KR20200114888A - Colored photosensitive resin composition and color filter and image display device using the same - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition including a colorant and a photopolymerizable compound, wherein the photopolymerizable compound includes a photopolymerizable monomer and an isocyanurate compound represented by chemical formula 1. The colored photosensitive resin composition prevents an increase in retardation (Rth) in the thickness direction, and thus can prevent degradation of contrast caused by light leakage generated by an increase in retardation in the thickness direction, shows excellent visibility, and provides excellent film hardness after post-baking and excellent reliability, including pencil hardness, solvent resistance, or the like. The present invention also relates to a color filter and an image display device obtained by using the colored photosensitive resin composition.

Description

A colored photosensitive resin composition, a color filter and an image display device manufactured using the same TECHNICAL FIELD [COLORED PHOTOSENSITIVE RESIN COMPOSITION AND COLOR FILTER AND IMAGE DISPLAY DEVICE USING THE SAME}

The present invention relates to a colored photosensitive resin composition, a color filter manufactured using the same, and an image display device.

A color filter is a thin film-type optical component that extracts three colors of red, green, and blue from white light and enables it in a fine pixel unit, and the size of one pixel is about tens to hundreds of micrometers. These color filters include a black matrix layer formed in a predetermined pattern on a transparent substrate to block light at the boundary between each pixel, and a plurality of colors (typically red (R), green (G) and a plurality of colors) to form each pixel. It has a structure in which pixel portions in which three primary colors of blue (B) are arranged in a predetermined order are sequentially stacked.

Recently, as one of the methods of implementing a color filter, a pigment dispersion method using a pigment dispersion type photosensitive resin has been applied. However, a part of the light is absorbed by the color filter while the light irradiated from the light source passes through the color filter. There is a problem in that the efficiency is deteriorated and color reproduction is deteriorated due to the characteristics of the pigment included in the color filter.

In recent years, not only thinning of color filters included in image display devices, but also additional high-definition, power-saving and low-cost have been demanded, and has sufficient color purity, brightness, and contrast, and exhibits birefringence that can cope with various liquid crystal display modes. There is a demand for a photosensitive resin composition capable of patterning a colored layer having a fine pattern, a counter substrate supporting layer, an extension layer for controlling the cell gap, and a retardation layer with precision and low cost.

In such a color filter, the retardation of about 10 nm is not completely corrected, and accordingly, the visibility tends to be slightly lowered. Compared with other materials used in image display devices such as liquid crystal display devices, the retardation of the color filter is relatively small, so it has not been greatly emphasized until now, but it has to be solved as the image display device requires high contrast and wide viewing angle characteristics. It became a task to do.

Accordingly, attempts have been made to reduce the retardation of the color filter by containing a polymer having a planar structure group in the side chain in the colored layer or by containing birefringence reducing particles having a birefringence opposite to that of the polymer in the colored layer. Is losing.

On the other hand, it is particularly important to improve color purity, luminance, and contrast, which are properties required for color filters. As the brightness is improved, it is possible to reduce the amount of light of the backlight with low power, which is advantageous in terms of environment.

Republic of Korea Patent Application Publication No. 2008-0071942 relates to a color filter, a colored composition for a color filter, and a liquid crystal display device, comprising a transparent resin, an organic pigment dispersed in the transparent resin and a compound having a function of increasing retardation. Disclosed is the content of a colored composition for color filters containing a data adjustment agent.

However, in the case of the conventional literature, reliability and development speed such as heat resistance and light resistance are somewhat inferior, and since the taper angle is low, a problem that is difficult to apply to a high resolution model having a small pixel size may arise.

Republic of Korea Patent Publication No. 2008-0071942

The present invention is to improve the above-described conventional technical problem, and to suppress the increase in thickness direction retardation (Rth) to show high contrast and excellent visibility, and at the same time to provide a colored photosensitive resin composition having excellent development speed and reliability do.

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

The present invention is a colorant; And a photopolymerizable compound comprising an isocyanurate compound and a photopolymerizable monomer represented by the following Formula 1,

The isocyanurate compound represented by Formula 1 is contained in an amount of 8 to 35 parts by weight based on 100 parts by weight of the total solid content of the colored photosensitive resin composition, providing a colored photosensitive resin composition.

[Formula 1]

(In Formula 1,

Each of R1 to R3 is independently any one of the following Formulas 2 to 4, provided that at least one of R1 to R3 is represented by the following Formula 2.)

[Formula 2]

[Formula 3]

[Formula 4]

(In Chemical Formulas 2 to 4, * represents a bonding hand.)

In addition, the present invention provides a color filter including a colored pattern made of the colored photosensitive resin composition.

Further, the present invention provides an image display device including the color filter.

In the colored photosensitive resin composition according to the present invention, some pigment particles are arranged in a regular manner by heat during postbake in a coating state, thereby inhibiting crystal growth from progressing and increasing the thickness direction retardation (Rth). Can be prevented. Accordingly, a decrease in contrast due to light leakage caused by an increase in retardation in the thickness direction can be prevented, and excellent visibility can be exhibited.

In addition, since the colored photosensitive resin composition of the present invention has excellent film hardness after postbake, it is possible to provide excellent effects such as pencil hardness and solvent resistance.

Therefore, the above-described colored photosensitive resin composition can be usefully applied to a color filter and an image display device requiring high color reproducibility.

The present invention includes a colorant, an isocyanurate compound represented by Formula 1, and a photopolymerizable monomer, and the photopolymerizable compound includes an isocyanurate compound represented by Formula 1 in a specific content range, thereby By preventing the increase of Rth, the contrast can be prevented from decreasing due to light leakage caused by the increase in retardation in the thickness direction, and excellent visibility can be displayed, as well as the film hardness after postbake. It provides a colored photosensitive resin composition having excellent reliability such as pencil hardness and solvent resistance, and a color filter and an image display device manufactured using the same.

