KR20150109879A - A color photosensitive resin composition, color filter and display device comprising the same - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition, and a color filter and a display device comprising the same and, more specifically, to a colored photosensitive resin composition capable of maintaining a developing speed and sensitivity, and significantly improving smear development, and a color filter and a display device comprising the same.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color photosensitive resin composition, a color filter and a display device using the same,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored photosensitive resin composition, a color filter and a display device including the colored photosensitive resin composition, and more particularly, to a colored photosensitive resin composition having excellent quality that does not cause surface defects such as development unevenness and water stain while maintaining development speed and sensitivity , A color filter including the same, and a display device.

A color filter is manufactured by a dyeing method, a printing method, an electrodeposition method, a pigment dispersion method, a film transfer method, and the like, and is used not only in a liquid crystal display panel (LCD) ) And liquid crystal shutters. Particularly, since the color filter is one of the most important parts for reproducing the color tone in the LCD, researches on a manufacturing method of a color filter having excellent processability and product reliability for improving the productivity in the LCD manufacturing process have been steadily continued.

Recently, materials for color filters are required to have high sensitivity, high reliability in pattern formation and high color reproducibility. Accordingly, the pigment concentration of the colored photosensitive resin composition used for manufacturing the color filter is continuously increased, and a colored photosensitive resin composition having the same sensitivity and reliability at a low exposure dose is required in order to improve process productivity and yield. However, when a color filter is manufactured using a high color ratio or a highly colored colored photosensitive resin composition in order to improve the developing speed and sensitivity, unevenness or surface abnormality occurs during vacuum drying, and color filter defects frequently occur . This problem is further increased when the process time is shortened to increase the production amount of the color filter.

On the other hand, Korean Patent Laid-Open No. 10-2007-0076083 discloses a thermosetting resin for a color filter protective film which improves adhesiveness, surface hardness and the like by using a polyfunctional monomer having both an ethylenic unsaturated bond and an unsaturated carboxylic acid anhydride bond in one molecule Although the composition is disclosed, the problem of surface defects of the colored photosensitive resin composition still remains unsolved.

Korean Patent Publication No. 10-2007-0076083

An object of the present invention is to provide a colored photosensitive resin composition which is free from problems of surface defects such as development unevenness and water stain while maintaining the developing speed and sensitivity, and a color filter and a display device including the colored photosensitive resin composition.

In order to achieve the above object,

The present invention relates to a colored photosensitive resin composition comprising a colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D) and a solvent (E) There is provided a colored photosensitive resin composition comprising a compound having the structure of Formula (1):

(Formula 1)

In the general formula (1), n is an integer of 1 to 4.

The present invention also provides a color filter comprising the colored photosensitive resin composition.

Further, the present invention provides a display device including the color filter.

The colored photosensitive resin composition of the present invention has an effect of remarkably improving development unevenness while maintaining the developing speed and sensitivity.

1 is a development stain and a water stain image under the green lamp of Example 1. Fig.
Fig. 2 shows the development unevenness and water stain image of Comparative Example 1. Fig.

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

1. A colored photosensitive resin composition comprising a colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D) and a solvent (E) ≪ RTI ID = 0.0 > 1, < / RTI >

(Formula 1)

In the general formula (1), n is an integer of 1 to 4.

In the present invention, it has been experimentally confirmed that the use of the photopolymerizable compound (C) containing the compound of formula (1) exhibits remarkably improved development unevenness while maintaining development speed and sensitivity.

Hereinafter, the contents of the present invention will be described in detail as follows.

The colorant (A)

The colorant (A) contains at least one kind of pigment (a1) or at least one kind of dye (a2) as essential components. Specifically, the colorant of the present invention can be used by preparing a pigment dispersion composition by mixing and dispersing a pigment together with a pigment dispersant and a solvent. Hereinafter, each configuration will be described.

The pigment (a1)

The pigment may be an organic pigment or an inorganic pigment generally used in the art. The above-mentioned pigments can be used in various kinds of pigments used in printing ink, ink jet ink and the like. Specific examples thereof include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, And an anthanthrone pigment, an anthanthrone pigment, a pravanthrone pigment, a pyranthrone pigment, an anthanthrone pigment, an anthanthrone pigment, an anthanthrone pigment, an anthanthrone pigment, an anthanthrone pigment, a pyranthrone pigment, pyranthrone pigments, diketopyrrolopyrrole pigments, and the like. The arms can be exemplified by metal compounds such as the pigment as the metal oxides, metal complex salts, specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, an oxide of a metal such as carbon black Or composite metal oxides. In particular, the as organic pigments and inorganic pigments can include compounds that are classified as pigments in the particular color index (The society of Dyers and Colourists Publishing), more specifically, the color index (CI) numbers as described below 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 and 58

C.I Pigment Brown 28

CI Pigment Black 1 and 7 Light

The above-mentioned pigments may be organic pigments or inorganic pigments generally used in the art. These 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 Red 177, CI Pigment Red 208, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Violet 23, CI Pigment Blue 15: 3, Pigment Blue 15: , CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58 can be preferably used.

