KR20170017534A - Colored photosensitive resin composition and color filter using the same - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition and, more specifically, to a colored photosensitive resin composition used in the process of manufacturing a color filter used in a color liquid crystal display device or the like, and to a color filter manufactured by using the same. The colored photosensitive resin composition can be cured in a low temperature curing process and shows excellent sensitivity, thereby providing a color filter of high reliability. The colored photosensitive resin composition comprises a colorant, an alkali soluble resin, a polyfunctional monomer, a photopolymerization initiator, a solvent and a mercapto compound.

Description

TECHNICAL FIELD [0001] The present invention relates to a colored photosensitive resin composition and a color filter using the colored photosensitive resin composition.

The present invention relates to a colored photosensitive resin composition, and more particularly, to a colored photosensitive resin composition for a color filter used for producing a color filter used in a color liquid crystal display device or the like, and a color filter manufactured using the same.

The 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, in an LCD in which the use thereof is widening, a color filter is one of the most important parts for reproducing a color tone.

In recent years, in order to improve the productivity in the LCD manufacturing process, researches for manufacturing a color filter with high reliability in a low-temperature firing process rather than a high-temperature firing process are being conducted. However, when the existing colored photosensitive resin composition is cured at 200 ° C or lower, the resin composition is not sufficiently cured and the adhesion with the lower substrate is deteriorated to cause peeling of the pattern or increase in exposure amount to form a thin film And the sensitivity is lowered. Therefore, there is a growing demand for a low-temperature curing type photosensitive resin composition capable of providing a color filter having sufficient curability at a temperature of 200 DEG C or less and having high sensitivity and high reliability. For example, in Korean Patent Publication No. 2012-0088026, a coloring agent, an alkali-soluble resin, a photopolymerization compound, a photopolymerization initiator, a solvent, an antioxidant, There is provided a colored photosensitive resin composition comprising an azo compound, a mercapto compound and an epoxy compound. However, in the above-mentioned prior art, since the transmittance of the color filter is lowered and the azo compound is thermally decomposed due to the inclusion of the azo compound, there is a fume problem, and the curing can be sufficiently performed on the substrate during the low- There is a continuing demand for colored photosensitive resin compositions.

Korea Public Patent No. 2012-0088026

An object of the present invention is to provide a colored photosensitive resin composition capable of sufficiently curing with a substrate in a low temperature firing step and exhibiting excellent sensitivity.

Another object of the present invention is to provide a color filter made of the colored photosensitive resin composition and having high reliability.

The present invention relates to a thermoplastic resin composition comprising a colorant (A), an alkali-soluble resin (B), a polyfunctional monomer (C), a photopolymerization initiator (D), a solvent (E) and a mercapto compound (F) (C-1) having three or more functional groups and a multifunctional monomer (C-2) represented by the following general formula (1).

[Chemical Formula 1]

Wherein X is an aliphatic hydrocarbon having 1 to 10 carbon atoms with or without a hetero atom,

_{R 1, R 2, R 3} , R 4, R 5 and R ₆ are each independently, an epoxy compound or to a compound of the formula 2, R ₁ to R ₆ Is at least one compound and an epoxy compound represented by the general formula (2)

(2)

n is an integer of 0 to 5;

In one embodiment, the multifunctional monomer (C-2) represented by the general formula (1) may be a compound represented by the following general formula (3).

(3)

In another embodiment, the (meth) acrylic multifunctional monomer (C-1) having three or more functional groups is selected from the group consisting of trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethyl (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (Meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.

In another embodiment, the mercapto compound (F) is 4-mercaptohydrocinnamic acid, 4-mercaptobenzoic acid, thiosalicylic acid, 3,4- Methoxybenzenethiol, 3-ethoxybenzenethiol, 4-hydroxybenzenethiol, 3-methoxybenzenethiol, 2-methoxybenzenethiol, 3-methoxybenzenethiol, 2-hydroxybenzenethiol, 4-methoxybenzenethiol, 3-hydroxybenzenethiol, 2-methoxybenzenethiol, methylthio Methylthiosalicylate, 2,3,5,6-Tetrafluoro-4-mercaptobe nzoic Acid, 2-mercaptobenzothiazole, Mercaptopropionic acid, methyl 3-mercaptopropionate, 2-ethyl-3-mercaptopropionate, N-octyl 3-mercaptopropionate, methoxybutyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, n-octyl 3-mercaptopropionate, Mercaptopropionate, stearyl 3-mercaptopropionate, trimethylolpropanetris (3-mercaptopropionate), tris [3-mercaptopropionate 3-Mercaptopropyloxy-ethyl] -isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate), tetra (3-mercaptopropionyloxy) A group consisting of ethylene glycol bis (3-mercaptopropionate) and dipentaerythritol hexakis (3-mercaptopropionate). Select from Or more.

