KR102108232B1 - Colored Photosensitive Resin Composition for Red Pixel, Color Filter and Display Device - Google Patents

Abstract

The present invention is a colored photosensitive resin composition for a red pixel comprising an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a colorant, and a solvent, wherein the alkali-soluble resin comprises a copolymer of a thioether group-containing (meth) acrylate compound , A coloring photosensitive resin composition for a red pixel including a brominated diketopyrrolopyrrole compound, a color filter formed using the same, and an image display device having the color filter. The colored photosensitive resin composition for a red pixel according to the present invention suppresses generation of residue on the black matrix and has excellent solubility in a developer.

Description

Colored Photosensitive Resin Composition for Red Pixel, Color Filter and Display Device

The present invention relates to a colored photosensitive resin composition for a red pixel, a color filter and an image display device, and more specifically, to suppress the occurrence of residue on the black matrix, and has excellent solubility in a developer, a colored photosensitive resin composition for a red pixel, using the same It relates to a color filter to be formed and an image display device having the color filter.

Color filters are widely used in imaging devices, liquid crystal displays (LCDs), and the like, and their application range is expanding. The color filter is usually coated uniformly with a colored photosensitive resin composition containing pigments corresponding to red, green, and blue colors on a substrate having a black matrix patterned thereon, followed by exposure and development of a coating film formed by heating and drying, It is manufactured by repeating the operation of further heat curing as necessary for each color to form pixels of each color.

Republic of Korea Patent Publication No. 10-2012-0112188 discloses a colored photosensitive resin composition for a red pixel using a benzimidazole pigment having a high luminance and contrast ratio as a color material for a red pixel.

However, in order to provide a high-quality color filter having high color reproducibility, development of a colored photosensitive resin composition for a red pixel that suppresses generation of residue on a black matrix and has excellent solubility in a developer is required.

Republic of Korea Patent Publication No. 10-2012-0112188

One object of the present invention is to provide a colored photosensitive resin composition for red pixels in which generation of residue on the black matrix is suppressed and solubility in a developer is excellent.

Another object of the present invention is to provide a color filter formed using the colored photosensitive resin composition for red pixels.

Another object of the present invention is to provide an image display device having the color filter.

On the other hand, the present invention is a colored photosensitive resin composition for a red pixel comprising an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a colorant and a solvent, wherein the alkali-soluble resin is a compound represented by Formula 1, unsaturated carboxylic acid and It provides a colored photosensitive resin composition for a red pixel comprising a copolymer of a compound having an unsaturated bond capable of copolymerizing with them, and the colorant comprises a compound represented by the following formula (2).

[Formula 1]

[Formula 2]

In the above formula,

X ¹ is hydrogen or a methyl group,

X ² is a C ₁ -C ₆ alkylene group or a C ₂ -C ₆ alkenylene group,

A is an aryl group, a C ₃ -C ₁₀ cycloalkyl group, a C ₁ -C ₆ alkyl group or a C ₂ -C ₆ alkenyl group.

On the other hand, the present invention provides a color filter formed using the colored photosensitive resin composition for red pixels.

On the other hand, the present invention provides an image display device characterized in that the color filter is provided.

The colored photosensitive resin composition for a red pixel according to the present invention includes an alkali-soluble resin containing a thioether group, and includes a red pigment containing a brominated diketopyrrolopyrrole compound, thereby suppressing the occurrence of residue on the black matrix and solubility in developer. Is excellent.

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

One embodiment of the present invention includes an alkali-soluble resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), a colorant (D) and a solvent (E), wherein the alkali-soluble resin contains a thioether group ( It relates to a colored photosensitive resin composition for a red pixel comprising a copolymer of a meth) acrylate compound, and the colorant comprises a brominated diketopyrrolopyrrole compound.

Alkali-soluble resin (A)

In one embodiment of the present invention, the alkali-soluble resin (A) usually has reactivity and alkali solubility by the action of light or heat, and acts as a dispersion medium for a coloring material.

The alkali-soluble resin (A) includes a copolymer of a compound represented by the following formula (1), an unsaturated carboxylic acid, and a compound having an unsaturated bond copolymerizable therewith.

[Formula 1]

In the above formula,

X ¹ is hydrogen or a methyl group,

X ² is a C ₁ -C ₆ alkylene group or a C ₂ -C ₆ alkenylene group,

A is an aryl group, a C ₃ -C ₁₀ cycloalkyl group, a C ₁ -C ₆ alkyl group or a C ₂ -C ₆ alkenyl group.

As used herein, the C ₁ -C ₆ alkylene group means a straight chain or branched divalent hydrocarbon composed of 1 to 6 carbon atoms, and includes, but is not limited to, methylene, ethylene, propylene, butylene, and the like. It does not work.

Alkenylene group of C ₂ -C ₆ as used herein refers to a straight-chain or branched divalent unsaturated hydrocarbon composed of 2 to 6 carbon atoms having at least one carbon-carbon double bond, for example, vinylene, pro Phenylene, buteneylene, pentylene, and the like.

The aryl group used herein includes both an aromatic group and a heteroaromatic group, and partially reduced derivatives thereof. The aromatic group is a 5 to 15 membered simple or fused cyclic, and the heteroaromatic group means an aromatic group containing one or more oxygen, sulfur or nitrogen. Examples of typical aryl groups are phenyl, naphthyl, pyridinyl, furanyl, thiophenyl, indolyl, quinolinyl, imidazolinyl, Oxazolyl, thiazolyl, tetrahydronaphthyl, and the like, but is not limited thereto.

The C ₃ -C ₁₀ cycloalkyl group used herein refers to a simple or fused cyclic hydrocarbon composed of 3 to 10 carbon atoms, and includes, but is not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like. It does not work.

As used herein, the alkyl group of C ₁ -C _{6 means} a straight chain or branched monovalent hydrocarbon composed of 1 to 6 carbon atoms, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl , i-butyl, t-butyl, n-pentyl, n-hexyl, and the like.

As used herein, an alkenyl group of C ₂ -C ₆ refers to a straight-chain or branched monovalent unsaturated hydrocarbon composed of 2 to 6 carbon atoms having one or more carbon-carbon double bonds, for example, ethyleneyl, pro Fenyl, butenyl, pentyl, and the like are included, but are not limited thereto.

