JP2019086781A - Coloring photosensitive resin composition, color filter manufactured using the same, and display device including color filter - Google Patents

Abstract

To provide a coloring photosensitive resin composition, a color filter manufactured using the same, and a display device including the color filter.SOLUTION: There are provided a coloring photosensitive resin composition that contains (A) a coloring agent, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, and (E) a solvent, in which a flattening characteristic (DOP) value calculated by Expression 1 of the film formed of the coloring photosensitive resin composition is 15-75%; a color filter that is produced using the same and contains a black matrix, a column spacer or a black column spacer; and a display device including the color filter. [Expression 1] DOP(%)={(a-d)/a}×100, 0≤d≤1.5 um, d≤a≤b.SELECTED DRAWING: Figure 1

Description

The present invention relates to a colored photosensitive resin composition, a color filter manufactured using the composition, 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. The processing of the 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. As an example, in a color filter of a color liquid crystal display, a light shielding layer using a black photosensitive composition is formed at the boundary between colored layers in order to enhance the contrast of red, green and blue and the coloring effect. In addition, recently, not only the role of the black matrix but also spacers for holding the cell gap are required to be formed on the array substrate to enable various roles at one time. This requires not only the optical effect for basic light shielding, but also the properties with good modulus and reliability.

In order to meet such requirements, Patent Document 1 describes a colored photosensitive resin composition having improved elastic recovery, resolution, and chemical resistance when forming a cured film. However, the prior art is not only insufficient in the NMP elution reliability using a common copolymer, but does not completely solve the problem of process margin even in the realization of the step. Therefore, there is a need to develop a more improved colored photosensitive resin composition.

Korean Registered Patent No. 10-1658374

The present invention has been made to solve the above-mentioned problems of the prior art, and includes a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, and has a leveling property (degree) It is an object of the present invention to provide a colored photosensitive resin composition not only excellent in planarity (DOP) and light blocking properties but also excellent in elastic recovery, pattern shape and chemical resistance, and resolution.

The present invention also provides a color filter including a black matrix and / or a column spacer, in which a column spacer and a black matrix are simultaneously formed integrally using the colored photosensitive resin composition described above, and a liquid crystal display device comprising the color filter. Intended to provide.

The present invention is a colored photosensitive resin composition comprising (A) a colorant; (B) an alkali-soluble resin; (C) a photopolymerizable compound; (D) a photopolymerization initiator; and (E) a solvent,
The colored photosensitive resin composition may have a flattening property (DOP) value of 15 to 75% as calculated by the following formula 1 of a film formed of the colored photosensitive resin composition.

[Equation 1]
DOP (%) = {(a−d) / a} × 100, 0 ≦ d ≦ 1.5 um, d ≦ a ≦ b

In the above formula 1,
a is the thickness of the lower pattern, d is the value of a + c−b, and b and c are defined as follows: b is the flatness formed by the colored photosensitive resin composition The thickness of the unpatterned portion at the bottom of the film, c, means the thickness of the portion of the film whose flatness is formed by the colored photosensitive resin composition excluding the highest point of the lower pattern.

The present invention provides a color filter comprising a black matrix, a column spacer or a black column spacer made of the above-described colored photosensitive resin composition.

The present invention provides a display device including the color filter described above.

The present invention is advantageous not only in excellent degree of planarization (DOP) and light blocking property but also in elastic recovery rate, pattern shape and chemical resistance, and resolution.

The present invention also provides a color filter including a black matrix and / or column spacers in which a column spacer and a black matrix are simultaneously formed integrally using the above-described colored photosensitive resin composition, and a liquid crystal display comprising the color filter. The device can be manufactured.

FIG. 2 illustrates the degree of planarization (DOP) of the present invention.

The present invention comprises a coloring agent, an alkali soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, and the leveling property has a value in the range of 15 to 75% to provide a degree of planarization. The present invention provides a colored photosensitive resin composition not only excellent in DOP) and light blocking properties but also excellent in elastic recovery rate, pattern shape and chemical resistance, and resolution.

The planarization property (DOP) value of the present invention is calculated by the following formula 1, and the planarization property (DOP) value of the film formed by the colored photosensitive resin composition is preferably 15 to 75%. Formula 1 below is calculated by the values of a to d as shown in FIG.

[Equation 1]
DOP (%) = {(a−d) / a} × 100, 0 ≦ d ≦ 1.5 um, d ≦ a ≦ b

In the above formula 1,
a is the thickness of the lower pattern, d is the value of a + c−b, and b and c are defined as follows: b is the flatness formed by the colored photosensitive resin composition The thickness of the unpatterned portion at the bottom of the film, c, means the thickness of the portion of the film whose flatness is formed by the colored photosensitive resin composition excluding the highest point of the lower pattern.

In the present invention, flatness means that when the composition is applied on the pattern formed on the lower substrate, the thickness of the coating film of the portion having no pattern on the lower side is formed uniformly. . That is, this means that the deviation of the position of the opening is minimized.

