KR101986408B1 - Colored Photosensitive Resin Composition, Color Filter and Display Device - Google Patents

Abstract

The present invention provides a colored photosensitive resin composition comprising an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a colorant and a solvent, wherein the alkali-soluble resin comprises an alkali-soluble resin polymerized with N-benzylmaleimide, The initiator comprises a colored photosensitive resin composition comprising an oxime ester fluorene photopolymerization initiator having a specific structure, a color filter formed using the colored photosensitive resin composition, and an image display device provided with the color filter. The colored photosensitive resin composition according to the present invention has a high developing speed, excellent adhesion, sensitivity and reliability, and can minimize outgassing.

Description

TECHNICAL FIELD [0001] The present invention relates to a colored photosensitive resin composition, a color filter,

The present invention relates to a colored photosensitive resin composition, a color filter, and an image display device, and more particularly, to a colored photosensitive resin composition which has a high developing speed, is excellent in adhesion, sensitivity and reliability, And an image display apparatus provided with the color filter.

BACKGROUND ART [0002] Color filters are widely used in imaging elements, liquid crystal displays (LCDs), and the like, and their application range is rapidly expanding. The color filter is usually prepared by uniformly applying a colored photosensitive resin composition containing a pigment corresponding to each color of red, green and blue on a substrate on which a black matrix is pattern-formed, exposing and developing a coating film formed by heating and drying, By repeating the operation of heating and curing as necessary according to each color to form pixels of each color. Thereafter, a color filter for a liquid crystal display device is formed with a step of forming an ITO electrode on its surface, and this step is exposed to a high temperature of about 200 캜 or more.

As a colored photosensitive resin composition for use in such a use, a colored resin composition obtained through a composition of an acrylic resin containing a carboxyl group in a side chain and a pigment and a polyfunctional acrylate as a resin having excellent solvent resistance and little change in color is disclosed. Korean Patent Laid-Open Publication No. 1995-0009350 discloses a photosensitive resin composition using an acrylic resin containing an alcoholic hydroxyl group skeleton having hydrophilicity to improve residue and adhesiveness.

However, when the conventional art as described above is introduced intact, there is a problem that an after-image is generated due to outgas generated by decomposition of the colored photosensitive resin composition after a high-temperature process. Recently, a colored photosensitive resin composition having a high developing speed and excellent adhesion, sensitivity, and reliability has been required to shorten the process time.

Korean Patent Publication No. 1995-0009350

An object of the present invention is to provide a colored photosensitive resin composition which has a high developing speed, is excellent in adhesion, sensitivity and reliability, and can minimize outgassing.

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

It is still another object of the present invention to provide an image display apparatus provided with the color filter.

On the other hand, the present invention provides a colored photosensitive resin composition comprising an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a colorant and a solvent, wherein the alkali-soluble resin comprises an alkali-soluble resin polymerized with N-benzylmaleimide , And the photopolymerization initiator comprises a photopolymerization initiator represented by the following general formula (1).

[Chemical Formula 1]

In this formula,

R ₁ to R ₃ are each independently selected from the group consisting of hydrogen, halogen, C ₁ -C ₂₀ alkyl, aryl, C ₁ -C ₂₀ alkoxy, aralkyl, C ₁ -C ₂₀ hydroxyalkyl, C ₂ -C A hydroxyalkoxyalkyl group having 1 to ₄₀ carbon atoms or a cycloalkyl group having _{3 to 20} carbon atoms;

R ₄ to R ₁₀ are each independently hydrogen, a C ₁ -C ₂₀ alkyl group, an aryl group, a C ₁ -C ₂₀ alkoxy group, an aralkyl group, a C ₁ -C ₂₀ hydroxyalkyl group, a C ₂ -C ₄₀ A hydroxyalkyl group, a hydroxyalkoxyalkyl group, a C ₃ -C ₂₀ cycloalkyl group, an amino group, a nitro group, a cyano group or a hydroxy group;

p is 0 or 1;

In one embodiment of the present invention, R ₁ to R ₃ are each independently hydrogen, a C ₁ -C ₆ alkyl group or a phenyl group, R ₄ to R ₁₀ are each independently hydrogen or a nitro group, p is 0 have.

In one embodiment of the present invention, R ₁ to R ₃ are each independently hydrogen or a C ₁ -C ₆ alkyl group, R ₄ to R ₁₀ are hydrogen, and p may be 1.

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

On the other hand, the present invention provides an image display device having the color filter.

The colored photosensitive resin composition according to the present invention comprises an alkali-soluble resin polymerized by incorporating N-benzylmaleimide as an alkali-soluble resin, and contains a oxime ester fluorene-based photopolymerization initiator having a specific structure as a photopolymerization initiator, Fast, excellent adhesion, sensitivity and reliability, and can minimize outgassing.

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

An embodiment of the present invention is a colored photosensitive resin composition comprising an alkali-soluble resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), a colorant (D) and a solvent (E) A) comprises an alkali-soluble resin polymerized with N-benzylmaleimide, and the photopolymerization initiator (C) comprises an oxime ester fluorene photopolymerization initiator.

The alkali-soluble resin (A)

In one embodiment of the present invention, the alkali-soluble resin (A) allows the exposed region of the resin layer formed using the colored photosensitive resin composition to remain, while the non-exposed region becomes alkali-soluble and can be removed.

The alkali-soluble resin (A) used in the present invention is polymerized including N-benzylmaleimide.

N-benzyl maleimide can be appropriately mixed according to the kind of the other monomers to be copolymerized. Therefore, the content and the mixing ratio are not particularly limited, and it is preferable that N-benzyl maleimide is used in an amount of 1 to 100 parts by weight based on 100% by mol of the entire monomer constituting the alkali- To 90% by mole, specifically 2 to 50% by mole, of the polymerizable monomer is preferable in view of developability, solubility and reliability.

