KR20190061813A - Photosensitive Resin Composition for Color Conversion Layer, Color Filter Comprising Color Conversion Layer Using the Same and Display Device - Google Patents

Abstract

The present invention relates to a photosensitive resin composition for forming a color conversion layer comprising: a fluorescent dye; an epoxy compound; a binder resin; a photopolymerizable compound; a photopolymerization initiator; and a solvent, to a color filter comprising the color conversion layer using the same, and to an image display device provided with the color filter. The photosensitive resin composition for forming a color conversion layer according to the present invention comprises the epoxy compound, and thus can improve heat resistance and reliability of the color conversion layer.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition for forming a color conversion layer, a color filter including the color conversion layer using the same, and an image display device using the color conversion layer.

The present invention relates to a photosensitive resin composition for forming a color conversion layer, a color filter including the color conversion layer using the same, and an image display apparatus, and more particularly, to a color conversion layer forming method capable of improving the heat resistance and reliability of the color conversion layer A color filter including a color conversion layer using the same, and an image display device provided with the color filter.

Recently, the display industry has undergone drastic changes from CRTs to flat panel displays represented by PDPs, OLEDs, and LCDs. Among them, a liquid crystal display (LCD) is widely used as an image display device in almost all industries, and its application range is continuously expanding. However, a separate backlight unit is necessary due to the absence of its own light emitting device in the LCD.

CCFL (Cold Cathode Fluorescent Lamp) was used as a light source of a general backlight unit. However, since the backlight unit using CCFL is always supplied with power to the CCFL, a considerable amount of power is consumed, and a color reproduction ratio of about 70% as compared with CRT and environmental pollution problems caused by the addition of mercury are pointed out as disadvantages. BACKGROUND ART [0002] As a substitute product for solving the above problem, researches on a backlight unit using an LED (Light Emitting Diode) have been actively conducted. When LEDs are used as a backlight unit, they exceed 100% of the NTSC (National Television System Committee) color reproduction range specification, and can provide a more vivid image quality to consumers.

In order to improve the efficiency of a backlight source in the same industry, efforts have been made to improve the light efficiency by changing the materials and structures of color filters and LCD panels (see Korean Patent Publication No. 10-2012-0048218).

The color filter forms a pixel of each color through a patterning process after applying a dispersion composition containing a pigment or a dye. Such a pigment and a dye cause a problem of lowering the transmission efficiency of the backlight light source. The lowering of the transmission efficiency results in lowering the color reproducibility of the display device, which makes it difficult to realize a high-quality screen.

This low color reproducibility problem can be improved by increasing the light efficiency of the color filter, and a method of introducing the color conversion layer (or the light conversion layer) by increasing the thickness of the color filter or stacking or adjacent thereto is proposed have.

Conventional dyes and pigments are used for the color conversion layer. However, it is difficult to expect the light efficiency improvement only with the dyes and pigments, and the luminance is lowered. A method of using a fluorescent material in the color conversion layer has been proposed (see Korean Patent Publication No. 10-2016-0112479). However, when a fluorescent material is used for the color conversion layer as described above, there is a problem that heat resistance and reliability of the color conversion layer are insufficient.

Korean Patent Publication No. 10-2012-0048218 Korean Patent Publication No. 10-2016-0112479

An object of the present invention is to provide a photosensitive resin composition for forming a color conversion layer which can improve heat resistance and reliability of a color conversion layer.

Another object of the present invention is to provide a color filter comprising a color conversion layer using the photosensitive resin composition for forming a color conversion layer.

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

On the other hand, the present invention provides a photosensitive resin composition for forming a color conversion layer comprising a fluorescent dye, an epoxy compound, a binder resin, a photopolymerizable compound, a photopolymerization initiator and a solvent.

In one embodiment of the present invention, the epoxy compound may be at least one of an alicyclic epoxy compound and an aliphatic epoxy compound.

In one embodiment of the present invention, the epoxy compound is selected from the group consisting of 3 ', 4'-epoxycyclohexanemethyl 3,4-epoxycyclohexyl carboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, Cyclohexanedimethanol bis (3,4-epoxycyclohexanecarboxylate), dicyclopentadiene dioxide, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexane, diglycidyl 1,2- Cyclohexanedimethanol diglycidyl ether, pentaerythritol tetraglycidyl ether, 1,4-butanediol diglycidyl ether, poly [(2-oxiranyl) -1 , 2-cyclohexanediol] -2-ethyl-2- (hydroxymethyl) -1,3-propanediol ether and 4,5-epoxytetrahydrophthalic acid diglycidyl ester. have.

