KR20170034580A - Colored photosensitive resin composition and color filter using the same - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition, and more particularly, to a colored photosensitive resin composition for a color filter used for producing a color filter used in such as a color liquid crystal display device, a color filter manufactured using the same, and a liquid crystal display device having the color filter. The colored photosensitive resin composition of the present invention is excellent in adhesion and can realize high resolution.

Description

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

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

BACKGROUND ART [0002] Color filters are widely used in imaging devices, liquid crystal display devices, and the like, and their application range is rapidly expanding. A color filter used for a color liquid crystal display device, an image pickup device, or the like is a device in which a colored photosensitive resin composition containing a coloring agent corresponding to each color of red, green and blue on a substrate on which a black matrix is patterned is sliced or spin- (Hereinafter, may be referred to as post-baking) is repeated for each color, if necessary, followed by further curing by heating Thereby forming pixels of respective colors (Korean Patent Publication No. 1998-0010626).

On the other hand, there has been a continuing demand in the art for a colored photosensitive resin composition which is excellent in adhesion and capable of realizing a high resolution. However, the colored photosensitive resin composition, which has remarkably improved adhesiveness and peeling property as compared with the prior art, It is not possible to present it.

Korean Patent Publication No. 1998-0010626

Accordingly, the present invention provides a colored photosensitive resin composition having excellent adhesion and high resolution when a color filter is manufactured.

(B) a photopolymerization initiator (C), a red pigment (D) and a solvent (E), wherein the photopolymerizable compound (B) , Wherein the photopolymerization initiator (C) comprises a compound represented by the following general formula (2).

[Chemical Formula 1]

X and R ₁ are aliphatic hydrocarbons having 1 to 10 carbon atoms and having 1 to 10 carbon atoms, R ₂ is independently an aliphatic hydrocarbon having 1 to 10 carbon atoms with or without a hetero atom, Is an integer of 1 to 4, A is a functional group represented by the following formula (3)

(2)

In Formula 2, R ₁ to R ₃ are each independently selected from the group consisting of hydrogen, a halogen group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, An alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, a hydroxyalkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms,

R ₄ to R ₁₀ are each independently selected from the group consisting of hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, A hydroxyalkyl group having 1 to 20 carbon atoms, a hydroxyalkoxy group having 1 to 20 carbon atoms, an amino group, a nitro group, a cyano group or a hydroxy group,

n is 0 or 1;

(3)

In the general formula (3), m is an integer of 2 to 6.

In another embodiment, the compound represented by the formula (1) may be a compound represented by the following formula (4).

[Chemical Formula 4]

In formula (4), the sum of m is 12 to 36.

In another embodiment, the compound represented by the general formula (2) may be a compound represented by the following general formula (5) or (6).

[Chemical Formula 5]

[Chemical Formula 6]

In another embodiment, the alkali-soluble resin (A) is contained in an amount of 1 to 40% by weight based on the colored photosensitive resin composition, the photopolymerizable compound (B) is contained in an amount of 1 to 20% by weight, The initiator (C) is contained in an amount of 0.1 to 10% by weight, the red pigment (D) is contained in an amount of 5 to 40% by weight, and the solvent (E) is contained in an amount of 20 to 85% by weight.

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

The present invention also provides a liquid crystal display provided with a color filter.

The colored photosensitive resin composition of the present invention is excellent in adhesion and can realize high resolution.

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

The present invention includes a photopolymerizable compound to which a polyfunctional EO (ethylene oxide) group is added and an oxime ester fluorene derivative as a photopolymerization initiator, thereby exhibiting a process characteristic that is excellent also in development speed and residue, while simultaneously realizing low line width and adhesion .

Hereinafter, the present invention will be described in detail.

The alkali-soluble resin (A)

(A1) having a carboxyl group as an essential component in order to have solubility in an alkali developing solution used in a development processing step for forming a pattern. Further, in order to ensure stability with time of the colored photosensitive resin composition, the acid value of the alkali-soluble resin (A) is preferably 30 to 150 mgKOH / g. When the acid value of the alkali-soluble resin (A) is less than 30 mgKOH / g, it is difficult to secure a sufficient developing rate of the colored photosensitive resin composition. When the acid value exceeds 150 mgKOH / g, the adhesion with the substrate is decreased, The stability with time of the resin composition is lowered, and the viscosity tends to rise.

