KR20160115654A - 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 for a color filter used when producing a color filter used in a color liquid display device or the like and to a color filter produced by using the same. The colored photosensitive resin composition does not change the color thickness and can lower horn stepped cone. The colored photosensitive resin composition comprises: (A) a coloring agent; (B) an alkali-soluble resin; (C) a photopolymerizable compound; (D) a photopolymerization initiator (D); an additive (E); and a solvent (F).

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.

BACKGROUND ART [0002] Color filters are widely used in imaging devices, liquid crystal display devices, and the like, and their application range is rapidly expanding. A color filter used for a color liquid crystal display device, an image pickup device, or the like is a device for uniformly applying a colored photosensitive resin composition containing a coloring agent corresponding to each color of red, green and blue on a substrate on which a black matrix is pattern- The coating film formed by heating and drying (hereinafter also referred to as preliminary firing) may be exposed and developed, and if necessary, further heat curing (hereinafter also referred to as post-firing) may be repeated for each color, Color pixels are formed.

In recent years, the issue of reducing the amount of PR patterns on the black matrix (BM) over the color pattern horns in the manufacture of LCD color filter substrates has become an issue. In general, a color filter has a black matrix on a substrate and a color filter layer between the black matrix, and the color filter layer is formed over the black matrix in a predetermined overlapping manner. At this time, the color filter layer formed on the black matrix overlaps the step of the black matrix to form a tapered step.

However, when the alignment film is applied to the color filter substrate and the rubbing is not performed properly at the periphery of the tapered portion, there arises a problem that the image quality of the liquid crystal display device is lowered, such as an increase in black luminance and a decrease in contrast ratio. Therefore, researches are actively carried out to reduce the horn step (the difference in height between the end of the pattern and the center). For example, in Korean Patent Laid-Open Publication No. 2009-0042341, a multifunctional thiol compound is used as a chain transfer agent to have a low viscosity relative to the same molecular weight, thereby reducing the taper of the horn. However, in the case of the above-mentioned document, defects such as a tearing may occur when applying a low viscosity alkaline binder resin, which may cause defects in the manufacture of color filters.

Korea Patent Publication No. 2009-0042341

Accordingly, it is an object of the present invention to provide a colored photosensitive resin composition which lowers a tapered step (difference in height between a pattern end and a center) without changing a predetermined color thickness.

The present invention therefore provides a photopolymerizable compound (C) comprising a colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), an additive (E) and a solvent (F) Is a trifunctional or tetrafunctional photopolymerizable compound.

One embodiment of the present invention may be one wherein the photopolymerizable compound (C) comprises at least one compound selected from the group consisting of formulas (1), (2) and (3)

[Chemical Formula 1]

(2)

(3)

In another embodiment, the photopolymerizable compound (C) may be contained in an amount of 5 to 50% by weight based on the total weight of the solid color photosensitive resin composition.

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 5 to 85 wt% based on the total weight of the solid colored photosensitive resin composition, The photopolymerization initiator (D) comprises an alkali-soluble resin (B) and a photopolymerizable compound (C), wherein the photopolymerization initiator (C) comprises 5 to 50 wt% And the solvent (F) may be contained in an amount of 60 to 90 wt% based on the total weight of the colored photosensitive resin composition.

In still another embodiment, the photopolymerization initiator (D) may include a oxime-based compound.

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

The colored photosensitive resin composition of the present invention is characterized in that it is possible to lower the step height of the horn without changing the color thickness.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a partial cross-sectional view showing an enlarged portion of a conventional color filter substrate. FIG.
≪ Brief Description of Drawings &
100: substrate
200: Black Matrix
300: Color filter layer
400: Horn step

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.

Hereinafter, the present invention will be described in detail.

The colorant (A)

The colorant (A) contains at least one pigment (a1) and at least one dye (a2) as essential components.

The pigment (a1) may be an organic pigment or an inorganic pigment generally used in the art. Examples of the organic pigment include various pigments used in printing ink, ink jet ink, etc. Specific examples thereof include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, Anthanthrone pigments, indanthrone pigments, pravanthrone pigments, anthraquinone pigments, anthraquinone pigments, anthanthrone pigments, anthanthrone pigments, indanthrone pigments, indanthrone pigments, 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 metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony and carbon black Oxides 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 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 (a1) 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 (a1) 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 (a3) include cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, polyester surfactants, and polyamine surfactants. These surfactants may be used alone or in combination of two or more. Can be used.

