TW201937295A - Self-emission type photosensitive resin composition, color conversion layer, and display device using the same capable of ensuring the characteristics of excellent optical density, fluorescent efficiency, and light emission intensity - Google Patents

Abstract

The present invention provides a self-emission type photosensitive resin composition, a color conversion layer, and a display device manufactured from the self-emission type photosensitive resin composition. The aforementioned self-emission photosensitive resin composition is characterized by comprising a dye and a tetraazaporphyrin-based compound having aluminum (Al) or cerium (Si) serving as a central metal. The self-emission photosensitive resin composition in accordance with the present invention is provided with the effect of excellent optical density, fluorescent efficiency, and light emission intensity.

Description

Self-luminous photosensitive resin composition, color conversion layer and display device

The present invention relates to a self-luminous photosensitive resin composition, a color conversion layer manufactured using the self-luminous photosensitive resin composition, and a display device.

In recent years, the display industry is moving from CRT (cathode-ray tube) to PDP (plasma display panel), OLED (organic light-emitting diode), and LCD (liquid -crystal display (liquid crystal display) and other flat panel displays are rapidly changing. Among them, LCDs are widely used as display devices used in almost all industries, and their application range is continuously expanding.

LCD uses white light generated from the backlight unit to adjust the transmittance while passing through the liquid crystal unit, and mixes the three primary colors from the red, green, and blue filters to achieve full color. color.

The CCFL (Cold Cathode Fluorescent Lamp) is used as the light source of the backlight unit. However, in this case, the backlight unit often needs to apply power to the CCFL, which causes a problem of power consumption. In addition, it has been pointed out that, compared with conventional CRTs, there is a color reproduction rate of about 70%, and there is a problem of environmental pollution with the addition of mercury.

As a substitute for solving the above problems, research on a backlight unit using an LED (Light Emitting Diode) is currently being actively conducted. When an LED is used as a backlight unit, it can exceed 100% of the color reproduction range of the NTSC (National Television System Committee) and provide consumers with more vivid image quality.

Therefore, in order to improve the light efficiency and the efficiency of backlight light sources by changing the materials and structure of color filters and LCD panels, etc., similar industries are working hard, but it is difficult to satisfy both due to the limitation of the transmission characteristics of coloring materials There is a problem that color reproducibility and brightness characteristics cannot exceed a certain level.

The problem of low color reproducibility can be solved by increasing the light efficiency of the color filter. To this end, it is proposed to increase the thickness of the color filter, or to introduce a color conversion layer (or light conversion layer) in a layered or close manner. Program.

FIG. 1 is a schematic diagram illustrating the function of a color conversion layer in a display device. As shown in FIG. 1, a light source generated from a backlight unit can directly increase light efficiency through the color conversion layer and color filters.

Korean Patent Application Publication No. 10-2012-0048218 discloses a display including a light conversion section having at least one fluorescent substance that converts incident light in a blue or ultraviolet wavelength band into light in a predetermined wavelength band. However, there are still disadvantages such as low fluorescence efficiency of the light conversion section.

Korean Patent Application Publication No. 10-2010-0056437 discloses a method for manufacturing a color conversion filter using an inkjet method, in which a color conversion layer can be formed at a desired position without forming a partition wall separately, but in this case There is a problem that the fluorescent efficiency is low using only the dye itself, and it is insoluble in general solvents due to the use of an organic EL (electro-luminescence) material.

Prior Art Literature Patent Literature Patent Literature 1: Korean Patent Application Publication No. 10-2012-0048218 Patent Literature 2: Korean Patent Application Publication No. 10-2010-0056437

Problems to be Solved by the Invention

The present invention is to solve the above-mentioned problems of the prior art, and an object thereof is to provide a self-luminous photosensitive resin capable of ensuring excellent fluorescent efficiency characteristics by including a specific tetraazaporphyrin-based compound. A composition, a color conversion layer produced using the self-luminous photosensitive resin composition, and a display device.

Methods for solving problems

The present invention provides a self-luminous photosensitive resin composition, which comprises a dye and a tetraazaporphyrin-based compound having aluminum (Al) or silicon (Si) as a center metal.

The present invention also provides a color conversion layer, which is produced from the above-mentioned self-luminous photosensitive resin composition.

Further, the present invention provides a display device, which is characterized in that it includes the above-mentioned color conversion layer.

Invention effect

The self-luminous photosensitive resin composition of the present invention, a color conversion layer manufactured using the self-luminous photosensitive resin composition, and a display device include a tetraaza-containing compound having aluminum (Al) or silicon (Si) as a center metal. Porphyrin-based compounds have the effect of ensuring excellent optical density (OD), fluorescence efficiency, and luminous intensity characteristics.

The present invention relates to a self-luminous photosensitive resin composition that can be used in a color conversion layer of a display device.

The color conversion layer is used to improve the reduced light efficiency caused by the use of the color filter. The color conversion layer is located adjacent to the color filter (refer to FIG. 1) and corresponds to the red color of the color filter ( R) and green (G) patterns are composed of fine patterns. In this case, the fine pattern can be formed using a self-luminous photosensitive resin composition.

In particular, the self-luminous photosensitive resin composition of the present invention may include a dye and a tetraazaporphyrin-based compound having aluminum (Al) or silicon (Si) as a central metal as an essential component.

The self-luminous photosensitive resin composition of the present invention may further include a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.

Hereinafter, each composition will be described.

Tetraazaporphyrins

Since the self-luminous photosensitive resin composition of the present invention contains a tetraazaporphyrin-based compound having aluminum or silicon as a central metal, it is possible to ensure excellent optical density, fluorescence efficiency, and luminous intensity characteristics.

According to an aspect of the present invention, the tetraazaporphyrin-based compound may be a compound represented by the following Chemical Formula 1.


