KR102385654B1 - 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 isocyanurate compound, a binder resin, a photopolymerizable compound, a photoinitiator and a solvent, a color filter comprising a color conversion layer using the same, and the color filter An image display device is provided. The photosensitive resin composition for forming a color conversion layer according to the present invention can improve the heat resistance and reliability of the color conversion layer by including an isocyanurate compound.

Description

Photosensitive resin composition for forming a color conversion layer, a color filter and an image display device including a color conversion layer using the same

The present invention relates to a photosensitive resin composition for forming a color conversion layer, a color filter including a color conversion layer using the same, and an image display device, and more particularly, to form a color conversion layer capable of improving the heat resistance and reliability of the color conversion layer It relates to a photosensitive resin composition for use, a color filter including a color conversion layer using the same, and an image display device having the color filter.

Recently, the display industry has undergone a rapid change from CRT to flat panel displays represented by PDP, OLED, and LCD. 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, the LCD requires a separate backlight unit due to the absence of its own light emitting device.

A CCFL (Cold Cathode Fluorescent Lamp) was used as a light source of a general backlight unit. However, a backlight unit using a CCFL consumes a significant amount of power because power is always applied to the CCFL, and has a color gamut of about 70% compared to a CRT, and environmental pollution problems due to the addition of mercury are pointed out as disadvantages. As an alternative to solve the above problems, research on a backlight unit using a Light Emitting Diode (LED) is being actively conducted. When an LED is used as a backlight unit, it can exceed 100% of the NTSC (National Television System Committee) color gamut specification to provide more vivid picture quality to consumers.

In addition, in the same industry, efforts have been made to improve the light efficiency by changing the material and structure of a color filter and LCD panel to improve the efficiency of the backlight light source [refer to Korean Patent Application Laid-Open No. 10-2012-0048218].

A color filter forms pixels of each color through a patterning process after applying a dispersion composition including a pigment or dye, and these pigments and dyes cause a problem of lowering the transmission efficiency of a backlight light source. As a result, the lowering of the transmission efficiency lowers the color reproducibility of the display device, making 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 increasing the thickness of the color filter or introducing a color conversion layer (or light conversion layer) in lamination or close to it is proposed. there is.

Existing dyes or pigments are used for the color conversion layer, but it is difficult to expect improvement in light efficiency with only these dyes and pigments, and a problem of lowering luminance occurs. Accordingly, a method of using a fluorescent material for the color conversion layer has been proposed [refer to Korean Patent Application Laid-Open No. 10-2016-0112479]. However, when a fluorescent material is used for the color conversion layer as described above, there is a problem in that the heat resistance and reliability of the color conversion layer are insufficient.

Republic of Korea Patent Publication No. 10-2012-0048218 Republic of Korea Patent Publication No. 10-2016-0112479

One object of the present invention is to provide a photosensitive resin composition for forming a color conversion layer capable of improving the heat resistance and reliability of the color conversion layer.

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

Another object of the present invention is to provide an image display device including 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 isocyanurate compound, a binder resin, a photopolymerizable compound, a photoinitiator and a solvent.

In one embodiment of the present invention, the isocyanurate compound may be a compound represented by the following formula (1).

[Formula 1]

In the above formula,

R ¹ to R ³ are each independently a C ₂ -C ₂₀ alkenyl group, an epoxy group, or a functional group represented by Formula 2 below,

[Formula 2]

In the above formula,

R ⁴ is a C ₁ -C ₂₀ alkyl group,

R ⁵ is a hydrogen atom or a functional group represented by the following formula (3),

[Formula 3]

In the above formula,

R ⁶ is a C ₁ -C ₂₀ alkyl group.

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

On the other hand, the present invention provides an image display device, characterized in that the color filter is provided.

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

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

One embodiment of the present invention is a color conversion comprising a fluorescent dye (A), an isocyanurate compound (B), a binder resin (C), a photopolymerizable compound (D), a photopolymerization initiator (E) and a solvent (F) It relates to the photosensitive resin composition for layer formation.

Fluorescent dye (A)

In one embodiment of the present invention, the fluorescent dye (A) can convert light of a specific wavelength region within 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.