In another embodiment, the colorant (A) is contained in an amount of 5 to 60 wt%, the alkali-soluble resin (B) is contained in an amount of 10 to 80 wt%, and the polyfunctional monomer (C) The photopolymerization initiator (D) is contained in an amount of 0.1 to 40% by weight based on the total content of the alkali-soluble resin (B) and the multifunctional monomer (C) , And the solvent (E) may be contained in an amount of 60 to 90% by weight based on the total weight of the colored photosensitive resin composition.

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

The colored photosensitive resin composition of the present invention can provide a highly reliable color filter because it can be cured sufficiently at a low temperature firing step and exhibits excellent sensitivity.

The present invention relates to a colored photosensitive resin composition and a color filter manufactured using the same.

Since the colored photosensitive resin composition of the present invention includes the multifunctional monomer (C-2) and the mercapto compound (F) represented by the general formula (1), it is possible to sufficiently cure the low temperature firing step and improve the reliability of the color filter to be.

Hereinafter, the present invention will be described in detail.

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.

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. Examples of the inorganic pigments include metallic compounds such as metal oxides and metal complex salts. Specific examples of the inorganic pigments include oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony and carbon black Or composite metal oxides. Particularly, the organic pigments and inorganic pigments may be specifically classified into pigments in the Society of Dyers and Colourists, and more specifically, those having a color index (CI) number And pigments. However, it is not necessarily limited to these pigments. These pigments may be used alone or in combination of two or more kinds.

CI 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

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

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

CI Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37 and 38

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

CI Pigment Green 7, 10, 15, 25, 36, 47 and 58

CI 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 .

Pigment dispersant ( a3 )

The pigment dispersant (a3) 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 Laid-Open 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 above 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 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.

dyes( a2 )

The dye (a2) may 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, solubility in solvent and stability with time.

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 dyes include, as CI 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;

Green dyes such as CI 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 is more preferable.

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 colorant (A) is preferably 5 to 60% by weight, more preferably 10 to 45% by weight, based on the solid content in the colored photosensitive resin composition. When the colorant (A) is contained in an amount of 5 to 60% by weight based on the above standard, the color density of the pixel is sufficient even when a thin film is formed, and the residue of the non- Do.

In the present invention, the solid content in the colored photosensitive resin composition means the total content of the remaining components excluding the solvent from the colored photosensitive resin composition.

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 stability with time 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 stability of the colored photosensitive resin composition with time is lowered, and the viscosity tends to increase.

A hydroxyl group may be added to secure further developability of the alkali-soluble resin (B). (B) and the hydroxyl value of (C) in the multifunctional monomer is limited to 50 mgKOH / g or more and 250 mgKOH / g or less. When the sum of the hydroxyl groups is less than 50 mgKOH / g, a sufficient developing rate can not be secured. When it exceeds 250 mgKOH / g, the dimensional stability of the formed pattern is lowered and the linearity of the pattern becomes poor and the compatibility with the dye is deteriorated A problem of stability over time is apt to occur.

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.

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 monomers exemplified for the glycidyl group-containing compound (b3) may be used alone or in combination of two or more.

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 N-substituted maleimide-based compounds such as methylphenyl maleimide, Np-methylphenyl maleimide, No-methoxyphenyl maleimide, Nm-methoxyphenyl maleimide and Np-methoxyphenyl 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 content of the alkali-soluble resin (B) should satisfy the condition that the sum of the hydroxyl value of the alkali-soluble resin (B) and the multifunctional monomer (C) is from 50 mgKOH / g to 250 mgKOH / g, 10 to 80% by weight, preferably 10 to 70% by weight. When the content of the alkali-soluble resin (B) is 10 to 80% by weight based on the above-mentioned criteria, the solubility in a developing solution is sufficient and pattern formation is easy. In the development, film reduction of the pixel portion of the exposed portion is prevented, It is preferable that the dropout property is improved.

Multifunctional  The monomer (C)

The multifunctional monomer (C) is required to contain a trifunctional or more (meth) acrylic multifunctional monomer (C-1) and a multifunctional monomer (C-2) represented by the following formula (1).

[Chemical Formula 1]

Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are independently an epoxy compound or an epoxy compound represented by the following formula (2): embedded image wherein X 1 is an aliphatic hydrocarbon having 1 to 10 carbon atoms, And R ₁ to R ₆ Is at least one compound and an epoxy compound represented by the general formula (2)

(2)

n is an integer of 0 to 5;

More specifically, the multifunctional monomer (C-2) represented by the formula (1) may be a compound represented by the following formula (3).