The alkali-soluble resin according to the present invention may be polymerized by further comprising at least one other monomer copolymerizable with the carboxyl group-containing monomer and the N-benzylmaleimide. Examples of the solvent include styrene,? -Methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p- -Vinylbenzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, Aromatic vinyl compounds; 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 Unsaturated carboxylic acids such as propyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate and 3- (acryloyloxy) -2-hydroxypropyl methacrylate. Carboxylic acid esters; 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; Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl 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; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; A monoacryloyl group or a monomethacryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, Macromonomers; Maleimide; N-phenylmaleimide; N-cyclohexylmaleimide; Carboxyl group-containing monomers and the like.

Examples of the carboxyl group-containing monomer include unsaturated carboxylic acids such as unsaturated polycarboxylic acids having at least one carboxyl group in the molecule such as unsaturated monocarboxylic acid, unsaturated dicarboxylic acid and unsaturated tricarboxylic acid. have.

Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid,? -Chloroacrylic acid, cinnamic acid, and the like. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid.

The unsaturated polycarboxylic acids include acid anhydrides such as maleic acid anhydride, itaconic acid anhydride and citraconic anhydride; (2-acryloyloxyethyl) succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl), phthalic acid mono (2-methacryloyloxyalkyl) ester having a carboxyl group; ? -carboxypolycaprolactone monoacrylate,? -carboxypolycaprolactone monoacrylate,? -carboxypolycaprolactone monoacrylate,? -carboxypolycaprolactone monomethacrylate, and the like.

The acid value of the alkali-soluble resin is not particularly limited and may be, for example, 20 to 200 (KOH mg / g), preferably 50 to 150 (KOH mg / g). When the acid value is within the above range, the solubility in the developer is improved, the non-exposed portion is easily dissolved and the sensitivity is increased, and as a result, the pattern of the exposed portion remains during development, and the film remaining ratio can be improved.

The acid value is a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the polymer, and can be generally determined by titration with an aqueous solution of potassium hydroxide. The acid value is adjustable by the content or mixing ratio of the monomers to be polymerized in the alkali-soluble resin.

The polystyrene reduced weight average molecular weight of the alkali-soluble resin (A) measured by gel permeation chromatography (using GPC and tetrahydrofuran as an elution solvent) is not particularly limited and may be, for example, from 3,000 to 200,000, 5,000 to 100,000. When the weight average molecular weight is within 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 can be improved.

The content of the alkali-soluble resin may be 5 to 80% by weight, preferably 20 to 70% by weight based on 100% by weight of the total solid content of the colored photosensitive resin composition. When the content of the alkali-soluble resin is within the above range, a good pattern can be formed, and the resolution and the residual film ratio can be improved.

In the present invention, the solid content means the remaining components except for the solvent of the colored photosensitive resin composition.

Photopolymerization  The compound (B)

In one embodiment of the present invention, the photopolymerizable compound (B) is a compound capable of polymerizing under the action of a photopolymerization initiator (C), which may be a monofunctional photopolymerizable compound, a bifunctional photopolymerizable compound, Compounds, and the like, but are not limited thereto.

Examples of the monofunctional photopolymerizable compound include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N- And vinyl pyrrolidone. Commercially available products include Aronix M-101 (Toagosei), KAYARAD TC-110S (Nippon Kayaku), and Viscot 158 (Osaka Yuki Kagaku Kogyo).

The bifunctional photopolymerizable compound may be, for example, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (Acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate and the like. Commercially available products include Aronix M-210, M-1100 and 1200 KAYARAD HDDA (Nippon Kayaku), Viscoat 260 (Osaka Yuki Kagaku Kogyo), AH-600, AT-600 or UA-306H (Kyoeisha Chemical Co., Ltd.).

The multifunctional photopolymerizable compound having three or more functional groups may be, for example, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (metha) (Meth) acrylate such as Aronix M-309, TO-1382 (Doagosei), KAYARAD TMPTA, KAYARAD DPHA or the like KAYARAD DPHA-40H (Nippon Kayaku) and others.

Of the photopolymerizable compounds exemplified above, trifunctional or more (meth) acrylic acid esters are preferred since they have excellent polymerizability and can improve the strength.

The photopolymerizable compound (B) may be contained in an amount of 5 to 50% by weight based on 100% by weight of the total solid content in the colored photosensitive resin composition of the present invention. The photopolymerizable compound can improve the strength and smoothness of the pixel portion in the above range.

Light curing Initiator (C)

In one embodiment of the present invention, the photopolymerization initiator (C) is a compound for initiating polymerization of the photopolymerizable compound (B) and includes an oxime ester fluorene photopolymerization initiator. In particular, by including the photopolymerization initiator represented by the following formula (1) as the oxime ester fluorene-based photopolymerization initiator, the colored photosensitive resin composition becomes highly sensitive to shorten the exposure time, thereby improving the patterning property and exhibiting high resolution .

[Chemical Formula 1]

In this formula,

R ₁ to R ₃ are each independently selected from the group consisting of hydrogen, halogen, C ₁ -C ₂₀ alkyl, aryl, C ₁ -C ₂₀ alkoxy, aralkyl, C ₁ -C ₂₀ hydroxyalkyl, C ₂ -C A hydroxyalkoxyalkyl group having 1 to ₄₀ carbon atoms or a cycloalkyl group having _{3 to 20} carbon atoms;

R ₄ to R ₁₀ are each independently hydrogen, a C ₁ -C ₂₀ alkyl group, an aryl group, a C ₁ -C ₂₀ alkoxy group, an aralkyl group, a C ₁ -C ₂₀ hydroxyalkyl group, a C ₂ -C ₄₀ A hydroxyalkyl group, a hydroxyalkoxyalkyl group, a C ₃ -C ₂₀ cycloalkyl group, an amino group, a nitro group, a cyano group or a hydroxy group;

p is 0 or 1;

As used herein, the C ₁ -C ₂₀ alkyl group means a linear or branched monovalent hydrocarbon having 1 to 20 carbon atoms and includes, for example, methyl, ethyl, n-propyl, i-propyl, butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decanyl, n-undecanyl and the like.

