KR20150014669A - Colored Photosensitive Resin Composition, Color Filter, and Liquid Crystal Display Device Having the Same - Google Patents

Abstract

The present invention provides a colored photosensitive resin composition comprising a colorant (A); an alkali soluble resin (B); a photo-polymerizable compound (C); a photopolymerization initiator (D); a solvent (E); and an additive (F), wherein the colorant (A) comprises one or more types of pigments (a1) and one or more types of pigments (a2), and the additive (F) comprises a compound represented by chemical formula 1; a color filter formed by using the same; and a liquid crystal display device having the color filter. According to the present invention, the colored photosensitive resin composition has excellent storage stability and can form a high-resolution color filter pattern.

Description

TECHNICAL FIELD [0001] The present invention relates to a colored photosensitive resin composition, a color filter, and a liquid crystal display device having the same,

The present invention relates to a colored photosensitive resin composition, a color filter, and a liquid crystal display device having the same. More particularly, the present invention relates to a colored photosensitive resin composition capable of forming a color filter pattern with high resolution and having excellent storage stability, A filter, and a liquid crystal display device including the color filter.

BACKGROUND ART [0002] Color filters are widely used in imaging elements, liquid crystal displays (LCDs), and the like, and the application range thereof has been expanded. The color filter is usually prepared by uniformly applying a colored photosensitive resin composition containing a pigment corresponding to each color of red, green and blue on a substrate on which a black matrix is pattern-formed, exposing and developing a coating film formed by heating and drying, And repeating an operation of heating and curing as needed, for each color to form pixels of each color.

Recently, display resolution has been rapidly increasing, and research and development for achieving miniaturization of a color filter pattern has been progressing steadily. Korean Patent Publication No. 1997-0049032 discloses a photopolymerization initiator, a compound having at least one ethylenically unsaturated double bond, a coloring material and a phosphoric acid (meth) acrylate compound and / or an anhydrous organic carboxylic acid having a molecular weight of 800 or less A photopolymerizable composition for a color filter is disclosed which is excellent in developability and high in resolution.

However, the above composition uses a pigment as a coloring material, and in the case of a composition using a dye together with a pigment for increasing the coloring power, the colored light-sensitive resin composition having high heat resistance and excellent storage stability due to low heat resistance and light resistance of the dye Has been urgently required.

It is an object of the present invention to provide a colored photosensitive resin composition capable of forming a color filter pattern of high resolution and having excellent storage stability.

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

It is still another object of the present invention to provide a liquid crystal display device provided with the color filter.

On the other hand, the present invention comprises a colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), a solvent (E) and an additive (F) The present invention provides a colored photosensitive resin composition comprising at least one pigment (a1) and at least one dye (a2), wherein the additive (F) comprises a compound represented by the following formula (1).

[Chemical Formula 1]

In this formula,

R ₁ is a hydrogen atom, methyl, ethyl, propyl, OH, phenyl, benzyl, methoxy, ethoxy or CH ₂ OCH ₃ , R ₂ and R ₃ are each independently a hydrogen atom, methyl or ethyl, and n + m Is an integer of 2 to 4, and R ₄ is a hydrogen atom, methyl or halogen.

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

On the other hand, the present invention provides a liquid crystal display provided with the color filter.

The color photosensitive resin composition according to the present invention can form a color filter pattern having high storage stability and high resolution by using the additive represented by the above formula (1) even though a dye having low heat resistance and low light resistance is used as a colorant.

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

An embodiment of the present invention comprises a colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), a solvent (E) and an additive (F) (A1) and at least one kind of dye (a2), and the additive (F) comprises a compound represented by the following general formula (1).

[Chemical Formula 1]

In this formula,

R ₁ is a hydrogen atom, methyl, ethyl, propyl, OH, phenyl, benzyl, methoxy, ethoxy or CH ₂ OCH ₃ , R ₂ and R ₃ are each independently a hydrogen atom, methyl or ethyl, and n + m Is an integer of 2 to 4, and R ₄ is a hydrogen atom, methyl or halogen.

