyan) consisting of three colored patterns.

The coloring pattern of each of the color filters is generally formed using a coloring 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. Ru. Processing of a colored pattern using the colored photosensitive resin composition is usually performed in a lithography process.

The colored photosensitive resin is an essential material for color filters, liquid crystal display materials, organic light emitting elements, displays and the like. For example, in the case of a color filter used in a liquid crystal display, it includes pixels of red (Red), green (Green), and blue (Blue), and prevents color mixing of these pixels, or an electrode. Form a black matrix at the boundary between the colored layers of each color to hide the pattern of. In addition, the black column spacer (Black Colum Spacer, BCS) is required to have excellent solvent resistance and the property that no residue remains on the organic film at the portion directly in contact with 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 all properties such as elastic recovery required for the column spacer and light blocking property required for the black matrix are satisfied. Discloses a colored photosensitive resin composition and a black column spacer. However, it is not sufficient in improving solvent resistance and storage stability.

Korean Registered Patent No. 10-1658374

The present invention has been made to solve the problems of the prior art described above, and it is an object of the present invention to provide a colored dispersion having excellent pigment dispersibility and storage stability.

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

Furthermore, the present invention has an object 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.

In order to achieve the above purpose
The present invention is a colored dispersion comprising a colorant, a dispersing resin, and a solvent, wherein
The colorant includes organic black pigment, blue pigment, and violet pigment.
The dispersion resin may provide a colored dispersion liquid including a copolymer of Formula 1 below.

(In 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.)

Further, the present invention provides a colored photosensitive resin composition comprising the colored dispersion liquid of the present invention, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.

Moreover, this invention provides the pattern layer manufactured with the colored photosensitive resin composition of the said this invention.

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

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

The colored dispersion liquid of the present invention has excellent effects on pigment dispersibility and storage stability by including a dispersion resin containing the copolymer of Formula 1.

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

Furthermore, in the colored photosensitive resin composition of the present invention, by using a mixture of two or more kinds of copolymers having different epoxy equivalents, a coating film produced using this has an excellent elastic recovery rate. Have an effect.

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

The present invention is a colored dispersion comprising a colorant, a dispersing resin, and a solvent, wherein
The colorant includes organic black pigment, blue pigment, and violet pigment.
The dispersion resin relates to a colored dispersion liquid including a copolymer of the following chemical formula 1.

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

The colored dispersion liquid of the present invention can improve the dispersibility and storage stability of the pigment by using the dispersion resin containing the copolymer of the above-mentioned chemical formula 1, and further, a colored photosensitive resin composition to which the same is applied Reliability such as solvent resistance and storage stability can be improved.

In the case of producing a colored dispersion using the dispersion resin containing the copolymer represented by Formula 1, it is possible to obtain a colored dispersion in a state in which the dispersion resin is uniformly coated on the surface of the pigment. Therefore, the colored photosensitive resin composition containing such a colored dispersion liquid improves the solvent resistance by preventing the pigment from eluting into the solvent by containing the pigment particles coated with the dispersing resin. 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 comprises 65 to 75% by weight of a colorant and 7 to 12% by weight of a dispersing resin based on the total weight of solids in the colored dispersion, relative to 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 range, a colored dispersion having excellent pigment dispersibility and storage stability can be produced.

In addition, the colored dispersion may additionally contain a dispersant. By adding a dispersing agent to the coloring dispersion and performing dispersion treatment, it is possible to obtain a coloring dispersion in which the pigment is more uniformly dispersed in the solution.

The present invention also relates to a colored photosensitive resin composition comprising the colored dispersion, 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 a colorant.

In addition, the colored photosensitive resin composition of the present invention may include the copolymer of the above-mentioned 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.

Furthermore, the colored photosensitive resin composition of the present invention uses 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 manufactured 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 light-shielding property to 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 one or more selected from the group consisting of lactam black, aniline black and perylene black, and preferably contains lactam black. By including the organic black pigment, it is possible to improve the optical density and not to affect the infrared region, and to improve the dielectric constant and the transmittance.

The violet pigment plays a role of decreasing the transmittance in the 400 to 600 nm region to improve the optical density (OD). Moreover, content of an organic black pigment can be reduced by use of the said violet pigment, and the reliability of a coloring photosensitive resin composition can be improved. Although the said violet pigment does not specifically limit the kind, C.I. I. It is preferable to use one or more selected from the group consisting of C.I. I. Most preferably, the pigment violet 29 is used.

The blue pigment is a compound containing no central metal, and the presence of the central metal can affect the driving of the liquid crystal, but in the present invention, by using a compound containing no central metal as the blue pigment, equipment is It is possible to secure the merit of driving. In the present invention, the type of blue pigment is not particularly limited as long as it is a compound not containing a central metal. I. C.I. pigment blue 16, 60, 63, and 66, preferably selected from the group consisting of C.I. I. Most preferably, the pigment blue 60 is used.