The content of the pigment (a1) is in the range of 10 to 50% by weight, preferably 15 to 45% by weight with respect to the total solid content in the pigment dispersion composition. When the content of the pigment is in the range of 15 to 40% by weight, the viscosity is low, the storage stability is excellent, and the dispersion efficiency is high, which is effective for increasing the contrast ratio.

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 pigment 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 pigment dispersant (a3) exceeds 60 parts by weight based on the above-mentioned criteria, the viscosity may be increased. If the content of the pigment dispersant is less than 5 parts by weight, it may be difficult to atomize the pigment or gelation after dispersion.

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

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, and 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, and 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 total 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)

In the present invention, the alkali-soluble resin may be an acrylic copolymer that is soluble in the solvent of the present invention and has reactivity to the action of light or heat, functions as a binder resin for the colorant and is soluble in an alkaline developer, Can be used without particular limitation.

Examples of the acrylic copolymer include a copolymer of a carboxyl group-containing monomer and other monomer copolymerizable with the monomer.

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

Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid,? -Chloroacrylic acid, cinnamic acid, and the like.

Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. The unsaturated polycarboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride, citraconic anhydride and the like.

The unsaturated polycarboxylic acid may be its mono (2-methacryloyloxyalkyl) ester, for example, mono (2-acryloyloxyethyl) succinate, mono (2-methacryloyloxyethyl) Phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl), and the like. The unsaturated polycarboxylic acid may be mono (meth) acrylate of the dicarboxylic polymer of both ends thereof, and examples thereof include ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate and the like. .

These carboxyl group-containing monomers may be used alone or in combination of two or more.

Specific examples of the other monomers copolymerizable with the carboxyl group-containing monomer include styrene,? -Methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o- P-methoxy styrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, Aromatic vinyl compounds such as vinylbenzyl glycidyl ether and indene;

Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, Acrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl Methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxy diethylene glycol acrylate, methoxy diethylene glycol methacrylate, methoxy triethylene glycol acrylate, methoxy triethylene glycol methacrylate Acrylate, methoxypropylene glycol methacrylate, methoxypropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadiene Acrylate, dicyclopentadienyl methacrylate, 2-hydroxy-3-phenoxy Acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, unsaturated carboxylic acid esters such as glycerol monoacrylate, glycerol monomethacrylate;

Aminoethyl methacrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2- Unsaturated carboxylates such as methyl acrylate, ethyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, Acid amino alkyl esters;

Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate;

Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate;

Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether;

Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile,? -Chloroacrylonitrile, and vinylidene cyanide;

Unsaturated amides such as acrylamide, methacrylamide,? -Chloroacrylamide, N-2-hydroxyethyl acrylamide and N-2-hydroxyethyl methacrylamide;

Maleimide, N-phenylmaleimide. Unsaturated imides such as N-cyclohexylmaleimide;

Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene;

Polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, polysiloxane having a monoacryloyl group or monomethacryloyl group at the end of the polymer molecular chain Macromers and the like.

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

The content of the carboxyl group-containing monomer unit in the alkali-soluble resin is usually 10 to 50% by weight, preferably 15 to 40% by weight, and more preferably 25 to 40% by weight. When the content of the carboxyl group-containing monomer unit is 10 to 50% by weight, the solubility in the developer is good and the pattern tends to be accurately formed at the time of development.

Examples of the acrylic copolymer include (meth) acrylic acid / methyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / 2- (Meth) acrylate / benzyl (meth) acrylate copolymer, a (meth) acrylic acid / methyl (meth) acrylate / polystyrene macromonomer copolymer, a (Meth) acrylic acid / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (Meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, 2-hydroxyethyl (meth) acrylate / benzyl Acrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / succinic acid mono (2-acryloyloxy Acrylic acid / succinic acid mono (2-acryloyloxyethyl) / styrene / allyl (meth) acrylate / N-phenylmaleimide copolymer / styrene / benzyl (Meth) acrylic acid / benzyl (meth) acrylate / N-phenylmaleimide / styrene / glycerol mono (meth) acrylate copolymer. Here, (meth) acrylate means acrylate or methacrylate.

