KR20180101915A - Colored Photosensitive Resin Composition, Color Filter and Display Device - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition including a colorant, a binder resin, a photopolymerizable compound, a photopolymerization initiator and solvent, a color filter manufactured by using the same, and an image display device. The photopolymerization initiator includes an oxime compound having an absorption band in a region of 300 nm or more; and an acetophenone compound having the absorption band in a region of 300 nm or less. The colored photosensitive resin composition according to the present invention can be sufficiently cured even by a low temperature sintering process, and the color filter formed by using the colored photosensitive resin composition exhibits excellent solvent resistance and cannot cause water stains and laminated residues.

Description

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

More particularly, the present invention relates to a colored photosensitive resin composition, a color filter, and an image display apparatus, and more particularly to a colored photosensitive resin composition, a color filter and an image display apparatus which can sufficiently cure even at a low temperature baking step of 150 캜 or less, A color filter formed using the same, and an image display device 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. Particularly, color filters are one of the most important parts for reproducing color tone in an LCD in which the use thereof is widening, and a manufacturing method of a color filter having excellent processability and product reliability for improving productivity in a LCD manufacturing process has been continuously studied.

In recent years, in order to improve the productivity in the LCD manufacturing process, researches for manufacturing a color filter of a high reliability in a low-temperature firing process rather than a high-temperature firing process have been carried out. For example, Japanese Patent No. 2,937,208 discloses a photosensitive resin composition containing a thermal crosslinking agent such as a melamine resin or an epoxy resin, which can be treated by a low-temperature baking process. However, when such a photosensitive resin composition is cured at 200 캜 or less, the resin composition is not sufficiently cured, resulting in a problem that reliability such as solvent resistance is lowered.

Accordingly, there is a growing demand for a low temperature curable photosensitive resin composition capable of curing sufficiently in a low-temperature firing step. Also, it is required to develop a technique for preparing such a low-temperature-curable photosensitive resin composition that is easy to generate water stains and laminated residue while being cleaned after curing.

Japanese Patent No. 2,937,208

An object of the present invention is to provide a colored photosensitive resin composition which can be sufficiently cured even at a low temperature baking process of 150 ° C or less and in which the pattern layer formed using the composition exhibits excellent solvent resistance and does not generate water stains and laminated residues will be.

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 a colorant, a binder resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, wherein the photopolymerization initiator is an oxime compound having an absorption band in a region of 300 nm or more, The present invention provides a colored photosensitive resin composition comprising the acetophenone compound.

In one embodiment of the present invention, the oxime compound may include at least one compound represented by any of the following formulas (1) to (3).

[Chemical Formula 1]

(2)

(3)

In this formula,

이며,R ¹ is a C ₁ -C ₁₂ alkyl group or

Lt;

R ² and R ³ are each independently a C ₁ -C ₁₂ alkyl group,

R ⁴ is an aryl group,

R ⁵ is a C ₁ -C ₁₂ alkyl group, an aryl group or an aralkyl group,

R ⁶ is a C ₁ -C ₁₂ alkyl or aryl group,

R ⁷ and R ⁸ are each independently a C ₁ -C ₁₂ alkyl group,

R ⁹ to R ¹⁶ are each independently selected from the group consisting of hydrogen, halogen, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy, C ₁ -C ₁₂ hydroxyalkyl, C ₂ -C ₂₄ hydroxyalkoxyalkyl , A C ₃ -C ₁₀ cycloalkyl group, an aryl group, an aralkyl group, an amino group, a nitro group, a cyano group or a hydroxy group.

In one embodiment of the present invention, the acetophenone compound may include at least one of acetophenone compounds having a hydroxy group or a C ₁ -C ₃ alkoxy group at the alpha position.

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 can be obtained by using a photopolymerization initiator comprising an oxime compound having an absorption band in a region of 300 nm or more and an acetophenone compound having an absorption band in a region of 300 nm or less, Sufficient curing is possible, and the pattern layer formed by using it exhibits excellent solvent resistance and may not cause water stains and laminated residues.

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

An embodiment of the present invention is a colored photosensitive resin composition comprising a colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D) and a solvent (E) Relates to a colored photosensitive resin composition comprising an oxime compound having an absorption band in a region of 300 nm or more and an acetophenone compound having an absorption band in a region of 300 nm or less.

The colorant (A)

In one embodiment of the present invention, the colorant comprises at least one pigment or at least one dye.

The pigment (a1)

The pigment may be an organic pigment or an inorganic pigment generally used in the art.

The organic pigments or inorganic pigments may be various pigments used in printing inks, ink jet inks, etc. Specific examples thereof include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, An anthanthrone pigment, an indanthrone pigment, a pravanthrone pigment, a pyranthrone pigment, an anthanthrone pigment, an anthanthrone pigment, an anthanthrone pigment, an anthanthrone pigment, a pyranthrone pigment, A pyranthrone pigment, a diketopyrrolopyrrole pigment, and the like.

