KR20190058126A - Colored Photosensitive Resin Composition, Color Filter and Display Device - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, wherein the colorant comprises a zinc phthalocyanine halide pigment, the alkali-soluble resin comprises a thioether group-containing repeating unit, and the solvent comprises a first solvent having a boiling point of 180 to 190°C and a vapor pressure of 0.18 to 0.32 mmHg at 20°C, to a color filter produced by using the same, and to an image display device. The colored photosensitive resin composition according to the present invention has high transmittance and is free from residue, stains, and pattern peeling in the production of the color filter, and is excellent in productivity.

Description

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

The present invention relates to a colored photosensitive resin composition, a color filter, and an image display device, and more particularly, to a colored photosensitive resin composition having a high transmittance and excellent in productivity without residue, stain and pattern peeling in the production of a color filter, And an image display apparatus having the color filter.

BACKGROUND ART Color filters are widely used in imaging elements, liquid crystal display elements, and the like, and their application range is rapidly expanding. The color filter is prepared by uniformly applying a colored photosensitive resin composition containing a coloring agent corresponding to each color of red, green and blue on a substrate on which a black matrix is pattern-formed by spin coating and then heating and drying (hereinafter, (Hereinafter sometimes referred to as post-baking) is repeated for each color to form pixels of each color, as required.

In recent years, there is a growing demand for high-quality displays with high coloring power. In the case of a colored photosensitive resin composition for generating green pixels, a coloring material of zinc phthalocyanine series is mainly used (see Korean Patent Publication No. 10-2012-0022668). However, in the case of a zinc halide phthalocyanine-based coloring material, a high-concentration pigment content is required in the colored photosensitive resin composition in order to realize a sufficient color density. As a result, unevenness or residue may occur during the color filter manufacturing process, or the pattern may be peeled off during the developing process, thereby reducing the reliability of the color filter. On the other hand, development of a colored photosensitive resin composition having excellent productivity in the production of a color filter is required.

Korean Patent Publication No. 10-2012-0022668

An object of the present invention is to provide a colored photosensitive resin composition having a high transmittance and free from residue, stain, and pattern peeling during the manufacture of a color filter, and having excellent productivity.

Another object of the present invention is to provide a color filter formed using the colored photosensitive resin composition.

It is still another object of the present invention to provide an image display apparatus provided with the color filter.

On the other hand, the present invention relates to a colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, wherein the colorant comprises a zinc phthalocyanine pigment and the alkali- Wherein the solvent has a boiling point of from 180 to 190 DEG C and a vapor pressure of from 0.18 mmHg to 0.32 mmHg at 20 DEG C, and a second solvent having an ethylenic unsaturation The present invention provides a colored photosensitive resin composition comprising

[Chemical Formula 1]

In this formula,

X ¹ is hydrogen or a methyl group,

X ² is a C ₁ -C ₆ alkylene group or a C ₂ -C ₆ alkenylene group,

A is an aryl group, a C ₃ -C ₁₀ cycloalkyl group, a C ₁ -C ₆ alkyl group or a C ₂ -C ₆ alkenyl group.

On the other hand, the present invention provides a color filter formed using the colored photosensitive resin composition.

On the other hand, the present invention provides an image display device having the color filter.

The colored photosensitive resin composition according to the present invention comprises a colorant containing a zinc phthalocyanine pigment and contains a thioether group-containing alkali-soluble resin and has a boiling point of 180 to 190 캜 and a vapor pressure of 0.18 mmHg to 0.32 mmHg at 20 캜. It is possible to realize a high color reproducibility including the first solvent, high transmittance, no residue, stain and pattern peeling in the production of color filter, and excellent productivity.

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

An embodiment of the present invention includes a colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D) and a solvent (E) (E) has a boiling point of 180 to 190 DEG C and a vapor pressure of 0.18 mmHg to 20 g / cm < 2 > at 20 DEG C, and the solvent (E) And 0.32 mmHg of a first solvent.

The colorant (A)

The pigment (a1)

In one embodiment of the present invention, the colorant (A) comprises a zinc phthalocyanine pigment.

The zinc halide phthalocyanine pigment has excellent transmittance and high contrast ratio. The zinc halide phthalocyanine pigments include, for example, C.I. Pigment Green 58, C.I. Pigment Green 59, etc. These may be used alone or in combination of two or more.

In addition to the zinc halide phthalocyanine pigments, organic pigments or inorganic pigments generally used in the art can be further used. The pigment may be any of various pigments used in printing ink, ink jet ink and the like. Specific examples thereof include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, Anthanthrone pigments, indanthrone pigments, pravanthrone pigments, pyranthrone pigments, anthraquinone pigments, anthraquinone pigments, anthanthrone pigments, anthanthrone pigments, anthanthrone pigments, indanthrone pigments, Pigments, diketopyrrolo pyrrole pigments, and the like. Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts, and carbon black. Specifically, examples of the metal compound include oxides or complex metal oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc and antimony. Green, yellow and blue pigments are preferable. Particularly, as the organic pigments and inorganic pigments, C.I.I., among the compounds classified as pigments in the color index (The Society of Dyers and Colourists). Pigment Yellow, C.I. Pigment Green, C.I. Pigment Blue, and more specifically, a pigment having a color index (C.I.) number as described below, and C.I. Pigment Yellow, C.I. Pigment greens are preferable, but they are not necessarily limited to these pigments, and they may be used alone or in combination of two or more.

C.I. Pigment Yellow 129, 138, 139, 150, 185 and 231

C.I. Pigment Green 7, 36, 62 and 63

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

The pigment dispersant (a2)

The pigment dispersant (a2) is added for maintenance of deagglomeration and stability of the pigment, and any of those generally used in the art can be used without limitation. Commercial dispersants include LPN-6919, Disperbyk-101, 103, 107, 108, 110, 111, 112, 116, 130, 140, 142, 154, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, And Lubrizol's SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, and the like.

