KR20150093331A - A color photosensitive resin composition, color filter and display device comprising the same - Google Patents

Abstract

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored photosensitive resin composition, a color filter including the same, and a display device. More particularly, the present invention relates to a colored photosensitive resin composition having high sensitivity to a 405 nm single wavelength laser beam exposure apparatus, .

Description

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

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored photosensitive resin composition, a color filter including the same, and a display device. More particularly, the present invention relates to a colored photosensitive resin composition having high sensitivity to a 405 nm single wavelength laser beam exposure apparatus, .

BACKGROUND ART [0002] Color filters are widely used in imaging elements, liquid crystal displays (LCDs), and the like, and their application range is rapidly expanding. A color filter used in a color liquid crystal display device, an image pickup device, or the like is a device in which a colored photosensitive resin composition containing a pigment corresponding to each color of red, green and blue is uniformly applied by spin coating on a substrate on which a black matrix is pattern- (Hereafter also referred to as "post-baking") is carried out for each color, if necessary, by exposing and developing the coating film formed by heating and drying And then repeatedly forming pixels of each color. Here, the black matrix on which the pattern is formed is usually formed of a black photosensitive resin composition.

As such a colored photosensitive resin composition, a composition containing a photopolymerizable compound and a photopolymerization initiator together with a pigment and a binder resin is widely used.

Recently, a colored photosensitive resin composition having a sensitivity and an adhesiveness equivalent to each other at a low exposure dose has been required to improve yield in the process.

 In addition, coloring materials of recent colored photosensitive resin compositions are becoming more and more minute to satisfy required performance such as high color purity and high brightness. Therefore, the coloring layer formed on the background when the pixels are formed by using them has a problem of a residue of development which is not removed during development. Conventional techniques for solving this problem are generally used for adjusting the acid value and molecular weight of the binder resin or the method for adjusting the acid value of the binder resin and the composition. However, when the acid value is too high, And the residue remaining on the metal oxide film or the silicon nitride film is difficult to be solved.

Korean Patent No. 10-1222390

The present invention relates to a process for producing a colored photosensitive resin composition by using an alkali-soluble resin having the following formula (1), a photopolymerization initiator containing the following formula (2), and a color filter using the colored photosensitive resin composition, It is an object of the present invention to provide such an excellent color filter.

In order to achieve the above object,

The present invention provides a colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, wherein the alkali-soluble resin comprises the following structural formula (1) The absorbance of the solution containing the photopolymerization initiator at a concentration of 0.01% or more is 0.5 or more at 405 nm, and the solvent comprises 4-hydroxy-4-methyl-2-pentanone.

[Chemical Formula 1]

(2)

R < ₁ > is hydrogen, a methyl group or a hydroxymethyl group,

Each of R ₂ to R ₉ is independently selected from the group consisting of hydrogen, a halogen group, an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms substituted with at least one alkoxy group, an alkyl group having 1 to 20 carbon atoms substituted with at least one aryl group, To 20 carbon atoms or a cyclic hydrocarbon having 3 to 20 carbon atoms,

R ₁₀ is an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms in which one hydrogen atom is substituted with OR ₁₂ or a halogen group, or an aryl group having 7 to 10 carbon atoms substituted with at least one substituent selected from the group consisting of OR ₁₂ and a halogen group Lt; / RTI > to 24,

R ₁₁ is an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an arylalkyl group having 7 to 24 carbon atoms,

R ₁₂ is an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms,

X is a linear or branched type of the following formula (3) or a linear or branched type of the following formula (4)

(3)

-C _n H _2n -

[Chemical Formula 4]

-CO- (OC _m H _2m ) _1-

And l, m and n are integers of 0 or more.

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

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

The colored photosensitive resin composition of the present invention is an alkali-soluble resin and contains a photopolymerization initiator represented by Chemical Formula 1 as a photopolymerization initiator and exhibits a high sensitivity upon exposure with a single wavelength of 405 nm including Formula 2, and has an excellent pattern formation effect.

In addition, the color filter manufactured from the colored photosensitive resin composition has excellent adhesion, pattern line width, and solvent resistance, so that the productivity can be improved in the process of manufacturing the color filter, and a color filter having high reliability can be manufactured.

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

The present invention provides a colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, wherein the alkali-soluble resin comprises the following structural formula (1) The absorbance of a solution containing a photopolymerization initiator at a concentration of 0.01% or more is 0.5 or more at 405 nm, and the solvent includes 4-hydroxy-4-methyl-2-pentanone.

[Chemical Formula 1]

(2)

R < ₁ > is hydrogen, a methyl group or a hydroxymethyl group,

Each of R ₂ to R ₉ is independently selected from the group consisting of hydrogen, a halogen group, an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms substituted with at least one alkoxy group, an alkyl group having 1 to 20 carbon atoms substituted with at least one aryl group, To 20 carbon atoms or a cyclic hydrocarbon having 3 to 20 carbon atoms,

Wherein R ₁₀ is one or more selected from an aryl group, or OR _12, and the group consisting of a halogen having 6 to 10 carbon atoms substituted with one or more substituents selected from the group consisting of a alkyl group, OR _12, halogen having 1 to 8 carbon atoms An arylalkyl group having 7 to 24 carbon atoms substituted with a substituent,

R ₁₁ is an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an arylalkyl group having 7 to 24 carbon atoms,

R ₁₂ is an alkyl group of 1 to 20 carbon atoms substituted with an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 8 carbon atoms,

X is a linear or branched type of the following formula (3) or a linear or branched type of the following formula (4)

(3)

-C _n H _2n -

[Chemical Formula 4]

-CO- (OC _m H _2m ) _1-

And l, m and n are integers of 0 or more.