The C ₁ -C ₆ alkylene group, C ₂ -C ₆ alkenylene group, C ₃ -C ₁₀ cycloalkyl group, C ₁ -C ₆ alkyl group and C ₂ -C ₆ alkenyl group is one or more The above hydrogen can be substituted with halogen, C ₁ -C ₆ alkyl group, C ₁ -C ₆ haloalkyl group, hydroxy, acyl group, alkoxycarbonyl, carboxy, amino, or the like.

In particular, the compound represented by Formula 1 may be a compound represented by Formula 3 below.

[Formula 3]

In the above formula,

X ¹ is hydrogen or a methyl group,

X ² is a C ₁ -C ₆ alkylene group or a C ₂ -C ₆ alkenylene group.

When the compound represented by Chemical Formula 3 is used, it is preferable in terms of developability and surface development.

Specific examples of the compound represented by Chemical Formula 1 are 2- (phenylthio) ethyl (meth) acrylate, 2- (cyclohexylthio) ethyl (meth) acrylate, 2- (hexylthio) ethyl (meth) acrylate And the like. These may be used alone or in combination of two or more.

The compound represented by Chemical Formula 1 may be included in a range of 2 to 50 mol% with respect to 100 mol% of the total monomers constituting the alkali-soluble resin (A).

As the unsaturated carboxylic acid, any carboxylic acid compound having an unsaturated double bond capable of polymerization can be used without limitation. Specific examples of the unsaturated carboxylic acid include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid, and itaconic acid; And anhydrides of these dicarboxylic acids; and mono (meth) acrylates of polymers having carboxyl groups and hydroxyl groups at both ends, such as ω-carboxypolycaprolactone mono (meth) acrylate. Of these, acrylic acid and methacrylic acid are preferred because of their excellent copolymerization reactivity and solubility in a developer. These may be used alone or in combination of two or more.

The unsaturated carboxylic acid may be included in the range of 2 to 70 mol% based on 100 mol% of the total monomers constituting the alkali-soluble resin (A).

The compound represented by Formula 1 and the compound having an unsaturated bond copolymerizable with an unsaturated carboxylic acid include an aromatic vinyl compound, an N-substituted maleimide compound, an unsubstituted or substituted alkyl ester of an unsaturated carboxylic acid, and an alicyclic substituent. Unsaturated carboxylic acid esters, vinyl carboxylic acid esters, unsaturated oxetanyl compounds containing an oxetane group, unsubstituted or substituted aryl esters of unsaturated carboxylic acids, and the like. Among the above compounds, an aromatic vinyl compound, an unsubstituted or substituted aryl ester of an unsaturated carboxylic acid, and an N-substituted maleimide compound are more preferable from the viewpoint of improving sensitivity and adhesion. These may be used alone or in combination of two or more.

Examples of the aromatic vinyl compound include vinyl toluene, styrene, α-methylstyrene, α-chlorostyrene, and divinylbenzene, which can be used alone or in combination of two or more. In particular, vinyl toluene is preferred in terms of sensitivity and adhesion.

Examples of the N-substituted maleimide compound include a compound represented by Formula 5 below.

[Formula 5]

In the above formula,

X ³ is a C ₁ -C ₂₀ aliphatic or aromatic hydrocarbon group with or without heteroatoms.

Specific examples of X ³ include a phenyl group, a benzyl group, a naphthyl group, a cyclohexyl group, a methyl group, an ethyl group, and a propyl group, and particularly preferably a benzyl group and a cyclohexyl group. These may be used alone or in combination of two or more.

Examples of the unsubstituted or substituted alkyl ester of the unsaturated carboxylic acid are methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and aminoethyl (meth) ) Acrylates and the like. These may be used alone or in combination of two or more.

As the unsaturated carboxylic acid ester containing the alicyclic substituent, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl ( Meth) acrylate, menthyl (meth) acrylate, cyclopentenyl (meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, menthadie Neil (meth) acrylate, isobornyl (meth) acrylate, pinanyl (meth) acrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, pinenyl (meth) acrylate, etc. Can be heard. These may be used alone or in combination of two or more.

Vinyl acetate, vinyl propionate, etc. are mentioned as said carboxylic acid vinyl ester. These may be used alone or in combination of two or more.

The unsaturated oxetanyl compound containing the oxetane group is 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyl) Oxymethyl) -2-methyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-pentafluoroethyl oxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 3- (methacryloyloxymethyl) -2,2-difluorooxetane, 3- (methacryloyloxymethyl) -2 , 2,4-Trifluorooxetane, 3- (methacryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (methacryloyloxyethyl) oxetane, 3 -(Methacryloyloxyethyl) -3-ethyloxetane, 2-ethyl-3- (methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -2-trifluoromethyl Oxetane, 3- (methacryloyloxyethyl) -2-pentafluoroethyl oxetane, 3- (methacryloyloxyethyl) -2-phenyloxetane, 2,2-difluoro-3- (Methacrylic Iloxyethyl) oxetane, 3- (methacryloyloxyethyl) -2,2,4-trifluorooxetane, 3- (methacryloyloxyethyl) -2,2,4,4-tetra And fluorooxetane. These may be used alone or in combination of two or more.

Examples of the unsubstituted or substituted aryl ester of the unsaturated carboxylic acid include phenyl (meth) acrylate and benzyl (meth) acrylate. These may be used alone or in combination of two or more.

The compound represented by Formula 1 and the compound having an unsaturated bond capable of copolymerizing with an unsaturated carboxylic acid may be included in a range of 2 to 70 mol% with respect to 100 mol% of the total monomers constituting the alkali-soluble resin (A).

The method for producing the copolymer is not particularly limited, and a conventionally known polymerization method may be used, and a solution polymerization method is preferable among known polymerization methods. In addition, the polymerization temperature or polymerization time varies depending on the type or ratio of the monomer to be introduced, the molecular weight and acid value of the desired alkali-soluble resin, but can be polymerized, for example, at 60 to 130 ° C. for 1 to 10 hours.

In the case of using a solvent in the polymerization, a solvent used in a normal radical polymerization reaction may be used, and specifically, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, acetone, methyl ethyl ketone , Methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, methanol, ethanol, propanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl Ether, toluene, xylene, ethylbenzene, chloroform, dimethyl sulfoxide and the like can be used. These solvents may be used alone or in combination of two or more.

