KR20160109834A - Colored photosensitive resin composition - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition comprising: (A) a coloring agent; (B) an alkali-soluble resin; (C) a photopolymerizable compound; (D) a photopolymerization initiator; and (E) a solvent and, more specifically, to a colored photosensitive resin composition having glass transition temperature of less than 0C. The coloring agent (A) comprises dyes and the alkali-soluble resin (B) comprises a compound represented by chemical formula 1 and chemical formula 2.

Description

COLORED PHOTOSENSITIVE RESIN COMPOSITION [0002]

The present invention relates to a colored photosensitive resin composition, a color filter manufactured using the same, and a liquid crystal display including the same.

The display is rapidly growing in size, and there is a growing demand for high-quality displays with high color yield. The power consumption of the panel due to the enlargement is increasing and the content of the coloring material and the thickness of the coating film of the colored photosensitive resin composition used for manufacturing the color filter are continuously increasing for the high color reproducibility. In order to improve the energy efficiency through the improvement of the light efficiency, high-throughput development of the color filter has been continuously carried out. However, since the conventional pigment dispersing system has reached the limit of the atomization of the pigment, the method of using the pigment and dye simultaneously . However, when a color filter is produced using a colored photosensitive resin composition containing a dye as a coloring agent, the developing speed is low and the sensitivity is insufficient, thereby causing a problem that the pattern formed in the developing process by the alkali developing solution is peeled off.

In this connection, Korean Patent Laid-Open Publication No. 2012-0080123 discloses a color photosensitive composition, a method of manufacturing a color filter, a color filter, a liquid crystal display, and an organic EL display device, but does not propose an alternative to the above problem .

Korean Patent Publication No. 2012-0080123

It is an object of the present invention to provide a colored photosensitive resin composition which exhibits excellent adhesion even at a very high developing speed, has a high transmittance and excellent heat resistance, and is suitable for producing a high quality color filter.

An object of the present invention is to provide a color filter made of the above-mentioned colored photosensitive resin composition.

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

The present invention provides a colored photosensitive resin composition comprising a colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D) and a solvent (E) And the alkali-soluble resin (B) comprises a compound represented by the following general formula (1) and (2), and has a glass transition temperature of less than 0 ° C.

The present invention provides a color filter manufactured using the colored photosensitive resin composition.

The present invention provides a liquid crystal display device including a color filter.

The colored photosensitive resin composition of the present invention exhibits excellent adhesion even when the developing speed is very high, has high transmittance and excellent heat resistance, and is suitable for manufacturing a high-quality color filter.

The present invention provides a colored photosensitive resin composition comprising a colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D) and a solvent (E) And the transition temperature is lower than 0 占 폚. The present invention is advantageous in manufacturing a high-quality color filter because it contains a specific alkali-soluble resin (B), exhibits excellent adhesion even at a high developing speed, has high transmittance and excellent heat resistance.

Hereinafter, the contents of the present invention will be described in detail for each constitution.

The colorant (A)

The colorant (A) may contain at least one dye (a1) as an essential component and the coloring agent pigment (a2).

Hereinafter, each configuration will be described.

The dye (a1)

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

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

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

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

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

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

C.I. Yellow dyes such as Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162;

C.I. Solvent Orange Orange dye such as 2, 7, 11, 15, 26, 56

C.I. Green dyes such as solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34,

C.I. Solvent dye having excellent solubility in an organic solvent. Solvent Red 8, 49, 89, 111, 122, 132, 146, 179; C.I. Solvent Blue 35, 36, 44, 45, 70; C.I. Solvent violet 13 is preferred, and C.I. Solvent Red 8, 122 and 132 are more preferred.

Also, C.I. As an acid dye

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;

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,

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,

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 color dyes such as C.I. Acid Violet 6B, 7, 9, 17, 19, 66

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

CI Acid Red 92, which is excellent in solubility in organic solvents in acid dyes; C. I. Acid Blue 80, 90; C.I. Acid Violet 66 is preferred.

As a C.I. direct dye,

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;

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;

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,

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 C.I. 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 pigment (a2)

The pigment may be an organic pigment or an inorganic pigment generally used in the art. The above-mentioned pigments can be used in various kinds of pigments used in printing ink, ink jet ink and the like. Specific examples thereof include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, And an anthanthrone pigment, an anthanthrone pigment, a pravanthrone pigment, a pyranthrone pigment, an anthanthrone pigment, an anthanthrone pigment, an anthanthrone pigment, an anthanthrone pigment, an anthanthrone pigment, a pyranthrone pigment, pyranthrone pigments, diketopyrrolopyrrole pigments, and the like. Examples of the inorganic pigments include metallic compounds such as metal oxides and metal complex salts. Specific examples of the inorganic pigments include oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony and carbon black Or composite metal oxides. Particularly, the organic pigments and inorganic pigments may be specifically classified into pigments in the Society of Dyers and Colourists, and more specifically, those having a color index (CI) number 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, etc.

The above-mentioned pigments (a2) may be used alone or in combination of two or more.

The exemplified C.I. Among the pigment pigments, 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 Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185, C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 58, C.I. Pigment Violet 23, C.I. Pigment Blue 15: 3, Pigment Blue 15: 6 can be preferably used.