Examples of the inorganic pigments include metal compounds such as metal oxides, complex metal oxides, and metal complex salts; Or carbon black. Specifically, examples of the metal include iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc and antimony.

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, etc.

These pigments (d1) may be used alone or in combination of two or more.

The exemplified C.I. Among the pigment pigments, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185, C.I. Pigment Orange 38, C.I. Pigment Red 122, C.I. Pigment Red 166, C.I. Pigment Red 177, C.I. Pigment Red 208, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Violet 23, C.I. Pigment Blue 15: 3, Pigment Blue 15: 6, C.I. Pigment Green 7, C.I. Pigment Green 36 and C.I. Pigment selected from Pigment Green 58 can be preferably used.

The pigment is preferably a pigment dispersion in which the particle diameter of the pigment is uniformly dispersed. Examples of a method for uniformly dispersing the particle diameter of the pigment include a method of dispersing the pigment dispersion (a2) by containing the pigment dispersant (a2), and a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained have.

The pigment dispersant (a2)

The pigment dispersant is added for deaggregation of the pigment and maintenance of stability. Specific examples of the pigment dispersant include cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, polyester surfactants and polyamine surfactants. , Which may be used alone or in combination of two or more.

It is also preferable to include an acrylate-based dispersant (hereinafter referred to as an acrylate-based dispersant) containing butyl methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA). Examples of commercially available acrylate dispersants include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070 and DISPER BYK-2150. The acrylate dispersants may be used alone or in combination of two or more. .

As the pigment dispersant (a2), other resin type pigment dispersants may be used in addition to the acrylate dispersant. The other resin type pigment dispersing agent may be a known resin type pigment dispersing agent, especially a polycarboxylic acid ester such as polyurethane, polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) An amine salt of a polycarboxylic acid, an alkylamine salt of a polycarboxylic acid, a polysiloxane, a long chain polyaminoamide phosphate salt, an ester of a hydroxyl group-containing polycarboxylic acid and a modified product thereof, or a free ) Oil-based dispersants such as amides formed by reaction of a polyester having a carboxyl group with poly (lower alkyleneimine) or salts thereof; Soluble resin or water-soluble polymer compound such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinylpyrrolidone; Polyester; Modified polyacrylates; Adducts of ethylene oxide / propylene oxide, and phosphate esters.

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

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

The content of the pigment dispersant (a2) is 5 to 60 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the solid content of the pigment (a1). If the content of the pigment dispersant (a2) exceeds 60 parts by weight, the viscosity may be increased. If the content of the pigment dispersant is less than 5 parts by weight, it may be difficult to atomize the pigment or cause gelation after dispersion.

The dye (a3)

The dye can be used without limitation as long as it has solubility in an organic solvent. It is preferable to use a dye which has solubility in an organic solvent and can ensure reliability such as solubility in an alkali developing solution, heat resistance and solvent resistance.

Examples of the dye include acid dyes having an acidic group such as a sulfonic acid and a carboxylic acid, salts of an acidic dye and a nitrogen-containing compound, sulfonamides of an acidic dye and derivatives thereof, and azo, xanthate, phthalocyanine Based acid dyes and derivatives thereof. Preferably, the dye is a compound classified as a dye in a color index (published by The Society of Dyers and Colourists), or a known dye described in a dyeing note (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, 45, 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.

C.I. Solvent dye having excellent solubility in an organic solvent. Solvent Yellow 14, 16, 21, 56, 79, 93, 151; C.I. Solvent Red 8, 49, 89, 111, 122, 132, 146, 179; C.I. Solvent Orange 41, 45, 62; C.I. Solvent Blue 35, 36, 44, 45, 70; C.I. Solvent violet 13 is preferable, and C.I. Solvent Yellow 21, 79; C.I. Solvent Red 8, 122, 132; C.I. Solvent orange 45, 62 is more preferable.

Also, C.I. As an acid dye

C.I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 266, 268, 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.

C.I. C.I., which is excellent in solubility in an organic solvent in an acid dye. Acid Yellow 42; C.I. Acid Red 92; C.I. Acid Blue 80, 90; C.I. Acid Violet 66; C.I. Acid Green 27 is preferred.

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;

C.I. Dyes such as Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79 and 82

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.

These dyes may be used alone or in combination of two or more.

The content of the colorant (A) 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.

The binder resin (B)

In one embodiment of the present invention, the binder resin (B) usually has reactivity and alkali solubility due to the action of light or heat and acts as a dispersion medium of the colorant. The binder resin (B) contained in the colored photosensitive resin composition of the present invention may be any binder resin that acts as a binder resin for the colorant (A) and is soluble in the alkaline developer used in the development step for the production of the color filter have.

The binder resin (B) includes, for example, a copolymer of a carboxyl group-containing monomer and another monomer copolymerizable with the monomer.