Of these, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate / styrene copolymer, (meth) acrylic acid / methyl / Methyl (meth) acrylate / styrene copolymer is preferably used.

The weight average molecular weight of the alkali-soluble resin in terms of polystyrene is usually 5,000 to 50,000, preferably 8,000 to 40,000, more preferably 10,000 to 35,000, and most preferably 10,000 to 30,000. When the molecular weight of the alkali-soluble resin is 5,000 to 50,000, the hardness of the coating film is improved, the residual film ratio is high, the solubility of the unexposed portion in the developing solution is good, and the resolution tends to be improved.

The acid value of the alkali-soluble resin is usually 50 to 150, preferably 60 to 140, more preferably 80 to 135, and most preferably 80 to 130. When the acid value is from 50 to 150, the solubility in a developing solution is improved, the unexposed portion is easily dissolved, and the high sensitivity is obtained, so that the pattern of the exposed portion tends to remain and the residual film ratio tends to be improved. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the acrylic polymer, and can be generally determined by titration using an aqueous solution of potassium hydroxide.

The alkali-soluble resin may be contained in an amount of 5 to 85% by weight, and preferably 10 to 70% by weight based on the total solid content (100% by weight) in the colored photosensitive resin composition of the present invention. When such a content is included, the solubility in the developing solution is sufficient, so that development residue does not easily occur on the substrate of the non-pixel portion, and film reduction of the pixel portion of the exposed portion is hardly caused at the time of development, It is preferable since it tends to be good.

Photopolymerization  The compound (C)

In the present invention, the photopolymerizable compound is a photopolymerizable compound that can be polymerized by an active radical, acid, or the like generated from a photopolymerization initiator by irradiation of light. The photopolymerizable compound may be a trifunctional or tetrafunctional photopolymerizable compound.

Specific examples of the triblock polymerizable compound include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylate trimethylolpropane tri (meth) acrylate, propyloxylate trimethylolpropane tri (Meth) acrylate, glyceryl propyloxytriacrylate, isocyanurate triarylate, and the like.

Specific examples of the tetrafunctional polymerizable compound include pentaerythritol tetra (meth) acrylate, dimethylol propane tetra (methyl) acrylate, and the like.

Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate are preferable.

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

Light curing Initiator (D)

In the present invention, the photopolymerization initiator can be used without any particular limitation as long as it can polymerize the alkali-soluble resin and the photopolymerizable compound. In particular, from the viewpoints of polymerization characteristics, initiation efficiency, absorption wavelength, availability, and price, it is preferable to use an acetophenone, benzoin, benzophenone, thioxanthone, triazine, oxime, And a benzoin tosylate-based compound, and a light stabilizer may be used in combination. The photopolymerization initiator may be divided into an active radical generator which generates an active radical upon irradiation with light, a sensitizer, an acid generator, and the like.

Examples of the active radical generator include benzoin, acetophenone, benzophenone, thioxanthone, triazine, and oxime compounds.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan- Phenylpropane-1-one, benzyldimethylketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) Oligomers of 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan- Methylthiophenyl) propan-1-one are more preferable. The acetophenone-based compounds may be used alone or in combination of two or more, and may be used in combination with other photopolymerization initiators.

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

Specific examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'- Butyl peroxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

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

Specific examples of triazine compounds 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- (4- methoxystyryl) Bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4- (Trichloromethyl) -6- [2- (4-diethylamino-2- (trifluoromethyl) Methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4- dimethoxyphenyl) ethenyl] -1,3,5- Triazine, and the like.

Specific examples of the oxime compounds include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (4-methylsulfanyl-phenyl) -butan-1-one oxime-O-acetate, hydroxyimino- -Acetic acid ethyl ester-O-acetate, hydroxyimino- (4-methylsulfanyl-phenyl) -acetic acid ethyl ester-O-benzoate, 1- [ -Acetyloxime), 1- [4- (phenylthio) phenyl]] - 3-cyclohexyl-propane- (O-acetyloxime), and the like.