In the present invention, the use of the alkali-soluble resin having the formula (1) can improve the adhesion and reliability of the colored photosensitive resin composition. When the photopolymerization initiator having the formula 2 is used, the absorbance of the solution containing the photopolymerization initiator at a concentration of 0.01% or more becomes 0.5 or more at 405 nm. When the pattern is formed by exposure with a 405 nm laser exposure apparatus, High efficiency and high sensitivity and excellent reliability of the colored photosensitive resin composition can be obtained without using an excessive amount of a photopolymerization initiator. Further, the solubility of the photopolymerization initiator can be increased by using a solvent containing 4-hydroxy-4-methyl-2-pentanone.

Hereinafter, the colored photosensitive resin composition of the present invention will be described in detail for each component.

(A) Colorant

The colorant is characterized in that it comprises at least one pigment, at least one dye or a mixture thereof.

( a1 ) Pigment

The pigment may be an organic pigment or an inorganic pigment generally used in the art. The pigment may be subjected to a surface treatment using a pigment treatment, a pigment derivative into which an acidic group or a basic group is introduced, a graft treatment of the surface of the pigment with a polymer compound, an atomization treatment using a sulfuric acid atomization method or the like, A cleaning treatment with an organic solvent or water, or a treatment for removing ionic impurities by ion exchange or the like.

The organic pigments may be various pigments used in printing ink, ink jet ink, etc. Specific examples thereof include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, A pyranthrone pigment, a diketopyrrolopyrrole pigment, an anthraquinone pigment, an anthraquinone pigment, an anthrone pigment, an anthrone pigment, an indanthrone pigment, a pravanthrone pigment, a pyranthrone pigment, a diketopyrrolopyrrole pigment And the like.

As the inorganic pigment, metal compounds such as metal oxides and metal complex salts can be used. Specific examples of the inorganic pigments include iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, A black pigment, a titanium black, and an oxide of a metal such as a pigment that mixes red, green, and blue to give a black color, or a composite metal oxide.

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;

And C.I. Pigment Black 1 and 7 pigments.

Preferably C.I. Pigment Yellow 138, 139, 150, 185; C. I. Pigment Orange 38; C.I. Pigment Red 255; C.I. Pigment Violet 23; C.I. Pigment Blue 15: 3, 15: 6; And C.I. Pigment Green 7, 36, and 58 are used.

The pigment is preferably a pigment dispersion in which the particle diameter of the pigment is uniformly dispersed. Examples of a method for uniformly dispersing the particle diameter of the pigment include a method of dispersing the pigment dispersion (a2) by containing the pigment dispersant (a2), and a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained have.

( a2 ) Pigment Dispersant

The pigment dispersant is added for deaggregation of the pigment and maintenance of stability. Specific examples of the pigment dispersant include a cationic surfactant, an anionic surfactant, a nonionic surfactant, a positive surfactant, a polyester surfactant, and a polyamine surfactant. , Which may be used alone or in combination of two or more.

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts.

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, alkylsulfates such as sodium laurylsulfate and ammonium laurylsulfate, sodium dodecylbenzenesulfonate, And alkylarylsulfonic acid salts such as sodium dodecylnaphthalenesulfonate.

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.

In addition, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines have.

Also, the pigment dispersant preferably includes an acrylate-based dispersant (hereinafter referred to as an acrylate-based dispersant) containing butyl methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA). Examples of commercially available acrylate dispersants include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070 and DISPER BYK-2150. The acrylate dispersants may be used alone or in combination of two or more. .

As the pigment dispersant, other resin type pigment dispersants other than the acrylate 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-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, and DISPER BYK-160 available from BYK (Big) Chemie are examples of commercially available pigment dispersants of other resin types. BYK-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 acrylate-based 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 acrylate-based dispersant.

The pigment dispersant is contained in an amount of 5 to 60 parts by weight, preferably 15 to 50 parts by weight, based on 100 parts by weight of the solid content in the pigment. If the content of the pigment dispersant is more than 60 parts by weight, the viscosity of the pigment becomes high. If the content of the pigment dispersant is less than 5 parts by weight, it may be difficult to atomize the pigment and cause gelation after dispersion.

( a3 )dyes

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

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

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

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

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

C.I. Solvent Violet 8, 9, 13, 14, 36, 37, 47 and 49;

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

C.I. Solvent Orange 2, 7, 11, 15, 26 and 56;

C.I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34 and 35.

The C.I. Among the solvent dyes, C.I. Solvent Red 8, 49, 89, 111, 122, 132, 146 and 179; C.I. Solvent Blue 35, 36, 44, 45 and 70; C.I. Solvent violet 13 is excellent in solubility in an organic solvent, and preferably C.I. Solvent Red 8, 122 and 132, respectively.

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, 195, 198, 206, 211, 215, 216 , 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 308, 312, 315, 316, 339, 341, 345, 346, 349 , 382, 383, 394, 401, 412, 417, 418, 422 and 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 , 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243 and 251;

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

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

C.I. Acid Violet 6B, 7, 9, 17, 19 and 66;

Dyes such as C.I. Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106 and 109.

CI Acid Red 92 in the above CI acid dyes; C. I. Acid Blue 80, 90; And C.I. Acid Violet 60 are excellent in solubility in an organic solvent.