Examples of the carboxyl group-containing monomer include unsaturated carboxylic acids such as unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated polycarboxylic acids having at least one carboxyl group in the molecule such as unsaturated tricarboxylic acid and the like . 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 acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride, citraconic anhydride and the like. The unsaturated polycarboxylic acid may also be a mono (2-methacryloyloxyalkyl) ester thereof, for example, succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl ), Phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl), and the like. The unsaturated polycarboxylic acid may be mono (meth) acrylate of the dicarboxylic polymer of both ends thereof, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate . These carboxyl group-containing monomers may be used alone or in combination of two or more. Examples of other monomers copolymerizable with the carboxyl group-containing monomer include styrene,? -Methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o- P-methoxy styrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, Aromatic vinyl compounds such as vinylbenzyl glycidyl ether and indene; 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, adamantyl (meth) acrylate, (Meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate and the like Unsaturated 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; Unsaturated imides such as maleimide, benzylmaleimide, N-phenylmaleimide and N-cyclohexylmaleimide; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; And a monoacryloyl group or monomethacryloyl group at the end of the polymer molecular chain of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, And the like. These monomers may be used alone or in combination of two or more. Particularly, as other monomers copolymerizable with the carboxyl group-containing monomer, a bulky monomer such as a monomer having a norbornyl skeleton, a monomer having an adamantane skeleton, or a monomer having a rosin skeleton tends to lower the dielectric constant value, which is preferable .

 The acid value of the binder resin is preferably in the range of 20 to 200 (KOH mg / g). When the acid value is in 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, thereby improving the film remaining ratio. Here, 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 using an aqueous solution of potassium hydroxide.

The weight average molecular weight (hereinafter simply referred to as "weight average molecular weight") in terms of polystyrene measured by gel permeation chromatography (GPC; tetrahydrofuran as an elution solvent) is 3,000 to 200,000, preferably 5,000 to 100,000 Binder resins are preferred. When the 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 tends to be improved.

The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the binder resin (B) is preferably 1.5 to 6.0, more preferably 1.8 to 4.0. When the molecular weight distribution (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) is 1.5 to 6.0, development is preferable.

The binder resin (B) may be contained in an amount of usually 5 to 85% by weight, preferably 10 to 70% by weight based on 100% by weight of the total solid content in the colored photosensitive resin composition. When the binder resin (B) is contained in the above range, the solubility in the developing solution is sufficient, so that development residue is not easily generated on the substrate of the non-pixel portion, and film reduction of the pixel portion of the exposure portion is difficult to occur at the time of development, Is preferable because it tends to have a good dropout characteristic.

Photopolymerization  The compound (C)

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

Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N- Ralidon, and the like. Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) , Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like. Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) And pentaerythritol hexa (meth) acrylate. Of these, multifunctional monomers having two or more functional groups are preferably used.

The photopolymerizable compound (C) may be contained in an amount of usually 5 to 50% by weight, preferably 7 to 45% by weight based on 100% by weight of the total solid content in the colored photosensitive resin composition. When the photopolymerizable compound (C) is contained in the above range, the strength and smoothness of the pixel portion tends to be favorable.

Light curing Initiator (D)

In one embodiment of the present invention, the photopolymerization initiator includes an oxime compound having an absorption band in a region of 300 nm or more and an acetophenone compound having an absorption band in a region of 300 nm or less.

The oxime compound has a higher initiation efficiency in an absorption band of 300 nm or more than the acetophenone compound. Accordingly, the oxime compound is used as a main component of the photopolymerization initiator and initiates photopolymerization with high sensitivity in the main curing step performed in the region of 300 nm or more.

On the other hand, the acetophenone compound is used as an auxiliary component of a photopolymerization initiator. The acetophenone compound can initiate photopolymerization upon further exposure in the region of 300 nm or less after the development process, thereby enabling sufficient curing even after the low-temperature baking process, thereby enhancing reliability such as solvent resistance and preventing generation of water stains and laminated residues can do.

In one embodiment of the present invention, the oxime compound may include at least one compound represented by any of the following formulas (1) to (3).

[Chemical Formula 1]

(2)

(3)

In this formula,

이며,R ¹ is a C ₁ -C ₁₂ alkyl group or

Lt;

R ² and R ³ are each independently a C ₁ -C ₁₂ alkyl group,

R ⁴ is an aryl group,

R ⁵ is a C ₁ -C ₁₂ alkyl group, an aryl group or an aralkyl group,

R ⁶ is a C ₁ -C ₁₂ alkyl or aryl group,

R ⁷ and R ⁸ are each independently a C ₁ -C ₁₂ alkyl group,

R ⁹ to R ¹⁶ are each independently selected from the group consisting of hydrogen, halogen, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy, C ₁ -C ₁₂ hydroxyalkyl, C ₂ -C ₂₄ hydroxyalkoxyalkyl , A C ₃ -C ₁₀ cycloalkyl group, an aryl group, an aralkyl group, an amino group, a nitro group, a cyano group or a hydroxy group.