[Chemical Formula 1]


(In Chemical Formula 1, R ²⁶ to R ³³ are each independently hydrogen; unsubstituted phenyl; alkyl group having 1 to 8 carbon atoms; alkoxy group having 1 to 8 carbon atoms; nitro group; halogen atom; A cyano group; an alkylamino group having 1 to 8 carbon atoms; an aminoalkyl group having 1 to 8 carbon atoms; or an alkoxy group having 1 to 8 carbon atoms and an alkyl group having 1 to 8 carbon atoms A phenyl group, a nitro group, a halogen atom, an alkylamino group having 1 to 8 carbon atoms, an aminoalkyl group having 1 to 8 carbon atoms, and a phenyl group having one or more substituents,
M is Al or Si having one or more ligands selected from ammonia, water, and a halogen atom, or no ligands. )

In the self-luminous photosensitive resin composition of the present invention, the content of the tetraazaporphyrin-based compound is preferably 0.001 to 15% by weight, more preferably 0.1 to 10, based on the total weight of the self-luminous photosensitive resin composition. weight%. When the content of the above-mentioned tetraazaporphyrin-based compound is within the above-mentioned range, it is preferable that it exhibits excellent fluorescence efficiency, and when the content of the above-mentioned tetraazaporphyrin-based compound exceeds the above-mentioned range. There are problems of reduced fluorescence and adverse effects on processability.

In this specification, "substituted or unsubstituted" means substituted with one or more substituents selected from the group consisting of halo, nitrile, nitro, hydroxy, alkyl, cycloalkyl, Alkenyl, alkoxy, aryloxy, thiol, alkylthio, arylthio, sulfoxy, alkylsulfoxy, arylsulfoxy, silyl, boron , Arylamino, aralkylamino, alkylamino, aryl, arylalkyl, arylalkenyl, heterocyclyl, and ethynyl, or it does not have any substituents.

In the present specification, "halogen" means -F, -Cl, -Br, or -I.

dye

As the dye contained in the self-luminous photosensitive resin composition of the present invention, a dye generally used for a color conversion layer can be used.

In addition, as a feature, the dye may be a fluorescent dye, preferably a red fluorescent dye, and more preferably a perylene bis-imide-based compound.

According to an embodiment of the present invention, the fluorene-bisfluorene imide-based compound may be a compound represented by the following Chemical Formula 2.
[Chemical Formula 2]


(In Chemical Formula 2, R1 and R2 are each independently a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted linear or branched alkyl group,
R3, R4, R5 and R6 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted phenoxy group, a substituted or An unsubstituted thiophenoxy group or a substituent represented by the following Chemical Formula 3, and not all of R3, R4, R5, and R6 are the same. )

[Chemical Formula 3]


(In Chemical Formula 3, X1 and X5 are hydrogen atoms,
X2, X3 and X4 are each independently a hydrogen atom or a halogen atom, and at least one of X2, X3 and X4 is a halogen atom,
Y is an oxygen atom or a sulfur atom. )

The compound represented by the above Chemical Formula 2 may be a compound substituted with at least one aryloxy group or a thiophenoxy group substituted with a halogen.

A self-luminous photosensitive resin composition containing a fluorene-bisfluorene imide-based compound substituted with at least one halogen-substituted aryloxy group or thiophenoxy group can increase the fluorescence of the color conversion layer. In addition, by introducing an asymmetric form of a substituent into a fluorene bisphosphonium imine-based compound, the structure is distorted, which can increase its solubility in a solvent, thereby exhibiting excellent chemical, thermal, and optical stability. The application of the process has very advantageous effects.

According to another aspect of the present invention, the fluorene-bisfluorene imide-based compound may be a compound represented by the following Chemical Formula 4.


[Chemical Formula 4]


(In Chemical Formula 4, R1 and R2 are each independently a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted linear alkyl group, or a substituted or unsubstituted Substituted branched alkyl,
R11, R12, R13 and R14 are each independently selected from the group consisting of a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, a hydroxyl group, and an alkane having 1 to 10 carbon atoms Oxygen, an ester group having 1 to 10 carbon atoms, and a substituent in an amine group, and at least one of R11, R12, R13, and R14 is in the kind of the substituent or the position of the substituent with the remaining substituents Is different,
Y ₁ , Y ₂ , Y ₃ and Y ₄ are each independently an oxygen (O) atom or a sulfur (S) atom,
a, b, c, and d are each independently an integer of 1 to 5. )

Moreover, in the compound represented by the said Chemical Formula 4, any one of said R11, R12, R13, and R14 may be substituted in para or meta. The R1 and R2 may be a substituent represented by the following Chemical Formula 5.


[Chemical Formula 5]


(In Chemical Formula 5, R21 to R25 are each independently a substituent selected from a hydrogen atom and a substituted or unsubstituted linear or branched alkyl group having 1 to 5 carbon atoms.)

According to still another aspect of the present invention, the fluorenimidine-imide-based compound may be any one of the compounds represented by the following chemical formulae 4-1 to 4-12.
[Chemical Formula 4-1]


[Chemical Formula 4-2]

[Chemical Formula 4-3]


[Chemical Formula 4-4]


[Chemical Formula 4-5]


[Chemical Formula 4-6]


[Chemical Formula 4-7]


[Chemical Formula 4-8]


[Chemical Formula 4-9]


[Chemical Formula 4-10]


[Chemical Formula 4-11]


[Chemical Formula 4-12]

In the self-luminous photosensitive resin composition of the present invention, the content of the dye is preferably 0.001 to 30% by weight, more preferably 0.1 to 10% by weight, based on the total weight of the self-luminous photosensitive resin composition. When the content of the dye is within the above range, it is advantageous from the standpoint of fluorescent efficiency and processability. If the content exceeds the above range, there is a decrease in fluorescence efficiency due to aggregation of the dye, which may cause a decrease in processability. Problems with adverse effects.

