KR20190053131A - Colored photosensitive resin composition, color filter prepared by using the same, and display device comprising the color filter - Google Patents

Abstract

An objective of the present invention is to provide a colored photosensitive resin composition which not only is excellent in degree of planarization (DOP) and light blocking properties, but also is excellent in elastic recovery rate, pattern shape, chemical resistance and resolution by comprising a coloring agent, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The present invention relates to a colored photosensitive resin composition comprising: a coloring agent (A); an alkali soluble resin (B); a photopolymerizable compound (C); a photopolymerization initiator (D); and a solvent (E), a color filter including a black matrix, a column spacer or a black column spacer manufactured by using the colored photosensitive resin composition, and a display device including the color filter. A film formed by the colored photosensitive resin composition has a light transmittance of 10% or less in a wavelength range of 700 to 750 nm, has a light transmittance of 15% or more at a wavelength of 950 nm, and degree of planarization (DOP) characteristic value of the film, which is formed by the colored photosensitive resin composition, calculated by expression 1, DOP(%) = {(a - d) / a} x 100, 0 <= d <= 1.5 um, d <= a <= b, is 15 to 75%.

Description

TECHNICAL FIELD [0001] The present invention relates to a colored photosensitive resin composition, a color filter manufactured using the same, and a display device including the color filter. BACKGROUND ART &lt; RTI ID = 0.0 &gt;

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.

BACKGROUND ART [0002] Color filters are widely used in various display devices such as an image pickup device and a liquid crystal display (LCD), and their application range is rapidly expanding. The color filter used in the image pickup device or the liquid crystal display device may be a color pattern of three colors of red, green and blue or a color pattern of three colors of yellow, magenta and cyan Cyan).

The coloring pattern of each of the color filters is generally formed using a colored photosensitive resin composition comprising a coloring agent such as pigment or dye, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The coloring pattern processing using the colored photosensitive resin composition is usually performed by a lithography process.

The colored photosensitive resin is an essential material such as a color filter, a liquid crystal display material, an organic light emitting element, and a display. For example, a color filter of a color liquid crystal display is provided with a light-shielding layer using a black photosensitive composition at a boundary portion between coloring layers to enhance the contrast, coloring effect of red, green and blue. In recent years, a spacer for cell gap is formed not only as a black matrix but also on an array substrate, and is required to have various roles at a time. Accordingly, not only the optical effect for the basic light shielding but also the characteristics of good elasticity and reliability are required.

In order to meet these demands, Japanese Unexamined Patent Application Publication No. 10-1658374 discloses a colored photosensitive resin composition having improved elastic recovery rate, resolution and chemical resistance when formed into a cured film. However, the prior art has not sufficient NMP elution reliability using a general copolymer, and has not completely solved the process margin problem even in the step difference implementation. Therefore, there is a need to develop a more improved colored photosensitive resin composition.

Korean Registered Publication No. 10-1658374

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made keeping in mind the above problems occurring in the prior art, and an object of the present invention is to provide a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, It is another object of the present invention to provide a colored photosensitive resin composition excellent in elastic recovery rate, pattern shape, 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 integrally formed at the same time using the above-mentioned colored photosensitive resin composition, and a liquid crystal display device provided with the color filter .

(A) a colorant; (B) an alkali-soluble resin; (C) a photopolymerizable compound; (D) a photopolymerization initiator; And (E) a solvent, wherein the coloring photosensitive resin composition comprises

Wherein the film formed by the colored photosensitive resin composition has a light transmittance of 10% or less in a 700-750 nm wavelength range, a light transmittance of 15% or more at 950 nm,

And a planarization property (DOP) value of the film formed by the colored photosensitive composition calculated by the following formula 1 is 15 to 75%.

 [Formula 1]

DOP (%) = {(a-d) / a} x100, 0???? 1.5 ?,??? A?

In Equation (1)

Ⓑ is the thickness of the lower pattern, ⓓ is the value of ⓐ + ⓒ-ⓑ, and ⓑ and ⓒ are defined as follows: ⓑ is the thickness of the part without pattern in the lower part of the film formed by the colored photosensitive composition, Ⓒ means the thickness of the portion excluding the peak of the lower pattern at the highest point of the film formed flat by the colored photosensitive composition.

The present invention provides a color filter comprising a black matrix, a column spacer, or a black column spacer made of the above-mentioned 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 terms of the degree of planarization (DOP) and light diffusivity, but also in elastic recovery, pattern shape, 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 integrally formed at the same time using the above-mentioned colored photosensitive resin composition, and a liquid crystal display device including the color filter Do.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram showing a planarization characteristic (DOP) of the present invention. FIG.

A colored photosensitive resin composition comprising a coloring agent, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, wherein the film formed by the colored photosensitive resin composition has a light transmittance of 10% or less in a 700-750 nm wavelength range , The light transmittance at 950 nm is not less than 15%, and the planarization property is in the range of 15 to 75%, the planarization characteristics (degree of planarization) and light diffusibility are excellent, and the elastic recovery rate, pattern shape, , And provides a colored photosensitive resin composition excellent in resolution.

The planarization characteristic (DOP) value of the present invention is calculated by the following formula 1, and the planarization characteristic (DOP) value of the film formed by the colored photosensitive composition is preferably 15 to 75%. The following Equation 1 is calculated by the values of a to as shown in Fig.