Hereinafter, each component constituting the colored photosensitive resin composition of the present invention will be described in detail. However, the present invention is not limited by these components.

<Colored photosensitive resin composition>

The colored photosensitive resin composition according to the present invention includes a colorant, and a photopolymerizable compound including a photopolymerizable monomer and an isocyanurate compound of a specific chemical structure, and may further include an alkali-soluble resin, a photopolymerization initiator, and a solvent, If necessary, an additive may be further included.

coloring agent

The colored photosensitive resin composition according to the present invention contains a colorant.

The colorant may be used in combination of any one or two or more of a pigment, a dye, or a natural colorant, and among them, a pigment may be preferably used in view of excellent heat resistance and color development.

As the organic or inorganic pigment, various pigments used in printing ink, inkjet ink, etc. may be used, and specifically, water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoin Doline Pigment, Ferriene Pigment, Perinone Pigment, Dioxazine Pigment, Anthraquinone Pigment, Dianthraquinonyl Pigment, Anthrapyrimidine Pigment, Antanthrone Pigment, Indanthrone Pigment, Fravantron Pigment, Pyran A pyranthrone pigment, a diketopyrropyrrole pigment, etc. are mentioned. Examples of the inorganic pigment include metal compounds such as metal oxides, complex metal oxides or metal complex salts; Or carbon black. Specifically, examples of the metal include iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony. In particular, the organic pigments and inorganic pigments specifically include compounds classified as pigments in the color index (published by The Society of Dyers and Colorists), and more specifically, the color index (CI) number as follows. Although a pigment can be mentioned, it is not necessarily limited to these.

For example, C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 179, 180, 192, 208, 209, 215, 216, 224, 242, 254, 255, 264 and 269 ;

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

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

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

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

C.I. Pigment Green 7, 10, 15, 25, 36, 47, 58, 59, 62 and 63;

C.I Pigment Brown 28;

C.I Pigment Black 1 and 7 and the like.

Each of the pigments (a1) may be used alone or in combination of two or more.

C.I. Among the pigment pigments, C.I. Pigment Red 179, C.I. Pigment Red 208, C.I. Pigment Red 254, C.I. Pigment Red 264, C.I. Pigment Red 269, C.I. Pigment Yellow 139, C.I. Pigments selected from Pigment Yellow 185 and C.I Pigment Violet 23 may be preferably used.

In one embodiment of the present invention, the colorant may be included in an amount of 3 to 60 parts by weight, preferably 5 to 55 parts by weight, based on 100 parts by weight of the total solid content in the colored photosensitive resin composition.

When the content of the colorant satisfies the above range based on the above criteria, the color concentration is sufficient when the color filter is manufactured, and the polymer to be described later included in the colored photosensitive resin composition may be included in a required amount, so that the mechanical strength is sufficient. There is an advantage that the pattern can be formed.

Among the above pigments, the organic pigment is a surface treatment using a pigment derivative into which an acidic group or a basic group is introduced as necessary, a grafting treatment on the surface of the pigment with a polymer compound, etc., atomization treatment by sulfuric acid refinement, or impurities. It can be treated by washing treatment with an organic solvent for removal, water, etc., removal treatment by an ion exchange method of ionic impurities, or the like.

When using a pigment as the colorant, it is preferable to use a pigment having a uniform average particle diameter. As a method of making the particle diameter of the pigment uniform, a method of performing a dispersion treatment by containing a surfactant as a pigment dispersant, etc. can be exemplified, and according to this method, a pigment dispersion in a state in which the pigment is uniformly dispersed in a solution can be obtained.

Examples of the pigment dispersant include surfactants such as cationic, anionic, nonionic, and amphoteric, and these may be used alone or in combination of two or more. The pigment dispersant is used in an amount of 1 part by weight or less based on 1 part by weight of the colorant in the colored photosensitive resin composition, and preferably in an amount of 0.05 to 0.5 parts by weight. When the pigment dispersant is used within the above range based on the above criteria, it is preferable because a pigment having a uniform average particle diameter can be obtained.

Photopolymerizable compound

The colored photosensitive resin composition according to the present invention includes a photopolymerizable compound including an isocyanurate compound represented by a specific chemical structure.

In one embodiment, the isocyanurate compound included in the photopolymerizable compound may be represented by Formula 1 below.

[Formula 1]

(In Formula 1,

R1 to R3 are each independently any one of the following formulas 2 to 4, provided that at least one of R1 to R3 is the following formula 2)

[Formula 2]

[Formula 3]

[Formula 4]

(In Chemical Formulas 2 to 4, * represents a bonding hand.)

The isocyanurate compound represented by Formula 1 may be exemplified by Formula 1-1 or 1-2 below, but is not limited thereto.

[Formula 1-1]

[Formula 1-2]

In the present invention, the isocyanurate compound represented by Formula 1 may play a role of controlling retardation in the blue photosensitive resin composition according to the present invention.

For example, a crystal is an arrangement in which atoms or molecules are arranged with a certain regularity, and some pigments grow crystals by arranging pigment molecules uniformly by structural characteristics and heat. In this case, as the coating film is thickened, a thickness direction retardation (Rth), that is, a retardation in the thickness direction, occurs, birefringence occurs, and the contrast and visibility are deteriorated.

Accordingly, the colored photosensitive resin composition of the present invention includes the isocyanurate compound represented by Formula 1, so that some pigment particles are arranged in a regular manner by heat during postbake in a coating state, thereby growing crystals. By suppressing the progress of Rth, it prevents the increase of Rth, and the contrast decreases due to light leakage caused by the increase of Rth.