Specific examples of the sensitizer include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl- Benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compounds, and the like can be given. have.

Specific examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate , 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyl iodonium p-toluenesulfonate, di Onium salts such as phenyl iodonium hexafluoroantimonate, and nitrobenzyl tosylates, benzoin tosylates and the like. Among the above compounds, for example, there are compounds which simultaneously generate an active radical and an acid such as a triazine-based compound.

The photopolymerization initiator may be contained in an amount of 0.1 to 40% by weight, preferably 1 to 30% by weight, based on the total solids content (100% by weight) of the alkali-soluble resin and the photopolymerizable compound of the present invention. When such a content is included, 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.

In the present invention, a photopolymerization initiator may be further added together with a photopolymerization initiator. The photopolymerization initiator is used in combination with a photopolymerization initiator and is used to promote polymerization of the photopolymerizable compound initiated by the photopolymerization initiator. Examples of the photopolymerization initiator include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and the like.

Specific examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, (Dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (dimethylamino) benzophenone, Bis (ethylmethylamino) benzophenone, and 4,4'-bis (diethylamino) benzophenone are preferable.

Specific examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, .

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

The photopolymerization initiator may be used alone or in combination of two or more. A commercially available product, EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may be used.

Specific examples of the combination of the preferred photopolymerization initiator and the photopolymerization initiator are diethoxyacetophenone and 4,4'-bis (diethylamino) benzophenone; 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one and 4,4'-bis (diethylamino) benzophenone; 2-hydroxy-2-methyl-phenylpropan-1-one and 4,4'-bis (diethylamino) benzophenone; 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one and 4,4'-bis (diethylamino) benzophenone; 1-hydroxycyclohexyl phenyl ketone and 4,4'-bis (diethylamino) benzophenone; Oligomers of 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one and 4,4'-bis (diethylamino) benzophenone; A combination of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one and 4,4'-bis (diethylamino) benzophenone, Methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one and 4,4'-bis (diethylamino) benzophenone.

When the photopolymerization initiator and the photopolymerization initiator are used together, the content of the photopolymerization initiator is preferably 10 mol or less, more preferably 0.01 to 5 mol based on 1 mol of the photopolymerization initiator. When the photopolymerization initiator is used in the same amount as described above, the sensitivity of the colored photosensitive resin composition is higher and the productivity of the color filter formed using the composition tends to be improved.

Additive (E)

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

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

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

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

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

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

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

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

Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- ( 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- 3-isocyanatopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and the like. The adhesion promoters exemplified above may be used alone or in combination of two or more. The adhesion promoter may be contained in an amount of usually 0.01 to 10% by weight, preferably 0.05 to 2% by weight based on the solid content of the colored photosensitive resin composition.

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

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

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

Solvent (F)

The solvent (F) may be any solvent which is effective in dissolving the other components contained in the colored photosensitive resin composition, and is not particularly limited, and may be selected from ethers, aromatic hydrocarbons, ketones, Alcohols, esters, amides and the like are preferable.

The solvent (F) specifically includes ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate Alkylene glycol alkyl ether acetates such as methylene glycol alkyl ether acetates; 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, Alcohols such as glycol and glycerin, esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and cyclic esters such as? -Butyrolactone. For example, 4-hydroxy-4-methyl-2-pentanone or propylene glycol monomethyl ether acetate can be used as a solvent.

The solvent (F) 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 Tartrate, butylacetate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like.

The above-exemplified solvents (F) may be used alone or as a mixture of two or more thereof. The solvent (F) may contain 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 have. When the solvent (F) is in the range of 60 to 90% by weight as described above, when the solvent (F) is applied by a coating apparatus such as a roll coater, a spin coater, a slit and spin coater, a slit coater Thereby providing an effect of improving the property.

In the present invention, the solvent is not particularly limited as long as it is effective in dispersing or dissolving the other components contained in the colored photosensitive resin composition. The solvent may be selected from esters, aromatic hydrocarbons, ketones, alcohols, Drew and the like are preferable.

Specific examples of the ethers include tetrahydrofuran, tetrahydropyrane, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol mono Methyl ethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol methyl ether, propylene Propyleneglycol monomethyl ether acetate, propyleneglycol monopropyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl carbitol acetate, butyl carbitol acetate, propyleneglycol methyl ether acetate, methoxy Butylacetate And the like can be given site, methoxy pentyl acetate, anisole, phenetole or methyl anisole.