As the polymerization initiator used in the polymerization, a polymerization initiator usually used may be added, and is not particularly limited. Specifically, diisopropylbenzene hydroperoxide, di-t-butylperoxide, benzoylperoxide, t-butylperoxyisopropylcarbonate, t-amylperoxy-2-ethylhexanoate, t-butyl Organic peroxides such as peroxy-2-ethylhexanoate; 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylbareronitrile), dimethyl 2,2'-azobis (2-methylpropionate), etc. And nitrogen compounds. These may be used alone or in combination of two or more.

In the polymerization, a chain transfer agent may be used to control the molecular weight or molecular weight distribution of the copolymer. Examples of the chain transfer agent include mercapto compounds such as n-dodecanethiol, mercaptoacetic acid, and methyl mercaptoacetate; α-methylstyrene dimer and the like can be used.

In one embodiment of the present invention, the alkali-soluble resin (A) is an unsaturated bond in one molecule to the copolymer of the compound represented by the formula (1), an unsaturated carboxylic acid, and a compound having an unsaturated bond copolymerizable therewith. It may be obtained by further reacting a compound having an epoxy group. By adding a compound having an unsaturated bond and an epoxy group in one molecule to the copolymer, light / thermosetting property can be imparted to the alkali-soluble resin.

Specific examples of the compound having an unsaturated bond and an epoxy group in the one molecule include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and 3,4-epoxycyclohexylmethyl (meth) acrylate And methyl glycidyl (meth) acrylate. Among them, glycidyl (meth) acrylate is preferably used. These may be used alone or in combination of two or more.

The compound having an unsaturated bond and an epoxy group in the one molecule may be used in a range of 5 to 80 mol%, for example, 10 to 70 mol%, based on 100 mol% of the unsaturated carboxylic acid. When a compound having an unsaturated bond and an epoxy group in the one molecule is used in the above range, sufficient photocurability or thermosetting property is obtained, so that sensitivity and pencil hardness are compatible and reliability can be excellent.

The acid value of the alkali-soluble resin (A) is preferably 30 to 200 mgKOH / g. When the acid value of the alkali-soluble resin (A) is less than 30 mgKOH / g, the coloring photosensitive resin composition for red pixels is difficult to secure a sufficient developing speed, and when it exceeds 200 mgKOH / g, adhesion to the substrate is reduced and short circuit of the pattern occurs. It is easy, and the compatibility with the colorant is poor, so that the colorant in the color photosensitive resin composition for red pixels precipitates or the storage stability of the color photosensitive resin composition for red pixels is lowered, so that the viscosity tends to increase.

In addition, the weight average molecular weight in terms of polystyrene (hereinafter simply referred to as 'weight average molecular weight') measured by gel permeation chromatography (GPC; tetrahydrofuran as an elution solvent) is 3,000 to 100,000, preferably 5,000 to 50,000. Alkali-soluble resins are preferred. When the molecular weight is in the above range, the hardness of the coating film is improved, the residual film ratio is high, the solubility of the non-exposed portion in the developer is excellent, and the resolution tends to be improved, which is preferable.

The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the alkali-soluble resin (A) is preferably 1.5 to 6.0, and more preferably 1.8 to 4.0. A molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of 1.5 to 6.0 is preferable because of its excellent developability.

The alkali-soluble resin (A) may be included in an amount of 10 to 80% by weight, preferably 20 to 70% by weight, based on 100% by weight of the total solids in the colored photosensitive resin composition for red pixels. When the alkali-soluble resin (A) is included in the above range, solubility in a developer may be sufficient to facilitate pattern formation.

Photopolymerization  Compound (B)

In one embodiment of the present invention, the photopolymerizable compound (B) is a compound that can be polymerized by the action of the following photopolymerization initiator (C), a monofunctional monomer, a bifunctional monomer or a polyfunctional monomer can be used, preferably It can be used a polyfunctional monomer of two or more functional.

Specific examples of the monofunctional monomer, nonylphenylcarbitolacrylate, 2-hydroxy-3-phenoxypropylacrylate, 2-ethylhexylcarbitolacrylate, 2-hydroxyethylacrylate or N-vinylpy Lollydon, and the like, but is not limited thereto.

Specific examples of the bifunctional monomer, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate , Bis (acryloyloxyethyl) ether of bisphenol A, or 3-methylpentanediol di (meth) acrylate, but is not limited thereto.

Specific examples of the polyfunctional monomer, trimethylol propane tri (meth) acrylate, ethoxylated trimethylol propane tri (meth) acrylate, propoxylated trimethylol propane tri (meth) acrylate, pentaerythritol tree (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) Acrylate or dipentaerythritol hexa (meth) acrylate, but is not limited thereto.

The photopolymerizable compound (B) may be included in an amount of 1 to 45% by weight, particularly 3 to 45% by weight, based on 100% by weight of the total solids in the colored photosensitive resin composition for red pixels. When the photopolymerizable compound (B) is included in the above range, intensity or smoothness of the pixel portion may be improved.

Light polymerization Initiator (C)

In one embodiment of the present invention, the photopolymerization initiator (C) may be used without particular limitation as long as it can polymerize the photopolymerizable compound (B). Particularly, the photopolymerization initiator (C) is an acetophenone-based compound, a benzophenone-based compound, a triazine-based compound, a biimidazole-based compound, an oxime-based compound, and the like in terms of polymerization characteristics, initiation efficiency, absorption wavelength, availability, and price. It is preferable to use at least one compound selected from the group consisting of thioxanthone compounds.

Specific examples of the acetophenone-based compound are diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-1- [4- (2-hydroxy Hydroxyethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1 -One, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.

Examples of the benzophenone-based compound include benzophenone, 0-benzoylbenzoate methyl, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'-tetra ( tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Specific examples of the triazine-based compound are 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6 -(4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (Trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2- 1) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl ) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.

Specific examples of the biimidazole-based compound are 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimi Dazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, 2,2-bis (2,6-dichlorophenyl) -4 And an imidazole compound in which the phenyl group at the 4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole or 4,4', 5,5 'position is substituted with a carboalkoxy group. . Of these, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4' , 5,5'-tetraphenylbiimidazole, 2,2-bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole is preferred Is used.