[Formula 1]

DOP (%) = {(a-d) / a} x100, 0???? 1.5 ?,??? A?

In Equation (1)

Ⓑ is the thickness of the lower pattern, ⓓ is the value of ⓐ + ⓒ-ⓑ, and ⓑ and ⓒ are defined as follows: ⓑ is the thickness of the part without pattern in the lower part of the film formed by the colored photosensitive composition, Ⓒ means the thickness of the portion excluding the peak of the lower pattern at the highest point of the film formed flat by the colored photosensitive composition.

In the present invention, the flatness means that the thickness of a coating film on a portion without a pattern is uniformly formed when a composition is applied on a pattern formed on a lower substrate, and generally refers to the opposite of Thixotropic: Quot; thickness &quot;). That is, this means that the deviation of the position of the opening is minimized.

The planarization characteristics (DOP) values may vary depending on the design value of each layer constituting the panel, but may be preferably 15 to 75%, more preferably 30 to 60%. This is a characteristic that can be exhibited when the solids content of the colored photosensitive resin composition is in the range of 15 wt% to 22 wt% and the viscosity is 2.8 to 4.2 cP. If the planarization property is less than the above range, the optical density is lowered, the light shielding property becomes poor, and light leakage from the backlight and visibility to external light may occur. In addition, when the thickness exceeds the above range, the step is lowered, the step is not formed well, and a problem that the spacer can not act can be caused, and the liquid crystal margin may be poor, which may greatly affect the yield of the product.

(A) Colorant

The colorant used in the present invention is one having a visible light shielding property. Preferably, the colorant of the present invention may include an organic black pigment, a violet pigment, and a blue pigment, and may further include carbon black. It is not limited.

The organic black pigment includes at least one member selected from the group consisting of lactam black, aniline black and perylene black, and preferably includes 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 serves to improve the optical density (O.D.) by reducing the transmittance in the region of 400 to 600 nm. In addition, the content of the organic black pigment can be reduced through the use of the violet pigment, and the reliability of the colored photosensitive resin composition can be improved. The type of the violet pigment is not particularly limited, but C.I. Pigment Violet 14, 19, 23, 29, 32, 33, 36 and / or 37 is preferably used. It is more preferable to use Pigment Violet 29.

The blue pigment is a compound which does not contain a center metal. By using a blue pigment which does not include the center metal, it does not cause a problem in contact with the liquid crystal used in the process, have. In the present invention, the type of the blue pigment is not particularly limited as long as it is a compound that does not include a center metal. Pigment Blue 16, 60, 61 and / or 66 is preferably used. Pigment Blue 60 is more preferably used.

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 the solid content of the colored photosensitive resin composition. When the colorant is contained in an amount of from 13 to 50% by weight, an effect of improving the optical density can be obtained.

When the colorant of the present invention further contains carbon black, a colored photosensitive resin composition having an excellent optical density can be obtained.

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

In addition, it is preferable to use a pigment dispersion in which the particle diameter of the pigment is uniformly dispersed. Examples of a method for uniformly dispersing the particle diameter of the pigment include a method of dispersing the pigment dispersion (a1) by containing the pigment dispersant (a1), and a method of obtaining a pigment dispersion in which the pigment is uniformly dispersed in the solution have.

(a1) pigment dispersant

The pigment dispersant is added for deaggregation of the pigment and maintenance of stability. Specific examples of the pigment dispersant include a cationic surfactant, an anionic surfactant, a nonionic surfactant, a positive surfactant, a polyester surfactant, and a polyamine surfactant. , Which may 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 sulfuric acid ester salts such as sodium lauryl alcohol sulfate ester and sodium oleyl alcohol sulfate ester, alkylsulfates such as sodium laurylsulfate and ammonium laurylsulfate, sodium dodecylbenzenesulfonate, And alkylarylsulfonic acid salts such as sodium dodecylnaphthalenesulfonate.

Specific examples of the nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan 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, and polyethyleneimines have.

Also, the pigment dispersant preferably includes an acrylate-based dispersant (hereinafter referred to as an acrylate-based dispersant) containing butyl methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA). Dispersing BYK-2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150 and the like may be used as the acrylate-based dispersing agent, The rate-based dispersing agents may be used alone or in combination of two or more.

As the pigment dispersant, other resin type pigment dispersants other than the acrylate dispersant may be used. The other resin type pigment dispersing agent may be a known resin type pigment dispersing agent, especially a polycarboxylic acid ester such as polyurethane, polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) Amine 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 ) Oil-based dispersants such as amides formed by reaction of a polyester having a carboxyl group with poly (lower alkyleneimine) or salts thereof; Soluble resin or water-soluble polymer compound such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinylpyrrolidone; Polyester; Modified polyacrylates; Adducts of ethylene oxide / propylene oxide; And phosphate esters.

DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, and DISPER BYK-160 available from BYK (Big) Chemie are examples of commercially available pigment dispersants of other resin types. BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; EFKA-4060, EFKA-4060, EFKA-4055, EFKA-4055, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA- 4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10 from Lubirzol; Hinoact T-6000, Hinoact T-7000, Hinoact T-8000; available from Kawaken Fine Chemicals; AJISPUR PB-821, Ajisper PB-822, Ajisper PB-823 manufactured by Ajinomoto; FLORENE DOPA-17HF, fluorene DOPA-15BHF, fluorene DOPA-33, and fluorene DOPA-44 are trade names of Kyoeisha Chemical Co.,

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

The pigment dispersant is contained in an amount of more than 0 to 1 part by weight, preferably 0.05 to 0.5 part by weight based on 1 part by weight of the colorant. When the pigment dispersant is contained in an amount exceeding 0 to 1 part by weight, the uniformly dispersed pigment can be obtained.

(B) an alkali-soluble resin

The alkali-soluble resin (B) used in the present invention is a component that imparts solubility to an alkali developing solution used in a development processing step for forming a pattern.

The alkali-soluble resin (B) according to the present invention can be used without particular limitation insofar as it is a resin soluble in the solvent of the present invention and reactive to the action of light or heat and soluble in an alkaline developer. Specifically, carboxyl group-containing monomers and monomers copolymerizable therewith can be used.

Specific examples of the carboxyl group-containing monomer include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid,? -Chloroacrylic acid and cinnamic acid; Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid; And unsaturated carboxylic acids having at least one carboxyl group in the molecule such as unsaturated tricarboxylic acid. These may 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. Specific examples thereof include maleic anhydride, itaconic anhydride, citraconic anhydride and the like. The unsaturated carboxylic acid may also be mono (2-methacryloyloxyalkyl) ester thereof, for example, mono (2-acryloyloxyethyl) succinate, mono (2-methacryloyloxyethyl) ), Phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl), and the like. The unsaturated carboxylic acid may be a mono (meth) acrylate of the both terminal dicarboxylic 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 ] decan-9-yl acrylate, 3,4-epoxytricyclo [5.2.1.0 ^{2, 6} ] decane-8-yl acrylate and the like, an alkali-soluble resin having a 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane ring such as dicyclopentane ring (tricyclo [5.2.1.0 ^2,6 ] 3-decene ring); Styrene,? -Methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p- Aromatic vinyl compounds such as ether, m-vinylbenzyl methyl ether and p-vinyl benzyl methyl ether; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, Acrylate, 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 triethylene glycol methacrylate Acrylate, methoxypropylene glycol methacrylate, methoxypropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadiene Acrylate, dicyclopentadienyl methacrylate, 2-hydroxy-3-phenoxy Acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, unsaturated carboxylic acid esters such as glycerol monoacrylate, glycerol monomethacrylate; Aminoethyl methacrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2- Unsaturated carboxylates such as methyl acrylate, ethyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, Acid amino alkyl esters; 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,? -Chloroacrylonitrile, and vinylidene cyanide; Unsaturated amides such as acrylamide, methacrylamide,? -Chloroacrylamide, N-2-hydroxyethyl acrylamide and N-2-hydroxyethyl methacrylamide; Maleimide, N-phenylmaleimide. Unsaturated imides such as N-cyclohexylmaleimide; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; Polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, polysiloxane having a monoacryloyl group or monomethacryloyl group at the end of the polymer molecular chain Macromonomers; A monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenic unsaturated bond; 3- (methacryloyloxymethyl) -2-trifluoromethyl oxetane, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, and the like Unsaturated oxetane compounds; Unsaturated oxirane compounds such as methyl glycidyl (meth) acrylate; A (meth) acrylate substituted with a cycloalkane or a dicycloalkane ring having 4 to 16 carbon atoms; And the like. These may be used alone or in combination of two or more.

The alkali-soluble resin of the present invention may more preferably be a copolymer of a carboxyl group-containing monomer and a monomer copolymerizable with the carboxyl group-containing monomer and capable of forming the structure of formula (1). It has been found that the use of an alkali-soluble resin having the structure represented by the general formula (1) results in formation of a cured film having excellent hardness, solvent resistance, heat resistance and excellent performance, and is more preferable from the viewpoint of improving storage stability.

[Chemical Formula 1]

R ₁ and R ₂ in Formula 1 are independently hydrogen or an alkyl group having 1 to 4 carbon atoms, and a and b are each independently an integer of 1 to 20.

In view of this, it is preferable to use 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-9-yl acrylate, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan- Is more preferable in that it is a monomer capable of forming the formula structure 1.

The molecular weight of the alkali-soluble resin (B) may be 5,000 to 20,000, preferably 7,000 to 15,000, and the acid value is 30 to 100 mg / KOH in terms of polystyrene equivalent weight average molecular weight (hereinafter, More preferably 40 to 80 mg / KOH. When the weight average molecular weight and the acid value range are satisfied, the viscosity of the resin can be controlled within the range of from 15 wt% to 22 wt% in the range of 2.8 to 4.2 cP to improve the planarization property, and the acid value of the alkali- It is possible to control the developing characteristic of the image forming apparatus. In addition, when the acid value falls within the above-described range, problems such as occurrence of no development or afterimage due to no development are not caused, and the problem of the development rate becoming too fast and the process margin becoming poor can be solved. Thus, the planarization characteristic (DOP) is excellent and the step forming margin is improved.

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 of the colored photosensitive resin composition. When the content of the alkali-soluble resin is within the above-mentioned range, pattern formation is easy and resolution and residual film ratio are improved.

