KR20160115560A - Colored photosensitive resin composition and color filter manufactured by the same - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition and, more specifically, relates to a colored photosensitive resin composition comprising a thiol epoxy-based compound, thereby having excellent sensitivity. The colored photosensitive resin composition has excellent heat resistance of a manufactured pattern, and has reduced generation of yellowing.

Description

TECHNICAL FIELD [0001] The present invention relates to a colored photosensitive resin composition and a color filter produced therefrom. BACKGROUND OF THE INVENTION [0002]

The present invention relates to a colored photosensitive resin composition and a color filter produced therefrom, and more particularly to a colored photosensitive resin composition excellent in heat resistance and sensitivity and suppressed in yellowing, and a color filter manufactured therefrom.

Recently, liquid crystal display devices have been attracting attention as next generation advanced display devices with low power consumption, good portability, and high value-added.

Among these liquid crystal display devices, an active matrix type liquid crystal display device having a thin film transistor, which is a switching device capable of controlling voltage on / off for each pixel, It is attracting attention.

In general, a liquid crystal display device forms an array substrate and a color filter substrate through an array substrate manufacturing process for forming thin film transistors and pixel electrodes, and a color filter substrate manufacturing process for forming color filters and common electrodes, And a liquid crystal cell interposed therebetween.

The color filter includes pixels composed of red (R), green (G), and blue (B) colors, and light passing through the liquid crystal cell passes through the color filter to express a desired color.

However, with the recent spread of liquid crystal display devices, its use has been expanded to various monitors and TVs, and further improvement in color reproducibility has been demanded. In order to meet this demand, it is required to provide a color filter having a wider color reproduction area. Particularly, in TV applications, it has been required to expand the color reproduction area more than ever.

Further, in addition to the enlargement of the color reproduction range, there is also a demand for improvement in display quality due to high brightness and high contrast. However, there is a trade-off relationship between the color reproduction range, the transmittance, the color reproduction range and the contrast ratio, and there is a problem that the transmittance and the contrast ratio are lowered when the color reproduction range is enlarged.

In this regard, Korean Patent Laid-Open Publication No. 2005-0014725 discloses a color filter of C.I. Pigment Green 7 alone or C.I. Pigment Green 7 and C.I. Pigment Yellow 150. < / RTI >

However, CI Pigment Green 7 alone can not satisfactorily satisfy the required properties, and CI Pigment Yellow 150 contains environmentally regulated substances, which limits its use.

Korean Patent Publication No. 2005-0014725

An object of the present invention is to provide a colored photosensitive resin composition capable of producing a pattern having excellent heat resistance and suppressed yellowing.

It is another object of the present invention to provide a colored photosensitive resin composition excellent in sensitivity.

It is still another object of the present invention to provide a color filter manufactured using a colored photosensitive resin composition and an image display device including the same.

1. A colored photosensitive resin composition comprising a thiol epoxy compound.

2. The colored photosensitive resin composition according to 1 above, wherein the thiol epoxy compound is a compound represented by the following formula (1)

[Chemical Formula 1]

(Wherein R ₁ represents a linear or branched alkylene group having 2 to 8 carbon atoms, an arylene group having 6 to 20 carbon atoms in which the alkyl group having 1 to 5 carbon atoms is substituted or unsubstituted, or an alkyl group having 1 to 5 carbon atoms, A substituted or unsubstituted cycloalkylene group having 3 to 15 carbon atoms,

The alkyl group, the alkylene group, the arylene group or the cycloalkylene group may contain a hetero atom).

3. The colored photosensitive resin composition according to item 1, wherein the thiol epoxy compound is a compound represented by the following formula (2) or (3):

 (2)

 (3)

.

.

4. The colored photosensitive resin composition according to 1 above, wherein the thiol epoxy compound is contained in an amount of 0.01 to 1% by weight based on the solid content in the colored photosensitive resin composition.

5. The colored photosensitive resin composition according to 1 above, further comprising an alkali-soluble resin, a colorant, a photopolymerizable compound, a photopolymerization initiator and a solvent.

6. The colored photosensitive resin composition according to item 5 above, wherein, based on the solid content in the colored photosensitive resin composition,

10 to 80% by weight of an alkali-soluble resin,

10 to 80% by weight of a colorant,

1 to 45% by weight of photopolymerizable compound,

0.1 to 10% by weight of a photopolymerization initiator and

0.01 to 1% by weight of a thiol epoxy compound,

Wherein the coloring photosensitive resin composition is a colored photosensitive resin composition.

7. A color filter made of a colored photosensitive resin composition according to any one of the above 1 to 6.

8. An image display device comprising the color filter of 7 above.

The colored photosensitive resin composition of the present invention has excellent sensitivity by containing a compound having a specific structure and is excellent in heat resistance of the produced pattern and is capable of suppressing yellowing to maintain excellent transmittance and brightness.