It is preferable to use a pigment dispersion in which the particle diameter of the pigment is uniformly dispersed. An example of a method for uniformly dispersing the particle diameter of the pigment includes a method of dispersing the pigment dispersion (a3) by containing the pigment dispersant (a3). According to this method, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained have.

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

The pigment dispersant (a3)

The pigment dispersant (a2) is added for maintenance of deagglomeration and stability of the pigment, and any of those generally used in the art can be used without limitation. (Hereinafter referred to as an acrylic dispersant) containing BMA (butyl methacrylate) or DMAEMA (N, N-dimethylaminoethyl methacrylate). At this time, it is preferable to apply the acrylic dispersant prepared by a living control method as disclosed in Korean Patent Publication No. 2004-0014311. DISCLOSURE OF INVENTION It is an object of the present invention to provide an acrylic dispersant, 2000, DISPER BYK-2001, DISPER BYK-2070, and DISPER BYK-2150.

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

As the dispersant (a3), other resin type pigment dispersants other than the acrylic dispersant may be used. The other resin type pigment dispersing agent may be a known resin type pigment dispersing agent, especially a polycarboxylic acid ester such as polyurethane, polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) Amine salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long chain polyaminoamide phosphate salts, esters of hydroxyl group-containing polycarboxylic acids and their modified products, or free ) Oil-based dispersants such as amides formed by reaction of a polyester having a carboxyl group with poly (lower alkyleneimine) or salts thereof; Soluble resin or water-soluble polymer compound such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinylpyrrolidone; Polyester; Modified polyacrylates; Adducts of ethylene oxide / propylene oxide, and phosphate esters. DISPER BYK-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, or may be used in combination with acrylic dispersion.

The amount of the dispersant (a3) to be used is in the range of 5 to 60 parts by weight, more preferably 15 to 50 parts by weight, based on 100 parts by weight of the solid content of the pigment (a1). If the content of the dispersant (a3) exceeds 60 parts by weight, the viscosity may be increased. If the content of the dispersant (a3) is less than 5 parts by weight, it may be difficult to atomize the pigment or cause gelation after dispersion.

The dye (a2)

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. Yellow dyes such as Solvent Yellow 4, 14, 15, 16, 21, 23, 24, 38, 56, 62, 63, 68, 79, 82, 93, 94, 98, 99, 151, 162, 163;

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

C.I. Orange dyes such as solvent orange 2, 7, 11, 15, 26, 41, 45, 56, 62;

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

C.I. Violet dyes such as solvent violet 8, 9, 13, 14, 36, 37, 47, 49;

C.I. Green dyes such as Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 and the like.

CI Solvent Yellow 14, 16, 21, 56, 151, 79, 93 having excellent solubility in organic solvents in 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 an acid dye

CI Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112 , 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184 Yellow dyes such as 1,1,1,2,2,2,2,2,2,23,28, 240,242, 243,251 and the like, such as, for example, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, ;

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, 198, 206, 211, 215, 216, 217 , 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349 Red dyes such as 382, 383, 394, 401, 412, 417, 418, 422, 426;

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

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

Violet dyes such as C.I. Acid Violet 6B, 7, 9, 17, 19, 66 and the like;

Green dyes such as CI Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106,

CI Acid Yellow 42, which is excellent in solubility in organic solvents in acid dyes; CI Acid Red 92; CI Acid Blue 80, 90; CI Acid Violet 66; CI Acid Green 27 is preferred.

As a C.I. direct dye,

CI Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129 , Yellow dyes such as 136, 138, and 141;

CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211 , 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

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

CI Direct Blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113 , 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189 , 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248 , 250, 251, 252, 256, 257, 259, 260, 268, 274, 275 and 293;

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

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

Also, C.I. As a modantoic dye

Yellow dyes such as C.I. Modatto Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

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

CI Modanato Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, dyes;

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

Violet colored dyes such as C.I. Modanth violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;

Green dyes such as CI Modatto Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43,

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

The content of the dye in the colorant (A) is preferably 0.5 to 80% by weight, more preferably 0.5 to 60% by weight, particularly preferably 1 to 50% by weight, based on the solid content in the colorant (A) Do. When the content of the dye in the colorant (A) is in the above range, it is possible to prevent the problem of lowering the reliability of elution of the dye by the organic solvent after formation of the pattern.