Although not wishing to be limited by theory, the isocyanurate compound represented by Chemical Formula 1 has a high shrinkage rate because it has a plate shape and thus has an advantage of excellent color reproduction.

In particular, since an epoxy group is bonded to the isocyanurate compound represented by Formula 1, it is possible to improve reliability such as pencil hardness and solvent resistance since the film hardness is excellent after postbake.

In addition, since the colored photosensitive resin composition according to the present invention contains the isocyanurate compound represented by Formula 1, there is an advantage in that the pattern angle is excellent and the residual film rate is excellent.

The isocyanurate compound represented by Formula 1 may be included in an amount of 8 to 35 parts by weight, and preferably 9.5 to 20 parts by weight, based on 100 parts by weight of the total solid content of the colored photosensitive resin composition.

In this case, the decrease in luminance can be suppressed, sensitivity and adhesion are improved, and the phenomenon of increasing the viscosity of the colored photosensitive resin composition is suppressed, so that the coating property is excellent, and since it has appropriate reactivity, the dispersion stability is excellent and yellowing occurs. There is an advantage that can be suppressed.

The colored photosensitive resin composition according to the present invention may be used by adding a conventional photopolymerizable monomer to the isocyanurate compound represented by Chemical Formula 1 in terms of improving the development speed.

The photopolymerizable monomer is a photopolymerizable monomer compound having a carbon-carbon double bond, and may refer to a compound that polymerizes by a radical generated by exposure and binds in the form of a polymer that is insoluble in a developing solution.

The photopolymerizable monomer may include, for example, a monofunctional monomer, a bifunctional monomer, and other polyfunctional monomers, and one or two or more photopolymerizable monomers may be used in combination.

Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpi And rolidone.

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) acrylic Rate, bis(acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, butylene glycol dimethacrylate, hexanediol di(meth)acrylate, diethylene glycol di(meth) )Acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, ethoxylate Neopentyl glycol diacrylate, propyloxylate neopentyl glycol diacrylate, etc. are mentioned.

Specific examples of the trifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylic Rate, bis(acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, and the like.

Specific examples of the 4-functional monomer include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, ditrimethyrolpropane tetraacrylate, ditrimethyrolpropane tetramethacrylate, and dipentaerythritol tetraacrylate. , Tetramethylolmethane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, glycerin tetraacrylate, glycerin tetramethacrylate, and the like.

Specific examples of the 5-functional monomer include dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol monohydroxypentamethacrylate, etc. Can be lifted.

Specific examples of the 6-functional monomer include dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the like.

Among these, as the photopolymerizable monomer, a polyfunctional monomer having a bifunctional or higher function may be preferably used, and in particular, a polyfunctional monomer having a pentafunctional or higher function may be preferably used. The photopolymerizable monomer may be included in an amount of 5 to 50 parts by weight, preferably 20 to 40 parts by weight, based on 100 parts by weight of the total solid content in the colored photosensitive resin composition. When the photopolymerizable monomer is included within the above range, the strength and smoothness of the pixel portion are improved, which is preferable.

In another embodiment of the present invention, the colored photosensitive resin composition may further include at least one selected from the group consisting of alkali-soluble resin, photopolymerization initiator, additive, and solvent, but is not limited thereto.

Alkali-soluble resin

The alkali-soluble resin may be used without limitation as long as it is generally used in a general field. The alkali-soluble resin generally has reactivity and alkali solubility by the action of light or heat, and serves as a dispersion resin for a colorant.

For example, the alkali-soluble resin contained in the colored photosensitive resin composition of the present invention acts as an alkali-soluble resin for the colorant, and any polymer soluble in the alkaline developer used in the developing step for the production of a color filter can be used, and preferred Preferably, an acrylic alkali-soluble resin may be used.

Examples of the alkali-soluble resin include a carboxyl group-containing monomer and a copolymer of another monomer copolymerizable with this monomer.

Examples of the carboxyl group-containing monomer include unsaturated carboxylic acids such as unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated polycarboxylic acids having at least one carboxyl group in the molecule. I can.

Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid.

As said unsaturated dicarboxylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, etc. are mentioned, for example.

The unsaturated polyhydric carboxylic acid may be an acid anhydride, specifically maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. In addition, the unsaturated polyhydric carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester thereof, for example, succinate mono (2-acryloyloxyethyl), succinate mono (2-methacryloyl) Oxyethyl), monophthalate (2-acryloyloxyethyl), monophthalate (2-methacryloyloxyethyl), and the like. The unsaturated polyhydric carboxylic acid may be a mono(meth)acrylate of the dicarboxylic polymer at both ends, for example, ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, etc. have. Each of the carboxyl group-containing monomers may be used alone or in combination of two or more. Other monomers that can be copolymerized with the carboxyl group-containing monomer include, for example, styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxy. Toxoxystyrene, p-methoxystyrene, o-vinylbenzylmethylether, m-vinylbenzylmethylether, p-vinylbenzylmethylether, o-vinylbenzyl glycidyl ether, m-vinylbenzylglycidyl ether, p- Aromatic vinyl compounds such as vinyl benzyl glycidyl ether and indene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxy Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxy Roxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allylacrylic Rate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl meth Crylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate Rate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl Acrylate, dicyclopentadiethyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate, etc. Unsaturated carboxylic acid esters of; 2-Aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethyl Unsaturated carboxyl, such as aminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, and 3-dimethylaminopropyl methacrylate Acid aminoalkyl esters; Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate; Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether; Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and vinylidene cyanide; Unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide, and N-2-hydroxyethyl methacrylamide; Maleimide, N-phenylmaleimide. Unsaturated imides such as N-cyclohexylmaleimide; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; And a monoacryloyl group or a monomethacryloyl group at the end of the polymer molecular chain of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, and polysiloxane. And macromonomers to have. These monomers can be used alone or in combination of two or more.

