KR20160112645A

KR20160112645A - Colored photosensitive resin composition and color filter using the same

Info

Publication number: KR20160112645A
Application number: KR1020150038751A
Authority: KR
Inventors: 우창호; 황진아; 박승준
Original assignee: 동우 화인켐 주식회사
Priority date: 2015-03-20
Filing date: 2015-03-20
Publication date: 2016-09-28

Abstract

The present invention relates to a colored photosensitive resin composition and, more specifically, to a colored photosensitive resin composition for a color filter used in producing a color filter for a color liquid crystal display device or the like, and to a color filter produced by using the same. The colored photosensitive resin composition has improved curing degree through a cross-linking reaction of a melamine-based compound (A) and acrylic polyol (B) during thermal-curing, and does not change colors in the high processing temperature.

Description

TECHNICAL FIELD [0001] The present invention relates to a colored photosensitive resin composition and a color filter using the colored photosensitive resin composition.

The present invention relates to a colored photosensitive resin composition, and more particularly, to a colored photosensitive resin composition for a color filter used for producing a color filter used in a color liquid crystal display device or the like, and a color filter manufactured using the same.

A color filter used in a liquid crystal display device is formed by forming fine pixels such as red, green, and blue on a transparent substrate such as glass by a dyeing method, a printing method, an electrodeposition method, a pigment dispersion method or the like. In recent years, a pigment dispersion method having high productivity and excellent in fine workability, that is, a method using a photosensitive resin composition in which pigments are dispersed is widely used for the production of a color filter for a liquid crystal display device. In this method, a photosensitive resin composition in which a pigment is dispersed is coated on a transparent substrate such as glass to form a coating film, and the coating film is exposed to radiation through a photomask, and then the non-visible portion is removed by development And then the pattern is formed. The photosensitive resin composition usually contains a pigment, a polymer resin for a binder, a photopolymerizable monomer, a photoinitiator, and a solvent, and a surfactant, an adhesion promoter, a residue reducing compound and the like are added thereto. In recent years, color filters have become increasingly colored in color and reproduced in high color, so that the pigment concentration in a composition for a color filter is increasing. However, when a pixel is formed using a colored photosensitive resin composition having a high content of a coloring material, the degree of curing of the pixel formed in the exposed portion is insufficient, resulting in a problem of surface defects of the coating film or insufficient solvent resistance. Also, as the pigment content increases, there is a problem that the pigment is discolored by UV or heat. Accordingly, researches for increasing the degree of curing of pixels have been actively conducted. For example, Korean Unexamined Patent Publication No. 2004-0031228 discloses a photosensitive resin composition having excellent curability by heat by crosslinking with a monomer in a binder using a silane coupling agent having at least one isocyanate group. However, in the above-mentioned literature, only the excellent effect of adhesion to the substrate is shown, and the effects on heat resistance and solvent resistance are not described at all, and further improvement in the cured drawing is required. Research on a photosensitive resin composition capable of increasing the degree of curing while maintaining a transmittance without discoloration has been continuously required.

Korean Patent Publication No. 2004-0031228

Accordingly, it is an object of the present invention to provide a colored photosensitive resin composition which is not discolored even at a high process temperature and has improved curability while maintaining a transmittance.

Accordingly, the present invention provides a colored photosensitive resin composition comprising a melamine compound (A), an acrylic polyol (B), a photoinitiator (C), a photopolymerizable compound (D), a solvent (E), a colorant (F) and an alkali- To provide a resin composition.

In one embodiment, the melamine compound (A) may be one or more selected from the group consisting of the following formulas (1) and (2).

[Chemical Formula 1]

(2)

In another embodiment, the hydroxyl value of the acrylic polyol (B) may be 10 to 60 (KOH) mg / g.

In another embodiment, the total content of the melamine compound (A) and the acrylic polyol (B) may be 0.5 to 5% by weight based on the total weight of the composition.

