KR20170110814A - A photosensitive resin composition, color filter and display device comprising the same - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition having excellent developability including a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, and a color filter and a display device including the colored photosensitive resin composition.

Description

TECHNICAL FIELD [0001] The present invention relates to a colored photosensitive resin composition, a color filter including the same,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored photosensitive resin composition, a color filter and a display device including the colored photosensitive resin composition, and more particularly to a colored photosensitive resin composition having excellent developability including a coloring agent, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, And a display device.

(PDP), an organic light emitting diode (PDP), an organic light emitting diode (PDP), a liquid crystal display diode (OLED)) are being used, and the related art researches are actively proceeding.

The liquid crystal display device has advantages such as light weight, thinness, low cost, low power consumption driving ability and bonding with an excellent integrated circuit, and its use range is expanding for notebook computers, monitors, and TV images. Such a liquid crystal display device includes a lower substrate on which a black matrix, a color filter, and ITO pixel electrodes are formed, and an upper substrate on which an active circuit composed of a liquid crystal layer, a thin film transistor, a capacitor capacitor layer and an ITO pixel electrode are formed.

A color filter is manufactured by coating a fine area colored with three or more colors onto a solid state imaging element or a transparent substrate. Such a colored thin film is usually formed by a dyeing method, an electrodeposition method, a pigment dispersion method or the like, but recently, a pigment dispersion method excellent in heat resistance and durability is used.

In the pigment dispersion method, a colored thin film is formed by repeating a series of processes of coating, exposing, developing and thermosetting a photopolymerizable composition containing a colorant on a transparent substrate provided with a light shielding layer (black matrix). The pigment dispersion method can improve the heat resistance and durability, which are the most important properties of the color filter, and has an advantage that the thickness of the film can be uniformly maintained.

The colored photosensitive resin composition used in the production of the color filter according to the pigment dispersion method generally comprises a binder resin, a photopolymerizable monomer, a photopolymerization initiator, an epoxy resin, a solvent and other additives.

Recent color filter manufacturing processes are being produced in a continuous process capable of mass production. Recently, a color filter is manufactured using a colored photosensitive resin composition having a small particle diameter according to a high-quality specification. This results in a decrease in the process yield due to the increase of the stain on the fine pattern of the color filter.

Korean Patent Laid-Open No. 10-2009-0072754 discloses a colored photosensitive resin composition capable of solving the above-mentioned problems, but has a problem of low developability.

Korean Patent Publication No. 10-2009-0072754

It is an object of the present invention to provide a colored photosensitive resin composition which does not cause development unevenness and is excellent in developability.

Another object of the present invention is to provide a color filter and a display device manufactured using the colored photosensitive resin composition.

In order to achieve the above object,

The present invention relates to a colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent,

The alkali-soluble resin includes monomers of the following general formulas (1) and (2)

The alkali-soluble resin has a molecular weight of 12,000 to 17,000, an acid value of 60 to 120 KOH mg / g,

Wherein the photopolymerization initiator comprises an oxime ester fluorene derivative compound.

[Chemical Formula 1]

(2)

R ₁ to R ₁₀ are the same or different and each is hydrogen or an alkyl group having 1 to 5 carbon atoms.

The present invention also provides a color filter made of 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 does not cause development unevenness, has excellent developing property, and has an advantage of ensuring fairness.

Further, the color filter and the display device made of the colored photosensitive resin composition of the present invention have an excellent color reproduction effect.

1 is a photograph showing that development unevenness did not occur.
2 is a photograph showing that development unevenness is good.
3 is a photograph showing that the development unevenness is poor.
Fig. 4 is a photograph showing excellent developability.
5 is a photograph showing that the developability is poor.

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

The present invention relates to a colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent,

The alkali-soluble resin includes monomers of the following general formulas (1) and (2)

The alkali-soluble resin has a molecular weight of 12,000 to 17,000, an acid value of 60 to 120 KOH mg / g,

The photopolymerization initiator relates to a colored photosensitive resin composition comprising an oxime ester fluorene derivative compound.

[Chemical Formula 1]

(2)

R ₁ to R ₁₀ are the same or different and each is hydrogen or an alkyl group having 1 to 5 carbon atoms.