The colored photosensitive resin composition of the present invention can also contain a black pigment as an additional colorant. The type of black pigment is not particularly limited as long as it has a light-shielding property with visible light, but it is preferable to use one or more types selected from the group consisting of titanium black and carbon black It is more preferable to use it including carbon black. The carbon black is not particularly limited as long as it is a light-shielding pigment, and known carbon blacks can be used. Specific examples of 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 may have lower conductivity than uncoated carbon black, and may have excellent electrical properties when forming a black matrix or column spacer. It is possible to impart insulation.

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 13 to 60% by weight of the coloring agent is contained, the optical density and the reliability are excellent.

More specifically, the colorant is an organic black pigment, a violet pigment, a blue pigment, and a black pigment in a ratio of 1: 0.08 to 2.5: 0.2 to 3.3: 0.12 to 1.7. It can be mixed at a weight ratio of Moreover, Preferably it can mix in the weight ratio of 1: 0.27-1: 0.47-1.88: 0.27-0.87. When the organic black pigment, the violet pigment, the blue pigment, and the black pigment are contained in the weight ratio, a colored photosensitive resin composition excellent in optical density and reliability can be obtained.

Dispersion resin The dispersion resin coats the pigment particles present in the coloring dispersion with the dispersion resin to prevent dissolution in the solvent, suppresses aggregation between the pigment particles, and causes aggregation among the pigment particles. It plays a role of preventing viscosity increase.

The dispersion resin of the present invention comprises a copolymer of the following chemical formula 1.

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

In the present invention, the solvent resistance, the storage stability and the residual film ratio can be improved by containing the copolymer represented by 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. It is also good.

The acid value of the dispersion resin is 50 to 200 mg KOH / g based on 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 the chemical formula 1 and other copolymerizable monomers.

Specific examples of the monomer copolymerizable with the chemical formula 1 of the dispersion resin include styrene, vinyl toluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, aromatic vinyl compounds such as o-vinylbenzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether; methyl ( Meta) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl Alkyl (meth) acrylates such as meth) acrylate; cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.02,6] decane-8-yl Alicyclic (meth) acrylates such as (meth) acrylate, 2-dicyclopentanyloxyethyl (meth) acrylate and isobornyl (meth) acrylate; aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate ) Acrylates; Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; N-cyclohexyl maleimide, N-benzyl maleimide, N-phenyl maleimide Reimide, N-o-hydroxyphenyl maleimide, N-m-hydroxyphenyl maleimide, N-p-hydroxyphenyl maleimide, N-o-methylphenyl maleimide, N-m-methylphenyl maleimide, N-p-methylphenyl maleimide, N-substituted maleimide compounds such as N-o-methoxyphenyl maleimide, N-m-methoxyphenyl maleimide, N-p-methoxyphenyl maleimide, etc .; unsaturated such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide Amide compounds; 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyl oxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyl oxetane, 3- (methacryloyloxymethyl) -2 Phenyl oxetane, 2- (methacryloyloxy) oxetane, such as 2- (methacryloyloxy methyl) -4-trifluoromethyl Oki unsaturated oxetane compounds such as cetane the like.

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

The dispersion resin of the present invention may, if necessary, be additionally mixed and used with various other known alkali-soluble resins generally 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 solids in the colored dispersion. If the content of the dispersion resin is within the above range, pigment particles are uniformly dispersed, aggregation between pigment particles can be prevented, and solvent resistance and storage stability are improved, which is preferable.

Dispersing agent The dispersing agent is added for deaggregation and stability maintenance of the pigment, and specific examples of the dispersing agent include cationic, anionic, nonionic, polyester, Polyamine-based surfactants and the like can be mentioned, and these can be used alone or in combination of two or more.

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

Specific examples of the anionic surfactant include higher alcohol sulfate salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzene sulfonate, And alkylaryl sulfonates such as sodium dodecyl naphthalene sulfonate and the like.

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

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

The dispersant preferably contains an acrylate dispersant (hereinafter, acrylate dispersant) containing butyl methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA). It is preferable to use the acrylate type dispersant manufactured by the living control method, and as a commercial product, DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150, etc. are mentioned. The acrylate dispersants may be used alone or in combination of two or more.