The content of the colorant (A) is preferably 5 to 60% by weight based on the total weight of the colored photosensitive resin composition. This is because even if a thin film is formed in the above range, the color density of the pixel is sufficient, And the residue is not easily deteriorated because the dropout property is not deteriorated.

The alkali-soluble resin (B)

Is copolymerized with an ethylenically unsaturated monomer (b1) having a carboxyl group as an essential component in order to obtain solubility in an alkali developing solution used in a development processing step for forming a pattern. In order to ensure compatibility with the dye (a2) and storage stability of the colored photosensitive resin composition, the acid value of the alkali-soluble resin (B) is preferably 30 to 150 mgKOH / g. When the acid value of the alkali-soluble resin (B) is less than 30 mgKOH / g, it is difficult to ensure a sufficient developing rate of the colored photosensitive resin composition. When the acid value exceeds 150 mgKOH / g, the adhesion with the substrate is decreased, , The dye in the colored photosensitive resin composition is precipitated or the storage stability of the colored photosensitive resin composition is lowered, and the viscosity tends to rise.

Specific examples of the ethylenically unsaturated monomer (b1) having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid; And anhydrides of these dicarboxylic acids; (meth) acrylates of a polymer having a carboxyl group and a hydroxyl group at both terminals such as? -carboxypolycaprolactone mono (meth) acrylate, and acrylic acid and methacrylic acid are preferable.

A hydroxyl group may be added to secure further developability of the alkali-soluble resin (B). The ethylenically unsaturated monomer (b1) having a carboxyl group and the ethylenically unsaturated monomer (b2) having a hydroxyl group can be produced by copolymerizing an ethylenically unsaturated monomer (b1) having a carboxyl group and an ethylenically unsaturated monomer (b2) having a hydroxyl group in order to impart a hydroxyl group to the alkali- (B3) having a glycidyl group in the copolymer of the present invention. (B3) having a glycidyl group in addition to a copolymer of an ethylenically unsaturated monomer (b1) having a carboxyl group and an ethylenically unsaturated monomer (b2) having a hydroxyl group.

Specific examples of the butylenically unsaturated monomer (b2) having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl Hydroxy-3-phenoxypropyl (meth) acrylate, N-hydroxyethylacrylamide and the like, and 2-hydroxyethyl (meth) acrylate is preferable, and two or more kinds thereof can be used in combination.

Specific examples of the glycidyl group-containing compound (b3) include butyl glycidyl ether, glycidyl propyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, glycidyl butyrate, glycidyl methyl ether, Ethyl glycidyl ether, glycidyl isopropyl ether, t-butyl glycidyl ether, benzyl glycidyl ether, glycidyl 4-t-butyl benzoate, glycidyl stearate, aryl glycidyl ether, Methacrylic acid glycidyl ester, etc., and butyl glycidyl ether, aryl glycidyl ether, and methacrylic acid glycidyl ester are preferable, and two or more kinds may be used in combination.

The copolymerizable unsaturated monomers (b3) in the preparation of the alkali-soluble resin (B) are exemplified below, but are not limited thereto.

Specific examples of the polymerizable monomer (b4) having an unsaturated bond capable of copolymerization include styrene, vinyltoluene,? -Methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p- Aromatic vinyls such as vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m- vinyl benzyl glycidyl ether and p- compound;

N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm -phenyl maleimide, phenyl maleimide Np-, No- methoxyphenyl maleimide, Nm- methoxyphenyl maleimide, Np- methoxy-N- substituted maleimide-based compounds such as phenyl maleimide;

Propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth) acrylates such as sec-butyl (meth) acrylate and t-butyl (meth) acrylate; (Meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6] decan- Alicyclic (meth) acrylates such as dicyclopentanyloxyethyl (meth) acrylate and isobornyl (meth) acrylate;

Aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate;

3- (methacryloyloxymethyl) -2-trifluoromethyl oxetane, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, and the like Unsaturated oxetane compounds.

The monomers exemplified in the above (b3) may be used alone or in combination of two or more.

The content of the alkali-soluble resin (B) is preferably 1 to 20% by weight, based on the total weight of the photosensitive resin composition, because the solubility in the developer is satisfactory within the above range, The reduction of the film thickness of the sub pixel portion is prevented, and the non-pixel portion is less likely to be missing.

Photopolymerization  The compound (C)

The photopolymerizable compound (C) is a compound capable of polymerizing under the action of a photopolymerization initiator described later, and includes a compound having a structure represented by the following formula (1). The present invention is characterized by using the compound of the above formula (1) as a photopolymerizable compound (C) to remarkably improve development unevenness while maintaining the developing speed and sensitivity.