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

Specific examples of the ketone include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone or cyclohexanone.

Specific examples of the alcohols include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin.

Specific examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, butyl butyrate, alkyl esters, Methyl methoxyacetate, methyl methoxyacetate, methyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, 3- Ethyl propionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, Methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2- Methyl propionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy- But are not limited to, methyl ethyl ketone, ethyl methyl ketone, ethyl methyl ketone, ethyl methyl ketone, ethyl methyl ketone, ethyl methyl ketone, ethyl methyl ketone, ethyl methyl ketone, ethyl methyl ketone, And lactones.

Specific examples of amides include N, N-dimethylformamide or N, N-dimethylacetamide.

Examples of other solvents include N-methylpyrrolidone and dimethylsulfoxide.

Preferably, ethyl 3-ethoxypropionate, propylene glycol monomethyl ether acetate or propylene glycol methyl ether are used alone or in combination of two or more.

The solvent may be contained in an amount of 60 to 90% by weight, preferably 70 to 85% by weight based on the total amount (100% by weight) of the colored photosensitive resin composition of the present invention containing the above-mentioned solvent. When it is contained in the above-mentioned amounts, when it is coated with a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (or a "die coater") or an inkjet, desirable.

The colored photosensitive resin composition of the present invention can be produced, for example, by the following method. The colorant is mixed with a solvent in advance and dispersed using a bead mill or the like until the average particle diameter of the colorant becomes about 0.2 탆 or less. At this time, a pigment dispersant may be used if necessary, and some or all of the alkali-soluble resin may be blended. The remainder of the alkali-soluble resin, the photopolymerizable compound, the photopolymerization initiator and the reactive silicone surfactant, and other components which are used if necessary, and the additional solvent (if necessary) are added to the obtained dispersion (hereinafter also referred to as "mill base" Is further added to a predetermined concentration to obtain a desired colored photosensitive resin composition.

Hereinafter, the present invention will be described in more detail with reference to Examples, Comparative Examples and Experimental Examples. However, the following examples, comparative examples and experimental examples are for illustrating the present invention, and the present invention is not limited by the following examples, comparative examples and experimental examples, and can be variously modified and changed. In the following Examples and Comparative Examples, "%" and "part" representing the content are based on weight unless otherwise specified.

Example  1. Preparation of colored photosensitive resin composition

As shown in the following Table 1, 5.66 parts of CI Pigment Red 254 (A-1) as a coloring agent, a copolymer of methacrylic acid and benzyl methacrylate as the alkali-soluble resin (the molar ratio of methacrylic acid unit to benzylmethacrylate unit , 5.56 parts of (B-1) as a photopolymerizable compound, 3.11 parts of pentaerythritol tetraacrylate (C-1) as a photopolymerizable compound, 2-methyl-2-morpholinecarboxylic acid 0.25 part of polyno-1- (4-methylthiophenyl) propane-1-one (D-1), 0.12 part of 4,4'-bis (diethylamino) benzophenone (D- 0.25 part of 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione (D-3) as a photopolymerization initiator, and Megapax (registered trademark) F554 0.13 part of methacryloxypropyltrimethoxysilane (E-2) as an adhesion promoter, 16.98 parts of ethyl 3-ethoxypropionate (F-1) and 1 part of methoxy-2-propanol -2), 8.49 parts of propylene glycol Monomethyl ether acetate (F-3) were mixed and dispersed, and 59.43 parts to thereby prepare a colored photosensitive resin composition.

Example  2 to 15 and Comparative Example  1 to 9. Preparation of colored photosensitive resin composition

In the same manner as in Example 1, colored photosensitive resin compositions were prepared with the compositions and contents shown in Table 1 below.