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

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

The content of the pigment (a2) is in the range of 20 to 90% by weight, preferably 30 to 70% 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 20 to 90% 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.

As the dispersant (a3), other resin type pigment dispersants other than the acrylic dispersant may be used. The other resin type pigment dispersing agent may be a known resin type pigment dispersing agent, especially a polycarboxylic acid ester such as polyurethane, polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) Amine salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long chain polyaminoamide phosphate salts, esters of hydroxyl group-containing polycarboxylic acids and their modified products, or free ) Oil-based dispersants such as amides formed by reaction of a polyester having a carboxyl group with poly (lower alkyleneimine) or salts thereof; Soluble resin or water-soluble polymer compound such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinylpyrrolidone; Polyester; Modified polyacrylates; Adducts of ethylene oxide / propylene oxide, and phosphate esters. DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-160, BYK (trade name) 164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; EFKA-4060, EFKA-4060, EFKA-4055, EFKA-4055, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA- 4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10 from Lubirzol; Hinoact T-6000, Hinoact T-7000, Hinoact T-8000; available from Kawaken Fine Chemicals; AJISPUR PB-821, Ajisper PB-822, Ajisper PB-823 manufactured by Ajinomoto; FLORENE DOPA-17HF, fluorene DOPA-15BHF, fluorene DOPA-33, and fluorene DOPA-44 are trade names of Kyoeisha Chemical Co., In addition to the acrylic dispersant, other resin type pigment dispersants may be used alone or in combination of two or more, or may be used in combination with acrylic dispersion.

The amount of the dispersant (a3) to be used is in the range of 5 to 60 parts by weight, more preferably 15 to 50 parts by weight, based on 100 parts by weight of the solid content of the pigment (a2). If the content of the dispersant (a3) exceeds 60 parts by weight, the viscosity may be increased. If the content of the dispersant (a3) is less than 5 parts by weight, it may be difficult to atomize the pigment or cause gelation after dispersion.

The 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 colorant may be contained in an amount of 5 to 60% by weight, preferably 10 to 50% by weight based on the total solid content in the colored photosensitive resin composition of the present invention. When the colorant is included in the above-mentioned range, even if a thin film is formed, the color density of the pixel is sufficient, and the residue of the non-curing portion is not lowered during development, so that residue is less likely to occur.

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)

The alkali-soluble resin of the present invention has a glass transition temperature of less than 0 占 폚, and may specifically include compounds represented by the following general formulas (1) and (2). By using an alkali-soluble resin having a glass transition temperature of less than 0 ° C, the present invention significantly improves the development speed of the composition and improves adhesion, thereby preventing the short circuit of the pattern due to an increase in the developing speed.

[Chemical Formula 1]

Wherein R ₁ and R ₂ are each independently hydrogen or an aliphatic or aromatic hydrocarbon containing or not containing C ₁ to C ₁₂ heteroatoms and R ₃ to R ₆ are each independently hydrogen or an aliphatic or aromatic hydrocarbon containing or not containing a C1 to C30 heteroatom and two of R ₃ to R ₆ may be linked to form a ring.

(2)

(Wherein R ₇ is independently hydrogen or an aliphatic or aromatic hydrocarbon with or without a C1 to C12 heteroatom and R ₈ is a substituted or unsubstituted linear or branched alkyl group having from 2 to 30 carbon atoms to be.)

The compound represented by Formula 1 may be any one of the following compounds.

The acrylic copolymer containing the repeating units represented by the above formulas (1) and (2) may be in the form of a block copolymer in which the repeating units are repeatedly formed in a uniform manner, or a random copolymer Lt; / RTI >

In addition, the compound represented by the above-mentioned general formula (2) is preferably selected from the group consisting of ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, Acrylate, n-pentyl methacrylate, 2-methylbutyl acrylate, 2-methylbutyl methacrylate, 2-ethylpropyl acrylate, 2-methylbutyl methacrylate, N-heptyl acrylate, n-decyl acrylate, n-dodecyl acrylate, n-tridecyl acrylate, n-hexadecyl acrylate, , n-haptadecyl acryl Acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, Ethyl acrylate, ethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, Hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl methacrylate, Methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxy diethylene glycol acrylate, methoxy diethylene glycol methacrylate, methoxy triethylene glycol Acrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, 2-hydroxy-3- Unsaturated carboxylic acid esters such as phenoxy propyl acrylate, 2-hydroxy-3-phenoxy propyl methacrylate, glycerol monoacrylate and 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; A macromonomer having a monoacryloyl group or monomethacryloyl group at the end of a polymer molecular chain of polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, And the like.

The alkali-soluble resin (B) may further comprise a compound represented by the following general formula (3).

(3)

(Wherein p is an integer of 1 to 100, R ₉ is a residue containing a carboxylic acid derived from an acid anhydride, and R ₁₀ and R ₁₁ are each independently hydrogen or a methyl group.)

The acid anhydride may be selected from the group consisting of phthalic anhydride, (2-dodecen-1-yl) succinic anhydride, maleic anhydride, succinic anhydride, anhydride, citraconic anhydride, glutaric anhydride, methylsuccinic anhydride, 3,3-dimethylglutaric anhydride, phenylsuccinic anhydride, Itaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, hexahydrophthalic anhydride, And may be at least one selected from the group consisting of Hexahydrophthalic anhydride and Carbic anhydride.