As the fluorescent dye, for example, a coumarin-based, naphthalimide-based, quinacridone-based, cyanine-based, xanthine-based, pyridine-based dye can be used. In addition, various low-molecular light-emitting materials and high-molecular light-emitting materials can also be used.

Specifically, the fluorescent dye is 3-(2-benzothiazolyl)-7-diethylaminocoumarin (coumarin 6), 3-(2-benzoimidazolyl)-7-diethylaminocoumarin (coumarin 7) and coumarin-based fluorescent dyes such as coumarin 135; naphthalimide-based fluorescent dyes including Solvent Yellow 43 and Solvent Yellow 44; quinacridone-based fluorescent dyes such as diethylquinacridone (DEQ); Cyanine, including 4-dicynomethylene-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran (DCM-1(I)), DCM-2(II), DCJTB(III)) and the like fluorescent dyes; xanthine-based fluorescent dyes including rhodamine B and rhodamine 6G; pyridine-based fluorescent dyes including pyridine 1; 4,4-difluoro-1,3,5,7-tetraphenyl-4-bora-3a,4a-diaza-s-indacene (IV), Lumogen F red, Nile red (V), etc. low molecular weight light emitting materials; Polyphenylene (polyphenylene), polyarylene (polyarylene), a polymer light emitting material including polyfluorene (polyfluorene) may be used. These can be used individually or in mixture of 2 or more types, respectively.

In addition, the fluorescent dye is a solvent (Solvent), acid (Acid), basic (Basic), reactive (Reactive), direct (Direct), disperse (Disperse) in the color index (published by The Society of Dyers and Colorists) or and dyes classified as Vat. More specifically, a dye having a color index (C.I.) number as follows, but is 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, 0.1 to 70% by weight, preferably 0.1 to 10% by weight, based on 100% by weight of the total solid content in the photosensitive resin composition for forming a color conversion layer. . If the content of the fluorescent dye is less than 0.1% by weight, it may be difficult to sufficiently secure the color conversion characteristics to be obtained in the present invention because light efficiency cannot be secured. can

isocyanurate Compound (B)

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

As the isocyanurate compound (B), a compound represented by the following Chemical Formula 1 may be used.

[Formula 1]

In the above formula,

R ¹ to R ³ are each independently a C ₂ -C ₂₀ alkenyl group, an epoxy group, or a functional group represented by Formula 2 below,

[Formula 2]

In the above formula,

R ⁴ is a C ₁ -C ₂₀ alkyl group,

R ⁵ is a hydrogen atom or a functional group represented by the following formula (3),

[Formula 3]

In the above formula,

R ⁶ is a C ₁ -C ₂₀ alkyl group.

As used herein, C ₂ -C ₂₀ alkenyl group refers to a straight-chain or branched unsaturated hydrocarbon having 2 to 20 carbon atoms having one or more carbon-carbon double bonds, for example, ethyleneyl, propenyl, Tenyl, pentenyl, and the like are included, but are not limited thereto.

As used herein, C ₁ -C ₂₀ Alkyl group refers to a straight-chain or branched hydrocarbon consisting of 1 to 20 carbon atoms, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i -butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decanyl and the like are included, but are not limited thereto.

In the C ₂ -C ₂₀ alkenyl group and C ₁ -C ₂₀ alkyl group, one or more hydrogens are C ₁ -C ₆ alkyl group, C ₂ -C ₆ alkenyl group, C ₂ -C ₆ alkynyl group , C ₃ -C ₁₀ Cycloalkyl group, C ₃ -C ₁₀ Heterocycloalkyl group, C ₃ -C ₁₀ Heterocycloalkyloxy group, C ₁ -C ₆ Haloalkyl group, C ₁ -C ₆ Alkoxy group, It may be substituted with a C ₁ -C ₆ thioalkoxy group, aryl group, acyl group, hydroxy, thio, halogen, amino, alkoxycarbonyl, carboxy, carbamoyl, cyano, nitro or the like.

In one embodiment of the present invention, R ¹ to R ³ may each independently be ethyleneyl or oxiranyl.

Specifically, the isocyanurate compound may be a compound represented by the following Chemical Formula 4 or 5.