A hydroxyl group may be added to secure the further developability of the alkali-soluble resin (A). The developing rate for imparting hydroxyl groups is improved, but the sum of the hydroxyl value of the alkali-soluble resin (A) and the photopolymerizable compound (B) is limited to 50 mgKOH / g or more and 250 mgKOH / g or less. When the sum of the hydroxyl groups is less than 50 mgKOH / g, a sufficient development rate can not be secured. When the sum of the hydroxyl groups is more than 250 mgKOH / g, the dimensional stability of the formed pattern is lowered and the linearity of the pattern tends to become poor.

Examples of the ethylenically unsaturated monomer (a1) having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid; 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 acrylic acid and methacrylic acid are preferable.

In order to impart a hydroxyl group to the alkali-soluble resin (A), an ethylenically unsaturated monomer (a1) having a carboxyl group and an ethylenically unsaturated monomer (a2) having a hydroxyl group can be copolymerized with an ethylenically unsaturated monomer (a1) (A3) having a glycidyl group in a copolymer of the compound (a3). (A3) having a glycidyl group in addition to a copolymer of an ethylenically unsaturated monomer (a1) having a carboxyl group and an ethylenically unsaturated monomer (a2) having a hydroxyl group.

Specific examples of the hydroxyl group-containing butylene unsaturated monomer (a2) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) Hydroxy-3-phenoxypropyl (meth) acrylate, N-hydroxyethylacrylamide and the like, and 2-hydroxyethyl (meth) acrylate is preferable, and two or more kinds thereof can be used in combination.

Specific examples of the glycidyl group-containing compound (a3) include butyl glycidyl ether, glycidyl propyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, glycidyl butyrate, glycidyl methyl ether, Ethyl glycidyl ether, glycidyl isopropyl ether, t-butyl glycidyl ether, benzyl glycidyl ether, glycidyl 4-t-butyl benzoate, glycidyl stearate, aryl glycidyl ether, Methacrylic acid glycidyl ester, etc., and butyl glycidyl ether, aryl glycidyl ether, and methacrylic acid glycidyl ester are preferable, and two or more kinds may be used in combination.

The copolymerizable unsaturated monomers (a3) in the production of the alkali-soluble resin (A) are illustrated below, but are not limited thereto.

Specific examples of the polymerizable monomer (a4) having an unsaturated bond capable of copolymerization include styrene, vinyltoluene,? -Methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p- Aromatic vinyls such as vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m- vinyl benzyl glycidyl ether and p- compound;

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.

The monomers exemplified for (a3) may be used alone or in combination of two or more.

The content of the alkali-soluble resin (B) is preferably 1 to 40% by weight based on the colored photosensitive resin composition. When the amount is within the above range, solubility in a developing solution is sufficient, pattern formation is easy, and reduction of the film portion of the pixel portion of the exposed portion is prevented at the time of development, so that the missing property of the non-pixel portion is improved.

Photopolymerization  The compound (B)

The photopolymerizable compound (B) is a compound capable of polymerizing under the action of light and a photopolymerization initiator described later, and contains a compound represented by the following formula (1) as an essential component.

[Chemical Formula 1]

X and R ₁ are aliphatic hydrocarbons having 1 to 10 carbon atoms and having 1 to 10 carbon atoms, R ₂ is independently an aliphatic hydrocarbon having 1 to 10 carbon atoms with or without a hetero atom, Is an integer of 1 to 4, A is a functional group represented by the following formula (3)

(3)

In the general formula (3), m is an integer of 2 to 6.

In Formula (1), Formula (1) may be a compound represented by Formula (4). In Formula (4), m may be 12 to 24, preferably 12 or 24.

[Chemical Formula 4]

In formula (4), the sum of m is 12 to 36.

The photopolymerizable compound (B) is preferably contained in an amount of 1 to 20% by weight based on the colored photosensitive resin composition. When such a content is included, it is preferable that the strength and reliability of the pixel portion are improved.