As used herein, an aryl group includes both an aromatic group and a heteroaromatic group and a partially reduced derivative thereof. The arromatic group is a simple or fused ring of 5 to 15 members, and the heteroaromatic group means an aromatic group containing at least one of oxygen, sulfur or nitrogen. Exemplary aryl groups include, but are not limited to, phenyl, naphthyl, pyridinyl, furanyl, thiophenyl, indolyl, quinolinyl, imidazolinyl, But are not limited to, oxazolyl, thiazolyl, tetrahydronaphthyl, and the like.

As used herein, the C ₁ -C ₂₀ alkoxy group means a straight or branched alkoxy group having 1 to 20 carbon atoms, and includes, but is not limited to, methoxy, ethoxy, n-propaneoxy, and the like.

As used herein, an aralkyl group refers to a multifunctional group in which an aryl group (aromatic hydrocarbon group) is substituted with a carbon atom of an alkyl group, and includes, for example, benzyl, phenethyl, and the like, but is not limited thereto.

As used herein, the C ₁ -C ₂₀ hydroxyalkyl group means a straight or branched hydrocarbon having 1 to 20 carbon atoms substituted with a hydroxy group, and includes, for example, hydroxymethyl, hydroxyethyl, hydroxypropyl and the like. But is not limited thereto.

As used herein, the C ₂ -C ₄₀ hydroxyalkoxyalkyl group means a multifunctional group in which a straight or branched alkoxy group having 1 to 20 carbon atoms substituted with a hydroxy group is substituted with a carbon of an alkyl group having 1 to 20 carbon atoms, But are not limited to, for example, hydroxymethoxymethyl, hydroxyethoxymethyl, hydroxymethoxyethyl, and the like.

As used herein, a C ₃ -C ₂₀ cycloalkyl group refers to a simple or fused ring hydrocarbon having from 3 to 20 carbon atoms, including, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like, It is not.

In one embodiment of the present invention, R ₁ to R ₃ are each independently hydrogen, a C ₁ -C ₆ alkyl group or a phenyl group, R ₄ to R ₁₀ are each independently hydrogen or a nitro group, p is 0 have.

In one embodiment of the present invention, R ₁ to R ₃ are each independently hydrogen or a C ₁ -C ₆ alkyl group, R ₄ to R ₁₀ are hydrogen, and p may be 1.

Examples of the photopolymerization initiator represented by the above formula (1) wherein p is 0 include the following compounds.

Also, for example, as the photopolymerization initiator represented by the above formula (1) wherein p is 1, the following compounds may be mentioned.

.

.

In an embodiment of the present invention, the photopolymerization initiator (C) may contain, in addition to the photopolymerization initiator represented by the above formula (1), an acetophenone compound, a benzophenone compound, a triazine compound, a biimidazole compound, And at least one compound selected from the group consisting of an electron-donating compound, an electron-donating compound, and an electron donating compound.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- (4-methylthioxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2- 2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1-one, 1-one and 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.

Specific examples of the benzophenone compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Specific examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) (Trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) Bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) -Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- Azine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine and 2,4- Methyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Specific examples of the imidazole-based compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'- Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) Bis (2,6-dichlorophenyl) -4, 5,5'-tetra (trialkoxyphenyl) bimidazole, 2,2- , 4 ', 5,5'-tetraphenyl-1,2'-biimidazole and imidazole compounds wherein the phenyl group at the 4,4', 5,5 'position is substituted by a carboalkoxy group . Among them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- , 5,5'-tetraphenylbiimidazole and 2,2-bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'- Can be used.

Specific examples of the oxime-based compounds include o-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one and the like. Commercially available products include OXE-01 and OXE-02 from BASF.

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

In addition to the photopolymerization initiators exemplified above, other photopolymerization initiators may be further used in combination within the scope of not impairing the effects of the present invention.

Other photopolymerization initiators include benzoin compounds, anthracene compounds, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethyl anthraquinone, benzyl, 9,10- Methylmorpholine, triphenone, camphorquinone, methylphenylcloxysilicate and titanocene compounds.

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

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

The photopolymerization initiator may further include a photopolymerization initiator to improve the sensitivity of the colored photosensitive resin composition of the present invention. The colored photosensitive resin composition according to the present invention contains a photopolymerization initiation auxiliary agent, whereby the sensitivity can be further increased and the productivity can be improved.

As the photopolymerization initiation auxiliary, for example, at least one compound 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.

As the amine compound, an aromatic amine compound is preferably used. Examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone Heiller ketone) and 4,4'-bis (diethylamino) benzophenone.

The carboxylic acid compound is preferably an aromatic heteroacetic acid. Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxy Phenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid.

The organic sulfur compounds having thiol groups include, for example, 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl ) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -thione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), and the like can be used. .

The content of the photopolymerization initiator (C) may be 0.1 to 30% by weight, specifically 0.1 to 10% by weight based on 100% by weight of the total solid content of the colored photosensitive resin composition. When the content of the photopolymerization initiator is within the above range, it is possible to prevent the phenomenon that the sensitivity is lowered and the pattern is dropped off during the development process, and excessive reaction causes excessive cross-linking reaction to cause wrinkling, Can be prevented.

The content of the photopolymerization initiator represented by the general formula (1) may be 10 to 100% by weight, specifically 50 to 100% by weight based on 100% by weight of the total photopolymerization initiator. When the content of the photopolymerization initiator represented by the general formula (1) is within the above range, a pattern having good sensitivity and adhesion can be formed.

When the photopolymerization initiator is further used, it may be used in an amount of 10 mol or less, preferably 0.01 to 5 mol per mol of the photopolymerization initiator. When the photopolymerization initiator is used within the above range, the sensitivity of the colored photosensitive resin composition is improved and the productivity of the color filter including the photopolymerization initiator can be improved.

The colorant (D)

In one embodiment of the present invention, the colorant (D) may comprise at least one pigment (d1), at least one dye (d3) or a mixture thereof.