The alkali-soluble resin (B) of the present invention contains a repeating unit represented by the general formula (3) in the repeating units represented by the general formulas (1) and (2) to exhibit a glass transition temperature of less than 0 ° C, At the same time, the adherence is also improved, thereby making it possible to suppress the problem of falling-out of the pattern due to the increase in the developing speed.

Further, in the case of forming a pattern using the composition containing the alkali-soluble resin (B), it is possible to minimize the step of the pattern that can be enlarged by the colorant in the composition, thereby significantly improving the smoothness and improving the transmittance, Thereby making it possible to manufacture a color filter.

With respect to 100 mol% of the alkali-soluble resin (B)

(A1) 2 to 20 mol% of units derived from the above formula (1)

(A2) 2 to 70 mol% of the constitutional unit derived from the above formula (2), and

(A3) It is preferable to contain 10 to 90 mol% of the constituent unit derived from the above formula (3). When the above constitution ratio is in the above range, a good copolymer is obtained because of good developability, have.

The alkali-soluble resin (B) may be prepared by further copolymerizing a monomer (A4) having an unsaturated double bond in addition to the above (A1) to (A3).

The monomer having a copolymerizable unsaturated double bond is not particularly limited and specific examples thereof include styrene, vinyltoluene,? -Methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p Vinylbenzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether Aromatic vinyl compounds such as diesters; 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;

(Meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6] decan- Alicyclic (meth) acrylates such as isobornyl (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. These monomers may be used alone or in combination of two or more.

The content of the compound having a copolymerizable unsaturated double bond is not particularly limited and may be, for example, from 5 to 50 mol% based on 100 mol% of the alkali-soluble resin (B). When the above range is satisfied, the glass transition temperature of the resin is less than 0 DEG C, and the step can be minimized

In one embodiment of the present invention, an example of the method for producing the copolymer can be produced by copolymerization in the following manner.

Copolymerizing (A1), (A2) and (S1) glycidyl (meth) acrylate in a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube;

(S2) comprises the steps of: reacting the produced copolymer with an ethylenically unsaturated monomer having a carboxyl group; And (S3) reacting the reacted copolymer with an acid anhydride.

The step (S2) is a step for imparting photo-curability to the alkali-soluble resin (A) of the present invention. In the step (S2), the type of the ethylenically unsaturated monomer having a carboxyl group is not particularly limited But are not limited to, (meth) acrylic acid, ethyl acrylic acid, butyl acrylic acid and the like, preferably methacrylic acid. And preferably methacrylic acid.

The step (S3) is a step for imparting an appropriate acid value to the alkali-soluble resin (B) of the present invention. More specifically, the step (S3) is a step of reacting the hydroxyl group derived from the glycidyl group of the alkali- And introducing a carboxyl group into the side chain of the resin.

The kind of acid anhydride used in step (S3) is not particularly limited as long as it is within the range of its function. For example, acid anhydrides include phthalic anhydride, (2-dodecen-1-yl) (2-Dodecen-1-yl) succinic anhydride, maleic anhydride, succinic anhydride, citraconic anhydride, glutaric anhydride, methyl succinic anhydride, It is preferable to use an anhydride such as methylsuccinic anhydride, 3,3-dimethylglutaric anhydride, phenylsuccinic anhydride, itaconic anhydride, 3,4,5,6-tetrahydro (3,4,5,6-Tetrahydrophthalic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, and carbic anhydride), and the like. In terms of ease of reaction, A maleic anhydride, a phthalic anhydride, a trimellitic anhydride, a succinic anhydride, a hexahydrophthalic anhydride and a carbamic anhydride are preferable, Trimellitic anhydride, succinic anhydride, and hexahydrophthalic anhydride are more preferable.

The acid value of the alkali-soluble resin (B) according to the present invention may be 30 to 150 mgKOH / g in order to ensure compatibility with the dye contained in the composition and storage stability of the composition. When the acid value of the alkali-soluble resin (B) is less than 30 mgKOH / g, it may be difficult to secure a sufficient developing rate of the colored photosensitive resin composition. When the acid value exceeds 150 mgKOH / g, There is a problem that compatibility with the dye occurs, so that 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 may increase.

In another embodiment of the present invention, the weight average molecular weight of the alkali-soluble resin (B) in terms of polystyrene is preferably in the range of 3,000 to 100,000, more preferably 5,000 to 50,000. When the weight average molecular weight of the binder resin (A) is in the range of 3,000 to 100,000, film reduction is not easily caused at the time of development, and the non-pixel portion tends to be satisfactorily missed at the time of development.

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

The content of the alkali-soluble resin (B) according to the present invention is not particularly limited, but is, for example, in the range of 5% to 80% by weight, preferably 10 to 70% by weight based on the total solid content in the photosensitive resin composition. When the range is satisfied, the solubility in the developing solution is sufficient, the pattern formation is easy, and the development is preferable because the decrease in the film thickness of the pixel portion of the open tube portion is prevented, and the non-pixel portion is satisfactorily missed.

The photopolymerizable compound (C)

The photopolymerizable compound (C) is a compound capable of polymerizing under the action of the photopolymerization initiator (D) described below, and a monofunctional monomer, a bifunctional monomer or a polyfunctional monomer can be used, and preferably a bifunctional or more polyfunctional monomer Can be used.

Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate or 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 or 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 (meth) acrylate, propoxylated dipentaerythritol hexa ) Acrylate or dipentaerythritol hexa (meth) acrylate, but are not limited thereto.

The photopolymerizable compound is in the range of 1 to 60% by weight, preferably 5 to 50% by weight, based on the total solid content in the photosensitive resin composition. When the photopolymerizable compound is included in the above range, it is preferable that the strength and smoothness of the pixel portion are improved.

Photopolymerization initiator (D)

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

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy- 1- [4- 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-methylcyclohexyl phenyl ketone, 2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1-one 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.

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

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

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

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

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

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

(D2) may be preferably 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.

As the amine compound, an aromatic amine compound is preferably used. Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Dimethylaminobenzoic acid, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone ), 4,4'-bis (diethylamino) benzophenone, and the like.

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

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

The photopolymerization initiator (D) may be contained in an amount of 0.1 to 40% by weight, preferably 1 to 30% by weight based on the total solid content in the colored photosensitive resin composition of the present invention. When the photopolymerization initiator (D) is in the above-mentioned range, the colored photosensitive resin composition has high sensitivity and shortens the exposure time, which is preferable because productivity can be improved and high resolution can be maintained. Further, the strength of the pixel portion formed using the composition of the above-described conditions and the smoothness of the surface of the pixel portion can be improved.

When the photopolymerization initiator (d2) is further used, the photopolymerization initiator (d2) is added in an amount of 0.1 to 50% by weight, preferably 1 to 40% by weight, based on the total solid content of the colored photosensitive resin composition of the present invention. May be included.

 When the amount of the component (d2) is in the range of 0.1 to 50% by weight, the sensitivity of the colored photosensitive resin composition becomes higher and the productivity of the color filter formed using the composition is improved.

Solvent (E)

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

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

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

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

Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, 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, glycerin, and 4-hydroxy-

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

The solvent (E) is preferably an organic solvent having a boiling point of 100 ° C to 200 ° C on the application and drying surface, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate , Butalactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like. Hydroxy-4-methyl-2-pentanone or the like which can improve the storage stability by inhibiting the precipitation of the dye.

The solvent may be used alone or in admixture 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 weight of the colored photosensitive resin composition of the present invention containing the solvent . When it is contained in the above-mentioned contents, it provides the effect of improving the coating property when applied with a coating apparatus such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater) .

Additive (F)

The additive (F) may be optionally added, for example, other polymer compounds, a curing agent, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an antiflocculant.

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 total 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.

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

First, the pigment (a2) in the colorant (A) is mixed with the solvent (F) and dispersed using a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 μm or less. At this time, if necessary, a part or all of the pigment dispersant (a3), the alkali-soluble resin (B), or the dye (a1) may be mixed and dissolved with the (E) solvent.

(B), the photopolymerizable compound (C), the photopolymerization initiator (D), the optional (F) additive and the solvent (E) are added to the mixed dispersion in a predetermined concentration The colored photosensitive resin composition according to the present invention can be prepared.

The present invention includes a liquid crystal display device including the color filter manufactured using the colored photosensitive resin composition and including the color filter. The color filter and the liquid crystal display of the present invention may be manufactured by a known method.

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

Manufacturing example : Preparation of pigment dispersion composition

<Pigment dispersion composition M1>

C.I. , 12 parts by weight of Pigment Red 177, 4.0 parts by weight of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, 1.2 parts by weight of Acid Red 52, 44 parts by weight of propylene glycol methyl ether acetate as a solvent and 4 parts by weight of 4-hydroxy- 20 parts by weight of 2-pentanone were mixed / dispersed by a bead mill for 12 hours to prepare a pigment dispersion M1.

<Pigment dispersion composition M2>

C.I. 13.2 parts by weight of Pigment Red 177, 4.0 parts by weight of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, 44 parts by weight of propylene glycol methyl ether acetate as a solvent and 20 parts by weight of 4-hydroxy-4-methyl- And then mixed / dispersed by a bead mill for 12 hours to prepare a pigment dispersion M2.

Synthesis Example: Synthesis of alkali-soluble resin

&Lt; Synthesis Example 1 &

An alkali-soluble resin was synthesized as follows using 2-norbornene and 2-ethylhexyl acrylate as the compound of the present invention and the compound of the formula (2), respectively.

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 90 g of propylene glycol monomethyl ether acetate, 90 g of propylene glycol monomethyl ether, and nitrogen in air in a flask, followed by azobisisobutyl 8.2 g of ronitryl, 4.7 g of 2-norbornene, 55.2 g of 2-ethylhexyl acrylate, 5.9 g of 4-methylstyrene, 85.2 g of glycidyl methacrylate and 6.0 g of n-dodecanethiol. Thereafter, the temperature of the reaction solution was raised to 80 DEG C with stirring, and the reaction was carried out for 4 hours.

After the temperature of the reaction solution was lowered to room temperature and the atmosphere of the flask was replaced with air in nitrogen, 0.2 g of triethylamine, 0.1 g of 4-methoxyphenol and 43.2 g of acrylic acid were added to the dropping funnel together with 136 g of propylene glycol monomethyl ether acetate for 2 hours Followed by reaction at 100 ° C for 6 hours. Thereafter, the temperature of the reaction solution was lowered to room temperature, 6.0 g of succinic anhydride was added, and the mixture was reacted at 80 DEG C for 6 hours.