In the present invention, there is provided a colored photosensitive resin composition which is free from development unevenness and has excellent developing property by using an alkali-soluble resin containing the monomers of the formulas (1) and (2) and containing oxime ester fluorene derivative compound as a photopolymerization initiator .

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

(A) Colorant

In the present invention, the colorant comprises at least one pigment, at least one dye or a mixture thereof, preferably at least one pigment.

(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

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

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

The C.I. Among the pigment pigments, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185, C.I. Pigment Orange 38, C.I. Pigment Red 122, C.I. Pigment Red 166, C.I. Pigment Red 177, C.I. Pigment Red 208, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Violet 23, C.I. Pigment Blue 15: 3, Pigment Blue 15: 6, C.I. Pigment Green 7, C.I. Pigment Green 36 and C.I. Pigment Green 58. It is preferable that at least one selected from the group consisting of Pigment Green 58 is included.

The content of the pigment is 10 to 50 wt%, preferably 15 to 45 wt%, based on the total weight of the colored photosensitive resin composition. When the content of the pigment is in the range of 10 to 50% by weight, the viscosity is low, the storage stability is excellent, the dispersion efficiency is high, and the contrast ratio can be increased.

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 content of the pigment dispersant may be 5 to 60% by weight, specifically 15 to 50% by weight based on the total weight of the colored photosensitive resin composition. When the content of the pigment dispersant is within the above range, The pigment is easily atomized, and there is an advantage that problems such as gelation after dispersion can be prevented.

(a3) Dye

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, 16, 21, 23, 24, 38, 56, 62, 63, 68, 79, 82, 93, 94, 98, 99, 151, 162 and 163;

C.I. Solvent Orange 2, 7, 11, 15, 26 41, 45, 56 and 62;

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 Yellow 14, 16, 21, 56, 151, 79 and 93; C.I. Solvent Red 8, 49, 89, 111, 122, 132, 146 and 179; C.I. Solvent Orange 41, 45 and 62; C.I. Solvent Blue 35, 36, 44, 45 and 70; And C.I. Solvent violet 13 is preferred, and C.I. Solvent Yellow 21 and 79; C.I. Solvent Red 8, 122 and 132; And C.I. Solvent Orange 45 and 62 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 , 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.

C.I. Acid Yellow 42 having excellent solubility in an organic solvent in the above CI acid dye; C.I. Acid Red 92; C. I. Acid Blue 80, 90; C.I. Acid Gurane 27 and C.I. Acid Violet 66 are preferred.

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.

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

The content of the dye 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 colored photosensitive resin composition. 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 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 a component of the colored photosensitive resin composition of the present invention, includes monomers represented by the following general formulas (1) and (2).

[Chemical Formula 1]

(2)

R ₁ to R ₁₀ are the same or different and each is hydrogen or an alkyl group having 1 to 5 carbon atoms.

More preferably, R ₁ to R ₁₀ are the same or different and each is hydrogen or a methyl group.

In the present invention, by using the alkali-soluble resin comprising the monomers of the formulas (1) and (2), it is possible to provide a colored photosensitive resin composition which does not cause development unevenness and is excellent in developability.

In order to obtain solubility in an alkali developing solution used in a developing process at the time of forming a pattern, the alkali-soluble resin is mixed with monomers of the above formulas (1) and (2) together with an ethylenically unsaturated monomer (b1) As a component.

Specific examples of the ethylenically unsaturated monomer (b1) containing a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid; Anhydrides of dicarboxylic acids; mono (meth) acrylates of a polymer containing a carboxyl group and a hydroxyl group at both terminals such as? -carboxypolycaprolactone mono (meth) acrylate; And acrylic acid and methacrylic acid are preferable.

Further, a hydroxyl group may be added to the alkali-soluble resin in order to secure further developability.

Examples of the method for imparting the hydroxyl group include (1) a method of copolymerizing an ethylenically unsaturated monomer containing a carboxyl group and an ethylenically unsaturated monomer containing a hydroxyl group, (2) a method of producing an ethylenically unsaturated monomer containing a carboxyl group (3) a method of preparing a copolymer containing an ethylenically unsaturated monomer containing a carboxyl group and an ethylenically unsaturated monomer containing a hydroxyl group by further reacting a compound containing a glycidyl group with a glycidyl group, and And a method of reacting the compound with the compound of the present invention.