These may be used alone or in admixture of two or more. Preferred are LPN-6919 of BYK, Disperbyk-2000, 2001 of BYK, which is an acid functional group-containing dispersant, SOLSPERSE-3000, 21000, 26000, 36600 of Lubrizol , 41000, and the like, but are not limited thereto.

The content of the pigment dispersant (a2) is 5 to 60 parts by weight, preferably 15 to 50 parts by weight based on 100 parts by weight of the pigment (a1). If the content of the pigment dispersant (a2) is more than 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 gelation after dispersion.

The dye (a3)

In one embodiment of the present invention, the colorant (A) may further comprise a dye (a3) generally used in the art.

The dye (a3) may be used additionally 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. Yellow dyes such as Solvent Yellow 4, 14, 15, 16, 21, 23, 24, 38, 56, 62, 63, 68, 79, 82, 93, 94, 98, 99, 151, 162, 163;

C.I. Solvent dye having excellent solubility in an organic solvent. Solvent Yellow 14, 16, 21, 56, 151, 79, 93 are preferred, and C.I. Solvent Yellow 21, 79 is even more preferred.

Also, C.I. C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 112, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, Yellow dyestuffs such as silver halide emulsions, silver halide emulsions, silver halide emulsions, silver halide emulsions, silver halide emulsions, silver halide emulsions, silver halide emulsions, silver halide emulsions, silver halide emulsions, . And C.I. solubility of the above acid dye in an organic solvent. Acid Yellow is preferred.

C.I. As a direct dye,

C.I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 136, 138 and 141, and the like.

Also, C.I. As a modantoic dye

C.I. Yellow dyes such as Modan Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65 and the like.

These dyes (a3) may be used alone or in combination of two or more.

The colorant (A) may be contained in an amount of 15 to 60% by weight, preferably 15 to 50% by weight based on 100% by weight of the total solid content in the colored photosensitive resin composition. When the colorant is included in the above-described range, even if a thin film is formed, the color density of the pixel is sufficient, and the dropping property of the non-curing portion during development is not lowered.

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

The alkali-soluble resin (B)

In one embodiment of the present invention, the alkali-soluble resin (B) generally has reactivity and alkali solubility due to the action of light or heat and acts as a dispersion medium of the coloring material.

The alkali-soluble resin (B) includes a copolymer (b1) of a compound represented by the following formula (1), an unsaturated carboxylic acid, and a compound having an unsaturated bond copolymerizable therewith.

[Chemical Formula 1]

In this formula,

X ¹ is hydrogen or a methyl group,

X ² is a C ₁ -C ₆ alkylene group or a C ₂ -C ₆ alkenylene group,

A is an aryl group, a C ₃ -C ₁₀ cycloalkyl group, a C ₁ -C ₆ alkyl group or a C ₂ -C ₆ alkenyl group.

As used herein, a C ₁ -C ₆ alkylene group means a linear or branched divalent hydrocarbon having 1 to 6 carbon atoms, and includes, for example, methylene, ethylene, propylene, and butylene. It is not.

As used herein, the C ₂ -C ₆ alkenylene group means a linear or branched divalent unsaturated hydrocarbon composed of 2 to 6 carbon atoms having at least one carbon-carbon double bond and includes, for example, vinylene, Butylene, phenylene, butylene, phenylene, and the like.

As used herein, an aryl group includes both an aromatic group and a heteroaromatic group and a partially reduced derivative thereof. The arromatic group is a simple or fused ring of 5 to 15 members, and the heteroaromatic group means an aromatic group containing at least one of oxygen, sulfur or nitrogen. Exemplary aryl groups include, but are not limited to, phenyl, naphthyl, pyridinyl, furanyl, thiophenyl, indolyl, quinolinyl, imidazolinyl, But are not limited to, oxazolyl, thiazolyl, tetrahydronaphthyl, and the like.

C ₃ -C ₁₀ cycloalkyl group as used herein means a simple or fused ring hydrocarbon having 3 to 10 carbon atoms and includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like, It is not.

As used herein, the C ₁ -C ₆ alkyl group means a linear or branched monovalent hydrocarbon having 1 to 6 carbon atoms, for example, methyl, ethyl, n-propyl, i-propyl, , i-butyl, t-butyl, n-pentyl, n-hexyl, and the like.

As used herein, the C ₂ -C ₆ alkenyl group means a linear or branched monovalent unsaturated hydrocarbon having 2 to 6 carbon atoms having at least one carbon-carbon double bond and includes, for example, ethylene, propyl But are not limited to, pentyl, pentyl, pentyl, and the like.

The C ₁ -C ₆ alkylene group, the C ₂ -C ₆ alkenylene group, the aryl group, the C ₃ -C ₁₀ cycloalkyl group, the C ₁ -C ₆ alkyl group and the C ₂ -C ₆ alkenyl group may be the same or different, One or more hydrogens may be substituted with halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, hydroxy, acyl, alkoxycarbonyl, carboxy, amino, and the like.

In particular, the compound represented by Formula 1 may be a compound represented by Formula 2 below.

(2)

In this formula,

X ¹ is hydrogen or a methyl group,

X ² is a C ₁ -C ₆ alkylene group or a C ₂ -C ₆ alkenylene group.

The use of the compound represented by the above formula (2) is preferable from the viewpoint of development.

Specific examples of the compound represented by Formula 1 include 2- (phenylthio) ethyl (meth) acrylate, 2- (cyclohexylthio) ethyl (meth) acrylate, 2- And the like. These may be used alone or in combination of two or more. Particularly, when 2- (phenylthio) ethyl (meth) acrylate is used, the development speed is high and it is difficult to generate a residue, which is preferable.

The compound represented by the formula (1) may be contained in an amount of 2 to 50 mol% based on 100 mol% of all the monomers constituting the alkali-soluble resin (b1).

