KR102655819B1 - Self emission type photosensitive resin composition, color conversion layer color filter and display device using the same - Google Patents

Abstract

The present invention relates to a dye; and a tetraazaporphyrin-based compound having aluminum (Al) or silicon (Si) as a central metal.

Description

Self-luminous photosensitive resin composition, color conversion layer and display device manufactured using the same {SELF EMISSION TYPE PHOTOSENSITIVE RESIN COMPOSITION, COLOR CONVERSION LAYER COLOR FILTER AND DISPLAY DEVICE USING THE SAME}

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

Recently, the display industry has undergone a rapid change from CRT (cathode-ray tube) to flat panel displays such as PDP (plasma display panel), OLED (organic light-emitting diode), and LCD (liquid-crystal display). Among them, LCD is widely used as a display device in almost all industries, and its application range is continuously expanding.

LCD's transmittance is adjusted as white light generated from the backlight unit passes through the liquid crystal cell, and the three primary colors passing through the color filters of red, green, and blue are mixed to achieve full color.

CCFL (Cold Cathode Fluorescent Lamp) is used as the light source of the backlight unit, but in this case, the backlight unit must always supply power to the CCFL, which causes the problem of power consumption. In addition, compared to existing CRTs, a color reproduction rate of about 70% and environmental pollution problems due to the addition of mercury are pointed out as disadvantages.

As a replacement to solve the above problems, research is currently being actively conducted on backlight units using LEDs (Light Emitting Diodes). When using LED as a backlight unit, it can exceed 100% of the NTSC (National Television System Committee) color reproduction range specification, providing consumers with more vivid picture quality.

Accordingly, in the same industry, efforts are being made to improve luminous efficiency by changing the materials and structures of color filters and LCD panels to improve the efficiency of backlight light sources. However, due to limitations in the transmission characteristics of coloring materials, color reproducibility and luminance are reduced. It has the problem of not being able to exceed a certain level because it is difficult to satisfy the characteristics at the same time.

The problem of low color reproducibility can be solved 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) laminated or close to it has been proposed. .

Figure 1 is a schematic diagram showing the role of the color conversion layer in a display device. As shown in Figure 1, the light source generated from the backlight unit can directly increase light efficiency through the color conversion layer and color filter.

Republic of Korea Patent Publication No. 10-2012-0048218 discloses a display including a light conversion unit having at least one fluorescent material that converts incident light in a blue or ultraviolet wavelength range into light in a predetermined wavelength range. However, there is still a disadvantage in that the fluorescence efficiency of the light conversion unit is low.

Republic of Korea Patent Publication No. 10-2010-0056437 discloses a method of manufacturing a color conversion filter using an inkjet method that can form a color conversion layer at a desired location without forming a separate partition. However, in this case, the dye itself is not used to produce fluorescent light. It has low efficiency and has the problem of being insoluble in general solvents due to the use of organic EL materials.

Republic of Korea Patent Publication No. 10-2012-0048218 Republic of Korea Patent Publication No. 10-2010-0056437

The present invention was made to solve the problems of the prior art, and includes a self-luminous photosensitive resin composition capable of securing excellent fluorescence efficiency characteristics by including a specific tetraazaporphyrin-based compound, a color conversion layer and a display manufactured using the same. The purpose is to provide a device.

The present invention relates to a dye; and a tetraazaporphyrin-based compound having aluminum (Al) or silicon (Si) as a central metal.

In addition, the present invention provides a color conversion layer characterized in that it is manufactured from the self-luminous photosensitive resin composition.

Additionally, the present invention provides a display device comprising the color conversion layer.

The self-luminous photosensitive resin composition according to the present invention, the color conversion layer and the display device manufactured using the same contain a tetraazaporphyrin-based compound having aluminum (Al) or silicon (Si) as a center metal, thereby providing excellent optical density. , O.D.), fluorescence efficiency, and luminous intensity characteristics.

Figure 1 is a schematic diagram showing the role of the color conversion layer in a display device.

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

The color conversion layer is intended to improve the reduced light efficiency caused by the use of a color filter, and is located adjacent to the color filter (see Figure 1), and corresponds to the red (R) and green (G) patterns of the color filter. It is made up of fine patterns. At this time, the fine pattern can be formed using a self-luminous photosensitive resin composition.

In particular, the self-luminous photosensitive resin composition according to the present invention may be characterized as including a dye and a tetraazaporphyrin-based compound having aluminum (Al) or silicon (Si) as a central metal as essential ingredients.