Further, 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 and 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 , 136, 138 and 141;

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

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

Dyes such as C.I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79 and 82

Also, as C.I. modantoic dyes,

CI. Modetto Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62 and 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, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94 and 95;

C. I. Modanto orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47 and 48;

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;

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

Dyes such as C.I. Modatto Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43 and 53.

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

The content of the dye in the colorant is 0.5 to 80% by weight, preferably 0.5 to 60% by weight, and more preferably 1 to 50% by weight based on the total weight of the solid content of the colorant. If the content of the dye in the colorant is in the range of 0.5 to 80% by weight, the problem of lowering the reliability of dye elution by the organic solvent after the pattern formation can be prevented, and the sensitivity is increased.

The content of the colorant is 5 to 60% by weight, preferably 10 to 45% by weight based on the total weight of the solid content of the colored photosensitive resin composition. When the colorant is included in the amount of 5 to 60% by weight, the color density of the pixel is sufficient when the thin film is formed, and the residue of the non-decomposed part is not deteriorated during the development.

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

(B) an alkali-soluble resin

The alkali-soluble resin, which is one of the colored photosensitive resin compositions of the present invention, is a copolymer necessarily containing the following formula (1), and is used together with a copolymer of a monomer containing a carboxyl group and another monomer copolymerizable with the monomer containing a carboxyl group do.

[Chemical Formula 1]

R < ₁ > is hydrogen, a methyl group or a hydroxymethyl group,

Each of R ₂ to R ₉ is independently selected from the group consisting of hydrogen, a halogen group, an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms substituted with at least one alkoxy group, an alkyl group having 1 to 20 carbon atoms substituted with at least one aryl group, To 20 carbon atoms or a cyclic hydrocarbon having 3 to 20 carbon atoms,

X is a linear or branched type of the following formula (3) or a linear or branched type of the following formula (4)

(3)

-C _n H _2n -

[Chemical Formula 4]

-CO- (OC _m H _2m ) _1-

And l, m and n are integers of 0 or more.

The compound represented by Chemical Formula 1 is characterized by containing a carbazole group. Examples of the compound represented by Chemical Formula 1 include N-vinylcarbazole, N-arylcarbazole, N-methacryloylcarbazole, N- (1-methylethyl) carbazole, calbazoyl ethyl acureate, calbazoyl ethylmethacrylate, calbazoyltoxime ethyl acureate, calbazoyltoxime ethyl methacrylate, (2-methylethyl) acrylate, calbazoyl (1-methylethyl) methacrylate and calbazoyl (2-methylethyl) methacrylate. In the present invention, Is used as the alkali-soluble resin (1). Among these compounds, preferred are N-vinylcarbazole, N-arylcarbazole, calbazoylethylcarrinate, calbazoylethylmethacrylate, calbazoyl (1-methylethyl) acrylate, It is preferable to use at least one member selected from the group consisting of 2-methylethyl acrylate, calbazoyl (1-methylethyl) methacrylate and calbazoyl (2-methylethyl) methacrylate.

The formula 1 is contained in an amount of 5 to 50% by weight, preferably 10 to 40% by weight, and more preferably 25 to 40% by weight based on the total weight of the alkali-soluble resin in the colored photosensitive resin composition. If the formula 1 is contained in an amount of 5 to 50% by weight based on the total weight of the alkali-soluble resin, the adhesion and reliability of the colored photosensitive resin composition can be improved.

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

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

Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid and mesaconic acid.

The unsaturated polycarboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride and citraconic anhydride. The unsaturated polycarboxylic acid may also be mono (2-methacryloyloxyalkyl) ester, and examples thereof include mono (2-acryloyloxyethyl) succinate, mono (2-methacryloyloxyethyl) ), Phthalic acid mono (2-acryloyloxyethyl), and phthalic acid mono (2-methacryloyloxyethyl). The unsaturated polycarboxylic acid may be a mono (meth) acrylate of a dicarboxylic polymer at both ends, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. . The carboxyl group-containing monomers may be used alone or in combination of two or more.

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

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

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

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

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

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

Unsaturated imides such as maleimide, N-phenylmaleimide and N-cyclohexylmaleimide;

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

Having a monoacryloyl group or monomethacryloyl group at the end of the polymer molecular chain of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate and polysiloxane Macromers and the like. These monomers may be used alone or in combination of two or more.

The other monomer copolymerizable with the carboxyl group-containing monomer is contained in an amount of 10 to 50% by weight based on the total weight of the constituent units of the copolymer of the carboxyl group-containing monomer and the other monomer copolymerizable with the carboxyl group-containing monomer By weight, preferably 15 to 40% by weight, more preferably 25 to 40% by weight. When 10 to 50% by weight of the other monomer capable of copolymerizing with the carboxyl group-containing monomer is contained in the above-described standard, solubility in a developing solution is good, and a pattern is accurately formed upon development.

The carboxyl group-containing monomer is also contained in an amount of 10 to 50% by weight based on the total weight of the constituent units of the copolymer of the carboxyl group-containing monomer and the other monomer copolymerizable with the carboxyl group-containing monomer, 15 to 40% by weight, and more preferably 25 to 40% by weight.

The alkali-soluble resin, which is one of the colored photosensitive resin compositions of the present invention, is contained in an amount of 1 to 60% by weight, preferably 5 to 50% by weight based on the total weight of the solid content of the colored photosensitive resin composition. When the alkali-soluble resin is contained in the amount of 1 to 60% by weight, the solubility becomes good and the pattern formation becomes excellent.