The unsaturated carboxylic acid is not limited as long as it is a carboxylic acid compound having an unsaturated double bond capable of being polymerized. Specific examples of the unsaturated carboxylic acid include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid; And anhydrides of these 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 the like. Of these, acrylic acid and methacrylic acid are preferred because of their excellent copolymerization reactivity and solubility in a developing solution. These may be used alone or in combination of two or more.

The unsaturated carboxylic acid may be contained in an amount of 2 to 70 mol% based on 100 mol% of the total monomers constituting the alkali-soluble resin (b1).

Examples of the compound having an unsaturated bond that can be copolymerized with the compound represented by Formula 1 and the unsaturated carboxylic acid include an aromatic vinyl compound, an N-substituted maleimide compound, an unsubstituted or substituted alkyl ester of an unsaturated carboxylic acid, and an alicyclic substituent Unsaturated carboxylic acid esters, carboxylic acid vinyl esters, unsaturated oxetanyl compounds containing an oxetane group, and unsubstituted or substituted aryl esters of unsaturated carboxylic acids. Among these compounds, aromatic vinyl compounds, unsubstituted or substituted aryl esters of unsaturated carboxylic acids, and N-substituted maleimide compounds are more preferable in terms of improvement in sensitivity and adhesion. These may be used alone or in combination of two or more.

Examples of the aromatic vinyl compound include vinyl toluene, styrene,? -Methyl styrene,? -Chlorostyrene, and divinyl benzene. These aromatic vinyl compounds may be used alone or in combination of two or more. Particularly, vinyltoluene is preferable because it is excellent in sensitivity and adhesion, and has high solubility in a solvent.

Examples of the N-substituted maleimide compound include N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np- Methylphenylmaleimide, N-methylphenylmaleimide, N-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, Np-methoxyphenylmaleimide, and the like. These may be used alone or in combination of two or more.

Examples of the unsubstituted or substituted alkyl ester of the unsaturated carboxylic acid include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, Butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, aminoethyl (meth) acrylate, And the like. These may be used alone or in combination of two or more.

Examples of the unsaturated carboxylic acid ester having an alicyclic substituent include cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, cycloheptyl Acrylates such as octyl (meth) acrylate, menthyl (meth) acrylate, cyclopentenyl (meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (Meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, pinanyl (meth) acrylate, adamantyl rate, and the like tricyclo [5.2.1.0 ^2,6] decane-8-yl (meth) acrylate, 2-dicyclopentanyloxy (meth) acrylate. These may be used alone or in combination of two or more.

Examples of the carboxylic acid vinyl ester include vinyl acetate and vinyl propionate. These may be used alone or in combination of two or more.

Examples of the unsaturated oxetanyl compound containing an oxetane group include 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-pentafluoroethyloxetane, 3- 3- (methacryloyloxymethyl) -2-phenyloxetane, 3- (methacryloyloxymethyl) -2,2-difluorooxetane, 3- (methacryloyloxymethyl) -2 , 3- (methacryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (methacryloyloxyethyl) oxetane, 3 - (methacryloyloxyethyl) -3-ethyloxetane, 2-ethyl-3- (methacryloyloxyethyl) oxetane, 3- (Methacryloyloxyethyl) -2-phenyloxetane, 2,2-difluoro-3- (methacryloyloxyethyl) -2-pentafluoroethyloxetane, 3- (Methacrylic 3- (methacryloyloxyethyl) -2,2,4-trifluorooxetane, 3- (methacryloyloxyethyl) -2,2,4,4-tetra And fluorooxetane. These may be used alone or in combination of two or more.

Examples of the unsubstituted or substituted aryl ester of the unsaturated carboxylic acid include phenyl (meth) acrylate and benzyl (meth) acrylate. These may be used alone or in combination of two or more.

The compound having the unsaturated bond capable of copolymerization with the compound represented by the formula (1) and the unsaturated carboxylic acid may be contained in an amount of 2 to 70 mol% based on 100 mol% of the total monomers constituting the alkali-soluble resin (b1).

Specifically, the alkali-soluble resin (b1) may preferably include a copolymer of 2- (phenylthio) ethyl (meth) acrylate, an unsaturated carboxylic acid, and vinyltoluene.

The method for producing the copolymer is not particularly limited, and conventionally known polymerization methods can be used, and among the known polymerization methods, a solution polymerization method is preferable. The polymerization temperature and the polymerization time vary depending on the type and ratio of the monomers to be introduced, the molecular weight and the acid value of the desired alkali-soluble resin, but can be, for example, polymerized at 60 to 130 ° C for 1 to 10 hours.

When a solvent is used in the polymerization, a solvent used in a conventional radical polymerization reaction may be used. Specific examples thereof include tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, acetone, methyl ethyl ketone Propyl alcohol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propyleneglycol monomethyl ether, propyleneglycol monomethyl ether, propyleneglycol monomethyl ether, propyleneglycol monomethylether acetate, Ether, toluene, xylene, ethylbenzene, chloroform, dimethylsulfoxide, and the like. These solvents may be used alone or in combination of two or more.

As the polymerization initiator to be used in the polymerization, a commonly used polymerization initiator may be added and is not particularly limited. Specific examples thereof include diisopropylbenzene hydroperoxide, di-t-butyl peroxide, benzoyl peroxide, t-butyl peroxyisopropyl carbonate, t-amyl peroxy-2-ethylhexanoate, Organic peroxides such as peroxy-2-ethylhexanoate; Azo compounds such as 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile) and dimethyl 2,2'-azobis (2-methylpropionate) Nitrogen compounds. These may be used alone or in combination of two or more.

In the polymerization, a chain transfer agent may be used to control the molecular weight or the molecular weight distribution of the copolymer. Examples of the chain transfer agent include mercapto compounds such as n-dodecanethiol, mercaptoacetic acid and methyl mercaptoacetate; methylstyrene dimer, and the like.