 The alkali-soluble resin (B) may include (B) 40 to 80% by weight of an alkali-soluble resin, based on the total weight of the alkali-soluble resin and the photopolymerizable compound (C) described below. When it is contained within the above range, the solubility in the developing solution is sufficient, the pattern formation is easy, and the decrease in the film thickness of the pixel portion of the exposed portion at the time of development is prevented, so that the non-pixel portion is satisfactorily missed.

 (C) Photopolymerizable compound

The photopolymerizable compound (C) is a compound capable of polymerizing under the action of light and a photopolymerization initiator described later, and examples thereof include monofunctional monomers, bifunctional monomers, and other polyfunctional monomers.

The photopolymerizable compound (C) used in the present invention is a compound having two or more different structures or functional groups of the functional group in order to improve developability, sensitivity, adhesion, surface problems, etc. of the photosensitive resin composition for forming the front light- And a photopolymerizable compound may be mixed and used. As long as it is generally used in this field, the kind thereof is not particularly limited.

 Specific examples of monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N- Money and so on. 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) Bis (acryloyloxyethyl) ether of bisphenol 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, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, (Meth) acrylate such as dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, dipentaerythritol hexa ) Acrylate, and polypentaerythritol (meth) acrylate. Of these, multifunctional monomers having two or more functional groups are preferably used.

The photopolymerizable compound may be contained in an amount of 5 to 50% by weight based on the total weight of solid components in the black photosensitive resin composition. Such a content range is a range selected in consideration of various factors such as strength or smoothness as a black matrix or spacer finally obtained. If the content is less than the above range, strength and smoothness are insufficient and conversely, , There arises a problem that patterning is not easy due to high strength, and therefore, it is appropriately used within the above range.

The photopolymerizable compound (C) may be contained in an amount of 20 to 60% by weight of the photopolymerizable compound (C) based on the total weight of the alkali-soluble resin (B) and the photopolymerizable compound (C). When the thickness is within the above range, the sensitivity of the pixel portion is improved, and the strength and flatness of the pattern are improved, so that the step can be easily formed.

(D) a photopolymerization initiator

The photopolymerization initiator is a compound for initiating the polymerization of the photopolymerizable compound and is not specifically limited in the present invention, but may be an acetophenone, benzophenone, triazine, thioxanthone, oxime, benzoin, anthraquinone, Imidazole-based compounds, etc. These may 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, benzyldimethylketal, 2- hydroxy- 1- [4- 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2- Oligomers of benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one and 2-hydroxy-2- methyl [4- (1-methylvinyl) phenyl] propan- Among them, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one can be preferably used.

Examples of the benzophenone compound include benzophenone, benzoyl benzoic acid, benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis (dimethylamino) benzophenone, Bis (diethylamino) benzophenone, and the like.

Examples of the triazine compound include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) (trichloromethyl) -s-triazine, 2 - (p-methoxyphenyl) -4,6-bis -Bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) -4,6 (Trichloromethyl) -s-triazine, 2- (4-methoxynaphtho 1-yl) -4,6-bis (trichloromethyl) (Piperonyl) -6-triazine, 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine and the like.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone and 1-chloro-4-propanecioxanthone. have.

Examples of the oxime-based compound include o-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one, and OXE01 and OXE02 commercially available from BASF.

Examples of the benzoin compound include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal.

Examples of the anthraquinone-based compounds include 2-ethyl anthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, and 2,3-diphenylanthraquinone.

Examples of the nonimidazole-based compounds include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'- ) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, a phenyl group in the 4,4', 5,5 'position is bonded to a carboalkoxy group And an imidazole compound substituted by a halogen atom.

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 the solid content in the colored photosensitive resin composition. When the photopolymerization initiator is contained within the above-mentioned range, the colored photosensitive resin composition becomes highly sensitive, and the strength of the pixel portion formed using the colored photosensitive resin composition and the smoothness on the surface of the pixel portion can be improved.

The photopolymerization initiator may be used in combination with a photopolymerization initiator. When the photopolymerization initiator is used in combination with the photopolymerization initiator, the black photosensitive resin composition containing the photopolymerization initiator is more preferable because productivity is improved when the support spacer for holding the cell gap is formed by using the black photosensitive resin composition.

The photopolymerization initiation auxiliary may be used for increasing the polymerization efficiency, and amine compounds, alkoxyanthracene compounds, and thioxanthone compounds may be used.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid isoamyl, benzoic acid- (Dimethylamino) benzophenone (collectively, Michler's ketone), 4,4'-bis (diethylamino) benzoate, 2-ethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, Phenanone, 4,4'-bis (ethylmethylamino) benzophenone, and the like, among which 4,4'-bis (diethylamino) benzophenone is preferable.

Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, .

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- And the like.

The photopolymerization initiator may be directly produced or commercially available. For example, a trade name of "EAB-F" [manufactured by Hodogaya Chemical Industry Co., Ltd.] may be used.

The photopolymerization initiator is preferably used in an amount of usually not more than 10 mol, preferably 0.01 to 5 mol, per mol of the photopolymerization initiator. When the photopolymerization initiator is used within the above range, the polymerization efficiency can be increased and the productivity improvement effect can be expected.

(E) Solvent

The solvent may be any solvent capable of dissolving or dispersing the above-mentioned composition, and is not particularly limited in the present invention. Preferably, an organic solvent having a boiling point of 100 to 200 DEG C in terms of coatability and dryness can be used.