As the dispersant, in addition to acrylate dispersants, pigment dispersants of other resin types can also be used. As the other resin type dispersants, known resin type dispersants, in particular, polycarboxylic acid esters represented by polyurethanes and polyacrylates, unsaturated polyamides, polycarboxylic acids and (partially) polycarboxylic acids Amine salt, ammonium salt of polycarboxylic acid, alkylamine salt of polycarboxylic acid, polysiloxane, long chain polyaminoamide phosphate salt, ester of hydroxyl group-containing polycarboxylic acid, and modified products thereof, or free ) Oily dispersants such as amides formed by the reaction of polyesters having carboxyl groups with poly (lower alkylenimines) or salts thereof; (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acids ) Acrylate ester copolymer, styrene-maleic Copolymers, polyvinyl alcohol or water-soluble resin or a water-soluble polymeric compounds such as polyvinyl pyrrolidone; polyesters; modified polyacrylate; ethylene oxide / propylene oxide addition product of; and and phosphate esters.

Commercially available dispersants of the above-mentioned other resin types include, for example, trade names of BYK (BIC) Chemie Co., Ltd. as a cationic resin dispersant: 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 name: 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-44 0, EFKA-4406, EFKA-4510, EFKA-4800; trade name of Lubirzol: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204 / 10; trade name of Kawaken Fine Chemical Co., Ltd .: HINOACT T-6000, Hinoac T-7000, Hinoac T-8000; trade name of Ajinomoto Co., Ltd .: AJISPAR PB-821, AJISPER PB-822, AJISPARB PB-823; trade name of Kyoeisha Chemical Co., Ltd. Examples include DOPA-15BHF, flowlen DOPA-33, flowlen DOPA-44 and the like.

In addition to the above-mentioned acrylate dispersants, dispersants of other resin types can be used singly or in combination of two or more, and can also be used in combination with the acrylate dispersant.

The dispersant is included in an amount of more than 0 and 1 part by weight, preferably 0.05 to 0.5 parts by weight, with respect to 1 part by weight of the colorant. It is preferable that the dispersing agent is contained in an amount of 0 or more and 1 part by weight or less, since a uniformly dispersed pigment can be obtained.

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 development step. In the present invention, the alkali-soluble resin is not particularly limited, but is preferably a monomer having a carboxyl group and a copolymer of 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 acids and unsaturated dicarboxylic acids. Specific examples of these include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid and the like. The monomer which has the said carboxyl group is a compound which has a carbon-carbon unsaturated bond, and can use individually or 2 types or more, respectively.

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 And carboxylate compounds.

Specific examples of the vinyl compound include styrene, α-methylstyrene, vinyl toluene 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 -Phenylthioethyl acrylate etc. are mentioned. An aminoethyl acrylate etc. are mentioned as a specific example of the said unsaturated aminoalkyl carboxylate compound. A glycidyl methacrylate etc. are mentioned as a specific example of the said unsaturated glycidyl carboxylate compound. 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, azobisdimethylvaleronitrile and the like. 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 ester An oxetane etc. are mentioned. The other monomers may be used alone or in combination of two or more.

In addition, the alkali-soluble resin may be characterized by containing the copolymer of the formula 1, and the alkali-soluble resin may contain the copolymer of the formula 1 containing an epoxy group, so that the solvent resistance and Storage stability can be improved.

In the present invention, the alkali-soluble resin can be used as a copolymer of the above-mentioned formula 1 by mixing two or more kinds of copolymers having different epoxy equivalents with each other. Preferably, the copolymer (b1) is used And the copolymer (b2) can be mixed and used.

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

Furthermore, the copolymers (b1) and (b2) are contained in a weight ratio of 1: 0.1-5, preferably in a weight ratio of 1: 0.25-3. When the copolymers (b1) and (b2) satisfy the range of the epoxy equivalent and the range of the weight ratio, they are preferable in that they can exhibit excellent elastic recovery.

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 the solid content in the colored photosensitive resin composition. If the content of the alkali-soluble resin is within the above range, pattern formation is easy and resolution and 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 alkali-soluble resin and the photopolymerizable compound. When the alkali-soluble resin is mixed within the above range, the solubility is sufficient and pattern formation is easy, film reduction of the pixel portion of the exposed portion is prevented at the time of development, and coloring of the non-pixel portion is excellent. A photosensitive resin composition can be provided.

Photopolymerizable Compound The photopolymerizable compound contains an unsaturated bond, and causes a photoreaction with a photopolymerization initiator to form a colored photosensitive resin layer, which is a photopolymerization initiator to be described later. 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, preferably 4 to 8 functional groups.

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

Among the above polyfunctional monomers, specific examples of tetrafunctional monomers include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, ditrimethylolpropane tetraacrylate, ditrimethylolpropane tetramethacrylate, dipentaerythritol tetraacrylate, and tetra 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, dipentaerythritol monohydroxypentamethacrylate, etc. Can be mentioned.

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

Among the above polyfunctional monomers, specific examples of 7 to 10 functional monomers include tripentaerythritol octamethacrylate, tripentaerythritol octaacrylate, tetrapentaerythritol heptamethacrylate, and tetrapentaerythritol heptaacrylate Can be mentioned.