Specific examples of the oxime-based compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, and commercially available products are BASF's OXE01 and OXE02.

Examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like. There is this.

Further, the photopolymerization initiator (C) may be used in combination with the photopolymerization initiator (c1) in order to improve the sensitivity of the colored photosensitive resin composition for red pixels of the present invention. The colored photosensitive resin composition for a red pixel according to an embodiment of the present invention contains a photopolymerization initiation auxiliary agent (c1), so that the sensitivity can be further increased to improve productivity.

As the photopolymerization initiation aid (c1), for example, one or more compounds selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group can be preferably used.

Examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 4-dimethyl Aminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler Ketone), 4,4'-bis (di An aromatic amine compound such as ethylamino) benzophenone can be used, and it is particularly preferable to use an aromatic amine compound.

The carboxylic acid compound is preferably an aromatic heteroacetic acid, specifically phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthio And acetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

Specific examples of the organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercapto Butylate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), etc. Can be lifted.

The photopolymerization initiator (C) may be included in an amount of 0.1 to 40 parts by weight, preferably 1 to 30 parts by weight, based on 100 parts by weight of the total amount of the alkali-soluble resin (A) and the photopolymerizable compound (B) based on the solid content. When the photopolymerization initiator (C) is included in the above range, the coloring photosensitive resin composition for a red pixel is highly sensitive, which is preferable because the exposure time is shortened, thereby improving productivity and maintaining high resolution. In addition, the intensity of the pixel portion formed using the composition of the above-described conditions and the smoothness on the surface of the pixel portion may be improved.

Moreover, when using the said photoinitiator (c1) further, the said photoinitiator (c1) is 0.1-40 weight part with respect to 100 weight part of total amount of alkali-soluble resin (A) and photopolymerizable compound (B), Preferably It may be included in 1 to 30 parts by weight. When the amount of the photopolymerization initiation aid (c1) used is within the above range, the sensitivity of the colored photosensitive resin composition for a red pixel is increased, and productivity of a color filter formed using the composition can be improved.

Coloring agent (D)

In one embodiment of the present invention, the coloring agent (D) includes a brominated diketopyrrolopyrrole compound represented by the following Chemical Formula 2 as a pigment.

[Formula 2]

The compound represented by Chemical Formula 2 may be included in an amount of 5 to 100% by weight, for example, 50 to 100% by weight based on 100% by weight of the total colorant. When the compound represented by Chemical Formula 2 is included below the above range, coloring power may be slightly lowered.

The coloring agent (D) is a compound represented by the following formula (4) and C.I. Pigment Red 177 may be further included.

[Formula 4]

The compound represented by Chemical Formula 2 and the compound represented by Chemical Formula 4 may be used by directly synthesizing or purchasing a commercially available form. As a commercial product of the compound represented by Formula 2, there is Irgaphor® Red S 3620 CF from BASF, and as a commercial product of the compound represented by Formula 4, there is CI Pigment Red 254.

The compound represented by Chemical Formula 2 and the compound represented by Chemical Formula 4 may be included in a weight ratio of 1: 9 to 9: 1.

The compound represented by the formula (4) may be included in an amount of 5 to 60% by weight relative to 100% by weight of the total colorant, the C.I. Pigment Red 177 may be included in an amount of 5 to 70% by weight based on 100% by weight of the total colorant.

Compound represented by Formula 4 and C.I. When the pigment red 177 is included in each of the above ranges, the coloring power may be slightly lowered, and when it exceeds the above range, pattern formation may be somewhat difficult, which may cause a decrease in adhesion.

When the compound represented by Chemical Formula 4 and CI Pigment Red 177 satisfy each of the above-described content ranges, adhesion deterioration can be prevented and reliability can be increased.

The colorant is a compound represented by Formula 2, a compound represented by Formula 4, and C.I. In addition to Pigment Red 177, another pigment may be included.

The pigment may be an organic pigment or an inorganic pigment commonly used in the art. In addition, the pigment may be subjected to resin treatment, surface treatment using a pigment derivative having an acidic or basic group introduced, if necessary, graft treatment of a pigment surface with a polymer compound, atomization treatment with a sulfuric acid atomization method, etc. to remove impurities. A washing treatment with an organic solvent, water, or the like, or removal treatment of ionic impurities by an ion exchange method or the like can also be performed.

The organic pigments are specifically water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindolin pigments, perylene pigments, perinone pigments, dioxazine pigments, anthra And quinone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments, anthanthrone pigments, indantrone pigments, pravanthrone pigments, pyranthrone pigments, and diketopyrrolopyrrole pigments. have.

Examples of the inorganic pigments include metal compounds such as metal oxides and metal complex salts, and specifically, oxides or complexes of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony. And metal oxides.

In particular, examples of the organic pigments and inorganic pigments include compounds classified as pigments in the color index (published by The Society of Dyers and Colourists), and more specifically, the following color index (CI) numbers. Although a pigment is mentioned, it is not necessarily limited to these, These can be used individually or in combination of 2 or more types, respectively.

CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 180, 192, 208, 215, 216, 224, 242, 255 and 264

The pigment may use a yellow pigment together with the red pigment, and specifically, a yellow pigment having the following color index (C.I.) number may be used.

C.I. Pigment Yellow 13, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180 And 185

C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 and 71

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

It is preferable to use a pigment dispersion in which the particle size is uniformly dispersed. An example of a method for uniformly dispersing the particle diameter of a pigment may include a method of dispersing by containing a pigment dispersant, and according to this method, a pigment dispersion liquid in which the pigment is uniformly dispersed in a solution can be obtained.

Specific examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, and polyamine surfactants. These may be used alone or in combination of two or more. .

The pigment dispersant is added to deagglomerate and maintain stability of the pigment, and can be used without limitation what is generally used in the art. It is preferable to contain an acrylate-based dispersant (hereinafter, referred to as an acrylic dispersant) containing butyl methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA). At this time, it is preferable to apply the acrylic dispersant manufactured by the living control method as presented in Korean Patent Publication No. 2004-0014311. As a commercial product of the acrylic dispersant prepared through the living control method, DISPER BYK-2000, And DISPER BYK-2001, DISPER BYK-2070, and DISPER BYK-2150.