Adhesive resin

The adhesive resin contained in the self-luminous photosensitive resin composition of the present invention generally has reactivity based on the action of light and heat and alkali solubility, and can function as a dispersion medium of a coloring material. As long as the binder resin contained in the self-luminous photosensitive resin composition of the present invention functions as a binder resin for a dye, it can be used in an alkaline developing solution used in a developing step for producing a color conversion layer. Any dissolved binder resin can be used.

Examples of the binder resin include a carboxyl group-containing monomer and a copolymer of the monomer with another monomer that can be copolymerized with the monomer.

Examples of the carboxyl group-containing monomer include unsaturated carboxylic acids such as unsaturated monocarboxylic acids, unsaturated polycarboxylic acids, and unsaturated polycarboxylic acids having one or more carboxyl groups in molecules such as unsaturated dicarboxylic acids and unsaturated tricarboxylic acids. Here, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and the like. The unsaturated polycarboxylic acid may be an acid anhydride, and specific examples include maleic anhydride, itaconic anhydride, and citraconic anhydride. In addition, the unsaturated polycarboxylic acid may be a mono (2-methacrylfluorenyloxyalkyl) ester, and examples thereof include a mono (2-acrylfluorenyloxyethyl) succinate and a succinic acid mono ( 2-methacrylfluorenyloxyethyl) ester, phthalic acid mono (2-propenylfluorenyloxyethyl) ester, phthalic acid mono (2-methacrylfluorenyloxyethyl) ester, and the like. The unsaturated polycarboxylic acid may be a mono (meth) acrylate of a dicarboxyl polymer at both ends thereof, and examples thereof include ω-carboxy polycaprolactone monoacrylate and ω-carboxy polycaprolactone monomethacrylic acid. Esters, etc. Each of these carboxyl group-containing monomers can be used alone or as a mixture of two or more.

Examples of other monomers that can be copolymerized with the carboxyl group-containing monomer include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, and o-methyl Oxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl Aromatic vinyl compounds such as methyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, indene; methyl acrylate, methyl methacrylate, ethyl acrylate, methyl Ethyl acrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate Ester, secondary butyl acrylate, secondary butyl methacrylate, tertiary butyl acrylate, tertiary butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylic acid- 2-hydroxypropyl ester, 2-hydroxymethacrylic acid Propyl ester, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, methacrylic acid 3-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate Ester, 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 triethyl Glycol methacrylate, methoxy propylene glycol acrylate, methoxy propylene glycol methacrylate, methoxy dipropylene glycol acrylate, methoxy dipropylene glycol methacrylate, isopropyl acrylate, methacrylate isopropyl Fluorenyl ester, dicyclopentadiene acrylate, dicyclopentyl diethyl methacrylate, (methyl) Adamantane enoate, norbornyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, Unsaturated carboxylic acid esters such as glycerol monomethacrylate; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, methacrylic acid- 2-dimethylaminoethyl acrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylmethacrylate Aminopropylpropyl, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate Unsaturated carboxylic acid amino alkyl esters such as esters; unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; vinyl acetate, vinyl propionate, vinyl butyrate, benzoic acid Vinyl carboxylates such as vinyl esters; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether; acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, Vinyl cyanide compounds such as cyanethylene vinylene; acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide, N-2-hydroxyethylmethacrylamine And other unsaturated amines; maleimides, benzylmaleimides, N-phenylmaleimides, N-cyclohexylmaleimides and other unsaturated amines; 1, 3-butadiene, isoprene, chlorinated aliphatic conjugated diene; and polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate The macromolecules of the polymer chain of an ester or a polysiloxane having a monopropenyl group or a monomethacryl group at the end of the molecular chain. These monomers can be used individually or in mixture of 2 or more types. In particular, as other monomers that can be copolymerized with the carboxyl group-containing monomer described above, a large-volume single system such as a monomer having a fluorenyl skeleton, a monomer having an adamantyl skeleton, and a monomer having a rosin skeleton has a relatively large Since the dielectric constant value tends to decrease, it is preferred.

The acid value of the binder resin of the present invention is preferably in the range of 20 to 200 (mgKOH / g (mg KOH / g)). If the acid value is within the above range, the solubility in the developing solution is improved, but the exposed part is not easily dissolved, and the sensitivity is increased. As a result, the pattern of the exposed part remains during development and the film remaining ratio can be improved. Is better.

Here, the acid value refers to a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and is usually obtained by titration with an aqueous potassium hydroxide solution.

In addition, it is preferable to have a binder resin having a polystyrene-equivalent weight average molecular weight (hereinafter, referred to as "" "Weight average molecular weight") is 3,000 to 200,000, preferably 5,000 to 100,000. When the molecular weight is within the above range, it is preferred because the hardness of the coating film is increased, the residual film rate is high, the solubility in a non-exposed portion in the developing solution is excellent, and the resolution is improved.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the binder resin is preferably 1.5 to 6.0, and more preferably 1.8 to 4.0. When the molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] is 1.5 to 6.0, the developability is excellent, and therefore it is preferable.

The content of the binder resin of the present invention is usually in the range of 5 to 85% by weight, and preferably in the range of 10 to 70% by weight based on the total weight of the solid content in the self-luminous photosensitive resin composition. When the content of the binder resin is within the above range, the film having sufficient solubility in the developing solution and having less pixel portions on the substrate when developing on the substrate is less likely to cause residues, and the pixel portion of the exposed portion is less likely to occur during development. The non-pixel portion tends to have good exfoliation properties, and is therefore preferred.

Photopolymerizable compound

The photopolymerizable compound contained in the self-luminous photosensitive resin composition of the present invention is a compound that can be polymerized by the action of a photopolymerization initiator described later, and examples thereof include monofunctional monomers, difunctional monomers, and other polyfunctional monomers. Monomer and so on.

Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, and 2-acrylate Hydroxyethyl, N-vinylpyrrolidone and the like.

Specific examples of the difunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and Ethylene glycol di (meth) acrylate, bis (propenyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like.