As used herein, the C ₁ -C ₁₂ alkyl group means a linear or branched hydrocarbon group having 1 to 12 carbon atoms, and examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, But are not limited thereto.

As used herein, the C ₁ -C ₁₂ alkoxy group means a straight or branched alkoxy group having 1 to 12 carbon atoms, including methoxy, ethoxy, propanoxy, butoxy, pentoxy and the like. It is not.

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. Representative examples of aryl groups include, but are not limited to, phenyl, naphthyl, pyridinyl, furanyl, pyrrolyl, thiophenyl, benzothiophenyl, indolyl, But are not limited to, quinolinyl, imidazolinyl, oxazolyl, thiazolyl, tetrahydronaphthyl, and the like.

As used herein, an aralkyl group refers to a multifunctional group formed by substituting an aryl group (aromatic hydrocarbon group) for the carbon of an alkyl group, and includes, for example, benzyl, phenethyl, thiophenyl, and pyridinylmethyl However, the present invention is not limited thereto.

As used herein, the C ₁ -C ₁₂ hydroxyalkyl group means a straight or branched hydrocarbon group having 1 to 12 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 ₂₄ hydroxyalkoxyalkyl group means a multifunctional group in which a linear or branched alkoxy group having 1 to 12 carbon atoms substituted with a hydroxy group is substituted with a carbon of an alkyl group having 1 to 12 carbon atoms, But are not limited to, for example, hydroxymethoxymethyl, hydroxyethoxymethyl, hydroxymethoxyethyl, and the like.

C ₃ -C ₁₀ cycloalkyl group as used herein means a simple or fused ring hydrocarbon having 3 to 10 carbon atoms and includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like, It is not.

The aryl group and the aralkyl group may be substituted with one or more hydrogen atoms by a C ₁ -C ₁₂ alkyl group, a C ₁ -C ₁₂ alkoxy group, and the like.

이고, R² 은 메틸기이며, R³은 에틸기이고, R⁴는 메틸페닐기, 피롤릴기, 티오페닐기, 벤조티오페닐기 또는 나프틸기일 수 있다.In one embodiment of the present invention, in the general formula (1), R ¹ is a methyl group or

R ² is a methyl group, R ³ is an ethyl group, and R ⁴ is a methylphenyl group, a pyrrolyl group, a thiophenyl group, a benzothiophenyl group or a naphthyl group.

In one embodiment of the present invention, in Formula 2, R ⁵ is a hexyl group, a thiophenyl group, a furanyl group, a thiophenylpropyl group or a pyridinylmethyl group, and R ⁶ may be a phenyl group or a methyl group.

In one embodiment of the present invention, R ⁷ is a methyl group or a propyl group, R ⁸ is a methyl group, an ethyl group, a butyl group, a pentyl group or a hexyl group and R ⁹ is a hydrogen, a methyl group, And R ¹⁰ to R ¹⁶ may be hydrogen.

Specific examples of the oxime compounds represented by the formula (1) include oxime compounds represented by any one of the following formulas (4) to (8).

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

Specific examples of the oxime compounds represented by the above formula (2) include oxime compounds represented by any one of the following formulas (9) to (12).

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

Specific examples of the oxime compounds represented by the above formula (3) include the following oxime compounds.

The acetophenone compound may include at least one of acetophenone compounds having a hydroxy group or a C ₁ -C ₃ alkoxy group at the alpha position. The acetophenone compound is excellent in reactivity on the surface with a short absorption wavelength of 205 to 260 nm.

Specific examples of the acetophenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one (DAROCURE 1173), 1- (4-isopropylphenyl) -2- 1-one (DAROCURE 1116), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy- Hydroxyglycylhexyl phenyl ketone (IRGACURE 184), 2,2-dimethoxy-2-phenylacetophenone (IRGACURE 651) and 2,2-diethoxy-2-phenylacetophenone (UVATONE 8302). These acetophenone compounds may be used alone or in combination of two or more.

In one embodiment of the present invention, the weight ratio of the oxime compound and the acetophenone compound may be 70 to 99: 1 to 30, preferably 70 to 90: 10 to 30. When the weight ratio of the oxime compound and the acetophenone compound is in the above range, sufficient curing can be performed even at a low temperature baking step, and the pattern layer formed using the oxime compound and the acetophenone compound may exhibit excellent solvent resistance and may not generate water stains and laminated residues.

The oxime compound and the acetophenone compound may be contained in an amount of 50 to 100% by weight based on 100% by weight of the total photopolymerization initiator.

The photopolymerization initiator (D) may further include a benzophenone compound, a triazine compound, a nonimidazole compound or a thioxanthone compound in addition to the oxime compound and the acetophenone compound. These photopolymerization initiators may be used alone or in combination of two or more.