Another embodiment may further comprise a surfactant (G).

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

The colored photosensitive resin composition of the present invention is characterized in that the curing degree is improved through the crosslinking reaction of the melamine compound (A) and the acrylic polyol (B) upon thermosetting, and that the coloring photosensitive resin composition is not discolored even at a high process temperature.

The present invention relates to a colored photosensitive resin composition, and more particularly, to a colored photosensitive resin composition for a color filter used for producing a color filter used in a color liquid crystal display device or the like, and a color filter manufactured using the same. The colored photosensitive resin composition of the present invention is characterized in that the curing degree is improved through the crosslinking reaction of the melamine compound (A) and the acrylic polyol (B) upon thermosetting, and that the coloring photosensitive resin composition is not discolored even at a high process temperature.

Hereinafter, the present invention will be described in detail.

The melamine compound (A)

The melamine compound may be at least one compound selected from the group consisting of the compounds represented by formulas (1) and (2).

[Chemical Formula 1]

(2)

Acrylic Polyol (acrylic polyols ) (B)

Acrylic polyols are not limited, but preferably have a hydroxyl value of 10 to 60 (KOH) mg / g.

Examples of the acrylic polyol include, but are not limited to, AA2160, AA-2184, AA1552, AOF-2024, and AA-2160T manufactured by Aegyung Chemical Co.,

With respect to the content of the melamine compound and the acrylic polyol, it is preferable that the sum of the melamine compound and the acrylic polyol is 0.5 to 5 wt% based on the total weight of the composition. Within this range, the degree of curing by the crosslinking reaction is better.

Photoinitiator (C)

The type of the photoinitiator (C) is not particularly limited as long as it can polymerize the photopolymerizable compound (D).

In particular, from the viewpoints of polymerization characteristics, initiation efficiency, absorption wavelength, availability, or price, the photoinitiator is preferably an acetophenone compound, a benzophenone compound, a triazine compound, a biimidazole compound, an oxime compound or a thioxantone compound It is preferable to use at least one compound selected from the group consisting of

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

Specific examples of the benzophenone compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'- -Butylperoxycarbonyl) benzophenone or 2,4,6-trimethylbenzophenone.

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

Specific examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbimidazole, 2,2'-bis (2,3- Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) , 2,2'-bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) 4 ', 5,5'-tetraphenyl-1,2'-biimidazole or an imidazole compound in which the phenyl group at the 4,4', 5,5 'position is substituted by a carboalkoxy group. Among them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- , 5,5'-tetraphenylbiimidazole or 2,2-bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'- Is used.

Specific examples of the oxime compounds include o-ethoxycarbonyl- [alpha] -oxyimino-1-phenylpropan-1-one, and commercially available products are OXE-01 and OXE-02 from BASF.

Specific examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone or 1-chloro-4- propanedioxanthone and the like have.

In addition, other photoinitiators and the like may be further used in combination within the range not impairing the effect of the present invention. For example, a benzoin compound or an anthracene compound may be used, and these may be used alone or in combination of two or more.

Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Examples of the anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, etc. .

Other examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylclyoxylic acid A methyl or a titanocene compound can be used in combination as a photoinitiator.

The photoinitiator may further include a photopolymerization initiator (C-1) to improve the sensitivity of the photosensitive resin composition of the present invention. The photosensitive resin composition according to the present invention contains the photopolymerization initiation auxiliary (C-1), thereby further enhancing the sensitivity and improving the productivity.

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 of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Dimethylaminobenzoic acid, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone ) Or 4,4'-bis (diethylamino) benzophenone.

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

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

The photoinitiator may be contained in an amount of 0.1 to 10% by weight, preferably 0.5 to 5% by weight based on the total weight of the photosensitive resin composition of the present invention. When the amount of the photoinitiator is within the above range, the sensitivity of the photosensitive resin composition is increased and the exposure time is shortened, so that productivity is improved and high resolution can be maintained. In addition, the strength of the pixel portion formed using the composition and the smoothness of the surface of the pixel portion can be improved.