Specific examples of the other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, neopentaerythritol tri (meth) acrylate, neopentaerythritol tetra (meth) acrylate, Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. Among these, it is preferable to use a difunctional or more polyfunctional monomer.

The photopolymerizable compound is usually used in a range of 5 to 50% by weight, and preferably in a range of 7 to 45% by weight based on the total weight of the solid content in the self-luminous photosensitive resin composition. When the content of the photopolymerizable compound is within the above-mentioned range, the strength, smoothness, etc. of the pixel portion tend to be improved, and therefore, it is preferable.

Photopolymerization initiator

The photopolymerization initiator system used in the present invention preferably contains an acetophenone-based compound. Examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, diacetophenone dimethyl ketal, and 2 -Hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methyl Thiophenyl) -2-morpholinylpropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) butane- An oligomer of 1-ketone, 2-hydroxy-2-methyl [4- (1-methylvinyl) phenyl] propane-1-one, etc., preferably 2-benzyl-2-dimethyl Aminoamino-1- (4-morpholinylphenyl) butane-1-one and the like. In addition, a photopolymerization initiator other than the acetophenone-based may be used in combination. Examples of the photopolymerization initiator other than the acetophenone system 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-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Examples of the benzophenone-based compound include benzophenone, methyl orthobenzoylbenzoate, 4-phenylbenzophenone, and 4-benzophenyl-4'-methyldiphenyl. Sulfide, 3,3 ', 4,4'-tetrakis (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, etc. Examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2, 4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like. Examples of the triazine-based compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (tri Chloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5 -Triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) vinyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) Group) -6- [2- (4-diethylamino-2-methylphenyl) vinyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6 -[2- (3,4-dimethoxyphenyl) vinyl] -1,3,5-triazine and the like. Examples of the sensitizer include 2,4,6-trimethylbenzylidenediphenylphosphine oxide, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5' -Tetraphenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, diphenylethylene dione, 9,10-phenanthrenequinone, camphorquinone, phenyl Methyl glyoxylate, titanocene compounds, etc. Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-ethoxyloxyphenyldimethylformate. Hydrazone p-toluenesulfonate, 4-ethoxyfluorenylmethylbenzyl hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyl Onium salts such as iodoium p-toluenesulfonate, diphenyl iodonium hexafluoroantimonate; and nitrobenzyl tosylate, benzoin tosylate, and the like. In addition, among the above-mentioned compounds that are active radical generators, there are also compounds that generate both an active radical and an acid. For example, a triazine-based photopolymerization initiator can be used as the acid generator.

The content of the photopolymerization initiator used in the self-luminous photosensitive resin composition of the present invention is generally from 0.1 to 40% by weight, and preferably from the total weight of the solid content of the binder resin and the photopolymerizable compound. 1 to 30% by weight. When the content of the photopolymerization initiator is within the above range, it is preferred that the self-luminous photosensitive resin composition has high sensitivity, the strength of the pixel portion formed using the composition, and The smoothness of the surface of the pixel portion is improved.

Further, in the present invention, a photopolymerization initiation aid can be used. The photopolymerization initiation adjuvant may be used in combination with a photopolymerization initiator, and is a compound used to promote the polymerization of a photopolymerizable compound that is polymerized by the photopolymerization initiator. Examples of the photopolymerization initiation aid include amine compounds, alkoxyanthracene compounds, and thiaxanthone compounds. Examples of the amine-based compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-diamine. Isoamyl methylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethyl-p-toluidine, 4 , 4'-bis (dimethylamino) benzophenone (commonly known as Michelin), 4,4'-bis (diethylamino) benzophenone, 4,4'-bis ( Ethylmethylamino) benzophenone and the like, among them, 4,4'-bis (diethylamino) benzophenone is preferred. Examples of the alkoxyanthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl Group-9,10-diethoxyanthracene and the like. Examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2, 4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like. Such a photopolymerization initiation adjuvant can be used individually or in combination of multiple types.

In addition, as a commercially available photopolymerization initiation aid, a commercially available photopolymerization initiation aid may be used. For example, a product named "EAB-F" [manufacturer: Hodogaya Chemical Industry Co., Ltd.] .

In the case of using such a photopolymerization initiation aid, the usage amount thereof is usually 10.0 mol or less per mol of the photopolymerization initiator, preferably 0.01 to 5.0 mol. When the amount of the photopolymerization initiation aid is within the above range, the sensitivity of the self-luminous photosensitive resin composition is further increased, and the productivity of the color conversion layer formed by using the composition tends to be improved. Good.

Solvent

The solvent contained in the self-luminous photosensitive resin composition of the present invention is not particularly limited, and various organic solvents used in the field of coloring photosensitive resin compositions 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; diethyl ether; Diethylene glycol dialkyl ethers such as glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, etc .; Glycol alkyl ether acetates such as acid esters, ethyl celulose acetate; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methyl ester Alkyl glycol alkyl ether acetates such as oxybutyl acetate, methoxypentyl acetate; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene; methyl ethyl ketone , Acetone, methylpentyl ketone, methyl isobutyl ketone, cyclohexanone and other ketones; ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol and other alcohols; 3-ethyl Esters such as ethyl oxypropionate and methyl 3-methoxypropionate; cyclic esters such as γ-butyrolactone.

Regarding the above-mentioned solvents, from the viewpoints of coating properties and drying properties, an organic solvent having a boiling point of 100 ° C to 200 ° C in the above-mentioned solvents is preferably used, and more preferably, alkylene glycol alkyl ether acetates and ketones can be used. Esters, such as ethyl 3-ethoxypropionate or methyl 3-methoxypropionate, and further preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone , Ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like. These solvents may be used alone or in combination of two or more.