The photopolymerization initiator (D) may be contained in an amount of 0.1 to 10% by weight based on 100% by weight of the total of the colored photosensitive resin composition. When the photopolymerization initiator (D) is included in the above range, photopolymerization occurs sufficiently during exposure in the pattern formation step, and the transmittance decrease due to the unreacted initiator remaining after the photopolymerization may not occur.

Solvent (E)

In one embodiment of the present invention, the solvent (E) may be any solvent used in the art without any particular limitation, and various organic solvents may be used.

Specific examples of the solvent (E) 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; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Propylene glycol dialkyl ethers such as propylene glycol monomethyl ether; Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate; Aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin; Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; and cyclic esters such as? -butyrolactone.

Among the above-mentioned solvents (E), an organic solvent preferably having a boiling point of 100 ° C to 200 ° C in terms of coatability and dryness can be mentioned, and more preferably alkylene glycol alkyl ether acetates, ketones, 3- Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxypropionate, and the like, and more preferably, an ester such as ethyl propionate or methyl 3-methoxypropionate. More preferred examples thereof include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Ethyl methoxypropionate, methyl 3-methoxypropionate, and the like.

These solvents (E) may be used alone or in combination of two or more.

The solvent (E) may be contained in an amount of usually 60 to 90% by weight, preferably 70 to 85% by weight based on 100% by weight of the total of the colored photosensitive resin composition. When the above-mentioned solvent (E) is included in the above-described range, when the solvent (E) is applied by a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater It is preferable because there is a tendency.

Additive (F)

The colored photosensitive resin composition according to one embodiment of the present invention may further include an additive.

The additive may be optionally added, for example, other polymer compounds, a curing agent, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber and an anti-aggregation agent.

Specific examples of the other polymer compound include a curable resin such as an epoxy resin and a maleimide resin, a thermoplastic resin such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane But is not limited thereto.

The curing agent is used for increasing the curing depth and mechanical strength, and specifically includes, but is not limited to, an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound.

More specifically, the epoxy compound in the curing agent may be at least one selected from the group consisting of a bisphenol A epoxy resin, a hydrogenated bisphenol A epoxy resin, a bisphenol F epoxy resin, a hydrogenated bisphenol F epoxy resin, a novolak epoxy resin and other aromatic epoxy resins, Aliphatic, alicyclic or aromatic epoxy compounds, butadiene (co) polymeric epoxides, isoprene (co) polymers other than glycidyl ester resins, glycidyl amine resins, brominated derivatives of the above epoxy resins, epoxy resins and their brominated derivatives ) Polymer epoxides, glycidyl (meth) acrylate (co) polymers, and triglycidyl isocyanurate.

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

The curing agent may be used in combination 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 auxiliary 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. Examples of the commercially available products include Adekahadona EH-700 (manufactured by Adeka Kogyo Co., Ltd.), Rikashido HH (manufactured by Shin-Nihon Ehwa Co., Ltd.), and MH-700 (manufactured by Shin-Etsu Chemical Co., Ltd.). The above-mentioned curing agent and curing auxiliary compound may be used alone or in combination of two or more.

The surfactant may be used to further improve the film formation of the colored photosensitive resin composition, and silicon, fluorine, ester, cationic, anionic, nonionic, amphoteric surfactant and the like may be preferably used.

Examples of the silicone surfactant include DC3PA, DC7PA, SH11PA, SH21PA and SH-8400 from Dow Corning Toray Silicone Co., Ltd. and TSF-4440, TSF-4445 and TSF-4446 from GE Toshiba Silicone Co., , 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.

Other commercially available products include KP (Shinetsugaku Kagaku Kogyo Co., Ltd.), POLYFLOW (Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by TOKEM PRODUCTS CO., LTD.), MEGAFAC Asoui guard, Surflon (available from Asahi Glass Co., Ltd.), SOLSPERSE (Lubrisol) (available from Dainippon Ink and Chemicals Inc.), Flourad (Sumitomo 3M Co., Ltd.) , EFKA (EFKA Chemical), PB 821 (Ajinomoto), and Disperbyk-series (BYK-chemi).

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

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.

The nonionic surfactants include, for example, 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 above-mentioned surfactants may be used alone or in combination of two or more.

The type of the adhesion promoter is not particularly limited and specific examples of the adhesion promoter that can be used include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl Aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, -Glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxy Propyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane.

These adhesion promoters 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 the total weight of the solid content of the colored photosensitive resin composition.

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

The ultraviolet absorber is not particularly limited, but specific examples thereof include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole and alkoxybenzophenone .