The flattening property (DOP) value may have a difference in the flattening property requirement value according to the design value of each layer constituting the panel, but is preferably 15 to 75%, more preferably 30 to 60%. May be This is a characteristic that appears when the solid content of the colored photosensitive resin composition is in the range of 15% by weight to 22% by weight and the viscosity is 2.8 to 4.2 cP. If the planarization characteristic value is less than the above range, the optical density is lowered, the light shielding characteristic is deteriorated, and a problem of light leakage from the backlight and a problem of visibility to external light may occur. If the above range is exceeded, the level difference may be lowered, so that the generation of the level difference may be defective and the spacer may not play a role, and the liquid crystal margin may be defective to significantly affect the production yield of the product. Furthermore, the present invention can show a remarkably excellent elastic recovery when the planarization characteristic value is in the range of 30 to 60%.

(A) Colorant In the present invention, the colorant used is one having a light-shielding property to visible light, and preferably, the colorant of the present invention can include organic black pigment, violet pigment, and blue pigment And carbon black may additionally be included, but is not limited thereto.

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, the optical density can be improved, which is also advantageous in terms of dielectric constant and transmittance.

The violet pigment plays a role in reducing the transmittance in the 400-600 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. Pigment violet 14, 19, 23, 29, 32, 33, 36 and / or 37 etc. are preferred; I. It is more preferable to use pigment violet 29.

Further, the blue pigment is a compound which does not contain a central metal, and by using the blue pigment which does not contain the central metal, it causes no problem at the time of contact with the liquid crystal used on the process, which is advantageous for driving the equipment. Can be secured. 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. Pigment blue B15: 3, B15: 4, B15: 6, 16, 60, 61 and / or 66, and the like, and C.I. I. It is more preferable to use pigment blue 60.

In the present invention, the colorant is contained in an amount of 13 to 50% 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 the range of 13 to 50% by weight, an effect of excellent optical density can be obtained.

When carbon black is further contained in the coloring agent of the present invention, a colored photosensitive resin composition excellent in optical density can be obtained.

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

Moreover, it is preferable that the said coloring agent uses the pigment dispersion liquid which the particle size of the pigment disperse | distributed uniformly. An example of a method for uniformly dispersing the particle size of the pigment includes a method of dispersing the pigment dispersant (a1) and the like, and the pigment is uniformly dispersed in the solution by the above method. A pigment dispersion can be obtained.

(A1) Pigment dispersant The pigment dispersant is added for deaggregation and stability maintenance of the pigment, and specific examples of the pigment dispersant include cationic, anionic, nonionic and amphoteric. Surfactants, such as a system, polyester type, a polyamine type, etc. are mentioned, These can be used individually or in combination of 2 or more types, respectively.

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 dodecyl benzene sulfonate and And alkylaryl sulfonates such as sodium dodecylnaphthalene sulfonate.

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 pigment 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 pigment dispersant, in addition to the acrylate dispersant, pigment dispersants of other resin types may be used. The other resin type pigment dispersants include known resin type pigment dispersants, in particular, polyurethanes, polycarboxylic acid esters represented by polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acids (portions ) Ammonium salts, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphate salts, esters of hydroxyl group-containing polycarboxylic acids and 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) acrylate ester copolymer, styrene- Maleic acid copolymer, 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.

As a commercial item of the pigment dispersing agent of said other resin type, as a cationic resin dispersing agent, the brand name of BYK (BIC) Chemie company: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, for example , DISPER BYK-163, DISPER BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; 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-4400, EFKA-4406 EFKA-4510, EFKA-4800; trade name of Lubrizol company: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204 / 10; trade name of Kawaken Fine Chemicals Co., Ltd .: HINOACT T-6000, Hinoact T-7000, Hinoact T-8000; trade name of Ajinomoto Co., Ltd .: Ajispar (AJIS PUR) PB-821, Ajispar PB-822, Ajispar PB-823; -33, Floren DOPA-44 and the like.

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

The pigment dispersant is contained 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 pigment dispersant is contained in an amount of 0 or more and 1 part by weight or less because a uniformly dispersed pigment is obtained.

(B) Alkali-Soluble Resin The alkali-soluble resin (B) used in the present invention is a component that imparts solubility to an alkali developer used in the development processing step when forming a pattern.

The alkali-soluble resin (B) according to the present invention is not particularly limited in kind as long as it is a resin which is soluble in the solvent of the present invention and has reactivity to the action of light or heat and is soluble in an alkaline developer. It can be used. Specifically, carboxyl group-containing monomers and monomers copolymerizable therewith can be used.