(3)

Since the colored photosensitive resin composition of the present invention contains the above-mentioned polyfunctional monomer (C), it is possible to sufficiently cure the substrate with the substrate during the low-temperature firing step, thereby providing excellent sensitivity and thus providing a color filter with high reliability. In addition, due to high photopolymerization density, adhesion and coloring power to glass substrates are excellent.

The multifunctional monomer (C) may be used in combination with a monofunctional monomer or a bifunctional monomer, and preferably a bifunctional or multifunctional monomer may be used.

Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N- Examples of commercially available products include Aronix M-101 (Toagosei), KAYARAD TC-110S (Nippon Kayaku), and Viscot 158 (Osaka Yuki Kagaku Kogyo).

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) (Acryloyloxyethyl) ether of bisphenol A and 3-methylpentanediol di (meth) acrylate. Commercially available products include Aronix M-210, M-1100, 1200 (Doagosei), KAYARAD HDDA (Nippon Kayaku), Viscoat 260 (Osaka Yuki Kagaku Kogyo), AH-600, AT-600 and UA-306H (Kyoeisha Chemical Co., Ltd.).

Specific examples of the trifunctional or more (meth) acrylic polyfunctional monomer (C-1) include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylol (Meth) acrylate, propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) Acrylate, propoxylated dipentaerythritol hexa (meth) acrylate and dipentaerythritol hexa (meth) acrylate. Commercially available products include Aronix M-309, TO-1382 (Doagosei) KAYARAD TMPTA, KAYARAD DPHA, and KAYARAD DPHA-40H (Nippon Kayaku), but the (meth) acrylate and urethane (meth) acrylate have excellent polymerizability and can improve the strength In particular, it is preferable in that.

(Meth) acryl-based polyfunctional monomer (C-1) having three or more functional groups on the basis of all monomers when used in combination with the trifunctional or more (meth) acrylic multi-functional monomer (C-1) The total content of the monomer (C-1) and the multifunctional monomer (C-2) represented by the formula (1) is preferably 80% by weight or less. When it is used in excess of 80% by weight, the performance of the multifunctional monomer is hardly realized.

The multifunctional monomer (C) is preferably contained in an amount of 5 to 80% by weight, more preferably 20 to 70% by weight, based on the solid content in the colored photosensitive resin composition. When the photopolymerizable compound (C) is contained in an amount of 20 to 45% by weight based on the above-mentioned criteria, the strength and smoothness of the pixel portion are preferably improved.

The multifunctional monomer (C-2) represented by the general formula (1) is preferably contained in an amount of 0.01 to 60% by weight, more preferably 1 to 40% by weight.

Light curing Initiator (D)

The photopolymerization initiator (D) can be used without particular limitation as long as it can polymerize the multifunctional monomer (C). In particular, the photopolymerization initiator (D) 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 an oxime compound in terms of polymerization characteristics, initiation efficiency, absorption wavelength, availability, It is preferable to use at least one compound selected from the group consisting of an oxalic acid compound and an oxalic acid compound.

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 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.

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

Specific examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -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, 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) Imidazole compounds in which 4'5,5'-tetraphenyl-1,2'-biimidazole or phenyl groups at 4,4 ', 5,5' positions are substituted by carboalkoxy groups. Among them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- , 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole is preferably used do.

Specific examples of the oxime compounds include o-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one and commercially available products such as OXE01 and OXE02 from BASF.

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

The photopolymerization initiator (D) may further comprise a photopolymerization initiator (d2) to improve the sensitivity of the colored photosensitive resin composition of the present invention. The colored photosensitive resin composition according to the present invention contains a photopolymerization initiation auxiliary (d2), whereby the sensitivity can be further increased and the productivity can be improved.

As the photopolymerization initiation auxiliary (d2), 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 ), 4,4'-bis (diethylamino) benzophenone, and the like.

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, naphthoxyacetic acid and the like.

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 hexacis (3-mercaptopropionate), and tetraethylene glycol bis (3-mercaptopropionate) .

The photopolymerization initiator (D) is used in an amount of 0.1 to 40% by weight, preferably 1 to 40% by weight, based on the total amount of the alkali-soluble resin (B) and the polyfunctional monomer (C), based on the total solid weight of the colored photosensitive resin composition of the present invention. 30% by weight. When the photopolymerization initiator (D) is in the range of 0.1 to 40 wt%, the colored photosensitive resin composition is highly sensitized and the exposure time is shortened, which is preferable because productivity can be improved and high resolution can be maintained. Further, the strength of the pixel portion formed using the composition of the above-described conditions and the smoothness of the surface of the pixel portion can be improved.