(Formula 1)

In the general formula (1), n is an integer of 1 to 4.

Specifically, the compound having the structure of Formula 1 may be a compound having the structure of Formula 2 or 3.

(2)

(Formula 3)

The compounds having the structures of the above formulas (2) and (3) may be those commercially available under the following trade names:

(2-propenoic acid, reaction products with? H,? H,? H,? H-fluorinated triethylene glycol) (NK Corporation)

(2-propenoic acid, reaction products with? H,? H,? H,? H-fluorinated tetraethylene glycol (NK)).

Since the photopolymerizable compound contains a fluorine group and has hydrophobic characteristics, it can be expected to have an effect on improvement of water stain. In addition, since there is a reactive group at the terminal, a certain degree of sensitivity can be secured.

In order to ensure sufficient curing of the colored photosensitive resin composition of the present invention, monomers may be used together with the compound having the structure of the above formula (1). The monomer may be a polyfunctional photopolymerizable compound, and specific examples of the polyfunctional photopolymerizable compound include 2-hydroxy-3-acryloyloxypropyl methacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate And the like, and two or more of them may be used in combination. Commercial products 701 (NK ESTER), 701A (NK ESTER), A-TMM-3L (NK ESTER) and KAYARAD DPHA (Nippon Kayaku) are commercially available products.

The photopolymerizable compound (C) is preferably contained in an amount of 1 to 20% by weight based on the total weight of the colored photosensitive resin composition, and it is preferable that the strength and smoothness of the pixel portion are improved in the above range.

Light curing Initiator (D)

The photopolymerization initiator (D) can be used without particular limitation as long as it can polymerize the photopolymerizable compound (C).

In particular, the photopolymerization initiator is preferably selected from the group consisting of an acetophenone based compound, a benzophenone based compound, a triazine based compound, a nonimidazole based compound, an oxime compound, and a thioxanthone based compound from the viewpoints of polymerization characteristics, initiation efficiency, absorption wavelength, availability, It is preferable to use at least one compound selected from the group consisting of compounds.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy- 1- [4- 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-methylcyclohexyl phenyl ketone, 2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1-one -On or 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'- -Butylperoxycarbonyl) benzophenone or 2,4,6-trimethylbenzophenone.

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

Specific examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbimidazole, 2,2'-bis (2,3- Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) , 2,2'-bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) 4 ', 5,5'-tetraphenyl-1,2'-biimidazole or an imidazole compound in which 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 or 2,2-bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'- Is used.

Specific examples of the oxime compounds include o-ethoxycarbonyl- [alpha] -oxyimino-1-phenylpropan-1-one, and commercially available products are OXE-01 and OXE-02 from BASF.

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

Further, other photopolymerization initiators and the like may be further used in combination within the range not impairing the effects of the present invention. For example, a benzoin compound or an anthracene compound may be used, and these may be used alone or in combination of two or more.

Examples of the benzoin-based 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, 2-ethyl-9,10-diethoxyanthracene, etc. .

Other examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylclyoxylic acid A methyl or a titanocene compound may be used in combination as a photopolymerization initiator.

The photopolymerization initiator may further include a photopolymerization initiator (d-1) to improve the sensitivity of the photopolymerizable resin composition of the present invention. The photocurable resin composition according to the present invention contains a photopolymerization initiation auxiliary (d-1), 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. Specific 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 ) Or 4,4'-bis (diethylamino) benzophenone.

The carboxylic acid compound is preferably an aromatic heteroacetic acid, and more specifically, it is preferably an aromatic heteroaromatic acid such as phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthio Acetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine or naphthoxyacetic acid.

Specific examples of the organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -thione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexaquis (3-mercaptopropionate), or tetraethylene glycol bis (3-mercaptopropionate). .

The photopolymerization initiator may be contained in an amount of 0.1 to 10% by weight, preferably 0.5 to 5% by weight based on the total weight of the colored photosensitive resin composition of the present invention. When the photopolymerization initiator is in the above range, the photopolymerizable resin composition is highly sensitized and the exposure time is shortened, so that productivity is improved and high resolution can be maintained. In addition, the strength of the pixel portion formed using the composition and the smoothness of the surface of the pixel portion can be improved.

When the photopolymerization initiator is further used, it is preferable to use the same content range as that of the photopolymerization initiator. When the photopolymerization initiator is used in the above amount, the sensitivity of the photopolymerizable composition is further improved, The productivity of the filter can be improved.