Specific examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) 3-phenoxypropyl (meth) acrylate, N-hydroxyethyl acrylamide and the like. Of these, 2-hydroxyethyl (meth) acrylate is preferable, and the ethylenically unsaturated monomer containing a hydroxyl group Two or more species can be used in combination.

Specific examples of the compound containing the glycidyl group include butyl glycidyl ether, glycidyl propyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, glycidyl butylate, glycidyl methyl But are not limited to, ether, ethyl glycidyl ether, glycidyl isopropyl ether, t-butyl glycidyl ether, benzyl glycidyl ether, glycidyl 4-t-butyl benzoate, glycidyl stearate, Ethers and methacrylic acid glycidyl esters. Of these, preferred are butyl glycidyl ether, aryl glycidyl ether and methacrylic acid glycidyl ester, and the glycidyl group-containing compound may be at least two kinds Can be used in combination.

The unsaturated monomers copolymerizable with the ethylenic unsaturated monomer having a carboxyl group in the production of the alkali-soluble resin may be aromatic vinyl compounds, N-substituted maleimide compounds, alicyclic (meth) acrylates, hydroxyethyl (meth) Acrylates, aryl (meth) acrylates and unsaturated oxetane compounds, but are not limited thereto.

The aromatic vinyl compound is specifically exemplified by styrene, vinyltoluene,? -Methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o- , m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether.

The N-substituted maleimide compound is specifically exemplified by N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-methylphenylmaleimide, Nm-methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide and Np-methoxyphenylmaleimide .

Specific examples of the alicyclic (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, Alkyl (meth) acrylates such as butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate and t-butyl (meth) acrylate; (Meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6] decan- Dicyclopentanyloxyethyl (meth) acrylate, and isobornyl (meth) acrylate.

Specific examples of the hydroxyethyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) 2-hydroxy-3-phenoxypropyl (meth) acrylate, and N-hydroxyethyl acrylamide.

Specific examples of the aryl (meth) acrylates include phenyl (meth) acrylate and benzyl (meth) acrylate.

Specific examples of the unsaturated oxetane compound include 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl 2- (methacryloyloxymethyl) oxetane and 2- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) ) -4-trifluoromethyloxetane, and the like.

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

The alkali-soluble resin preferably has an acid value of 60 to 120 mgKOH / g, preferably 70 to 100, in order to ensure compatibility with the dye and storage stability of the colored photosensitive resin composition.

When the acid value of the alkali-soluble resin is less than 60 mgKOH / g, it is difficult to secure a sufficient developing rate of the colored photosensitive resin composition. When the acid value exceeds 120 mgKOH / g, the adhesion between the colored photosensitive resin composition and the substrate decreases, And a problem of compatibility with the dye occurs, so that the dye in the colored photosensitive resin composition is precipitated or the stability with time is lowered and the viscosity is increased.

The alkali-soluble resin preferably has a molecular weight of 12000 to 17000, more preferably a molecular weight of 13000 to 15000.

If the molecular weight of the alkali-soluble resin is less than 12,000, short circuiting of the pattern tends to occur. If the molecular weight of the alkali-soluble resin is more than 17000, pattern residue tends to occur.

The alkali-soluble resin is contained in an amount of 10 to 80% by weight, preferably 10 to 70% by weight based on the total weight of the colored photosensitive resin composition.

When the content of the alkali-soluble resin is 10 to 80% by weight, the solubility in the developer is sufficient and the formation of the pattern is easy, and the reduction of the film thickness of the pixel portion of the exposed portion is prevented during development, .

(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.

As the photopolymerizable compound, monofunctional monomers, bifunctional monomers or polyfunctional monomers can be used, and preferably bifunctional monomers are used, but the present invention is not limited thereto.

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 Acrylate, trimethylolpropane trimethacrylate, tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like, but are not limited thereto.

The photopolymerizable compound is contained in an amount of 5 to 50% by weight, and preferably 7 to 50% by weight based on the total weight of the colored photosensitive resin composition of the present invention. The photopolymerizable compound can improve the strength and reliability of the pixel portion in the range of 5 to 50% by weight.