When the alkali-soluble resin is a copolymer of a carboxyl group-containing monomer and another monomer copolymerizable with this monomer, the content ratio of the constituent units derived from the carboxyl group-containing monomer is mass based on the total content of the constituent units constituting the copolymer. The fraction is 10 to 50% by mass, preferably 15 to 40% by mass, and more preferably 25 to 40% by mass. When the content ratio of the constituent units derived from the carboxyl group-containing monomer satisfies the above criteria, the solubility in the developer is good, and the pattern is accurately formed during development.

More specifically, as the alkali-soluble resin, (meth)acrylic acid/methyl (meth)acrylate copolymer, (meth)acrylic acid/benzyl (meth)acrylate copolymer, (meth)acrylic acid/2-hydroxyethyl (meth) Acrylate/benzyl(meth)acrylate copolymer, (meth)acrylic acid/methyl(meth)acrylate/polystyrene macromonomer copolymer, (meth)acrylic acid/methyl(meth)acrylate/polymethyl(meth)acrylate macro Monomer copolymer, (meth)acrylic acid/benzyl(meth)acrylate/polystyrene macromonomer copolymer, (meth)acrylic acid/benzyl(meth)acrylate/polymethyl(meth)acrylate macromonomer copolymer, (meth)acrylic acid /2-hydroxyethyl (meth)acrylate/benzyl (meth)acrylate/polystyrene macromonomer copolymer, (meth)acrylic acid/2-hydroxyethyl (meth)acrylate/benzyl (meth)acrylate/polymethyl (Meth)acrylate macromonomer copolymer, (meth)acrylic acid/styrene/benzyl (meth)acrylate/N-phenylmaleimide copolymer, (meth)acrylic acid/succinic acid mono(2-acryloyloxy)/styrene/ Benzyl (meth)acrylate/N-phenylmaleimide copolymer, (meth)acrylic acid/succinic acid mono (2-acryloyloxyethyl)/styrene/allyl (meth)acrylate/N-phenylmaleimide copolymer, ( Meth)acrylic acid/benzyl(meth)acrylate/N-phenylmaleimide/styrene/glycerol mono(meth)acrylate copolymer, etc. Among these, (meth)acrylic acid/benzyl(meth)acrylate copolymer, (Meth) acrylic acid / benzyl (meth) acrylate / styrene copolymer, (meth) acrylic acid / methyl (meth) acrylate copolymer, (meth) acrylic acid / methyl (meth) acrylate / styrene copolymer can be preferably used have.

The alkali-soluble resin preferably has an acid value in the range of 30 to 150 (mgKOH/g). When the acid value of the alkali-soluble resin is within the above range, the solubility in the developer is improved, the non-exposed portion is easily dissolved and the sensitivity is increased, as a result, the pattern of the exposed portion remains during development to improve the film remaining ratio. It is desirable to do it. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and can be usually determined by titration using an aqueous potassium hydroxide solution.

In addition, the alkali-soluble resin has a weight average molecular weight in terms of polystyrene (hereinafter simply referred to as'weight average molecular weight') measured by gel permeation chromatography (GPC; tetrahydrofuran as an elution solvent) from 3,000 to 200,000, preferably Is preferably 5,000 to 100,000. When the weight average molecular weight of the alkali-soluble resin is in the above range, the residual film ratio is high, the solubility of the non-exposed portion in the developer is excellent, and the resolution is improved.

The alkali-soluble resin is preferably contained in an amount of 10 to 80 parts by weight, more preferably 20 to 70 parts by weight, based on 100 parts by weight of the total solid content in the colored photosensitive resin composition. If the content of the alkali-soluble resin is within the above range based on the above criteria, a pattern can be formed, and resolution and residual film rate are improved.

Photopolymerization initiator

It is preferable that the photopolymerization initiator contains an acetophenone compound. Specific examples of the acetophenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one, and 2-benzyl-2-dimethylamino-1 (4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-2-methyl-1-[4- (2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane-1 -One oligomer etc. are mentioned, Preferably, 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one, etc. are mentioned.

The acetophenone-based compounds may be used alone or in combination of two or more. The photopolymerization initiator may be used in combination with other types of photopolymerization initiators in addition to the acetophenone compound. Other types of photopolymerization initiators include active radical generators, sensitizers, and acid generators that generate active radicals by irradiation with light. Examples of the active radical generator include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and triazine-based compounds.

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

Specific examples of the benzophenone-based compound include methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3',4,4'-tetra (t-butylper Oxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Specific examples of the thioxanthone compound are 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, 1-chloro-4 -Propoxy oxantone, etc. are mentioned.

Specific examples of the triazine-based 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-(4-methoxystyryl)-1,3,5-triazine , 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl) -6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2 -Methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4dimethoxyphenyl)ethenyl]-1,3,5- Triazine, etc. are mentioned. As the sensitizer, specifically, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2' -Biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compounds, and the like. . As the acid generator, specifically, 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate , 4-acetoxyphenylmethylbenzylsulfoniumhexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfoniumhexafluoroantimonate, diphenyliodonium p-toluenesulfonate, di Onium salts, such as phenyliodonium hexafluoroantimonate, or nitrobenzyl tosylate, benzointosylate, etc. are mentioned.

Among the above compounds, there are also compounds that generate an active radical and an acid at the same time. For example, a triazine-based compound is also used as an acid generator.