In addition, the self-luminous photosensitive resin composition according to the present invention may further include a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.

Each composition is described below.

Tetraazaporphyrin compounds

The self-luminous photosensitive resin composition according to the present invention contains a tetraazaporphyrin-based compound having aluminum or silicon as a central metal, and thus has excellent optical density (OD.), fluorescence efficiency, and luminous intensity. characteristics can be secured.

According to one embodiment of the present invention, the tetraazaporphyrin-based compound may be a compound represented by the following formula (1).

[Formula 1]

(In Formula 1, R ²⁶ to R ³³ are each independently hydrogen; unsubstituted phenyl group; alkyl group with 1 to 8 carbon atoms; alkoxy group with 1 to 8 carbon atoms; nitro group; halogen atom; cyano group; 1 to 8 carbon atoms Alkylamino group of 8; Aminoalkyl group of 1 to 8 carbon atoms; or alkoxy group of 1 to 8 carbon atoms, alkyl group of 1 to 8 carbon atoms, nitro group, halogen atom, alkylamino group of 1 to 8 carbon atoms, aminoalkyl group of 1 to 8 carbon atoms and a phenyl group having one or more substituents selected from cyano groups,

M is Al or Si with one or more ligands selected from ammonia, water, and halogen atoms, or without a ligand.)

The content of the tetraazaporphyrin-based compound in the self-luminous photosensitive resin composition of the present invention is preferably 0.001 to 15% by weight, more preferably 0.1 to 10% by weight, based on the total weight of the self-luminous photosensitive resin composition. . If the content of the tetraazaporphyrin-based compound is within the above range, it is preferable because it can exhibit excellent fluorescence efficiency. However, if the content of the tetraazaporphyrin-based compound exceeds the above range, it may reduce fluorescence and adversely affect fairness.

In this specification, “substituted or unsubstituted” means halogen group, nitrile group, nitro group, hydroxy group, alkyl group, cycloalkyl group, alkenyl group, alkoxy group, aryloxy group, thiol group, alkylthio group, arylthio group, sulfoxide group. 1 selected from the group consisting of group, alkylsulfoxy group, arylsulfoxy group, silyl group, boron group, arylamine group, aralkylamine group, alkylamine group, aryl group, arylalkyl group, arylalkenyl group, heterocyclic group and acetylene group. It means being substituted with one or more substituents or not having any substituents.

As used herein, “halogen group” means -F, -Cl, -Br or -I.

dyes

The dye included in the self-luminous photosensitive resin composition of the present invention may be a dye commonly used in the color conversion layer.

Additionally, the dye may be a fluorescent dye, preferably a red fluorescent dye, and more preferably a perylene bis-imide-based compound.

According to one embodiment of the present invention, the perylene bisimide-based compound may be a compound represented by the following formula (2).

[Formula 2]

(In 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 straight-chain or branched-chain alkyl group,

R3, R4, R5 and R6 are each independently a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted phenoxy group, a substituted or unsubstituted thiophenoxy group, or A substituent represented by the following formula (3), but R3, R4, R5 and R6 are not all the same.)

[Formula 3]

(In Formula 3, X1 and X5 are hydrogen atoms,

X2, X3 and X4 are each independently a hydrogen atom or a halogen atom, but at least one of X2,

Y is an oxygen atom or a sulfur atom.)

Additionally, the compound represented by Formula 2 may be one in which at least one halogen-substituted aryloxy group or thiophenoxy group is substituted.

The self-luminescent photosensitive resin composition containing the halogen-substituted aryloxy group or the perylene bisimide-based compound having at least one thiophenoxy group substituted can increase the fluorescence of the color conversion layer. In addition, by introducing an asymmetrical substituent to the perylene bisimide-based compound to induce structural distortion, the solubility in the solvent can be increased, thereby showing excellent chemical, thermal and optical stability, making it very suitable for process application. It has a beneficial effect.

According to another embodiment of the present invention, the perylene bisimide-based compound may be a compound represented by the following formula (4).

[Formula 4]

(In Formula 4, R1 and R2 are each independently a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted straight-chain alkyl group, or a substituted or unsubstituted branched-chain alkyl group. ,

R11, R12, R13, and R14 are each independently a halogen atom, a straight-chain or branched alkyl group with 1 to 10 carbon atoms, a haloalkyl group with 1 to 10 carbon atoms, a hydroxy group, an alkoxy group with 1 to 10 carbon atoms, and an ester group with 1 to 10 carbon atoms. and a substituent selected from an amine group, wherein at least one of R11, R12, R13 and R14 is different from the others in type or position of the substituent,

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 integers from 1 to 5.)