When the photopolymerization initiator is further used, it is preferable to use the same amount of the photopolymerization initiator as the photopolymerization initiator. When the photopolymerization initiator is used in the above amount, the sensitivity of the photosensitive resin composition is further improved, The productivity can be improved.

Photopolymerization Compound (D)

The photopolymerizable compound (D) is a compound capable of polymerizing under the action of light and a photopolymerization initiator described later, and examples thereof include monofunctional monomers, bifunctional monomers, and other multifunctional monomers. Specific examples of monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N- Money and so on. Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like. Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) And pentaerythritol hexa (meth) acrylate. Of these, multifunctional monomers having two or more functional groups are preferably used.

The photopolymerizable compound (D) is used in an amount of usually 5 to 50% by weight, preferably 7 to 45% by weight based on the solid content in the colored photosensitive resin composition. When the photopolymerizable compound (D) is in the range of 5 to 50% by weight based on the above-mentioned criteria, the strength and smoothness of the pixel portion tends to be favorable.

Solvent (E)

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

Specific 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; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; And alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate.

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

Examples of the ketones include 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 esters such as ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; And cyclic esters such as? -Butyrolactone.

Of these solvents, organic solvents having a boiling point of 100 ° C to 200 ° C are more preferably used in terms of coatability and dryness. Examples thereof include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate , Butyl lactate, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate.

The solvent may be used alone or in combination of two or more. The solvent may be contained in an amount of 60 to 95% by weight, preferably 70 to 85% by weight based on the total weight of the photosensitive resin composition of the present invention. When the amount of the solvent is in the range of 60 to 95% by weight, the coating property becomes good when 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) Effect.

(F) Colorant

The colorant may be added as needed, and is characterized by containing one or more pigments or one or more dyes.

( f1 ) Pigment

The pigment may be an organic pigment or an inorganic pigment generally used in the art.

The organic pigments or inorganic 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 An anthanthrone pigment, an indanthrone pigment, an anthraquinone pigment, an anthraquinone pigment, an anthanthrone pigment, an anthanthrone pigment, an indanthrone pigment, an anthanthrone pigment, Pigments, pyranthrone pigments, diketopyrrolopyrrole pigments, and the like.

Examples of the inorganic pigments include metallic compounds such as metal oxides and metal complex salts. Specific examples of the inorganic pigments include oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony and carbon black Or composite metal oxides.

Particularly, the organic pigments and inorganic pigments may be specifically classified into pigments in the Society of Dyers and Colourists, and more specifically, those having a color index (CI) number Pigments, but are not limited thereto.

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

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

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

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

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

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

C.I Pigment Brown 28

C.I Pigment Black 1 and 7, etc.

The pigment (f1) may be used alone or in combination of two or more.

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

The pigment is preferably a pigment dispersion in which the particle diameter of the pigment is uniformly dispersed. An example of a method for uniformly dispersing the particle diameter of the pigment includes a method of dispersing the pigment dispersant (f2) and the like, and a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained have.

( f2 ) Pigment Dispersant

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

It is also preferable to include 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 (f2), 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-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-160, BYK (trade name) 164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; EFKA-4060, EFKA-4060, EFKA-4055, EFKA-4055, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA- 4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10 from Lubirzol; Hinoact T-6000, Hinoact T-7000, Hinoact T-8000; available from Kawaken Fine Chemicals; AJISPUR PB-821, Ajisper PB-822, Ajisper PB-823 manufactured by Ajinomoto; FLORENE DOPA-17HF, fluorene DOPA-15BHF, fluorene DOPA-33, and fluorene DOPA-44 are trade names of Kyoeisha Chemical Co.,

In addition to the acrylic dispersant, other resin type pigment dispersants may be used alone or in combination of two or more, and may be used in combination with an acrylic dispersant.