The photopolymerization initiator is 0.1 to 40 parts by weight, preferably 1 to 30 parts by weight based on 100 parts by weight of the total of the photopolymerizable compound including an alkali-soluble resin and an isocyanurate compound and/or a photopolymerizable monomer based on solid content. Can be included. When the content of the photopolymerization initiator is included within the above range based on the above criteria, the colored photosensitive resin composition is highly sensitive to shorten the exposure time, thereby improving productivity and maintaining high resolution.

The photopolymerization initiator may be used in combination with a photopolymerization initiation aid. The photopolymerization initiation aid may be used to promote polymerization of a photopolymerizable monomer in which polymerization is initiated by a photopolymerization initiator.

Examples of the photopolymerization initiator auxiliary agent include amine compounds and alkoxyanthracene compounds. Specific examples of the amine-based compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoic acid. , 4-dimethylaminobenzoic acid 2-ethylhexyl, N,N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (common name, Mihilers' ketone), 4,4'-bis (diethylamino )Benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, and the like, among which 4,4'-bis(diethylamino)benzophenone is preferable.

Specific examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, etc. Can be mentioned. The photopolymerization initiation aids may be used alone or in combination of two or more. In addition, the photopolymerization initiation aid may be a commercially available product such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.).

Specific examples of a preferred combination of the photopolymerization initiator and the photopolymerization initiation aid include diethoxyacetophenone and 4,4'-bis(diethylamino)benzophenone; 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one and 4,4'-bis(diethylamino)benzophenone; 2-hydroxy-2-methyl-1-phenylpropan-1-one and 4,4'-bis(diethylamino)benzophenone; 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one and 4,4'-bis(diethylamino)benzophenone; 1-hydroxycyclohexylphenyl ketone and 4,4'-bis(diethylamino)benzophenone; Oligomer of 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one and 4,4'-bis(diethylamino)benzophenone; A combination of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one and 4,4'-bis(diethylamino)benzophenone, and the like, preferably 2 -Methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one and a combination of 4,4'-bis(diethylamino)benzophenone, etc. are mentioned.

When the photopolymerization initiator and the photopolymerization initiator are used together, the content of the photopolymerization initiator is preferably 0.01 to 5 moles per 1 mole of the photopolymerization initiator. When the photopolymerization initiation auxiliary agent is included within the above content range, the sensitivity of the colored photosensitive resin composition is further increased, and the productivity of the color filter formed using the composition is improved.

solvent

As long as the solvent is effective in dissolving other components included in the colored photosensitive resin composition, the solvent used in the usual colored photosensitive resin composition may be used without particular limitation, and in particular, ethers, aromatic hydrocarbons, ketones, alcohols, esters And amides are preferred.

The solvent is specifically 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 dimethyl ether, diethylene glycol diethyl ether, Diethylene glycol dialkyl ethers such as diethylene glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, alkylene glycol alkyl ether acetates such as methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, methyl ethyl ketone , Acetone, methyl amyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, 3-ethoxy ethylpropionate, 3- Esters such as methyl methoxypropionate, and cyclic esters such as γ-butyrolactone.

The solvent is preferably an organic solvent having a boiling point of 100°C to 200°C in terms of applicability and drying properties, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butalac Tate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like can be used.

Each of the exemplified solvents may be used alone or in combination of two or more, and may be included in an amount of 60 to 90 parts by weight, preferably 70 to 88 parts by weight, based on the total 100 parts by weight of the colored photosensitive resin composition of the present invention.

When the solvent satisfies the above range, it provides the effect of improving the coating properties when applied with a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), or inkjet. do.

additive

The additives may be selectively added as needed, and for example, other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, and the like.

Specific examples of the other polymer compounds include curable resins such as epoxy resins and maleimide resins, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, polyurethane, etc. Can be lifted.

The curing agent is used to increase deep curing and mechanical strength, and specific examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, an oxetane compound, and the like.

Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, noblock epoxy resin, other aromatic epoxy resins, alicyclic epoxy resins , Glycidyl ester resins, glycidylamine resins, or brominated derivatives of these epoxy resins, aliphatic, alicyclic or aromatic epoxy compounds other than the epoxy resins and brominated derivatives thereof, butadiene (co)polymer epoxides, isoprene ( Co) polymer epoxidation product, glycidyl (meth)acrylate (co)polymer, triglycidyl isocyanurate, etc. are mentioned.

Specific examples of the oxetane compound in the curing agent include carbonate bisoxetane, xylene bis oxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane.

The curing agent may be used in combination with a curing agent and 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. Examples of the curing auxiliary compound include polyvalent carboxylic acids, polyvalent carboxylic anhydrides, and acid generators. The polyhydric carboxylic anhydrides may be commercially available as an epoxy resin curing agent. Specific examples of the epoxy resin curing agent include a brand name (Adeka Hadona EH-700) (manufactured by Adeka Industries, Ltd.), a brand name (Rika Shiddo HH) (manufactured by Shin Nippon Ewha Corporation), and a brand name (MH-700) (New Japan Ewha Corporation) and the like. The curing agent exemplified above may be used alone or in combination of two or more.

The surfactant may be used to further improve the film-forming property of the photosensitive resin composition, and a fluorine-based surfactant or a silicone-based surfactant may be preferably used.

Examples of the silicone surfactants are commercially available products such as DC3PA, DC7PA, SH11PA, SH21PA, and SH8400 of Dow Corning Toray Silicone, and TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460 of GE Toshiba Silicone. , TSF-4452, etc. Examples of the fluorine-based surfactant are commercially available products such as Megapieces F-470, F-471, F-475, F-482, and F-489 manufactured by Dai Nippon Ink Kagaku Kogyo. Each of the above-exemplified surfactants 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- (2-Aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-( 3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrime A oxysilane, 3-isocyanate propyl trimethoxy silane, 3-isocyanate propyl triethoxy silane, etc. are mentioned. The adhesion promoters exemplified above may be used individually or in combination of two or more. The adhesion promoter may be included in a weight fraction of usually 0.01 to 10 parts by weight, preferably 0.05 to 2 parts by weight based on 100 parts by weight of the total solid content of the colored photosensitive resin composition.