The colorant (A)

In one embodiment of the present invention, the colorant (A) is characterized by comprising at least one pigment (a1) and at least one dye (a2).

The pigment (a1)

As the pigment (a1), an organic pigment or an inorganic pigment generally used in the related art can be used. The above-mentioned pigments include various pigments used in printing ink, ink-jet ink and the like, and specifically include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments , Anthanthrone pigments, indanthrone pigments, pravanthrone pigments, pyranthrone pigments (for example, pyranthrone pigments, perynone pigments, perynone pigments, perynone pigments, anthraquinone pigments, dianthraquinone pigments, anthrapyrimidine pigments, anthanthrone 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 oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, Oxide, carbon black and the like.

Particularly, the organic pigments and inorganic pigments include compounds classified as pigments in the Color Index (published by The Society of Dyers and Colourists), and more specifically, those having the following color index (CI) numbers Pigments, but are not limited thereto.

C.I. Pigment Yellow 13, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180 And 185;

C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 and 71;

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

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

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

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

C.I. Pigment Brown 28;

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

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

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

The pigment is preferably used as a pigment dispersion in which the particle size is uniformly dispersed. Examples of a method for uniformly dispersing the particle diameter of the pigment include a method in which the pigment dispersant (a3) is contained and dispersed. According to this method, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained .

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 alone or in combination of two or more.

The pigment dispersant (a3)

The pigment dispersant (a3) is added to maintain deactivation and stability of the pigment. Those commonly used in the art can be used without limitation. An acrylate-based dispersant (hereinafter also referred to as an " acrylic dispersant ") containing butyl methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA) is preferably used. DISCLOSURE OF THE INVENTION The acrylic dispersant used in the present invention is preferably prepared by a living control method as disclosed in Korean Patent Publication No. 2004-0014311. DISPER BYK-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. Examples of the other resin type pigment dispersants include polycarboxylic acid esters represented by polyurethanes and polyacrylates, unsaturated polyamides, polycarboxylic acids, (partial) amine salts of polycarboxylic acids, polycarboxylic acids An alkylamine salt of a polycarboxylic acid, a polysiloxane, a long chain polyaminoamide phosphate salt, an ester of a hydroxyl group-containing polycarboxylic acid and a modified product thereof, or a polyester having a free carboxyl group and a poly An amide formed by the reaction of an alkyleneimine) or a salt 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, DISPER BYK-160, and DISPER BYK-160 , 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 pigment dispersant (a3) to be used is preferably 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, the viscosity may be increased. If the content of the pigment dispersant is less than 5 parts by weight, it may be difficult to atomize the pigment or cause gelation after dispersion.

The dye (a2)

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

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 their derivatives can also be used.

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

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

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

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

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

C.I. Blue dyes such as Solvent Blue 5, 35, 36, 37, 44, 45, 59, 67 and 70;

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

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

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

Also, C.I. As the acid dye,

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

C.I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 266, 268, Red dyes such as 382, 383, 394, 401, 412, 417, 418, 422, 426;

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

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

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

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

In the exemplified acid dyes described above, C.I. Acid Yellow 42; C.I. Acid Red 92; C.I. Acid Blue 80, 90; C.I. Acid Violet 66; C.I. Acid Green 27 is preferred.

C.I. As a direct dye,

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

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

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

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

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

C.I. Green dyes such as 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 modatto dyes,

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

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

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

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

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

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

The above-exemplified 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 more preferably 1 to 50% by weight based on the solid content in the colorant (A) desirable. 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 dye elution by organic solvent after pattern formation, and it is preferable because of excellent sensitivity.

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 of the present invention. When the colorant (A) is contained in an amount of 5 to 60% by weight, the color density of a pixel is sufficient even if a thin film is formed, and the residue of the non-curing portion is not lowered during development.