The acrylic dispersants illustrated above may be used alone or in combination of two or more.

The pigment dispersant may be a resin dispersant other than the acrylic dispersant described above. As the other resin type pigment dispersant, known resin type pigment dispersants, in particular of polyurethanes, polycarboxylic acid esters represented by polyacrylates, unsaturated polyamides, polycarboxylic acids, (partial) of polycarboxylic acids Amine 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 or salts thereof formed by the reaction of polyesters having carboxyl groups with poly (lower alkyleneimines); Water-soluble resins or water-soluble polymer compounds such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinyl pyrrolidone; Polyester; Modified polyacrylates; And adducts of ethylene oxide / propylene oxide and phosphate esters. Commercially available products of the above-mentioned resin-type dispersants are cationic resin dispersants, for example, trade names of BYK (Big) Chemicals: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK- 164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; BASF brand names: EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA- 4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; Trade names of Lubirzol: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204 / 10; Trade names of Kawaken Fine Chemicals: HINOACT T-6000, Hinoact T-7000, Hinoact T-8000; Ajinomoto's trade names: AJISPUR PB-821, AJISPUR PB-822, AJISPUR PB-823; Trade names of Kyoeisha Chemicals: FLORENE DOPA-17HF, Floren DOPA-15BHF, Floren DOPA-33, Floren DOPA-44, and the like. Pigment dispersants of other resin types other than the above-described acrylic dispersants may be used alone or in combination of two or more, or may be used in combination with acrylic dispersants.

The amount of the pigment dispersant used may be in the range of 5 to 60 parts by weight, more preferably 15 to 50 parts by weight based on 100 parts by weight of the solid content of the pigment used. If the content of the pigment dispersant exceeds 60 parts by weight based on the above, the viscosity may be increased, and if it is less than 5 parts by weight, it may be difficult to atomize the pigment or cause problems such as gelation after dispersion.

In one embodiment of the present invention, the colorant (D) may further include one or more dyes.

The dye can be used without limitation as long as it has solubility in an organic solvent. Preferably, it is preferable to use a dye which has a solubility in an organic solvent and can secure reliability such as solubility in an alkali developer, solvent resistance, and aging stability.

As the dye, an acidic dye having an acidic group such as sulfonic acid or carboxylic acid, a salt of an acidic dye and a nitrogen-containing compound, a sulfonamide body of an acidic dye, and the like, and derivatives thereof can be used. In addition, azo, xanthene, and phthalocyanine Systemic acid dyes and derivatives thereof can also be selected.

Preferably, the dye is a compound classified as a dye in the color index (published by The Society of Dyers and Colourists), or a known dye described in a dyeing note (dyeing company).

The content of the colorant (D) may be 1 to 60% by weight, preferably 5 to 50% by weight, based on 100% by weight of the total solid content in the colored photosensitive resin composition for red pixels. When the colorant (D) is included in the above range, it is preferable because even when a thin film is formed, the color density of the pixel is sufficient, and since the omission of the non-pixel portion does not decrease during development, residues are unlikely to be generated.

Solid content in the present invention means the rest of the components except the solvent.

Solvent (E)

In one embodiment of the present invention, if the solvent (E) is effective for dissolving other components included in the colored photosensitive resin composition for a red pixel of the present invention, the solvent used in the conventional colored photosensitive resin composition is not particularly limited. It can be used, and ethers, acetates, aromatic hydrocarbons, ketones, alcohols or esters are particularly preferred.

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

Examples of the acetates include methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3-methoxybutyl acetate, and 3 -Methyl-3-methoxy-1-butyl acetate, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, methyl 3-methoxypropionate, propylene glycol methyl ether acetate, 3-methoxy-1- Butyl acetate, 1,2-propylene glycol diacetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, diethylene glycol monobutyl ether Acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, di Ethylene glycol monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate and propylene carbonate, etc. Can be lifted.

Examples of the aromatic hydrocarbons include benzene, toluene, xylene and mesitylene.

Examples of the ketones include methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone.

Examples of the alcohols include ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin and 4-hydroxy-4-methyl-2-pentanone.

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

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

The solvent is preferably an organic solvent having a boiling point of 100 ° C to 200 ° C in terms of coatability and dryness, for example, alkylene glycol alkyl ether acetates, alkylene glycol monoalkyl ethers, ketones, 3- And esters such as ethyl ethoxypropionate and methyl 3-methoxypropionate. More preferably, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, ethyl lac Tate, butyl lactate, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate.

The solvent (E) may be included in 60 to 90% by weight based on 100% by weight of the colored photosensitive resin composition for red pixels. When the solvent is included in the above range, the coatability may be improved when applied with an application device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes also referred to as a die coater), and an inkjet.

Additive (F)

The colored photosensitive resin composition for red pixels of the present invention can be used in combination with other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, and aggregation inhibitors, if necessary.

Specific examples of the other polymer compound include curable resins such as epoxy resins and maleimide resins, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and thermoplastic resins such as polyurethane, etc. Can be lifted.

The curing agent is used to increase the core hardening and mechanical strength, and specific examples of the curing agent include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, and oxetane compounds.

Specific examples of the epoxy compound in the curing agent, bisphenol A-based epoxy resin, hydrogenated bisphenol A-based epoxy resin, bisphenol F-based epoxy resin, hydrogenated bisphenol F-based epoxy resin, no-block type epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin , Glycidyl ester-based resins, glycidylamine-based resins, or brominated derivatives of these epoxy resins, epoxy resins and aliphatic, alicyclic or aromatic epoxy compounds other than the brominated derivatives, butadiene (co) polymer epoxides, isoprene ( Co-polymer epoxides, glycidyl (meth) acrylate (co) polymers, triglycidyl isocyanurate, and the like.

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

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

The curing agent may be used in combination with a curing agent, an epoxy group of the epoxy compound, a curing auxiliary compound capable of ring-opening polymerization of the oxetane skeleton of the oxetane compound. Examples of the curing auxiliary compound include polyvalent carboxylic acids, polyvalent carboxylic anhydrides, and acid generators. The polyhydric carboxylic acid anhydride may be used as a commercially available epoxy resin curing agent. Specific examples of the epoxy resin curing agent, trade name (Adeka Hadona EH-700) (manufactured by Adeka Industries Co., Ltd.), trade name (Rikasitdo HH) (manufactured by Shin Nippon Ewha Co., Ltd.), trade name (MH-700) (New Japan Ewha Corporation).