[Formula 4]

[Formula 5]

The content of the isocyanurate compound (B) may be 0.1 to 40 wt%, preferably 0.1 to 20 wt%, based on 100 wt% of the total solid content in the photosensitive resin composition for forming a color conversion layer. When the content of the isocyanurate compound (B) is less than 0.1% by weight, it is difficult to expect improvement in heat resistance and reliability, and when it exceeds 40% by weight, the addition amount of a photopolymerizable compound or a photoinitiator is limited and the film hardness is weakened, resulting in sufficient process characteristics can't get

Binder Resin (C)

In one embodiment of the present invention, the binder resin (C) usually has reactivity and alkali solubility under the action of light or heat, and acts as a dispersion medium for the coloring material. The binder resin (C) contained in the photosensitive resin composition for forming a color conversion layer of the present invention acts as a binder resin for a coloring material, and any binder resin that is soluble in the alkaline developer used in the developing step for the production of color filters. can be used

Examples of the binder resin (C) include a carboxyl group-containing monomer and a copolymer of this monomer and another monomer copolymerizable with the monomer.

Examples of the carboxyl group-containing monomer include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated carboxylic acids such as unsaturated polycarboxylic acids having two or more carboxyl groups in molecules such as unsaturated tricarboxylic acids. can be heard Here, as an unsaturated monocarboxylic acid, acrylic acid, methacrylic acid, a crotonic acid, (alpha)-chloroacrylic acid, cinnamic acid etc. are mentioned, for example. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. The unsaturated polyhydric carboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride. In addition, the unsaturated polyhydric carboxylic acid may be its mono(2-methacryloyloxyalkyl) ester, for example, succinic acid mono(2-acryloyloxyethyl), succinic acid mono(2-methacryloyloxyethyl) ), mono(2-acryloyloxyethyl phthalate), mono(2-methacryloyloxyethyl) phthalate, etc. are mentioned. The unsaturated polyhydric carboxylic acid may be a mono (meth) acrylate of the dicarboxy polymer at both terminals, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. . These carboxyl group-containing monomers can be used individually or in mixture of 2 or more types, respectively.

Examples of the other monomer copolymerizable with the carboxyl group-containing monomer include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methyl Toxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethylether, p-vinylbenzylmethylether, o-vinylbenzylglycidylether, m-vinylbenzylglycidylether, 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 Oxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acryl Rate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate acrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylic Rate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl Acrylate, dicyclopentadienyl methacrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3- unsaturated carboxylic acid esters such as phenoxypropyl methacrylate, glycerol monoacrylate, and glycerol monomethacrylate; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethyl Unsaturated carboxyl groups 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, a vinyl propionate, a vinyl butyrate, and a 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-hydroxyethylmethacrylamide; Maleimide, benzylmaleimide, N-phenylmaleimide. unsaturated imides such as N-cyclohexyl maleimide; 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 polysiloxane. macromonomers and the like. These monomers can be used individually or in mixture of 2 or more types, respectively.

The binder resin (C) may have an acid value of 20 to 200 (KOH mg/g). When the acid value is within the above range, the solubility in the developer is improved, so that the non-exposed portion is easily dissolved and the sensitivity is increased, so that the pattern of the exposed portion remains at the time of development, which is preferable, thereby improving the film remaining ratio. The acid value here is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the polymer, and can be determined by titration using an aqueous potassium hydroxide solution normally.

The binder resin (C) has a polystyrene equivalent weight average molecular weight (hereinafter simply referred to as 'weight average molecular weight') measured by gel permeation chromatography (GPC; using tetrahydrofuran as the elution solvent) of 3,000 to 200,000, preferably may be 5,000 to 100,000. When the molecular weight is in the above range, the hardness of the coating film is improved, the film remaining rate is high, the solubility of the non-exposed part in the developer is excellent, and the resolution tends to be improved, which is preferable.

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 molecular weight distribution exists in the said range, since it is excellent in developability, it is preferable.