(D) Light curing Initiator

The photopolymerization initiator, which is one of the colored photosensitive resin compositions of the present invention, is a compound capable of polymerizing the above-mentioned photopolymerizable compound (C).

In the present invention, the photopolymerization initiator essentially includes an oxime ester fluorene derivative compound. By including the oxime ester fluorene derivative compound, the sensitivity of the colored photosensitive resin composition is increased and high curing degree can be exhibited.

From the standpoints of polymerization characteristics, initiation efficiency, absorption wavelength, availability, and cost, the photopolymerization initiator is preferably used in combination with an acetophenone compound, a benzophenone compound, a triazine compound, a biimidazole compound, It is preferable to further include at least one compound selected from the group consisting of compounds.

Specific examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1 (2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] Propan-1-one and 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-based compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4- (Trichloromethyl) -6-piperonyl-1,3,5-triazine, 2, 3-bis (Trichloromethyl) -6- [2- (5-methylfuran) -1,3,5-triazine, 2,4-bis Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- -Triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine and 2,4- Trichloromethyl) -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'- 4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, 2,2-bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and imidazole compounds in which the phenyl group at the 4,4', 5,5 'position is substituted by a carboalkoxy group . Among them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- , 5,5'-tetraphenylbiimidazole and 2,2-bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'- Is used.

Specific examples of the oxime compound include o-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one and the like. Commercially available products include OXE01 and OXE02 of BASF.

The thioxanthone compound is specifically exemplified by 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone and 1-chloro- Santon et al.

The photopolymerization initiator may further include a photopolymerization initiator (d1) in order 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 (d1), so that the sensitivity is further increased and the productivity can be improved.

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

As the amine compound, an aromatic amine compound is preferably used. Specific examples thereof include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine; 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid isoamyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N, N-dimethylparatoluidine, 4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone) and 4,4'-bis (diethylamino) benzophenone.

The carboxylic acid compound is preferably an aromatic heteroacetic acid. Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenyl Thioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid.

The organic sulfur compound having a thiol group is specifically exemplified by 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyl Trimethylolpropane tris (3-mercaptopropionate), pentaerythritoltetrakis (3-hydroxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) (Mercaptobutylate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate) and tetraethylene glycol bis (3-mercaptopropionate ) And the like.

The photopolymerization initiator may be contained in an amount of 0.1 to 40% by weight, preferably 1 to 30% by weight based on the total weight of the solid content of the colored photosensitive resin composition of the present invention.

When the photopolymerization initiator is contained in an amount of 0.1 to 40% 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 and the smoothness on the surface of the pixel portion can be improved.

Also. The photopolymerization initiator 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.

If the photopolymerization initiator is contained in an amount of less than 10% by weight, the decrease in sensitivity due to the dye can not be overcome and the pattern is likely to be short-circuited during the development process.

(E) Solvent

The solvent used in the conventional colored photosensitive resin composition can be used without particular limitation so long as it is effective to dissolve the other components contained in the colored photosensitive resin composition. In particular, the solvent may be selected from ethers, acetates, aromatic hydrocarbons, ketones, Alcohols, esters, amides and the like are preferable.

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

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

Examples of the acetates include methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3-methoxybutyl acetate, 3 Methoxy-1-butylacetate, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, methyl 3-methoxypropionate, propylene glycol methyl ether acetate, 3-methoxy- Butyl acetate, 1,2-propylene glycol diacetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, diethylene glycol monobutyl ether Acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, di Ethylene glycol monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate and propylene carbonate. .

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.

The alcohols include, for example, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin and 4-hydroxy-4-methyl-2-pentanone.

Examples of the esters include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and? -Butyrolactone.

The amides include, for example, dimethylformamide (DMF) and N-methyl-2-pyrrolidone (NMP).

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

It is preferable to use an organic solvent having a boiling point of 100 ° C to 200 ° C on the application and drying surface, and examples thereof include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate Tetra, butyl lactate, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate.

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. When the solvent is contained in the range of 60 to 90% by weight, when the solvent is applied by a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater) .

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

(B), the photopolymerizable compound (C), the photopolymerization initiator (D) and, if necessary, the additive (F) and the solvent (E) are further added to the mixed colorant so as to have a predetermined concentration The colored photosensitive resin composition according to the invention can be produced.