In addition, the alkali-soluble resin (b2) usually used in this field can be mixed and used as long as the effect of the present invention is not impaired. Specific examples thereof include benzyl methacrylate / methacrylic acid copolymer and the like, but are not limited thereto.

The acid value of the alkali-soluble resin (B) is preferably 30 to 200 mgKOH / g. When the acid value of the alkali-soluble resin (B) is less than 30 mgKOH / g, it is difficult to secure a sufficient development rate of the colored photosensitive resin composition. When the acid value exceeds 200 mgKOH / g, the adhesion with the substrate is reduced,

The weight average molecular weight (hereinafter simply referred to as "weight average molecular weight") of the polymer in terms of polystyrene measured by gel permeation chromatography (GPC; tetrahydrofuran as an elution solvent) is 3,000 to 100,000, preferably 5,000 to 50,000 Alkali-soluble resins are preferable. When the molecular weight is within the above range, the hardness of the coating film is improved, the residual film ratio is high, the solubility of the non-exposed portion in the developer is excellent, and the resolution tends to be improved.

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

The alkali-soluble resin (B) may be contained in an amount of 10 to 80% by weight, preferably 10 to 70% by weight based on 100% by weight of the total solid content in the colored photosensitive resin composition. When the alkali-soluble resin (B) is contained in the above-described range, the solubility of the alkali-soluble resin (B) in the developer is satisfactory and pattern formation is easy, and the reduction in film thickness of the pixel portion of the exposed portion is prevented during development, .

Photopolymerization  The compound (C)

In one embodiment of the present invention, the photopolymerizable compound (C) is a compound capable of polymerizing under the action of the photopolymerization initiator (D) described below, and monofunctional monomers, bifunctional monomers or other polyfunctional monomers can be used. Preferably, a multifunctional monomer having two or more functional groups can be used.

Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate or N- But are not limited thereto.

Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) , Bis (acryloyloxyethyl) ether of bisphenol A or 3-methylpentanediol di (meth) acrylate, but are not limited thereto.

Specific examples of the other polyfunctional monomer include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, penta (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, but are not limited thereto.

The photopolymerizable compound (C) may be contained in an amount of 5 to 45% by weight, particularly 7 to 45% by weight based on 100% by weight of the total solid content in the colored photosensitive resin composition. When the photopolymerizable compound (C) is included in the above range, the strength and smoothness of the pixel portion can be improved.

Light curing Initiator (D)

In an embodiment of the present invention, the photopolymerization initiator generates radicals capable of initiating polymerization of the photopolymerizable compound (C) by exposure to radiation such as visible light, ultraviolet light, deep ultraviolet light, electron beam, X- / RTI >

The photopolymerization initiator preferably includes an oxime ester compound (d1).

Examples of the oxime ester compound include 1,2- octanedione, 1- [4- (phenylthio) phenyl] -, 2- (O-benzoyloxime), 1- [ -9H-carbazol-3-yl] ethanone 1- (O-acetyloxime). Commercially available products include IGACURE OXE 01, IGACURE OXE 02 and IGACURE OXE 03 from BASF. Since each oxime ester compound differs in absorbance and radical species to be generated, it is preferable to use two or more species in combination.

Further, a photopolymerization initiator (d2) other than the oxime ester compound may be further used in combination within the range not impairing the effects of the present invention. Specifically, it is preferable to use at least one compound selected from the group consisting of an acetophenone-based compound, a benzophenone-based compound, a triazine-based compound, a nonimidazole-based compound and a thioxanthone-based compound.

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

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

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

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

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

The photopolymerization initiator (D) may be used in combination with the photopolymerization initiator (d3) to improve the sensitivity of the colored photosensitive resin composition of the present invention. The colored photosensitive resin composition according to one embodiment of 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 auxiliary (d3), for example, at least one compound selected from the group consisting of an amine compound, a carboxylic acid compound and a polyfunctional thiol compound can be preferably used.

Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine; 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid isoamyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N, N-dimethylparatoluidine, Aromatic amine compounds such as 4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone) and 4,4'-bis (diethylamino) benzophenone can be used, Do.

The carboxylic acid compound is preferably an aromatic heteroacetic acid compound. Specific examples thereof include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenyl Thioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.

Examples of the polyfunctional thiol compounds include tris- [(3-mercaptopropionyloxy) -ethyl] -isocyanurate, trimethylolpropane tris-3-mercaptopropionate, pentaerythritol tetrakis- Mercaptopropionate, dipentaerythritol hexa-3-mercaptopropionate, and the like.

The photopolymerization initiator (D) may be contained in an amount of 0.1 to 40 parts by weight, preferably 1 to 30 parts by weight, based on 100 parts by weight of the total amount of the alkali-soluble resin (B) and the photopolymerizable compound (C). When the photopolymerization initiator (D) is included in the above range, the colored photosensitive resin composition of the present invention has high sensitivity and shortens the exposure time, which is preferable because productivity can be improved and high resolution can be maintained. Further, the strength of the pixel portion formed using the composition of the above-described conditions and the smoothness of the surface of the pixel portion can be improved.

When the photopolymerization initiator (d3) is further used, the photopolymerization initiator (d3) is added in an amount of 0.1 to 40 parts by weight per 100 parts by weight of the total amount of the alkali-soluble resin (B) , Preferably from 1 to 30 parts by weight, based on the weight of the composition. When the photopolymerization initiator (d3) is included in the above range, the sensitivity of the colored photosensitive resin composition becomes higher and the productivity of the color filter formed using the composition can be improved.

Solvent (E)

In one embodiment of the present invention, the solvent (E) comprises as essential components a first solvent (e1) having a boiling point of 180 to 190 占 폚 and a vapor pressure of 0.18 mmHg to 0.32 mmHg at 20 占 폚. When the first solvent is used, it is possible to suppress the drying of the colored photosensitive resin composition in the nozzle during coating of the colored photosensitive resin composition, thereby controlling the smear caused by the drying in the nozzle.