The content of the binder resin (C) may be usually 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. If the content of the binder resin (C) is within the above range, the solubility in the developer is sufficient, so that it is difficult to generate a developing residue on the substrate of the non-pixel portion, and it is difficult to reduce the film in the pixel portion of the exposed portion during development. It is preferable because it tends to have good omission properties.

photopolymerization compound (D)

In one embodiment of the present invention, the photopolymerizable compound (D) is a compound capable of polymerization by the action of light and a photopolymerization initiator to be described later, and includes monofunctional monomers, difunctional monomers, and other polyfunctional monomers. .

Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinyl p Rollidone etc. are mentioned. Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene glycol di (meth) acrylate. , 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)acrylate, and di Pentaerythritol hexa(meth)acrylate etc. are mentioned. Among these, the polyfunctional monomer more than bifunctional is used preferably.

The content of the photopolymerizable compound (D) may be usually 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 forming a color conversion layer. When the content of the photopolymerizable compound (D) is within the above range, it is preferable because the intensity and smoothness of the pixel portion tend to be good.

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-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1-[4-( 2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1 -one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl[4-(1-methylvinyl)phenyl]propane-1 -one oligomer etc. are mentioned, Preferably, 2-benzyl-2- dimethylamino-1-(4-morpholinophenyl)butan-1-one etc. are mentioned.

Moreover, it can be used combining photoinitiators other than the said acetophenone type. Examples of the photopolymerization initiator other than acetophenone include active radical generators, sensitizers, and acid generators that generate active radicals by irradiating light.

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

As said benzoin compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzo isobutyl ether, etc. are mentioned, for example.

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

As the thioxanthone-based compound, for example, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro -4-propoxythioxanthone etc. are mentioned.

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(trichloro methyl)-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-(3,4-dimethoxyphenyl)ethenyl]-1,3 , 5-triazine, etc. are mentioned.

Examples of the active radical generator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2-bis(o-chlorophenyl)-4,4′,5,5′-tetraphenyl- 1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound, etc. may be used. may be

The acid generator includes, for example, 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfo nate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, Onium salts, such as diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, benzointosylate, etc. are mentioned.

In addition, as an active radical generator, there are also compounds that generate an acid simultaneously with an active radical among the above compounds. For example, a triazine-based photopolymerization initiator is also used as an acid generator.

The content of the photoinitiator (E) is usually 0.1 to 40 parts by weight, preferably 1 to 30 parts by weight, based on the solid content, based on 100 parts by weight of the total amount of the binder resin (C) and the photopolymerizable compound (D). can be negative When the content of the photoinitiator (E) is within the above range, the photosensitive resin composition for forming a color conversion layer is highly sensitive, 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. It is preferable because there is

Moreover, in this invention, a photoinitiation adjuvant can be used. A photoinitiation adjuvant may be used in combination with a photoinitiator, It is a compound used for accelerating|stimulating the polymerization of the photopolymerizable compound whose polymerization was started by the photoinitiator. As a photoinitiation adjuvant, an amine-type compound, an alkoxyanthracene-type compound, etc. are mentioned.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethyl benzoate. Aminoethyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (common name, Michler's ketone), 4,4'-bis(di ethylamino)benzophenone and 4,4'-bis(ethylmethylamino)benzophenone are mentioned, Among these, 4,4'-bis(diethylamino)benzophenone is preferable. Examples of the alkoxyanthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxy. Anthracene etc. are mentioned. There is no problem even if such a photoinitiation adjuvant is used individually or in combination of plurality. Moreover, a commercially available thing can be used as a photoinitiation adjuvant, As a commercially available photoinitiation adjuvant, the brand name "EAB-F" [manufacturer: Hodogaya Chemical Industry Co., Ltd.] etc. are mentioned, for example.

In the case of using these photopolymerization initiating aids, the amount used is usually 10 moles or less, preferably 0.01 to 5 moles per mole of the photopolymerization initiator. When the usage-amount of the said photoinitiation adjuvant is within the said range, the sensitivity of the photosensitive resin composition for color conversion layer formation becomes higher, and since productivity of the color filter formed using this composition tends to improve, it is preferable.