Specific examples of the antioxidant may include 2,2'-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butyl-4-methylphenol, and the like.

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

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

The additive can be added in an appropriate amount within a range that does not impair the object of the present invention. For example, the additive may be included in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, and more preferably 0.1 to 3 parts by weight, based on the total 100 parts by weight of the colored photosensitive resin composition, but is not limited thereto.

The colored photosensitive resin composition according to the present invention has an advantage in that it is easy to control the retardation of the colored pattern layer manufactured by using the same, that is, the colored pixels. For this reason, the color filter according to the present invention has an advantage of excellent contrast and visibility.

In addition, the colored photosensitive resin composition according to the present invention can be usefully used for photocurable ink, photosensitive printing plate, various photoresists, color filter photoresist for LCD, photoresist for resin black matrix, or transparent photosensitive material.

<Color filter>

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

In an embodiment, the colored pattern layer may obtain a retardation Rth in the thickness direction by Equation 1 below.

[Equation 1]

Rth={(Nx+Ny)/2-Nz}×d

In Equation 1 above,

Nx is the refractive index in the x direction in the plane of the colored pattern layer,

Ny is the refractive index in the y direction in the plane of the colored pattern layer,

Nz is the refractive index in the thickness direction of the colored pattern layer,

Let Nx be the slow axis with Nx≥Ny,

d is the thickness (nm) of the colored pattern layer.

In the present invention, the thickness direction retardation value is measured at a wavelength of 5 nm in the range of 400 nm to 700 nm from an orientation that is inclined by 40° from the normal direction of the substrate on which the coating film is formed, and is expressed using Equation 1 above. It can be obtained by doing.

In still another embodiment of the present invention, the colored pattern layer is a difference (Nx-Ny) between the refractive index (Nx) in the x direction in the plane of the colored pattern layer and the refractive index in the y direction (Ny) in the plane of the colored pattern layer. May be less than or equal to 0.01. In this case, it is preferable to have an advantage of having a low value of Rth, specifically the range of the aforementioned Rth value. More specifically, when the difference between the refractive indices is less than 0.01, the retardation Rth in the thickness direction of the color filter may have a value of -5 to 5 nm, and when the difference in the refractive index exceeds 0.01, Rth increases, so that the retardation in the thickness direction is Since it may be out of the above range, it is preferable to satisfy the above range.

Since the color filter according to the present invention has the Rth value as described above, there is an advantage of being able to manufacture a colored pattern layer, particularly a red pattern layer having excellent performance.

Specifically, in the color filter, a phenomenon in which display visibility is slightly deteriorated due to internal or external light such as sunlight or a fluorescent lamp, and a problem of deteriorating the visibility of the display may occur somewhat above a certain angle. However, the color filter according to the present invention has an advantage in that the contrast is excellent, the retardation in the thickness direction, that is, the low Rth performance can be satisfied, so that the visibility is excellent, the color mixing phenomenon between pixels is suppressed, and the occurrence of light leakage problems is suppressed. .

The substrate may be a substrate of the color filter itself, or may be a portion where the color filter is located in a display device, and the like, and is not particularly limited. The substrate may be glass, silicon (Si), silicon oxide (SiOx), or a polymer substrate, and the polymer substrate may be polyethersulfone (PES) or polycarbonate (PC).

The color filter including the substrate and the colored pattern layer as described above may further include a partition wall formed between each pattern, and may further include a black matrix, but is not limited thereto.

In addition, a protective layer formed on the pattern layer of the color filter may be further included.

<Image display device>

The present invention includes an image display device including the color filter described above.

The color filter of the present invention can be applied not only to an ordinary liquid crystal display device, but also to various image display devices such as an electroluminescent display device, a plasma display device, and a field emission display device.

The image display device may include a light-emitting device such as a light source, a light guide plate, and other configurations that can be included in an image display device in general, such as an image display unit including a color filter according to the present invention. Does not.

The color filter and image display device manufactured by using the colored photosensitive resin composition according to the present invention have excellent pattern angles and excellent residual properties, film residual rate, chemical resistance, and mechanical properties.

Hereinafter, examples will be described in detail to describe the present specification in detail. However, the embodiments according to the present specification may be modified in various forms, and the scope of the present specification is not construed as being limited to the embodiments described below. The embodiments of the present specification are provided to more completely describe the present specification to those of ordinary skill in the art. In addition, "%" and "parts" indicating content hereinafter are based on weight unless otherwise noted.

<Example>

Synthesis Example 1: Preparation of isocyanurate compound of formula 1-1

30.0 g of isocyanuric acid (Aldrich), 28 g of aryl bromide (Aldrich), and 48 g of potassium carbonate (Aldrich) were added to 780 ml DMSD and stirred at room temperature for 10 minutes. After that, the reaction was performed at 80°C for 24 hours. After allowing the temperature to cool to room temperature, 129 g of epichlorohydrin and 96 g of potassium carbonate were added and stirred at room temperature for 10 minutes, and the temperature was raised to 80 degrees and reacted for 20 hours. After cooling to room temperature, H ₂ O and 400 ml of ethyl acetic acid were added. After discarding the water layer, MgSO ₄ was added to ethyl acetic acid and added to the organic layer to remove the remaining H ₂ O, and then ethylacetic acid was removed. 9.8 g of the isocyanurate compound of 1 was obtained.