Pigment ( d1 )

As the pigment (d1), an organic pigment or an inorganic pigment generally used in the related art can be used. The pigment may be subjected to a surface treatment using a pigment treatment, a pigment derivative into which an acidic group or a basic group is introduced, a graft treatment of the surface of the pigment with a polymer compound, an atomization treatment using a sulfuric acid atomization method or the like, A cleaning treatment with an organic solvent or water, or a treatment for removing ionic impurities by ion exchange or the like.

The organic pigments include various pigments used in printing inks, inkjet inks and the like. Specific examples thereof include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, Anthanthrone pigments, indanthrone pigments, pyranthrone pigments, pyranthrone pigments, diketopyrrolopyrrole pigments, and the like can be used. .

The inorganic pigment may be a metal compound such as a metal oxide or a metal complex salt and may be a metal such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, Oxides or composite metal oxides, carbon black, and the like.

Particularly, 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, those having the following color index (CI) numbers Pigments, but are not limited thereto.

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;

C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 208, 215, 216, 224, 242, 254, 255 and 264;

C.I. Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37 and 38;

C.I. Pigment Blue 15 (15: 3, 15: 4, 15: 6, etc.), 21, 28, 60, 64 and 76;

C.I. Pigment Green 7, 10, 15, 25, 36, 47, 58, 59, 62 and 63;

C.I. Pigment Brown 28;

C.I. Pigment Black 1 and 7 and the like.

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

Of the CI pigment pigments exemplified above, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 185, CI Pigment Orange 38, CI Pigment Red 122, CI Pigment Red 166, CI Pigment Blue 23: CI Pigment Blue 15: 3, CI Pigment Blue 25: CI Pigment Red 255, CI Pigment Red 23: CI Pigment Blue 23: 6, CI Pigment Green 7, CI Pigment Green 36 and CI Pigment Green 58. It is preferable to use at least one pigment selected from the group consisting of CI Pigment Green 7,

The pigment is preferably used as a pigment dispersion in which the particle size is uniformly dispersed. Examples of a method for uniformly dispersing the particle diameter of the pigment include a method of dispersing the pigment dispersion (d2) by containing the pigment dispersant (d2). According to this method, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained have.

Pigment dispersant ( d2 )

The pigment dispersant (d2) is added to maintain deactivation and stability of the pigment. Specific examples of the pigment dispersant include cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, polyester surfactants, and polyamine surfactants. These 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.

The content of the pigment dispersant (d2) may be 5 to 60% by weight based on the total weight of the solid content of the pigment (d1). If the content of the pigment dispersant is less than 5% by weight, it may be difficult to atomize the pigment or gelation after dispersion. If the content of the pigment dispersant is more than 60% by weight, the viscosity may be increased.

dyes( d3 )

The dye (d3) can be used without limitation as long as it has solubility in an organic solvent. Preferably, a dye having solubility in an organic solvent and securing reliability such as solubility in an alkali developing solution, heat resistance and solvent resistance can be used.

Examples of the dyes include acid dyes having acidic groups such as sulfonic acid and carboxylic acid, salts of acidic dyes and salts of nitrogen-containing compounds, sulfonamide derivatives of acidic dyes and derivatives thereof, and azo dyes, xanthates dyes, Phthalocyanine-based acid dyes and derivatives thereof may also be used.

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

Specific examples of the dye include C.I. As solvent dyes,

C.I. Solvent Red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146 and 179;

C.I. Solvent Blue 5, 35, 36, 37, 44, 59, 67 and 70;

C.I. Solvent Violet 8, 9, 13, 14, 36, 37, 47 and 49;

C.I. Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99 and 162;

C.I. Solvent Orange 2, 7, 11, 15, 26 and 56;

C.I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34 and 35.

CI Solvent Yellow 14, 16, 21, 56, 79, 93, 151 having excellent solubility in an organic solvent among the above exemplified CI solvent dyes; CI Solvent Red 8, 49, 89, 111, 122, 132, 146, 179; CI Solvent Orange 41, 45, 62; CI Solvent Blue 35, 36, 44, 45, 70; CI Solvent Violet 13 is preferred, and CI Solvent Yellow 21, 79; CI Solvent Red 8, 122, 132; CI Solvent Orange 45, 62 is more preferred.

Also, C.I. As the acid dye,

CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88 , 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 195, 198, 206, 211, 215, 216 , 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 308, 312, 315, 316, 339, 341, 345, 346, 349 , 382, 383, 394, 401, 412, 417, 418, 422 and 426;

C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 112, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243 and 251;

C.I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169 and 173;

C.I. Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 1, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 335 and 340;

C.I. Acid Violet 6B, 7, 9, 17, 19 and 66;

C.I. Dyes such as Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106 and 109.

Among the above exemplified CI acid dyes, CI Acid Yellow 42; CI Acid Red 92; CI Acid Blue 80, 90; CI Acid Violet 66; CI Acid Green 27 is preferable because of its excellent solubility in an organic solvent.

C.I. As a direct dye,

C.I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246 and 250;

C.I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 136, 138 and 141;

C.I. Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106 and 107;

C.I. Direct Blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 164, 166, 167, 170, 171, 172, 173, 188, 189, 169, 169, 160, 161, 162, 163, 164, 248, 242, 243, 244, 245, 247, 248, 228, 229, 238, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275 and 293;

C.I. Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103 and 104;

CI Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79 and 82.

Also, C.I. As modatto dyes,

C.I. Modetto Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62 and 65;

C.I. Modal Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41 , 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94 and 95;

C.I. Modott Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47 and 48;

C.I. 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43 , 44, 48, 49, 53, 61, 74, 77, 83 and 84;

C.I. Modott Violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53 and 58;

C.I. Dyes such as Modan Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43 and 53.

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

The content of the colorant (D) may be 10 to 70% by weight based on 100% by weight of the total solid content in the colored photosensitive resin composition of the present invention. When the colorant is included in the above range, it is possible to form a pattern having sufficient color density and sufficient mechanical strength when made of a color filter.

Solvent (E)

In one embodiment of the present invention, the solvent (E) may be used without any particular limitation, as long as it is effective in dissolving the other components contained in the colored photosensitive resin composition of the present invention, , In particular, ethers, acetates, aromatic hydrocarbons, ketones, alcohols or esters.