In addition, the compound represented by Formula 4 may be one in which any one of R11, R12, R13, and R14 is substituted at the para or meta position, and R1 or R2 is represented by Formula 5 below. It may be a substituent.

[Formula 5]

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

According to another embodiment of the present invention, the perylene bisimide-based compound may be any one of the compounds represented by the following formulas 4-1 to 4-12.

[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

[Formula 4-4]

[Formula 4-5]

[Formula 4-6]

[Formula 4-7]

[Formula 4-8]

[Formula 4-9]

[Formula 4-10]

[Formula 4-11]

[Formula 4-12]

The content of dye in the self-luminous photosensitive resin composition of the present invention 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. If the content of the dye is within the above range, it is advantageous in terms of fluorescence efficiency and fairness. If it exceeds the above range, it may reduce fluorescence efficiency and adversely affect fairness due to aggregation of the dye.

binder resin

The binder resin contained in the self-luminous photosensitive resin composition of the present invention usually has reactivity under the action of light or heat and alkali solubility, and acts as a dispersion medium for the coloring material. The binder resin contained in the self-luminous photosensitive resin composition of the present invention acts as a binder resin for the dye, and any binder resin soluble in the alkaline developer used in the development step for producing the color conversion layer can be used.

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

Examples of the carboxyl group-containing monomer include unsaturated carboxylic acids such as unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated tricarboxylic acids, etc., which have one or more carboxyl groups in the molecule. I can hear it. Here, examples of unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid. Examples of unsaturated dicarboxylic acids 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 include maleic anhydride, itaconic anhydride, and citraconic anhydride. In addition, the unsaturated polyhydric carboxylic acid may be its mono(2-methacryloyloxyalkyl) ester, for example, mono(2-acryloyloxyethyl) succinic acid, mono(2-methacryloyloxyethyl succinic acid), ), mono(2-acryloyloxyethyl) phthalate, mono(2-methacryloyloxyethyl) phthalate, etc. The unsaturated polycarboxylic acid may be a mono(meth)acrylate of the dicarboxylic polymer at both ends, and examples include ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, etc. . These carboxyl group-containing monomers can be used individually or in combination of two or more types.

Other monomers copolymerizable with the carboxyl group-containing monomer include, for example, styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, and m-methoxystyrene. Toxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p- aromatic vinyl compounds such as vinylbenzyl glycidyl ether and indene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butylacrylate, 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-hydroxypropyl acrylate Roxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate Latex, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate Crylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate Latex, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl Acrylate, dicyclopentadiethyl 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 such as aminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, and 3-dimethylaminopropyl methacrylate. acid aminoalkyl esters; Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and vinylidene cyanide; unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethyl acrylamide, and N-2-hydroxyethyl methacrylamide; Maleimide, benzylmaleimide, N-phenylmaleimide. Unsaturated imides such as N-cyclohexylmaleimide; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; and a monoacryloyl group or monomethacryloyl group at the end of the polymer molecule chain of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butylacrylate, poly-n-butyl methacrylate, and polysiloxane. Examples include large monomers with These monomers can be used individually or in combination of two or more types. In particular, as other monomers copolymerizable with the carboxyl group-containing monomer, bulky monomers such as monomers having a norbornyl skeleton, monomers having an adamantane skeleton, and monomers having a rosin skeleton are preferred because they tend to lower the relative dielectric constant value. .

The binder resin of the present invention preferably has an acid value in the range of 20 to 200 (KOH mg/g). If the acid value is in the above range, the solubility in the developer improves, so that the non-exposed portion is easily dissolved and the sensitivity increases, and as a result, the pattern of the exposed portion remains during development, which is preferable because the film remaining ratio can be improved.

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

In addition, the weight average molecular weight in terms of polystyrene (hereinafter simply referred to as 'weight average molecular weight') measured by gel permeation chromatography (GPC; using tetrahydrofuran as an elution solvent) is 3,000 to 200,000, preferably 5,000 to 100,000. Binder resins are preferred. When the molecular weight is within the above range, the hardness of the coating film is improved, the residual film rate is high, the solubility of non-exposed portions in the developer is excellent, and 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 is preferably 1.5 to 6.0, and more preferably 1.8 to 4.0. It is preferable that the molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] is 1.5 to 6.0 because developability is excellent.