In the self-luminous photosensitive resin composition of the present invention, the content of the solvent is usually 60 to 90% by weight, preferably 70 to 85% by weight, based on the total weight of the self-luminous photosensitive resin composition. When the content of the solvent is within the above range, when a coating device such as a roll coater, a spin coater, a slit spin coater, a slit coater (also sometimes referred to as a die coater), or an inkjet machine is used, When coating is performed, there is a tendency that the coatability is improved, etc., so it is preferable.

Other additives

The self-luminous photosensitive resin composition of the present invention may further contain additives such as fillers, other polymer compounds, pigment dispersants, adhesion promoters, antioxidants, ultraviolet absorbers, and anticoagulants, if necessary.

Specific examples of the filler include glass, silicon dioxide, and alumina.

Specific examples of other polymer compounds include curable resins such as epoxy resin and maleimide resin, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, Thermoplastic resins such as polyurethane.

As the pigment dispersant, a commercially available surfactant can be used, and examples thereof include silicone, fluorine, ester, cationic, anionic, nonionic, and amphoteric surfactants. These can be used individually or in combination of 2 or more types. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, and Grade amine modified polyurethanes, polyethylene / imine, etc. In addition, trade names include KP (made by Shin-Etsu Chemical Industry Co., Ltd.), POLYFLOW (made by Kyoeisha Chemical Co., Ltd.), and EFTOP (Tok products (Manufactured by Tohkem Products), MEGAFAC (manufactured by Dainippon Ink Chemical Industry Co., Ltd.), Flourad (manufactured by Sumitomo 3M Co., Ltd.), Asahi guard, Surflon (above, manufactured by Asahi Glass Co., Ltd.), SOLSPERSE Co., Ltd.), EFKA (manufactured by EFKA Chemical Co., Ltd.), PB821 (manufactured by Ajinomoto Co., Ltd.), etc.

Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyl ginseng (2-methoxyethoxy) silane, and 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-methacrylmethyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and the like.

Specific examples of the antioxidant include 2,2'-thiobis (4-methyl-6-tertiarybutylphenol), 2,6-di-tertiarybutyl-4-methylphenol, and the like. Specific examples of the ultraviolet absorber include 2- (3-tertiarybutyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, and alkoxybenzophenone. Specific examples of the anticoagulant include sodium polyacrylate.

The self-luminous photosensitive resin composition of the present invention can be produced, for example, by the following method. The dye is mixed with a solvent in advance and dissolved. In this case, if necessary, a pigment dispersant is used, and a part or all of the binder resin may be blended. To the obtained dispersion (hereinafter, also sometimes referred to as a mill base), a remaining binder resin, a photopolymerizable compound, a photopolymerization initiator, and an optional one are added so as to have a predetermined concentration. With other components and additional solvents as needed, the desired self-luminous photosensitive resin composition can be obtained.

Color conversion layer

The present invention also provides a color conversion layer produced from the self-luminous photosensitive resin composition.

When the color conversion layer of the present invention is applied to a display device, since the display device emits light by means of light from a light source, more excellent light efficiency can be achieved. In addition, since light having color is emitted, color reproducibility is more excellent, and light is emitted in all directions due to photoluminescence, so that the viewing angle can also be improved.

In more detail, in a general display device including a color conversion layer, white light is transmitted through the color conversion layer to present a color. However, part of the light is absorbed by the color conversion layer in this process, so there is a problem that the light efficiency is reduced. . However, when the color conversion layer produced from the self-luminous photosensitive resin composition of the present invention is included, since the color conversion layer is self-emissive by light from a light source, more excellent light efficiency can be achieved.

The color conversion layer includes a substrate and a pattern layer formed on the substrate.

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

The pattern layer is a layer containing the self-luminous photosensitive resin composition of the present invention, and may be a layer formed by applying the above-mentioned self-luminous photosensitive resin composition, and exposing, developing, and thermosetting in a predetermined pattern.

The pattern layer formed from the self-luminous photosensitive resin composition may include 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. When light is irradiated, the red pattern layer emits red light, the green pattern layer emits green light, and the blue pattern layer emits blue light. At this time, when applied to a display device, the light emitted from the light source is not particularly limited, and a light source that emits blue light can be used in terms of more excellent color reproducibility.

According to another aspect of the present invention, the pattern layer may include only two color pattern layers among a red pattern layer, a green pattern layer, and a blue pattern layer. In this case, the pattern layer further includes a transparent pattern layer that does not contain quantum dot particles.

When the pattern layer includes only two colors, a light source that emits light having a wavelength of a remaining color that is not included can be used. For example, when the red pattern layer and the green pattern layer are included, a blue light source may be used. In this case, the red quantum dot particles emit red light, the green quantum dot particles emit green light, and the transparent pattern layer directly transmits blue light to appear blue.

The color conversion layer including the substrate and the pattern layer as described above may further include a partition wall formed between the patterns, and may further include a black matrix. Further, a protective film formed on the pattern layer of the color conversion layer may be further included.

Display device

The present invention also provides a display device including the color conversion layer.

The color conversion layer of the present invention can be applied not only to ordinary liquid crystal display devices, but also to various image display devices such as electroluminescence display devices, plasma display devices, and field emission display devices.

The display device of the present invention may include a color conversion layer including 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. In this case, when applied to a display device, the light emitted from the light source is not particularly limited, and a light source that emits blue light is preferably used in terms of more excellent color reproducibility.

According to another embodiment of the present invention, the display device of the present invention may include a color conversion layer including only two color pattern layers among a red pattern layer, a green pattern layer, and a blue pattern layer. In this case, the color conversion layer further includes a transparent pattern layer containing no quantum dot particles.

When the pattern layer includes only two colors, a light source that emits light having a wavelength of a remaining color that is not included can be used. For example, when the red pattern layer and the green pattern layer are included, a blue light source may be used. In this case, the red quantum dot particles emit red light, the green quantum dot particles emit green light, and the transparent pattern layer directly transmits blue light to appear blue.

The display device of the present invention is excellent in light efficiency, exhibits high brightness, has excellent color reproducibility, and can have a wide viewing angle.