Representative examples of usable solvents include alkylene glycol monoalkyl ethers, alkylene glycol alkyl ether acetates, aromatic hydrocarbons, ketones, lower and higher alcohols, and cyclic esters. More specifically, alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; Alkylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate Ryu; Aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin; Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; and cyclic esters such as? -butyrolactone.

Among the above solvents, alkylene glycol alkyl ether acetates, ketones, esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate may be preferably used, and 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 may 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 contained in the above-mentioned range, the coating property can be improved when the resin is applied 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 ink jet.

(F) Additive

The black 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, and anti-aggregation agents.

The thermal initiator is a substance that generates acid by heat and refers to a component that generates an acid by a heat treatment (for example, post-baking) applied during the curing of the black photosensitive resin composition to promote curing of the pattern.

In another embodiment of the present invention, the thermal initiator may be represented by the following formula (2).

(2)

In Formula 2,

R2 is a C5-C8 cycloalkyl group,

R3 is a C1-C8 alkyl group or a C6-C10 aryl group.

In the present invention, the alkyl group is not particularly limited, but may be linear or branched, and preferably has 1 to 8 carbon atoms. Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1- methyl- methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-hexyl, Propyl, 1-dimethyl-propyl, isohexyl, 2-methylbutyl, 2-methylbutyl, 2-ethylbutyl, Methylpentyl, 4-methylhexyl, 5-methylhexyl and the like, but are not limited thereto.

In the present invention, the cycloalkyl group preferably has 5 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-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.

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 preferably has 6 to 8 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. Examples of the monocyclic aryl group include, but are not limited to, a phenyl group, a biphenyl group, a terphenyl group, and a stilbenyl group. Examples of the polycyclic aryl group include, but are not limited to, a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a klycenyl group and a fluorenyl group.

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

Specifically, the thermal initiator represented by the formula (2) may be represented by the following formulas (2-1) to (2-3), and may be used alone or as a mixture of two or more thereof.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

With respect to the thermal initiator content, when the additive is included alone in the thermal decomposition resin composition, it may be contained in an amount of 1 to 10% by weight based on the total solid content of the colored photosensitive resin composition, more preferably 1 to 5% by weight . When it is contained in the above-mentioned contents, it is more preferable for fairness and undercut.

If the amount of the thermal initiator is less than the above range, the effect of the solvent resistance may be insignificant. If the amount exceeds the above range, the developing speed may be increased and the developing performance of the peeling type may be problematic. .

As the dispersing agent, a commercially available surfactant may be used, and a fluorine-based surfactant, a urethane-based surfactant, or the like may be used. Examples of the fluorine-based surfactant include BM-1000, BM-1100 (BM Chemie), Proride FC-135 / FC-170C / FC-430 (Sumitomo 3M Co., Ltd.), SH-28PA / -190 / SZ- Ltd.) and the like can be used. The urethane surfactant includes DiperBYK-163 (BYK). Dispersion aids such as Solsperse 5000 (Lubrisol) may also be added.

Examples of the filler include glass, silica and alumina. Other polymer compounds include curable resins such as epoxy resin and maleimide resin, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate , Polyester, polyurethane and the like can be used.

Examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole and alkoxybenzophenone. Examples of the antiflocculating agent include sodium polyacrylate .

The other polymeric compound is not limited as far as it does not affect compatibility, but is preferably a bisphenol A type epoxy resin, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a cyclic aliphatic epoxy resin, a glycidyl ester type epoxy A resin obtained by (co) polymerization of a glycidylamine type epoxy resin, a heterocyclic epoxy resin, and glycidyl methacrylate. Among them, bisphenol A type epoxy resin, cresol novolak type epoxy resin, glycidyl ester type epoxy resin and the like are preferable.

These additives may be used alone or in combination of two or more. The additive may be included in an amount of 0.01 to 10% by weight, preferably 0.05 to 2% by weight based on the total weight of the solid content of the colored photosensitive resin composition.

For example, a coloring agent may be added to a solvent, followed by addition of the rest of the composition and other additives, followed by stirring. At this time, the colorant may be added in the form of a mill base in which a pigment or the like is dissolved or dispersed in advance in a solvent or an alkali-soluble resin. The additive, if in solution form, may be added in advance to the solvent along with the colorant.

The thus-prepared colored photosensitive resin composition can be preferably used for the production of a display device, preferably a black matrix of a liquid crystal display, a column spacer for maintaining a cell gap, or a black column spacer.

The present invention is also characterized in that the above-mentioned colored photosensitive resin composition exhibits a light transmittance of 0.1% or less with respect to a wavelength in the range of 400 to 600 nm when formed into a cured film having a thickness of 3.0 탆; Exhibits a light transmittance of less than 10% for wavelengths in the range of 700 nm to 750 nm; And exhibits a light transmittance of not less than 15% with respect to a wavelength in the range of 1050 to 950 nm.

In particular, the colored photosensitive resin composition of the present invention can be suitably 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, Means that the matrix and the column spacer are integrally formed.

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.