On the other hand, the present invention provides a color filter comprising a color conversion layer formed using the photosensitive resin composition for forming a color conversion layer.

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

The photosensitive resin composition for color conversion layer formation according to the present invention can improve the heat resistance and reliability of the color conversion layer by including an epoxy compound.

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

An embodiment of the present invention is a method for forming a color conversion layer comprising a fluorescent dye (A), an epoxy compound (B), a binder resin (C), a photopolymerizable compound (D), a photopolymerization initiator (E) To a photosensitive resin composition.

Fluorescent dye (A)

In one embodiment of the present invention, the fluorescent dye (A) can convert light of a specific wavelength range in incident light having a predetermined wavelength range (380 nm to 780 nm) into visible light and is not particularly limited as long as it has fluorescence properties Either can be used.

Examples of the fluorescent dye include dyes such as coumarin, naphthalimide, quinacridone, cyanine, xanthine, and pyridine. In addition, various low molecular weight light emitting materials and high molecular weight light emitting materials may be used.

Specifically, the fluorescent dye is at least one selected from the group consisting of 3- (2-benzothiazolyl) -7-diethylaminocoumarin (coumarin 6), 3- (2-benzoimidazolyl) Coumarin-based fluorescent dyes including coumarin 135 and the like; Naphthalimide fluorescent dyes including Solvent Yellow 43, Solvent Yellow 44 and the like; Quinacridone-based fluorescent dyes such as diethylquinacridone (DEQ); 2-methyl-6- (p-dimethylaminostyryl) -4H-pyran (DCM-1 (I)), DCM-2 (II), DCJTB (III) Based fluorescent dyes; Xanthine-based fluorescent dyes including rhodamine B and rhodamine 6G; A pyridine-based fluorescent dye containing pyridine 1; 4,4-difluoro-1,3,5,7-tetraphenyl-4-bora-3a, 4a-diaza-s-indacene (IV), lumogen F red, Low molecular weight luminescent material; It is possible to use a polymer light emitting material including polyphenylene, polyarylene, polyfluorene and the like. These may be used alone or in combination of two or more.

The fluorescent dyes may be selected from the group consisting of Solvent, Acid, Basic, Reactive, Direct, Disperse or the like in the color index (The Society of Dyers and Colourists) And dyes classified as Vat. More specifically, the dyes of the color index (C.I.) number as described below are not limited thereto.

C.I. Solvent Yellow 25, 79, 81, 82, 83, 89;

C.I. Acid Yellow 7, 23, 25, 42, 65, 76;

C.I. Reactive Yellow 2, 76, 116;

C.I. Direct Yellow 4, 28, 44, 86, 132;

C.I. Dispulse Yellow 54, 76;

C.I. Solvent Orange 41, 54, 56, 99;

C.I. Acid Orange 56, 74, 95, 108, 149, 162;

C.I. Reactive Orange 16;

C.I. Direct Orange 26;

C.I. Solvent Red 24, 49, 90, 91, 118, 119, 122, 124, 125, 127, 130, 132, 160, 218;

C.I. Acid Red 73, 91, 92, 97, 138, 151, 211, 274, 289;

C.I. Acid Violet 102;

C.I. Solvent Green 1, 5;

C.I. Acid Green 3, 5, 9, 25, 28;

C.I. Basic Green 1;

C.I. Bat Green 1

The content of the fluorescent dye (A) is not particularly limited and may be, for example, from 0.1 to 70% by weight, preferably from 0.1 to 10% by weight, based on 100% by weight of the total solid content in the photosensitive resin composition for color conversion layer formation . If the content of the fluorescent dye is less than 0.1 wt%, the light efficiency can not be ensured and it may be difficult to sufficiently secure the color conversion characteristics to be obtained in the present invention. If the content exceeds 70 wt%, the light efficiency improvement can not be expected or the cost rises excessively .

The epoxy compound (B)

In one embodiment of the present invention, the epoxy compound (B) serves to improve the heat resistance and reliability of the photosensitive resin composition for forming a color conversion layer.

As the epoxy compound (B), an alicyclic epoxy compound, an aliphatic epoxy compound, an aromatic epoxy compound and the like can be used.