As the first solvent (e1), 1,2-propanediol diacetate, 3-methoxy-3-methylbutyl acetate, diethylene glycol methyl ethyl ether, dipropylene glycol methyl ether acetate, diacetone alcohol, diethylene glycol methyl Ethyl ether and the like can be used. These may be used alone or in combination of two or more.

The first solvent (e1) may be contained in an amount of 1 to 20% by weight based on 100% by weight of the total of the colored photosensitive resin composition. When the first solvent is included in the above range, the occurrence of stains caused by the drying of the nozzle at the time of coating is small, the dispersibility of the colored photosensitive resin composition is appropriate, and foreign matter generation is suppressed and viscosity stability can be secured. If the content of the first solvent is more than 20% by weight, the drying process time after the coating process may increase and the productivity may be lowered.

In an embodiment of the present invention, the solvent has a second solvent (e2) having a boiling point of 140 to 150 DEG C and a vapor pressure of 3.4 mmHg to 4.1 mmHg at 20 DEG C and a second solvent (e2) having a boiling point of 115 to 125 DEG C and a vapor pressure of 8.5 mmHg to 9.5 and a third solvent (e3) which is in the range of 1 to 10 mmHg.

As the second solvent (e2), propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, ethyl lactate and the like can be used. These may be used alone or in combination of two or more.

The second solvent (e2) may be contained in an amount of 20 to 85% by weight based on 100% by weight of the total of the colored photosensitive resin composition.

As the third solvent (e3), propylene glycol methyl ether, methyl 3-methoxypropionate and the like can be used. These may be used alone or in combination of two or more.

The third solvent (e3) may be contained in an amount of 1 to 20% by weight based on 100% by weight of the total of the colored photosensitive resin composition.

In addition to the first to third solvents, the solvent (E) can be used in combination with a solvent (e4) which is effective in dissolving other components contained in the colored photosensitive resin composition and used in a conventional colored photosensitive resin composition . Particularly, ethers, aromatic hydrocarbons, ketones, alcohols, esters or amides are preferred.

The solvent (E) may be contained in an amount of 60 to 90% by weight, preferably 70 to 85% by weight based on 100% by weight of the total of the colored photosensitive resin composition. When the solvent (E) is contained in the above-mentioned range, when the solvent (E) is applied by a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater .

Additive (F)

The colored photosensitive resin composition according to one embodiment of the present invention may contain, in addition to the above components, antioxidants, fillers, other polymer compounds, curing agents, adhesion promoters, Or the like (F) may be used in combination.

The antioxidant may include at least one phenol-based antioxidant and at least one phosphorus-based antioxidant, and the phenol-based antioxidant is preferably a hindered phenol-based one.

The commercially available phenolic antioxidants include ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50F, ADK STAB AO-60 and ADK STAB AO-80. ADK STAB 1178, ADK STAB TPP, ADK STAB 1500, ADK STAB 135A and ADK STAB 3010 of Adeka.

The antioxidant may be contained in an amount of 1 to 100 parts by weight, preferably 2 to 50 parts by weight, based on 100 parts by weight of the photopolymerization initiator (D) based on the solid content. When the antioxidant is included in the above range, the transmittance of the colored layer can be expected to be improved without lowering the sensitivity of the colored photosensitive resin composition.

The filler may be glass, silica, alumina, or the like, but is not limited thereto.

Specific examples of the other polymer compound include a curable resin such as an epoxy resin and a maleimide resin, a thermoplastic resin such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, polyurethane and the like But is not limited thereto.

The curing agent is used for increasing the curing depth and mechanical strength. Specifically, an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound may be used, but the present invention is not limited thereto. Examples of the epoxy compound include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolak epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin, Aliphatic, alicyclic or aromatic epoxy compounds, butadiene (co) polymeric epoxides, isoprene (co) polymers other than the brominated derivatives, epoxy resins and their brominated derivatives of these epoxy resins, glycidyl ester resins, glycidyl amine resins, ) Polymeric epoxide, glycidyl (meth) acrylate (co) polymer, and triglycidyl isocyanurate, but are not limited thereto. Specific examples of the oxetane compound include, but are not limited to, carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane. .

The curing agent may be used together with a curing agent in combination with a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound. Specific examples of the curing auxiliary compound include polyvalent carboxylic acids, polyvalent carboxylic anhydrides, and acid generators. The polyvalent carboxylic acid anhydrides may be those commercially available as an epoxy resin curing agent. Examples of commercially available epoxy resin curing agents include Adekahadona EH-700 (manufactured by Adeka Kogyo Co., Ltd.), Rikashido HH (manufactured by Shin-Nihon Ehwa Co., Ltd.), MH-700 .

The curing agent and the curing auxiliary compound exemplified above may be used alone or in combination of two or more.

Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (2-aminoethyl) (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- Methoxysilane, 3-isocyanatepropyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane, or a mixture thereof. The adhesion promoter may be contained in an amount of 0.01 to 10% by weight, preferably 0.05 to 2% by weight based on 100% by weight of the solid content of the colored photosensitive resin composition.

Specific examples of the ultraviolet absorber include, but are not limited to, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole and alkoxybenzophenone.

The anti-aggregation agent may be, for example, sodium polyacrylate, but is not limited thereto.

The colored photosensitive resin composition according to one embodiment of the present invention can be produced, for example, by the following method.

First, the pigment (a1) in the colorant (A) is mixed with the solvent (E) and dispersed using a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 탆 or less. At this time, if necessary, the pigment dispersant (a2), part or all of the alkali-soluble resin (B), or the dye (a3) may be mixed and dissolved or dispersed together with the solvent (E). The remaining dispersion of the alkali-soluble resin (B), the photopolymerization initiator (D), the photopolymerizable compound (C) and the additive (F) and, if necessary, the solvent (E) To prepare a colored photosensitive resin composition.