Solvent (E)

The solvent used in the conventional colored photosensitive resin composition may be used without particular limitation as long as it is effective in dissolving the other components contained in the colored photosensitive resin composition. The solvent (E) may be selected from ethers, aromatic hydrocarbons, ketones, Alcohols, esters, amides and the like are preferable.

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,

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.

The solvent (E) is preferably an organic solvent having a boiling point of 100 ° C to 200 ° C on the application and drying surface, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate , Butalactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like.

The above-mentioned (E) solvents may be used alone or as a mixture of two or more thereof. The solvent may contain 30 to 90% by weight, preferably 40 to 85% by weight, based on the total weight of the colored photosensitive resin composition of the present invention have. When the solvent (E) is in the range of 30 to 90% by weight as described above, when it is coated with a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater Thereby providing an effect of improving the property.

Additive (F)

The colored photosensitive resin composition of the present invention may further comprise at least one additive selected from the group consisting of other polymer compounds, a curing agent, a surfactant, an adhesion promoter, an ultraviolet absorber and an anti-aggregation agent, if necessary.

The other polymer compound is not particularly limited, and examples thereof include curable resins such as epoxy resin and maleimide resin, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, Thermoplastic resins and the like.

The curing agent is a component for increasing deep curing and mechanical strength, and the type thereof is not particularly limited, and examples thereof include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, and oxetane compounds.

The epoxy compound is not particularly limited and includes, for example, 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, Epoxy resins, glycidyl ester resins, glycidyl amine resins, or brominated derivatives of such epoxy resins; Aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and brominated derivatives thereof; Butadiene (co) polymeric epoxide; Isoprene (co) polymeric epoxide; Glycidyl (meth) acrylate (co) polymers; Triglycidyl isocyanurate and the like.

The oxetane compound is not particularly limited and includes, for example, carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexanedicarboxylic acid bisoxetane and the like .

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 auxiliary compound is not particularly limited, and examples thereof include polyvalent carboxylic acids, polyvalent carboxylic acid anhydrides, and acid generators. Commercially available polyvalent carboxylic acid anhydrides can be used as an epoxy resin curing agent.

The commercially available epoxy resin curing agent that can be used in the present invention is not particularly limited and includes, for example, a trade name (Adeka Hadona EH-700) (manufactured by Adeka Kogyo Co., Ltd.), a trade name (Rikashido HH) Ltd.) and a trade name (MH-700) (manufactured by Shin-Etsu Chemical Co., Ltd.).

The kind of the surfactant is not particularly limited, and examples thereof include silicone, fluorine, ester, cationic, anionic, nonionic, amphoteric surfactant and the like.

Specific examples thereof include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, polyethyleneimines and the like .

Commercially available products include KP (Shinetsugaku Kogaku Co., Ltd.), POLYFLOW (Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by TOKEM PRODUCTS CO., LTD.), MEGAFAC (Dainippon Ink Asahi guard, Surflon (available from Asahi Glass Co., Ltd.), SOLSPERSE (Lubrisol), EFKA (EFKA (trade name) manufactured by Asahi Chemical Industry Co., Ltd.), Flourad (Sumitomo 3M Co., Ltd.) PB 821 (Ajinomoto Co., Ltd.) and Disperbyk-series (BYK-chemi).

Examples of the adhesion promoter include, but are not limited to, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyl (meth) acrylate, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and the like. These may be used alone or in combination of two or more.

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

The anti-aggregation agent is not particularly limited and may be, for example, sodium polyacrylate.

The content of the additive is not particularly limited and may be, for example, 0.01 to 10% by weight, preferably 0.05 to 2% by weight, based on the total weight of the colored photosensitive resin composition.

The thus-prepared colored photosensitive resin composition is advantageous for achieving a high concentration and a high transmittance, and is excellent in dispersion stability and excellent in characteristics according to time, and therefore is useful as a raw material for forming a coloring pattern constituting a color filter.

The present invention also provides a color filter made of a colored photosensitive resin composition and a display device having the same.

First, a colored photosensitive resin composition is coated on a substrate (usually glass) or a layer composed of a solid component of a previously formed colored photosensitive resin composition, followed by heating and drying to remove volatile components such as a solvent to obtain a smooth coated film.

The coating method can be carried out by, for example, a spin coating method, a flexible coating method, a roll coating method, a slit and spin coating method, a slit coating method or the like. After application, heating and drying (prebaking), or drying under reduced pressure to evaporate the volatile components such as solvent. Here, the heating temperature is usually 70 to 200 占 폚, preferably 80 to 130 占 폚. The thickness of the coating film after heat drying is usually about 1 to 8 mu m. The thus obtained coating film is irradiated with ultraviolet rays through a mask for forming a desired pattern. At this time, it is preferable to use an apparatus such as a mask aligner or a stepper so as to uniformly irradiate a parallel light beam onto the entire exposed portion and to precisely align the mask and the substrate. When ultraviolet light is irradiated, the site irradiated with ultraviolet light is cured.