Examples of the alicyclic epoxy compound include 3 ', 4'-epoxycyclohexanemethyl 3,4-epoxycyclohexylcarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, 1,4-cyclo (3,4-epoxycyclohexanecarboxylate), dicyclopentadiene dioxide, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexane, and the like, and commercially available products include diacel CELLOXIDE 2021P and CELLOXIDE 2081 from Daicel are representative.

Examples of the aliphatic epoxy compound include diglycidyl 1,2-cyclohexanedicarboxylate, 1,3-cyclohexanedimethanol diglycidyl ether, pentaerythritol tetraglycidyl ether, 1,4-butanediol diglyme (Hydroxymethyl) -1,3-propanediol ether, and commercially available products include di [(2-oxiranyl) -1,2-cyclohexanediol] Cell EHPE-3150 is representative.

Further, 4,5-epoxytetrahydrophthalic acid diglycidyl ester in which both alicyclic epoxy groups and aliphatic epoxy groups are present in the molecule can be used, and mixtures of alicyclic epoxy compounds and aliphatic epoxy compounds can also be used. A commercially available product is EHPE-3150CE from Daicel.

As the aromatic epoxy compound, bisphenol A type epoxy resin, bisphenol F type epoxy resin, cresol novolak type epoxy resin, phenol novolak type epoxy resin, BPA-novolak type epoxy resin and the like can be used.

As the epoxy compound (B), it is preferable to use at least one of an alicyclic epoxy compound and an aliphatic epoxy compound from the viewpoint of storage stability. Particularly, when an alicyclic epoxy compound is used, it is more preferable in terms of solvent resistance.

The content of the epoxy compound (B) may be 1 to 30% by weight based on 100% by weight of the total solid content in the photosensitive resin composition for forming a color conversion layer. When the content of the epoxy compound (B) is less than 1% by weight, it is difficult to expect improvement in heat resistance and reliability. When the content is more than 30% by weight, storage stability and development rate are likely to decrease.

The binder resin (C)

In one embodiment of the present invention, the binder resin (C) usually has reactivity and alkali solubility due to the action of light or heat and acts as a dispersion medium of the coloring material. The binder resin (C) contained in the photosensitive resin composition for forming a color conversion layer of the present invention functions as a binder resin for the coloring material, and if any binder resin soluble in the alkaline developer used in the development step for the production of the color filter Can be used.

The binder resin (C) may be, for example, a copolymer of a carboxyl group-containing monomer and another monomer copolymerizable with the 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 two or more carboxyl groups in the molecule such as unsaturated tricarboxylic acids . Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid,? -Chloroacrylic acid, cinnamic acid, and the like. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. The unsaturated polycarboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride, citraconic anhydride and the like. The unsaturated polycarboxylic acid may also be a mono (2-methacryloyloxyalkyl) ester thereof, for example, succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl ), Phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl), and the like. The unsaturated polycarboxylic acid may be mono (meth) acrylate of the dicarboxylic polymer of both ends thereof, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate . These carboxyl group-containing monomers may be used alone or in combination of two or more.

Examples of the other monomer copolymerizable with the carboxyl group-containing monomer include styrene,? -Methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o- P-methoxy styrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, Aromatic vinyl compounds such as vinylbenzyl glycidyl ether and indene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, Acrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl Methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxy diethylene glycol acrylate, methoxy diethylene glycol methacrylate, methoxy triethylene glycol acrylate, methoxy triethylene glycol methacrylate Acrylate, methoxypropylene glycol methacrylate, methoxypropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadiene Acrylate, dicyclopentadienyl methacrylate, adamantyl (meth) acrylate, (Meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate and the like Unsaturated carboxylic acid esters; Aminoethyl methacrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2- Unsaturated carboxylates such as methyl acrylate, ethyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, Acid amino alkyl 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,? -Chloroacrylonitrile, and vinylidene cyanide; Unsaturated amides such as acrylamide, methacrylamide,? -Chloroacrylamide, N-2-hydroxyethyl acrylamide and N-2-hydroxyethyl methacrylamide; Maleimide, benzyl maleimide, N-phenyl maleimide. Unsaturated imides such as N-cyclohexylmaleimide; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; And a monoacryloyl group or 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 the like. These monomers may be used alone or in combination of two or more.