One embodiment of the present invention relates to a color filter formed using the above-mentioned colored photosensitive resin composition. A color filter according to an embodiment of the present invention is characterized by including a colored layer formed by applying the above-mentioned colored photosensitive resin composition on a substrate, and exposing and developing in a predetermined pattern.

Hereinafter, the pattern forming method using the colored photosensitive resin composition of the present invention will be described in detail.

The method of forming a pattern using the colored photosensitive resin composition of the present invention can be carried out by a method known in the art, but usually includes a coating step; An exposure step; And a removing step. The colored photosensitive resin composition of the present invention is coated on a substrate, and the pattern is formed by photo-curing and development, so that it can be used as a colored pixel (colored image).

Specifically, the colored photosensitive resin composition is coated on a glass substrate coated with a glass substrate and a SiNx (protective film) with a thickness of 500 to 1,500 angstroms, using a suitable method such as spin coating or slit coating, 3.4 탆 thick. After the application, light is irradiated to form a pattern necessary for the color filter. After the light is irradiated and the coating layer is treated with an alkali developing solution, the unexposed portions of the coating layer are dissolved and a pattern necessary for the color filter is formed. By repeating this process according to the required number of R, G, and B colors, a color filter having a desired pattern can be obtained. In addition, in the above process, the image pattern obtained by development may be further heated or cured by actinic ray irradiation or the like to further improve crack resistance, solvent resistance, and the like.

One embodiment of the present invention relates to an image display apparatus provided with the color filter described above.

The color filter of the present invention can be applied to various image display devices such as an electroluminescence display device (EL), a plasma display device (PDP), a field emission display device (FED), an organic light emitting device (OLED) Applicable to devices.

The image display device of the present invention includes a configuration known in the art, except that it has the above-described color filter.

An image display apparatus according to an embodiment of the present invention includes, in addition to the above-described color filters, a red pattern layer containing red QD particles, a green pattern layer containing green quantum dot particles, and a blue pattern layer containing blue QDs A color filter may be additionally provided. In such a case, the emitted light of the light source applied to the image display device is not particularly limited, but a light source that emits blue light preferably in terms of better color reproducibility can be used.

The image display apparatus according to an embodiment of the present invention may further include a color filter including only a pattern layer of two colors of a red pattern layer, a green pattern layer, and a blue pattern layer in addition to the color filter described above. In such a case, the color filter further includes a transparent pattern layer not containing quantum dot particles. In the case where only the pattern layer of two colors is provided, a light source that emits light having a wavelength that represents the remaining color that is not included can be used. For example, when only the red pattern layer and the green pattern layer are included, a light source that emits blue light may be used. In such a case, red quantum dot particles emit red light and rust quantum dot particles emit green light, and the transparent pattern layer transmits blue light as it is and exhibits blue color.

Hereinafter, the present invention will be described more specifically with reference to Examples, Comparative Examples and Experimental Examples. It should be apparent to those skilled in the art that these examples, comparative examples and experimental examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.

Manufacturing example  1: Pigment dispersion M1 Manufacturing

C.I. 12 weight parts of Pigment Green 58, 3.0 weight parts of LPN-6919 (manufactured by BYK) as a pigment dispersant and 85.0 weight parts of propylene glycol monomethyl ether acetate as a solvent were mixed and dispersed for 12 hours by a bead mill to prepare a pigment dispersion M1 Respectively.

Manufacturing example  2: Pigment dispersion M2 Manufacturing

C.I. 12.0 parts by weight of Pigment Green 59, 3.0 parts by weight of LPN-6919 (BYK) as a dispersant, and 85.0 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed and dispersed for 12 hours by a bead mill to prepare a pigment dispersion M2 .

Manufacturing example  3: Pigment dispersion M3 Manufacturing

C.I. , 12.0 parts by weight of Pigment Green 36, 3.0 parts by weight of LPN-6919 (BYK) as a dispersant, and 85.0 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed and dispersed for 12 hours by a bead mill to prepare a pigment dispersion M3 .

Manufacturing example  4: Pigment dispersion M4 Manufacturing

C.I. 12.0 parts by weight of Pigment Yellow 138, 3.0 parts by weight of LPN-6919 (manufactured by BYK) as a dispersant, and 85.0 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed and dispersed for 12 hours by a bead mill to prepare a pigment dispersion M4 .

Manufacturing example  5: Pigment dispersion M5 Manufacturing

C.I. 12.0 parts by weight of Pigment Yellow 150, 3.0 parts by weight of LPN-6919 (BYK) as a dispersant, and 85.0 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed and dispersed for 12 hours by a bead mill to prepare a pigment dispersion M5 .

Synthetic example  1: Synthesis of alkali-soluble resin

A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 120 parts by weight of propylene glycol monomethyl ether acetate, 80 parts by weight of propylene glycol monomethyl ether, 5 parts by weight of AIBN, 15.0 parts by weight of acrylic acid, 65.0 parts by weight and 20.0 parts by weight of 2- (phenylthio) ethyl acrylate were charged and replaced with nitrogen. Thereafter, the temperature of the reaction solution was raised to 85 DEG C with stirring, and the reaction was allowed to proceed for 6 hours. The alkali-soluble resin thus synthesized had a solid dispersion value of 115.1 mgKOH / g and a weight-average molecular weight (Mw) of 14,100 as measured by GPC.

Synthetic example  2: Synthesis of alkali-soluble resin

A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 120 parts by weight of propylene glycol monomethyl ether acetate, 80 parts by weight of propylene glycol monomethyl ether, 2 parts by weight of AIBN, 13.0 parts by weight of acrylic acid, 87 parts by weight of acrylate and 3 parts by weight of n-dodecylmercaptan were charged and replaced with nitrogen. Thereafter, the temperature of the reaction solution was elevated to 110 DEG C with stirring, and the reaction was carried out for 6 hours. The alkali-soluble resin thus synthesized had a solid dispersion value of 93.2 mgKOH / g and a weight average molecular weight (Mw) of about 14,100 as measured by GPC.