Light curing Initiator (C)

The photopolymerization initiator (C) is capable of polymerizing the photopolymerizable compound (B), and includes a compound represented by the following formula (2) as an essential component.

(2)

In Formula 2, R ₁ to R ₃ are each independently selected from the group consisting of hydrogen, a halogen group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, An alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, a hydroxyalkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms;

R ₄ to R ₁₀ are each independently selected from the group consisting of hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, An alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, a hydroxyalkoxy group having 1 to 20 carbon atoms, an amino group, a nitro group, a cyano group or a hydroxy group;

n is 0 or 1;

The halogen is fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).

The alkyl group may be a linear or branched alkyl group having 1 to 20 carbon atoms, including a linear or branched alkyl group, preferably a straight or branched alkyl group having 1 to 10 carbon atoms, and most preferably a carbon number May be a straight or branched alkyl group of 1 to 6 carbon atoms. For example, the alkyl group may be methyl, ethyl, n-propyl, i-propyl, n-butyl, isobutyl, t-butyl, n-pentyl, n-hexyl,

The alkoxy group may be an oxygen-containing straight or branched alkoxy group having an alkyl moiety having 1 to 20 carbon atoms, preferably an alkoxy group having 1 to 20 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms have. For example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a t-butoxy group and the like. The alkoxy group may be further substituted by one or more halogen atoms such as fluoro, chloro or bromo to provide a haloalkoxy group, for example, a fluoromethoxy group, a chloromethoxy group, a trifluoromethoxy group, a trifluoromethoxy group, Methoxy group, ethoxy group, fluoroethoxy group, fluoropropoxy group and the like.

The cycloalkyl group may include not only a single ring system but also several cyclic hydrocarbons, preferably a cycloalkyl group having 3 to 10 carbon atoms, and more preferably a cycloalkyl group having 3 to 8 carbon atoms.

The aryl group means an aromatic monocyclic or multicyclic hydrocarbon ring system, wherein the ring system may be partially or fully saturated. The aryl group includes a single or fused ring system containing 4 to 7, preferably 5 or 6, ring atoms in the ring, and includes a plurality of aryls connected by a single bond. For example, the aryl group may be phenyl, biphenyl, terphenyl, stilbenyl, naphthyl, anthracenyl, phenanthryl, or pyrenyl.

The hydroxyalkyl group means that a hydroxy group is bonded to the alkyl group defined above, and the hydroxyalkoxyalkyl group means that the hydroxyalkyl group and the alkyl group are connected with oxygen. The hydroxyalkyl group is preferably a hydroxyalkyl group having 1 to 20 carbon atoms, more preferably a hydroxyalkyl group having 1 to 6 carbon atoms. The hydroxyalkoxyalkyl group is preferably a hydroxyalkoxyalkyl group having 2 to 20 carbon atoms, more preferably a hydroxyalkoxyalkyl group having 2 to 9 carbon atoms.

The arylalkyl group means that at least one hydrogen atom of the alkyl group defined above is substituted with an aryl group as defined above. The arylalkyl group is preferably an arylalkyl group having 7 to 28 carbon atoms, more preferably an arylalkyl group having 7 to 24 carbon atoms.

In the above formula (2), when n is 0, it may be represented by the following formula (7), and when n is 1,

(7)

In the general formula (7), R ₁₁ to R ₁₃ are each independently selected from the group consisting of hydrogen, a halogen group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, An alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, a hydroxyalkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms,

A represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, A hydroxyalkyl group, a hydroxyalkoxy group, a cycloalkyl group having 3 to 20 carbon atoms, amino, nitro, cyano or hydroxy.