(C) Photopolymerization  compound

The photopolymerizable compound which is one of the colored photosensitive resin compositions of the present invention should be a compound capable of polymerizing under the action of the photopolymerization initiator (D) described later. The number of functional groups of the photopolymerizable compound is not particularly limited, but a bifunctional or higher functional photopolymerizable compound is preferable. When trifunctional or more functional groups are used, polymerizable trifunctional or higher functional groups can be sufficiently cured, It is more preferable to use it.

The bifunctional photopolymerizable compound includes, for example, 2-hydroxy-1,3-dimethacryloxypropane and 2-hydroxy-1-acryloxy-3-methacryloxypropane.

The above-mentioned trifunctional or more polyfunctional photopolymerizable compound is, for example, pentaerythritol triacrylate and dipentaerythritol pentaacrylate, and they may be used in combination of two or more. Commercially available products include 701 (NK ESTER), 701A (NK ESTER), A-TMM-3L (NK ESTER) and KAYARAD DPHA (Nippon Kayaku).

The photopolymerizable compound is contained in an amount of 5 to 45% by weight, and preferably 7 to 45% by weight based on the total weight of the solid content of the colored photosensitive resin composition of the present invention. The photopolymerizable compound can improve the strength and flatness of the pixel portion in the range of 5 to 45% by weight.

(D) Light curing Initiator

The photopolymerization initiator of the present invention is characterized by containing an oxime ester compound in which NO ₂ is substituted with an ethyl carbazole structure represented by the following general formula (2). The photopolymerization initiator of the present invention is characterized in that the absorbance of the solution containing the photopolymerization initiator at a concentration of 0.01% or more is 0.5 or more at 405 nm. The solvent for dissolving the photopolymerization initiator should be one which can dissolve the photopolymerization initiator more effectively. Examples of the solvent include propylene glycol methyl ether acetate, 1,2-propylene glycol diacetate, 3-methoxybutyl acetate, propylene glycol methyl ether, 3-ethoxypropionate, and dipropylene glycol monomethyl ether acetate. It is preferable to use propylene glycol methyl ether acetate.

(2)

Wherein R ₁₀ is one or more selected from an aryl group, or OR _12, and the group consisting of a halogen having 6 to 10 carbon atoms substituted with one or more substituents selected from the group consisting of a alkyl group, OR _12, halogen having 1 to 8 carbon atoms An arylalkyl group having 7 to 24 carbon atoms substituted with a substituent,

R ₁₁ is an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an arylalkyl group having 7 to 24 carbon atoms,

R ₁₂ is an alkyl group having 1 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms substituted with an alkoxy group having 1 to 8 carbon atoms.

When the absorbance of the solution containing the photopolymerization initiator (Formula 2) at a concentration of 0.01% is 0.5 or more at 405 nm, when the pattern of the color filter is formed by exposure with a single wavelength exposing device of 405 nm, the initiation efficiency is increased, Excellent sensitivity and reliability of the colored photosensitive resin composition can be obtained without using an initiator.

Further, other photopolymerization initiators than those described above may be further used within the scope of not impairing the effects of the present invention. The photopolymerization initiator that can be further used includes, for example, at least one compound selected from the group consisting of an acetophenone compound, a benzophenone compound, a triazine compound, a nonimidazole compound, and a thioxanone compound .

The acetophenone-based compounds include, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- (4-methylthioxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2- 2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1-one, 1-one and 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.

The benzophenone compound may be, for example, 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.

Examples of the triazine-based compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4- (Trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) Bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) -Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- Azine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine and 2,4- Methyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

The non-imidazole compound may be, for example, 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 and imidazole compounds wherein the phenyl group at the 4,4', 5,5 'position is substituted by a carboalkoxy group . Among the imidazole compounds, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- 4,4 ', 5,5'-tetraphenylbiimidazole and 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole Is preferably used.

The thioxanthone compound may be, for example, 2-isopropylthioxanecone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone and 1-chloro-4- .

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

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.

The amine compounds include, for example, aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine; 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4- Aromatic amine compounds such as bis (dimethylamino) benzophenone (commonly known as Michler's ketone) and 4,4'-bis (diethylamino) benzophenone, and aromatic amine compounds are used as the amine compounds .

The carboxylic acid compound is, for example, selected from the group consisting of phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, , And aromatic heteroacetic acids such as dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid.

The organic sulfur compounds having thiol groups include, for example, 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), tetraethylene glycol bis (3-mercaptopropionate), and the like can be used. .

In the present invention, the photopolymerization initiator may be included in the colored photosensitive resin composition of the present invention in an amount of 0.1 to 30% by weight, preferably 1 to 20% by weight based on the total weight of the solid content. When the photopolymerization initiator is in the range of 0.1 to 30% by weight, the sensitivity of the colored photosensitive resin composition is increased, the exposure time is shortened, productivity is improved, and high resolution can be maintained. In addition, the strength of the pixel portion formed using the colored photosensitive resin composition and the smoothness of the surface of the pixel portion can be improved.

The formula (2) is contained in an amount of 10 to 100% by weight, preferably 20 to 100% by weight based on the total weight of the photopolymerization initiator, which is one of the colored photosensitive resin compositions of the present invention. When the formula (2) is contained in an amount of less than 10% by weight, the sensitivity can not be overcome by the dye, and the pattern is likely to be short-circuited during the development process.