The content of the pigment dispersant (f2) is 5 to 60 parts by weight, preferably 15 to 50 parts by weight, based on 100 parts by weight of the solid content of the pigment (f1). If the content of the pigment dispersant (f2) exceeds 60 parts by weight, the viscosity may be increased. If the content of the pigment dispersant is less than 5 parts by weight, it may be difficult to atomize the pigment or cause gelation after dispersion.

The dye (f3)

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

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

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

C.I. Solvent Blue 5, 35, 36, 37, 44, 45, 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.

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

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 C.I. acid dye; C.I. Acid Red 92; C. I. Acid Blue 80, 90; C.I. Acid Violet 66; C.I. Acid Green 27 is preferred.

As a C.I. direct dye,

CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211 , 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246 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

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 alkali-soluble resin (G)

The alkali-soluble resin is prepared by copolymerizing an ethylenically unsaturated monomer having a carboxyl group as an essential component in order to have solubility in an alkali developing solution used in a developing process for forming a pattern.

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

Further, a hydroxyl group may be added to the alkali-soluble resin in order to secure further developability. As a method for imparting the hydroxyl group, a method of copolymerizing an ethylenically unsaturated monomer having a carboxyl group and an ethylenically unsaturated monomer having a hydroxyl group, a method of adding a compound having a glycidyl group to a copolymer of an ethylenically unsaturated monomer having a carboxyl group And a method of reacting a copolymer of an ethylenically unsaturated monomer having a carboxyl group and an ethylenically unsaturated monomer having a hydroxyl group with a compound having a glycidyl group, and the like.

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 and N-hydroxyethylacrylamide. Of these, 2-hydroxyethyl (meth) acrylate is preferable, and the ethylenically unsaturated monomer having a hydroxyl group Can be used in combination.

Specific examples of the compound having a glycidyl group include butyl glycidyl ether, glycidyl propyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, glycidyl butylate, glycidyl methyl ether, Ethyl glycidyl ether, glycidyl isopropyl ether, t-butyl glycidyl ether, benzyl glycidyl ether, glycidyl 4-t-butyl benzoate, glycidyl stearate, And glycidyl methacrylate. Of these, butyl glycidyl ether, aryl glycidyl ether, and methacrylic acid glycidyl ester are exemplified. The glycidyl group-containing compounds may be used in combination of two or more. .

The unsaturated monomers copolymerizable in the preparation of the alkali-soluble resin are exemplified below, but are not limited thereto.

Specific examples of the polymerizable monomer having an unsaturated bond capable of copolymerization include styrene, vinyltoluene,? -Methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, Aromatic vinyl compounds such as methyl ether, m-vinylbenzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether;

N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm N-substituted maleimide-based compounds such as methylphenyl maleimide, Np-methylphenyl maleimide, No-methoxyphenyl maleimide, Nm-methoxyphenyl maleimide and Np-methoxyphenyl maleimide;

Propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth) acrylates such as sec-butyl (meth) acrylate and t-butyl (meth) acrylate; (Meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6] decan- Alicyclic (meth) acrylates such as dicyclopentanyloxyethyl (meth) acrylate and isobornyl (meth) acrylate;

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

Aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate;

3- (methacryloyloxymethyl) -2-trifluoromethyl oxetane, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, and the like Unsaturated oxetane compounds.

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

In order to ensure compatibility of the alkali-soluble resin with the dye and storage stability of the photosensitive resin composition, the acid value is preferably 30 to 150 mgKOH / g. When the acid value of the alkali-soluble resin is less than 30 mgKOH / g, the development speed of the photosensitive resin composition is slow. When the acid value is more than 150 mgKOH / g, the adhesion with the substrate is decreased and the pattern is easily short-circuited. And the dye in the photosensitive resin composition precipitates or the storage stability is lowered, and the viscosity tends to rise.