Further, the present invention relates to a display device including the color filter

A typical patterning process for forming a black matrix, column spacer or black column spacer according to the photolithography method

a) applying a colored photosensitive resin composition to a substrate;

b) prebaking step of drying the solvent;

c) applying a photomask onto the obtained film to irradiate an actinic ray to cure the exposed portion;

d) performing a developing step of dissolving the unexposed portion using an aqueous alkali solution; And

e) drying and post-baking.

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

The coating may be 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 (which may be referred to as a die coater), an ink jet or the like so as to obtain a desired thickness.

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

The exposure performed after the pre-baking is performed by an exposure machine, and exposed through a photomask to expose only the portion corresponding to the pattern. The light to be irradiated may be, for example, visible light, ultraviolet light, X-ray, electron beam, or the like.

The alkali development after exposure is performed for the purpose of removing the colored photosensitive resin composition in a portion where the non-exposed portion is not removed, and a desired pattern is formed by this development. As the developer suitable for the alkali development, for example, an aqueous solution of a carbonate of an alkali metal or an alkaline earth metal may be used. Particularly, a weakly alkaline aqueous solution containing 1 to 3% by weight of a carbonate such as sodium carbonate, potassium carbonate or lithium carbonate is used at a temperature of 10 to 50 캜, preferably 20 to 40 캜, using a developing machine or an ultrasonic cleaner .

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

In this case, the thickness of the black matrix is preferably 0.2 to 20 占 퐉, more preferably 0.5 to 10 占 퐉, and particularly preferably 0.8 to 5 占 퐉.

The film thickness of the column spacer and the black column spacer is preferably 0.1 탆 to 8 탆, more preferably 0.1 탆 to 6 탆, and particularly preferably 0.1 탆 to 4 탆.

The black matrix, the column spacer, or the black column spacer made of the colored photosensitive resin composition of the present invention is excellent in physical properties such as optical density, adhesion, electrical insulation and light shielding property, and is excellent in heat resistance and solvent resistance, It is possible to improve the reliability.

Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are intended to further illustrate the present invention, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.

Production Example 1: Production of alkali-soluble resin B1

277 g of propylene glycol monomethyl ether acetate (hereinafter referred to as &quot; PGMEA &quot;) was charged into a 1-liter separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube, A mixture of 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-9-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8- : 50 (molar ratio)] 301 g of the compound [Ra '= H] represented by the following formula 1-1 and / or formula 1-2, 49 g of methacrylic acid and 23 g of azobisdimethyl valeronitrile were dissolved in methoxybutyl acetate 350 g was added dropwise over 5 hours and aged for 3 hours to obtain a copolymer solution (solid concentration 35.0%). The obtained copolymer had an acid value (dry) of 60.2 KOH mg / g and a weight average molecular weight (Mw) of 9,000.

[Formula 1-1]

[Formula 1-2]

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

Represents a single bond or an alkylene group having 1 to 18 carbon atoms)

Production Example 2: Production of alkali binder resin B2

277 g of propylene glycol monomethyl ether acetate (hereinafter referred to as &quot; PGMEA &quot;) was charged into a 1-liter separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube, A mixture of 3,4-epoxytricyclo [5.2.1.0,2,6] decan-9-yl acrylate and 3,4-epoxytricyclo [5.2.1.0,2,6] decan-8-yl acrylate 301 g of [50:50 (molar ratio)] [compound represented by the formula (11), Ra '= H], 49 g of methacrylic acid and 23 g of azobisdimethyl valeronitrile were dissolved in 350 g of methoxybutyl acetate The mixed solution was added dropwise over 5 hours and aged for 3 hours to obtain a copolymer solution (solid concentration 35.0%). The obtained copolymer had an acid value (dry) of 61.5 KOH mg / g and a weight average molecular weight (Mw) of 15,000.

Production Example 3: Production of alkali binder resin B3

A separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 72 parts by weight of methyl methacrylate, 3 parts by weight of acrylic acid, and propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA" 5 parts by weight of 2,2'-azobis (2-methylbutyronitrile) was added to the total amount (100 parts by weight) of the total amount of the monomers and dissolved homogeneously. Thereafter, the mixture was stirred at 85 DEG C for 2 hours under a nitrogen stream, and then reacted at 100 DEG C for 1 hour. To the obtained solution, 25 parts by weight of glycidyl methacrylate, 10 parts by weight of triethylamine with respect to glycidyl methacrylate, 1 part by weight of hydroquinone with respect to glycidyl methacrylate, And glycidyl methacrylate in an amount of 35% by weight, and the mixture was stirred at 100 占 폚 for 5 hours to obtain a desired 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) thereof was 72 mgKOH / g.

Examples 1 to 12 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 carried out using 0.1 mm zirconia beads, followed by dispersion and filtration to prepare a colored dispersion.