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; 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, 3 Methoxy-1-butylacetate, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, methyl 3-methoxypropionate, propylene glycol methyl ether acetate, 3-methoxy- 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. .

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

The ketones include, for example, 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? -Butyrolactone.

These 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, and examples thereof include alkylene glycol alkyl ether acetates, alkylene glycol monoalkyl ethers, ketones, 3- Propyleneglycol monomethylether, propyleneglycol monomethylether, cyclohexanone, ethyl lactate, ethyl lactate, ethyl lactate, ethyl lactate, ethyl lactate, and ethyl lactate. Butyl acetate, ethyl lactate, methyl 3-methoxypropionate, and the like.

The solvent (E) may be contained in an amount of 60 to 90% by weight based on 100% by weight of the total of the colored photosensitive resin composition. When the above-mentioned solvent is included in the above-mentioned range, the coating property can be improved when the coating composition is applied by a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater)

The colored photosensitive resin composition of the present invention may be used in combination with additives such as other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, and anti-

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

The curing agent is used for deep curing and for increasing mechanical strength. Specific examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound.

Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolak epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin Alicyclic or aromatic epoxy compounds, butadiene (co) polymeric epoxides and isoprene (co) polymers other than the brominated derivatives, epoxy resins and brominated derivatives of these epoxy resins, glycidyl ester resins, glycidyl amine resins, (Co) polymer epoxides, glycidyl (meth) acrylate (co) polymers, and triglycidyl isocyanurate.

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

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

The curing agent may be used together with a curing agent in combination with a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound. The curing assistant compound includes, for example, polyvalent carboxylic acids, polyvalent carboxylic anhydrides, and acid generators. The polyvalent carboxylic acid anhydrides may be those commercially available as an epoxy resin curing agent. Specific examples of the above-mentioned epoxy resin curing agent include epoxy resin curing agents such as epoxy resins, epoxy resins, epoxy resins, epoxy resins, epoxy resins, epoxy resins, Manufactured by Japan Ehwa Co., Ltd.).

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

Examples of the silicone surfactant include DC3PA, DC7PA, SH11PA, SH21PA and SH8400 from Dow Corning Toray Silicone Co., Ltd. and TSF-4440, TSF-4300, TSF-4445, TSF-4446 and TSF-4460 , And TSF-4452. Examples of the fluorine-based surfactant include Megapis F-470, F-471, F-475, F-482 and F-489 commercially available from Dainippon Ink and Chemicals, Incorporated. The above-exemplified surfactants may be used alone or in combination of two or more.

Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- ( 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- 3-isocyanatopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and the like. The adhesion promoters exemplified above may be used alone or in combination of two or more. The adhesion promoter may be contained in an amount of usually 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) and 2,6-di-t-butyl-4-methylphenol.

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

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

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

First, the pigment (d1) in the colorant (D) is mixed with the solvent (E) and dispersed using a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 μm or less. At this time, the pigment dispersant, a part or all of the alkali-soluble resin (A) or the dye (d3) may be mixed with the solvent (E) to dissolve or disperse it. The dye (d3), the remainder of the alkali-soluble resin (A), the photopolymerization initiator (C), the photopolymerizable compound (B) and the additive (E) The photosensitive resin composition according to the present invention can be produced.

One embodiment of the present invention relates to a color filter formed using the above-mentioned colored photosensitive resin composition. A color filter according to an embodiment of the present invention is characterized by including a colored layer formed by applying the above-mentioned colored photosensitive resin composition on a substrate, and exposing and developing in a predetermined pattern.

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

The method of forming a pattern using the colored photosensitive resin composition of the present invention may be a method known in the art, An exposure step; And a removing step. The colored photosensitive resin composition of the present invention is applied onto a substrate and then subjected to photo-curing and development to form a pattern, so that it can be used as a black matrix or a colored pixel (colored image).

In the application step, the colored photosensitive resin composition of the present invention is applied on a substrate (not limited to a glass or silicon wafer in general) or a previously formed colored photosensitive resin composition layer and preliminarily dried to remove volatile components such as a solvent, . At this time, the thickness of the coating film is preferably 1 to 3 mu m.

The exposure step is a step of irradiating ultraviolet rays to a specific region through a mask to cure the coating film to obtain a desired pattern. At this time, it is preferable to use a mask aligner, a stepper, or the like so as to uniformly irradiate the entire exposed portion with a parallel light beam and accurately position the mask and the substrate.

The removing step is a step of obtaining a desired pattern by irradiating ultraviolet rays to bring the coated film, which has been cured, into contact with an alkali aqueous solution to dissolve and expose the non-exposed region. After development, if necessary, post-drying may be performed at about 150 to 230 DEG C for about 10 to 60 minutes.

Any developer known in the art may be used for the development, but preferably an aqueous solution containing an alkaline compound and a surfactant can be used.

The alkaline compound may be an inorganic or organic alkaline compound. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogenphosphate, sodium dihydrogenphosphate, ammonium dihydrogenphosphate, ammonium dihydrogenphosphate, potassium dihydrogenphosphate, sodium silicate, potassium silicate, sodium carbonate, Sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, and ammonia. Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, mono Isopropylamine, 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 contained in an amount of 0.01 to 10% by weight, preferably 0.03 to 5% by weight based on the developer.

The surfactant may be selected from the group consisting of a nonionic surfactant, an anionic surfactant, and a cationic surfactant, or a mixture thereof. 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. 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, alkylsulfuric acid salts such as sodium lauryl sulfate and ammonium lauryl sulfate, dodecylbenzenesulfonic acid And alkylarylsulfonic acid salts such as sodium or sodium dodecylnaphthalenesulfonate. Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts. These surfactants may be used alone or in combination of two or more. The surfactant may be contained in an amount of preferably 0.01 to 10% by weight, more preferably 0.05 to 8% by weight, and even more preferably 0.1 to 5% by weight based on the developer.