The content of the binder resin of the present invention is usually in the range of 5 to 85% by weight, preferably 10 to 70% by weight, based on the total weight of solids in the self-luminous photosensitive resin composition. When the content of the binder resin is within the above range, the solubility in the developer is sufficient, so it is difficult for residues to be generated on the substrate in the non-pixel area during development, and it is difficult for film reduction in the pixel part of the exposed area to occur during development, so the non-pixel area is difficult to produce. This is preferable because it tends to have good missingness.

photopolymerizable compound

The photopolymerizable compound contained in the self-luminous photosensitive resin composition of the present invention is a compound that can be polymerized under the action of a photopolymerization initiator described later, and includes monofunctional monomers, difunctional monomers, and other polyfunctional monomers.

Specific examples of monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrroli. Examples include money, etc.

Specific examples of bifunctional monomers include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, Bis(acryloyloxyethyl)ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, etc. are mentioned.

Specific examples of other polyfunctional monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, Pentaerythritol hexa(meth)acrylate, etc. can be mentioned. Among these, polyfunctional monomers having two or more functions are preferably used.

The photopolymerizable compound is usually used in an amount of 5 to 50% by weight, preferably 7 to 45% by weight, based on the total weight of solids in the self-luminous photosensitive resin composition. When the content of the photopolymerizable compound is within the above range, it is preferable because the strength and smoothness of the pixel portion tend to be good.

photopolymerization initiator

The photopolymerization initiator used in the present invention preferably contains an acetophenone-based compound. Acetophenone-based compounds include, for example, 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- oligomers, etc., and preferably 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one. Additionally, photopolymerization initiators other than the acetophenone series can be used in combination. Photopolymerization initiators other than acetophenone series include active radical generators, sensitizers, and acid generators that generate active radicals by irradiating light. Examples of active radical generators include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and triazine-based compounds. Examples of benzoin-based compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoisobutyl ether. Examples of benzophenone-based compounds include benzophenone, o-benzoylmethyl benzoate, 4-phenylzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 3,3',4,4'-tetra ( t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc. are mentioned. Thioxanthone-based compounds include, for example, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro- 4-propoxythioxanthone, etc. can be mentioned. Triazine-based compounds include, for example, 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-tri Azine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl )-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino- 2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4dimethoxyphenyl)ethenyl]-1,3,5 -Triazine, etc. can be mentioned. Examples of the active radical generator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2,-bis(o-chlorophenyl)-4,4', 5,5'-tetra Phenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene Compounds, etc. can be used. Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate. Nate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, Onium salts such as diphenyl iodonium hexafluoroantimonate, nitrobenzyl tosylate, and benzoin tosylate can be mentioned. In addition, among the above compounds as active radical generators, there are compounds that generate acids simultaneously with active radicals. For example, triazine-based photopolymerization initiators are also used as acid generators.

The content of the photopolymerization initiator used in the self-luminous photosensitive resin composition according to the present invention is usually 0.1 to 40% by weight, preferably 1 to 30% by weight, based on the total solid weight of the binder resin and the photopolymerizable compound. When the content of the photopolymerization initiator is within the above range, it is preferable because the self-luminous photosensitive resin composition becomes highly sensitive and the strength of the pixel portion formed using this composition and the smoothness on the surface of the pixel portion tend to be good.

Furthermore, a photopolymerization initiation aid can be used in the present invention. A photopolymerization initiation aid may be used in combination with a photopolymerization initiator, and is a compound used to promote polymerization of a photopolymerizable compound whose polymerization has been initiated by the photopolymerization initiator. Examples of photopolymerization initiation aids include amine-based compounds, alkoxyanthracene-based compounds, and thioxanthone-based compounds. Amine-based compounds include, for example, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylamino benzoate. Ethyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzphenone (common name, Michler's ketone), 4,4'-bis(diethyl) Amino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, etc. are mentioned, and among these, 4,4'-bis(diethylamino)benzophenone is preferable. Alkoxyanthracene compounds include, for example, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. etc. can be mentioned. Thioxanthone-based compounds include, for example, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro- 4-propoxythioxanthone, etc. can be mentioned. There is no problem even if these photopolymerization initiation aids are used individually or in combination.