Specifically, R ₁₁ to R ₁₃ are each independently selected from the group consisting of hydrogen, bromo, chloro, iodo, methyl, ethyl, n-propyl, i-propyl, n- n-propyloxy, i-propyloxy, n-propyloxy, n-pentyl, i-pentyl, Butoxy, i-butoxy, t-butoxy, hydroxymethyl, hydroxyethyl, hydroxy n-propyl, hydroxy n-butyl, Pentyl, n-hexyl, hydroxy i-hexyl, hydroxymethoxymethyl, hydroxymethoxyethyl, hydroxymethoxypropyl, hydroxymethoxybutyl, hydroxyethoxymethyl, hydroxyethoxyethyl, Hydroxyethoxyethyl, hydroxyethoxypropyl, hydroxyethoxybutyl, hydroxyethoxypentyl or hydroxyethoxyhexyl,

A is selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i- butyl, t- butyl, phenyl, naphthyl, biphenyl, terphenyl anthryl, indenyl, And examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, isobutyl, sec-butyl, Hydroxyethoxyethyl, hydroxyethoxypropyl, hydroxyethoxybutyl, amino, nitro, cyano or hydroxy, but is not limited thereto.

More specifically, R < ₁₁ > is hydrogen or n-butyl; R ₁₂ is methyl; R ₁₃ may be methyl, n-butyl or phenyl.

The oxime ester fluorene derivative represented by Formula 7 may be prepared as shown in Reaction Scheme 1 below.

[Reaction Scheme 1]

In Scheme 1, R ₁₁ to R ₁₃ and A are the same as defined in Formula (7), and X is halogen.

[Chemical Formula 8]

In Formula 8,

R ₁₄ to R ₂₃ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms , A hydroxyalkyl group having 1 to 20 carbon atoms, a hydroxyalkoxyalkyl group having 2 to 40 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms.

Specifically, each of R ₁₄ to R ₂₃ is independently hydrogen, bromo, chloro, iodo, methyl, ethyl, n-propyl, i- n-pentyl group, n-pentyl group, i-hexyl group, phenyl group, naphthyl group, biphenyl group, terphenyl group, anthryl group, indenyl group, phenanthryl group, methoxy group, ethoxy group, n Propyl group, a hydroxy n-butyl group, a hydroxy group, a hydroxypropyl group, an isopropyl group, an isopropyl group, a n-butyl group, butyl group, i-butyl group, hydroxy n-pentyl group, hydroxy i-pentyl group, hydroxy n-hexyl group, hydroxy i-hexyl group, hydroxymethoxymethyl group, hydroxymethoxyethyl group, Group, a hydroxymethoxybutyl group, a hydroxyethoxymethyl group, a hydroxyethoxyethyl group, a hydroxyethoxypropyl group, a hydroxyethoxybutyl group, a hydroxyethoxypentyl group or a Hydroxyethoxyhexyl group.

R ₁₄ is a hydrogen atom, a methyl group, an ethyl group, a propyl group or a butyl group, R ₁₅ is a methyl group, an ethyl group or a propyl group, R ₁₆ is a methyl group, ₁₇ to R < ₂₃ > may be hydrogen.

The oxime ester fluorene derivative represented by Formula 8 can be prepared as shown in Reaction Scheme 2 below.

[Reaction Scheme 2]

In the above Reaction Scheme 2, R ₁₄ to R ₂₃ and A are each independently selected from the group consisting of hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, , A hydroxyalkyl group having 1 to 20 carbon atoms, a hydroxyalkoxyalkyl group having 2 to 40 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms, and X is halogen.

As an example of the formula (2), the formula (5) or (6) may be used.

The photopolymerization initiator (C) is preferably contained in an amount of 0.1 to 10% by weight based on the colored photosensitive resin composition. When such a content is included, 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

The red pigment (D)

As the red pigment (D), an organic pigment which is a compound classified as a pigment in the color index (published by The Society of Dyers and Colourists) or an inorganic pigment which is a metal oxide, a metal complex salt and an inorganic salt of barium sulfate can be used And it is preferable to use an organic pigment in view of excellent heat resistance and color development.