A pixel or a black matrix corresponding to the color of the coloring material in the photosensitive resin composition is obtained through the operation of coating, drying, patterning exposure, and development of the colored photosensitive resin composition as described above. The color filter can be obtained. The configuration and manufacturing method of the color filter are well known in the art and will not be described in detail.

One embodiment of the present invention relates to an image display apparatus provided with the color filter described above.

The color filter of the present invention can be applied to various image display devices such as an electroluminescence display device (EL), a plasma display device (PDP), a field emission display device (FED), an organic light emitting device (OLED) Applicable to devices.

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

An image display apparatus according to an embodiment of the present invention includes, in addition to the above-described color filters, a red pattern layer containing red QD particles, a green pattern layer containing green quantum dot particles, and a blue pattern layer containing blue QDs 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 a light source that emits blue light preferably in terms of better color reproducibility can be used.

The image display apparatus according to an embodiment of the present invention may further include a color filter including only a pattern layer of two colors of a red pattern layer, a green pattern layer and a blue pattern layer in addition to the color filter described above. In such a case, the color filter further includes a transparent pattern layer not containing quantum dot particles. In the case where only the pattern layer of two colors is provided, a light source that emits light having a wavelength that represents the remaining color that is not included can be used. For example, when only the red pattern layer and the green pattern layer are included, a light source that emits blue light may be used. In such a case, red quantum dot particles emit red light and rust quantum dot particles emit green light, and the transparent pattern layer transmits blue light as it is and exhibits blue color.

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

Synthetic example  1: Preparation of alkali-soluble resin (A-1)

A copolymer of 10 mol% of N-benzylmaleimide, 30 mol% of vinyltoluene, 30 mol% of acrylic acid and 30 mol% of 3- (acryloyloxy) -2-hydroxypropylmethacrylate was prepared. The alkali-soluble resin had a solid dispersion value of 78.1 mgKOH / g and a weight average molecular weight (Mw) of about 13,800 as measured by GPC.

Synthetic example  2: Preparation of alkali-soluble resin (A-2)

(Acryloyloxy) -2-hydroxypropyl methacrylate 15 mol%, methyl methacrylate 35 mol%, benzyl methacrylate 25 mol%, acrylic acid 15 mol%, N-benzylmaleimide 10 mol% Was prepared. The alkali-soluble resin had a solid dispersion value of 80 mgKOH / g and a weight-average molecular weight (Mw) measured by GPC of about 16,000.

Synthetic example  3: Preparation of alkali-soluble resin (A-3)

A copolymer of 40 mol% benzyl methacrylate, 10 mol% tricyclodecyl methacrylate, 25 mol% acrylic acid, and 25 mol% 3- (acryloyloxy) -2-hydroxypropyl methacrylate was prepared. The alkali-soluble resin had a solid content of 115 mgKOH / g and a weight average molecular weight (Mw) of 10,000 as measured by GPC.

Synthetic example  4: Light curing Initiator (C-1) Synthesis

Reaction 1.

After dissolving 5.0 g of 2-nitrofluorene in 100 ml of anhydrous nitrobenzene and adding 6.31 g of anhydrous aluminum chloride, the reaction was heated to 45 ° C, and a solution of 2.79 g of acetyl chloride in 30 ml of anhydrous nitrobenzene was added for 30 minutes , And the reaction was heated to 65 DEG C and stirred for 1 hour. Then, the reaction mixture was cooled to room temperature, and 70 ml of distilled water was added thereto. The mixture was stirred for about 30 minutes, and the product was filtered. The obtained solid product was dispersed in 50 ml of ether and stirred at room temperature for 30 minutes, followed by filtration and drying to obtain pale yellow reactant 1 (1- (9,9-H-7-nitrofluoren-2-yl) 5.08 g was obtained.

Reaction 2.

1.5 g of the reactant 1 (1- (9,9-H-7-nitrofluoren-2-yl) -ethanone) was dispersed in 30 ml of ethanol, 0.49 g of hydrochloric acid hydroxylamine and 0.58 g of sodium acetate were added , The reaction solution was gradually heated and refluxed for 2 hours. The reaction product was cooled to room temperature and 20 ml of distilled water was added thereto. The mixture was stirred for about 30 minutes, and the resulting solid product was filtered, washed several times with distilled water and then dried to obtain reaction product 2 (1- (9,9- -Nitrofluoren-2-yl) -ethanone oxime) was obtained.

Reaction 3.

1.20 g of reactant 2 (1- (9,9-H-7-nitrofluoren-2-yl) -ethanone oxime) was dispersed in 50 ml of ethyl acetate, and 0.69 g of acetic anhydride was added. The mixture was heated to reflux reaction for 3 hours. The reaction mixture was cooled to room temperature, washed with 20 ml of a saturated aqueous solution of sodium hydrogencarbonate and 20 ml of distilled water. The recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The product was recrystallized from methanol To obtain 1.22 g of a photopolymerization initiator C-1 (1- (9,9-H-7-nitrofluorene-2-yl) -ethanone oxime-O-acetate).

Synthetic example  5: Light curing Initiator (C-2) Synthesis

Reaction 1.

200.0 g of fluorene, 268.8 g of potassium hydroxide and 19.9 g of potassium iodide were dissolved in 1 L of anhydrous dimethyl sulfoxide and the reaction was maintained at 15 DEG C. Then, 283.3 g of bromoethane was slowly added over 2 hours, Was stirred at 15 < 0 > C for 1 hour. Then, 2 L of distilled water was added to the reaction mixture, and the mixture was stirred for 30 minutes. The product was extracted with 2 L of dichloromethane. The extracted organic layer was washed with 2 L of distilled water twice, and the recovered organic layer was dried over anhydrous magnesium sulfate. The product obtained by vacuum distillation was subjected to fractional distillation under reduced pressure to obtain 248.6 g of reaction product 1 (9,9-diethyl-9H-fluorene) as a pale yellow liquid having a high viscosity.

Reaction 2.