The surfactant may be used to further improve the film-forming properties of the photosensitive resin composition, and a fluorine-based surfactant or silicone-based surfactant may be preferably used.

The silicone surfactant is, for example, commercially available products such as DC3PA, DC7PA, SH11PA, SH21PA, SH8400 from Dow Corning Toray Silicone, and TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460 from GE Toshiba Silicone. , TSF-4452. The fluorine-based surfactant is, for example, commercially available products such as Mega Nippon F-470, F-471, F-475, F-482, F-489 of Dai Nippon Ink Chemical Co., Ltd. The surfactants exemplified above may be used alone or in combination of two or more.

Specific examples of the adhesion promoter include vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrime And methoxysilane, 3-isocyanatepropyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane. The adhesion promoters exemplified above may be used alone or in combination of two or more. The adhesion promoter may be usually included in an amount of 0.01 to 10% by weight, preferably 0.05 to 2% by weight based on 100% by weight of the total solid content in the photosensitive resin composition.

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

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

Specific examples of the aggregation inhibitor include sodium polyacrylate and the like.

The colored photosensitive resin composition for red pixels according to an embodiment of the present invention can be produced, for example, by the following method.

First, the pigment in the coloring agent (D) is mixed with a solvent (E) and dispersed using a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. In this case, a pigment dispersant, an alkali-soluble resin (A), or all or a dye may be mixed with a solvent (E) to dissolve or disperse as necessary. The remainder of the alkali-soluble resin (A), the photopolymerization initiator (C), the photopolymerizable compound (B), and the additive (F) and the solvent (E), if necessary, are further added to the mixed dispersion to a predetermined concentration. Colored photosensitive resin composition for red pixels according to can be prepared.

One embodiment of the present invention relates to a color filter formed using the colored photosensitive resin composition for red pixels described above. The color filter according to an embodiment of the present invention is characterized in that it comprises a colored layer formed by applying a coloring photosensitive resin composition for a red pixel described above on a substrate and exposing and developing in a predetermined pattern.

Hereinafter, a method of forming a pattern using the colored photosensitive resin composition for red pixels of the present invention will be described in detail.

The method of forming a pattern by using the colored photosensitive resin composition for red pixels of the present invention can use a method known in the art, but is typically applied; Exposure step; And a removal step. The colored photosensitive resin composition for red pixels of the present invention is coated on a substrate, and photocured and developed to form a pattern, so that it can be used as a colored pixel (colored image).

In the coating step, the volatile component such as a solvent is removed and smoothed by applying the coloring photosensitive resin composition for a red pixel of the present invention to a substrate (but not limited to a glass or silicon wafer) or a photosensitive resin composition layer previously formed and preliminarily drying it. It is a step to get a coating. At this time, the thickness of the coating film is preferably 1 to 3 ㎛.

The exposing step is a step of irradiating ultraviolet rays to a specific region through a mask to obtain a desired pattern on the coating film and curing. At this time, it is preferable to use a device such as a mask aligner or a stepper so as to uniformly irradiate parallel light beams over the entire exposed portion and to accurately align the mask and the substrate.

The removing step is a step of obtaining a desired pattern by dissolving and developing a non-exposed region by irradiating ultraviolet rays and contacting a coating film having been cured to an aqueous alkali solution. After development, drying may be carried out after about 10 to 60 minutes at 140 to 200 ° C, particularly at about 150 ° C, if necessary.

The developer used for the above development can be used without limitation what is known in the art, it is usually possible to use an aqueous solution containing an alkaline compound and a surfactant.

The alkaline compound may be an inorganic or organic alkaline compound. Specific examples of the inorganic alkaline compound, sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, carbonic acid And sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, and ammonia. Further, specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, and triethylamine. , Monoisopropylamine, diisopropylamine, ethanolamine, and the like. These inorganic and organic alkaline compounds may be used alone or in combination of two or more. The alkaline compound may be included in the developer in an amount of 0.01 to 10% by weight, preferably 0.03 to 5% by weight.

As the surfactant, one or a mixture of nonionic surfactants, anionic surfactants, and cationic surfactants may be used. 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 fatty acid ester , Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, and the like. Specific examples of the anionic surfactant include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate or sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, and dodecylbenzenesulfonic acid And alkylaryl sulfonates such as sodium and sodium dodecylnaphthalenesulfonate. Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryl trimethylammonium chloride or quaternary ammonium salts. The surfactants may be used alone or in combination of two or more. The surfactant may be usually included in the developer, 0.01 to 10% by weight, preferably 0.05 to 8% by weight, more preferably 0.1 to 5% by weight.

One embodiment of the present invention relates to an image display device equipped with the above-described color filter.

The color filter of the present invention displays not only a normal liquid crystal display (LCD), but also various image displays such as an electroluminescence display (EL), a plasma display (PDP), an emission display (FED), and an organic light emitting device (OLED). Applicable to the device.

The image display device of the present invention includes a configuration known in the art, except that the above-described color filter is provided.

The image display apparatus according to an embodiment of the present invention includes a red pattern layer containing red quantum dot particles, a green pattern layer containing green quantum dot particles, and a blue pattern layer containing blue quantum dot particles in addition to the color filters described above. A color filter may be additionally provided. In such a case, the emitted light of the light source applied to the image display device is not particularly limited, but in view of better color reproducibility, a light source that emits blue light can be preferably used.

The image display apparatus according to an embodiment of the present invention may further include a color filter including only the pattern layers of two kinds of colors among the red pattern layer, the green pattern layer, and the blue pattern layer, in addition to the color filters described above. In such a case, the color filter further includes a transparent pattern layer that does not contain quantum dot particles. When only two types of color pattern layers are provided, a light source that emits light having a wavelength indicating the remaining color not included may be used. For example, when only the red pattern layer and the green pattern layer are included, a light source emitting blue light may be used. In such a case, the red quantum dot particles emit red light, the green quantum dot particles emit green light, and the transparent pattern layer transmits the blue light as it is and shows blue.