Specific examples of the red organic pigments include C.I. Pigment Orange 13, C.I. Pigment Orange 31, C.I. Pigment Orange 38, C.I. Pigment Orange 40, C.I. Pigment Orange 42, C.I. Pigment Orange 43, C.I. Pigment Orange 51, C.I. Pigment Orange 55, C.I. Pigment Orange 59, C.I. Pigment Orange 61, C.I. Pigment Orange 64, C.I. Pigment Orange 65, C.I. Pigment Orange 71, C.I. Orange pigments such as Pigment Orange 73; C.I. Pigment Red 9, C.I. Pigment Red 97, C.I. Pigment Red 105, C.I. Pigment Red 122, C.I. Pigment Red 123, C.I. Pigment Red 144, C.I. Pigment Red 149, C.I. Pigment Red 166, C.I. Pigment Red 168, C.I. Pigment Red 176, C.I. Pigment Red 177, C.I. Pigment Red 180, C.I. Pigment Red 192, C.I. Pigment Red 209, C.I. Pigment Red 215, C.I. Pigment Red 216, C.I. Pigment Red 224, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Red 264, C.I. Pigment Red 265, and other red pigments.

The red pigment (D) is preferably contained in an amount of 5 to 40% by weight based on the colored photosensitive resin composition. When the red pigment is contained within the above range, 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 lowered during development, so that it is preferable because residue is hardly generated.

Solvent (E)

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

The solvent (E) specifically includes ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether,

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

Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate,

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, and cyclic esters such as? -Butyrolactone.

The solvent (E) is preferably an organic solvent having a boiling point of 100 ° C to 200 ° C on the application and drying surface, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate , Butalactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like.

The above-exemplified solvents (E) may be used alone or in admixture of two or more, and they are preferably contained in an amount of 20 to 85% by weight based on the colored photosensitive resin composition of the present invention. When the solvent is contained in the above range, the coating property is improved when applied by a coating apparatus such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), or an ink jet .

In addition, the colored photosensitive resin composition of the present invention may further contain an additive. The additive may be optionally added, for example, a curing agent, a surfactant, an adhesion promoter, an antioxidant, And an anti-aggregation agent.

The present invention also provides a color filter made of the colored photosensitive resin composition and a liquid crystal display device provided with the color filter.

Hereinafter, the present invention will be described in more detail using Synthesis Examples, Examples, Comparative Examples and Experimental Examples. However, the following Synthesis Examples, Examples, Comparative Examples and Experimental Examples are for illustrating the present invention, and the present invention is not limited by the following Synthesis Examples, Examples, Comparative Examples and Experimental Examples, . In the following Synthesis Examples, Examples and Comparative Examples, "%" and "part" representing the content are based on weight unless otherwise specified.

Synthetic example  One. Light curing Initiator  Preparation of C-1

1-1. 1- (9,9-H-7-Nitroploren-2-yl) -ethanone Synthesis

5.0 g (23.7 mmol) of 2-nitropluorene (1) was dissolved in 100 ml of anhydrous nitrobenzene, 6.31 g (47.4 mmol) of anhydrous aluminum chloride was added and the reaction was warmed to 45 캜 to obtain 2.79 g ) In 30 ml of anhydrous nitrobenzene was added slowly over 30 minutes, and the reaction was heated to 65 ° C and stirred for 1 hour. Then, the reaction product was cooled to room temperature, 70 ml of distilled water was added thereto, stirred for about 30 minutes, and the product was filtered. The obtained solid product was dispersed in 50 ml of ether and stirred at room temperature for 30 minutes, followed by filtration and drying to obtain 5.08 g of 1- (9,9-H-7-nitrofluoren-2-yl) (84.7%).

1-2. 1- (9,9-H-7-Nitroploren-2-yl) -ethanone oxime Synthesis

1.5 g (5.92 mmol) of 1- (9,9-H-7-nitrofluoren-2-yl) -ethanone (2) were dispersed in 30 ml of ethanol, 0.49 g (7.1 mmol) of hydrochloric acid hydroxylamine, 0.58 g (7.1 mmol) of sodium was added, and then the reaction solution was gradually heated and refluxed for 2 hours. The reaction product was cooled to room temperature, and 20 ml of distilled water was added thereto. The mixture was stirred for about 30 minutes, and the resulting solid product was filtered, washed several times with distilled water and dried to obtain light gray 1- (9,9- 2-yl) -ethanone oxime (3) (1.38 g, 86.8%).