Hereinafter, the present invention will be described in more detail using examples and comparative examples. However, the following examples are intended to illustrate the present invention, and the present invention is not limited to the following examples, and may be modified and changed in various ways. The scope of the present invention is determined by the technical idea of the scope of the patent application scope described later. In addition, below, "%" and "part" which show content are based on a weight unless there is particular mention.

Synthesis example 1

By a method known in the literature (J. Am. Soc. (Journal of the American Chemical Society, 4839 (1952)), a tetraazaporphyrin represented by Chemical Formula 1-1 is synthesized as follows LINE Compounds.

50 parts by weight of metal-free octaphenyltetraporphyrin and 1.5 parts by weight of alumina were refluxed in a solvent of 25 parts by weight of o-dichlorobenzene for 1.5 hours. When the reaction is completed, the reaction mixture is refluxed in a hot state. After completion of the reaction, the resultant was cooled to room temperature, and the resulting solid was washed with hot water and ethanol, and then extracted with chlorobenzene. Next, the extract was crystallized to obtain pure octaphenyltetraazaporphyrin aluminum.

Synthesis example 2

A pure octaphenyltetraazaporphyrin silicon represented by Chemical Formula 1-2 was obtained in the same manner as in Synthesis Example 1 except that silicic acid was used instead of alumina.

Comparative Synthesis Example 1

A manganese anhydride was used in place of alumina, and pure octaphenyltetraporphyrin manganese represented by Chemical Formula 1-3 was obtained in the same manner as in Synthesis Example 1 above.

Comparative Synthesis Example 2

Except having used copper nitrate instead of alumina, it carried out similarly to the said synthesis example 1, and obtained the pure copper octaphenyltetraporphyrin represented by Chemical formula 1-4.

Synthesis Example 3

After adding 1,6,7,12-tetrachlorophosphonium tetracarboxylic dianhydride (0.11 mole) and 2,6-diisopropylaniline (0.44 mole) to 1 liter of propionic acid, the temperature was raised to 140 The reaction was maintained at 5 ° C for 5 hours. Then, the reaction solution was cooled to room temperature, and the precipitate was filtered under reduced pressure, and washed with methanol. The dispersion was dispersed in water for 30 minutes, and then filtered under reduced pressure. After being dispersed again in methanol for 30 minutes, it was filtered under reduced pressure. The filtrate was dried to obtain an intermediate compound (INT) in a yield of 80.5%.

The intermediate compound formed as described above was measured for mass spectrometry (MS) using a MALDI-TOF measurement device. As a result, it was confirmed that the molecular weight was 848.16.

Synthesis Example 4 : Synthesis of Compound of Chemical Formula 4-1

Potassium carbonate (0.04 mol) was added to the solution of the intermediate compound (0.04 mol) and N-methylpyrrolidone (266.1 g) synthesized in Synthesis Example 3, and the temperature was raised to 120 ° C. A solution prepared by dissolving 4-fluorophenol (0.04 mol) in N-methylpyrrolidone (88.7 g) was added to the reaction solution at 120 ° C over 2 hours. After the reaction was maintained at the same temperature for 1 hour, 4-chlorophenol (0.16 mol) and potassium carbonate (0.16 mol) were added and stirred for 4 hours. After that, the reaction solution was cooled to room temperature and discharged into 3 liters of distilled water. The purple precipitate thus produced was filtered under reduced pressure, and washed with methanol water. The above-mentioned filtered substance was re-dissolved in dichloromethane (MC, methylene chloride), filtered through silica to remove impurities, and recrystallized with MeOH to obtain a compound of the formula 4-1 in a yield of 40.4%. It was confirmed that The molecular weight is 1198.29.

Synthesis Example 5 : Synthesis of Compound of Chemical Formula 4-3

Potassium carbonate (0.04 mol) was added to the solution of the intermediate compound (0.04 mol) and N-methylpyrrolidone (266.1 g) synthesized in Synthesis Example 3, and the temperature was raised to 120 ° C. A solution prepared by dissolving 2,4- (tertiary butyl) phenol (0.04 mol) in N-methylpyrrolidone (88.7 g) was added to the reaction solution at 120 ° C over 2 hours. After the reaction was maintained at the same temperature for 1 hour, 4-chlorophenol (0.16 mol) and potassium carbonate (0.16 mol) were added and stirred for 4 hours. After that, the reaction solution was cooled to room temperature and discharged into 3 liters of distilled water. The purple precipitate thus formed was filtered under reduced pressure and washed with methanol water. The above-mentioned filtrate was re-dissolved in dichloromethane (MC), and then filtered through silica to remove impurities, and recrystallized with MeOH to obtain a compound of Chemical Formula 4-3 in a yield of 37.0%. It was confirmed that the molecular weight was 1236.37 .

Synthesis Example 6 : Synthesis of Compounds of Chemical Formula 4-7

Potassium carbonate (0.04 mol) was added to the solution of the intermediate compound (0.04 mol) and N-methylpyrrolidone (266.1 g) synthesized in Synthesis Example 3, and the temperature was raised to 120 ° C. A solution prepared by dissolving 4-butylparaben (0.04 mol) in N-methylpyrrolidone (88.7 g) was added to the reaction solution at 120 ° C over 2 hours. After the reaction was maintained at the same temperature for 1 hour, 4-chlorophenol (0.16 mol) and potassium carbonate (0.16 mol) were added and stirred for 4 hours. After that, the reaction solution was cooled to room temperature and discharged into 3 liters of distilled water. The purple precipitate thus produced was filtered under reduced pressure, and washed with methanol water. The above-mentioned filtered substance was re-dissolved in dichloromethane (MC), filtered through silica to remove impurities, and recrystallized with MeOH to obtain a compound of Chemical Formula 4-7 in a yield of 68.7%. It was confirmed that the molecular weight was 1280.35 .