MS: 281.26

Synthesis Example 2: Preparation of isocyanurate compound of formula 1-2

8.5 g of an isocyanurate compound of Formula 1-2 was obtained in the same manner, except for changing to 60 g of epichlorohydrin in the synthesis method of Formula 1 above.

MS: 265.27

Examples and Comparative Examples: Preparation of colored photosensitive resin composition

A colored photosensitive resin composition was prepared by mixing each component in the composition of Tables 1 and 2 below (unit: parts by weight).

Example One 2 3 4 5 6 7 8 9 Colorant (A) (A-1) 4.5 4.5 4.5 (A-2) 4.5 4.5 4.5 (A-3) 4.5 4.5 4.5 Alkali Soluble Resin (B) (B-1) 4.56 4.56 4.56 4.56 4.56 4.56 4.56 4.56 4.56 Photopolymerizable compound (C) (C-1) 3.8 3.8 2.5 3.8 3.8 2.5 3.8 3.8 2.5 (C-2) 1.45 2.75 1.45 2.75 1.45 2.75 (C-3) 1.45 1.45 1.45 Photoinitiator (D) (D-1) 0.67 0.67 0.67 0.67 0.67 0.67 0.67 0.67 0.67 Solvent (E) (E-1) 85 85 85 85 85 85 85 85 85 Additive (F) (F-1) 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 (A-1) Colorant: CI Pigment Red 254
(A-2) Colorant: CI Pigment Red 269
(A-3) Colorant: CI Pigment Yellow 185
(B-1) Alkali-soluble resin: a copolymer of methacrylic acid and benzyl methacrylate (the ratio of the methacrylic acid unit to the benzyl methacrylate unit is 31:69 in molar ratio,
The acid value is 10mgKOH/g. The weight average molecular weight in terms of polystyrene is 20,0000)
(C-1) Photopolymerizable compound (photopolymerizable monomer): dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
(C-2) Photopolymerizable compound (isocyanurate compound): isocyanurate compound of formula 1-1
(C-3) Photopolymerizable compound (isocyanurate compound): isocyanurate compound of formula 1-2
(D-1) Photopolymerization initiator: 2-benzyl-2-dimethylamino-1 (4-morpholinophenyl) butan-1-one (Irgacure 369; manufactured by Ciba SpecialtyChemical)
(E-1) Solvent: Propylene glycol monomethyl ether acetate
(F-1) Additive: Surfactant (SH-8400 manufactured by Toray Silicone)

Comparative example One 2 3 4 5 6 7 8 9 Colorant (A) (A-1) 4.5 4.5 4.5 (A-2) 4.5 4.5 4.5 (A-3) 4.5 4.5 4.5 Alkali Soluble Resin (B) (B-1) 4.56 4.56 4.56 4.56 4.56 4.56 4.56 4.56 4.56 Photopolymerizable compound (C) (C-1) 5.25 5 5.25 5 5.25 5 (C-2) 0.25 5.25 0.25 5.25 0.25 5.25 (C-3) Photopolymerization initiator (D) (D-1) 0.67 0.67 0.67 0.67 0.67 0.67 0.67 0.67 0.67 Solvent (E) (E-1) 85 85 85 85 85 85 85 85 85 Additive (F) (F-1) 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 (A-1) Colorant: CI Pigment Red 254
(A-2) Colorant: CI Pigment Red 269
(A-3) Colorant: CI Pigment Yellow 185
(B-1) Alkali-soluble resin: a copolymer of methacrylic acid and benzyl methacrylate (the ratio of the methacrylic acid unit to the benzyl methacrylate unit is 31:69 in molar ratio,
The acid value is 10mgKOH/g. The weight average molecular weight in terms of polystyrene is 20,0000)
(C-1) Photopolymerizable compound (photopolymerizable monomer): dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
(C-2) Photopolymerizable compound (isocyanurate compound): isocyanurate compound of formula 1-1
(C-3) Photopolymerizable compound (isocyanurate compound): isocyanurate compound of formula 1-2
(D-1) Photopolymerization initiator: 2-benzyl-2-dimethylamino-1 (4-morpholinophenyl) butan-1-one (Irgacure 369; manufactured by Ciba SpecialtyChemical)
(E-1) Solvent: Propylene glycol monomethyl ether acetate
(F-1) Additive: Surfactant (SH-8400 manufactured by Toray Silicone)

<Experimental Example>

A color filter was prepared as follows using the colored photosensitive resin composition prepared in the above Examples and Comparative Examples, and the sensitivity, adhesion, and development speed at this time were measured in the following manner, and the results are shown in Table 3 and Table below. It is shown in 4.

Manufacturing of color filters

The prepared colored photosensitive resin composition was applied onto a glass substrate (#1737, manufactured by Corning) by spin coating, and then placed on a heating plate and held at a temperature of 100° C. for 3 minutes to form a thin film. Subsequently, a test photomask having a stepwise changing pattern in the range of 1 to 100% transmittance was placed on the thin film, and the interval with the test photomask was 1000 µm, and an ultra-high pressure mercury lamp (USH-250D, Ushio Denki ( Note) manufactured) was irradiated with light at an exposure dose (365 nm) of 40 mJ/cm 2 in an air atmosphere.

The UV-irradiated thin film was developed in a developing solution of a KOH aqueous solution having a pH of 12.5 using a spray developer for 70 seconds. 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 pattern shape (thin film) thickness of the manufactured color filter was 2.0 to 2.5 μm.

(1) Sensitivity and development speed

During the manufacturing process of the color filter, the time at which peeling of the non-exposed thin film portion appeared during development was measured to measure the development speed (seconds). In addition, the sensitivity, which is the minimum exposure amount (mJ/cm2) required to form a thin film without tearing of the pattern after development during the manufacturing process of the color filter, is measured and is shown in Tables 3 and 4 below.