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 one embodiment of the present invention, the alkali-soluble resin (B) is prepared by copolymerizing an ethylenically unsaturated monomer (b1) having a carboxyl group in order to have solubility in an alkali developing solution used in a development processing step for forming a pattern can do.

In order to ensure compatibility with the dye (a2) and storage stability of the colored photosensitive resin composition of the present invention, the acid value of the alkali-soluble resin (B) is preferably 30 to 150 mgKOH / g. When the acid value of the alkali-soluble resin (B) is less than 30 mgKOH / g, it is difficult to ensure a sufficient developing rate of the colored photosensitive resin composition. When the acid value exceeds 150 mgKOH / g, the adhesion with the substrate is decreased, The dye in the colored photosensitive resin composition is precipitated or the storage stability of the colored photosensitive resin composition is lowered and the viscosity tends to rise.

Specific examples of the ethylenically unsaturated monomer (b1) having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid; And an anhydride of the dicarboxylic acid; (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.

In order to impart a hydroxyl group to the alkali-soluble resin (B), an alkali-soluble resin can be prepared by copolymerizing an ethylenically unsaturated monomer (b1) having a carboxyl group and an ethylenically unsaturated monomer (b2) having a hydroxyl group, (B3) having a glycidyl group may be further reacted with the copolymer of the unsaturated monomer (b1). (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 glycidyl group-containing compound (b3) include butyl glycidyl ether, glycidyl propyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, glycidyl butyrate, glycidyl methyl But are not limited to, ether, ethyl glycidyl ether, glycidyl isopropyl ether, t-butyl glycidyl ether, benzyl glycidyl ether, glycidyl 4-t-butyl benzoate, glycidyl stearate, Ether and methacrylic acid glycidyl ester, and butyl glycidyl ether, aryl glycidyl ether and methacrylic acid glycidyl ester are preferable, and two or more kinds of them can be used in combination.

The unsaturated monomer (b4) that can be copolymerized in the production of the alkali-soluble resin (B) is illustrated below but is not limited thereto.

Specific examples of the monomer (b4) having a copolymerizable unsaturated bond include styrene, vinyltoluene,? -Methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p- Aromatic vinyl compounds such as benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether;

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 [5.2.1.02,6] decan- Alicyclic (meth) acrylates such as chloropentanyloxyethyl (meth) acrylate and isobornyl (meth) acrylate;

(Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl Hydroxyethyl (meth) acrylates such as hydroxyethyl acrylamide;

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 above-exemplified monomers (b4) having a copolymerizable unsaturated bond may be used alone or in combination of two or more.

The content of the alkali-soluble resin (B) is preferably in the range of 10 to 80% by weight, more preferably 10 to 70% by weight based on the solid content in the photosensitive resin composition of the present invention. When the content of the alkali-soluble resin (B) is 10 to 80% by weight, solubility in a developing solution is sufficient, pattern formation is easy, and reduction in film thickness of the pixel portion of the exposed portion is prevented during development, It is preferable.

The photopolymerizable compound (C)

In one embodiment of the present invention, the photopolymerizable compound (C) is a compound which can be polymerized under the action of the photopolymerization initiator (D) described below, and a monofunctional monomer, a bifunctional monomer or a polyfunctional monomer can be used, A monomer having two or more functional groups can be used.

Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N- But are not limited thereto.

Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) , Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, but are not limited thereto.

Specific examples of the polyfunctional monomer include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (metha) acrylate, propoxylated dipentaerythritol hexa Acrylate, dipentaerythritol hexa (meth) acrylate, but are not limited thereto.

The photopolymerizable compound (C) is preferably contained in an amount of 5 to 45% by weight, more preferably 7 to 45% by weight based on the solid content in the colored photosensitive resin composition of the present invention. When the photopolymerizable compound is contained in an amount of 5 to 45% by weight, the strength and smoothness of the pixel portion can be improved.