When the photopolymerization initiator is further used, the photopolymerization initiator may be contained in an amount of 0.1 to 30% by weight, preferably 1 to 20% by weight based on the total weight of the solid components in the colored photosensitive resin composition of the present invention. When the content of the photopolymerization initiator is within the range of 0.1 to 30 wt%, the sensitivity of the colored photosensitive resin composition is further increased, and the productivity of the color filter formed using the colored photosensitive resin composition can be improved.

(E) Solvent

The solvent which is one of the colored photosensitive resin compositions of the present invention is characterized by containing 4-hydroxy-4-methyl-2-pentanone.

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

Examples of the ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di Propyl ether and diethylene glycol dibutyl ether.

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

The ketones include, for example, methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone.

Examples of the alcohols include ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin.

Examples of the esters include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methylcellosolve acetate, ethylcellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate Methoxybutyl acetate, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, methyl 3-methoxypropionate, methyl 3-methoxypropionate Propylene glycol, propylene glycol methyl ether acetate, 2-amino-2-methyl-1,3-propanediol, 2-amino- Propylene glycol monobutyl ether, 3-methoxy-1-butyl acetate, ethylene glycol monobutyl ether, diethylene glycol methyl ethyl ether, 1, 2-propylene glycolide Propylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether, gamma butyrolactone, diethylene glycol monoethyl ether acetate, dipropylene glycol Methyl ether acetate, diethylene glycol monobutyl ether, 1,3-butylene glycol diacetate, diethylene glycol monobutyl ether acetate ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol mono Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate, propylene carbonate, and? -Butyrolactone, and the like. Examples of the organic solvent include at least one selected from the group consisting of acetone, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, Rock And the like.

Among the solvents exemplified above, an organic solvent having a boiling point of 100 to 200 DEG C in terms of coatability and dryness is preferable, and examples thereof include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate , Butalactate, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate are used.

The solvents exemplified above may be used alone or in combination of two or more. The solvent is contained in an amount of 60 to 90% by weight, preferably 70 to 85% by weight based on the total weight of the colored photosensitive resin composition of the present invention. When the solvent is contained in the range of 60 to 90% by weight, it is preferable to use a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), a spray coater, And when applied with a coating device such as an inkjet, the coating property is improved.

In addition, 4-hydroxy-4-methyl-2-pentanone, which must necessarily be contained in the solvent, is preferably contained in the colored photosensitive resin composition of the present invention in an amount of 5 to 20% by weight based on the total weight of the solvent. If the content of 4-hydroxy-4-methyl-2-pentanone is less than 5% by weight, the dye in the colored photosensitive resin composition may precipitate and foreign matter may be generated. On the other hand, if the amount exceeds 20% by weight, the dispersibility of the colored photosensitive resin composition decreases and the viscosity increases.

(F) Additive

The additive may be optionally added as needed. For example, the additive may include at least one selected from the group consisting of another polymer compound, a curing agent, a surfactant, an adhesion promoter, an ultraviolet absorber and an anti-

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 and polyurethane .

The above-mentioned curing agent is used for enhancing deep curing and 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 Aliphatic, alicyclic or aromatic epoxy compounds, butadiene (co) polymeric epoxides, isoprene (co) polymers other than the brominated derivatives, epoxy resins and brominated derivatives of the above 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, and cyclohexanedicarboxylic acid bisoxetane.

The curing agent may be used together with a curing agent in combination with a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound.

The curing auxiliary compound 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. Examples of the commercially available products include Adekahadona EH-700 (manufactured by Adeka Kogyo Co., Ltd.), Rikashido HH (manufactured by Shin-Nihon Ehwa Co., Ltd.), and MH-700 (manufactured by Shin-Etsu Chemical Co., Ltd.). The curing agents exemplified above may be used alone or in combination of two or more.

The surfactant can be used for further improving the film formation of the colored photosensitive resin composition, and silicon, fluorine, ester, cationic, anionic, nonionic, amphoteric surfactant and the like can be preferably used.

Examples of the silicone surfactant include DC3PA, DC7PA, SH11PA, SH21PA and SH8400 of Dow Corning Toray Silicone Co., Ltd. as commercial products, and TSF-4440, TSF-4300, TSF-4445, 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.

Other commercially available products include KP (Shinetsugaku Kagaku Kogyo Co., Ltd.), POLYFLOW (Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by TOKEM PRODUCTS CO., LTD.), MEGAFAC Asoui guard, Surflon (available from Asahi Glass Co., Ltd.), SOLSPERSE (Lubrisol) (available from Dainippon Ink and Chemicals Inc.), Flourad (Sumitomo 3M Co., Ltd.) , EFKA (EFKA Chemical), PB 821 (Ajinomoto), and Disperbyk-series (BYK-chemi).

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

The type of the adhesion promoter is not particularly limited and specific examples of the adhesion promoter that can be used include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl Aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, -Glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxy Propyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane. 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 weight of the solid content of the colored photosensitive resin composition.

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

The kind of the anti-aggregation agent is not particularly limited, but specific examples that can be used include sodium polyacrylate and the like.

The process for producing the colored photosensitive resin composition of the present invention is as follows.

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

The dye (a3), the remainder of the alkali-soluble resin (B), the photopolymerizable compound (C), the photopolymerization initiator (D) and, if necessary, the additive (F) and the solvent (E) The colored photosensitive resin composition according to the present invention can be prepared.

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

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

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

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

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

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

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

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

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

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

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to examples. However, the embodiments according to the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of the present invention are provided to enable those skilled in the art to more fully understand the present invention.