Solvent (F)

In one 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 forming a color conversion layer may 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; Cyclic esters, such as (gamma)-butyrolactone, etc. are mentioned. Among the above solvents, an organic solvent having a boiling point of 100°C to 200°C can be preferably used in terms of coatability and dryness, and more preferably, alkylene glycol alkyl ether acetates, ketones, 3-ethoxypropionate ethyl However, esters such as 3-methoxy methyl propionate can be used, and more preferably, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxy propionate ethyl, 3-methoxy Methyl propionate, etc. are mentioned. These solvents (F) can be used individually or in mixture of 2 or more types, respectively.

The content of the solvent (F) may be usually 60 to 90% by weight, preferably 70 to 90% by weight based on 100% by weight of the total photosensitive resin composition for forming a color conversion layer. If the content of the solvent (F) is within the above range, the applicability tends to be good when applied with an application device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as a die coater), inkjet, etc. It is preferable because there is

Additive (G)

The photosensitive resin composition for forming a color conversion layer of the present invention is, if necessary, a filler, other polymer compounds, and a pigment dispersant. Additives, such as an adhesion promoter, antioxidant, a ultraviolet absorber, and aggregation inhibitor, can be used together.

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

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

As said pigment dispersant, commercially available surfactant can be used, For example, surfactant, such as silicone type, fluorine type, ester type, cationic type, anionic type, nonionic type, amphoteric type, etc. are mentioned. These may be used individually or in combination of 2 or more types, respectively. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes, There are polyethyleneimines, etc., and in addition, as trade names, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products), Mega MEGAFAC (manufactured by Dainippon Ink Chemical Kogyo Co., Ltd.), Florad (manufactured by Sumitomo 3M Co., Ltd.), Asahi guard, Surflon (above, manufactured by Asahi Glass Co., Ltd.), brush SOLSPERSE (manufactured by Zeneca Corporation), EFKA (manufactured by EFKA Chemicals Corporation), PB 821 (manufactured by Ajinomoto Corporation), and the like.

As the adhesion promoter, for example, 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-mercaptopropyl Trimethoxysilane etc. are mentioned.

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 aggregation inhibitor include sodium polyacrylate.

The photosensitive resin composition for color conversion layer formation of this invention can be manufactured by the following methods, for example. First, the fluorescent dye (A) is previously mixed with the solvent (F) and dissolved. At this time, a pigment dispersant is used as needed, and also some or all of binder resin (C) may be mix|blended. The remainder of the binder resin (C), the epoxy compound (B), the photopolymerizable compound (D), and the photopolymerization initiator (E) are added to the obtained dispersion (hereinafter, sometimes referred to as mill base) with other components used as needed They are added together, and if necessary, an additional solvent (F) is further added so that it may become a predetermined density|concentration, and the photosensitive resin composition for target color conversion layer formation is obtained.

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

The color conversion layer may be prepared by coating the photosensitive resin composition for forming the color conversion layer and then patterning it through a photolithography method to form patterns 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 the photosensitive resin composition is applicable.

For example, the patterned color conversion layer is

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

b) drying the solvent by precure (pre-bake);

c) applying a photomask on the obtained film and irradiating actinic light to cure the exposed portion;

d) performing a developing process for dissolving the unexposed portion using an aqueous alkali solution; and

e) It can be obtained by performing drying and post-baking.

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

At this time, the application may be performed by a wet coating method using an application 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 an inkjet so as to obtain a desired thickness.

The pre-baking can be performed by heating with an oven, a hot plate, or the like. The heating temperature and heating time in the pre-bake are appropriately selected depending on the solvent to be used, and for example, it can be carried out at a temperature of 80 to 150° C. for 1 to 30 minutes.

In addition, exposure performed after pre-baking is performed by an exposure machine, and only the part corresponding to a pattern is exposed by exposing through a photomask. In this case, the irradiated light may be, for example, visible light, ultraviolet light, X-ray, electron beam, or the like.

The alkali development after exposure is performed for the purpose of removing the resist of the unexposed portion, whereby a desired pattern is formed by this development. As a developing solution suitable for this alkali development, the aqueous solution of an alkali metal salt, an alkaline-earth metal salt, etc. can be used, for example. In particular, using an aqueous alkali solution containing sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc. in an amount of 1 to 3% by weight, within a temperature of 10 to 50°C, preferably 20 to 40°C, a developer or ultrasonic cleaner, etc. is performed using

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

The color conversion layer has a sufficient size and a thickness of several to several thousand micrometers, preferably 0.1 to 100 μm, more preferably 1 to 50 μm, so as to maintain high luminance and secure excellent color conversion characteristics and high light efficiency. to form with

The color conversion layer can be located at any position between the light source and the color layer, and is based on the configuration of the light source/color conversion layer/color layer, but the color conversion layer is in direct contact with the color layer or another film or substrate is used. It can also be introduced as an inserted structure.