The binder resin (C) may have an acid value of 20 to 200 (KOH mg / g). When the acid value is in the above range, the solubility in the developer is improved, the non-exposed portion is easily dissolved and the sensitivity is increased, and as a result, the pattern of the exposed portion remains during development, thereby improving the film remaining ratio. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the polymer, and can be generally determined by titration using an aqueous solution of potassium hydroxide.

The binder resin (C) has a weight average molecular weight (hereinafter simply referred to as "weight average molecular weight") in terms of polystyrene measured by gel permeation chromatography (GPC; tetrahydrofuran as an elution solvent) of 3,000 to 200,000, May be from 5,000 to 100,000. When the molecular weight is within the above range, the hardness of the coating film is improved, the residual film ratio is high, the solubility of the non-exposed portion in the developer is excellent, and the resolution tends to be improved.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the binder resin (C) may be 1.5 to 6.0, preferably 1.8 to 4.0. When the molecular weight distribution is within the above range, it is preferable because the developing property is excellent.

The content of the binder resin (C) may be generally 5 to 85% by weight, preferably 10 to 70% by weight based on 100% by weight of the total solid content in the photosensitive resin composition for forming a color conversion layer. When the content of the binder resin (C) is within the above range, solubility in a developing solution is sufficient, so that development residue does not easily occur on the substrate of the non-pixel portion, and film reduction of the pixel portion of the exposed portion is unlikely to occur during development, Is preferable because it tends to have a good dropout characteristic.

Photopolymerization  Compound (D)

In one embodiment of the present invention, the photopolymerizable compound (D) is a compound capable of polymerizing under the action of light and a photopolymerization initiator described later, and examples thereof include monofunctional monomers, bifunctional monomers, and other polyfunctional monomers .

Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N- Ralidon, and the like. Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) , Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like. Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) And pentaerythritol hexa (meth) acrylate. Of these, multifunctional monomers having two or more functional groups are preferably used.

The content of the photopolymerizable compound (D) may be generally 5 to 50% by weight, preferably 7 to 45% by weight based on 100% by weight of the total solid content in the photosensitive resin composition for color conversion layer formation. When the content of the photopolymerizable compound (D) is within the above range, the strength and smoothness of the pixel portion tends to be favorable.

Light curing Initiator (E)

In one embodiment of the present invention, the photopolymerization initiator (E) preferably contains an acetophenone-based compound. Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1 2-methyl [4- (1-methylvinyl) phenyl] propane-1-one, 2-benzyl- 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, and the like.

In addition, photopolymerization initiators other than the acetophenone-based photopolymerization initiator may be used in combination. Photopolymerization initiators other than acetophenone-based photopolymerization initiators include active radical generators, sensitizers, and acid generators that generate active radicals upon irradiation with light.

Examples of the active radical generator include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and triazine-based compounds.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoisobutyl ether and the like.

Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- Propoxyoctanoate and the like.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis ) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- Triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5- Methyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) Methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4- dimethoxyphenyl) ethenyl] -1,3 , 5-triazine, and the like.

Examples of the active radical generator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl- 1,2-bimidazole, 10-butyl-2-chloroacridone, 2-ethyl anthraquinone, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, It is possible.

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluene sulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluene sulfone 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium p-toluenesulfonate, Diphenyl iodonium hexafluoroantimonate and the like, and nitrobenzyl tosylates, benzoin tosylates and the like.

Also, as the active radical generator, there are compounds which generate an acid at the same time as an active radical, and for example, a triazine-based photopolymerization initiator is also used as an acid generator.

The content of the photopolymerization initiator (E) is usually 0.1 to 40 parts by weight, preferably 1 to 30 parts by weight, based on 100 parts by weight of the total amount of the binder resin (C) and the photopolymerizable compound (D) Can be. When the content of the photopolymerization initiator (E) is within the above range, the photosensitive resin composition for forming a color conversion layer is highly sensitized, and the strength of the pixel portion formed using the composition and the smoothness on the surface of the pixel portion tend to be good Therefore, it is desirable.

In the present invention, a photopolymerization initiator may be used. The photopolymerization initiator is sometimes used in combination with a photopolymerization initiator, and is a compound used for promoting polymerization of a photopolymerizable compound initiated by a photopolymerization initiator. Examples of the photopolymerization initiator include amine compounds, alkoxyanthracene compounds, and the like.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylbenzoic acid Aminoethyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (collectively, Michler's ketone), 4,4'- Ethylamino) benzophenone, and 4,4'-bis (ethylmethylamino) benzophenone. Of these, 4,4'-bis (diethylamino) benzophenone is preferable. Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxy Anthracene and the like. Such a photopolymerization initiator may be used singly or in combination of two or more. Commercially available photopolymerization initiators may be used. Examples of commercially available photopolymerization initiators include trade names " EAB-F " (manufactured by Hodogaya Chemical Industry Co., Ltd.) and the like.