The alkali-soluble resin thus synthesized had a solid dispersion value of 35.8 mgKOH / g and a weight average molecular weight Mw of about 7350 as measured by GPC

The glass transition temperature was measured with a differential scanning calorimeter and found to be -18 ° C.

&Lt; Synthesis Example 2 &

An alkali-soluble resin was synthesized as follows using 2-norbornene and 2-ethylhexyl acrylate as the compound of the present invention and the compound of the formula (2), respectively.

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 90 g of propylene glycol monomethyl ether acetate, 90 g of propylene glycol monomethyl ether, and nitrogen in air in a flask, followed by azobisisobutyl 8.2 g of ronitryl, 4.7 g of 2-norbornene, 55.2 g of 2-ethylhexyl acrylate, 5.9 g of 4-methylstyrene, 85.2 g of glycidyl methacrylate and 6.0 g of n-dodecanethiol. Thereafter, the temperature of the reaction solution was raised to 80 DEG C with stirring, and the reaction was carried out for 4 hours.

After the temperature of the reaction solution was lowered to room temperature and the atmosphere of the flask was replaced with air in nitrogen, 0.2 g of triethylamine, 0.1 g of 4-methoxyphenol and 43.2 g of acrylic acid were added to the dropping funnel together with 136 g of propylene glycol monomethyl ether acetate for 2 hours Followed by reaction at 100 ° C for 6 hours. Thereafter, the temperature of the reaction solution was lowered to room temperature, 12.5 g of succinic anhydride was added, and the mixture was reacted at 80 ° C for 6 hours.

The solid dispersion weight of the alkali-soluble resin thus synthesized was 69.6 mgKOH / g, and the weight average molecular weight Mw measured by GPC was about 6370

The glass transition temperature was measured with a differential scanning calorimeter and found to be -25.3 ° C.

&Lt; Synthesis Example 3 &

An alkali-soluble resin was synthesized as follows using 2-norbornene and n-butyl acrylate as the compound of the present invention and the compound of the formula (2) as follows.

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 90 g of propylene glycol monomethyl ether acetate, 90 g of propylene glycol monomethyl ether, and nitrogen in air in a flask, followed by azobisisobutyl 8.2 g of ronitryl, 4.7 g of 2-norbornene, 38.4 g of n-butyl acrylate, 5.9 g of 4-methylstyrene, 85.2 g of glycidyl methacrylate and 6.0 g of n-dodecanethiol. Thereafter, the temperature of the reaction solution was raised to 80 DEG C with stirring, and the reaction was carried out for 4 hours.

After the temperature of the reaction solution was lowered to room temperature and the atmosphere of the flask was replaced with air in nitrogen, 0.2 g of triethylamine, 0.1 g of 4-methoxyphenol and 43.2 g of acrylic acid were added to the dropping funnel together with 136 g of propylene glycol monomethyl ether acetate for 2 hours Followed by reaction at 100 ° C for 6 hours. Thereafter, the temperature of the reaction solution was lowered to room temperature, 6.0 g of succinic anhydride was added, and the mixture was reacted at 80 DEG C for 6 hours.

The solid dispersion weight of the alkali-soluble resin thus synthesized was 37.2 mgKOH / g, and the weight average molecular weight Mw measured by GPC was about 5870

The glass transition temperature was -8.3 ℃ as measured by a differential scanning calorimeter.

&Lt; Synthesis Example 4 &

An alkali-soluble resin was synthesized as follows using 2-norbornene and n-hexadecyl acrylate as the compound of the present invention and the compound of the formula (2) as follows.

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 90 g of propylene glycol monomethyl ether acetate, 90 g of propylene glycol monomethyl ether, and nitrogen in air in a flask, followed by azobisisobutyl 8.2 g of ronitryl, 4.7 g of 2-norbornene, 88.8 g of n-hexadecyl acrylate, 5.9 g of 4-methylstyrene, 85.2 g of glycidyl methacrylate and 6.0 g of n-dodecanethiol. Thereafter, the temperature of the reaction solution was raised to 80 DEG C with stirring, and the reaction was carried out for 4 hours.

After the temperature of the reaction solution was lowered to room temperature and the atmosphere of the flask was replaced with air in nitrogen, 0.2 g of triethylamine, 0.1 g of 4-methoxyphenol and 43.2 g of acrylic acid were added to the dropping funnel together with 136 g of propylene glycol monomethyl ether acetate for 2 hours Followed by reaction at 100 ° C for 6 hours. Thereafter, the temperature of the reaction solution was lowered to room temperature, 6.0 g of succinic anhydride was added, and the mixture was reacted at 80 DEG C for 6 hours.

The solid dispersion weight of the alkali-soluble resin thus synthesized was 38.0 mgKOH / g, and the weight average molecular weight Mw measured by GPC was about 7530

As a result of measuring the glass transition temperature with a differential scanning calorimeter, it was -45.0 ° C.