Specifically, as the carboxyl group-containing monomer, for example, unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, etc .; maleic acid, fumaric acid, itaconic acid And unsaturated dicarboxylic acids such as citraconic acid and mesaconic acid; unsaturated carboxylic acids having one or more carboxyl groups in the molecule such as unsaturated tricarboxylic acid. These can be used alone or in combination of two or more. In the present invention, the unsaturated carboxylic acid corresponding to the carboxyl group-containing monomer may be an acid anhydride, and specifically, maleic anhydride, itaconic anhydride, citraconic anhydride and the like. It can be mentioned. The unsaturated carboxylic acid may be its mono (2-methacryloyloxyalkyl) ester, for example, mono (2-acryloyloxyethyl) succinate, mono (2-methacryloyloxyethyl) succinate, Mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate and the like can be mentioned. Furthermore, the unsaturated carboxylic acid may be a mono (meth) acrylate of its both terminal dicarboxy polymer, and examples thereof include ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate and the like. .

Specific examples of other monomers copolymerizable with the carboxyl group-containing monomer include 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-9-yl acrylate, 3, Single dose with 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane ring, such as 4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate , A monomer having a dicyclopentene ring (tricyclo [5.2.1.0 ^2,6 ] -3-decene ring); styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p- Vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether Aromatic vinyl compounds such as tellurium; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2- Hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl ester Acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, Phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxy diethylene glycol acrylate, methoxy diethylene glycol methacrylate, methoxy triethylene glycol acrylate, methoxy triethyl ether Glycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, Unsaturated carboxylic acid esters such as 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, and glycerol monomethacrylate; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2- Dimethylaminoethyl acrylate, 2-Dimethylaminoethyl methacrylate 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, 3- Unsaturated carboxylic acid aminoalkyl esters such as dimethylaminopropyl methacrylate; carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; unsaturated ethers such as vinyl methyl ether and vinyl ethyl ether; Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinylidene cyanide; acrylamide, methacrylamide, α-chloroacrylic Unsaturated amides such as luamide, N-2-hydroxyethyl acrylamide, N-2-hydroxyethyl methacrylamide; unsaturated imides such as maleimide, N-phenyl maleimide, N-cyclohexyl maleimide, etc .; 1,3-butadiene, isoprene Aliphatic conjugated dienes such as chloroprene; polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, and polyacryloyl group at the end of the polymer molecular chain of polysiloxane, or monomethacryloyl Macromonomers having a group; monomers having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond; 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyl Oxetane 3- (Methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyl Unsaturated oxetane compounds such as oxetane; unsaturated oxirane compounds such as methyl glycidyl (meth) acrylate; (meth) acrylates substituted with a cycloalkane having 4 to 16 carbon atoms or a dicycloalkane ring; These can be used alone or in combination of two or more.

The alkali-soluble resin of the present invention may be more preferably a carboxyl group-containing monomer and a copolymer with a monomer that can be copolymerized with the monomer to form the structure of Formula 1. It is found that using an alkali-soluble resin having a structure represented by the chemical formula 1 forms a high-performance cured film excellent in hardness, solvent resistance, and heat resistance, and improves the storage stability. From, it is more preferable.

R ₁ and R _{2 in} the chemical formula 1 are each independently hydrogen, or an alkyl group having 1 to 4 carbon atoms such as a methyl group, and a and b are each independently an integer of 1 to 20.

In this regard, 3,4-epoxytricyclo [5.2.1.0 ^2,6] decan-9-yl acrylate, 3,4-epoxytricyclo [5.2.1.0 ^2,6] decane More preferable is that -8-yl acrylate is a monomer capable of forming the structure of Formula 1.

The molecular weight of the alkali-soluble resin (B) may be, for example, 5,000 to 20,000, preferably 7,000 to 15,000, in terms of polystyrene equivalent weight average molecular weight (hereinafter referred to as weight average molecular weight). The acid value may be 30 to 100 mg KOH / g, more preferably 40 to 80 mg KOH / g. When the weight average molecular weight and the acid value range are satisfied, the viscosity of the resist can be adjusted in the range of 2.8 to 4.2 cP within a solid content content range of 15% by weight to 22% by weight, and flattening is achieved The characteristics are improved, and the development characteristics can be controlled by the acid value of the alkali-soluble resin, which can have an advantageous effect of securing a margin. In addition, when the acid value range is satisfied, the problem of not developing and not developing and generating an afterimage does not occur, and it is possible to solve the problem that the developing speed becomes excessively high and the process margin becomes defective. Therefore, there is an effect that the step forming margin is improved with excellent planarization characteristics (DOP).

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 ratio are improved, which is preferable.

The alkali-soluble resin (B) may be contained in an amount of 40 to 80% by weight of the alkali-soluble resin (B) based on the total weight of the alkali-soluble resin and the photopolymerizable compound (C) described later. When the content is within the above range, the solubility in the developer is sufficient and the pattern formation is easy, and the film reduction of the pixel part of the exposed part is prevented at the time of development, and the missing property of the non-pixel part is improved. preferable.

(C) Photopolymerizable Compound The photopolymerizable compound (C) is a compound that can be polymerized by the action of light and a photopolymerization initiator described later, and is a monofunctional monomer, a bifunctional monomer, and the like. A polyfunctional monomer etc. are mentioned.