Synthesis Example 7 : Synthesis of a compound of Chemical Formula 4-10

Potassium carbonate (0.04 mol) was added to the solution of the intermediate compound (0.04 mol) and N-methylpyrrolidone (266.1 g) synthesized in Synthesis Example 3, and the temperature was raised to 120 ° C. A solution prepared by dissolving 4- (tertiarybutyl) phenol (0.04 mol) in N-methylpyrrolidone (88.7 g) was added to the reaction solution at 120 ° C over 2 hours. After the reaction was maintained at the same temperature for 1 hour, 4-chlorophenol (0.16 mol) and potassium carbonate (0.16 mol) were added and stirred for 4 hours. After that, the reaction solution was cooled to room temperature and discharged into 3 liters of distilled water. The purple precipitate thus produced was filtered under reduced pressure, and washed with methanol water. The above-mentioned filtered substance was re-dissolved in dichloromethane (MC), filtered through silica to remove impurities, and recrystallized with MeOH to obtain a compound of Chemical Formula 4-10 in a yield of 56.5%. .

Synthesis Example 8 : Synthesis of a compound of Chemical Formula 4-12

Potassium carbonate (0.04 mol) was added to the solution of the intermediate compound (0.04 mol) and N-methylpyrrolidone (266.1 g) synthesized in Synthesis Example 3, and the temperature was raised to 120 ° C. A solution prepared by dissolving 3- (trifluoromethyl) phenol (0.04 mol) in N-methylpyrrolidone (88.7 g) was added to the reaction solution at 120 ° C over 2 hours. After the reaction was maintained at the same temperature for 1 hour, 4-chlorophenol (0.16 mol) and potassium carbonate (0.16 mol) were added and stirred for 4 hours. After that, the reaction solution was cooled to room temperature and discharged into 3 liters of distilled water. The purple precipitate thus produced was filtered under reduced pressure, and washed with methanol water. The above-mentioned filtered substance was re-dissolved in dichloromethane (MC), filtered through silica to remove impurities, recrystallized with MeOH, and a compound of Chemical Formula 4-12 was obtained in a yield of 40.5%. It was confirmed that the molecular weight was 1248.29 .

Production example: Adhesive resin

A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube was prepared. As a monomer dropping funnel, 74.8 g (0.20 mole) of benzylmaleimide, 43.2 g (0.30 mole) of acrylic acid, 118.0 g (0.50 mole) of vinyl toluene, tertiary butyl peroxide- After adding 4 grams of 2-ethylhexanoate and 40 grams of propylene glycol monomethyl ether acetate (PGMEA), prepare it by stirring and mixing; as a chain transfer agent, add dropwise tanks and prepare to add positive ten 6 grams of dioxanethiol and 24 grams of PGMEA, which are stirred and mixed. After that, 395 g of PGMEA was introduced into the flask, and after changing the atmosphere in the flask from air to nitrogen, the temperature of the flask was raised to 90 ° C. while stirring. Next, the monomer and the chain transfer agent were added dropwise from the dropping funnel. The dropwise addition was performed for 2 hours while maintaining the temperature at 90 ° C. After 1 hour, the temperature was increased to 110 ° C and maintained for 3 hours, and then the gas introduction tube was introduced to start the oxygen / nitrogen = 5/95 (v / v) mixed gas. Bubbling. Next, 28.4 g of glycidyl methacrylate [(0.10 mole), (33 mole% with respect to the carboxyl group of acrylic acid used in this reaction)], 2,2'-methylenebis (4- 0.4 g of methyl-6-tert-butylphenol) and 0.8 g of triethylamine were charged into the flask and reacted at 110 ° C for 8 hours to obtain a solid component having an acid value of 70 mgKOH / g (mg KOH / g). Binder resin. The polystyrene equivalent weight average molecular weight measured by GPC was 16,000, and the molecular weight distribution (Mw / Mn) was 2.3.
Device: HLC-8120GPC (manufactured by Tosoh Corporation)
Column: TSK-GELG4000HXL ＋ TSK-GELG2000HXL (connected in series)
Column temperature: 40 ℃
Mobile phase solvent: tetrahydrofuran Flow rate: 1.0 ml / min Injection volume: 50 microliters (μl)
Detector: RI
Measurement sample concentration: 0.6% by mass (solvent = tetrahydrofuran)
Calibration reference materials: TSK STANDARD POLYSTYRENE (standard polystyrene) F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

The ratio of the weight-average molecular weight to the number-average molecular weight obtained above was defined as a molecular weight distribution (Mw / Mn).

Examples 1 to 6 And comparative examples 1 to 3

Each of the self-luminous photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 to 3 was produced in accordance with the compositions and contents shown in Table 1 below.

[Table 1]
(Unit: parts by weight)

TAP-1: Synthesis Example 1
TAP-2: Synthesis Example 2
TAP-3: Comparative Synthesis Example 1
TAP-4: Comparative Synthesis Example 2
A-1: Synthesis Example 4
A-2: Synthesis Example 5
A-3: Synthesis Example 6
A-4: Synthesis Example 7
A-5: Synthesis Example 8
B: Adhesive resin for production example
C: Dinepentaerythritol hexaacrylate (Kayarad DPHA: manufactured by Nippon Kayaku Co., Ltd.)
D-1: 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) butane-1-one (Irgacure369; Ciba Specialty Chemical)
D-2: 4,4'-bis (dimethylamino) benzophenone (EAB-F; manufactured by Hodogaya Chemical Co., Ltd.)
E: Propylene glycol monomethyl ether acetate (PGMEA)

Manufacturing Example of Color Conversion Layer

The color conversion layer was produced using the self-luminous photosensitive resin compositions produced in the above-mentioned Examples 1 to 6 and Comparative Examples 1 to 3. That is, each of the above self-luminous photosensitive resin compositions was coated on a glass substrate by a spin coating method, then placed on a hot plate, and maintained at 100 ° C. for 3 minutes to form a thin film. Next, the film was irradiated with ultraviolet rays. At this time, the ultraviolet light source was an ultra-high-pressure mercury lamp (trade name USH-250D) manufactured by Oxtail Electric Co., Ltd., with an exposure of 365 nm in an atmosphere of 40 mJ / cm ² (mJ / cm ² ). ) Irradiate light without using special optical filters. The film irradiated with the ultraviolet rays was developed in a KOH aqueous solution developing solution at pH 12.5 using a spray developer for 60 seconds, and then heated in a heating oven at 220 ° C. for 20 minutes to produce a pattern. The film thickness of the produced self-luminous color color conversion layer pattern was 3.0 micrometers. The thickness of the color conversion layer can be controlled to 500 microns in various ways.