Photopolymerization initiator (D)

In one embodiment of the present invention, the photopolymerization initiator (D) can be used without any particular limitation as long as it can polymerize the photopolymerizable compound (C). In particular, it is preferable to use at least one compound selected from the group consisting of an acetophenone-based compound, a benzophenone-based compound, a triazine-based compound, a nonimidazole-based compound, a thioxanthone-based compound and an oxime ester-based 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-based compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'- Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) Bis (2,6-dichlorophenyl) -4, 5,5'-tetra (trialkoxyphenyl) bimidazole, 2,2- , 4'5,5'-tetraphenyl-1,2'-biimidazole, or imidazole compounds in which the phenyl group at the 4,4 ', 5,5' position is substituted by a carboalkoxy group. Among them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- , 5,5'-tetraphenylbiimidazole or 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole is preferably used do.

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

Specific examples of the oxime ester compound include o-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one and commercially available products include Irgacure OXE-01 (BASF), Irgacure OXE-02 (BASF), N-1919 (Adeca) and NCI-831 (Adeca), and OXE-02, N-1919 and NCI-831 are preferable from the viewpoint of curing efficiency.

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

As the photopolymerization initiation auxiliary, for example, at least one compound selected from the group consisting of an amine compound, a carboxylic acid compound and an organic sulfur compound having a thiol group can be preferably used.

Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4- 2-ethylhexyl dimethylbenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis Diethylamino) benzophenone, and the like, and it is preferable to use an aromatic amine compound.

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) may be contained in an amount of preferably 0.1 to 40% by weight, more preferably 1 to 30% by weight based on the solid content of the alkali-soluble resin (B) and the photopolymerizable compound (C) . When the amount of the photopolymerization initiator (D) is in the range of 0.1 to 40% by weight, the color photosensitive resin composition of the present invention has high sensitivity and shortens the exposure time, thereby improving productivity and maintaining high resolution. 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.

As the photopolymerization initiator (D), it is preferable to use an oxime ester compound. The oxime ester compound may contain 10 to 100% by weight, preferably 20 to 100% by weight of the total photopolymerization initiator. If the ratio of the oxime ester compound in the total photopolymerization initiator is less than 10% by weight, the sensitivity deterioration due to the dye can not be overcome and the pattern is likely to be short-circuited during the development process.

When the photopolymerization initiator is used, the amount of the photopolymerization initiator is preferably 0.1 to 40% by weight, more preferably 0.1 to 40% by weight based on the solid content of the alkali-soluble resin (B) 1 to 30% by weight. When the amount of the photopolymerization initiator is within the range of 0.1 to 40% by weight, the sensitivity of the colored photosensitive resin composition of the present invention is higher and the productivity of the color filter formed using the composition is improved.

Solvent (E)

In one embodiment of the present invention, the solvent (E) is not particularly limited so long as it is effective for dissolving the other components contained in the colored photosensitive resin composition of the present invention. , In particular, ethers, aromatic hydrocarbons, ketones, alcohols, esters, amides and the like are preferable.

Examples of the solvent (E) include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether;

Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether;

Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate;

Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate;

Aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene;

Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone;

Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin;

Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and cyclic esters such as? -Butyrolactone.

The solvent (E) is preferably an organic solvent having a boiling point of 100 to 200 DEG C in terms of coatability and dryness, and examples thereof include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate , Butyl lactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like.

The above-mentioned solvents (E) may be used alone or in admixture of two or more. The solvent (E) may be used in an amount of preferably 35 to 90% by weight, more preferably 40 to 90% by weight based on the total weight of the colored photosensitive resin composition of the present invention 85% by weight. When the amount of the solvent (E) is in the range of 35 to 90% by weight, when the resin (E) is applied by a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater Provides a resolution effect.

Additive (F)

In one embodiment of the present invention, the additive is characterized by containing a compound represented by the following general formula (1).