Example  1: Preparation of colored photosensitive resin composition

26.25 parts by weight of the pigment dispersion M1 of Production Example 1, 17.50 parts by weight of the pigment dispersion M4 of Production Example 4, 11.71 parts by weight of the alkali-soluble resin of Synthesis Example 1, 3.90 parts by weight of KAYARAD DPHA (manufactured by Nippon Kayaku Co., 0.63 part by weight of OXE-03 (BASF), 6.00 parts by weight of 1,2-propanediol diacetate and 34.00 parts by weight of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition.

Example  2: Preparation of colored photosensitive resin composition

13.26 parts by weight of the pigment dispersion M2 of Production Example 2, 25.74 parts by weight of the pigment dispersion M4 of Production Example 4, 12.78 parts by weight of the alkali-soluble resin of Synthesis Example 1, 4.26 parts by weight of KAYARAD DPHA (manufactured by Nippon Kayaku Co., 0.63 part by weight of OXE-03 (BASF), 6.00 parts by weight of 1,2-propanediol diacetate and 37.33 parts by weight of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition.

Example  3: Preparation of colored photosensitive resin composition

28.84 parts by weight of the pigment dispersion M1 of Production Example 1, 11.78 parts by weight of the pigment dispersion M5 of Production Example 5, 12.78 parts by weight of the alkali-soluble resin of Synthesis Example 1, 4.26 parts by weight of KAYARAD DPHA (manufactured by Nippon Kayaku Co., 0.63 part by weight of OXE-03 (BASF), 6.00 parts by weight of 1,2-propanediol diacetate and 37.33 parts by weight of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition.

Example  4: Preparation of colored photosensitive resin composition

26.25 parts by weight of the pigment dispersion M1 of Production Example 1, 17.50 parts by weight of the pigment dispersion M4 of Production Example 4, 11.71 parts by weight of the alkali-soluble resin of Synthesis Example 1, 3.90 parts by weight of KAYARAD DPHA (manufactured by Nippon Kayaku Co., 0.63 part by weight of OXE-03 (BASF), 6 parts by weight of 1,2-propanediol diacetate, 33.08 parts by weight of propylene glycol monomethyl ether acetate and 4.25 parts by weight of propylene glycol methyl ether were mixed to prepare a colored photosensitive resin composition .

Comparative Example  1: Preparation of colored photosensitive resin composition

23.79 parts by weight of the pigment dispersion M3 of Production Example 3, 18.46 parts by weight of the pigment dispersion M4 of Production Example 4, 12.05 parts by weight of the alkali-soluble resin of Synthesis Example 1, 4.02 parts by weight of KAYARAD DPHA (manufactured by Nippon Kayaku Co., 0.63 part by weight of OXE-03 (BASF), 6.00 parts by weight of 1,2-propanediol diacetate and 35.05 parts by weight of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition.

Comparative Example  2: Preparation of colored photosensitive resin composition

26.25 parts by weight of the pigment dispersion M1 of Preparation Example 1, 17.50 parts by weight of the pigment dispersion M4 of Production Example 4, 11.71 parts by weight of the alkali-soluble resin of Synthesis Example 2, 3.90 parts by weight of KAYARAD DPHA (manufactured by Nippon Kayaku Co., 0.63 part by weight of OXE-03 (BASF), 6.00 parts by weight of 1,2-propanediol diacetate and 34.00 parts by weight of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition.

Comparative Example  3: Preparation of colored photosensitive resin composition

26.25 parts by weight of the pigment dispersion M1 of Production Example 1, 17.50 parts by weight of the pigment dispersion M4 of Production Example 4, 11.71 parts by weight of the alkali-soluble resin of Synthesis Example 1, 3.90 parts by weight of KAYARAD DPHA (manufactured by Nippon Kayaku Co., 0.63 part by weight of OXE-03 (manufactured by BASF) and 40.00 parts by weight of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition.

Comparative Example  4: Preparation of colored photosensitive resin composition

26.25 parts by weight of the pigment dispersion M1 of Production Example 1, 17.50 parts by weight of the pigment dispersion M4 of Production Example 4, 11.71 parts by weight of the alkali-soluble resin of Synthesis Example 1, 3.90 parts by weight of KAYARAD DPHA (manufactured by Nippon Kayaku Co., 0.63 part by weight of OXE-03 (BASF), 21.25 parts by weight of 1,2-propanediol diacetate and 18.75 parts by weight of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition.

Experimental Example  One

The color filter was prepared as follows using the colored photosensitive resin compositions prepared in Examples and Comparative Examples. The transmittance, adhesion, residue, reduced pressure drying rate and dry composition were measured by the following methods, Table 1 shows the results.

≪ Production of color filter &

The colored photosensitive resin composition was applied on a 2 inch wide glass substrate ("EAGLE XG", manufactured by Corning Incorporated) 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. Then, a test photomask having a line / space pattern of 1 mu m to 100 mu m was placed on the thin film and irradiated with ultraviolet rays at a distance of 300 mu m from the test photomask. At this time, the ultraviolet light source was irradiated at 40 mJ / cm 2 using 1 kW high pressure mercury lamp containing g, h and i lines, and no special optical filter was used. The thin film irradiated with ultraviolet rays was immersed in a KOH aqueous solution of pH 10.5 for 80 seconds to develop. The glass substrate 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 thickness of the color filter prepared above was 2.5 mu m.

(One) Color coordinates  And transmittance

A color filter was prepared in the same manner as the color filter except that the photomask was not used. The color coordinates and the transmittance were measured using a colorimeter (OSP-200, manufactured by Olympus Corporation).