The present invention relates to a colored photosensitive resin composition containing a thiol epoxy compound and having excellent sensitivity and excellent heat resistance in a produced pattern, and thus suppressing yellowing.

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

≪ Colored photosensitive resin composition &

The colored photosensitive resin composition of the present invention comprises a thiol epoxy compound. Of course, the colored photosensitive resin composition may further contain an alkali-soluble resin (A), a colorant (B), a photopolymerizable compound (C), a photopolymerization initiator (D) and a solvent (E) which are conventionally used in the art. In addition, it may further comprise additional components commonly used in the art, such as additives.

< Thiol epoxy system  Compound &gt;

The colored photosensitive resin composition of the present invention comprises a thiol epoxy compound.

When an alicyclic epoxy resin or a novolak epoxy resin is used as a curing agent for improving adhesion with a substrate in a colored photosensitive resin composition, yellowing occurs under high temperature conditions, and transmittance and luminance are lowered.

Accordingly, it is considered that the thiol epoxy compound according to the present invention maintains excellent sensitivity and improves heat resistance by increasing cross-linking density, thereby suppressing yellowing even under high temperature conditions. However, the present invention is not limited thereto.

The thiol epoxy compound according to the present invention can be used without particular limitation as long as it contains a thiol epoxy group, and preferred examples thereof include compounds represented by the following formula (1).

[Chemical Formula 1]

(Wherein R ₁ represents a linear or branched alkylene group having 2 to 8 carbon atoms, an arylene group having 6 to 20 carbon atoms in which the alkyl group having 1 to 5 carbon atoms is substituted or unsubstituted, or an alkyl group having 1 to 5 carbon atoms, A substituted or unsubstituted cycloalkylene group having 3 to 15 carbon atoms,

The alkyl group, the alkylene group, the arylene group or the cycloalkylene group may contain a hetero atom).

&Quot; Substituted or unsubstituted "means that at least one hydrogen atom in a hydrocarbon is, independently of each other, substituted with the same or different substituent .

More preferred examples of the thiol epoxy compound according to the present invention include compounds represented by the following general formula (2) or (3).

(2)

(3)

The thiol epoxy compound may be contained in an amount of 0.01 to 1% by weight, preferably 0.1 to 1% by weight, based on the solid content in the colored photosensitive resin composition. When the compound is contained in an amount of 0.01 to 1 wt% based on the above standard, a color filter having excellent sensitivity and excellent heat resistance and improved yellowing can be produced.

&Lt; Alkali-soluble resin (A) >

The alkali-soluble resin according to the present invention is a component that imparts solubility to an alkali developing solution used in a developing process when forming reactivity and pattern with respect to light or heat.

The alkali-soluble resin according to the present invention can be polymerized including a compound having an unsaturated bond and a carboxyl group.

 The compound having an unsaturated bond and a carboxy group is not limited as long as it is a carboxylic acid compound having an unsaturated double bond capable of being polymerized. Specific examples thereof include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, or unsaturated tricarboxylic acids, And a polyvalent carboxylic acid having a carboxyl group.

Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, and crotonic acid.

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

The polyvalent carboxylic acid may be an acid anhydride, and examples of the unsaturated polycarboxylic acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like.

The unsaturated polycarboxylic acid may also be a mono (2-methacryloyloxyalkyl) ester thereof, for example, mono (2-acryloyloxyethyl) succinate, mono (2-methacryloyloxy Ethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl), and the like.

The unsaturated polycarboxylic acid may be mono (meth) acrylate of the dicarboxylic polymer of both ends thereof, and examples thereof include ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, and the like. have.

The unsaturated polycarboxylic acid may be an unsaturated acrylate containing a hydroxyl group and a carboxyl group in the same molecule, and for example,? - (hydroxymethyl) acrylic acid and the like

Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used because of high copolymerization reactivity.

The compounds having an unsaturated bond and a carboxyl group according to the present invention may be used alone or in combination of two or more.

The alkali-soluble resin (A) according to the present invention may further comprise at least one other monomer copolymerizable with the unsaturated bond and a compound having a carboxyl group.

Methylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p- Aromatic vinyl compounds such as 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; 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; Unsaturated oxiranes such as glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate and methyl glycidyl compound; A (meth) acrylate substituted with a cycloalkane having 4 to 16 carbon atoms, a dicycloalkane, or a tricycloalkane ring; And the like. These may be used alone or in combination of two or more.

The acid value of the alkali-soluble resin is preferably in the range of 30 to 150 (KOH mg / g). When the acid value is in the above range, excellent developability for a developing solution, excellent sensitivity and adhesion, and excellent coating without pattern shorts can be produced.