[Chemical Formula 1]

In this formula,

R ₁ is a hydrogen atom, methyl, ethyl, propyl, OH, phenyl, benzyl, methoxy, ethoxy or CH ₂ OCH ₃ , R ₂ and R ₃ are each independently a hydrogen atom, methyl or ethyl, and n + m Is an integer of 2 to 4, and R ₄ is a hydrogen atom, methyl or halogen.

Preferably, R ₁ is a hydrogen atom, methyl, ethyl or propyl, R ₂ and R ₃ are hydrogen atoms, n + m is an integer of 2 to 4, and R ₄ is a hydrogen atom.

Specific examples of the compound represented by Formula 1 include 2,4-dihydroxybenzaldehyde, 2 ', 4'-dihydroxyacetophenone, 2,4,5-trimethoxybenzaldehyde, 2,3-dihydro Methoxybenzaldehyde, benzyl 2,4-dihydroxyphenylketone, 1- (2,4,5-trimethoxyphenyl) -1-butanone, alpha -methoxyfluoroacetophenone (alpha- methoxyphloroacetophenone), 2-hydroxy-3,4-dimethoxybenzoic acid, 2,4-diethoxybenzaldehyde, 5'-chloro-2 ', 4'-dihydroxyacetophenone, ethyl 2,4- 6-methylbenzoate, 2,4,5-trimethoxybenzoic acid and 5-bromo-2,4-dihydroxybenzoic acid. From the viewpoint of achieving high resolution and storage stability, 2,4-dihydroxy Benzaldehyde and 2 ', 4'-dihydroxyacetophenone are preferable, and 2,4-dihydroxybenzaldehyde is more preferable.

The compound represented by Formula 1 is commercially available or can be easily prepared by a method known in the art.

The compound represented by the formula (1) may be contained in an amount of preferably 0.1 to 40% by weight, more preferably 1 to 30% by weight based on the solid content of the alkali-soluble resin (B) and the photopolymerizable compound (C) . When the amount of the compound represented by the formula (1) is in the range of 0.1 to 40% by weight, the colored photosensitive resin composition of the present invention is preferable because high resolution can be maintained without peeling of the pattern. Specifically, when it is less than 0.1% by weight, it is difficult to achieve a high resolution, and when it exceeds 40% by weight, a short circuit of the pattern is likely to occur during the development process.

The colored photosensitive resin composition according to one embodiment of the present invention may contain fillers, other polymer compounds, a curing agent, a pigment dispersant, an adhesion promoter, an ultraviolet absorber, an aggregation inhibitor Or the like can be used in combination.

The filler may be glass, silica, alumina, or the like, but is not limited thereto.

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

The curing agent is used for increasing the curing depth and mechanical strength. Specifically, an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound may be used, but the present invention is not limited thereto.

Specific examples of the epoxy compound include epoxy resins such as 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, isoprene (co) polymers other than brominated derivatives of these epoxy resins, epoxy resins and their brominated derivatives, cidyl ester type resins, glycidyl amine type resins, (Glycidyl (meth) acrylate (co) polymer, triglycidyl isocyanurate, and the like, but are not limited thereto.

Specific examples of the oxetane compound include, but are not limited to, carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane. It is not.

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. Specific examples of the curing auxiliary compound include polyvalent carboxylic acids, polyvalent carboxylic anhydrides, and acid generators. The polyvalent carboxylic acid anhydrides may be those commercially available as epoxy resin curing agents. Examples of commercially available epoxy resin curing agents include trade name (ADEKA HARDONA EH-700) (ADEKA INDUSTRIAL CO., LTD.), Trade name (RICACIDO HH) (Manufactured by Shin-Etsu Chemical Co., Ltd.).