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

division coloring agent Dispersant Alkali-soluble resin Photopolymerizable compound Photopolymerization initiator additive solvent OBP V29 B60 CB B1 B2 B3 Example 1 1.95 1.25 2.15 1.05 1.79 7.75 - - 3.32 0.44 0.30 80 Example 2 1.50 0.85 1.75 0.90 1.40 8.92 - - 3.83 0.51 0.34 80 Example 3 1.50 0.85 1.75 0.90 1.40 7.01 - - 5.74 0.51 0.34 80 Example 4 2.40 1.80 3.20 1.60 2.52 5.56 - - 2.38 0.32 0.22 80 Example 5 2.40 1.80 3.20 1.60 2.52 - 5.95 - 1.99 0.32 0.22 80 Example 6 1.95 1.25 2.15 1.05 1.79 6.09 - - 4.98 0.44 0.30 80 Example 7 1.95 1.25 2.15 1.05 1.79 8.69 - - 2.38 0.44 0.30 80 Example 8 1.95 1.25 2.15 1.05 1.79 - 7.75 - 3.32 0.44 0.30 80 Example 9 1.95 1.25 2.15 1.05 1.79 3.90 3.85 - 3.32 0.44 0.30 80 Example 10 2.40 1.80 3.20 1.60 2.52 - 5.56 - 2.38 0.32 0.22 80 Example 11 1.50 0.85 1.75 0.90 1.40 - 8.92 - 3.83 0.51 0.34 80 Example 12 1.95 1.25 2.15 1.05 1.79 - 6.09 - 4.98 0.44 0.30 80 Comparative Example 1 1.95 1.25 2.15 1.05 1.79 - - 7.75 3.32 0.44 0.30 80 Comparative Example 2 1.50 0.85 1.75 0.90 1.40 - - 8.92 3.83 0.51 0.34 80 Comparative Example 3 2.40 1.80 3.20 1.60 2.52 - - 5.56 2.38 0.32 0.22 80 Comparative Example 4 1.50 0.85 1.75 0.90 1.40 - 10.01 - 2.74 0.51 0.34 80 Comparative Example 5 2.40 1.80 3.20 1.60 2.52 6.77 - - 1.17 0.32 0.22 80

OBP: Lactam-based organic black pigment

V29: C.I. Pigment Violet 29

B60: C.I. Pigment Blue 60

CB: carbon black

Alkali-soluble resin:

B1) The alkali-soluble resin prepared in Production Example 1

B2) The alkali-soluble resin prepared in Production Example 2

B3) The alkali-soluble resin prepared in Production Example 3

Photopolymerizable compound (using a (meth) acrylate group as a functional group)

Photopolymerizable compound: Viscoat # 802 (octanal, Osaka Organic Chemistry)

Photopolymerization initiator: 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethanone- 1- (O- acetyloxime) (Irgacure OXE-

Additives: I-PAG-250 (BASF) and / or F554 (DIC)

Solvent: Propylene glycol monomethyl ether acetate

Experimental Example 1. Measurement of Physical Properties of Colored Photosensitive Resin Composition

1-1. Viscosity Measurement

The viscosity of the colored photosensitive resin composition obtained by the composition of the above Example was measured with a Brookfield viscometer (Brookfield Viscometer DV-I +, manufactured by BROOKFIELD) at 25 ° C, and the results are shown in Table 2 below.

1-2. Optical property measurement (optical density, Uv-vis)

A 5 cm x 5 cm glass substrate (Corning) was cleaned with a neutral detergent and water and dried. Each of the colored photosensitive resin compositions prepared in Examples 1 to 12 and Comparative Examples 1 to 5 was spin-coated on the glass substrate to a final film thickness of 3.0 (+/- 0.2) 占 퐉 and prebaked at 80 to 120 占 폚 Followed by drying for 1 to 2 minutes to remove the solvent to form a pre-cured film.

Thereafter, the resist was exposed to light at an exposure dose of 25 to 35 mJ / cm ² to form a pattern, and an unexposed area was removed using an aqueous alkali solution. Followed by baking at 200 to 250 DEG C for 10 to 30 minutes to prepare a colored substrate.

The transmittance of the cured film formed at 550 nm was measured using an optical density meter (361T, manufactured by X-rite), and the optical density for a thickness of 1 mu m was determined.

The optical characteristics of the cured film were evaluated using UV-vis (UV-2550; Shimadzu). Evaluation criteria are as follows. The results are shown in Table 2 below.

&Lt; Criteria for evaluating optical characteristics 1: within a wavelength range of 700 to 750 nm >

○: excellent, 10% light transmittance or less

DELTA: insufficient, 10% light transmittance exceeding 12% light transmittance

X: worse, 12% exceeded light transmission

&Lt; Evaluation criterion of optical characteristics 2: within 950 nm wavelength range >

○: excellent, 15% light transmittance or more

DELTA: insufficient, 13% light transmissive or more

X: worse, 13% less light transmittance

1-3. Reliability measurement

The glass substrate on which the cured film formed by the method of 1-1 was cut was cut to 3 x 3 cm, and then immersed in an NMP solution, followed by heating at 100 ° C for 60 minutes. Thereafter, only the NMP solution was extracted, and the degree of elution in the NMP solvent was measured using a UV-vis spectrometer. The results are shown in Table 2 below.

<Reliability Evaluation Standard>

○: Excellent, absorbance less than 0.5

?: Insufficient, absorbance greater than 0.5 and less than 0.8

X: deterioration, absorbance 0.8 or more

1-4. Measurement of planarity (DOP: Degree of Planarization)

Each of the colored photosensitive resin compositions prepared in Examples 1 to 12 and Comparative Examples 1 to 9 was spin-coated on a substrate (5 cm x 5 cm glass substrate) having a pattern formed thereon so as to have a final film thickness of 3.0 (+/- 0.2) To 120 DEG C and dried for 1 to 2 minutes to remove the solvent to form a pre-cured film.