The kind of the anti-aggregation agent is not particularly limited, but specific examples that can be used 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 in the colorant (A) 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 탆 or less. At this time, if necessary, a part or all of the pigment dispersant, the binder resin (B), or the dye may be mixed and dissolved or dispersed together with the solvent (E). The remaining dispersion of the binder resin (B), the photopolymerization initiator (D), the photopolymerizable compound (C) and the additive (F) and, if necessary, the solvent (E) To prepare a colored photosensitive resin composition.

<Color filter>

One embodiment of the present invention relates to a color filter formed using the above-mentioned colored photosensitive resin composition.

The color filter includes a substrate and a pattern layer formed on the substrate.

The substrate may be the substrate of the color filter itself, or may be a portion where a color filter is placed on a display device or the like, and is not particularly limited. The substrate may be glass, silicon (Si), silicon oxide (SiOx), or a polymer substrate, and the polymer substrate may be polyethersulfone (PES) or polycarbonate (PC).

The pattern layer may be a layer including the colored photosensitive resin composition of the present invention, and may be a layer formed by applying the colored photosensitive resin composition and exposing, developing, and thermally curing the colored photosensitive resin composition in a predetermined pattern. The pattern layer may be formed by performing a method commonly known in the art.

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

Further, the color filter may further include a protective film formed on the pattern layer of the color filter.

<Image Display Device>

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

The image display apparatus of the present invention is provided with the above-described color filter, and a specific example thereof is a liquid crystal display, an OLED, a flexible display, and the like, but is not limited thereto.

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  One: Triazine  compound

As a triazine derivative, a compound of the following formula (13) was prepared as follows.

18.4 parts by weight of 2-chloro-4,6-diamino-1,3,5-triazine and 21 parts by weight of 3- (2-ethylhexyloxy) propylamine were added to 100 parts by weight of water, Lt; / RTI &gt; The obtained reaction product was reacted at 85 캜 for 5 hours. The obtained reaction product was leached, washed with water, and then allowed to stand in a constant temperature oven at 100 캜 overnight and dried to obtain a compound represented by the following formula (13).

[Chemical Formula 13]

Synthetic example  2: Compound of Formula 3

As the oxime compound, the compound of formula (3) was prepared as follows.

Reactant 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 &lt; 0 &gt; 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.

Reactant 2

100.5 g of the above reaction product 1 was dissolved in 1 L of dichloromethane and cooled to -5 캜. Then, 72.3 g of aluminum chloride was slowly added thereto. While taking care not to raise the temperature of the reaction product, the reaction mixture was diluted with 50 ml of dichloromethane g was slowly added over 2 hours and the reaction was stirred at -5 [deg.] 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.

Reactant 3

44.5 g of Reaction Product 2 was dissolved in 900 ml of tetrahydrofuran (THF), 150 ml of 4N HCl dissolved in 1,4-dioxane and 24.7 g of isobutyl nitrite were added in this order, and the reaction was stirred at 25 ° 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).

The compound of formula 3

Reaction product 3 was dissolved in 1 L of N-methyl-2-pyrrolidinone (NMP) under a nitrogen atmosphere, 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 A solution prepared by dissolving 27.5 g of acetyl chloride in 75 ml of N-methyl-2-pyrrolidinone was slowly added over 30 minutes and stirred for 30 minutes while careful not to raise the temperature of the reaction product. 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 1- (9,9-diethyl-9H-fluoren-2-yl) -1,2-propane 93.7 g of dione-2-oxime-O-acetate was obtained.

Synthetic example  3: Resin B-1

A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube was provided with 74.8 g (0.20 mol) of benzylmaleimide, 43.2 g (0.30 mol) of acrylic acid, 4 g of t-butylperoxy-2-ethylhexanoate and 40 g of propylene glycol monomethyl ether acetate (PGMEA) were charged and stirred to prepare a charge transfer additive dropping funnel. Then, n-dodecanethiol And 24 g of PGMEA were placed and stirred and mixed. Thereafter, 395 g of PGMEA was introduced into the flask, the atmosphere in the flask was replaced with nitrogen in air, and the temperature of the flask was raised to 90 DEG C with stirring. Then, the monomer and the chain transfer agent were added dropwise from the dropping funnel. The mixture was allowed to proceed for 2 hours each while maintaining the temperature at 90 캜. After 1 hour, the temperature was elevated to 110 캜 and maintained for 3 hours. Then, a gas introduction tube was introduced to obtain an oxygen / nitrogen mixed gas of 5/95 (v / v) And started bubbling. Then, 28.4 g of [(0.10 mol) of glycidyl methacrylate, 33 mol% of the carboxyl group of the acrylic acid used in the present reaction), 2,2'-methylenebis (4-methyl-6-t- ) And 0.8 g of triethylamine were placed in a flask, and the reaction was continued at 110 캜 for 8 hours to obtain a resin B-1 having a solid acid value of 70 mgKOH / g. The weight average molecular weight measured by GPC in terms of polystyrene was 16,000 and the molecular weight distribution (Mw / Mn) was 2.3.