The ultraviolet rays may be g-line (wavelength: 436 nm), h-line, i-line (wavelength: 365 nm), or the like. The dose of ultraviolet rays can be appropriately selected according to need, and the present invention is not limited thereto. When the coating film after curing is brought into contact with a developing solution to dissolve and develop the non-visible portion, a spacer having a desired pattern shape can be obtained.

The developing method is not particularly limited by a liquid addition method, a dipping method, a spraying method, or the like. Further, the substrate may be inclined at an arbitrary angle at the time of development. The developer is usually an aqueous solution containing an alkaline compound and a surfactant.

The alkaline compound is not particularly limited to an inorganic or organic alkaline compound. Examples of the inorganic alkaline compound include inorganic bases such as sodium hydroxide, potassium hydroxide, disodium hydrogenphosphate, sodium dihydrogenphosphate, ammonium dihydrogenphosphate, ammonium dihydrogenphosphate, potassium dihydrogenphosphate, sodium silicate, potassium silicate, Potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate and ammonia.

The organic alkaline compound includes, for example, tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine , Monoisopropylamine, diisopropylamine, and ethanolamine.

The inorganic or organic alkaline compound may be used alone or in combination of two or more. The concentration of the alkaline compound in the developer is 0.01 to 10% by weight, preferably 0.03 to 5% by weight based on the total weight of the developer.

As the surfactant in the developer, at least one selected from the group consisting of the nonionic surfactant, the anionic surfactant and the cationic surfactant can be used. The concentration of the surfactant in the developing solution is 0.01 to 10% by weight, preferably 0.05 to 8% by weight, more preferably 0.1 to 5% by weight based on the total weight of the developing solution. After development, the substrate is washed with water, and if necessary baked at 150 to 230 DEG C for 10 to 60 minutes.

Using the colored photosensitive resin composition of the present invention, a specific pattern can be formed on the substrate through each of the above steps.

The process for producing the colored photosensitive resin composition of the present invention will be described as follows.

First, the pigment (a1) 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 μm or less. At this time, if necessary, the pigment dispersant (a3), part or all of the alkali-soluble resin (B), or (a2) the dye may be dissolved or dispersed by mixing with the (E) solvent.

(D) and optionally (F) additives and (E) solvent are added to the mixed dispersion so as to have a predetermined concentration, the dye (a2), the remaining alkali-soluble resin (B), the photopolymerizable compound (C) and the photopolymerization initiator The colored photosensitive resin composition according to the present invention can be prepared.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the embodiments of the present invention described below are illustrative only and the scope of the present invention is not limited to these embodiments. The scope of the present invention is indicated in the claims, and moreover, includes all changes within the meaning and range of equivalency of the claims. In the following Examples and Comparative Examples, "%" and "part" representing the content are based on weight unless otherwise specified.

Manufacturing example  1: Preparation of pigment dispersion composition

13.0 parts by weight of CI Pigment Red 177 as a pigment, 3.5 parts by weight of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersing agent, 70.5 parts by weight of propylene glycol methyl ether acetate as a solvent and 4 parts by weight of 4-hydroxy- Were mixed and dispersed by a bead mill for 12 hours to prepare a pigment dispersion composition M1.

Synthetic example  1: Synthesis of alkali-soluble resin

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, 2 parts of AIBN, 13.0 parts of acrylic acid, 10 parts of benzyl methacrylate, 57.0 parts of 4-methylstyrene, 20 parts of methyl methacrylate and 3 parts of n-dodecyl mercapto were charged and replaced with nitrogen. Thereafter, the temperature of the reaction solution was elevated to 110 DEG C with stirring, and the reaction was carried out for 6 hours. The alkali-soluble resin thus synthesized had a solid dispersion value of 100.2 mgKOH / g and a weight average molecular weight Mw of about 15110 as measured by GPC. (Moving to Kyoue)

Example  1: Preparation of colored photosensitive resin composition ( Photopolymerization  Using a compound of formula (2) as a compound)

The pigment dispersion composition M1 was prepared by mixing 41.54 parts of the pigment dispersion, 3.09 parts of the resin of Synthesis Example 1, 2-propenoic acid of the formula 2 as the photopolymerizable compound, 5.02 parts of? H,? H,? H, 1.00 parts of TR-PBG-305 (TRONISA) as an initiator, 49.19 parts of propylene glycol monomethyl ether acetate, 0.14 parts of 3-methacryloxypropyltrimethoxysilane (Shinetsu) as an adhesion promoter, , And 0.01 part of a trade name SH-8400 (Dow Corning) were mixed to prepare a colored photosensitive resin composition.