When the photopolymerization initiator (d2) is further used, the photopolymerization initiator (d2) may be added to the alkali-soluble resin and the polyfunctional monomer (C) based on the total weight of solids of the colored photosensitive resin composition of the present invention. , Preferably 1 to 30 wt%, based on the total amount of the composition. When the amount of the photopolymerization initiator (d2) used is within the range of 0.1 to 40% by weight, the sensitivity of the colored photosensitive resin composition becomes higher and the productivity of the color filter formed using the composition is improved.

Solvent (E)

The solvent used in the conventional colored photosensitive resin composition is not particularly limited so long as it is effective in dissolving the other components contained in the colored photosensitive resin composition. The solvent may be selected from ethers, aromatic hydrocarbons, ketones, alcohols, esters And amides are preferred.

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 dimethyl ether, diethylene glycol di Diethylene glycol dialkyl ethers such as ethyl 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 monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate Alkylene glycol alkyl ether acetates such as < RTI ID = 0.0 >

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-exemplified solvents (E) may be used alone or as a mixture of two or more thereof. The solvent (E) may be contained in an amount of 60 to 90% by weight, preferably 70 to 85% by weight based on the total weight of the colored photosensitive resin composition of the present invention . When the solvent (E) is in the range of 60 to 90% by weight as described above, 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 Thereby providing an effect of improving the property.

Mercapto  Compound (F)

High crosslinking degree can be achieved even at low temperature baking by the polyfunctional monomer (C-2) represented by the above formula (1). However, when the polyfunctional monomer (C-2) is used alone, the efficiency of the polyfunctional monomer Pattern shorting may occur. Therefore, when the polyfunctional thiol compound is used in combination with the polyfunctional thiol compound, the efficiency of the polyfunctional monomer can be prevented from being lowered by the polyfunctional thiol compound.

The polyfunctional thiol compound may be a mercapto compound (F).

The mercapto compound (F) can be obtained by reacting 4-mercaptohydrocinnamic acid, 4-mercaptobenzoic acid, thiosalicylic acid, 3,4-dimeroxybenzenethiol 3-methoxybenzenethiol, 3-methoxybenzenethiol, 4-hydroxybenzenethiol, 3-methoxybenzenethiol, 2-hydroxybenzenethiol, 2-hydroxybenzenethiol, 4-methoxybenzenethiol, 3-hydroxybenzenethiol, 2-methoxybenzenethiol, methylthiosalicylate, ), 2,3,5,6-tetrafluoro-4-mercaptobe nzoic acid, 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane,?-Mercaptopropionic acid, methyl 3-mercaptopropionate, 2-ethylhexyl 3-mercapto Mercaptopropionate, n-octyl 3-mercaptopropionate, methoxybutyl 3-mercaptopropionate, stearyl (2-ethylhexyl) 3-mercaptopropionate, trimethylolpropanetris (3-mercaptopropionate), tris [3-mercaptopropionyloxy) -ethyl] (3-mercaptopropionyloxy) -isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropyloxy) (3-mercaptopropionate) and dipentaerythritol hexakis (3-mercaptopropionate), which are represented by the general formula Can All.

The mercapto compound (F) may be contained in the colored photosensitive resin composition in an amount of 0.1 to 5% by weight based on the total solid content. When the mercapto compound (F) is contained within the above range, the crosslinking degree can be prevented from being lowered by the polyfunctional monomer even at low temperature baking, and the sensitivity of the colored photosensitive resin composition becomes higher, Can be improved.

The colored photosensitive resin composition according to the present invention may further contain additives as required, and at least one selected from a dispersant, a wetting agent, a silane coupling agent, and an anti-aggregation agent may be used as a specific example.

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), a part or all of the alkali-soluble resin (B), or the dye (a2) may be mixed and dissolved or dispersed together with the solvent (E).

The dye (a2), the remainder (B) of the alkali-soluble resin, the polyfunctional monomer (C) and the photopolymerization initiator (D) and, if necessary, the additive and the solvent (E) The colored photosensitive resin composition according to the present invention can be produced.

Hereinafter, the present invention will be described in more detail using Synthesis Examples, Examples, Comparative Examples and Experimental Examples. However, the following Synthesis Examples, Examples, Comparative Examples and Experimental Examples are for illustrating the present invention, and the present invention is not limited by the following Synthesis Examples, Examples, Comparative Examples and Experimental Examples, .