Manufacturing example  1: Preparation of colorant dispersion 1

20.48 parts by weight of the compound represented by the formula (13) in Synthetic Example 1, 9.12 parts by weight of CI Pigment Blue 15: 6, 2.88 parts by weight of CI Acid Red 52, 10 parts by weight of an acrylic dispersant [Disperbyk (R) 2000; 2.84 parts by weight of Resin B-1 of Synthesis Example 3, 55.04 parts by weight of solvent propylene glycol monomethyl ether acetate and 5.76 parts by weight of propylene glycol monomethyl ether were mixed with 360 parts by weight of zirconia beads having a diameter of 0.2 mm, The mixture was put into a Mayonnaise bottle having a capacity of 140 ml and kneaded at 60 캜 for 10 hours by a paint conditioner to carry out dispersion treatment. Thereafter, zirconia beads were removed to obtain a dispersion. The dispersion was filtered through a membrane filter having a pore size of 1.0 占 퐉 to obtain a colorant dispersion 1.

Example  1 to 4 and Comparative Example  1 to 3: 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%).

division Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 The colorant dispersion (A) 40 40 40 40 40 40 40 The binder resin (B) 5 5 5 5 5 5 5 The photopolymerizable compound (C) 5 5 5 5 5 5 5 Photopolymerization initiator (D1) 2.4 2.4 1.2 3 1.5 Photopolymerization initiator (D2) 2.4 1.2 1.5 Photopolymerization initiator (D3) 0.6 0.6 3 Photopolymerization initiator (D4) 0.6 0.6 Solvent (E) 46.9 46.9 46.9 46.9 46.9 46.9 46.9 Additive (F) 0.5 0.5 0.5 0.5 0.5 0.5 0.5

Colorant dispersion (A): Colorant dispersion 1 of Production Example 1

Binder resin (B): methacrylic acid / benzyl methacrylate copolymer (weight ratio = 30/70, weight average molecular weight = 28,000)

Photopolymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)

Photopolymerization initiator (D1): Irgacure OXE02 (BASF)

Photopolymerization initiator (D2): Compound (3) of Synthesis Example 2

Photopolymerization initiator (D3): Irgacure 184 (BASF)

Photopolymerization initiator (D4): DARACURE 1173 (BASF)

Solvent (E): Propylene glycol monomethyl ether acetate (PGMEA)

Additive (F): SH-8400 (Dow Corning)

Experimental Example  One

The properties of the colored photosensitive resin compositions prepared in the above Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 2 below.

(1) water stains

Each of the colored photosensitive resin compositions prepared in the above Examples and Comparative Examples was applied to a glass having a size of 5 × 5 cm, dried, and then coated to a thickness of 2.5 μm. Thereafter, the solvent was removed by drying in a 100 ° C oven for 3 minutes, and then the color filter was prepared by exposing the solvent to 300 m in terms of the distance from the photomask to 40 mJ of the 313 nm wavelength of the fusion lamp. At this time, additional exposure was performed with a UV lamp having a main wavelength of about 254 nm after development. The color filter was soaked in the distilled water so as to be partially immersed and allowed to stand for 10 minutes. Then, nitrogen gas was blown and dried, and then stains were observed between the portion where the distilled water and the portion not immersed were observed with a surface inspection lamp (FY-100R).

<Evaluation Criteria of Water Stains>

○: Water stain observed

X: No water stain observed

(2) Solvent resistance  evaluation

Each of the colored photosensitive resin compositions prepared in the above Examples and Comparative Examples was coated on a 50 mm x 50 mm glass substrate using a spin coater by adjusting the number of revolutions so that the film thickness after drying was 2.5 占 퐉, Lt; 0 &gt; C for 3 minutes. The dried substrate was exposed so that the accumulated light quantity at a wavelength of 313 nm of the fusion lamp was 40 mJ at a distance of 300 mu m from the photomask to produce a color filter. Thereafter, the resultant was developed with a spray developing apparatus using a KOH aqueous solution having a pH of 10.5 for 1 minute, washed with water, and air-dried. And then cured in an oven at 150 ° C for 20 minutes to prepare a color filter. At this time, after development, additional exposure was performed with a UV lamp having a main wavelength of about 254 nm, and post-baking was performed. On the color filter having the pattern formed in this manner, the other color filters were stacked in the order of R, G, and B in the same manner.

The substrate was immersed in a NMP solution at room temperature for 30 minutes, washed with ultrapure water, dried on a hot plate heated to 120 占 폚 for 2 minutes, and then the chromaticity before and after immersion was measured. At this time, the color change value is calculated by the following equation (1) representing the color change in the three-dimensional colorimetry defined by L *, a *, b *, and a color filter with high reliability can be manufactured as the color change value is small.