Experimental example: Measurement of luminous intensity

A 3.0-micron-thick self-luminous color pattern produced using the self-luminous photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 to 3 was measured using a quantum efficiency tester (QE-1000, manufactured by Otsuka Corporation). The luminescence (Photo Luminescence, PL) for each coated substrate is described in Table 2 below. It can be judged that the higher the measured luminous intensity, the more excellent the fluorescence efficiency characteristics.

[Table 2]

With reference to Table 2 above, it can be seen that Examples 1 to 6 have higher light emission intensity values than Comparative Examples 1 to 3, so it can be understood that they are manufactured using the self-luminous photosensitive resin composition based on Examples 1 to 6 The fluorescent efficiency of the color conversion layer is more excellent than that of Comparative Examples 1 to 3.

R‧‧‧ red

G‧‧‧Green

B‧‧‧ blue

W‧‧‧White

FIG. 1 is a schematic diagram illustrating an operation of a color conversion layer in a display device.

Claims (12)

A self-luminous photosensitive resin composition comprising a dye and a tetraazaporphyrin-based compound having aluminum (Al) or silicon (Si) as a center metal. The self-luminous photosensitive resin composition according to claim 1, wherein the tetraazaporphyrin-based compound is a compound represented by the following Chemical Formula 1, [Chemical Formula 1] In Chemical Formula 1, R ²⁶ to R ³³ are each independently hydrogen; unsubstituted phenyl; alkyl group having 1 to 8 carbon atoms; alkoxy group having 1 to 8 carbon atoms; nitro group; halogen atom; cyanide An alkylamino group having 1 to 8 carbon atoms; an aminoalkyl group having 1 to 8 carbon atoms; or an alkyl group having an alkoxy group having 1 to 8 carbon atoms and 1 to 8 carbon atoms , A nitro group, a halogen atom, an alkylamino group having 1 to 8 carbon atoms, an aminoalkyl group having 1 to 8 carbon atoms, and a phenyl group having one or more substituents among cyano groups, and M is a phenyl group having a group selected from ammonia , One or more ligands of water and a halogen atom, or Al or Si without a ligand. The self-luminous photosensitive resin composition according to claim 1, wherein the dye is a fluorescent dye. The self-luminous photosensitive resin composition according to claim 3, wherein the fluorescent dye is a red fluorescent dye. The self-luminous photosensitive resin composition according to claim 4, wherein the red fluorescent dye is a perylene bis-imide-based compound. The self-luminous photosensitive resin composition according to claim 5, wherein the fluorenimidine compound is a compound represented by the following Chemical Formula 2, [Chemical Formula 2] In Chemical Formula 2, R1 and R2 are each independently a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted linear or branched alkyl group, R3, R4, R5 and R6 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted phenoxy group, a substituted or unsubstituted A substituted thiophenoxy group or a substituent represented by the following Chemical Formula 3, and not all of R3, R4, R5, and R6 are the same, [Chemical Formula 3] In Chemical Formula 3, X1 and X5 are hydrogen atoms, X2, X3, and X4 are each independently a hydrogen atom or a halogen atom, and at least one of X2, X3, and X4 is a halogen atom, and Y is an oxygen atom or a sulfur atom. The self-luminous photosensitive resin composition according to claim 5, wherein the fluorenimidine-imide-based compound is a compound represented by the following Chemical Formula 4, [Chemical Formula 4] In Chemical Formula 4, R1 and R2 are each independently a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted linear alkyl group, or a substituted or unsubstituted Substituted branched alkyl groups, R11, R12, R13 and R14 are each independently selected from halogen atoms, straight or branched chain alkyl groups having 1 to 10 carbon atoms, haloalkyl groups having 1 to 10 carbon atoms, hydroxyl group, carbon 1 to 10 alkoxy groups, 1 to 10 carbon atom ester groups and substituents in amine groups, and at least one of R11, R12, R13 and R14 is a kind of substituent with the remaining substituents Or the positions of the substituents are different, Y ₁ , Y ₂ , Y ₃ and Y ₄ are each independently an oxygen (O) atom or a sulfur (S) atom, and a, b, c and d are each independently an integer of 1 to 5. The self-luminous photosensitive resin composition according to claim 1, wherein the self-luminous photosensitive resin composition is used to form a color conversion layer. The self-luminous photosensitive resin composition according to claim 1, wherein the self-luminous photosensitive resin composition further comprises a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The self-luminous photosensitive resin composition according to claim 9, wherein the self-luminous photosensitive resin composition contains 5 to 85% by weight of a binder resin and 5 to 8% by weight of the solid content of the self-luminous photosensitive resin composition. 50% by weight, The photopolymerization initiator is contained in an amount of 0.1 to 40% by weight based on the total weight of the solid content of the binder resin and the photopolymerizable compound. Based on the total weight of the self-luminous photosensitive resin composition, 0.001 to 15% by weight of a tetraazaporphyrin-based compound, 0.001 to 30% by weight of a dye, and 60 to 90% by weight of a solvent are included. A color conversion layer manufactured from the self-luminous photosensitive resin composition according to any one of claims 1 to 10. A display device includes the color conversion layer according to claim 11.