<Preparation of pigment dispersion composition>

Manufacturing example  1. Pigment Dispersion Composition ( M1 ) Produce

13.5 parts by weight of CI Pigment Red 254 as a pigment, 5.0 parts by weight of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, 61.5 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and 4 parts by weight of 4-hydroxy- 20 parts by weight were mixed and dispersed by a bead mill for 12 hours to prepare a pigment dispersion composition M1.

Manufacturing example  2. Pigment Dispersion Composition ( M2 ) Produce

, 13.5 parts by weight of CI Pigment Green 58 as a pigment, 5.0 parts by weight of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, 61.5 parts by weight of propylene glycol monomethyl ether acetate as a solvent and 61.5 parts by weight of 4-hydroxy- Were mixed and dispersed for 12 hours by a bead mill to prepare a pigment dispersion composition M2.

Manufacturing example  3. Pigment Dispersion Composition ( M3 ) Produce

13.5 parts by weight of CI Pigment Red 254 as a pigment, 5.0 parts by weight of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, and 81.5 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed and dispersed for 12 hours by a bead mill, Composition M3 was prepared.

Synthetic example  1. Alkali-soluble resin synthesis

37.5 g of methacrylic acid (manufactured by Kyowaisha Chemical Co., Ltd.), 19.0 g of methyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd.), 12.5 g of N-vinylcarbazole (manufactured by Aldrich Co., Ltd.) were added to a four-necked flask equipped with a dropping funnel, a thermometer, g, and 225.0 g of propylene glycol methyl ether (manufactured by TCI), and the inside of the four-necked flask was replaced with nitrogen. Then, the four-necked flask containing the above compounds was heated to 70 DEG C, and 3.2 g of 2,2'-azobisisobutyronitrile (manufactured by Wako Co.) was gradually added to the four-necked flask heated to 70 DEG C over 1 hour . After the dropwise addition, the product was allowed to stand at room temperature. After the inside of the four-necked flask was replaced with nitrogen, 61.5 g of glycidyl methacrylate (manufactured by Mitsubishi Rayon Co., Ltd.) and 60.5 g of tetra-n-butylammonium bromide ) And 0.15 g of methoquinone (manufactured by Junsei Isa Co., Ltd.) were added and reacted at 80 占 폚 for 12 hours to add GMA to the carboxyl group of the copolymer to obtain an alkali-soluble resin. The weight average molecular weight of the alkali-soluble resin measured by GPC was 17,000.

Synthetic example  2. Light curing Initiator  synthesis

Step  One.

37.3 g of AlCl ₃ and 112.0 g of dichloroethane were charged into a reactor having a nitrogen atmosphere, and the mixture was stirred at a temperature of 5 ° C. 240.3 g of dichloroethane and 48.1 g of nitrocarbazole were dissolved in 17.27 g of acetyl chloride solution, and the dissolved solution was added dropwise to the reactor for 1 hour. The temperature was then raised to 15 ° C and stirring was continued for another 2 hours. Distilled water was added to the reaction solution, washed and separated, and then the solvent was dried to obtain a reactant 1 having a purity of 94%.

Step  2.

35.0 g of the above reaction product 1, 11.1 g of hydrochloric acid hydroxylamine, 15.1 g of sodium acetate, 90 g of ethanol and 30 g of distilled water were put into a reactor having a nitrogen atmosphere, and the mixture was stirred at the temperature of 80 캜 for 5 hours. Thereafter, distilled water was added to separate the precipitate and dried to obtain a reactant 2 having a purity of 92%.

Step  3.

26.0 g of Reactant 2 and 78 g of dichloromethane were charged into a reactor having a nitrogen atmosphere and stirred at room temperature. Then, a mixed solution obtained by diluting 15.0 g of acetic anhydride with 15.0 g of dichloroethane was added dropwise to the reactor for 1 hour, followed by stirring for 1 hour. After stirring, distilled water was added thereto, washed several times, and dichloromethane was evaporated to obtain a compound of formula 5 having a purity of 90%. The formula (5) is a structure in which R ₁₀ and R ₁₁ in the formula (2) are methyl groups, and can be represented as follows.

[Chemical Formula 5]

&Lt; Preparation of colored photosensitive resin composition &

Example  One.

38.89 parts by weight of the pigment-dispersed composition M1 prepared in Preparation Example 1, 10.65 parts by weight of the resin prepared in Synthesis Example 1, 3.55 parts by weight of KAYARAD DPHA (Nippon Kayaku Co., Ltd.) as a photopolymerizable compound, the photopolymerization initiator 0.71 part by weight of an absorbance at 405 nm of a propylene glycol methyl ether acetate solution containing a photopolymerization initiator at a concentration of 0.01% or more, 0.523), 0.72 part by weight of 4-hydroxy-4-methyl- And 45.48 parts by weight of ether acetate were mixed to prepare a colored photosensitive resin composition of Example 1.

Example  2.

38.89 parts by weight of the pigment dispersion composition M2 prepared in Preparation Example 2, 10.65 parts by weight of the resin prepared in Synthesis Example 1, 3.55 parts by weight of KAYARAD DPHA (Nippon Kayaku Co., Ltd.) as a photopolymerizable compound, the photopolymerization initiator 0.71 part by weight of an absorbance at 405 nm of a propylene glycol methyl ether acetate solution containing a photopolymerization initiator at a concentration of 0.01% or more, 0.523), 0.72 part by weight of 4-hydroxy-4-methyl- And 45.48 parts by weight of ether acetate were mixed to prepare a colored photosensitive resin composition of Example 2.

Comparative Example  One.