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.

<Synthesis of alkali-soluble resin>

Synthetic example  1 to 9.

Propylene glycol monomethyl ether acetate, AIBN, vinyl toluene, phenylthioethylacrylate, methacrylate and methacrylic acid were charged into a 1000 mL flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube and purged with nitrogen. Thereafter, the temperature of the reaction solution was elevated to 100 ° C with stirring, and the reaction was continued for a certain time after the rise.

The content (weight part) and the reaction time (h) of the above composition, the final solids content (%), the acid value (KOHmg / g) of the alkali-soluble resin synthesized by the above method and the weight average molecular weight measured by GPC are shown in Table 1 .

division Synthesis Example 1 Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 Synthesis Example 5 Synthesis Example 6 Synthesis Example 7 Synthesis Example 8 Synthesis Example 9 Propylene glycol monomethyl ether acetate 400 400 400 400 400 400 400 400 400 AIBN 7 7 7 7 7 7 7 7 7 Vinyl toluene 45 45 45 45 45 45 45 45 45 Phenylthioethyl acrylate 58 58 58 58 58 58 58 58 58 Methacrylate 20 20 20 20 20 20 20 20 20 Methacrylic acid 30 35 30 30 40 40 30 20 20 Reaction time (h) 7 7 9 11 11 13 5 9 11 Solids 31 31 31 31 31 31 31 31 31 Acid value 70 100 70 70 130 130 70 45 45 Molecular Weight 13000 13000 16000 20000 20000 23000 10000 16000 20000

Manufacturing example  1. Preparation of pigment dispersion composition

C.I. Pigment Green 58 12 parts by weight, C.I. 1.8 parts by weight of Pigment Yellow 150, 4 parts by weight of BYK-2001 as a pigment dispersing agent, and 82.2 parts by weight of propylene glycol monomethyl ether acetate as a solvent were thoroughly dispersed using a bead mill to prepare a pigment dispersion composition.

&Lt; Preparation of colored photosensitive resin composition &

Example  1 to 3 and Comparative Example  1 to 8.

The colored photosensitive resin compositions of Examples 1 to 3 and Comparative Examples 1 to 8 were prepared with the compositions shown in Table 2 below.

 (Unit: wt%) division Example Comparative Example One 2 3 One 2 3 4 5 6 7 8 Pigment dispersion composition 9.4 9.4 9.4 9.4 9.4 9.4 9.4 9.4 9.4 9.4 9.4 The alkali-soluble resin (B) B1 30 - - - - - - - 30 - B2 - 30 - - - - - - - 30 B3 - - 30 - - - - - - - B4 - - - 30 - - - - - - B5 - - - - 30 - - - - - B6 - - - - - 30 - - - - B7 - - - - - - 30 - - - B8 - - - - - - - 30 - - - B9 - - - - - - - - 30 - - The photopolymerizable compound (C) 6.6 6.6 6.6 6.6 6.6 6.6 6.6 6.6 6.6 6.6 6.6 Photopolymerization initiator (D) D1 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 - - D2 - - - - - - - - - 1.3 1.3 Solvent (E) 52.7 52.7 52.7 52.7 52.7 52.7 52.7 52.7 52.7 52.7

Pigment dispersion composition: The pigment dispersion composition prepared in Preparation Example 1

The alkali-soluble resin (B)

B1: The alkali-soluble resin prepared in Synthesis Example 1

B2: The alkali-soluble resin prepared in Synthesis Example 2

B3: The alkali-soluble resin prepared in Synthesis Example 3

B4: Alkali-soluble resin prepared in Synthesis Example 4

B5: The alkali-soluble resin prepared in Synthesis Example 5

B6: The alkali-soluble resin prepared in Synthesis Example 6

B7: The alkali-soluble resin prepared in Synthesis Example 7

B8: The alkali-soluble resin prepared in Synthesis Example 8

B9: The alkali-soluble resin prepared in Synthesis Example 9

Photopolymerizable compound (C): A9550 (Shin Nakamura)

Photopolymerization initiator (D):

D1: SPI-03 (Samyang)

D2: PBG-305 (TRON Lisa)

Solvent (E): Propylene glycol monomethyl ether acetate

Experimental Example  1. Color filter manufacturing and physical property measurement

Each of the colored photosensitive resin compositions of Examples 1 to 3 and Comparative Examples 1 to 8 was applied onto a 2-inch glass substrate (EAGLE XG, manufactured by Corning Incorporated) by spin coating, placed on a heating plate, To form a thin film.