Example  2: Preparation of colored photosensitive resin composition ( Photopolymerization  Using the compound of formula 3 as the compound)

41.54 parts of the above pigment dispersion composition M1, 3.09 parts of the resin of Synthesis Example 1, 2-propenoic acid as a photopolymerizable compound, 2-propenoic acid, reaction products with? H,? H,? H,? H-fluorinated tetraethylene glycol 5.02 parts 1.00 parts of TR-PBG-305 (TRONISA) as an initiator, 49.19 parts of propylene glycol monomethyl ether acetate, 0.14 parts of 3-methacryloxypropyltrimethoxysilane (Shinetsu) as an adhesion promoter, , And 0.01 part of a trade name SH-8400 (Dow Corning) were mixed to prepare a colored photosensitive resin composition.

Example  3: Preparation of colored photosensitive resin composition ( Photopolymerization  Compounds of formula (3) and Monomer  use)

The pigment dispersion composition M1 was prepared by mixing 41.54 parts of the above pigment dispersion, 3.09 parts of the resin of Synthesis Example 1, 2-propenoic acid of the formula 3 as the photopolymerizable compound, 2.51 parts of the reaction products with? H,? H,? H,? H-fluorinated tetraethylene glycol (NK Corporation), 2.51 parts of 2-hydroxy-3-acryloyloxypropyl methacrylate (NK Corporation) , 1.00 parts of TR-PBG-305 (TRONISA) as an initiator, 49.19 parts of propylene glycol monomethyl ether acetate, 0.14 part of 3-methacryloxypropyltrimethoxysilane (Shin-Etsu) as adhesion promoter and 0.01 part of a surfactant SH-8400 (Dow Corning) were mixed to prepare a colored photosensitive resin composition.

Comparative Example  1: Preparation of colored photosensitive resin composition

41.54 parts of the above pigment dispersion composition M1, 3.09 parts of the resin of Synthesis Example 1, 5.02 parts of 2-hydroxy-3-acryloyloxypropyl methacrylate (NK Corp.) as a photopolymerizable compound, 1.00 parts of PBG-305 (Tronisia), 49.19 parts of propylene glycol monomethyl ether acetate, 0.14 parts of 3-methacryloxypropyltrimethoxysilane (Shinetsu) as an adhesion promoter, and SH-8400 (Dow Corning) Were mixed to prepare a colored photosensitive resin composition.

Comparative Example  2: Preparation of colored photosensitive resin composition

, 41.54 parts of the above pigment dispersion composition M1, 3.09 parts of the resin of Synthesis Example 1, 5.02 parts of dimethiol tricyclodecane diacrylate (manufactured by NK Corporation) as a photopolymerizable compound, TR-PBG-305 , 49.19 parts of propylene glycol monomethyl ether acetate, 0.14 parts of 3-methacryloxypropyltrimethoxysilane (Shinetsu Co.) as an adhesion promoter, and 0.01 part of a surfactant SH-8400 (Dow Corning) as coloring sensitizers To prepare a resin composition.

Experimental Example  One. Photocurable  The resin composition Water stain  evaluation

Using the colored photosensitive resin compositions prepared in the above Examples and Comparative Examples, the following color filters were prepared. Sensitivity, development unevenness and development speed were measured by the following methods, and the results are shown in Table 1 .

≪ Production of color filter &

Each of the photo-curing resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 and 2 was applied onto a 50 mm x 50 mm glass substrate using a spin coater to adjust the number of rotations so that the film thickness after drying was 2.5 占 퐉 And dried in an oven at 100 ° 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. The time point at which the red paint film was washed away in the developing solution was measured as development time, and it is shown in Table 1. The developed substrate was washed with water for 10 seconds and then dried in an oven at 230 DEG C for 25 minutes.

* Sensitivity and development speed

The development time was measured by measuring the time at which peeling of the non-exposed thin film portion occurred during development of the color color filter. Further, during the manufacturing process of the color filter, the minimum exposure amount (mJ / cm 2) necessary for forming a thin film without peeling of the pattern after development was measured.