38.89 parts by weight of the pigment-dispersed composition M1 prepared in Preparation Example 1, 10.65 parts by weight of a resin prepared from a binder resin (a copolymer of methacrylic acid and benzyl methacrylate (weight average molecular weight in terms of polystyrene: 26,000) as a photopolymerizable compound 3.55 parts by weight of KAYARAD DPHA (Nippon Kayaku Co., Ltd.), 0.71 parts by weight of Irgacure OXE-01 (absorbance at 405 nm of the propylene glycol methyl ether acetate solution containing a photopolymerization initiator at a concentration of 0.01% or more of 0.013, BASF) as a photopolymerization initiator, 0.72 part by weight of 4-hydroxy-4-methyl-2-pentanone and 45.48 parts by weight of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition of Comparative Example 1. [

Comparative Example  2.

38.89 parts by weight of the pigment-dispersed composition M2 prepared in Preparation Example 2, 10.65 parts by weight of a resin prepared from a binder resin (a copolymer of methacrylic acid and benzyl methacrylate (weight average molecular weight in terms of polystyrene: 26,000) as a photopolymerizable compound 3.55 parts by weight of KAYARAD DPHA (Nippon Kayaku Co., Ltd.), 0.71 parts by weight of Irgacure OXE-01 (absorbance at 405 nm of the propylene glycol methyl ether acetate solution containing a photopolymerization initiator at a concentration of 0.01% or more of 0.013, BASF) as a photopolymerization initiator, 0.72 part by weight of 4-hydroxy-4-methyl-2-pentanone and 45.48 parts by weight of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition of Comparative Example 2. [

Comparative Example  3.

38.89 parts by weight of the pigment-dispersed composition M1 prepared in Preparation Example 1, 10.65 parts by weight of a resin prepared from a binder resin (a copolymer of methacrylic acid and benzyl methacrylate (weight average molecular weight in terms of polystyrene: 26,000) as a photopolymerizable compound 3.55 parts by weight of KAYARAD DPHA (Nippon Kayaku), 0.71 parts by weight of Irgacure OXE-02 (absorbance of propylene glycol methyl ether acetate solution containing a photopolymerization initiator at a concentration of 0.01% or more at 405 nm is 0.004, BASF) as a photopolymerization initiator, 0.72 parts by weight of 4-hydroxy-4-methyl-2-pentanone and 45.48 parts by weight of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition of Comparative Example 3.

Comparative Example  4.

38.89 parts by weight of the pigment-dispersed composition M1 prepared in Preparation Example 1, 10.65 parts by weight of a resin prepared from a binder resin (a copolymer of methacrylic acid and benzyl methacrylate (weight average molecular weight in terms of polystyrene: 26,000) as a photopolymerizable compound 3.55 parts by weight of KAYARAD DPHA (Nippon Kayaku), 0.71 parts by weight of N-1919 (absorbance at 405 nm of the propylene glycol methyl ether acetate solution containing a photopolymerization initiator at a concentration of 0.01% or more, 0.015, Adeka) as a photopolymerization initiator, 0.72 part by weight of 4-hydroxy-4-methyl-2-pentanone and 45.48 part by weight of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition of Comparative Example 4.

Comparative Example  5.

38.89 parts by weight of the pigment-dispersed composition M3 prepared in Preparation Example 3, 10.65 parts by weight of the resin prepared in Synthesis Example 1, 3.55 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, N-1919 As a solvent, and 46.2 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed so as to obtain a colored photosensitive resin composition of Comparative Example 5 at a concentration of 0.01% or more, and the absorbance at 405 nm was 0.015, Adeka Co., .

Experimental Example  1. Manufacture of color filters

Each of the colored photosensitive resin compositions of Examples 1 to 2 and Comparative Examples 1 to 5 was applied on a glass substrate (EAGLE XG, manufactured by Corning Incorporated) having a 2-inch square by spin coating, then placed on a heating plate, And kept for 3 minutes to form a thin film. Thereafter, 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 50 탆 was placed on the thin film, and the distance from the test photomask was set to 300 탆 And irradiated with ultraviolet rays. At this time, the ultraviolet light source was irradiated at a light intensity of 100 mJ / cm 2 using a 405 nm single wavelength laser light source, 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 respective color filters. The film thickness of the color filter prepared above was 2.3 탆.

Experimental Example  2. Manufacture of color filters

Each color filter was prepared in the same manner as in Experimental Example 1 except that the test photomask was not used.

Experimental Example  3. Experimental Example  1 and Experimental Example  2 Physical property measurement of color filter

Adhesiveness and pattern linewidth were measured with the respective color filters prepared in Experimental Example 1, and the solvent resistance was measured with the respective color filters prepared in Experimental Example 2. [ The results of the physical property measurement are shown in Table 1 below.

Adhesiveness

When the generated pattern was observed with an optical microscope, the degree of peeling was evaluated on the pattern.

?: No pattern peeling,?: 1 to 3 pattern peeling, X: Pattern peeling 4 or more

pattern Line width

The line width of the generated pattern was measured using a scanning electron microscope. When the line width of the pattern is measured to be not less than the line width of the photomask, the sensitivity of the colored photosensitive resin composition is sufficient and the line width is enlarged.

Solvent resistance

After the color filter was immersed in a NMP solution at room temperature for 30 minutes, it was washed with ultrapure water and dried on a hot plate heated to 120 占 폚 for 2 minutes, and the chromaticity before and after immersion was measured. The formula used here is calculated by the following equation (1) representing the color change in the three-dimensional colorimetry defined by L *, a *, b *, and a color filter with high reliability can be manufactured as the color change value becomes smaller.