The weight average molecular weight of the alkali-soluble resin in terms of polystyrene may be 5,000 to 50,000, and preferably 5,000 to 15,000. When the weight average molecular weight of the alkali-soluble resin is within the above range, it is preferable to prevent film reduction during development and to improve the missability of the pattern portion.

The content of the alkali-soluble resin is in the range of 10 to 80% by weight, preferably 10 to 70% by weight, based on the solid content in the colored photosensitive resin composition. When the content of the alkali-soluble resin is within the above range, the solubility in a developing solution is sufficient and the developing property is excellent. As the stability of the coating film is increased, the pattern is not short-circuited.

&Lt; Colorant (B) >

The colorant (B) according to the present invention may include pigments and dyes used in the art.

(b1) pigment

The pigment (b1) which can be used in the present invention includes organic pigments and inorganic pigments.

As the organic pigment, various pigments used in printing ink, inkjet ink and the like can be used. Specifically, phthalocyanine (water-soluble azo pigment, insoluble azo pigment), phthalocyanine pigment, quinacridone pigment, Anthanthrone pigments, anthanthrone pigments, anthanthrone pigments, anthraquinone pigments, anthanthrone pigments, anthanthrone pigments, anthanthrone pigments, indanthrone pigments, Pravantron pigments, pyranthrone pigments or diketopyrrolopyrrole pigments, and the like.

Examples of the inorganic pigments include metallic compounds such as metal oxides and metal complex salts and specifically oxides or complexes of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, Metal oxides and the like.

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.

As the pigment used in the pigment dispersion composition according to the present invention, organic pigments or inorganic pigments commonly used in the art can be used, and these pigments can be used singly or in combination of two or more kinds.

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 has been introduced, a graft treatment on the surface of a 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, a treatment for removing ionic impurities by an ion exchange method, or the like.

Specific examples of the above-

C.I. Pigment Yellow 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 147, 148, 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, 215, 216, 224, 242, 254, 255 and 264;

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

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

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

C.I. Pigment Brown 28; And the like.

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

In the colored photosensitive resin composition of the present invention, the (b1) pigment may be contained in the form of a pigment dispersion composition.

The pigment dispersion composition includes (b1) a pigment, (b2) a dispersant, and (b3) a dispersion aid, and (b4) a dispersion resin may be added to facilitate storage stability and dispersion.

The pigment (b1) may be contained in an amount of 20 to 90% by weight, preferably 30 to 70% by weight, based on the total weight of the solid content in the pigment dispersion composition. If the content of the pigment is not within the above range, the viscosity is high, the storage stability is bad, and the dispersion efficiency is low, which adversely affects the contrast ratio.

(b2) dispersant

The dispersing agent is added for maintaining deagglomeration and stability of the pigment, and any of those generally used in the art can be used without limitation. The dispersant preferably includes an acrylate-based dispersant (hereinafter referred to as an acrylate-based dispersant) comprising 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 dispersant according to the present invention, other resin type pigment dispersants other than the above acrylate dispersant may be used. Examples of the other resin type pigment dispersants include known resin type pigment dispersants, in particular, polycarboxylic acid esters such as polyurethane, polyacrylate, unsaturated polyamides, polycarboxylic acids, amine salts of polycarboxylic acids, An ammonium salt of a polycarboxylic acid, an alkylamine salt of a polycarboxylic acid, a polysiloxane, a long chain polyaminoamide phosphate salt, an ester of a polycarboxylic acid substituted with a hydroxyl group, a modified product thereof, a free carboxyl group (Meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylate ester copolymers, styrene-maleic acid copolymers, Water-soluble resins or water-soluble polymer compounds such as polymers, polyvinyl alcohol, and 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, manufactured by BYK (Big) Chemie Co., -164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; EFKA-4060, EFKA-4060, EFKA-4055, EFKA-4055, EFKA-4020, EFKA-4055, 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 trademarks of Kyoeisha Chemical Co.,

The dispersant is contained in an amount of 5 to 60 parts by mass, more preferably 15 to 50 parts by mass with respect to 100 parts by mass of the pigment in the colorant. If the amount of the dispersing agent is more than 60 parts by mass, the viscosity may be increased. If the amount is less than 5 parts by mass, it may be difficult to atomize the pigment, and gelation may occur after dispersion.

In addition to the above-mentioned dispersing agents, surfactants such as cationic, anionic, nonionic, amphoteric, polyester, and polyamine surfactants and the like may be used as a dispersant, and these may be used alone or in combination of two or more.