The photopolymerizable compound (C) used in the present invention has a functional group structure in order to improve the developability, sensitivity, adhesion, surface problems and the like of the photosensitive resin composition for forming the entire light-shielding layer of a display device. Alternatively, two or more photopolymerizable compounds having different numbers of functional groups can be mixed and used, and the type is not particularly limited as long as it is generally used in this field.

Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinyl pyrrolidone and the like. Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bisphenol Examples include bis (acryloyloxyethyl) ether of A, 3-methylpentanediol di (meth) acrylate and the like. Specific examples of other polyfunctional monomers include tripentaerythritol (meth) acrylate, polypentaerythritol (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxy Fluorinated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipenta And erythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc., and tripentaerythritol (meth) acrylate DOO, if it contains poly pentaerythritol (meth) acrylate, more preferable. Among these, bifunctional or higher polyfunctional monomers are preferably used.

The photopolymerizable compound may be contained in an amount of 5 to 50% by weight based on the total weight of the solid content in the colored photosensitive resin composition. Such a content range is a range selected taking into consideration the tendency that the strength and smoothness as a black matrix or spacer finally obtained become better and the like are diversified, and the content is the above-mentioned range. If it is less than the range, the strength and smoothness are insufficient, and conversely, if it exceeds the range, high intensity causes problems that patterning is not easy, so it is suitably used within the range.

The photopolymerizable compound (C) is contained in an amount of 20 to 60% by weight of the (C) photopolymerizable compound based on the total weight of the alkali-soluble resin (B) and the photopolymerizable compound (C). It is also good. When it is included in the above range, the sensitivity of the pixel portion is improved, the strength and flatness of the pattern become good, and there is an effect that the step formation is easy.

(D) Photopolymerization Initiator The photopolymerization initiator is a compound for initiating the polymerization of the photopolymerizable compound, and is not particularly limited in the present invention, but acetophenone type, benzophenone type, triazine type, triazine type, thioxanthone type, oxime type Benzoin compounds, anthraquinone compounds, biimidazole compounds and the like can be used, and these can be used alone or in combination of two or more.

Examples of the acetophenone compound include 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- ( Examples thereof include oligomers of 4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl [4- (1-methylvinyl) phenyl] propan-1-one and the like, and in particular, among these, 2-benzyl -2-dimethylamino-1- (4-morpholinophenyl) butan-1-one is preferably used. It can be.

Examples of the benzophenone compounds include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) ) Benzophenone and the like.

Examples of the triazine compounds include 2,4,6-borochloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (3 ', 4'-dimethoxystyryl) -4,6-Bis (trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4, 6-bis (卜 -chloro-methyl) -s-triazine, 2- (p-tolyl) -4,6-bis- 卜 -chloro-methyl-s-triazine, 2-biphenyl-4,6-bis- 卜 -chloro-methyl-s- Triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-me Xynaphtho 1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl (piperonyl) -6-triazine, 2,4-trichloromethyl (4'-methoxystyryl) -6- Triazine etc. are mentioned.

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

Examples of the oxime-based compound include o-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one and the like, and commercially available products such as OXE01 and OXE02 from BASF Corporation are representative.

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

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

Examples of the biimidazole compounds include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2,3-dichlorophenyl) -4. 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, a biimidazole compound in which the phenyl group at the 4,4 ′, 5,5 ′ position is substituted by a carboalkoxy group Etc.

In the present invention, the photopolymerization initiator is contained in an amount of 0.05 to 10% by weight, preferably 0.1 to 5% by weight, based on the total weight of solids in the colored photosensitive resin composition. When the photopolymerization initiator is included in the range described above, the sensitivity of the colored photosensitive resin composition is enhanced, and the intensity of the pixel portion formed using the colored photosensitive resin composition and the smoothness on the surface of the pixel portion Sex is good.

The photopolymerization initiator may be used in combination with a photopolymerization initiation aid. When a photopolymerization initiator is used in combination with the photopolymerization initiator, the colored photosensitive resin composition containing them is further enhanced in sensitivity, and when using this to form a support spacer for holding a cell gap, productivity is increased. It is preferable because it improves.

The photopolymerization initiation aid can be used to enhance the polymerization efficiency, and amine compounds, alkoxyanthracene compounds, thioxanthone compounds and the like can be used.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate 4-dimethylaminobenzoic acid 2-ethylhexyl, N, N-dimethyl paratoluidine, 4,4'-bis (dimethylamino) benzphenone (common name: Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 4, 4'-bis (ethyl methyl amino) benzophenone etc. are mentioned, Especially, 4, 4 '-bis (diethylamino) benzophenone is preferable.

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

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

The said photopolymerization start adjuvant can purchase and use a thing manufactured directly or a commercial thing, and uses brand name "EAB-F" [Manufacturer: Hodogaya Chemical Industry Co., Ltd.] series etc. as an example. Can.

It is preferable to use the said photopolymerization start adjuvant normally in 10 mol or less, preferably in the range of 0.01-5 mol, per 1 mol of photoinitiators. When using a photopolymerization start adjuvant in the said range, polymerization efficiency can be raised and the productivity improvement effect can be anticipated.