Hereinafter, the present invention will be described in more detail with reference to Examples, Comparative Examples and Experimental Examples. It is apparent to those skilled in the art that these examples, comparative examples and experimental examples are only for describing the present invention, and the scope of the present invention is not limited to them.

Manufacturing example  1: Preparation of colorant dispersion D-1

40 parts by weight of CI Pigment Red 254 represented by Chemical Formula 4 as a pigment, 24 parts by weight of BYK2001 (dispervic: manufactured by BYK, solid content concentration 45.1% by weight) (about 10.8 parts by weight in terms of solid content) and solvent As a mixture, the mixture containing 136 parts by weight of propylene glycol methyl ether acetate was mixed and dispersed with a bead mill for 12 hours to prepare a colorant dispersion D-1.

Manufacturing example  2: Preparation of colorant dispersion D-2

40 parts by weight of brominated diketopyrrolopyrrole (Irgaphor® Red S 3620 CF from BASF) represented by Chemical Formula 2 as a pigment, and 24 parts by weight of BYK2001 (Disperbic: manufactured by BYK, solid content concentration 45.1% by weight) as a dispersant A mixed solution comprising (about 10.8 parts by weight in terms of solid content) and 136 parts by weight of propylene glycol methyl ether acetate as a solvent was mixed and dispersed for 12 hours with a bead mill to prepare a colorant dispersion D-2.

Manufacturing example  3: Preparation of colorant dispersion D-3

40 parts by weight of CI Pigment Red 177 as a pigment, 24 parts by weight of BYK2001 (disperbic: manufactured by BYK, 45.1% by weight of solid content) as a dispersant (about 10.8 parts by weight in terms of solid content) and propylene glycol methyl ether as a solvent A colorant dispersion D-3 was prepared by mixing and dispersing a mixed solution containing 136 parts by weight of acetate with a bead mill for 12 hours.

Synthetic example  1: Synthesis of alkali-soluble resin A-1

A flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping lot, and a nitrogen introduction tube was prepared, while 52 g (0.25 mol) of 2-phenylthioethylacrylate and 44 g (0.25 mol) of benzyl methacrylate were added as a monomer dropping lot. , 12.9 g (0.15 mol) of methacrylic acid, 41.3 g (0.35 mol) of vinyl toluene, 4 g of t-butylperoxy-2-ethylhexanoate and 40 g of propylene glycol monomethyl ether acetate (PGMEA) were added and stirred and mixed. Prepared and prepared as a chain transfer agent dropping tank, 6 g of n-dodecanthiol and 24 g of PGMEA were added and stirred and mixed. Thereafter, 395 g of PGMEA was introduced into the flask, and the atmosphere in the flask was changed to nitrogen from air, and the temperature of the flask was raised to 90 ° C. while stirring. Subsequently, the monomer and the chain transfer agent were dripped from the dropping lot. The dropwise addition, while maintaining at 90 ° C, proceeded for 2 hours each, and after 1 hour, the temperature was raised to 110 ° C to proceed the reaction for 8 hours to obtain alkali-soluble resin A-1 having a solid acid value of 70 mgKOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 23,000, and the molecular weight distribution (Mw / Mn) was 2.4.

Synthetic example  2: Synthesis of alkali-soluble resin A-2

A flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping lot, and a nitrogen introduction tube was prepared, while 52 g (0.25 mol) of 2-phenylthioethylacrylate and 15 g (0.15 mol) of methylmethacrylate were added as a monomer dropping lot. , Methacrylic acid 21.5 g (0.25 mol), benzyl maleimide 65.4 g (0.35 mol), t-butyl peroxy-2-ethyl hexanoate 4 g and propylene glycol monomethyl ether acetate (PGMEA) 40 g was added followed by stirring and mixing And prepared as a chain transfer agent dropper, 6 g of n-dodecanethiol and 24 g of PGMEA were added and stirred and prepared. Thereafter, 395 g of PGMEA was introduced into the flask, and the atmosphere in the flask was changed to nitrogen from air, and the temperature of the flask was raised to 90 ° C. while stirring. Subsequently, the monomer and the chain transfer agent were dripped from the dropping lot. The dropping, while maintaining 90 ° C, proceeds for 2 hours each, and after 1 hour, the temperature is raised to 110 ° C and maintained for 5 hours, and then a gas introduction pipe is introduced to mix oxygen / nitrogen = 5/95 (v / v) Started bubbling. Subsequently, 21.3 g (0.15 mol) of glycidyl methacrylate, 0.4 g of 2,2'-methylenebis (4-methyl-6-t-butylphenol), and 0.8 g of triethylamine were introduced into the flask at 110 ° C. The reaction proceeded for 8 hours to obtain alkali-soluble resin A-2 having a solid acid value of 73 mgKOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 18,000, and the molecular weight distribution (Mw / Mn) was 2.2.

Synthetic example  3: Synthesis of alkali-soluble resin A-3

A flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping lot, and a nitrogen introduction tube was prepared. Meanwhile, as a monomer dropping lot, 88 g (0.5 mol) of benzyl methacrylate, 12.9 g (0.15 mol) of methacrylic acid, and vinyl 41.3 g (0.35 mol) of toluene, 4 g of t-butylperoxy-2-ethylhexanoate and 40 g of propylene glycol monomethyl ether acetate (PGMEA) were prepared by stirring and mixing. As a chain transfer agent dropping tank, n-dode 6 g of canthiol and 24 g of PGMEA were added and stirred and prepared. Thereafter, 395 g of PGMEA was introduced into the flask, and the atmosphere in the flask was changed to nitrogen from air, and the temperature of the flask was raised to 90 ° C. while stirring. Subsequently, the monomer and the chain transfer agent were dripped from the dropping lot. Dropping, while maintaining at 90 ° C., proceeded for 2 hours each, and after 1 hour, the temperature was raised to 110 ° C. and the reaction was performed for 8 hours to obtain alkali-soluble resin A-3 having a solid acid value of 70 mg KOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 21,000, and the molecular weight distribution (Mw / Mn) was 2.2.