100.5 g of the reactant 1 (9,9-diethyl-9H-fluorene) was dissolved in 1 L of dichloromethane, and the reaction was cooled to -5 ° C. Then, 72.3 g of aluminum chloride was added slowly and then the temperature of the reaction was raised , 50.1 g of propionyl chloride diluted in 50 ml of dichloromethane was slowly added over 2 hours and the reaction was stirred at -5 ° C for 1 hour. Then, the reaction mixture was slowly poured into 1 L of ice water and stirred for 30 minutes. The organic layer was separated, washed with 500 ml of distilled water, and the recovered organic layer was distilled under reduced pressure. The resulting product was purified by silica gel column chromatography (eluent: ethyl acetate: n- Hexane = 1: 4) to obtain 75.8 g of reactant 2 (1- (9,9-diethyl-9H-fluoren-2-yl) -1-propanone) as a pale yellow solid.

Reaction 3.

44.5 g of the reactant 2 (1- (9,9-diethyl-9H-fluoren-2-yl) -1-propanone) was dissolved in 900 ml of tetrahydrofuran (THF) and dissolved in 1,4- 150 ml of 4N HCl and 24.7 g of isobutyl nitrite were added in this order, and the reaction was stirred at 25 DEG C for 6 hours. Then, 500 ml of ethyl acetate was added to the reaction solution, and the mixture was stirred for 30 minutes. The organic layer was separated and washed with 600 ml of distilled water. The recovered organic layer was dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure. Recrystallization was performed using 300 ml of a mixed solvent of acetate and hexane (1: 6), followed by drying to obtain a reaction product 3 (1- (9,9-diethyl-9H- fluoren- 2-propanedione-2-oxime).

Reaction 4.

(NMP) in a nitrogen atmosphere was added to the reaction mixture 3 (1- (9,9-diethyl-9H-fluoren-2-yl) -1,2-propanedione- 1 L and the reaction was maintained at -5 ° C. Then, 35.4 g of triethylamine was added and the reaction solution was stirred for 30 minutes. 27.5 g of acetyl chloride was dissolved in 75 ml of N-methyl-2-pyrrolidinone The solution was slowly added over 30 minutes and stirred for 30 minutes, taking care not to raise the temperature of the reaction. Then 1 L of distilled water was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer. The recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained solid product was recrystallized using 1 L of ethanol and then dried to obtain a light gray solid photopolymerization initiator C-2 (1- (9,9-diethyl-9H-fluoren-2-yl) Propanedione-2-oxime-O-acetate).

Manufacturing example  1: Preparation of colorant

12.5 parts by weight of CI Pigment Blue 15: 6 as a pigment, 7.5 parts by weight of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, 1.2 parts by weight of CI Pigment Acid Red 52 as a dye and 72 parts by weight of propylene glycol methyl ether acetate as a solvent And 8 parts by weight of propylene glycol monomethyl ether were mixed and dispersed by a bead mill for 12 hours to prepare a colorant.

Example  1 to 6 and Comparative Example  1 to 6: Preparation of colored photosensitive resin composition

Each of the components was mixed with the composition shown in Table 1 below to prepare a colored photosensitive resin composition (unit: wt%).

Furtherance Alkali-soluble resin Photopolymerizable compound ⁴⁾ Photopolymerization initiator Colorant ^{9 )} Solvent ^{10 )} A-1 ¹⁾ A-2 ²⁾ A-3 ³⁾ C-1 ⁵⁾ C-2 ⁶⁾ C-3 ⁷⁾ C-4 ⁸⁾ Example 1 5.3 - - 4.8 - 0.4 0.4 - 18.2 70.9 Example 2 5.3 - - 0.4 - 0.4 - Example 3 5.3 - - - 0.8 - - Example 4 - 5.3 - - 0.4 0.4 - Example 5 - 5.3 - 0.4 - 0.4 - Example 6 - 5.3 - - 0.8 - - Comparative Example 1 - - 5.3 - - - 0.8 Comparative Example 2 - - 5.3 - 0.4 0.4 - Comparative Example 3 5.3 - - - - - 0.8 Comparative Example 4 - 5.3 - - - - 0.8 Comparative Example 5 - 5.3 - - - 0.8 - Comparative Example 6 - 5.3 - - - 0.4 0.4

1) The alkali-soluble resin of Synthesis Example 1

2) The alkali-soluble resin of Synthesis Example 2

3) The alkali-soluble resin of Synthesis Example 3

4) KAYADA DPHA (manufactured by Nippon Kayaku)

5) The photopolymerization initiator of Synthesis Example 4

6) The photopolymerization initiator of Synthesis Example 5

7) Oxime photopolymerization initiator, OXE-02 (BASF)

8) Acetophenone photopolymerization initiator I-369 (BASF)

9) The colorant of Production Example 1

10) Propylene glycol monomethyl ether acetate (69.1% by weight) and propylene glycol monomethyl ether (1.8% by weight)

Experimental Example  One

Color filters were prepared as follows using the colored photosensitive resin compositions prepared in Examples and Comparative Examples and the developing speed, adhesion, sensitivity, heat resistance, chemical resistance and outgassing amount were measured by the following methods, The results are shown in Table 2 below.

≪ Production of color filter &

Each of the colored photosensitive resin compositions was applied to a 2 inch square glass substrate ("EAGLE XG", manufactured by Corning Incorporated) by a spin coating method, and then placed on a heating plate and maintained at 100 ° C for 3 minutes to form a thin film. Thereafter, a test photomask having a pattern for changing the transmittance in the range of 1 to 100% in a stepwise manner and a line / space pattern of 1 m to 100 m was placed on the thin film and the interval between the test photomask and the test mask was set to 300 mu m And irradiated with ultraviolet rays. At this time, the ultraviolet light source was irradiated with a high pressure mercury lamp of 1 kW including g, h and i lines at an illuminance of 60 mJ / cm 2, and no special optical filter was used. The thin film irradiated with ultraviolet rays was immersed in a KOH aqueous solution of pH 10.5 for 2 minutes to develop. The glass substrate coated with the thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 230 캜 for 20 minutes to prepare respective color filters. The film thickness of the color filter prepared above was 2.5 占 퐉.