(E) Solvent Any solvent can be used as the solvent as long as it can dissolve or disperse the composition of the above-mentioned one, and is not particularly limited in the present invention. Preferably, an organic solvent having a boiling point of 100 to 200 ° C. can be used in terms of coating property and drying property.

Typically, usable solvents include alkylene glycol monoalkyl ethers, alkylene glycol alkyl ether acetates, aromatic hydrocarbons, ketones, lower and higher alcohols, cyclic esters and the like. More specifically, alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol diethylene glycol Diethylene glycol dialkyl ethers such as butyl ether; methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxy Alkylene glycol alkyl ether acetates such as ethyl acetate; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone; ethanol, propanol, butanol And alcohols such as hexanol, cyclohexanol, ethylene glycol and glycerin; esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; cyclic esters such as γ-butyrolactone.

Among the above solvents, preferably, alkylene glycol alkyl ether acetates, ketones, esters such as ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate can be used, and more preferably propylene glycol monomethyl ether Acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and the like can be used. These solvents can be used singly or in combination of two or more.

The solvent is contained in an amount of 78 to 85% by weight based on the total weight of the colored photosensitive resin composition. When the solvent is included in the above-mentioned range, the coating property is good when coated by 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. become.

(F) Additives The colored photosensitive resin composition of the present invention may further contain additives known in the art for various purposes. Such additives include thermal initiators, dispersants, fillers, other polymer compounds, ultraviolet absorbers, aggregation inhibitors, curing agents, adhesion promoters, antioxidants, surface modifiers, etc. Be

The thermal initiator is a substance that generates an acid by heat, and generates an acid by a heat treatment (for example, post-baking etc.) applied in the process of curing the colored photosensitive resin composition to accelerate the curing of the pattern. Referred to as

In another embodiment of the present invention, the thermal initiator may be represented by Formula 2 below.

In the chemical formula 2,
R2 is a C3-8 cycloalkyl group,
R3 is a C1-8 alkyl group or a C6-10 aryl group.

In the present invention, the alkyl group is not particularly limited, but may be linear or branched, and one having 1 to 8 carbon atoms is preferable. Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, n-pentyl, isopentyl, neopentyl, tert -Pentyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3, 3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, tert -Octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4 -But is not limited to-methylhexyl, 5-methylhexyl and the like

In the present invention, the cycloalkyl group preferably has 3 to 8 carbon atoms. Specific examples include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethyl Examples include, but are not limited to, cyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl and the like.

The cycloalkyl group may be substituted or unsubstituted with a hydroxy group, but is not limited thereto.

In the present invention, the aryl group is not particularly limited, but is preferably one having 6 to 8 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. The monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, a stilbenyl group or the like, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group and the like, but is not limited thereto.

The aryl group may be substituted or unsubstituted with an alkyl group, specifically, a methyl group.

Specifically, the thermal initiator represented by Chemical Formula 2 may be represented by the following Chemical Formulas 2-1 to 2-3, and can be used alone or in combination of two or more.

In relation to the content of the thermal initiator, when the thermal initiator is contained alone among the additives, it may be contained in an amount of 1 to 10% by weight based on the total weight of the solid content in the colored photosensitive resin composition It may be more preferable if it is contained in an amount of 1 to 5% by weight. When it is contained by the above content, it is preferable by processability and undercut.

If the thermal initiator is included in the above range, the effect of solvent resistance may be slight, and if it exceeds the range, the development speed may be increased to cause problems of peelable type developability. It is preferable to be included in the range.

A commercially available surfactant can be used as the dispersing agent, and a fluorine-based surfactant, a urethane-based surfactant and the like can be used. As said fluorine-type surfactant, BM-1000, BM-1100 (BM Chemie company), Florard FC-135 / FC-170C / FC-430 (Sumitomo 3 M Co., Ltd.), SH-28PA / -190 / SZ -6032 (Toray Silicone Co., Ltd.) etc. can be used. As said urethane type surfactant, DiperBYK-163 (BYK company) is mentioned. Dispersion aids such as Solsperse 5000 (Lubrizol) can also be added.

As the filler, glass, silica, alumina and the like can be used, and as other polymer compounds, curable resins such as epoxy resin and maleimide resin, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, Thermoplastic resins such as polyfluoroalkyl acrylate, polyester and polyurethane can be used.

As the ultraviolet absorber, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, alkoxybenzophenone and the like can be used, and as an aggregation inhibitor, polyacrylic acid Sodium and the like can be used.

The other polymer compound is not limited as long as the compatibility is not affected, but preferably, bisphenol A epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, cyclic aliphatic epoxy resin, glycidyl ester Type epoxy resin, glycidyl amine type epoxy resin, heterocyclic epoxy resin, resin obtained by (co) polymerizing glycidyl methacrylate, and the like. Among these, bisphenol A epoxy resin, cresol novolac epoxy resin, glycidyl ester epoxy resin and the like are preferable.