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 the solid content 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 may be used without limitation as long as it is capable of polymerizing a photopolymerizable compound, but preferably, polymerization properties, initiation efficiency, absorption wavelength, availability, At least one compound selected from the group consisting of acetophenone compounds, benzoin compounds, benzophenone compounds, triazine compounds, biimidazole compounds, oxime compounds, and thioxanthone compounds in consideration of the price etc. May be

Specific examples of the acetophenone-based compound include, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2) -Hydroxyethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl 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 It is.

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 compounds include, for example, benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (Tert-butylperoxycarbonyl) benzophenone, and 2,4,6-trimethyl benzophenone and the like.

Specific examples of the triazine compound include, for example, 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 Etc. trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Specifically as the biimidazole compound, for example, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2, 3-Dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (alkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, 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 by 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.

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 or OXE02 from BASF Corporation. .

Specific examples of the thioxanthone compound include 2-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, and 1-chloro-4-propoxy thioxanthone.

The said photoinitiator can be used individually or in mixture of 2 or more types.

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.

The sensitivity of the colored photosensitive resin composition is enhanced within the range of 0.1 to 20% by weight, and the strength of the pixel portion formed using the colored photosensitive resin composition and the smoothness on the surface of the pixel portion It becomes good.

In the present invention, a photopolymerization initiator can be additionally used as the photopolymerization initiator.

The said photopolymerization start adjuvant is a compound used in order to accelerate | stimulate superposition | polymerization of the photopolymerizable compound in which superposition | polymerization was started by the photopolymerization initiator, For example, an amine compound or The alkoxyanthracene type compound etc. are mentioned.

Specific examples of the amine compound include, for example, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, benzoate 2-dimethylaminoethyl acid, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethyl paratoluidine, 4,4'-bis (dimethylamino) benzphenone (common name, Michler's ketone), 4,4'-bis (bis (dimethylamino) benzphenone) Diethylamino) benzophenone, and 4,4'- bis (ethyl methyl amino) benzophenone etc. is mentioned, Among them, 4,4 '-bis (diethylamino) benzophenone is preferred.

Specifically, examples of the alkoxyanthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-. Diethoxyanthracene and the like can be mentioned.

Moreover, a commercial thing can be used as a photopolymerization start adjuvant, As a commercial photopolymerization start adjuvant, a brand name "EAB-F" (a maker: Hodogaya Chemical Industry Co., Ltd.) etc. are mentioned.

When using the said photopolymerization start adjuvant, it is preferable to use by more than 0 normally 10 mol or less and 0.01-5 mol normally with respect to 1 mol of photoinitiators. When the photopolymerization start auxiliary agent is used in the range of more than 0 and not more than 10 moles, the sensitivity of the colored photosensitive resin composition is further enhanced, and the productivity of the color filter formed using the colored photosensitive resin composition is improved. it can.

Solvent The solvent used in a conventional colored photosensitive resin composition, as long as it is effective and does not react to dissolve other components contained in the colored photosensitive resin composition. Can be used without particular limitation, and in particular, ethers, acetates, aromatic hydrocarbons, ketones, alcohols, or esters are 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;
And 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-methoxyacetate. Butyl acetate, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, methyl 3-methoxy propionate, 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 diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol And 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 alcohol include ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, 4-hydroxy-4-methyl-2-pentanone and the like.

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

The said solvent can be used individually or in mixture of 2 or more types, respectively.

The solvent is preferably an organic solvent having a boiling point of 100 ° C. to 200 ° C. in terms of coating property and drying property, and for example, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxy Ethyl propionate, methyl 3-methoxypropionate and the like can be mentioned.

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 apparatus such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), and an inkjet, Applicability becomes good.

Additives The colored photosensitive resin composition of the present invention includes, in addition to the components described above, other additives as long as the object of the present invention is not impaired, according to the needs of a common engineer.

Specifically, the additive comprises, 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 aggregation inhibitor. It may additionally contain one or more additives selected from the group.

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 Etc.

The thermal initiator causes a curing reaction by heat to play a role of maximizing the initiation efficiency. The thermal initiator may be a peroxide compound.