Surfactant (H)

The surfactant may be optionally added as needed. The surfactant may be added to improve the film formation of the colored photosensitive resin composition. The surfactant may be selected from silicone, fluorine, ester, cationic, anionic, nonionic, amphoteric surfactant And specific examples thereof include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes And polyethylene imines.

Examples of the silicone surfactant include commercially available products such as DC3PA, DC7PA, SH11PA, SH21PA and SH8400 from Dow Corning Toray Silicone Co., and TSF-4440, TSF-4300, TSF-4445, TSF-4446 and TSF -4460 and TSF-4452.

Examples of the fluorine-based surfactant include Megaface 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).

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.

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

Applying the colored photosensitive resin composition on a substrate, and curing the photocurable resin composition to form a pattern. 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 coat method or a slit coat method. 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 coated film after curing is brought into contact with a developing solution to dissolve and develop the non-visible portion, a color filter having a desired pattern shape can be obtained.

The developing method may be any of a liquid addition method, a dipping method, and a spraying method. Further, the substrate may be inclined at an arbitrary angle during development. The developer is usually an aqueous solution containing an alkaline compound and a surfactant. The alkaline compound may be either an inorganic or organic alkaline compound. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogenphosphate, sodium dihydrogenphosphate, ammonium dihydrogenphosphate, ammonium dihydrogenphosphate, potassium dihydrogenphosphate, sodium silicate, potassium silicate, sodium carbonate, Sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate and ammonia. Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Monoisopropylamine, diisopropylamine, ethanolamine, and the like.

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

The surfactant in the alkali developer may be at least one selected from the group consisting of a nonionic surfactant, an anionic surfactant, and a cationic surfactant.

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 cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts. These surfactants may be used alone or in combination of two or more.

The concentration of the surfactant in the developer is usually 0.01 to 10% by weight, preferably 0.05 to 8% by weight, more preferably 0.1 to 5% by weight. After development, it may be washed with water and, if necessary, subjected to post-baking at 150 to 230 ° 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.

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

Example 1 to 3 and Comparative Example 1-2. Preparation of colored photosensitive resin composition

The composition and the content (% by weight) shown in Table 1 below were used to prepare colored photosensitive resin compositions.

Example Comparative Example One 2 3 One 2 The melamine compound (A) 0.8 0.5 0.2 One The acrylic polyol (B) 0.2 0.5 0.8 One The photoinitiator (C) One One One One One The photopolymerizable compound (D) 4.1 4.1 4.1 4.1 4.1 Solvent (E) 46.7 46.7 46.7 46.7 46.7 The colorant (F) 43 43 43 43 43 The alkali-soluble resin (G) 4.1 4.1 4.1 4.1 4.1 Surfactant (H) 0.1 0.1 0.1 0.1 0.1 Melamine compound (A): Jeramin-641 (Aekyung Chemical Co., Ltd.) (Formula 1)
Acrylic polyol (B): AA-2160 (A-11) (Aekyung Chemical Co., hydroxyl value 42 (KOH) mg / g)
Photopolymerization initiator (C): Ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranyloxybenzoyl) -9H-carbazol- ) (Irgacure OXE-02: Ciba)
Photopolymerizable compound (D): Dipentaerythritol hexaacrylate
Solvent (E): Propylene glycol monomethyl ether acetate
Coloring material (F): Pigment Green 7 (DIC)
Alkali-soluble resin (G): a copolymer of methacrylic acid and benzyl methacrylate (the ratio of methacrylic acid unit to benzyl methacrylate unit was 31:69 in molar ratio, acid value was 100 mgKOH / g, polystyrene reduced weight average molecular weight 20,000)
Surfactant (H): SH-8400 (Dow Corning)

Experimental Example 1. Evaluation of Heat Resistance of Colored Photosensitive Resin Composition