In this case, LED, cold cathode tube, inorganic EL, organic EL, fluorescent lamp, incandescent lamp, etc. are used as the light source, but preferably, LED may be used as the light source.

A display device having such a color conversion layer maintains high luminance and secures excellent color conversion characteristics and high light efficiency, thereby realizing high-quality and vivid image quality.

Accordingly, one embodiment of the present invention relates to an image display device provided with the above-described color filter.

The color filter of the present invention can display various images such as an electroluminescent display (EL), a plasma display (PDP), a field emission display (FED), and an organic light emitting diode (OLED), as well as a general liquid crystal display (LCD). Applicable to the device.

The image display apparatus of the present invention includes a configuration known in the art, except for having the above-described color filter.

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

The image display device according to an embodiment of the present invention may further include a color filter including only two color pattern layers among a red pattern layer, a green pattern layer, and a blue pattern layer in addition to the above-described color filter. In such a case, the color filter further includes a transparent pattern layer that does not contain quantum dot particles. When only two types of color pattern layers are provided, a light source emitting light of a wavelength representing the remaining colors that is not included may be used. For example, when only the red pattern layer and the green pattern layer are included, a light source emitting blue light may be used. In such a case, the red quantum dot particles emit red light, the green quantum dot particles emit green light, and the transparent pattern layer transmits the blue light as it is to display blue color.

Hereinafter, the present invention will be described in more detail by way of Examples, Comparative Examples and Experimental Examples. These Examples, Comparative Examples, and Experimental Examples are only for illustrating the present invention, and it is apparent to those skilled in the art that the scope of the present invention is not limited thereto.

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

A flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel and a nitrogen introduction tube was prepared, and as a monomer dropping funnel, 74.8 g (0.20 mole) of benzylmaleimide, 43.2 g (0.30 mole) of acrylic acid, and 118.0 of vinyltoluene were prepared. g (0.50 mol), 4 g of t-butylperoxy-2-ethylhexanoate and 40 g of propylene glycol monomethyl ether acetate (PGMEA) were added and stirred and mixed, and as a chain transfer agent dropping tank, n-dodecanthiol 6g and 24g of PGMEA were added and stirred and mixed was prepared. Thereafter, 395 g of PGMEA was introduced into the flask, the atmosphere in the flask was changed from air to nitrogen, and the temperature of the flask was raised to 90° C. while stirring. Then, the monomer and the chain transfer agent were started dripping from the dropping lot. The dripping was carried out for 2 hours while maintaining 90° C., and after 1 hour, the temperature was raised to 110° C. and maintained for 3 hours. Then, a gas introduction tube was introduced, and oxygen/nitrogen = 5/95 (v/v) mixed gas started bubbling. Next, 28.4 g of glycidyl methacrylate [(0.10 mol), (33 mol% based on the carboxyl group of acrylic acid used in this reaction)], 2,2'-methylenebis(4-methyl-6-t-butylphenol ) 0.4 g and triethylamine 0.8 g were put into the flask, and the reaction was continued at 110° C. for 8 hours to obtain binder resin C-1 having a solid content acid value of 70 mgKOH/g. The polystyrene equivalent weight average molecular weight 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 formation

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 isocyanurate compound B-1 0.59 - - B-2 - 0.59 - binder resin C-1 7.1 7.1 7.4 photopolymerizable compound D-1 4.7 4.7 4.9 photopolymerization initiator E-1 0.4 0.4 0.4 solvent F-1 86.11 86.11 86.2

A-1: Lumogen F Red

B-1: isocyanurate compound of formula 4 (MA-DGIC, SHIKOKU Chemicals)

B-2: isocyanurate compound of formula 5 (DA-MGIC, SHIKOKU Chemicals)

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

A color filter was prepared as follows using the photosensitive resin composition for forming a color conversion layer prepared in Examples and Comparative Examples, and heat resistance and surface properties of the coating film were measured in the following manner, and the results are shown in the table below. 2 is shown.