Synthetic example  1. Synthesis of A-1

The reaction mixture in which pentaerythritol (10 mmol), NaOH (20 mmol) and epichlorohydrin (80 ml) were dissolved in 200 ml of ethanol was heated to 90 ° C and stirred for 12 hours. After 12 hours, NaOH (2.89 g, 72.20 mmol) was dissolved in 20 ml of distilled water, slowly dropped at 60 ° C for 1 hour, and reacted at 80 ° C for 2 hours. After completion of the reaction, 50 ml of purified water and 50 ml of THF were added, and the mixture was stirred for 30 minutes and the organic layer was separated. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The concentrated residue was subjected to removal of impurities by adding methanol and distilled water to obtain 5.3 g (yield 84%) of A-1 as a white solid.

Synthetic example  2. Synthesis of T-1

The reaction mixture obtained by dissolving 30 mmol of A-1, 40 ml of pent-4-enoyl chloride, 0.1 wt% sodium bispentaerythritol, 0.02 wt% calcium and p-toluenesulfonic acid monohydrate in 200 ml of toluene was introduced into the reactor at 120 ° C After the temperature was elevated, the mixture was stirred. After the reaction was completed, the reaction mixture was cooled to room temperature and 400 ml of toluene was added thereto. The organic layer was washed with 200 ml of purified water, and anhydrous magnesium sulfate was added to the organic layer, followed by stirring for 30 minutes. The organic layer was filtered and concentrated under reduced pressure. The concentrated residue was purified by silica gel column chromatography (ethyl acetate: n-hexane = 1: 4) to obtain T-1.

Synthetic example  3. Synthesis of alkali-soluble resin (B)

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, 19.0 parts of acrylic acid, 10 parts of benzyl methacrylate, 51.0 parts of styrene and 3 parts of n-dodecylmercaptan were charged and replaced with nitrogen. After that, the temperature was raised to 110 ° C with stirring, and the reaction was carried out for 6 hours. Subsequently, the temperature of the reaction solution was lowered to room temperature, and air in the flask was replaced with ordinary air. Then, 0.3 part of triethylamine and 20 parts of glycidyl methacrylate were added thereto, and the mixture was reacted at 110 DEG C for 5 hours. The alkali-soluble resin thus synthesized had a solid dispersion value of 80 mgKOH / g and a weight average molecular weight Mw of about 22,000 as measured by GPC.

Example  1. Preparation of colored photosensitive resin composition

12 parts by weight of CI Pigment Blue 15: 6 (pigment), 1.8 parts by weight of CI Acid Red 52, 4.0 parts by weight of BYK-2001 as a pigment dispersant, and 82.2 parts by weight of propylene glycol monomethyl ether acetate were mixed, 18.2 parts by weight of the alkali-soluble resin (B) of Synthesis Example 3, 4.9 parts by weight of the polyfunctional monomer (C-1) (trade name: DPHA, manufactured by Nippon Kayaku Co., Ltd.) 1.2 parts by weight of the polyfunctional monomer (C-2) of T-1 in Example 2, 1 part by weight of PBG-305 (D manufactured by Troni) as an oxime ester initiator, 48.4 parts by weight of propylene glycol monomethyl ether acetate And 0.2 part by weight of trimethylolpropane tris (F-2) as a mercapto compound (trade name: TMMP, manufactured by Sakai Chemical Co., Ltd.) were mixed to obtain a colored photosensitive resin composition.

Example  2. Preparation of colored photosensitive resin composition

12 parts by weight of CI Pigment Blue 15: 6 (pigment), 1.8 parts by weight of CI Acid Red 52, 4.0 parts by weight of BYK-2001 as a pigment dispersant, and 82.2 parts by weight of propylene glycol monomethyl ether acetate were mixed, 18.2 parts by weight of the alkali-soluble resin (B) of Synthesis Example 3, 4.9 parts by weight of the polyfunctional monomer (C-1) (trade name: DPHA, manufactured by Nippon Kayaku Co., Ltd.) 1.2 parts by weight of the polyfunctional monomer (C-2) of T-1 in Synthesis Example 2, 1 part by weight of PBG-305 (D, manufacturer: Troni) as an oxime ester initiator, 48.4 parts by weight of propylene glycol monomethyl ether acetate And 0.2 part by weight of dipentaerythritol hexakis (F-2) (product name: DPMP, manufactured by Sakai Chemical) as a mercapto compound were mixed to obtain a colored photosensitive resin composition (see Table 1).