When these photopolymerization initiators are used, the amount of the photopolymerization initiator is usually 10 moles or less, preferably 0.01 to 5 moles per mole of the photopolymerization initiator. When the amount of the photopolymerization initiator used is within the above range, the sensitivity of the photosensitive resin composition for color conversion layer formation is higher and the productivity of the color filter formed using the composition tends to be improved.

Solvent (F)

In the embodiment of the present invention, the solvent (F) is not particularly limited, and various organic solvents used in the field of the photosensitive resin composition for color conversion layer formation can be used. Specific examples thereof include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; 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. Among these solvents, an organic solvent preferably having a boiling point of 100 ° C to 200 ° C can be used from the viewpoints of coatability and dryness, more preferably alkylene glycol alkyl ether acetates, ketones, ethyl 3-ethoxypropionate Or methyl 3-methoxypropionate, and more preferred examples thereof include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, 3-methoxy Methyl propionate and the like. These solvents (F) may be used alone or in combination of two or more.

The content of the solvent (F) may be generally 60 to 90% by weight, preferably 70 to 90% by weight based on 100% by weight of the entire color conversion layer forming photosensitive resin composition. When the content of the solvent (F) is within the above range, the coating property tends to be good when applied with a coating apparatus such as a roll coater, a spin coater, a slit and spin coater, a slit coater Therefore, it is desirable.

Additive (G)

The photosensitive resin composition for forming a color conversion layer of the present invention may optionally contain fillers, other polymer compounds, and pigment dispersants. An adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-aggregation agent, and the like can be used in combination.

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

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

As the pigment dispersant, commercially available surfactants can be used, and examples thereof include surfactants such as silicone, fluorine, ester, cationic, anionic, nonionic, and amphoteric surfactants. These may be used alone or in combination of two or more. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, (Trade name) manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by TOKEM PRODUCTS CO., LTD.), Mega (Manufactured by Asahi Glass Co., Ltd.), Surfon (manufactured by Asahi Glass Co., Ltd.), Mitsubishi Kagaku Kogyo Co., Ltd., MEGAFAC (manufactured by Dainippon Ink and Chemicals Inc.), Flourad (manufactured by Sumitomo 3M Limited), Asahi guard, Surflon SOLSPERSE (manufactured by Genene), EFKA (manufactured by EFKA Chemical), PB 821 (manufactured by Ajinomoto), and the like.

Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2 (aminoethyl) - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- Trimethoxysilane, and the like.

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

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

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

 The photosensitive resin composition for forming a color conversion layer of the present invention can be produced, for example, by the following method. First, the fluorescent dye (A) is previously mixed with the solvent (F) and dissolved. At this time, a pigment dispersant may be used if necessary, and some or all of the binder resin (C) may be blended. (B), the photopolymerizable compound (D) and the photopolymerization initiator (E) are mixed with the other component (s), if necessary, in the dispersion (hereinafter sometimes referred to as a mill base) And further added with an additional solvent (F) to a predetermined concentration, if necessary, to obtain a desired photosensitive resin composition for color conversion layer formation.

One embodiment of the present invention relates to a color filter including a color conversion layer formed using the photosensitive resin composition for color conversion layer formation described above.

The color conversion layer may be formed by coating a photosensitive resin composition for forming a color conversion layer and then patterning the composition through a photolithography method to form a pattern corresponding to R and G of the color filter. The photolithography method is not particularly limited in the present invention, and any known method using a photosensitive resin composition can be applied.

As an example, the patterned color conversion layer

a) applying a photosensitive resin composition for forming a color conversion layer to a surface of a substrate;

b) drying the solvent by pre-cure (prebaking);

c) applying a photomask onto the obtained film to irradiate an actinic ray to cure the exposed portion;

d) performing a developing process of dissolving the non-visible portion using an aqueous alkali solution; And

e) drying and post-baking.

A glass substrate or a polymer substrate is used as the substrate. As the polymer substrate, a polymer substrate made of polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, polysulfone or the like can be used.