One or more of these additives can be used, and the additive is preferably contained in an amount of 0.01 to 10% by weight based on the total weight of solids in the colored photosensitive resin composition. May be contained 0.05 to 2% by weight.

As an example, after the colorant is added to the solvent, the remaining composition and other additives can be added and obtained by stirring. At this time, the colorant is added in the form of mill base in which a pigment or the like is previously dissolved or dispersed in a solvent or an alkali-soluble resin. The additives, when in solution form, may be pre-added to the solvent along with the colorant.

The colored photosensitive resin composition thus produced can be preferably used for producing 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 present invention also exhibits a light transmittance of 0.1% or less with respect to a wavelength in the range of 400 to 600 nm when the above-mentioned colored photosensitive resin composition is formed on a cured film having a thickness of 3.0 μm; A colored photosensitive resin composition exhibiting a light transmittance of 10% or less to a wavelength in the range of 700 nm to 750 nm; and a light transmittance of 15% or more to a wavelength in the range of 950 nm Do.

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. 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 made of the colored photosensitive resin composition.

The present invention also relates to a display device including the color filter.

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.

As the substrate, a glass substrate or a polymer plate is used. As the glass substrate, particularly, soda lime glass, barium or strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, quartz or the like can preferably be 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 is performed by a wet coating method 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 ink jet to obtain a desired thickness. It is done by

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 carbonates such as sodium carbonate, potassium carbonate and lithium carbonate, a developing device or ultrasonic waves within a temperature range of 10 to 50 ° C., preferably 20 to 40 ° C. Carry out using a washing machine etc.

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 solvent resistance Thus, the reliability of the liquid crystal display device can be improved.

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

Production Example 1: Production of Alkali-Soluble Resin B1 Propylene glycol monomethyl ether acetate (hereinafter "PGMEA") in a 1-liter separate type flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introducing pipe. After charging to 80 ° C., 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-9-yl acrylate and 3,4-epoxytricyclo [5.2]. .1.0 ^2,6 ] mixture with decane-8-yl acrylate [50: 50 (molar ratio)] (ie, compounds represented by the following chemical formula 1-1 and chemical formula 1-2, R ^a = H) A mixed solution of 301 g of methacrylic acid, 49 g of methacrylic acid, and 23 g of azobisdimethylvaleronitrile dissolved in 350 g of methoxybutyl acetate is dropped over 5 hours, and By ripening for 3 hours to obtain a copolymer solution (solids concentration 35.0%). The acid value (dry) of the obtained copolymer was 60.2 mg KOH / g, and the weight average molecular weight (Mw) was 9,000.

(Wherein, R ^a represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, etc., and R ^b represents a single bond, an alkylene group having 1 to 18 carbon atoms, etc.)

Production Example 2: Production of Alkali-Soluble Resin B2 Propylene glycol monomethyl ether acetate (hereinafter, "PGMEA") in a 1-liter separate type flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction pipe. After charging to 80 ° C., 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-9-yl acrylate and 3,4-epoxytricyclo [5.2]. .1.0 ^2,6 ] mixture with decane-8-yl acrylate [50: 50 (molar ratio)] (ie, compounds represented by the above-mentioned chemical formula 1-1 and chemical formula 1-2, R ^a = H) A mixed solution of 301 g of methacrylic acid, 49 g of methacrylic acid, and 23 g of azobisdimethylvaleronitrile dissolved in 350 g of methoxybutyl acetate is dropped over 8 hours, By ripening time, to obtain a copolymer solution (solids concentration 35.0%). The acid value (dry) of the obtained copolymer was 61.5 mg KOH / g, and the weight average molecular weight (Mw) was 15,000.

Production Example 3 Production of Alkali-Soluble Resin B3 72 parts by weight of methyl methacrylate, 3 parts by weight of acrylic acid, propylene glycol monomethyl ether in a separate type flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen introducing pipe Acetate (hereinafter referred to as "PGMEA") in an amount of 2 times the total amount of monomers, and 5 parts by weight of 2,2'-azobis (2-methylbutyronitrile) in the total amount (100 parts by weight) of monomers A portion was added and dissolved uniformly. Then, it stirred at 85 degreeC under nitrogen stream for 2 hours, and made it react at 100 degreeC again for 1 hour. To the resulting solution, 25 parts by weight of glycidyl methacrylate, 10 parts by weight of triethylamine to glycidyl methacrylate, 1 part by weight of hydroquinone to glycidyl methacrylate, and 35% by weight of the combined injected monomers and glycidyl methacrylate Further, PGMEA was further added so as to be the mixture, and the mixture was stirred at 100 ° C. for 5 hours to obtain a target copolymer solution (solid content concentration: 31.5%). The weight average molecular weight (Mw) of the obtained copolymer was 30,000, and the acid value (dry) was 72 mg KOH / g.

Examples 1 to 16 and Comparative Examples 1 to 5
A mixture of a colorant, an alkali-soluble resin, a dispersant, and a solvent was dispersed in a paint shaker at room temperature for 8 hours. Dispersion was allowed to proceed using 0.1 mm zirconia beads, and filtered after completion of dispersion to produce a colored dispersion.