Although the specific type of the thermal initiator is not particularly limited, tetramethylbutylperoxyneodecanoate (ex. Perocta ND, manufactured by NOF (made)), bis (4-butylcyclohexyl) peroxydicarbonate (ex. Peroyl) TCP, NOF (made), di (2-ethylhexyl) peroxycarbonate, butyl peroxy neodecanoate (ex. Perbutyl ND, NOF (made)), dipropyl peroxydicarbonate (ex. Peroyl NPP, NOF) (Made), diisopropyl peroxydicarbonate (ex. Peroyl IPP, made by NOF (made)), diethoxyethyl peroxydicarbonate (ex. Peroyl EEP, made by NOF (made)), diethoxyhexyl peroxydicarbonate (Ex. Peroyl OEP, NOF (made)), hexyl peroxydicarbonate (ex. Perhexyl ND, NOF (made)), dimethoxybutyl peroxydicarbonate (ex. Peroyl MBP, NOF (made)), bis (bis. 3-methoxy-3-methoxybutyl) peroxydicarbonate (ex. Peroyl SOP, manufactured by NOF), dibutylperoxydicarbonate, dicetylperoxydicarbonate, dimyristyl peroxydicarbonate, 1,1, 3, 3-Tetramethylbutylperoxypivalate, hexylperoxypivalate (ex. Perhexyl PV, manufactured by NOF company), butylperoxypivalate (Ex. Perbutyl, NOF (made)), trimethylhexanoyl peroxide (ex. Peroyl 355, NOF (made)), dimethylhydroxybutyl peroxy neodecanoate (ex. Luperox 610M75, Atofina (made)), amyl peroxy Neodecanoate (ex. Luperox 546M75, Atofina (made)), Butylperoxyneodecanoate (ex. Luperox 10M75, Atofina (made)), t-Butylperoxyneoheptanoate, amyl peroxypivalate (pivalate) (Ex. Luperox 546 M 75, Alofina (made)), t-butyl peroxypivalate, t-amyl peroxy-2-ethylhexanoate, t-butyl peroxy Ci-2-ethylhexanoate, 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-butyl hydroperoxide, tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, cumene hydride From the group consisting of xyl peroxide, dicumyl peroxide, lauroyl peroxide, 2,4-pentanedione peroxide, tert-butyl peracetate, peracetic acid, and potassium persulfate It may be one or more selected.

The content of the thermal initiator is preferably 1 to 10% by weight, and more preferably 1 to 5% by weight, based on the total weight of the solid content in the colored photosensitive resin composition. When it contains in the said content, it is preferable by processability and an undercut.

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

In the curing agent, 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 resin, and other aromatic compounds. Epoxy resins, alicyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, or brominated derivatives of such epoxy resins, epoxy resins and aliphatic, alicyclic or aromatic epoxy resins other than brominated derivatives thereof Compounds, butadiene (co) polymer epoxidates, isoprene (co) polymer epoxidates, glycidyl (meth) acrylate (co) polymers, triglycidyl isocyanurate and the like can be mentioned.

As a specific example of the oxetane compound in the said hardening | curing agent, carbonate bisoxetane, xylene bis oxetane, adipate bis oxetane, terephthalate bis oxetane, cyclohexane dicarboxylic acid bis oxetane etc. are mentioned.

The curing agent may be used in combination with a curing agent capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound. Examples of the curing auxiliary compound include polyvalent carboxylic acids, polyvalent carboxylic acid anhydrides, and an acid generator. The polyvalent carboxylic acid anhydrides may be commercially available as an epoxy resin curing agent. As a specific example of the epoxy resin curing agent, as a commercial product, trade name (Adeca Hardener EH-700) (produced by Adeca Kogyo Co., Ltd.), trade name (Rikasid HH) (produced by Shin Nippon Rika Co., Ltd.) Name (MH-700) (manufactured by Shin Nippon 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 for example, silicone type, fluorine type, ester type, cation type, anion type, nonionic type, Surfactants such as amphoteric surfactants can be used, and silicone surfactants or fluorosurfactants can be preferably used.

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

Other examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes, polyethylene imines Besides, as commercial products, KP (Shin-Etsu Chemical Co., Ltd.), Polyflow (Keiei Chemical Co., Ltd.), F-Top (Tochem Products), Megafuck (Dainippon Ink Chemical Co., Ltd.), Florard (Sumitomo 3 M Co., Ltd.), Asahi Guard, Surfron (above, Asahi Glass Co., Ltd.), Sols Spas (Zeneca Co., Ltd.), EFKA (EFKACHEMICALS), PB 821 (Ajinomoto Co.) and the like.

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

The adhesion promoter is an additive used to promote coating and adhesion to a substrate, and is a reaction selected from the group consisting of carboxyl group, methacryloyl group, isocyanate group, epoxy group, and a combination thereof. It is possible to include a silane coupling agent containing a functional substituent. Specifically, the silane coupling agent is, 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 Vinyltriacetoxysilane and γ- isocyanatepropyltriethoxysilane and the like.

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 UV absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole and alkoxybenzophenone.

A sodium polyacrylate etc. are mentioned as a specific example of the said aggregation inhibitor.

The additive may be contained 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 the production of a display, preferably a black matrix of a liquid crystal display, a column spacer for holding a cell gap, or a black column spacer.

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

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. This means that the black matrix and the column spacer are integrally formed in one pattern.

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

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 color filter itself or may be 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 (PC) Or the like.

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

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

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

The present invention also relates to a display 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 including a cured product of the above-described colored photosensitive resin composition.