The coating may be performed by a wet coating method using a coating apparatus such as a roll coater, a spin coater, a slit and spin coater, a slit coater (which may be referred to as a die coater), an ink jet or the like so as to obtain a desired thickness.

Prebaking can be performed by heating with an oven, a hot plate or the like. The heating temperature and the heating time in the prebaking may be appropriately selected depending on the solvent used and may be, for example, from 80 to 150 ° C for 1 to 30 minutes.

The exposure performed after the pre-baking is performed by an exposure machine and is exposed through a photomask to thereby sensitize only the portion corresponding to the pattern. The light to be irradiated may be, for example, visible light, ultraviolet light, X-ray, electron beam, or the like.

The alkali development after the exposure is performed for the purpose of removing the resist of the non-exposed portion, and a desired pattern is formed by this development. As the developer suitable for the alkali development, for example, an aqueous solution of an alkali metal salt or an alkaline earth metal salt may be used. Particularly, an alkali aqueous solution containing sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or the like in an amount of 1 to 3% by weight is used as a developer or an ultrasonic cleaner in a temperature of 10 to 50 캜, preferably 20 to 40 캜 .

The post-baking is performed in order to improve the adhesion between the patterned color conversion layer and the substrate, and is performed by heat treatment at 80 to 220 ° C for 10 to 120 minutes. The post-bake can be performed by using an oven, a hot plate, or the like as in pre-baking.

The color conversion layer may have a sufficient size, several to several thousand micrometers, preferably 0.1 to 100 占 퐉, more preferably 1 to 50 占 퐉, to maintain a high luminance and ensure excellent color conversion characteristics and high light efficiency. .

The color conversion layer may be disposed between the light source and the color layer at any position, and is based on the structure of the light source / color conversion layer / color layer, wherein the color conversion layer is in direct contact with the color layer, It can be introduced as an inserted structure.

At this time, an LED, a cold cathode tube, an inorganic EL, an organic EL, a fluorescent lamp, an incandescent lamp or the like is used as a light source, but LEDs can be used as a light source.

A display device having such a color conversion layer can achieve high quality and vivid image quality by maintaining high luminance and securing excellent color conversion characteristics and high light efficiency.

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

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

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

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

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

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

Synthetic example  1: Synthesis of binder resin (C-1)

A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube was provided with 74.8 g (0.20 mol) of benzylmaleimide, 43.2 g (0.30 mol) of acrylic acid, 4 g of t-butylperoxy-2-ethylhexanoate and 40 g of propylene glycol monomethyl ether acetate (PGMEA) were charged and stirred to prepare a charge transfer additive dropping funnel. Then, n-dodecanethiol And 24 g of PGMEA were placed and stirred and mixed. Then, 395 g of PGMEA was introduced into the flask, the atmosphere in the flask was changed to nitrogen in air, and the temperature of the flask was elevated to 90 DEG C with stirring. Then, the monomer and the chain transfer agent were added dropwise from the dropping funnel. The mixture was allowed to stand for 2 hours while maintaining the temperature at 90 占 폚. After 1 hour, the temperature was elevated to 110 占 폚 and maintained for 3 hours. A gas introduction tube was then introduced to prepare an oxygen / nitrogen mixed gas of 5 / Of bubbling. Then, 28.4 g of [(0.10 mol) of glycidyl methacrylate (33 mol% based on the carboxyl group of the acrylic acid used in the present reaction)], 2,2'-methylenebis (4-methyl-6-t- ) And 0.8 g of triethylamine were placed in a flask, and the reaction was continued at 110 캜 for 8 hours to obtain a binder resin C-1 having a solid acid value of 70 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 16,000 and the molecular weight distribution (Mw / Mn) was 2.3.

Example  1 to 2 and Comparative Example  One: Color conversion layer  Preparation of photosensitive resin composition for forming

Each component was mixed with the composition shown in Table 1 below to prepare a photosensitive resin composition for forming a color conversion layer (unit: wt%).

Example 1 Example 2 Comparative Example 1 Fluorescent dye A-1 1.1 1.1 1.1 Epoxy compound B-1 1.13 B-2 1.13 Binder resin C-1 6.8 6.8 7.4 Photopolymerizable compound D-1 4.5 4.5 4.9 Photopolymerization initiator E-1 0.3 0.3 0.4 solvent F-1 86.17 86.17 86.2

A-1: Lumogen F Red

B-1: CELLOXIDE 2021P (Daicel)

B-2: EHPE3150 (Daicel)

C-1: Binder resin of Synthesis Example 1

D-1: dipentaerythritol hexaacrylate (Kayarad DPHA: manufactured by Nippon Kayaku Co., Ltd.)