Specific examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, polyethyleneimine (Manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by TOKEM PRODUCTS CO., LTD.), Megafac (Manufactured by Asahi Glass Co., Ltd.), SOLSPERSE (manufactured by Asahi Glass Co., Ltd.), Mitsubishi Kasei MEGAFAC (manufactured by Dainippon Ink and Chemicals, Inc.), Flourad (manufactured by Sumitomo 3M Limited), Asahi guard, Surflon EFKA (manufactured by EFKA Chemical), PB 821 (manufactured by Ajinomoto Co., Ltd.), and the like.

(b3)

Dispersion auxiliaries are those agents that disperse pigments into fine particles to prevent re-aggregation. The dispersion auxiliary is effective for forming a colored layer having a high contrast ratio and an excellent transmittance.

Examples of the dispersion aid that can be used in the present invention include 1,8-diamino-4,5-dihydroxyanthraquinone, 1,5-bis {[2- (diethylamino) ethyl] (4-hydroxyphenyl) ethyl] amino} anthra-9,10-quinone, 1,4-bis -Bis {[2- (dimethylamino) ethyl] amino} -5,8-dihydroxyanthra-9,10-quinone, 1,8- dihydroxy- 4- [4- (2- ) Anilino] -5-nitroanthra-9,10-quinone, 1,4-dihydroxy anthraquinone, 1,4-bis (4-butylanilino) -5,8-dihydroxy anthraquinone, 4'- (4-hydroxy-1-anthraquinonylamino) -acetanilide, 1,4-bis [(2,6-diethyl- Bis (3-methylphenyl) amino] -9,10-anthracene dione, 1,4-bis (4-butyl anilino) -5,8-dihydroxy anthraquinone, , 10-anthracene Bis (isopropylamino) anthraquinone, 1,4-bis (methylamino) anthraquinone, 1,4-bis (2,6-diethyl (5-methylsulfonate), 1-anilino-4-hydroxynaphthalene-2-one Hydroxy-4 - [(4-methylphenyl) amino] -9,10-anthracenepione, 1,4-bis (para- tolylamino) anthraquinone, 1-amino- 1- (methylamino) -4- (4-methylanilino) anthracene-9,10-dicarboxylic acid anhydride, anthraquinone, N- [4- [ -Dioion and 1,4,5,8-tetrahydroxyanthraquinone, and the like.

In addition to the above-mentioned dispersion aid, if necessary, a commercially available dispersion aid may be further included. Specific examples thereof include SOLSPERSE-5000, SOLSPERSE-12000 and SOLSPERSE-22000 from Lubrizol, BYK-SYNERGIST 2100, BYK-SINERGIST 2105 from BYK, EFKA-6745 and EFKA-6750 from BASF.

The dispersion aid includes 1 to 30 parts by mass based on 100 parts by mass of the pigment in the colorant. If the amount exceeds 30 parts by mass of the dispersion aid, inherent color of the colorant (B) may be altered, and discoloration due to hard bake may occur during the production of the colored layer.

(b4)

The dispersion resin may be selectively added as a dispersion medium of the colorant (B), and it is possible to produce a more excellent pigment dispersion composition by mixing the dispersion resin (a4) with the dispersant (b2) alone. In the case of a dispersion resin, it is possible to use the dispersion resin as long as it can function as a dispersion medium. However, in consideration of the developability of the colored photosensitive resin composition prepared from the pigment dispersion composition, it is preferable to have an acid value in order to have solubility in an alkali developer.

Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the acrylic polymer, and can be generally determined by titration using an aqueous solution of potassium hydroxide.

In the case of a dispersion resin having an acid value, it can be prepared by copolymerizing a compound having a carboxyl group and an unsaturated bond and a compound having an unsaturated bond capable of copolymerization.

Specific examples of the compound having a carboxylic acid group and an unsaturated bond include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid; And an anhydride of the dicarboxylic acid; (meth) acrylates of a polymer having a carboxyl group and a hydroxyl group at both terminals such as? -carboxypolycaprolactone mono (meth) acrylate, and acrylic acid and methacrylic acid are preferable. In the present invention, (meth) acrylate refers to acrylate, methacrylate, or both.

The compounds exemplified as the above compounds may be used alone or in combination of two or more. Examples of the compound having an unsaturated bond capable of copolymerizing with the above compound include styrene, vinyltoluene,? -Methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p- Aromatic vinyls such as vinylbenzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m- vinyl benzyl glycidyl ether and p- compound; Propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth) acrylates such as sec-butyl (meth) acrylate or 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 or isobornyl (meth) acrylate; Aryl (meth) acrylates such as phenyl (meth) acrylate or benzyl (meth) acrylate; Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate; 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; Unsaturated amide compounds such as (meth) acrylamide and N, N-dimethyl (meth) acrylamide; 3- (methacryloyloxymethyl) -2-trifluoromethyl oxetane, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, etc. Unsaturated oxetane compounds, and the like.

The compounds exemplified as the above compounds may be used alone or in combination of two or more.