1-3. 1- (9,9-H-7-Nitroploren-2-yl) -ethanone oxime-O-

1.20 g (4.47 mmol) of 1- (9,9-H-7-nitropluoren-2-yl) -ethanone oxime (3) were dispersed in 50 ml of ethyl acetate, and 0.69 g (6.76 mmol) Then, the reaction solution was gradually heated and refluxed for 3 hours. The reaction mixture was cooled to room temperature, washed with 20 ml of a saturated aqueous sodium hydrogencarbonate solution and then with 20 ml of distilled water. The recovered organic layer was dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure. The product was recrystallized from methanol (20 ml) (87.9%) of (9,9-H-7-nitrofluoren-2-yl) -ethanone oxime-O-acetate (4).

Synthetic example  2. Light curing Initiator  Preparation of C-2

2-1. Synthesis of 9,9-diethyl-9H-fluorene

(1.80mol) of fluorene (1), 268.8g (4.80mol) of potassium hydroxide and 19.9g (0.12mol) of potassium iodide were dissolved in 1L of anhydrous dimethylsulfoxide under a nitrogen atmosphere, the reaction was maintained at 15 占 폚, 283.3 g (2.60 mol) of bromoethane was slowly added over 2 hours, and the reaction was stirred at 15 ° C for 1 hour. Then, 2 L of distilled water was added to the reaction mixture and stirred for 30 minutes. The product was extracted with 2 L of dichloromethane. The extracted organic layer was washed twice with 2 L of distilled water, and the recovered organic layer was dried over anhydrous magnesium sulfate. The resulting product was fractionally distilled under reduced pressure to obtain 248.6 g (93.3%) of pale yellow 9,9-diethyl-9H-fluorene (2) as a viscous liquid.

2-2. Synthesis of 1- (9,9-diethyl-9H-fluoren-2-yl) -1-propanone

After dissolving 100.5 g (0.45 mol) of 9,9-diethyl-9H-fluorene (2) in 1 L of dichloromethane, the reaction was cooled to -5 DEG C and then 72.3 g (0.54 mol) While taking care not to raise the temperature of the reaction product, 50.1 g (0.54 mol) of propionyl chloride diluted in 50 ml of dichloromethane was slowly added over 2 hours, and the reaction product was stirred at -5 ° C for 1 hour. Then, the reaction mixture was poured slowly into 1 L of ice water and stirred for 30 minutes. The organic layer was separated, washed with 500 ml of distilled water, and the recovered organic layer was distilled under reduced pressure. The resulting product was purified by silica gel column chromatography (developing solvent; ethyl acetate: n-hexane = 1: 4) to obtain 75.8 g (60.6%) of light yellow solid 1- (9,9-diethyl-9H- fluoren-2-yl) -1-propanone (3).

2-3. Synthesis of 1- (9,9-diethyl-9H-fluoren-2-yl) -1,2-propanedione-

44.5 g (0.16 mol) of 1- (9,9-diethyl-9H-fluoren-2-yl) -1-propanone (3) was dissolved in 900 ml of tetrahydrofuran (THF) , And 24.7 g (0.24 mol) of isobutyl nitrite were added in this order, and the reaction was stirred at 25 ° C for 6 hours. The organic layer was washed with 600 ml of distilled water, and the recovered organic layer was dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the obtained solid product was dissolved in ethyl acetate: (9,9-diethyl-9H-fluoren-2-yl) -1,2-propanedione-2-yl) -acetic acid was obtained by recrystallization using 300 ml of a mixed solvent of hexane (1: 6) 27.5 g (56.0%) of oxime (4) was obtained.

2-4. Synthesis of 1- (9,9-diethyl-9H-fluoren-2-yl) -1,2-propanedione-2-oxime-O-

(0.29 mol) of 1- (9,9-diethyl-9H-fluoren-2-yl) -1,2-propanedione- (0.35 mol) of triethylamine was added to the reaction solution, and the reaction solution was stirred for 30 minutes. 27.5 g (0.35 mol) of acetyl chloride was dissolved in N -Methyl-2-pyrrolidinone was slowly added over 30 minutes, and the mixture was stirred for 30 minutes while taking care not to raise the temperature of the reaction product. Then 1 L of distilled water was slowly added to the reaction mixture and stirred for 30 minutes to separate the organic layer. The recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained solid product was recrystallized using 1 L of ethanol and then dried to obtain a pale-gray solid 1- (9,9-diethyl-9H-fluoren-2-yl) -1,2-propanedione- 93.7 g (92.6%) of O-acetate (5) was obtained.