Example  3. Preparation of colored photosensitive resin composition

12 parts by weight of CI Pigment Blue 15: 6 (pigment), 1.8 parts by weight of CI Acid Red 52, 4.0 parts by weight of BYK-2001 as a pigment dispersant, and 82.2 parts by weight of propylene glycol monomethyl ether acetate were mixed, 18.2 parts by weight of the alkali-soluble resin (B) of Synthesis Example 3, 3.1 parts by weight of the polyfunctional monomer (C-1) (product name: DPHA, manufactured by Nippon Kayaku Co., Ltd.) , 3.1 parts by weight of the polyfunctional monomer (C-2) of T-1 in Example 2, 1 part by weight of PBG-305 (D manufactured by Troni) as an oxime ester initiator, 48.4 parts by weight of propylene glycol monomethyl ether acetate And 0.2 part by weight of trimethylolpropane tris (F-1) as a mercapto compound (product name: TMMP, manufactured by Sakai Chemical) were mixed to obtain a colored photosensitive resin composition (see Table 1).

Example  4. Preparation of colored photosensitive resin composition

12 parts by weight of CI Pigment Blue 15: 6 (pigment), 1.8 parts by weight of CI Acid Red 52, 4.0 parts by weight of BYK-2001 as a pigment dispersant, and 82.2 parts by weight of propylene glycol monomethyl ether acetate were mixed, 18.2 parts by weight of the alkali-soluble resin (B) of Synthesis Example 3, 3.1 parts by weight of the polyfunctional monomer (C-1) (product name: DPHA, manufactured by Nippon Kayaku Co., Ltd.) , 3.1 parts by weight of the polyfunctional monomer (C-2) of T-1 in Example 2, 1 part by weight of PBG-305 (D manufactured by Troni) as an oxime ester initiator, 48.4 parts by weight of propylene glycol monomethyl ether acetate And 0.2 part by weight of dipentaerythritol hexakis (F-2) (product name: DPMP, manufactured by Sakai Chemical) as a mercapto compound were mixed to obtain a colored photosensitive resin composition (see Table 1).

Example  5. Preparation of colored photosensitive resin composition

12 parts by weight of CI Pigment Blue 15: 6 (pigment), 1.8 parts by weight of CI Acid Red 52, 4.0 parts by weight of BYK-2001 as a pigment dispersant, and 82.2 parts by weight of propylene glycol monomethyl ether acetate ) And CI Acid Violet 66 (A-2) were thoroughly dispersed using a bead mill, and then 18.4 parts by weight of the alkali-soluble resin (B) of Synthesis Example 3 and 4.9 parts by weight of the polyfunctional monomer (C- 1.2 parts by weight of polyfunctional monomer (C-2) of T-1 of Synthesis Example 2, 1 part by weight of PBG-305 (D, manufacturer: Troni) as an oxime ester initiator, 50.4 parts by weight of glycol monomethyl ether acetate (E) and 0.2 parts by weight of trimethylolpropane tris (F-1) as a mercapto compound (trade name: TMMP, manufactured by Sakai Chemical) were mixed to obtain a colored photosensitive resin composition Reference).

Example  6. Preparation of colored photosensitive resin composition

12 parts by weight of CI Pigment Blue 15: 6 (pigment), 1.8 parts by weight of CI Acid Red 52, 4.0 parts by weight of BYK-2001 as a pigment dispersant, and 82.2 parts by weight of propylene glycol monomethyl ether acetate ) And CI Acid Violet 66 (A-2) were thoroughly dispersed using a bead mill, and then 18.4 parts by weight of the alkali-soluble resin (B) of Synthesis Example 3 and 4.9 parts by weight of the polyfunctional monomer (C- 1.2 parts by weight of polyfunctional monomer (C-2) of T-1 of Synthesis Example 2, 1 part by weight of PBG-305 (D, manufacturer: Troni) as an oxime ester initiator, 50.4 parts by weight of glycol monomethyl ether acetate (E) and 0.2 parts by weight of dipentaerythritol hexacis (F-2) as a mercapto compound (product name: DPMP, manufactured by Sakai Chemical) were mixed to obtain a colored photosensitive resin composition See Table 1).

Comparative Example  1. Preparation of colored photosensitive resin composition

12 parts by weight of CI Pigment Blue 15: 6 (pigment), 1.8 parts by weight of CI Acid Red 52, 4.0 parts by weight of BYK-2001 as a pigment dispersant, and 82.2 parts by weight of propylene glycol monomethyl ether acetate were mixed, 18.2 parts by weight of the alkali-soluble resin (B) of Synthesis Example 3, 4.9 parts by weight of the polyfunctional monomer (C-1) (product name: DPHA, manufactured by Nippon Kayaku Co., Ltd.) 1.2 parts by weight of polyfunctional monomer (C-2) of T-1 in Example 2, 1.2 parts by weight of PBG-305 (D, manufacturer: Troni) as an oxime ester initiator, 48.4 parts by weight of propylene glycol monomethyl ether acetate Were mixed to obtain a colored photosensitive resin composition (see Table 1).