* Evaluation of development stains

The prepared colored photosensitive resin composition was applied on a glass substrate (# 1737, Corning) by spin coating, and then placed on a heating plate and held at a temperature of 100 ° C for 3 minutes to form a thin film. Subsequently, light was irradiated at an exposure dose (365 nm) of 40 mJ / cm 2 in an atmospheric environment using an ultra-high pressure mercury lamp (USH-250D, manufactured by Ushio DENKI CO., LTD.). The ultraviolet-irradiated thin film was developed in a KOH aqueous solution of pH 12.5 for 80 seconds using a spray developing machine. The glass substrate coated with the thin film was rinsed with distilled water, and then a small amount of distilled water was added dropwise to the dried thin film by blowing nitrogen gas, and the roundness was maintained. The glass substrate was allowed to stand at room temperature for 2 minutes and then blown dry with nitrogen gas. Subsequently, the substrate was irradiated with an Na lamp, and the surface state of the coating film was observed to visually judge whether or not a circular spot was formed, and the evaluation was made according to the following criteria.

○: Circular water stains were not recognized on the surface of the coating film.

△: Circular water stain was finely recognized on the surface of the coating film.

X: Circular water stain clearly observed on the surface of the film.

Exposure dose (40 mJ / cm 2) Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Sensitivity (mJ / cm2) 12 12 13 12 13 Stain ○ ○ ○ X △ Development speed 19 19 17 18 20

As shown in Table 1, the colored photosensitive resin compositions of Examples 1 to 3 including the photopolymerizable compound represented by the formula (1) according to the present invention are superior to the colored photosensitive resin compositions of Comparative Examples 1 and 2 It can be confirmed that the development unevenness is not recognized while exhibiting similar sensitivity and development speed.

1 is a development unevenness / water stain image under the green lamp of Example 1, and Fig. 2 is a development unevenness and water stain image of Comparative Example 1. Fig. Comparing FIG. 1 and FIG. 2, the colored photosensitive resin composition containing the photopolymerizable compound represented by the formula (1) according to the present invention is remarkably distinguished from the colored light sensitive resin composition of the comparative example using the conventional photopolymerizable compound Can be confirmed.

The results of the above experiments show that Examples 1 to 3 containing the photopolymerizable compound according to the present invention exhibit remarkable development unevenness while maintaining the developing speed and sensitivity as compared with the colored photosensitive resin compositions of Comparative Examples 1 and 2, It is possible to manufacture a color filter of excellent quality even at a low exposure dose.

Claims (11)

A colored photosensitive resin composition comprising a colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D) and a solvent (E)
The colored photosensitive resin composition according to claim 1, wherein the photopolymerizable compound (C) comprises a compound having a structure represented by the following formula (1):
(Formula 1)

In the general formula (1), n is an integer of 1 to 4.
The colored photosensitive resin composition according to claim 1, wherein the photopolymerizable compound (C) comprises a compound having a structure represented by the following general formula (2) or (3)
(2)

(Formula 3)

.
The method according to claim 1,
The photopolymerizable compound (C) further comprises at least one monomer selected from 2-hydroxy-3-acryloyloxypropyl methacrylate, pentaerythritol triacrylate and dipentaerythritol pentaacrylate By weight based on the total weight of the colored photosensitive resin composition.
The method according to claim 1,
Wherein the alkali-soluble resin (B) has an acid value of 30 to 150 mgKOH / g.
The method according to claim 1,
The photopolymerization initiator (D) comprises at least one compound selected from the group consisting of an acetophenone compound, a benzophenone compound, a triazine compound, a nonimidazole compound, an oxime compound and a thioxanthone compound By weight based on the total weight of the colored photosensitive resin composition.
The method according to claim 1,
The solvent (E) is at least one alkylene glycol alkyl ether acetate selected from propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate. Wherein the coloring photosensitive resin composition is a colored photosensitive resin composition.
The photosensitive resin composition according to claim 1, wherein, based on the total weight of the colored photosensitive resin composition,
5 to 60% by weight of the colorant (A);
1 to 20% by weight of an alkali-soluble resin (B);
1 to 20% by weight of a photopolymerizable compound (C);
0.1 to 10% by weight of a photopolymerization initiator (D); And
And 30 to 90% by weight of a solvent (E).
The method according to claim 1,
(F) selected from the group consisting of a polymer compound, a curing agent, a surfactant, an adhesion promoter, an ultraviolet absorber and an anti-aggregation agent.
The photosensitive resin composition according to claim 8, wherein, based on the total weight of the colored photosensitive resin composition,
5 to 60% by weight of the colorant (A);
1 to 20% by weight of an alkali-soluble resin (B);
1 to 20% by weight of a photopolymerizable compound (C);
0.1 to 10% by weight of a photopolymerization initiator (D);
30 to 90% by weight of a solvent (E); And
And 0.01 to 10% by weight of an additive (F).
A color filter comprising the colored photosensitive resin composition of claim 1.
A display device comprising the color filter of claim 10.

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