(2) Pencil hardness

The hardness of the coating film (heat cured film) was measured according to the test method of JIS-K-5400. When a load of 9.8 N was applied to the heat-cured film using a pencil hardness tester, the highest hardness that did not cause a flaw in the coating film was taken as the hardness. The pencil used as a contrast was "Mitsubishi High Uni".

<Evaluation criteria>

◎: 6H or more

○: 4H to 5H

△: 2H to 3H

×: 1H or less

(3) contrast

A polarizing plate having a polarization degree of 49.99% was superimposed on both sides of the substrate on which the coating film was formed, and the ratio Lp/Lc of the luminance (Lp) when the polarizing plates were parallel and the luminance (Lc) when it was orthogonal was calculated as the contrast (C). .

(4) Thickness direction retardation value (Rth)

The thickness direction retardation value was measured at a wavelength of 5 nm in the range of 400 nm to 700 nm from a direction tilted by 40° from the normal direction of the substrate on which the coating film was formed using Axoscan, and the thickness direction retardation value (Rth) from the following equation 1 Was calculated.

However, measurement was performed at a wavelength of 610 nm in a red color pixel, 550 nm in a green color pixel, and 450 nm in a blue color pixel.

[Equation 1]

Rth={(Nx+Ny)/2-Nz}×d

(5) NMP solvent resistance

The prepared substrate was cut into 3×3 cm, and then immersed in 14.6 ml of NMP solution for 80° C./40 minutes. Then, the liquid was evaluated for absorbance with a UV-Vis spectrometer.

Example One 2 3 4 5 6 7 8 9 Sensitivity (mJ/cm ² ) 30 30 30 20 20 20 20 20 20 Development speed (sec) 10 13 18 12 15 19 12 14 17 Pencil hardness ◎ ◎ ◎ ○ ○ ○ ○ ○ ○ Contrast 10,010 10,300 10,400 4,000 4,200 4,300 5,100 5,200 5,400 Rth -3 -2.7 -2.2 -4.5 -4.6 -3.7 -4.3 -4.7 -3.5 Solvent resistance 1.7 1.1 1.2 1.8 One 1.3 2.1 2.1 1.9

Comparative example One 2 3 4 5 6 7 8 9 Sensitivity (mJ/cm ² ) 25 25 40 10 10 35 10 10 35 Development speed (sec) 8 10 80 9 12 100 9 12 90 Pencil hardness ○ ○ ◎ △ △ ○ △ △ ○ Contrast 9,000 9,800 10,400 3,400 3,700 4,500 4,000 4,200 5,600 Rth -8.7 -6.5 -2 -11.5 -8.7 -3.1 -13.5 -9.9 -3.2 Solvent resistance 2.7 2.3 One 2.8 2.4 0.9 3.5 2.8 1.7

With reference to Tables 3 and 4, the results of comparing Examples and Comparative Examples using the same colorant are as follows. Specifically, the color filters manufactured using Examples 1, 4 and 7 according to the present invention are isocyanu Compared to the color filters prepared using Comparative Examples 1, 4 and 7 that do not contain a nate compound, it exhibits excellent sensitivity, development speed, pencil hardness, and solvent resistance, and exhibits high contrast and retardation in the thickness direction (Rth). It was confirmed that this was not significantly increased.

In addition, Examples 2, 5, and 8 satisfying the isocyanate content range were all superior to Comparative Examples 2, 5, and 8 out of the isocyanonate content range, excellent sensitivity, development speed, pencil hardness, contrast, and retardation in the thickness direction. Dation and solvent resistance were shown.

In addition, in the case of Examples 3, 6 and 9 containing both an isocyanate compound and a photopolymerizable monomer, the sensitivity, development speed, contrast, thickness direction retardation and solvent resistance were relatively higher than those of Comparative Examples 3, 6, and 9. All were excellent.

Therefore, from the above experimental results, the present invention prevents the contrast from deteriorating due to light leakage caused by the increase in thickness direction retardation, can exhibit excellent visibility, and has excellent thinness after heat treatment, such as pencil hardness and solvent resistance. It can be seen that reliability can provide excellent effects.

Claims (6)

coloring agent; And
Including a photopolymerizable compound comprising an isocyanurate compound and a photopolymerizable monomer represented by the following formula (1),
The isocyanurate compound represented by Formula 1 is contained in an amount of 8 to 35 parts by weight based on 100 parts by weight of the total solid content of the colored photosensitive resin composition, a colored photosensitive resin composition:
[Formula 1]

(In Formula 1,
Each of R1 to R3 is independently any one of the following Formulas 2 to 4, provided that at least one of R1 to R3 is represented by the following Formula 2.)
[Formula 2]

[Formula 3]

[Formula 4]

(In Chemical Formulas 2 to 4, * represents a bonding hand.) The method according to claim 1,
The photopolymerizable monomer is contained in an amount of 5 to 50 parts by weight based on 100 parts by weight of the total solid content in the colored photosensitive resin composition. The colored photosensitive resin composition according to claim 1, further comprising at least one selected from the group consisting of an alkali-soluble resin, a photoinitiator, and a solvent. A color filter comprising a colored pattern layer made of the colored photosensitive resin composition according to any one of claims 1 to 3. The method according to claim 4, wherein the colored pattern layer has a difference (Nx-Ny) between the refractive index (Nx) in the x direction in the plane of the colored pattern layer and the refractive index (Ny) in the y direction in the plane of the colored pattern layer is 0.01 or less. Color filter. A display device comprising the color filter of claim 4.