&Lt; Synthesis Example 5 &

An alkali-soluble resin was synthesized as follows using 2-norbornene and n-hexadecyl acrylate as the compound of the present invention and the compound of the formula (2) as follows.

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 90 g of propylene glycol monomethyl ether acetate, 90 g of propylene glycol monomethyl ether, and nitrogen in air in a flask, followed by azobisisobutyl 8.2 g of ronitryl, 9.4 g of 2-norbornene, 88.8 g of n-hexadecyl acrylate, 85.2 g of glycidyl methacrylate and 6.0 g of n-dodecanethiol are introduced. Thereafter, the temperature of the reaction solution was raised to 80 DEG C with stirring, and the reaction was carried out for 4 hours.

After the temperature of the reaction solution was lowered to room temperature and the atmosphere of the flask was replaced with air in nitrogen, 0.2 g of triethylamine, 0.1 g of 4-methoxyphenol and 43.2 g of acrylic acid were added to the dropping funnel together with 136 g of propylene glycol monomethyl ether acetate for 2 hours Followed by reaction at 100 ° C for 6 hours. Thereafter, the temperature of the reaction solution was lowered to room temperature, 6.0 g of succinic anhydride was added, and the mixture was reacted at 80 DEG C for 6 hours.

The solid dispersion weight of the alkali-soluble resin thus synthesized was 36.0 mgKOH / g and the weight average molecular weight Mw measured by GPC was about 6530

The glass transition temperature was -32.1 ℃ as measured by differential scanning calorimetry.

<Comparative Synthesis Example 1>

An alkali-soluble resin in which the compound of Formula 1 and the compound of Formula 2 were not used was synthesized as follows.

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 100 g of propylene glycol monomethyl ether acetate, 120 g of propylene glycol monomethyl ether and nitrogen in air, 3.2 g of ronitryl, 9.4 g of acrylic acid, 35.2 g of benzyl methacrylate, 55.5 g of 4-methylstyrene, 20.0 g of methyl methacrylate and 6.0 g of n-dodecanethiol were charged and replaced with nitrogen. Thereafter, the temperature of the reaction solution was raised to 80 DEG C with stirring, and the reaction was carried out for 8 hours. The alkali-soluble resin thus synthesized had a solid dispersion value of 99.2 mgKOH / g and a weight average molecular weight Mw of about 14560 as measured by GPC.

The glass transition temperature was measured by a differential scanning calorimeter and found to be 98 ° C.

&Lt; Comparative Synthesis Example 2 &

An alkali-soluble resin in which the compound of Formula 1 and the compound of Formula 2 were not used was synthesized as follows.

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 100 g of propylene glycol monomethyl ether acetate, 120 g of propylene glycol monomethyl ether and nitrogen in air, 3.2 g of ronitryl, 9.4 g of acrylic acid, 35.2 g of benzyl methacrylate, 67.3 g of 4-methylstyrene, 10.0 g of methyl methacrylate and 6.0 g of n-dodecanethiol were charged and replaced with nitrogen. Thereafter, the temperature of the reaction solution was raised to 80 DEG C with stirring, and the reaction was carried out for 8 hours. The alkali-soluble resin thus synthesized had a solid dispersion value of 83.2 mgKOH / g and a weight-average molecular weight Mw of about 17305 as measured by GPC.

The glass transition temperature was measured with a differential scanning calorimeter and found to be 87 ° C.

&Lt; Comparative Synthesis Example 3 >

An alkali-soluble resin in which the compound of Formula 1 and the compound of Formula 2 were not used was synthesized as follows.

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 100 g of propylene glycol monomethyl ether acetate, 120 g of propylene glycol monomethyl ether and nitrogen in air, 3.2 g of ronitryl, 3.6 g of acrylic acid, 70.4 g of benzyl methacrylate, 41.3 g of 4-methylstyrene, 20.0 g of methyl methacrylate and 6.0 g of n-dodecanethiol were charged and replaced with nitrogen. Thereafter, the temperature of the reaction solution was raised to 80 DEG C with stirring, and the reaction was carried out for 8 hours. The alkali-soluble resin thus synthesized had a solid dispersion value of 17.2 mgKOH / g and a weight average molecular weight Mw of about 17702 as measured by GPC.

The glass transition temperature was measured with a differential scanning calorimeter and found to be 80 ° C.

&Lt; Comparative Synthesis Example 4 >

An alkali-soluble resin in which the compound of formula (1) of the present application (2-norbornene) was used and the compound of formula (2) was not used was synthesized as follows.

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 100 g of propylene glycol monomethyl ether acetate, 120 g of propylene glycol monomethyl ether and nitrogen in air, 3.2 g of ronitryl, 9.4 g of acrylic acid, 9.4 g of 2-norbornene, 52.8 g of benzyl methacrylate, 43.7 g of 4-methylstyrene, 10.0 g of methyl methacrylate and 6.0 g of n-dodecanethiol were charged and replaced with nitrogen . Thereafter, the temperature of the reaction solution was raised to 80 DEG C with stirring, and the reaction was carried out for 8 hours. The alkali-soluble resin thus synthesized had a solid dispersion value of 100.3 mgKOH / g and a weight-average molecular weight Mw of about 15340 as measured by GPC. The glass transition temperature was measured with a differential scanning calorimeter and found to be 110 ° C.