The dispersion resin is contained in an amount of 5 to 60 parts by mass, preferably 10 to 50 parts by mass, based on 100 parts by mass of the pigment solid in the colorant. When the dispersing resin exceeds 60 parts by mass, the viscosity can be increased by the dispersing resin. When the dispersing resin is less than 5 parts by mass, the amount of the dispersing resin is insufficient, and an atomized pigment dispersion composition can not be obtained.

(b5) 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 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 Yellow 4, 14, 15, 21, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, and 162;

C.I. Solvent Red 8, 45, 49, 122, 125 and 130;

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

C.I. Solvent Blue 35, 37, 59 and 67;

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

C.I. As an acid dye

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;

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;

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 and 19;

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

As a C.I. direct dye

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;

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;

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, C.I. As a modantoic dye

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 content of the dye may be 0.5 to 80% by weight, preferably 0.5 to 60% by weight, and more preferably 1 to 50% by weight based on the solid content in the colorant. When the content of the dye is in the above range, it is possible to prevent the dye from being eluted by the organic solvent after the pattern formation, and it is preferable since the sensitivity is excellent.

The colorant (B) may be contained in an amount of 10 to 80% by weight, preferably 35 to 50% by weight, based on the solid content in the colored photosensitive resin composition of the present invention. When the colorant is contained in an amount of 10 to 80% by weight based on the above standard, the color density of the pixel is sufficient even when the thin film is formed, and the residue of the non-cured portion is not deteriorated during development.

The colorant components may be previously dispersed / dissolved in a part of the composition solvent described later and added to the colored photosensitive resin composition.

< Photopolymerization  The compound (C)

The photopolymerizable compound contained in the colored photosensitive resin composition of the present invention 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.

The photopolymerizable compound used in the present invention may be a mixture of two or more photopolymerizable compounds having different functional groups or different functional groups in order to improve developability, sensitivity, adhesion, surface problems, etc. of the colored photosensitive resin composition, There is no limit to the range.

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, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol Hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. Of these, multifunctional monomers having two or more functional groups are preferably used.

The photopolymerizable compound may be contained in an amount of 1 to 45% by weight, preferably 1 to 30% by weight, based on the solid content in the colored photosensitive resin composition. When the photopolymerizable compound is contained in an amount of 1 to 45% by weight based on the above standard, the strength and smoothness of the pixel portion are preferably improved.

< Light curing  Initiator (D) &gt;

The photopolymerization initiator in the invention is a compound which generates a radical capable of initiating polymerization of the photopolymerizable compound by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. Typical examples of such a photopolymerization initiator include an acetophenone-based compound, a benzophenone-based compound, a nonimidazole-based compound, a triazine-based compound, an oxime ester-based compound, and a thioxanthone-based compound. In the present invention, the photopolymerization initiator may be used alone or in combination of two or more, and it is preferable to use at least one oxime ester compound.

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

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

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

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

Examples of the oxime ester compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl], 2- (O-benzoyloxime), 1- [ carbazol-3-yl] ethanone 1- (O-acetyloxime).

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

The photopolymerization initiator (D) may further comprise a photopolymerization initiator (d3) 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 (d3), whereby the sensitivity is further increased and the productivity can be improved.

As the photopolymerization initiation assistant (d3), 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 ), 4,4'-bis (diethylamino) benzophenone, and the like.

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

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

The photopolymerization initiator (D) may be contained in an amount of 1 to 5% by weight, preferably 1 to 3% by weight, based on the solid content in the colored photosensitive resin composition according to the present invention. When the photopolymerization initiator (D) is in the range of 1 to 5% by weight based on the above standard, the colored photosensitive resin composition is highly sensitized and the exposure time is shortened, which is preferable because productivity can be improved and high resolution can be maintained. Further, the strength of the pixel portion formed using the composition of the above-described conditions and the smoothness of the surface of the pixel portion can be improved.

When the photopolymerization initiator (d3) is further used, the photopolymerization initiator (d3) is added in an amount of 0.1 to 10% by weight, preferably 0.1 to 5% by weight, based on the solid content in the colored photosensitive resin composition according to the present invention. . When the content of the photopolymerization initiator (d3) is within the range of 0.1 to 10% by weight based on the above standard, the sensitivity of the colored photosensitive resin composition is higher and the productivity of the color filter formed using the composition is improved .

&Lt; Solvent (E) >

The solvent according to the present invention is used for dissolving other components of the colored photosensitive resin composition of the present invention and is not particularly limited as long as it is a solvent used in a commonly used colored photosensitive resin composition and includes ethers, Ketones, alcohols, esters, amides and the like are preferable.

Specific examples of the solvent 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;

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

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

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

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

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

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

Amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone.

An example thereof is ethyl 3-ethoxypropionate.