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

When the liquid crystal display device includes a color filter including the pattern layer according to the present invention, there is an advantage that the shielding property and the reliability are excellent.

The usual patterning process to form black matrix, column spacer or black column spacer by photolithography method is
a) applying a colored photosensitive resin composition to a substrate;
b) prebaking step of drying the solvent;
c) applying a photo mask on the obtained coating and irradiating an actinic ray to cure the exposed portion;
d) performing a developing step of dissolving the unexposed area using an alkaline aqueous solution;
e) comprising a drying and post-baking step.

A glass substrate or a polymer plate is used as the substrate. As the glass substrate, particularly, soda lime glass, glass containing barium or strontium, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, quartz or the like can be preferably used. Moreover, as a polymer board, a polycarbonate, an acryl, a polyethylene terephthalate, polyether sulfide, or a polysulfone etc. are mentioned.

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

Pre-baking is performed by heating with an oven, a hot plate or the like. At this time, the heating temperature and heating time in prebaking are suitably selected according to the solvent to be used, for example, are performed at the temperature of 80-150 degreeC for 1 to 30 minutes.

Further, the exposure to be performed after the pre-baking is performed by the exposure unit and exposed through the photomask to sensitize only the portion corresponding to the pattern. At this time, light to be emitted may be, for example, visible light, ultraviolet light, X-rays, and electron beams.

It is carried out for the purpose of removing the colored photosensitive resin composition of the non-removed part of the alkali-developed non-exposed part after exposure, and a desired pattern is formed by this development. As a developing solution 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 a carbonate such as sodium carbonate, potassium carbonate or lithium carbonate, the developing unit or ultrasonic cleaning within a temperature of 10 to 50 ° C., preferably 20 to 40 ° C. Do this using a machine.

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

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

Moreover, as film thickness of a column spacer and a black column spacer, 0.1 micrometer-8 micrometers are preferable, 0.1 micrometer-6 micrometers are more preferable, and 0.1 micrometer-4 micrometers are especially preferable.

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

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

Production Example 1 Preparation of Dispersion Resin A1 277 g of methoxybutyl acetate was charged into a 1 L separate type flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet 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 of 301 g of a mixture of decane-8-yl acrylate mixed at a molar ratio of 50:50, 49 g of methacrylic acid, and 23 g of azobisdimethylvaleronitrile in 350 g of methoxybutyl acetate was prepared. 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 A1 [solid content (NV) 35.0% by weight]. The acid value (dry) of the manufactured dispersion resin A1 is 69.8 KOHmg / g, the weight average molecular weight (Mw) is 12,300, the degree of dispersion (Mw / Mn) is 2.1, and the epoxy equivalent is 1,130. there were.

Production Example 2 Preparation of Dispersion Resin A2 A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet was prepared. As a monomer dropping funnel, 14.4 parts by weight (0.2 mol) of acrylic acid, 140.8 parts by weight (0.8 mol) of benzyl methacrylate, 2.0 parts by weight of t-butylperoxy-2-ethylhexanoate, 40.0 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) was mixed and prepared. As a chain transfer agent dropping tank, 3.0 parts by weight of n-dodecanethiol and 24.0 parts by weight of PGMEA were mixed and prepared. After this, 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 allowed to proceed for 4 hours while maintaining the temperature at 70 ° C. After 1 hour, the temperature was raised to 90 ° C. and the reaction was allowed to proceed for 8 hours to produce a 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 degree of dispersion (Mw / Mn) was 2.8.

Production Example 3 Preparation of Dispersion Resin A3 A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet was prepared. Monomer dropping funnel: 52.1 parts by weight (0.25 mol) of 2-phenylthioethyl acrylate, 44.0 parts by weight (0.25 mol) of benzyl methacrylate, 12.9 parts by weight (0.15 mol) of methacrylic acid A mixture of 41.3 parts by weight (0.35 mol) of vinyl toluene, 4.0 parts by weight of t-butylperoxy-2-ethylhexanoate, and 40.0 parts by weight of PGMEA was prepared. As a chain transfer agent dropping tank, 6.0 parts by weight of n-dodecanethiol and 24.0 parts by weight of PGMEA were mixed and prepared. After this, 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 allowed to proceed for 2 hours while maintaining the temperature at 90 ° C. After 1 hour, the temperature was raised to 110 ° C. and the reaction was allowed to proceed for 8 hours to produce a 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 degree of dispersion (Mw / Mn) was 2.4.