&Lt; Comparative Synthesis Example 5 >

An alkali-soluble resin, which was prepared by using n-butyl acrylate as the compound of Formula 2 and not using the compound of Formula 1, was synthesized as follows.

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen-introducing tube was charged with 150 g of propylene glycol monomethyl ether acetate, 70 g of propylene glycol monomethyl ether, and nitrogen in air in a flask to prepare an azobisisobutyl 3.2 g of ronitryl, 9.4 g of acrylic acid, 51.2 g of n-butyl acrylate, 43.7 g of 4-methylstyrene, 10.0 g of methyl methacrylate and 6.0 g of n-dodecanethiol were charged and replaced with nitrogen. Thereafter, the temperature of the reaction solution was raised to 80 DEG C with stirring, and the reaction was carried out for 8 hours. The alkali-soluble resin thus synthesized had a solid dispersion value of 102.0 mgKOH / g and a weight average molecular weight Mw of about 8760 as measured by GPC.

The glass transition temperature was -40 ° C as measured by a differential scanning calorimeter.

Examples and Comparative Examples

The colored photosensitive resin compositions of Examples and Comparative Examples were prepared by mixing the colorant (A), the alkali-soluble resin (B), the photopolymerizable compound (C), the photopolymerization initiator (D) and the solvent (E) Respectively.

division
(weight%) The alkali-soluble resin (B) Photopolymerization
The compound (C) Light curing
Initiator (D) The colorant (A) solvent
(E) ingredient content Tg (占 폚) ingredient content Example 1 A-1 10.9 -18 3.6 0.9 M1 39.8 44.8 Example 2 A-2 10.9 -25.3 3.6 0.9 M1 39.8 44.8 Example 3 A-3 10.9 -8.3 3.6 0.9 M1 39.8 44.8 Example 4 A-4 10.9 -45.0 3.6 0.9 M1 39.8 44.8 Example 5 A-5 10.9 -32.1 3.6 0.9 M1 39.8 44.8 Comparative Example 1 A-6 10.9 98 3.6 0.9 M1 39.8 44.8 Comparative Example 2 A-1 10.9 -18 3.6 0.9 M2 39.8 44.8 Comparative Example 3 A-7 10.9 87 3.6 0.9 M2 39.8 44.8 Comparative Example 4 A-8 10.9 80 3.6 0.9 M2 39.8 44.8 Comparative Example 5 A-9 10.9 110 3.6 0.9 M1 39.8 44.8 Comparative Example 6 A-10 10.9 -40 3.6 0.9 M1 39.8 44.8 A-1: An alkali-soluble resin of Synthesis Example 1
A-2: An alkali-soluble resin of Synthesis Example 2
A-3: An alkali-soluble resin of Synthesis Example 3
A-4: An alkali-soluble resin of Synthesis Example 4
A-5: An alkali-soluble resin of Synthesis Example 5
A-6: An alkali-soluble resin of Comparative Synthesis Example 1
A-7: An alkali-soluble resin of Comparative Synthesis Example 2
A-8: An alkali-soluble resin of Comparative Synthesis Example 3
A-9: The alkali-soluble resin of Comparative Synthesis Example 4
A-10: The alkali-soluble resin of Comparative Synthesis Example 5

C: PBG-305 (manufactured by Tronis)
M1: Pigment dispersion composition of Production Example
M2: Pigment dispersion composition of Production Example
E: Propylene glycol monomethyl ether acetate (27.8 wt%) + 4-hydroxy-4-methyl-2-pentanone (17.0 wt%

Experimental Example

Experimental Example  1: Manufacture of color filter and evaluation of development speed and adhesion

(1) Manufacture of color filters

A color filter was prepared using the colored photosensitive resin compositions prepared in the above Examples and Comparative Examples.

Specifically, each of the above colored photosensitive resin compositions was applied on a 2-inch-square glass substrate ("EAGLE XG", manufactured by Corning Inc.) by spin coating, then placed on a heating plate and held at a temperature of 100 ° C. for 3 minutes to form a thin film . Subsequently, a test photomask having a pattern for changing the transmittance in the range of 1 to 100% in a stepwise manner and a line / space pattern of 1 to 100 m was placed on the thin film, and the interval between the test photomask and the test photomask was set to 300 [ Respectively. At this time, the ultraviolet light source was irradiated with a high pressure mercury lamp of 1 KW containing g, h and i lines at an illuminance of 60 mJ / cm 2, and no special optical filter was used. The thin film irradiated with ultraviolet rays was immersed in a KOH aqueous solution of pH 10.5 for 2 minutes to develop. The glass plate coated with the thin film was washed with distilled water, 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 2.4 占 퐉.

(2) Evaluation of development speed

The color filter was evaluated for the developing speed in the following manner.

The time (developing rate) required for the non-exposed portion to completely dissolve in the developer during development in the above process was measured and described in Table 2 below.

(3) Evaluation of adhesion

The color filter was evaluated for adhesion by the following method.

The resultant pattern was evaluated by an optical microscope, and the result was evaluated in terms of the degree of grazing phenomenon of the following 20 탆 pattern, and it is shown in Table 2 below.