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

As the pigment dispersant, a commercially available surfactant may be used, and specifically, a surfactant selected from the group consisting of silicone, fluorine, ester, cationic, anionic, nonionic, and amphoteric surfactants, . More specifically, examples thereof include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes, polyethylene imines and the like. (Trade name) manufactured by Shin-etsu Chemical Industry Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by TOKEM PRODUCTS CO., LTD.), MEGAFAC Asahi guard, Surflon (Asahi Glass Co., Ltd.), SOLSPERSE (Lubrisol), EFKA (Nippon Ink Chemical Industries Co., Ltd.), Flourad (Sumitomo 3M Co., Ltd.) (EFKA Chemical), PB 821 (Ajinomoto), and Disperbyk-series (BYK-chemi).

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- (2-aminoethyl) (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- Methoxysilane, 3-isocyanatepropyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane, or a mixture thereof.

The adhesion promoter may be contained in an amount of preferably 0.01 to 10 parts by weight, more preferably 0.05 to 2 parts by weight, based on the solid content of the composition.

Specific examples of the ultraviolet absorber include, but are not limited to, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole and alkoxybenzophenone.

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

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

First, the pigment (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, the pigment dispersant, 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), if necessary. The dye (a2), the remainder of the alkali-soluble resin (B), the photopolymerizable compound (C), the photopolymerization initiator (D) and the additive (F) and, if necessary, the solvent (E) The colored photosensitive resin composition according to the present invention can be prepared.

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

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

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

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

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

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

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

The alkaline compound may be an inorganic or organic alkaline compound. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogenphosphate, sodium dihydrogenphosphate, ammonium dihydrogenphosphate, ammonium dihydrogenphosphate, potassium dihydrogenphosphate, sodium silicate, potassium silicate, sodium carbonate, Sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, and ammonia. Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, mono Isopropylamine, diisopropylamine, ethanolamine, and the like. These inorganic and organic alkaline compounds may be used alone or in combination of two or more. The alkaline compound may be contained in an amount of 0.01 to 10 parts by weight, preferably 0.03 to 5 parts by weight, based on the developing solution.

The surfactant may be selected from the group consisting of a nonionic surfactant, an anionic surfactant, and a cationic surfactant, or a mixture thereof. Specific examples of the nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters , Polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines. Specific examples of the anionic surfactant include higher alcohol sulfuric acid ester salts such as sodium lauryl alcohol sulfate ester and sodium oleyl alcohol sulfate ester, alkylsulfuric acid salts such as sodium lauryl sulfate and ammonium lauryl sulfate, dodecylbenzenesulfonic acid And alkylarylsulfonic acid salts such as sodium or sodium dodecylnaphthalenesulfonate. Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts. These surfactants may be used alone or in combination of two or more. The amount of the surfactant is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 8 parts by weight, and even more preferably 0.1 to 5 parts by weight based on the developer.

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

One embodiment of the present invention relates to a liquid crystal display provided with the color filter described above.

The liquid crystal display device of the present invention includes configurations known in the art, except that the liquid crystal display device is provided with the color filter described above. That is, all liquid crystal display devices to which the color filter of the present invention can be applied are included in the present invention. For example, a transmissive liquid crystal display device in which a counter electrode substrate having a thin film transistor (TFT element), a pixel electrode, and an alignment layer are faced at predetermined intervals and a liquid crystal material is injected into the gap portion to form a liquid crystal layer . There is also a reflective liquid crystal display device in which a reflective layer is provided between the substrate of the color filter and the colored layer. As another example, a thin film transistor (TFT) substrate integrated on a transparent electrode of a color filter and a liquid crystal display device including a backlight fixed to a position where a TFT substrate overlaps a color filter can be given.

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

Production Example 1: Preparation of pigment dispersion (M1)

4.0% by weight of DISPER BYK-2001 (manufactured by BYK) as a pigment dispersant, and 84.0% by weight of propylene glycol monomethyl ether acetate as a solvent were mixed / dispersed for 12 hours by using a bead mill as a pigment, 12.0% by weight of CI Pigment Green 36 To prepare a pigment dispersion (M1).