Each of the colored photosensitive resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 and 2 was applied to a glass having a size of 5 X 5 cm and dried, followed by bar coating to a thickness of 2.5 μm. The solvent was removed by drying in a 100 ° C oven for 3 minutes to expose the photomask to a total exposure of 300 m at a wavelength of 313 nm of 40 mJ at a wavelength of 300 nm and then cured in an oven at 230 ° C for 20 minutes to prepare a color filter. This color filter was evaluated for color change (heat resistance) before and after 230 占 폚 for 2 hours. At this time, it was judged that the variation width of calculated Eab was 1 or less, 3 or less, and 3 or more. The formula used here is calculated by the following equation (1) representing the color change in the three-dimensional colorimeter defined by L *, a *, b *, and as the color change value is smaller, a highly reliable color filter can be manufactured.

[Equation 1]

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

Experimental Example 2. Preparation of colored photosensitive resin composition Solvent resistance evaluation

Each of the colored photosensitive resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 and 2 was applied to a glass having a size of 5 X 5 cm and dried, followed by bar coating to a thickness of 2.5 μm. The solvent was removed by drying in a 100 ° C oven for 3 minutes to expose the photomask to a total exposure of 300 m at a wavelength of 313 nm of 40 mJ at a wavelength of 300 nm and then cured in an oven at 230 ° C for 20 minutes to prepare a color filter. The color filter was immersed in a NMP solution at room temperature for 30 minutes, 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 at this time is calculated by Equation (1) representing the color change in the three-dimensional colorimeter defined by L *, a *, b *, and a color filter with high reliability can be manufactured as the color change value becomes smaller.

Experimental Example 3. Evaluation of curing degree of colored photosensitive resin composition

Each of the colored photosensitive resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 and 2 was applied to a glass of 5 * 5 cm, dried, and then bar-coated to a thickness of 2.5 탆. The solvent was removed by drying in a 100 ° C oven for 3 minutes, and then the color filter was prepared by exposing the solvent to 300 m of the distance between the photomask and the Fusion Lamp so that the accumulated light quantity of 313 nm was 40 mJ.

The color filter was immersed in a 14 KOH aqueous solution for 3 minutes and then taken out. The color filter was then immersed in distilled water for 1 minute and then taken out. The color filter was cured in an oven at 230 deg. C for 20 minutes to measure the pattern line width and tearing of the color filter.

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

The degree of curing is measured by plotting the difference between the line width X1 of the pattern and the line width X2 of the photomask

division Heat resistance Solvent resistance Snatch Degree of hardening Example 1 equal 1.4 ○ +10 Example 2 Great 1.2 ○ +12 Example 3 Great 1.8 ○ +8 Comparative Example 1 Bad 2.7 Δ +7 Comparative Example 2 equal 3.6 X -2

As shown in Table 2, the colored photosensitive resin compositions of Examples 1 to 3, each containing a melamine compound as a photopolymerizable compound and an acryl polyol having a hydroxyl value of 10-60 (KOH) mg / g, ~ 2, it was confirmed that the degree of curing was high and the solvent resistance was excellent, but no color shift was caused by the temperature.

Claims

A colored photosensitive resin composition comprising a melamine compound (A), an acrylic polyol (B), a photoinitiator (C), a photopolymerizable compound (D), a solvent (E), a colorant (F) and an alkali soluble resin (G).

The method according to claim 1,
Wherein the melamine compound (A) is at least one selected from the group consisting of the following general formulas (1) and (2).
[Chemical Formula 1]

(2)

The method according to claim 1,
Wherein the hydroxyl value of the acrylic polyol (B) is 10 to 60 (KOH) mg / g.

The method according to claim 1,
Wherein the total content of the melamine compound (A) and the acrylic polyol (B) is 0.5 to 5% by weight based on the total weight of the composition.

The method according to claim 1,
Wherein the colored photosensitive resin composition further comprises a surfactant (G).

A color filter made of the colored photosensitive resin composition according to any one of claims 1 to 5.