[Equation 1]

? Eab * = [(? L *) 2+ (? A *) 2+ (? B *) 2] ^0.5

division Adhesiveness Pattern line width Solvent resistance Example 1 ○ +15 2.5 Example 2 ○ +19 2.3 Comparative Example 1 × -2 16.3 Comparative Example 2 × -2 13.0 Comparative Example 3 × -One 10.1 Comparative Example 4 × -2 9.5 Comparative Example 5 × -One 9.8

As a result, it was confirmed that the compound of formula 1 prepared in Synthesis Example 1, the compound of Formula 2 prepared in Synthesis Example 2 as a photopolymerization initiator, and 4-hydroxy-4-methyl-2-pentanone , Color filters prepared from the colored photosensitive resin compositions of Examples 1 and 2 using the colored photosensitive resin composition of the present invention showed excellent results in both adhesion, pattern line width and solvent resistance.

On the other hand, the color filters prepared from the colored photosensitive resin compositions of Comparative Examples 1 to 5, which did not contain the above-mentioned Chemical Formula 1, Chemical Formula 2 and 4-hydroxy-4-methyl-2-pentanone, The pattern line width was decreased and the color change value was increased due to poor solvent resistance.

Accordingly, the colored photosensitive resin composition of the present invention is excellent in sensitivity and adhesion when exposed to light with a single wavelength exposure apparatus of 405 nm, and the pattern of the color filter is hardly scratched during the development process of the color filter, Accordingly, the reliability of manufacturing the color filter can be improved.

Claims (11)

1. A colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, wherein the alkali-soluble resin comprises the following formula (1), the photopolymerization initiator includes the following formula The absorbance of the solution containing 0.01% or more of the concentration is 0.5 or more at 405 nm, and the solvent comprises 4-hydroxy-4-methyl-2-pentanone.
[Chemical Formula 1]

(2)

R &lt; ₁ &gt; is hydrogen, a methyl group or a hydroxymethyl group,
Each of R ₂ to R ₉ is independently selected from the group consisting of hydrogen, a halogen group, an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms substituted with at least one alkoxy group, an alkyl group having 1 to 20 carbon atoms substituted with at least one aryl group, To 20 carbon atoms or a cyclic hydrocarbon having 3 to 20 carbon atoms,
Wherein R ₁₀ is one or more selected from an aryl group, or OR _12, and the group consisting of a halogen having 6 to 10 carbon atoms substituted with one or more substituents selected from the group consisting of a alkyl group, OR _12, halogen having 1 to 8 carbon atoms An arylalkyl group having 7 to 24 carbon atoms substituted with a substituent,
R ₁₁ is an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an arylalkyl group having 7 to 24 carbon atoms,
R ₁₂ is an alkyl group of 1 to 20 carbon atoms substituted with an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 8 carbon atoms,
X is a linear or branched type of the following formula (3) or a linear or branched type of the following formula (4)
(3)
-C _n H _2n -
[Chemical Formula 4]
-CO- (OC _m H _2m ) _1-
And l, m and n are integers of 0 or more. The colored photosensitive resin composition according to claim 1, wherein the coloring agent comprises at least one pigment, at least one dye, or a mixture thereof. [Claim 2] The method according to claim 1, wherein the compound represented by Formula 1 is at least one compound selected from the group consisting of N-vinylcarbazole, N-arylcarbazole, N-methacryloylcarbazole, N-acryloylcarbazole, (1-methylethyl) acrylate, calbazoyl (2-methylethyl) acrylate, calbazoyl (1-methylethyl) (1-methylethyl) methacrylate, and calbazoyl (2-methylethyl) methacrylate. 2. The colored photosensitive resin composition according to claim 1, [3] The method according to claim 1, wherein the solvent of the solution containing the photopolymerization initiator at a concentration of 0.01% or more is at least one selected from the group consisting of propylene glycol methyl ether acetate, 1,2-propylene glycol diacetate, 3- methoxybutyl acetate, propylene glycol methyl ether, Ethoxy propionate, dipropylene glycol monomethyl ether acetate, and mixtures thereof. The colored photosensitive resin composition according to claim 1, 5. The colored photosensitive resin composition according to claim 4, wherein the solvent of the solution containing the photopolymerization initiator at a concentration of 0.01% or more is propylene glycol methyl ether acetate. The photosensitive resin composition according to claim 1, which comprises 5 to 60% by weight of a colorant, 1 to 60% by weight of an alkali-soluble resin, 5 to 45% by weight of a photopolymerizable compound and 0.1 to 30% by weight of a photopolymerization initiator based on the total solid content of the colored photosensitive resin composition By weight based on the total weight of the colored photosensitive resin composition, and 60 to 90% by weight of a solvent based on the total weight of the colored photosensitive resin composition. 7. The colored photosensitive resin composition according to claim 6, wherein the alkali-soluble resin comprises 5 to 50% by weight of the compound of formula (1) based on the total weight of the alkali-soluble resin. [7] The colored photosensitive resin composition according to claim 6, wherein the photopolymerization initiator comprises 10 to 100% by weight of the compound of formula (2) based on the total weight of the photopolymerization initiator. The colored photosensitive resin composition according to claim 6, wherein the solvent comprises 5 to 20% by weight of 4-hydroxy-4-methyl-2-pentanone based on the total weight of the solvent. A color filter comprising the colored photosensitive resin composition of claim 1. A display device comprising the color filter of claim 10.