<Manufacture of color filter>

Each photosensitive resin composition for forming a color conversion layer was applied on a glass substrate by spin coating, placed on a heating plate, and maintained at a temperature of 100° C. for 3 minutes to form a thin film. Then, ultraviolet rays were irradiated on the thin film. At this time, the ultraviolet light source was irradiated with light at an exposure dose (365 nm) of 40 mJ/cm 2 in an atmospheric atmosphere using an ultra-high pressure mercury lamp (trade name: USH-250D) manufactured by Ushio Denki Co., Ltd., and no special optical filter was used. The thin film irradiated with ultraviolet light was developed for 60 seconds using a spray developer with a KOH aqueous solution developing solution of pH 12.5, and then heated in a heating oven at 220° C. for 20 minutes to prepare a pattern. The thickness of the color conversion layer pattern prepared above was 3.0㎛. The thickness of the color conversion layer could be variously controlled up to 500 μm.

(1) heat resistance

Heat resistance was evaluated according to the following evaluation criteria by measuring color change values (ΔE ^* ab) before and after heating at 230° C. for 120 minutes. ΔE ^* ab is a value defined by Equation 1 below.

[Equation 1]

ΔE ^* ab = {(ΔL) ² +(Δa) ² +(Δb) ² } ^1/2

<Evaluation criteria>

○: △E ^* ab value is 3 or less

△: △E ^* ab value greater than 3 and less than or equal to 10

×: ΔE ^* ab value greater than 10

(2) Surface properties of the coating film

Each of the photosensitive resin compositions for forming a color conversion layer prepared in Examples and Comparative Examples were coated on glass and left for 10 minutes, then the surface of the coating film was checked with an optical microscope and evaluated according to the following evaluation criteria.

<Evaluation criteria>

○: No foreign matter

△: the surface is opaque

×: Foreign matter occurs

heat resistance Surface properties of the coating film Example 1 ○ ○ Example 2 ○ ○ Comparative Example 1 × ×

As shown in Table 2, the photosensitive resin composition for forming a color conversion layer of Examples 1 and 2 containing an isocyanurate compound according to the present invention has excellent heat resistance and does not generate foreign matter on the surface of the coating film, so reliability is also It was confirmed that it was excellent. On the other hand, it was confirmed that the photosensitive resin composition for forming a color conversion layer of Comparative Example 1 not including the isocyanurate compound had poor heat resistance and reliability.

As the specific part of the present invention has been described in detail above, for those of ordinary skill in the art to which the present invention pertains, it is clear that these specific techniques are only preferred embodiments, and the scope of the present invention is not limited thereto. Do. Those of ordinary skill in the art to which the present invention pertains will be able to make various applications and modifications within the scope of the present invention based on the above contents.

Accordingly, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

Claims (6)

a fluorescent dye, an isocyanurate compound, a binder resin, a photopolymerizable compound, a photoinitiator and a solvent;
The fluorescent dye is Lumogen F red photosensitive resin composition for forming a color conversion layer. The photosensitive resin composition for forming a color conversion layer according to claim 1, wherein the isocyanurate compound is a compound represented by the following Chemical Formula 1:
[Formula 1]

In the above formula,
R ¹ to R ³ are each independently a C ₂ -C ₂₀ alkenyl group, an epoxy group, or a functional group represented by Formula 2 below,
[Formula 2]

In the above formula,
R ⁴ is a C ₁ -C ₂₀ alkyl group,
R ⁵ is a hydrogen atom or a functional group represented by the following formula (3),
[Formula 3]

In the above formula,
R ⁶ is a C ₁ -C ₂₀ alkyl group. The photosensitive resin composition for forming a color conversion layer according to claim 2, wherein R ¹ to R ³ are each independently ethyleneyl or oxiranyl. The photosensitive resin composition for forming a color conversion layer according to claim 1, wherein the content of the isocyanurate compound is 0.1 to 40 wt% based on 100 wt% 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 device comprising the color filter according to claim 5 .