Example  1. Preparation of colored photosensitive resin composition

A colored photosensitive resin composition was prepared with the composition and the content (unit: parts by weight) as shown in Table 1 below.

division Alkali-soluble resin Photopolymerizable compound Photopolymerization initiator Red pigment menstruum A B-1 B-2 B-3 C-1 C-2 C-3 C-4 D E Comparative Example 1 10 5 - - 0.6 - - - 29 56 Comparative Example 2 10 5 - - - 0.6 - - 29 56 Comparative Example 3 10 5 - - - - 0.6 - 29 56 Comparative Example 4 10 5 - - - - - 0.6 29 56 Comparative Example 5 10 5 - - - - 0.2 - 29 56 Comparative Example 6 10 - 5 - - - 0.6 - 29 56 Comparative Example 7 10 - 5 - - - - 0.6 29 56 Example 1 10 - 5 - 0.6 - - - 29 56 Example 2 10 - 5 - - 0.6 - - 29 56 Example 3 10 - - 5 0.6 - - - 29 56 Binder resin (A): SPCY-1L (Showa Denko)
The photopolymerizable compound (B)
B-1: A9550 (Shin-Nakamura Co., Chemical formula 9)
B-2: A-DPH-12E (Shin Nakamura, formula 4 when m is 12)
B-3: A-DPH-24E (Shin Nakamura, formula 4 when m is 24)
The photopolymerization initiator (C)
C-1: Photopolymerization initiator (5) of Synthesis Example 3
C-2: Photopolymerization initiator (Synthesis Example 6) of Synthesis Example 4
C-3: I-369 (BASF)
C-4: OXE-01 (BASF)
Red pigment (D): DC-254-78 (Sakata)
Solvent (E): Propylene glycol monomethyl ether acetate

[Chemical Formula 4]

[Chemical Formula 9]

Experimental Example

(1) Manufacture of color filters

The colored photosensitive resin compositions prepared in Examples and Comparative Examples were applied to the top of a glass substrate by spin coating and then placed on a heating plate and held at a temperature of 100 ° C for 3 minutes to form a color layer thin film. Then, a test photomask having a line / space pattern of 1 to 50 mu m was placed thereon, and ultraviolet light was irradiated at a distance of 250 mu m from the test photomask. At this time, the ultraviolet light source was irradiated with 50 kJ / cm 2 using 1 kW high pressure mercury containing g, h and i lines, and no special optical filter was used. The color layer thin film irradiated with ultraviolet rays was immersed in a KOH aqueous solution of pH 10.5 for 2 minutes for development. The glass substrate on which the developed color layer thin film was formed was washed with distilled water, dried in a nitrogen gas atmosphere, and heated for 1 hour in a heating oven at 200 ° C to thermally cure the color filter.

(2) Evaluation of line width

Using the colored photosensitive resin compositions of Examples and Comparative Examples, a coating film having a pattern formed by the above-described method for producing a color filter was obtained. Thereafter, the prepared color substrate was measured for its length in a 100-μm pattern using an optical microscope, and the results are shown in Table 2.

<Evaluation Criteria>

100 ~ 103um: ◎

103 ~ 106um: ○

106 ~ 110um: Δ

110um ~: X

(3) Adhesion evaluation

Using the colored photosensitive resin compositions of Examples and Comparative Examples, a coating film having a pattern formed by the above-described method for producing a color filter was obtained. Thereafter, the prepared red color substrate was observed by using an optical microscope to confirm pattern peeling, and the results are shown in Table 2.

<Evaluation Criteria>

No snatch: ◎

Partial cut: △

Fragmentation: X

(4) Evaluation of process characteristics (development rate and residues)

The development speed was observed by the process of obtaining a patterned film in the color filter manufacturing method using the colored photosensitive resin compositions of Examples and Comparative Examples, and the presence or absence of the remaining film was determined after development, and the results are shown in Table 2 .