The colored dispersion liquid, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent were mixed to produce a colored photosensitive resin composition, and the content thereof is shown in Table 1 below. (Unit: g)

OBP: lactam organic black pigment V29: C.I. I. Pigment violet 29
B60: C.I. I. Pigment blue 60
CB: carbon black alkali soluble resin:
B1) Alkali-soluble resin B2 produced in Production Example 1) Alkali-soluble resin B3 produced in Production Example 2) Alkali-soluble resin photopolymerizable compound produced in Production Example 3 (use of (meth) acrylate group as a functional group)
Photopolymerizable compound: Viscoat # 802 (8 functional, Osaka organic chemistry)
Photopolymerization initiator: 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethanone-1- (O-acetyloxime) (Irgacure OXE-02: manufactured by Ciba)
Additive: I-PAG-250 (BASF) and / or F 554 (DIC; surface modifier)
Solvent: Propylene glycol monomethyl ether acetate

Experimental Example 1 Measurement of physical properties of colored photosensitive resin composition 1-1. Measurement of Viscosity The viscosity of the colored photosensitive resin composition obtained from the composition of the above example was measured with a Brookfield Viscometer (Brookfield Viscometer DV-I +, manufactured by BROOK FIELD) at 25 ° C., and the results are shown in Table 2 below. It was shown to.

1-2. Preparation of substrate and measurement of optical properties (optical density, Uv-vis)
A 5 cm × 5 cm glass substrate (Corning) was washed with a neutral detergent and water and then dried. Each of the colored photosensitive resin compositions produced in Examples 1 to 16 and Comparative Examples 1 to 5 is spin-coated on the glass substrate to a final film thickness of 3.0 (± 0.2) μm. And prebaked at 80 to 120 ° C. and dried for 1 to 2 minutes to remove the solvent to form a precured film.

Then, it exposed by exposure amount 25-35 mJ / cm < ² >, formed the pattern, and removed the non-exposure part using alkaline aqueous solution. Next, post-baking was performed at 200 to 250 ° C. for 10 to 30 minutes to produce a colored substrate.

The transmittance of the cured film thus formed was measured at 550 nm using an optical densitometer (361 T, manufactured by X-rite Co., Ltd.), and the optical density with respect to a thickness of 1 μm was determined and is shown in Table 2 below.

Moreover, the light characteristic was evaluated using UV-vis (UV-2550; Shimadzu) about the formed said cured film, the evaluation criteria were as follows, and the result was shown in following Table 2.

<Optical characteristics evaluation criteria 1: Within the wavelength range of 700 to 750 nm>
○: excellent, light transmission of 10% or less Δ: insufficient, light transmission of more than 10% 12% or less ×: worse, light transmission of 12%

<Optical characterization criteria 2: Within the wavelength range of 950 nm>
○: excellent, light transmission 15% or more Δ: insufficient, light transmission 13% or more and less than 15% ×: worse, light transmission 13%

1-3. Evaluation of Reliability After the glass substrate covered with the cured film formed by the method 1-2 was cut into 3 × 3 cm, it was immersed in an NMP solution, and then heat was applied at 100 ° C. for 60 minutes. Thereafter, only the NMP solution was extracted, and the degree of elution of the NMP solvent was measured for absorbance using a UV-vis spectrometer, and the results are shown in Table 2 below.

<Reliability evaluation criteria>
○: Excellent, Absorbance 0.5 or less Δ: Insufficient, Absorbance 0.5 exceeded 0.8 or less ×: Deteriorated, Absorbance 0.8 exceeded

1-4. Evaluation of Elastic Recovery Rate As in the preparation of the substrate 1-2, a substrate having a column spacer pattern was prepared. The thickness and height of the pattern were measured in a standard state using SNU (SIS-2000, SNU Co., Ltd.). After that, a hardness tester (Nano-indenter HM500, Fisher) was pressed at a speed of 2 mN / sec to a point where the pattern was deformed by 1 μm using a flat clamber, and Holding Time was held for 5 seconds at the point of 1 μm deformation. After this, the thickness and height of the pattern were measured using SNU, and the elastic recovery rate was measured from the change in thickness of the pattern before and after. The specific evaluation criteria are as follows, and the evaluation results are shown in Table 2 below.

<Elastic Recovery Rate Evaluation Criteria>
Excellent :: 98% or more good ○: 96% or more to less than 98% insufficient Δ: 94% or more to less than 96% worse ×: less than 94%

1-5. Colored photosensitive resin compositions produced in Examples 1 to 16 and Comparative Examples 1 to 5 on a substrate (a glass substrate of 5 cm × 5 cm) on which a measurement pattern of planarization characteristics (DOP: Degree of Planarization) is formed Each is spin-coated to a final film thickness of 3.0 (± 0.2) μm, pre-baked at 80 to 120 ° C., dried for 1 to 2 minutes to remove the solvent, and pre-cured film It formed.