Among the solvents exemplified above, organic solvents having a boiling point of 100 占 폚 to 200 占 폚 are preferably used in view of the coating property and dry surface, more preferably alkylene glycol alkyl ether acetates, ketones, 3-ethoxypropionic acid Ethyl, and 3-methoxypropionate, and more preferred examples thereof include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, 3- Methyl propoxypropionate, and the like. These solvents may be used alone or in combination of two or more.

The content of the solvent in the colored photosensitive resin composition of the present invention may be 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 in the range of 60 to 90% by weight on the basis of the above-mentioned standard, the coating property can be improved when applied with a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (die coater)

&Lt; Additive (F) >

The photosensitive resin composition according to the present invention may further contain additives such as fillers, other polymer compounds, leveling agents, adhesion promoters, antioxidants, ultraviolet absorbers, coagulation inhibitors, chain transfer agents and the like as necessary.

Specific examples of the filler include glass, silica and alumina.

Specific examples of the other polymer compound include curable resins such as epoxy resin and maleimide resin; And thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane.

As the leveling agent, commercially available surfactants can be used, and examples thereof include surfactants such as silicone, fluorine, ester, cationic, anionic, nonionic, and amphoteric surfactants. Two or more species may be used in combination.

Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, (Manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), F-top (manufactured by TOKEM PRODUCTS CO., LTD.), Megapak (manufactured by Dainippon Ink Chemical Industry Co., (Manufactured by Asahi Glass Co., Ltd.), SORPARS (manufactured by Zeneca), EFKA (manufactured by EFKA CHEMICALS Co., Ltd.), FERRAD (manufactured by Sumitomo 3M Ltd.) , And PB821 (manufactured by Ajinomoto Co., Ltd.).

As the adhesion promoter, silane compounds are preferable, and specific examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) Aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N- 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3- Propyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and the like.

Specific examples of the antioxidant include 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- -3,5-di-tert-butylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 6- [3- (3- Bis [2- {3- [3- tert -butyl] benzo [d, f] [1,3,2] dioxaphospepine, 3,9- -Butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,2'-methylenebis 6-tert-butyl-4-methylphenol), 4,4'-butylidenebis (6-tert- Methylphenol), 2,2'-thiobis (6-tert-butyl-4-methylphenol), dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate , Distearyl 3,3'-thiodipropionate, pentaerythrityl tetrakis (3-laurylthiopropionate), 1,3,5-tris (3,5-di-tert (3H, 3H, 5H) -triene, 3,3 ', 3 ", 5,5' 5 '' - hexa-tert-butyl-a, a ', a' '- (mesitylene-2,4,6-triyl) tri-p-cresol, pentaerythritol tetrakis [3- Di-tert-butyl-4-hydroxyphenyl) propionate], 2,6-di-tert-butyl-4-methylphenol and the like.

Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole and alkoxybenzophenone.

Specific examples of the anti-aggregation agent include sodium polyacrylate and the like.

Specific examples of the chain transfer agent include dodecyl mercaptan, 2,4-diphenyl-4-methyl-1-pentene, and the like

&Lt; Color filter and image display device >

The present invention provides a color filter made of the colored photosensitive resin composition and an image display device including the color filter.

The image display device having such a color filter may be a liquid crystal display device, an OLED, a flexible display, or the like, but is not limited thereto and all applicable image display devices known in the art are applicable.

The color filter can be produced by applying the above-mentioned colored photosensitive resin composition of the present invention on a substrate, and photo-curing and developing it to form a pattern.

First, the colored photosensitive resin composition is coated on a substrate and then heated and dried 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, volatile components such as solvents are volatilized. 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. Ultraviolet rays are applied to the thus obtained coating film 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 accurately 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. The desired pattern shape can be formed by dissolving the unexposed portion and developing the coated film after the hardening is brought into contact with the developing solution.

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 an 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, potassium 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 alkaline developer is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass.

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 nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.

Specific examples of the anionic surfactant include higher alcohol sulfuric acid ester salts such as sodium lauryl alcohol sulfate ester and sodium oleyl alcohol sulfate ester, 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. Each of 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 mass, preferably 0.05 to 8% by mass, and more preferably 0.1 to 5% by mass. 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.

It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to be illustrative of the invention and are not intended to limit the scope of the claims. It will be apparent to those skilled in the art that such variations and modifications are within the scope of the appended claims.

Synthetic example

Of the alkali-soluble resin Synthetic example

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was provided with 74.8 g (0.20 mol) of benzylmaleimide, 43.2 g (0.30 mol) of acrylic acid, 4 g of t-butylperoxy-2-ethylhexanoate and 40 g of propylene glycol monomethyl ether acetate (PGMEA) were charged and stirred to prepare a charge transfer additive dropping funnel. To this was added n-dodecanethiol And 24 g of PGMEA were placed and stirred and prepared.