Production Example 4 Preparation of Alkali-Soluble Resin A4 277 g of methoxybutyl acetate was charged into a 1 L separate-type flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet 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 of 321 g of a mixture of decane-8-yl acrylate mixed at a molar ratio of 50:50, 32 g of methacrylic acid, and 20 g of azobisdimethylvaleronitrile in 350 g of methoxybutyl acetate was prepared. 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 is 59.8 KOHmg / g, the weight average molecular weight (Mw) is 9,300, the dispersion degree (Mw / Mn) is 1.9, and the epoxy equivalent is 665. The

Example 1 and Comparative Examples 1 and 2
A mixture of the dispersion resin, a colorant, a dispersant and a solvent was prepared. Next, zirconia beads (average particle diameter 0.1 mm) were mixed with the above mixture at a weight ratio of 50:50, and dispersed using a bead mill for 6 hours. After completion of the dispersion, the dispersion was filtered to prepare a colored dispersion, the contents of which are 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 A2 prepared in Preparation Example 1: Dispersion resin A3 prepared in Preparation Example 2: Dispersed resin dispersion prepared in Preparation Example 3: DisperBYK-2000 (BYK Co.)
Solvent: Propylene glycol monomethyl ether acetate (PGMEA)

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

Colored dispersion B1: Colored dispersion B2 prepared in Example 1: Colored dispersion B3 prepared in Comparative Example 1: Colored dispersion B prepared in Comparative Example 2 Alkali-soluble resin A1: Resin A2 prepared in Preparation Example 1: Resin A3 prepared in Preparation Example 2: Resin A4 prepared in Preparation Example 3: resin photopolymerizable compound prepared in Preparation Example 4: Dipentaerythritol hexaacrylate (DPHA) (Nippon Kayaku Co., Ltd.)
Photopolymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (Irgacure 369: manufactured by Ciba)
Additive: DisperBYK-163 (BYK)
Solvent: Propylene glycol monomethyl ether acetate (PGMEA)

Experimental Example 1 Measurement of Physical Properties of Colored Dispersion 1-1. Evaluation of Dispersion of Pigment The dispersion characteristics of the colored dispersion prepared in Example 1 and Comparative Examples 1 and 2 were measured using a particle sizer (ELSZ-2000, Otsuka Co., Ltd.), and the results (average particle size) were as follows: It is shown in Table 3.

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

Evaluation criteria are shown as follows.
<Evaluation criteria>
○: Viscosity change rate less than 105% Δ: Viscosity change rate 105% or more, less than 110% ×: Viscosity change rate 110% or more

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

In the colored dispersions of Comparative Examples 1 and 2 containing "Dispersion Resin A2" and "Dispersion Resin A2 and A3", respectively, which are not "Dispersion Resin A1", the average particle size is measured relatively large, and the result of insufficient pigment dispersibility is In addition, the viscosity change rate increased and the storage stability was not good.

Experimental Example 2 Measurement of physical properties of colored photosensitive resin composition 2-1. Evaluation of solvent resistance of coating film After drying of a 5 cm × 5 cm glass substrate (Corning Co.) washed with a neutral detergent and water, the colored photosensitive resin produced in the above Examples 2 to 7 and Comparative Examples 3 to 8 Each composition was spin coated to a final film thickness of 3.0 μm. Then, it 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, it exposed by exposure amount 25-35 mJ / cm < ² >, baked at 200-250 degreeC for 10 to 30 minutes, and produced the colored substrate by which the coloring photosensitive resin composition was apply | coated to the whole surface without a pattern.

The substrate was cut into a size of 3 cm × 3 cm, and immersed in a 100 ° C. N-Methyl pyrolidone (NMP) solvent for 60 minutes. Thereafter, only the NMP solvent was extracted, and then the absorbance at a visible light wavelength was measured using a UV-vis spectrometer (UV-2600, Shimadzu) to evaluate the solvent resistance. The measurement results of absorbance are shown in Table 4 below.

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

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% Δ: 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 manufactured in Examples 2 to 7 and Comparative Examples 3 to 8 was measured, and the measurement results are shown in Table 4 below.

After post-drying a 5 cm × 5 cm glass substrate (Corning Inc.) washed with a neutral detergent and water, the film thickness of each of the colored photosensitive resin compositions produced in Examples 2 to 7 and Comparative Examples 3 to 8 was final film thickness It spin-coated so that it might be set to 3.0 micrometers. Then, it 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, it exposed by exposure amount 25-35 mJ / cm < ² >, and measured film thickness (film thickness 1). Thereafter, the substrate 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 produce a colored substrate. The film thickness (film thickness 2) of the manufactured colored substrate was measured, and the residual film ratio (film thickness 2 / film thickness 1 × 100) was confirmed.

2-4. Evaluation of Elastic Recovery Rate After a 5 cm × 5 cm glass substrate (Corning Inc.) washed with a neutral detergent and water was post-dried, the colored photosensitive resin compositions produced in Examples 2 to 7 and Comparative Examples 3 to 8 were each prepared. Was spin-coated to a final film thickness of 3.0 μm. Then, it 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, it exposed by exposure amount 25-35 mJ / cm < ² >, the pattern was formed, and the non-exposed part was removed using alkaline aqueous solution. Next, it baked at 200-250 degreeC for 10 to 30 minutes, and manufactured the coloring board | substrate with which the coloring photosensitive resin composition was apply | coated.