Thereafter, the entire surface is exposed at an exposure amount of 25 to 35 mJ / cm ² to form an entire surface pattern, and development is advanced using an aqueous alkaline solution. Next, post-baking was performed at 200 to 250 ° C. for 10 to 30 minutes to produce an all-colored substrate.

The thickness of the pattern of the lower substrate measured in advance after measuring the thickness of the portion with the pattern on the lower side and the portion without the pattern on the lower surface with the film thickness measuring device (DEKTAK 6M, Veeco) of the entire colored substrate produced Measure the planarization characteristics (DOP) using

<Flattening Characteristic (DOP) Evaluation Criteria>
Thickness of lower pattern: 1.17 um, thickness of flattened portion without lower pattern: 3.20 um,
:: extremely excellent, 30% or more and 60% or less ○: excellent, 15% or more and less than 30%, 60% or more and 75% or less Δ: insufficient, 10% or more and less than 15%, 75% or more and 85% or less ×: deteriorated, Less than 10%, over 85%

As confirmed from the above-mentioned table, the colored photosensitive resin compositions of Examples 1 to 16 which satisfy the range of the leveling property value of the present invention show excellent optical density, light shielding property, reliability and viscosity property. As well as the elastic recovery rate also showed excellent results. In particular, it can be confirmed that Examples 1 to 12 having flattening characteristic values in the range of 30% to 60% show remarkably excellent elastic recovery value values.

On the other hand, in the case of Comparative Examples 1 to 5 exceeding the range of the flattening characteristic value of the present invention, the optical density, the light shielding property, the reliability, the viscosity and the elastic recovery rate effect significantly reduced compared to the examples of the present invention. Indicated.

Claims (13)

(A) Colorant;
(B) alkali soluble resins;
(C) photopolymerizable compounds;
A colored photosensitive resin composition comprising (D) a photopolymerization initiator; and (E) a solvent,
A colored photosensitive resin composition having a flattening property (DOP) value of 15 to 75% calculated by the following formula 1 of a film formed of the colored photosensitive resin composition:
[Equation 1]
DOP (%) = {(a−d) / a} × 100, 0 ≦ d ≦ 1.5 um, d ≦ a ≦ b
(In the above formula 1,
a is the thickness of the lower pattern, d is the value of a + c−b, and b and c are defined as follows:
b is the thickness of the unpatterned portion at the lower part of the film formed with flatness by the colored photosensitive resin composition,
c is the thickness of a portion excluding the highest point of the lower pattern from the highest point of the film of which flatness is formed by the colored photosensitive resin composition). The colored photosensitive resin composition according to claim 1, wherein the solid content of the colored photosensitive resin composition is in the range of 15% by weight to 22% by weight and the viscosity of the resist is 2.8 to 4.2 cP. . The colored photosensitive resin composition according to claim 1, wherein the (A) colorant comprises one or more of an organic black pigment, a violet pigment, a blue pigment, and a carbon black. The colored photosensitive resin composition according to claim 1, wherein the (B) alkali-soluble resin has a weight average molecular weight of 5,000 to 20,000. The colored photosensitive resin composition according to claim 4, wherein the (B) alkali-soluble resin has an acid value of 30 to 100 mg KOH / g. The colored photosensitive resin composition according to claim 1, wherein the alkali-soluble resin is an alkali-soluble resin containing a structure represented by 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 composition according to claim 1, wherein 40 to 80% by weight of the alkali-soluble resin (B) and 20 to 60% by weight of the photopolymerizable compound (C) are contained with respect to the total weight of the alkali-soluble resin and the photopolymerizable compound. The colored photosensitive resin composition as described. The organic black pigment is one or more selected from the group consisting of lactam black, aniline black, and perylene black; the violet pigment is C.I. I. Pigment violet 14, 19, 23, 29, 32, 33, 36 and 37; and one or more selected from the group consisting of C.I. I. The colored photosensitive resin composition according to claim 3, which is one or more selected from the group consisting of pigment blue B15: 3, B15: 4, B15: 6, 16, 60, 61 and 66. The colored photosensitive resin composition is one or more selected from the group consisting of a thermal initiator, a filler, 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 1, further comprising (F) an additive. (A) 13 to 50% by weight of a colorant, (B) 5 to 60% by weight of an alkali-soluble resin, and (C) a photopolymerizable compound 5 to 5 based on the total weight of solid components in the colored photosensitive resin composition 50% by weight and (D) 0.05 to 10% by weight of a photopolymerization initiator, wherein 78 to 85% by weight of a solvent (E) is included with respect to the total weight of the colored photosensitive resin composition The colored photosensitive resin composition according to claim 1, wherein The colored photosensitive resin according to claim 10, wherein the additive (F) is further contained in an amount of 0.01 to 10% by weight based on the total weight of the solid content in the colored photosensitive resin composition. Composition. A color filter comprising a black matrix, a column spacer or a black column spacer made of the colored photosensitive resin composition according to any one of claims 1 to 11. A display device comprising the color filter according to claim 12.

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