(2) Adhesion

The resulting pattern was observed through an optical microscope and the adhesion was evaluated according to the following evaluation criteria as a degree of peeling in the pattern.

<Evaluation Criteria>

○: No pattern peeling

△: Pattern peeling 1 to 4

×: 5 or more patterns peeled off

(3) Residue

The colored photosensitive resin composition was applied on a 2 inch wide glass substrate ("EAGLE XG", manufactured by Corning Incorporated) 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. The thin film was developed by immersing in a KOH aqueous solution of pH 10.5 for 80 seconds. The glass substrate was washed with distilled water and dried by blowing nitrogen gas. The transmittance of the glass substrate was measured using a colorimeter (OSP-200, manufactured by Olympus Corporation) and the residue was evaluated according to the following evaluation criteria.

<Evaluation Criteria>

○: 99.7% or more

?: 99.5% or more and less than 99.7%

X: less than 99.5%

(4) Decompression Drying Rate

The colored photosensitive resin composition was applied on a 2 inch wide glass substrate ("EAGLE XG", manufactured by Corning) by spin coating, and then the glass substrate on which the coated film was formed was placed in a decompression chamber and dried under reduced pressure to a final pressure of 65 Pa And the time to reach 65 Pa was measured. The faster the decompression drying rate, the better the productivity.

(5) Drying

0.4 占 퐇 of the colored photosensitive resin composition was dropped onto a glass substrate ("EAGLE XG", manufactured by Corning Inc.) having a size of 2 inches by 2 mm by using a micropipette, followed by natural drying for 1 minute to 10 minutes. Then, the glass substrate was set at an angle of 90 degrees, and it was confirmed whether or not the colored photosensitive resin composition dropped and dried to maintain the flowability, thereby confirming the maximum drying time at which the flowability was maintained. The longer the drying time in which the flowability is maintained, the better the drying property is, and the unevenness due to the drying in the coater nozzle during coating is less likely to occur.

Adhesiveness Residue The color coordinates (x, y) Transmittance Drying Decompression Drying Rate Example 1 ○ ○ (0.284, 0.585) 62.51 7min 25.8 Example 2 ○ ○ (0.284, 0.586) 60.33 8min 25.4 Example 3 ○ ○ (0.283, 0.586) 59.13 8min 25.6 Example 4 ○ ○ (0.282, 0.586) 62.47 7min 25.0 Comparative Example 1 ○ ○ (0.283, 0.584) 58.67 8min 25.5 Comparative Example 2 △ X (0.284, 0.586) 62.53 7min 26.5 Comparative Example 3 ○ ○ (0.284, 0.585) 62.43 3min 24.9 Comparative Example 4 ○ ○ (0.285, 0.585) 62.33 7min 30.7

As shown in Table 1, when the coloring agent comprises a zinc phthalocyanine pigment and the alkali-soluble resin comprises a thioether group-containing alkali-soluble resin, and the solvent has a boiling point of 180 to 190 ° C and a vapor pressure of 0.18 mmHg The color photoresponsive compositions of Examples 1 to 4 including the first solvent of 0.32 mmHg had a high transmittance and were free from residue, stain, and pattern peeling during the production of the color filter, and were excellent in productivity. On the other hand, it was confirmed that the colored photosensitive resin compositions of Comparative Examples 1 to 4 exhibited low transmittance, residue, stain, pattern peeling, or poor productivity in the production of a color filter.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention. Do. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Accordingly, the actual scope of the invention is defined by the appended claims and their equivalents.

Claims (10)

1. A colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent,
Wherein the colorant comprises a zinc phthalocyanine pigment,
Wherein the alkali-soluble resin comprises a copolymer of a compound represented by the following formula (1), an unsaturated carboxylic acid, and a compound having an unsaturated bond copolymerizable therewith,
Wherein the solvent comprises a first solvent having a boiling point of 180 to 190 캜 and a vapor pressure of 0.18 mmHg to 0.32 mmHg at 20 캜.
[Chemical Formula 1]

In this formula,
X ¹ is hydrogen or a methyl group,
X ² is a C ₁ -C ₆ alkylene group or a C ₂ -C ₆ alkenylene group,
A is an aryl group, a C ₃ -C ₁₀ cycloalkyl group, a C ₁ -C ₆ alkyl group or a C ₂ -C ₆ alkenyl group. The colorant according to claim 1, wherein the colorant is C.I. Pigment Green 58 and C.I. Pigment Green 59. The colored photosensitive resin composition according to Claim 1, The colored photosensitive resin composition according to claim 1, wherein the content of the coloring agent is 15 to 60% by weight based on 100% by weight of the total solid content in the colored photosensitive resin composition. The colored photosensitive resin composition according to claim 1, wherein the compound represented by Formula 1 is a compound represented by Formula 2:
(2)

In this formula,
X ¹ is hydrogen or a methyl group,
X ² is a C ₁ -C ₆ alkylene group or a C ₂ -C ₆ alkenylene group. The colored photosensitive resin composition according to claim 1, wherein the alkali-soluble resin comprises a copolymer of 2- (phenylthio) ethyl (meth) acrylate, an unsaturated carboxylic acid and vinyl toluene. The colored photosensitive resin composition according to claim 1, wherein the photopolymerization initiator comprises an oxime ester compound. The colored photosensitive resin composition according to claim 1, wherein the first solvent is contained in an amount of 1 to 20% by weight based on 100% by weight of the total of the colored photosensitive resin composition. The method of claim 1, wherein the solvent is a second solvent having a boiling point of 140 to 150 ° C and a vapor pressure of 3.4 mmHg to 4.1 mmHg at 20 ° C, and a third solvent having a boiling point of 115 to 125 ° C and a vapor pressure of 8.5 mmHg to 9.5 mmHg &Lt; / RTI &gt; A color filter formed using the colored photosensitive resin composition according to any one of claims 1 to 8. An image display apparatus comprising the color filter according to claim 9.