[Equation 1]

? Eab ^* = [(? L ^* ) ² + (? A ^* ) ² + (? B ^* ) ² ] ^0.5

(3) Lamination Residue  evaluation

The colored photosensitive resin composition was applied to a glass of 5 x 5 cm, dried and then bar-coated to a thickness of 2.5 m. After drying for 3 minutes in a 100 ° C oven to remove the solvent, the color filter was prepared by exposing the mixture to 300 m in terms of the distance from the photomask to 40 mJ of the 313 nm wavelength of the fusion lamp, and curing in an oven at 150 ° C for 20 minutes . At this time, after development, additional exposure was performed with a UV lamp having a main wavelength of about 254 nm, and post-baking was performed. On the color filter having the pattern formed in this manner, the other color filters were stacked in the order of R, G, and B in the same manner.

After the color filter was laminated, the completed substrate was observed with a reflection type optical microscope (observation magnification: 50 times), and the degree of occurrence of the laminated residue was evaluated according to the following criteria.

&Lt; Standard for evaluation of laminated residue &

?: Occurrence of laminated residue

X: No residue of laminate

Water stain Solvent resistance Laminated residue Comparative Example 1 ○ 3.6 ○ Comparative Example 2 ○ 4.7 ○ Comparative Example 3 ○ 5.3 ○ Example 1 × 1.7 × Example 2 × 1.1 × Example 3 × 1.6 × Example 4 × 1.3 ×

As shown in Table 2, the colored photosensitive resin compositions of Examples 1 to 4, which contained an oxime compound having an absorption band in a region of 300 nm or more as a photopolymerization initiator and an acetophenone compound having an absorption band in a region of 300 nm or less, And it was confirmed that water spots and laminated residues were not generated. On the other hand, the colored photosensitive resin compositions of Comparative Examples 1 to 3, which did not contain any one of the oxime compound having an absorption band in a region of 300 nm or more and the acetophenone compound having an absorption band in a region of 300 nm or less, were poor in solvent resistance, It was confirmed that a laminated residue occurred.

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 (10)

Wherein the photopolymerization initiator comprises an oxime compound having an absorption band in a region of 300 nm or more and an acetophenone compound having an absorption band in a region of 300 nm or less, wherein the photopolymerization initiator Based on the total weight of the colored photosensitive resin composition. The colored photosensitive resin composition according to claim 1, wherein the oxime compound comprises at least one compound represented by any one of the following formulas (1) to (3):
[Chemical Formula 1]

(2)

(3)

In this formula,
R ¹ is a C ₁ -C ₁₂ alkyl group or

Lt;
R ² and R ³ are each independently a C ₁ -C ₁₂ alkyl group,
R ⁴ is an aryl group,
R ⁵ is a C ₁ -C ₁₂ alkyl group, an aryl group or an aralkyl group,
R ⁶ is a C ₁ -C ₁₂ alkyl or aryl group,
R ⁷ and R ⁸ are each independently a C ₁ -C ₁₂ alkyl group,
R ⁹ to R ¹⁶ are each independently selected from the group consisting of hydrogen, halogen, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy, C ₁ -C ₁₂ hydroxyalkyl, C ₂ -C ₂₄ hydroxyalkoxyalkyl , A C ₃ -C ₁₀ cycloalkyl group, an aryl group, an aralkyl group, an amino group, a nitro group, a cyano group or a hydroxy group. 3. The compound according to claim 2, wherein R &lt; 1 ^&gt; is a methyl group or

, R ² is a methyl group, R ³ is an ethyl group, and R ⁴ is a methylphenyl group, a pyrrolyl group, a thiophenyl group, a benzothiophenyl group or a naphthyl group. The colored photosensitive resin composition according to claim 2, wherein, in the general formula (2), R ⁵ is a hexyl group, a thiophenyl group, a furanyl group, a thiophenylpropyl group or a pyridinylmethyl group and R ⁶ is a phenyl group or a methyl group. The method of claim 2 wherein in Formula 3, R ⁷ is methyl group or propyl group, R ⁸ is a methyl group, an ethyl group, a butyl group, Pen a group or hexyl group, R ⁹ is hydrogen, methyl, ethyl or butyl group, And R ¹⁰ to R ¹⁶ are hydrogen. The colored photosensitive resin composition according to claim 1, wherein the acetophenone compound comprises at least one acetophenone compound having a hydroxy group or a C ₁ -C ₃ alkoxy group at the alpha position. 7. The method of claim 6, wherein the acetophenone compound is selected from the group consisting of 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2- 2-methyl-1-propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,2- -Dimethoxy-2-phenylacetophenone, and 2,2-diethoxy-2-phenylacetophenone. The colored photosensitive resin composition according to claim 1, wherein the weight ratio of the oxime compound and the acetophenone compound is 70 to 99: 1 to 30. A color filter formed using the colored photosensitive resin composition according to any one of claims 1 to 8. An image display apparatus comprising the color filter according to claim 9.