&Lt; Development rate evaluation standard &

1 to 10 sec: ◎

10 ~ 20sec: ○

20 to 30 sec:

30 to 40 sec: X

<Evaluation Criteria>

With residue: ◎

No residue: X

Evaluation items Line width Adhesion Development speed Residue Comparative Example 1 X ◎ △ X Comparative Example 2 X ◎ △ X Comparative Example 3 △ △ △ X Comparative Example 4 △ △ △ X Comparative Example 5 ○ X △ X Comparative Example 6 ◎ X ◎ ◎ Comparative Example 7 ◎ X ◎ ◎ Example 1 ◎ ◎ ◎ ◎ Example 2 ◎ ◎ ◎ ◎ Example 3 ◎ ◎ ◎ ◎

As shown in Table 2, in the case of the example using the colored photosensitive resin composition according to the present invention, it was confirmed that a color filter excellent in adhesion, suitable for the implementation of fine patterns, and excellent in process speed and residue, Respectively.

Specifically, in the case of Comparative Examples 1 to 5 in which a conventional 5 to 6-functional acrylate photopolymerizable compound was used in place of the photopolymerizable compound to which the polyfunctional EO group (ethylene oxide) was added, the developing speed was somewhat slow, Is difficult to implement. In Comparative Example 4 using a conventional oxime ester photopolymerization initiator in place of the oxime ester fluorene derivative compound, a pattern having a low line width was realized, but the result was inferior in adhesion. In the case of Comparative Example 7 in which a conventional oxime ester photopolymerization initiator was used in place of the oxime ester fluorene derivative compound in the state where the photopolymerizable compound was applied, a pattern having a very low line width was realized. However, Resulting in a bundle of patterns.

On the other hand, in Examples 1 to 3, the application of the photopolymerizable compound to the polyfunctional EO group and the application of the oxime ester fluorene derivative compound as the photopolymerization initiator simultaneously realized both low line width and adhesion, .

Claims (6)

(A), a photopolymerizable compound (B), a photopolymerization initiator (C), a red pigment (D) and a solvent (E)
The photopolymerizable compound (B) comprises a compound represented by the following formula (1)
Wherein the photopolymerization initiator (C) comprises a compound represented by the following formula (2):
[Chemical Formula 1]

X and R ₁ are aliphatic hydrocarbons having 1 to 10 carbon atoms and having 1 to 10 carbon atoms, R ₂ is independently an aliphatic hydrocarbon having 1 to 10 carbon atoms with or without a hetero atom, Is an integer of 1 to 4, A is a functional group represented by the following formula (3)
(2)

In Formula 2, R ₁ to R ₃ are each independently selected from the group consisting of hydrogen, a halogen group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, An alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, a hydroxyalkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms,
R ₄ to R ₁₀ are each independently selected from the group consisting of hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, A hydroxyalkyl group having 1 to 20 carbon atoms, a hydroxyalkoxy group having 1 to 20 carbon atoms, an amino group, a nitro group, a cyano group or a hydroxy group,
n is 0 or 1,
(3)

In the general formula (3), m is an integer of 2 to 6. The method according to claim 1,
The colored photosensitive resin composition according to claim 1, wherein the compound represented by the formula (1) is a compound represented by the following formula (4)
[Chemical Formula 4]

In formula (4), the sum of m is 12 to 36. The method according to claim 1,
Wherein the compound represented by the general formula (2) is a compound represented by the following general formula (5) or (6).
[Chemical Formula 5]

[Chemical Formula 6]

The method according to claim 1,
Based on the colored photosensitive resin composition,
The alkali-soluble resin (A) is contained in an amount of 1 to 40% by weight,
The photopolymerizable compound (B) is contained in an amount of 1 to 20% by weight,
The photopolymerization initiator (C) is contained in an amount of 0.1 to 10% by weight,
The red pigment (D) is contained in an amount of 5 to 40% by weight,
Wherein the solvent (E) is contained in an amount of 20 to 85% by weight. A color filter formed using the colored photosensitive resin composition according to any one of claims 1 to 4. A liquid crystal display device comprising the color filter according to claim 5.