The components in Table 1 are as follows:

(A-1) Colorant: C.I. Pigment Red 254

(B-1) Alkali-soluble resin: copolymer of methacrylic acid and benzylmethacrylate as alkali-soluble resin (the molar ratio of methacrylic acid unit to benzylmethacrylate unit was 27:73, acid value was 83, weight average molecular weight was 18,000 )

(C-1) Photopolymerizable compound: pentaerythritol tetraacrylate (Formula 1)

(C-2) Photopolymerizable compound: trimethylolpropane triacrylate (Formula 2)

(C-3) Photopolymerizable compound: pentaerythritol triacrylate (Formula 3)

(C-4) Photopolymerizable compound: dipentaerythritol hexaacrylate

(C-5) Photopolymerizable compound: ethoxylate dipentaerythritol hexaacrylate

(C-6) Photopolymerizable compound: propoxylated dipentaerythole hexaacrylate

(D-1) Photopolymerization initiator: 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-

(D-2) Photopolymerization initiator: 4,4'-bis (diethylamino) benzophenone

(D-3) Photopolymerization initiator: 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl]

(D-4) Copolymerization initiator: 1- [9-ethyl-6- (2-methylbenzonyl) -9H-carbazol-

(D-5) Copolymerization initiator: 1- [4- (phenylthio) phenyl]] -3-cyclohexyl-propane-

(E-1) Additive: Megafox (registered trademark) F554 (manufactured by Dainippon Ink and Chemicals, Inc.)

(E-2) Additive: methacryloxypropyltrimethoxysilane as adhesion promoter

(F-1) Solvent: ethyl 3-ethoxypropionate

(F-2) Solvent: 1-methoxy-2-propanol

(F-3) Solvent: Propylene glycol monomethyl ether acetate

Experimental Example

The colored photosensitive resin compositions prepared in the above Examples and Comparative Examples were applied on a 2 inch glass substrate ("EAGLE XG", manufactured by Corning Incorporated) by spin coating, and then vacuum dried and placed on a heating plate with pins. And maintained at a temperature 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 100 kJ / cm 2 using 1 kW high pressure mercury containing g, h and i lines, 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, dried by blowing nitrogen gas, and heated in a heating oven at 200 ° C for 25 minutes to prepare a color filter.

The film thickness of the color filter prepared above was 2.3 탆.

The thus obtained color filter was subjected to measurement and evaluation as shown in the following Table 2. The results are shown in Table 2 below.

<Measuring the primum step of the PR pattern>

The BM pattern was measured by using an alpha stepper (thickness gauge) in the vertical direction of the color pattern on the BM pattern (BM used, thickness: 1.5 μm).

&Lt; Sensitivity (mJ / cm2) >

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

<Pattern straightness>

When the generated pattern was evaluated by an optical microscope, the degree of occurrence of concavity and convexity on the pattern was judged as follows.

○: No error in pattern

C: Errors in pattern 1 to 3

×: 4 or more errors in the pattern

 [Table 2]

As shown in Table 2, in Examples 1 to 15, it was confirmed that the tapered steps (height difference between the pattern end and the center) were relatively low as compared with Comparative Examples 1 to 9. Sensitivity and pattern straightness were also compared with the comparative example And showed excellent results.

Claims (6)

(A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), an additive (E) and a solvent (F)
Wherein the photopolymerizable compound (C) is a trifunctional or tetrafunctional photopolymerizable compound. The method according to claim 1,
Wherein the photopolymerizable compound (C) comprises at least one compound selected from the group consisting of formulas (1), (2) and (3).
[Chemical Formula 1]

(2)

(3)

The method according to claim 1,
Wherein the photopolymerizable compound (C) is contained in an amount of 5 to 50% by weight based on the total weight of the solid content of the colored photosensitive resin composition. The method according to claim 1,
Based on the total solid weight of the colored photosensitive resin composition,
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 5 to 85% by weight,
The photopolymerizable compound (C) is contained in an amount of 5 to 50% by weight,
The additive (E) comprises 0.01 to 10% by weight,
The photopolymerization initiator (D) is contained in an amount of 0.1 to 40% by weight based on the total weight of the solid content of the alkali-soluble resin (B) and the photopolymerizable compound (C)
Wherein the solvent (F) is contained in an amount of 60 to 90% by weight based on the total weight of the colored photosensitive resin composition. The colored photosensitive resin composition according to claim 1, wherein the photopolymerization initiator (D) comprises a oxime compound. A color filter made of the colored photosensitive resin composition according to any one of claims 1 to 5.

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