E-1: 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (IGACURE 369, BASF)

F-1: Propylene glycol monomethyl ether acetate

Experimental Example  One

Using the photosensitive resin composition for forming a color conversion layer prepared in the above Examples and Comparative Examples, a color filter was prepared as follows. The heat resistance and the surface properties of the coating film were measured by the following methods, Respectively.

≪ Production of color filter &

Each of the photosensitive resin compositions for color conversion layer formation was coated on a glass substrate by a spin coating method, and then placed on a heating plate and held at a temperature of 100 캜 for 3 minutes to form a thin film. Then, the thin film was irradiated with ultraviolet rays. At this time, the ultraviolet light source was irradiated with light at an exposure dose (365 nm) of 40 mJ / cm 2 using an ultrahigh pressure mercury lamp (trade name: USH-250D) manufactured by Usuo Denki Co., Ltd., and no special optical filter was used. The thin film irradiated with ultraviolet rays was developed with a developing solution of KOH aqueous solution of pH 12.5 for 60 seconds using a spray developing machine and heated in a heating oven at 220 캜 for 20 minutes to prepare a pattern. The thickness of the color conversion layer pattern prepared above was 3.0 mu m. The thickness of the color conversion layer could be controlled to various values up to 500 mu m.

(1) Heat resistance

The color change value (DELTA E ^* ab) before and after heating at 230 DEG C for 120 minutes was measured and evaluated according to the following evaluation criteria. ? E ^* ab is a value defined by the following equation (1).

[Equation 1]

? E ^* ab = {(? L) ² + (? A) ² + (? B) ² } ^1/2

<Evaluation Criteria>

?: The value of? E ^* ab is not more than 3

?: The value of? E ^* ab is more than 3 but not more than 10

X: When the value of DELTA E ^* ab exceeds 10

(2) Surface properties of coating

Each of the photosensitive resin compositions for color conversion layer formation prepared in the above Examples and Comparative Examples was coated on glass and allowed to stand for 10 minutes. The surface of the coated film was confirmed by an optical microscope and evaluated according to the following evaluation criteria.

<Evaluation Criteria>

○: No foreign matter

△: The surface is opaque

X: Foreign body occurred

Heat resistance Surface Properties of Coating Films Example 1 ○ ○ Example 2 ○ ○ Comparative Example 1 × ×

As shown in Table 2, it was confirmed that the photosensitive resin compositions for forming color conversion layers of Examples 1 and 2 containing an epoxy compound according to the present invention had excellent heat resistance and did not generate foreign matter on the surface of the coating film, I could. On the other hand, it was confirmed that the photosensitive resin composition for forming a color conversion layer of Comparative Example 1 containing no epoxy compound had poor heat resistance and reliability.

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

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

Claims (6)

A photosensitive resin composition for forming a color conversion layer comprising a fluorescent dye, an epoxy compound, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The photosensitive resin composition according to claim 1, wherein the epoxy compound is at least one of an alicyclic epoxy compound and an aliphatic epoxy compound. The epoxy resin composition according to claim 1, wherein the epoxy compound is selected from the group consisting of 3 ', 4'-epoxycyclohexanemethyl 3,4-epoxycyclohexyl carboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, Dimethanol bis (3,4-epoxycyclohexanecarboxylate), dicyclopentadiene dioxide, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexane, diglycidyl 1,2-cyclohexane Dicarboxylate, 1,3-cyclohexanedimethanol diglycidyl ether, pentaerythritol tetraglycidyl ether, 1,4-butanediol diglycidyl ether, poly [(2-oxiranyl) -1,2 -Cyclohexanediol] -2-ethyl-2- (hydroxymethyl) -1,3-propanediol ether and 4,5-epoxytetrahydrophthalic acid diglycidyl ester. Sensitive resin composition. The photosensitive resin composition for forming a color conversion layer according to claim 1, wherein the content of the epoxy compound is 1 to 30% by weight based on 100% by weight of the total solid content in the photosensitive resin composition for forming a color conversion layer. A color filter comprising a color conversion layer formed using the photosensitive resin composition for forming a color conversion layer according to any one of claims 1 to 4. An image display apparatus comprising the color filter according to claim 5.