(1) Development speed

The time taken for the non-visible portion to completely dissolve in the developing solution in the developing process during the above process was measured.

(2) Adhesion

The generated pattern was observed with an optical microscope, and the degree of the peeling phenomenon of the 20 mu m pattern was evaluated by the following evaluation criteria.

<Evaluation Criteria>

○: No pattern peeling

DELTA: pattern peeling 1 to 10

X: Pattern peeling exceeded 10

(3) Sensitivity

The pixel portion obtained as described above was observed to observe the surface roughness or Na lamp. At this time, the minimum necessary exposure dose (mJ / cm ² ) for forming a pattern having no surface roughness was measured.

(4) Evaluation of heat resistance

The heat resistance was evaluated by measuring the color change value (? Eab) after heating at 230 占 폚 for 60 minutes. △ Eab is a value required by the following saturation formula by the CIE 1976 (L *, a *, b *) spatial colorimetric system (New Color Science Handbook, 1986).

? E ^* ab = {(? L) ² + (? A) ² + (? B) ² } ^1/2

<Evaluation Criteria>

?:? E ^* ab = less than 3

Δ: ΔE ^* ab = 3 or more and 5 or less

X: DELTA E ^* ab exceeding 5

(5) Chemical resistance

The color filter was immersed in N-methyl-2-pyrolidone (NMP) solution at 80 ° C for 30 minutes, and color difference before and after immersion was confirmed.

<Evaluation Criteria>

?:? E ^* ab = less than 3

Δ: ΔE ^* ab = 3 or more and 5 or less

X: DELTA E ^* ab exceeding 5

(6) Outgassing amount

The prepared color filter was pyrolyzed at 230 ° C for 30 minutes via Py-GC / MS to analyze the collected compounds. The result was obtained as a percentage based on the total amount of outgas of Comparative Example 1 as 100%.

division Development speed (s) Adhesiveness Sensitivity (mJ / cm ² ) Heat resistance Chemical resistance
(NMP) Out gas Example 1 17 ○ 25 ○ ○ 49% Example 2 16 ○ 25 ○ ○ 55% Example 3 16 ○ 20 ○ ○ 24% Example 4 11 ○ 25 ○ ○ 65% Example 5 12 ○ 25 ○ ○ 62% Example 6 13 ○ 20 ○ ○ 31% Comparative Example 1 36 △ 45 △ △ 100% Comparative Example 2 38 △ 45 △ △ 105% Comparative Example 3 19 ○ 25 △ ○ 95% Comparative Example 4 12 ○ 20 △ △ 90% Comparative Example 5 11 △ 50 ○ △ 120% Comparative Example 6 12 △ 50 ○ △ 125%

As shown in Table 2, the colored photosensitive resin compositions of Examples 1 to 6 including the alkali-soluble resin polymerized with N-benzyl maleimide according to the present invention and containing the photopolymerization initiator represented by the general formula (1) Compared with the colored photosensitive resin compositions of Comparative Examples 1 to 6 which do not contain all of them or contain only one of them, the photosensitive resin composition of the present invention has a faster developing speed and excellent adhesion, sensitivity and reliability, Respectively.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention. Do. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Accordingly, the actual scope of the invention is defined by the appended claims and their equivalents.

Claims (9)

1. A colored photosensitive resin composition comprising an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a colorant and a solvent, wherein the alkali-soluble resin comprises an alkali-soluble resin polymerized with N-benzylmaleimide, A colored photosensitive resin composition comprising a photopolymerization initiator represented by the following formula (1):
[Chemical Formula 1]

In this formula,
R ₁ to R ₃ are each independently selected from the group consisting of hydrogen, halogen, C ₁ -C ₂₀ alkyl, aryl, C ₁ -C ₂₀ alkoxy, aralkyl, C ₁ -C ₂₀ hydroxyalkyl, C ₂ -C A hydroxyalkoxyalkyl group having 1 to ₄₀ carbon atoms or a cycloalkyl group having _{3 to 20} carbon atoms;
R ₄ to R ₁₀ are each independently hydrogen, a C ₁ -C ₂₀ alkyl group, an aryl group, a C ₁ -C ₂₀ alkoxy group, an aralkyl group, a C ₁ -C ₂₀ hydroxyalkyl group, a C ₂ -C ₄₀ A hydroxyalkyl group, a hydroxyalkoxyalkyl group, a C ₃ -C ₂₀ cycloalkyl group, an amino group, a nitro group, a cyano group or a hydroxy group;
p is 0 or 1; The colored photosensitive resin composition according to claim 1, wherein the N-benzyl maleimide is contained in an amount of 1 to 90 mol% based on 100 mol% of all the monomers constituting the alkali-soluble resin. The colored photosensitive resin composition according to claim 1, wherein the content of the alkali-soluble resin is 5 to 80% by weight based on 100% by weight of the total solid content of the colored photosensitive resin composition. The photosensitive resin composition according to claim 1, wherein R ₁ to R ₃ are each independently hydrogen, a C ₁ -C ₆ alkyl group or a phenyl group, R ₄ to R ₁₀ are independently hydrogen or a nitro group, and p is 0 Composition. The colored photosensitive resin composition according to claim 1, wherein R ₁ to R ₃ are each independently hydrogen or a C ₁ -C ₆ alkyl group, R ₄ to R ₁₀ are hydrogen, and p is 1. The colored photosensitive resin composition according to claim 1, wherein the content of the photopolymerization initiator is 0.1 to 30% by weight based on 100% by weight of the total solid content of the colored photosensitive resin composition. The colored photosensitive resin composition according to claim 1, wherein the content of the photopolymerization initiator represented by the general formula (1) is 10 to 100% by weight based on 100% by weight of the total photopolymerization initiator. A color filter formed using the colored photosensitive resin composition according to any one of claims 1 to 7. An image display apparatus comprising the color filter according to claim 8.