Example  1 to 3 and Comparative example  1 to 6: Red Pixel  Preparation of colored photosensitive resin composition

Each component was mixed with the composition of Table 1 below to prepare a colored photosensitive resin composition for red pixels (unit: wt%).

division
(weight%) Alkali-soluble resin Photopolymerization
compound Photopolymerization initiator Colorant dispersion solvent additive A-1 A-2 A-3 B C D-1 D-2 D-3 E F Comparative Example 1 - 10 - 5 0.6 20 - 10 54.3 0.1 Comparative Example 2 10 - - 5 0.6 20 - 10 54.3 0.1 Comparative Example 3 - - 10 5 0.6 - 20 10 54.3 0.1 Comparative Example 4 - - 10 5 0.6 4 16 10 54.3 0.1 Comparative Example 5 - - 10 5 0.6 10 16 4 54.3 0.1 Comparative Example 6 - - 10 5 0.6 10 10 10 54.3 0.1 Example 1 10 - - 5 0.6 4 16 10 54.3 0.1 Example 2 10 - 5 0.6 10 16 4 54.3 0.1 Example 3 10 - - 5 0.6 - 30 - 54.3 0.1

Alkali-soluble resin

A-1: Alkali-soluble resin of Synthesis Example 1

A-2: Alkali-soluble resin of Synthesis Example 2

A-3: Alkali-soluble resin of Synthesis Example 3

Photopolymerizable compound (B): A9550 (Cinnakamura Co.)

Photopolymerization initiator (C): OXE-01 (BASF)

Colorant dispersion (D)

D-1: Colorant dispersion of Preparation Example 1

D-2: Colorant dispersion of Preparation Example 2

D-3: Colorant dispersion of Preparation Example 3

Solvent (E): Propylene glycol monomethyl ether acetate

Additive (F): Silicone surfactant SH8400 (Dow Corning Toray Silicone Co., Ltd.)

Experimental Example  One

Using the colored photosensitive resin composition for red pixels prepared in Examples and Comparative Examples, residue generation and re-solubility on the black matrix were evaluated as follows, and the results are shown in Table 2 below.

(1) Black Matrix Award Residue

The colored photosensitive resin composition for red pixels was coated on a substrate on which a black matrix was formed by spin coating, and then placed on a heating plate and maintained at a temperature of 100 ° C. for 3 minutes to form a color layer thin film. Subsequently, a test photomask having a line / space pattern of 1 to 50 µm was placed, and ultraviolet light was irradiated with a distance from the test photomask of 250 µm. At this time, the ultraviolet light source was irradiated with an illuminance of 50 mJ / cm 2 using a high pressure mercury lamp of 1 kW containing all g, h, and i rays, and no special optical filter was used. The color layer thin film irradiated with ultraviolet rays was developed by immersing it in a KOH aqueous solution developing solution at pH 10.5 for 2 minutes. Then, the presence or absence of development residue on the black matrix was observed and evaluated according to the following evaluation criteria.

<Evaluation criteria>

○: No developing residue on the black matrix

×: There is a developing residue on the black matrix

(2) Re-solubility

After the colored photosensitive resin composition for red pixels was applied to the top of the glass substrate by spin coating, it was placed on a heating plate and maintained at a temperature of 100 ° C. for 3 minutes to form a thin film of color layer. The formed color layer thin film was immersed in a KOH aqueous solution developing solution having a pH of 10.5, and then observed for soluble form for 3 minutes, and evaluated by the following evaluation criteria.

<Evaluation criteria>

○: completely dissolved

×: dissolved in the form of peeling

Black matrix award Residue Re-solubility Comparative Example 1 × × Comparative Example 2 × × Comparative Example 3 × × Comparative Example 4 × × Comparative Example 5 × × Comparative Example 6 × × Example 1 ○ ○ Example 2 ○ ○ Example 3 ○ ○

As shown in Table 2, a copolymer of a compound represented by Formula 1, an unsaturated carboxylic acid, and a compound having an unsaturated bond copolymerizable therewith as an alkali-soluble resin according to the present invention, and a brominated diketopy as a colorant It was confirmed that the colored photosensitive resin composition for red pixels of Examples 1 to 3 containing the rollopyrrole compound had no black matrix phase residue and had excellent solubility in a developer. On the other hand, for the red pixel of Comparative Examples 1 to 6, which does not contain any one of the compound represented by Formula 1, the unsaturated carboxylic acid and the copolymer of the compound having an unsaturated bond capable of copolymerizing with them, and the brominated diketopyrrolopyrrole compound. It was confirmed that the colored photosensitive resin composition had black matrix residue and poor solubility in the developer.

Since the specific parts of the present invention have been described in detail above, it is obvious that for those skilled in the art to which the present invention pertains, this specific technology is only a preferred embodiment, and the scope of the present invention is not limited thereto. Do. Those skilled in the art to which the present invention pertains will be able to make various applications and modifications within the scope of the present invention based on the above.

Accordingly, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

Claims (6)

A colored photosensitive resin composition for red pixels comprising an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a colorant, and a solvent,
The alkali-soluble resin comprises a copolymer of a compound represented by the following formula (1), an unsaturated carboxylic acid and a compound having an unsaturated bond capable of copolymerizing them,
The colorant is composed of a pigment, and the pigment includes a compound represented by the following Chemical Formula 2, a compound represented by the following Chemical Formula 4, and CI Pigment Red 177,
The compound represented by the formula (2) is a colored photosensitive resin composition for red pixels contained in an amount of 5 to 100% by weight relative to 100% by weight of the total colorant:
[Formula 1]

[Formula 2]

[Formula 4]

In the above formula,
X ¹ is hydrogen or a methyl group,
X ² is a C ₁ -C ₆ alkylene group or a C ₂ -C ₆ alkenylene group,
A is an aryl group, a C ₃ -C ₁₀ cycloalkyl group, a C ₁ -C ₆ alkyl group or a C ₂ -C ₆ alkenyl group. The colored photosensitive resin composition for red pixels according to claim 1, wherein the compound represented by Chemical Formula 1 is a compound represented by Chemical Formula 3:
[Formula 3]

In the above formula,
X ¹ is hydrogen or a methyl group,
X ² is a C ₁ -C ₆ alkylene group or a C ₂ -C ₆ alkenylene group. delete delete A color filter formed by using the colored photosensitive resin composition for red pixels according to any one of claims 1 to 2. An image display device characterized in that the color filter according to claim 5 is provided.