The thickness and height of the pattern in a reference state are measured on the produced substrate by a three-dimensional surface shape measuring device (SIS-2000, SNU). Thereafter, using a hardness tester (Nano-indenter HM500, Fisher), the pattern is pressed to a point where the pattern is deformed by 1 μm. The hardness tester uses a flat indenter and presses at a speed of 2 mN / sec. It has Holding Time for 5 seconds at the point of 1 μm deformation. After this, the thickness and height of the pattern were measured using a three-dimensional surface shape measurement device (SIS-2000, manufactured by SNU), and the elastic recovery rate was measured by the change in the thickness of the pattern before and after. The relative elastic recovery 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, all showed excellent results in solvent resistance, storage stability and residual film rate. In particular, the colored photosensitive resin compositions of Examples 5 to 7 which contain all the alkali-soluble resins A1 and A4 show excellent solvent resistance, storage stability and residual film ratio while being compared with Examples 2 to 4 The evaluation results of the elastic recovery rate are shown.

The colored photosensitive resin compositions of Comparative Examples 3 to 8 which do not contain the colored dispersion liquid of the present invention exhibit relatively high absorbance and show insufficient solvent resistance, and also the viscosity change rate after 3 months. The results were extremely bad, and the residual film rate was relatively low.

Claims (20)

A colored dispersion comprising a colorant, a dispersing resin, and a solvent, wherein
The colorant includes organic black pigment, blue pigment, and violet pigment.
A colored dispersion liquid, characterized in that the dispersion resin comprises a copolymer of the following chemical formula 1:

(In the above Chemical Formula 1, R ₁ and R ₂ are each independently hydrogen or a methyl group, and the molar ratio of a monomer and b monomer is 1:20 to 20: 1.) The colored dispersion according to claim 1, wherein the organic black pigment comprises one or more selected from the group consisting of lactam black, aniline black and perylene black. The colored dispersion according to claim 1, wherein the organic black pigment comprises lactam black. The colored dispersion according to claim 1, wherein the blue pigment does not contain a central metal. The blue pigment is C.I. I. The colored dispersion according to claim 4, characterized in that it contains one or more selected from the group consisting of C.I. pigment blue 16, 60, 63 and 66. The violet pigment is C.I. I. The colored dispersion according to claim 1, characterized in that it contains one or more selected from the group consisting of C.I. Pigment Violet 19, 23, 29, 31, and 37. The colored dispersion according to claim 1, further comprising a black pigment as an additional colorant. The colored dispersion according to claim 7, wherein the black pigment comprises one or more selected from the group consisting of titanium black and carbon black. The organic black pigment, the violet pigment, the blue pigment and the black pigment in the colorant have a weight ratio of 1: 0.08 to 2.5: 0.2 to 3.3: 0.12 to 1.7. The colored dispersion according to claim 7, characterized in that it is mixed. The colored dispersion according to claim 1, wherein the weight average molecular weight of the dispersion resin is 3,000 to 100,000. The coloring dispersion contains 65 to 75% by weight of a colorant and 7 to 12% by weight of a dispersing resin based on the total weight of solids in the coloring dispersion, and the solvent 70 based on the total weight of the coloring dispersion. A colored dispersion according to claim 1, characterized in that it comprises -80% by weight. A colored photosensitive resin composition comprising the colored dispersion according to claim 1, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The colored photosensitive resin composition according to claim 12, wherein the alkali-soluble resin comprises a copolymer represented by Formula 1 below:

(In the chemical formula 1, R ₁ and R ₂ are each independently hydrogen or a methyl group, and in the chemical formula 1, the molar ratio of a monomer and b monomer is 1:20 to 20: 1. Is) 13 to 60% by weight of a colorant, 5 to 60% by weight of an alkali-soluble resin, 5 to 50% by weight of a photopolymerizable compound, and a photopolymerization initiator based on the total weight of solid components in the colored photosensitive resin composition The colored photosensitive resin composition according to claim 12, comprising 0.1 to 20% by weight, and comprising 60 to 90% by weight of a solvent based on the total weight of the colored photosensitive resin composition. . 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 light absorber, and an aggregation inhibitor. The colored photosensitive resin composition according to claim 12, wherein the above additive is additionally contained. The colored photosensitive resin composition according to claim 13, wherein the alkali-soluble resin comprises two or more kinds of copolymers having different epoxy equivalents. The pattern layer manufactured with the colored photosensitive resin composition of Claim 12. The patterned layer according to claim 17, wherein the patterned layer is at least one 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 17. A display device comprising the color filter according to claim 19.