Production Example 2: Preparation of alkali-soluble resin

A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 120 parts by weight of propylene glycol monomethyl ether acetate, 80 parts by weight of propylene glycol monomethyl ether, 2 parts by weight of azobisisobutyronitrile (AIBN) , 13 parts by weight of acrylic acid, 10 parts by weight of benzylmethacrylate, 57 parts by weight of 4-methylstyrene, 20 parts by weight of methylmethacrylate and 3 parts by weight of n-dodecylmercapto. Then, the temperature of the reaction solution was elevated to 110 DEG C with stirring, and the reaction was carried out for 6 hours to prepare an alkali-soluble resin.

The prepared alkali-soluble resin had a solid content of 100.2 mgKOH / g and a weight-average molecular weight (Mw) measured by GPC of about 15110.

Example 1: Preparation of colored photosensitive resin composition

39.37% by weight of the pigment dispersion (M1) obtained in Production Example 1, 0.52% by weight of Solvent Yellow 21 as a dye, 10.22% by weight of an alkali-soluble resin obtained in Production Example 2, dipentaerythritol hexaacrylate (KAYARAD DPHA, 3.99% by weight of Irgacure OXE-02 (BASF), 3.99% by weight of 2,4-dihydroxybenzaldehyde (Aldrich) and 41.50% by weight of propylene glycol monomethyl ether acetate, To prepare a resin composition.

Example 2: Preparation of colored photosensitive resin composition

39.37% by weight of the pigment dispersion (M1) obtained in Production Example 1, 0.52% by weight of Solvent Yellow 21 as a dye, 10.22% by weight of an alkali-soluble resin obtained in Production Example 2, dipentaerythritol hexaacrylate (KAYARAD DPHA, 3.99% by weight of Irgacure OXE-02 (BASF), 3.99% by weight of 2,4-dihydroxyacetophenone (Aldrich) and 41.50% by weight of propylene glycol monomethyl ether acetate To prepare a photosensitive resin composition.

Comparative Example 1: Preparation of colored photosensitive resin composition

39.37% by weight of the pigment dispersion (M1) obtained in Production Example 1, 0.52% by weight of Solvent Yellow 21 as a dye, 10.22% by weight of an alkali-soluble resin obtained in Production Example 2, dipentaerythritol hexaacrylate (KAYARAD DPHA, 1.00% by weight of Irgacure OXE-02 (manufactured by BASF), and 45.40% by weight of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition.

Comparative Example 2: Preparation of colored photosensitive resin composition

39.37% by weight of the pigment dispersion (M1) obtained in Production Example 1, 10.22% by weight of the alkali-soluble resin obtained in Production Example 2, 3.40% by weight of dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku) A colored photosensitive resin composition was prepared by mixing 1.00 wt% of OXE-02 (BASF), 3.99 wt% of 2,4-dihydroxybenzaldehyde (Aldrich) and 42.02 wt% of propylene glycol monomethyl ether acetate.

Comparative Example 3: Preparation of colored photosensitive resin composition

39.37% by weight of the pigment dispersion (M1) obtained in Production Example 1, 10.22% by weight of the alkali-soluble resin obtained in Production Example 2, 3.40% by weight of dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku) 1.00% by weight of OXE-02 (BASF), 3.99% by weight of 2,4-dihydroxyacetophenone and 42.02% by weight of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition.

Experimental Example 1: Evaluation of resolution and viscosity change

A color filter was prepared using the colored photosensitive resin compositions prepared in Examples 1 and 2 and Comparative Examples 1 to 3. Specifically, each of the above-mentioned colored photosensitive resin compositions was applied on a 2-inch-square glass substrate ("EAGLE XG" manufactured by Corning Inc.) by spin coating, and then placed on a heating plate and maintained at 100 ° C. for 3 minutes to form a thin film . Then, a test photomask having a line / space pattern of 1 μm to 100 μm was placed on the thin film and irradiated with ultraviolet rays at a distance of 300 μm from the test photomask. At this time, the ultraviolet light source was irradiated at 60 mJ / cm 2 using a 1 kW high pressure mercury lamp 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 230 ° C for 25 minutes to prepare a color filter. The film thickness of the color filter prepared above was 2.4 占 퐉.