Thereafter, 395 g of PGMEA was introduced into the flask, the atmosphere in the flask was changed to nitrogen in air, and the temperature of the flask was raised to 90 캜 while stirring. Then, the monomer and the chain transfer agent were added dropwise from the dropping funnel. The mixture was heated at 110 ° C. for 1 h and maintained at 90 ° C. for 1 h. The temperature was raised to 110 ° C. for 3 h. Then, a gas introduction tube was introduced to bubbling oxygen / nitrogen gas with 5/95 (v / v) .

Then, 28.4 g of [(0.10 mol) of glycidyl methacrylate (33 mol% based on the carboxyl group of the acrylic acid used in the present reaction)], 2,2'-methylenebis (4-methyl-6-t- ) And 0.8 g of triethylamine were placed in a flask, and the reaction was continued at 110 캜 for 8 hours to obtain a resin A having a solid acid value of 70 mgKOH / g. The weight average molecular weight measured by GPC in terms of polystyrene was 16,000 and the molecular weight distribution (Mw / Mn) was 2.3.

Apparatus: HLC-8120GPC (manufactured by TOSOH CORPORATION)

 Column: TSK-GELG4000HXL + TSK-GELG2000HXL (Serial connection)

 Column temperature: 40 DEG C

 Mobile phase solvent: tetrahydrofuran

 Flow rate: 1.0 ml / min

 Injection amount: 50 μl

 Detector: RI

 Measurement sample concentration: 0.6 mass% (solvent = tetrahydrofuran)

 Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by TOSOH CORPORATION)

The ratio of the weight average molecular weight to the number average molecular weight obtained above was defined as a molecular weight distribution (Mw / Mn).

Example  And Comparative Example

A colored photosensitive resin composition was prepared with the components and compositions shown in Tables 1 and 2 below (parts by weight).

Example One 2 3 4 5 6 7 8 Hardener G-1 0.08 0.25 0.41 0.56 0.78 - - - G-2 - - - - - 0.25 - 0.1 G-3 - - - - - - 0.25 0.1 G-4 - - - - - - - - G-5 - - - - - - - - The alkali-soluble resin (A) 6.59 6.42 6.42 6.11 5.89 - - - The colorant (B) B-1 14.56 B-2 16.30 The photopolymerizable compound (C) 5.04 Photopolymerization initiator (D) 1.18 Solvent (E) 52.26

A:합성예의 알칼리 가용성 수지

B-1: 피그먼트 그린 G7
B-2: 피그먼트 옐로우 Y129

C: 디펜타에리트리톨헥사아크릴레이트(Kayarad DPHA: 닛본 카야꾸㈜)
D: TR-PBG-305 (트론니社)
E: 프로필렌글리콜모노메틸에테르아세테이트G-1: Compound of formula (2)
G-2: Compound of formula (3)
G-3: Compound of formula 4
G-4: Orthocresol novolac epoxy resin (SUMI-EPOXY ESCN-195XL manufactured by Sumitomo Chemical Co., Ltd.)
G-5: Alicyclic epoxy resin (EPHE-3150, manufactured by Diese Chemical Industry Co., Ltd.)
[Chemical Formula 4]

A: An alkali-soluble resin

B-1: Pigment Green G7
B-2: Pigment Yellow Y129

C: dipentaerythritol hexaacrylate (Kayarad DPHA: Nippon Kayaku Co., Ltd.)
D: TR-PBG-305 (Tronny)
E: Propylene glycol monomethyl ether acetate

Comparative Example One 2 3 Hardener G-1 - - - G-2 - - - G-3 - - - G-4 0.08 - - G-5 - - 0.08 The alkali-soluble resin (A) 6.67 6.42 6.67 The colorant (B) B-1 14.56 B-2 16.30 The photopolymerizable compound (C) 5.04 Photopolymerization initiator (D) 1.18 Solvent (E) 52.26

Experimental Example

&Lt; Production of color filter &

A color filter was prepared using the colored photosensitive resin compositions prepared in Examples 1 to 8 and Comparative Examples 1 to 3.

Specifically, each of the above colored photosensitive resin compositions was applied on a 2-inch-square glass substrate ("EAGLE XG", manufactured by Corning Inc.) by spin coating, then placed on a heating plate and held at a temperature of 100 ° C. for 3 minutes to form a thin film .

Subsequently, a test photomask having a pattern for changing the transmittance in the range of 1 to 100% to a step-like pattern and a line / space pattern of 1 to 50 m was placed on the thin film and the distance between the test photomask and the test photomask was set to 100 m. Respectively. At this time, the ultraviolet light source was irradiated with a high pressure mercury lamp of 1 KW containing g, h and i lines at an illuminance of 100 mJ / cm 2, and no special optical filter was used.