Thereafter, a photomask of 100% transmittance at 3 cm x 3 cm was placed on the thin film, and the distance between the photomask and the test photomask was set to 200 m to irradiate ultraviolet rays. At this time, ultraviolet rays were irradiated with a high pressure mercury lamp of 1 kW including g, h and i lines at an illuminance of 50 mJ / cm 2, and no special optical filter was used.

1-1. Measuring staining

The thin film irradiated with ultraviolet rays was immersed in 0.04% KOH aqueous solution developing solution for 2 minutes to develop. The post-process Bake did not proceed to check for developing stains.

The film thickness of the color filter prepared above was 2.5 탆.

The fabricated color filter was checked for development unevenness on the Green Lamp.

The evaluation results are shown below, and the results are shown in Table 3 below.

<Evaluation Criteria>

Good: Excellent (Fig. 1)

?: Good (FIG. 2)

X: defective (Fig. 3)

1-2. Developability  Measure

To the thin film not irradiated with ultraviolet rays, 0.28 ml of 0.008% aqueous KOH solution was dropped and developed for 2 minutes. The post-process Bake did not proceed to check for developing stains.

The film thickness of the color filter prepared above was 2.5 탆.

The developed color filter was visually inspected for its developability.

The evaluation results are shown below, and the results are shown in Table 3 below.

<Evaluation Criteria>

Good: Excellent (FIG. 4)

X: Bad (Figure 5)

division Stain Developability Example 1 ○ ○ Example 2 ○ ○ Example 3 ○ ○ Comparative Example 1 △ X Comparative Example 2 △ X Comparative Example 3 △ X Comparative Example 4 X △ Comparative Example 5 △ X Comparative Example 6 △ X Comparative Example 7 X △ Comparative Example 8 X △

In the results of Table 3 above, an alkali-soluble resin having a molecular weight of 12000 to 17000 and an acid value of 60 to 120 KOH mg / g and a oxime ester fluorene derivative compound as a photopolymerization initiator were used It was confirmed that the colored photosensitive resin composition of the present invention did not cause development unevenness and was excellent in developability.

On the other hand, the colored photosensitive resin compositions of Comparative Examples 1 to 6 in which the acid value and the molecular weight of the alkali-soluble resin were not in the range of the present invention exhibited development unevenness or poor developability.

The colored photosensitive resin compositions of Comparative Examples 7 to 8, which did not use the oxime ester fluorene derivative compound as a photopolymerization initiator, exhibited good developability, but showed many development unevenness.

Thus, it has been found through experiment that the colored photosensitive resin composition of the present invention does not cause development unevenness and is excellent in developing property.

Claims (6)

A colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent,
The alkali-soluble resin includes monomers of the following general formulas (1) and (2)
The alkali-soluble resin has a molecular weight of 12,000 to 17,000, an acid value of 60 to 120 KOH mg / g,
Wherein the photopolymerization initiator is a colored photosensitive resin composition comprising an oxime ester fluorene derivative compound;
[Chemical Formula 1]

(2)

R ₁ to R ₁₀ are the same or different and each is hydrogen or an alkyl group having 1 to 5 carbon atoms. [3] The method of claim 1, wherein the alkali-soluble resin is a monomer of the general formulas (1) and (2); And an ethylenically unsaturated monomer containing a carboxyl group. The colored photosensitive resin composition according to claim 1, wherein R ₁ to R ₁₀ in the general formulas (1) and (2) are the same or different and each is hydrogen or a methyl group. The photosensitive resin composition according to claim 1, which comprises 5 to 60% by weight of a colorant, 10 to 80% by weight of an alkali-soluble resin, 5 to 50% by weight of a photopolymerizable compound and 0.1 to 40% by weight of a photopolymerization initiator based on the total weight of solid components in 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. A color filter made of the colored photosensitive resin composition of claim 1. A display device comprising the color filter of claim 5.

Images