Thereafter, the entire surface is exposed with an exposure amount of 25 to 35 mJ / cm 2 to form a front pattern, and development is carried out using an aqueous alkaline solution. Followed by baking at 200 to 250 DEG C for 10 to 30 minutes to prepare a front colored substrate.

The fabricated front colored substrate was measured for the thickness of the patterned portion and the portion having no pattern at the bottom through a film thickness meter (DEKTAK6M, Veeco Co.), and then the flatness (DOP) was measured using the pattern thickness of the lower substrate .

<Evaluation criteria for flatness (DOP)>

Bottom pattern thickness: 1.17 um, flattening thickness without bottom pattern: 3.20 um

◎: Excellent, 30% or more and less than 60%

○: Excellent, 15% or more and less than 30%, 60% or more and less than 75%

△: insufficient, 10% or more, less than 15%, 75% or more, less than 85%

X: worse, less than 10, more than 85%

Light transmittance Viscosity
(cP) responsibility Planarization characteristics (%)
(DOP) Optical density (/ 占 퐉) 700 to 750 nm 950 nm Example 1 1.35 ○ ○ 3.5 ○ 42 Example 2 1.30 ○ ○ 4.0 ○ 33 Example 3 1.31 ○ ○ 3.8 ○ 44 Example 4 1.45 ○ ○ 3.3 ○ 48 Example 5 1.44 ○ ○ 3.9 ○ 46 Example 6 1.34 ○ ○ 3.1 ○ 51 Example 7 1.35 ○ ○ 3.9 ○ 36 Example 8 1.35 ○ ○ 3.8 ○ 40 Example 9 1.35 ○ ○ 3.7 ○ 41 Example 10 1.46 ○ ○ 3.2 ○ 54 Example 11 1.30 ○ ○ 4.2 ○ 31 Example 12 1.36 ○ ○ 3.4 ○ 49 Comparative Example 1 1.35 ○ ○ 4.4 X 14 Comparative Example 2 1.27 △ ○ 5.8 X 7 Comparative Example 3 1.44 ○ △ 4.3 X 12 Comparative Example 4 1.27 △ ○ 5.1 △ 9 Comparative Example 5 1.47 ○ △ 2.3 X 86

Claims (13)

(A) a colorant;
(B) an alkali-soluble resin;
(C) a photopolymerizable compound;
(D) a photopolymerization initiator; And
(E) a photosensitive resin composition,
Wherein the film formed by the colored photosensitive resin composition has a light transmittance of 10% or less in a 700-750 nm wavelength range, a light transmittance of 15% or more at 950 nm,
(DOP) value of the film formed by the colored photosensitive composition is 15 to 75% calculated by the following formula 1:
[Formula 1]
DOP (%) = {(a-d) / a} x100, 0???? 1.5 ?,??? A?
(In the above formula 1,
Ⓐ is the thickness of the lower pattern, ⓓ is the value of ⓐ + ⓒ-ⓑ, and ⓑ and ⓒ are defined as follows:
(B) indicates the thickness of the portion without pattern in the lower portion of the film formed with flatness by the colored photosensitive composition,
(C) is the thickness of the portion of the film, excluding the peak of the lower pattern, at the highest point of the film formed by the colored photosensitive composition. The colored photosensitive resin composition according to claim 1, wherein the colored photosensitive resin composition has a viscosity of 2.8 to 4.2 CP in a range of 15 to 22 wt% solids. The colored photosensitive resin composition according to claim 1, wherein the colorant (A) comprises at least one of an organic black pigment, a violet pigment, a blue pigment, and 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 alkali-soluble resin (B) has an acid value of 30 to 100 mg / KOH. The colored photosensitive resin composition according to claim 1, wherein the alkali-soluble resin is an alkali-soluble resin having a structure represented by formula (1)
[Chemical Formula 1]

(Wherein 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 photosensitive resin composition according to claim 1, which comprises 40 to 80% by weight of the alkali-soluble resin (B) and 20 to 60% by weight of the photopolymerizable compound (C), based on the total weight of the alkali- Composition. 4. The organic black pigment according to claim 3, wherein the organic black pigment is at least one selected from the group consisting of lactam black, aniline black and perylene black; The violet pigment may be C.I. Pigment Violet 14, 19, 23, 29, 32, 33, 36 and 37; The blue pigment is a mixture of C.I. At least one selected from the group consisting of Pigment Blue 15: 3, B15: 4, B15: 6, 16, 60, 61 and 66. The colored photosensitive resin composition according to claim 1, wherein the colored photosensitive resin composition further comprises one or more (F) additives selected from the group consisting of a thermal initiator, a filler, a curing agent, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber and an anti- Wherein the coloring photosensitive resin composition is a colored photosensitive resin composition. (A) from 13 to 50% by weight of a colorant, (B) from 5 to 60% by weight of an alkali-soluble resin, (C) from 5 to 50% by weight of a photopolymerizable compound, (D) 0.05 to 10% by weight of a photopolymerization initiator, and (E) 78 to 85% by weight of a solvent based on the total weight of the colored photosensitive resin composition. The colored photosensitive resin composition according to claim 10, further comprising (F) an additive in an amount of 0.01 to 10% by weight based on the total solid content of the colored photosensitive resin 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 of claim 12.

Images