Comparative Example  2. Preparation of colored photosensitive resin composition

12 parts by weight of CI Pigment Blue 15: 6 (pigment), 1.8 parts by weight of CI Acid Red 52, 4.0 parts by weight of BYK-2001 as a pigment dispersant, and 82.2 parts by weight of propylene glycol monomethyl ether acetate were mixed, 18.2 parts by weight of the alkali-soluble resin (B) of Synthesis Example 3, 4.9 parts by weight of the polyfunctional monomer (C-1) (product name: DPHA, manufactured by Nippon Kayaku Co., Ltd.) 1.2 parts by weight of polyfunctional monomer (C-2) of T-1 in Example 2, 1.2 parts by weight of PBG-305 (D, manufacturer: Troni) as an oxime ester initiator, 48.4 parts by weight of propylene glycol monomethyl ether acetate Were mixed to obtain a colored photosensitive resin composition (see Table 1).

Comparative Example  3. Preparation of colored photosensitive resin composition

12 parts by weight of CI Pigment Blue 15: 6 (pigment), 1.8 parts by weight of CI Acid Red 52, 4.0 parts by weight of BYK-2001 as a pigment dispersant, and 82.2 parts by weight of propylene glycol monomethyl ether acetate ) And CI Acid Violet 66 (A-2) were sufficiently dispersed using a bead mill, and then 18.4 parts by weight of the alkali-soluble resin (B) of Synthesis Example 3 and 6.1 parts by weight of the polyfunctional monomer (C- 1 part by weight of PBG-305 (D manufactured by Troni) as an oxime ester initiator, 50.4 parts by weight of propylene glycol monomethyl ether acetate (E), trimethylolpropane tris (F-1 ) (Trade name: TMMP, manufactured by Sakai Chemical Co., Ltd.) were mixed to obtain a colored photosensitive resin composition (see Table 1).

Comparative Example  4. Preparation of colored photosensitive resin composition

12 parts by weight of CI Pigment Blue 15: 6 (pigment), 1.8 parts by weight of CI Acid Red 52, 4.0 parts by weight of BYK-2001 as a pigment dispersant, and 82.2 parts by weight of propylene glycol monomethyl ether acetate ) And CI Acid Violet 66 (A-2) were thoroughly dispersed using a bead mill, and then 18.4 parts by weight of the alkali-soluble resin (B) of Synthesis Example 3 and 4.9 parts by weight of the polyfunctional monomer (C- 1.2 parts by weight of polyfunctional monomer (C-2) of T-1 in Synthesis Example 2, 1.2 parts by weight of PBG-305 (D manufactured by Troni) as an oxime ester initiator, And 50.4 parts by weight of glycol monomethyl ether acetate (E) were mixed to obtain a colored photosensitive resin composition (see Table 1).

Experimental Example  1. Sensitivity measurement, adhesion evaluation and Solvent resistance  evaluation

A color filter was prepared using the colored photosensitive resin compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 4.

Specifically, each of the above colored photosensitive resin compositions was applied on a 2-inch-square glass substrate ("EAGLE XG", manufactured by Corning Inc.) by spin coating, then placed on a heating plate and held at a temperature of 100 ° C. for 3 minutes to form a thin film . Subsequently, a test photomask having a pattern for changing the transmittance in the range of 1 to 100% to a step-like pattern and a line / space pattern of 1 to 50 m was placed on the thin film and the distance between the test photomask and the test photomask was set to 100 m. Respectively. At this time, the ultraviolet light source was irradiated with a high pressure mercury lamp of 1 KW containing g, h and i lines at an illuminance of 100 mJ / cm 2, and no special optical filter was used. The thin film irradiated with ultraviolet rays was immersed in a KOH aqueous solution of pH 10.5 for 2 minutes to develop. The glass plate coated with the thin film was washed with distilled water, blown with nitrogen gas, dried, and heated in a heating oven at 150 캜 for 20 minutes to prepare a color filter.

The film thickness of the color filter prepared above was 2.0 mu m. The colored photosensitive resin compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 4 were subjected to reliability evaluation in the following manner, and the results are shown in Table 2 below

<Sensitivity>

The minimum amount of exposure required to form a thin film without peeling of the pattern after development was measured.

&Lt; Adhesion >

When the generated pattern was evaluated through an optical microscope, the following pattern was evaluated as a degree of peeling phenomenon.

 ○: No pattern peeling

 △: 1 to 3 pattern peeling

X: Pattern peeling 4 or more

<Solvent resistance>

The prepared color filter was immersed in an N-methylpyrrolidone solvent for 30 minutes to compare and evaluate the color change before and after the evaluation. The equation to be used at this time is calculated by the following equation (1) representing the color change in the three-dimensional colorimetry defined by L *, a *, b *, and as the color change value is smaller, a highly reliable color filter can be manufactured.