<Evaluation Criteria>

○: No pattern peeling

△: 1 to 3 pattern peeling

X: Pattern peeling 4 or more

Experimental Example  2: Manufacture of color filter and evaluation of transmittance

Test A color filter was prepared in the same manner as in Experimental Example 1 except that the photomask was not used. Then, the transmittance (%) was measured in the following manner.

Among the formed patterns, a line pattern portion of 100 mu m was measured using a colorimeter (OSP-200, manufactured by Olympus Corporation) and is shown in Table 2 below.

Experimental Example  3: Manufacture of color filter and evaluation of heat resistance

A color filter was prepared in the same manner as in Experimental Example 1. Thereafter, the heat resistance (DELTA E * ab) was measured in the following manner.

The heat resistance was measured at 230 DEG C for 120 minutes before and after the color change.

division Development speed (s) Adhesiveness Transmittance (Relative transmittance value) * Heat resistance Example 1 12 ○ 13.8 103.6814425 2.1 Example 2 9 ○ 13.77 103.4560481 2.3 Example 3 15 ○ 13.79 103.606311 2.2 Example 4 24 △ 13.75 103.3057851 2.5 Example 5 24 △ 13.75 103.3057851 2.5 Comparative Example 1 42 △ 13.53 101.6528926 4.3 Comparative Example 2 15 ○ 13.42 100.8264463 2.3 Comparative Example 3 55 X 13.31 100 4.5 Comparative Example 4 78 X 13.35 100.3005259 6.0 Comparative Example 5 60 △ 13.56 101.878287 4.5 Comparative Example 6 60 △ 13.70 7.0

* The value obtained by converting 13.31 of Comparative Example 3 into 100

Referring to Table 2, the colored photosensitive resin composition (Example 1-5) according to the present invention exhibited excellent adhesion even at a very high developing speed, and also had a high transmittance and excellent heat resistance, It was confirmed that it is suitable for manufacturing.

Particularly, when the development speed is less than 25 seconds, the color filter manufacturing process time is shortened, and when the pattern cut-off is less than 3, the yield of the color filter is improved. When the transmittance is 13.7 or more, And the heat resistance is 2.5 or less, it is possible to minimize the occurrence of defects due to the color change in the additional thermal process.

In the case of the transmittance, even if a difference of only 1% is exerted, the lightness of the color filter greatly affects the lightness. Therefore, the improvement of the transmittance is a very important characteristic indicating the quality of the photosensitive resin composition. And the transmittance was improved.

Claims (9)

A colored photosensitive resin composition comprising a colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D) and a solvent (E)
Wherein the colorant (A) comprises a dye, and the alkali-soluble resin (B) comprises a compound represented by the following Chemical Formula 1 and Chemical Formula 2, and the glass transition temperature is less than 0 占 폚.
[Chemical Formula 1]

Wherein R ₁ and R ₂ are each independently hydrogen or an aliphatic or aromatic hydrocarbon with or without a C1 to C12 heteroatom, and R ₃ to R ₆ are independently selected from the group consisting of Each independently hydrogen or an aliphatic or aromatic hydrocarbon containing or not containing a C1 to C30 heteroatom, and two of R ₃ to R ₆ may be linked to form a ring.
(2)

Wherein R _{7 is} independently hydrogen or an aliphatic or aromatic hydrocarbon containing or not containing a C1 to C12 heteroatom and R ₈ is a substituted or unsubstituted linear or branched alkyl group having from 2 to 30 carbon atoms .)
The colored photosensitive resin composition according to claim 1, wherein the compound represented by the formula (1) is any one of the following compounds.

The colored photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (B) further comprises a compound represented by the following formula (3).
(3)

(Wherein p is an integer of 1 to 100, R ₉ is a residue containing a carboxylic acid derived from an acid anhydride, and R ₁₀ and R ₁₁ are each independently hydrogen or a methyl group.)
4. The method of claim 3, wherein the acid anhydride is selected from the group consisting of phthalic anhydride, (2-dodecen-1-yl) succinic anhydride, maleic anhydride, Succinic anhydride, citraconic anhydride, glutaric anhydride, methylsuccinic anhydride, 3,3-dimethylglutaric anhydride, and the like. ), Phenylsuccinic anhydride, itaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, trimellitic anhydride, an anhydride, a hexahydrophthalic anhydride, and a carbic anhydride. The colored photosensitive resin composition according to claim 1,
The positive resist composition according to claim 1, wherein the alkali-soluble resin (B) comprises, relative to 100 mol% of the alkali-soluble resin (B)
2 to 20 mol% of units derived from the above formula (1)
2 to 70 mol% of the constitutional unit derived from the above formula (2), and
And 10 to 90 mol% of the constitutional unit derived from the above formula (3).
The photosensitive resin composition according to claim 1, wherein, based on the total weight of the solid content of the colored photosensitive resin composition,
5 to 60% by weight of the colorant (A);
5 to 80% by weight of an alkali-soluble resin (B);
1 to 60% by weight of a photopolymerizable compound (C); And
And 0.1 to 40% by weight of a photopolymerization initiator (D)
And 60 to 90% by weight of a solvent (E) based on the total weight of the colored photosensitive resin composition.
The method according to claim 1,
And at least one additive selected from other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers and antiflocculating agents.
A color filter produced by using the colored photosensitive resin composition of any one of claims 1 to 7.
A liquid crystal display device comprising the color filter of claim 8.