 The ultraviolet-irradiated thin film was immersed in a KOH aqueous solution of pH 10.5 for 2 minutes to develop. The glass plate coated with the thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 230 ° C for 20 minutes to prepare a color filter. The film thickness of the color filter prepared above was 2.0 mu m.

1. Evaluation of heat resistance

The fabricated color filter was immersed in a heating oven at 230 deg. C for 2 hours to evaluate color change before and after heating. Then, the chromaticity change rate (? E * ab) was calculated and shown in Table 3 below. The equation to be used at this time is calculated by the following Equation 1 representing the color change in the three-dimensional colorimetry defined by L *, a *, b *, and is shown in Table 3 below. The smaller the color change value is, the more reliable the color filter can be manufactured. If the value of (ΔE * ab) is 3.0 or less, a person can not feel color difference.

[Equation 1]

ΔE * ab = [(△ L *) 2 + (△ a *) 2 + (△ b *) 2] (1/2)

2. Yellow  Occurrence evaluation

The fabricated color filter was immersed in a heating oven at 230 deg. C for 2 hours to evaluate color change before and after heating. Next, the chromaticity change rate (? E * ab) is calculated by the above-mentioned formula (1) and shown in the following Table 3, and the occurrence of the yellowing was evaluated by the following criteria.

○: No yellowing occurred

?: Less yellowing

X: Severe yellowing

3. Sensitivity evaluation

(The film thickness before development / the film thickness after development) x 100) ≥ 90% of the film thickness of the film was changed in the same manner as in the luminance measurement method except that a pattern mask for changing the transmittance in the range of 1 to 100% The minimum exposure dose was expressed as sensitivity and evaluated according to the following criteria. The results are shown in Table 3 below.

○: When the pattern remains at a sensitivity of less than 50 (mJ / cm 2)

X: When the pattern remains at a sensitivity of 50 (mJ / cm2) or more

Chromaticity change rate Yellowing Sensitivity
(mJ / cm ² ) Example 1 1.9 ○ ○ Example 2 2.2 ○ ○ Example 3 2.3 ○ ○ Example 4 2.7 △ ○ Example 5 3.0 △ ○ Example 6 2.3 ○ ○ Example 7 2.2 ○ ○ Example 8 2.3 ○ ○ Comparative Example 1 3.2 x ○ Comparative Example 2 4.1 x x Comparative Example 3 3.3 x ○

As shown in Table 3, it was confirmed that the embodiments containing the thiol epoxy compound of the present invention had better sensitivity than the comparative examples containing no thiol epoxy compound.

In addition, in Examples, the image display device including the color filter made of the colored photosensitive resin composition of the present invention was excellent in heat resistance, and it was confirmed that the occurrence of yellowing was suppressed and the possibility of display failure was low.

However, in Examples 4 and 5, which contained a slight excess of the thiol epoxy compound of the present invention, it was confirmed that a little yellowing occurred.

Claims (8)

A thiol epoxy compound, and a thiol epoxy compound.
The colored photosensitive resin composition according to claim 1, wherein the thiol epoxy compound is a compound represented by the following formula (1)
[Chemical Formula 1]

(Wherein R ₁ represents a linear or branched alkylene group having 2 to 8 carbon atoms, an arylene group having 6 to 20 carbon atoms in which the alkyl group having 1 to 5 carbon atoms is substituted or unsubstituted, or an alkyl group having 1 to 5 carbon atoms, A substituted or unsubstituted cycloalkylene group having 3 to 15 carbon atoms,
The alkyl group, the alkylene group, the arylene group or the cycloalkylene group may contain a hetero atom).
The colored photosensitive resin composition according to claim 1, wherein the thiol epoxy compound is a compound represented by Formula 2 or Formula 3:
(2)

(3)

.
The colored photosensitive resin composition according to claim 1, wherein the thiol epoxy compound is contained in an amount of 0.01 to 1% by weight based on the solid content in the colored photosensitive resin composition.
The colored photosensitive resin composition according to claim 1, further comprising an alkali-soluble resin, a colorant, a photopolymerizable compound, a photopolymerization initiator, and a solvent.
6. The colored photosensitive resin composition according to claim 5, wherein, based on the solid content in the colored photosensitive resin composition,
10 to 80% by weight of an alkali-soluble resin,
10 to 80% by weight of a colorant,
1 to 45% by weight of photopolymerizable compound,
0.1 to 10% by weight of a photopolymerization initiator and
0.01 to 1% by weight of a thiol epoxy compound,
Wherein the coloring photosensitive resin composition is a colored photosensitive resin composition.
A color filter made of the colored photosensitive resin composition according to any one of claims 1 to 6.
An image display apparatus comprising the color filter of claim 7.