When the value of DELTA E * ab is 3.0 or less, a person can not feel color difference.

[Equation 1]

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

As shown in Table 2, it was confirmed that the colored photosensitive resin compositions of Examples 1 to 6 had excellent heat resistance and solvent resistance and excellent curability.

Specifically, the colored photosensitive resin compositions of Examples 1 to 6 exhibited excellent adhesion with the substrate and improved solvent resistance as the curing was sufficiently performed in the low-temperature firing step. Thus, it was confirmed that even if the colored photosensitive resin composition of the present invention is used in a low-temperature firing step, a color film with high reliability can be provided.

On the other hand, Comparative Example 2 and Comparative Example 4 relate to a colored photosensitive resin composition to which a mercapto compound is not added, and it has been confirmed that the solvent resistance is good but the adhesion of patin is deteriorated. Further, it was confirmed that the colored photosensitive resin compositions of Comparative Examples 1 and 3, to which the polyfunctional monomer (C-2) represented by Chemical Formula 1 was not added, had poor solvent resistance after curing at low temperature.

Claims (6)

(A), an alkali-soluble resin (B), a polyfunctional monomer (C), a photopolymerization initiator (D), a solvent (E) and a mercapto compound (F)
Wherein the polyfunctional monomer (C) comprises a trifunctional or more (meth) acryl-based polyfunctional monomer (C-1) and a polyfunctional monomer (C-2)
[Chemical Formula 1]

Wherein X is an aliphatic hydrocarbon having 1 to 10 carbon atoms with or without a hetero atom,
_{R 1, R 2, R 3} , R 4, R 5 and R ₆ are each independently, an epoxy compound or to a compound of the formula 2, R ₁ to R ₆ Is at least one compound and an epoxy compound represented by the general formula (2)
(2)

n is an integer of 0 to 5; The method according to claim 1,
The colored photosensitive resin composition according to claim 1, wherein the polyfunctional monomer (C-2) represented by the formula (1) is a compound represented by the following formula (3).
(3)

The method according to claim 1,
The (meth) acryl-based polyfunctional monomer (C-1) having three or more functional groups is preferably selected from the group consisting of trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tetra , Propoxylated dipentaerythritol hexa (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. The colored photosensitive resin composition according to claim 1, The method according to claim 1,
The mercapto compound (F) can be obtained by reacting 4-mercaptohydrocinnamic acid, 4-mercaptobenzoic acid, thiosalicylic acid, 3,4-dimeroxybenzenethiol 3-methoxybenzenethiol, 3-methoxybenzenethiol, 4-hydroxybenzenethiol, 3-methoxybenzenethiol, 2-hydroxybenzenethiol, 2-hydroxybenzenethiol, 4-methoxybenzenethiol, 3-hydroxybenzenethiol, 2-methoxybenzenethiol, methylthiosalicylate, ), 2,3,5,6-tetrafluoro-4-mercaptobe nzoic acid, 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane,?-Mercaptopropionic acid, methyl 3-mercaptopropionate, 2-ethylhexyl 3-mercapto Mercaptopropionate, n-octyl 3-mercaptopropionate, methoxybutyl 3-mercaptopropionate, stearyl (2-ethylhexyl) 3-mercaptopropionate, trimethylolpropanetris (3-mercaptopropionate), tris [3-mercaptopropionyloxy) -ethyl] (3-mercaptopropionyloxy) -isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropyloxy) (3-mercaptopropionate) and dipentaerythritol hexakis (3-mercaptopropionate), which are commercially available, for example, from the group consisting of Tetraethyleneglycol bis (3-mercaptopropionate) and dipentaerythritol hexakis Above Wherein the coloring photosensitive resin composition is a colored photosensitive resin composition. The method according to claim 1,
The colored photosensitive resin composition contains, based on the total solid weight,
The colorant (A) is contained in an amount of 5 to 60% by weight,
The alkali-soluble resin (B) is contained in an amount of 10 to 80% by weight,
The polyfunctional monomer (C) is contained in an amount of 5 to 80% by weight,
The mercapto compound (F) is contained in an amount of 0.1 to 5% by weight,
The photopolymerization initiator (D) is contained in an amount of 0.1 to 40% by weight based on the total content of the alkali-soluble resin (B) and the polyfunctional monomer (C)
Wherein the solvent (E) is contained in an amount of 60 to 90% by weight based on the total weight of the colored photosensitive resin composition. A color filter made of the colored photosensitive resin composition according to any one of claims 1 to 5.