(1) Resolution measurement

The pattern of the color filter manufactured as described above is analyzed by an optical microscope (x1000) and the minimum pattern size that can be formed without loss of the pattern is shown in Table 1 below

(2) Development speed measurement

As described above, when the color filter was manufactured, the time taken for the non-visible portion to completely dissolve in the developing solution was measured, and the results are shown in Table 1 below

(3) Evaluation of viscosity change

The initial viscosity of the colored photosensitive resin compositions prepared in Examples and Comparative Examples was measured, and after storing for 3 months at 5 캜, the viscosity was measured to observe the viscosity change. The viscosity was measured with a Brookfield viscometer (Brookfield Viscometer DVI +, manufactured by BROOKFIELD) at 25 ° C. The measurement results are shown in Table 1 below.

○: Viscosity change 5% or less

: Change in viscosity: more than 5% and not more than 10%

×: Viscosity change exceeding 10%

division Minimal pattern Development speed Viscosity change Example 1 20 탆 15 △ Example 2 25 m 20 ○ Comparative Example 1 45 탆 52 × Comparative Example 2 50 탆 13 △ Comparative Example 3 85 탆 34 ○

As can be seen from Table 1, the colored photosensitive resin composition of the present invention has a significantly smaller minimum pattern size and no change in viscosity compared to the comparative example in which no additive of formula (1) I can confirm that it is low.

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

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

Claims (9)

Wherein the colorant (A) comprises at least one pigment (a1), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), a solvent (E) and an additive (F) ) And at least one dye (a2), wherein the additive (F) comprises a compound represented by the following general formula (1):
[Chemical Formula 1]

In this formula,
R ₁ is a hydrogen atom, methyl, ethyl, propyl, OH, phenyl, benzyl, methoxy, ethoxy or CH ₂ OCH ₃ , R ₂ and R ₃ are each independently a hydrogen atom, methyl or ethyl, and n + m Is an integer of 2 to 4, and R ₄ is a hydrogen atom, methyl or halogen. The colored photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (B) has an acid value of 30 to 150 mgKOH / g. The colored photosensitive resin composition according to claim 1, wherein the photopolymerization initiator (D) comprises an oxime ester compound. 2. The compound according to claim 1, wherein R ₁ is a hydrogen atom, methyl, ethyl or propyl, R ₂ and R ₃ are hydrogen atoms, n + m is an integer of 2 to 4, and R ₄ is a hydrogen atom Colored photosensitive resin composition. 2. The process according to claim 1, wherein the compound represented by the general formula (1) is 2,4-dihydroxybenzaldehyde, 2 ', 4'-dihydroxyacetophenone, 2,4,5-trimethoxybenzaldehyde, Methoxybenzaldehyde, benzyl 2,4-dihydroxyphenylketone, 1- (2,4,5-trimethoxyphenyl) -1-butanone, α-methoxyfluoroacetophenone (alpha -methoxyphloroacetophenone), 2-hydroxy-3,4-dimethoxybenzoic acid, 2,4-diethoxybenzaldehyde, 5'-chloro-2 ', 4'-dihydroxyacetophenone, ethyl 2,4- Methylbenzoate, 2,4,5-trimethoxybenzoic acid or 5-bromo-2,4-dihydroxybenzoic acid. The colored photosensitive resin composition according to claim 1, wherein the compound represented by the formula (1) is 2,4-dihydroxybenzaldehyde or 2 ', 4'-dihydroxyacetophenone. The colored photosensitive resin composition according to claim 1, wherein the compound represented by the formula (1) is contained in an amount of 0.1 to 40% by weight based on the solid content of the alkali-soluble resin (B) and the photopolymerizable compound (C). A color filter formed using the colored photosensitive resin composition according to any one of claims 1 to 7. A liquid crystal display device comprising the color filter according to claim 8.