Additionally, a commercially available photopolymerization initiation aid can be used. Examples of the commercially available photopolymerization initiation aid include the brand name "EAB-F" (manufacturer: Hodogaya Chemical Co., Ltd.).

When using these photopolymerization initiation aids, the amount used is usually 10.0 mol or less, preferably 0.01 to 5.0 mol, per mole of photopolymerization initiator. When the amount of the photopolymerization initiation aid used is within the above range, it is preferable because the sensitivity of the self-luminous photosensitive resin composition increases and the productivity of the color conversion layer formed using this composition tends to improve.

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 colored photosensitive resin compositions can be used. Specific examples 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 dimethyl ether, diethylene glycol diethyl ether, and diethylene. Diethylene glycol dialkyl ethers such as glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol Alkylene glycol alkyl ether acetates such as monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene, methyl ethyl ketone, and acetone. , Ketones such as methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin, ethyl 3-ethoxypropionate, and 3-methoxy Ester, such as methyl propionate, and cyclic ester, such as γ-butyrolactone, are mentioned.

The above solvent is preferably an organic solvent with a boiling point of 100°C to 200°C in terms of coating and drying properties, and more preferably alkylene glycol alkyl ether acetate, ketone, or 3-ethoxypropionic acid. Ester such as ethyl or methyl 3-methoxypropionate can be used, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, 3-meth Methyl toxypropionate, etc. can be used. These solvents can be used individually or in mixture of two or more types.

The content of the solvent in the self-luminous photosensitive resin composition of the present invention 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 solvent content is within the above range, the applicability tends to be good when applied with a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes called a die coater), or inkjet. desirable.

Other additives

The self-luminous photosensitive resin composition of the present invention may optionally contain fillers, other polymer compounds, and pigment dispersants. It is also possible to include additives such as adhesion promoters, antioxidants, ultraviolet absorbers, and anti-agglomerates.

Specific examples of fillers include glass, silica, alumina, etc.

Other polymer compounds include curable resins such as epoxy resins and maleimide resins, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane. there is.

As the pigment dispersant, commercially available surfactants can be used, examples of which include silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, and amphoteric surfactants. These may be used individually or in combination of two or more types. Examples of the above surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl ethers, polyethylene glycol diesters, sorbitan fatty esters, fatty acid-modified polyesters, and tertiary amine-modified polyurethanes. , polyethylene imines, etc. In addition, product names include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products Co., Ltd.), MEGAFAC (manufactured by Dainipbon Ink Chemicals Co., Ltd.), Flourad (manufactured by Sumitomo 3M Co., Ltd.), Asahi guard, Surflon (manufactured by Asahi Glass Co., Ltd.), brush Examples include SOLSPERSE (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by EFKA Chemicals Co., Ltd.), and PB 821 (manufactured by Ajinomoto Co., Ltd.).

As the adhesion promoter, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminoprotriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2 -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyl Trimethoxysilane, etc. can be mentioned.

Specific examples of the antioxidant include 2,2'-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butyl-4-methylphenol, and the like. Specific examples of ultraviolet absorbers include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzothyriazole and alkoxybenzophenone. Specific examples of the anti-agglomeration agent include sodium polyacrylate.

The self-luminous photosensitive resin composition of the present invention can be manufactured, for example, by the following method. The dye is dissolved by mixing it with a solvent in advance. At this time, a pigment dispersant is used as needed, and part or all of the binder resin may be blended. To the obtained dispersion (hereinafter sometimes referred to as mill base), the remainder of the binder resin, the photopolymerizable compound and the photopolymerization initiator, other components used as needed, and additional solvents as necessary are further added to reach a predetermined concentration. The desired self-luminous photosensitive resin composition can be obtained.

color conversion layer

Additionally, the present invention provides a color conversion layer made from the self-luminous photosensitive resin composition.

When applied to a display device, the color conversion layer of the present invention emits light from a light source of the display device, so it can achieve superior light efficiency. In addition, since colored light is emitted, color reproducibility is better, and since light is emitted in all directions by photoluminescence, the viewing angle can also be improved.

More specifically, in a typical display device including a color conversion layer, white light passes through the color conversion layer to create color. In this process, part of the light is absorbed by the color conversion layer, which may reduce light efficiency. However, when it includes a color conversion layer made of the self-luminous photosensitive resin composition of the present invention, the color conversion layer self-lumines by light from a light source, so superior light efficiency can be realized.

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

The substrate may be the color conversion layer's own substrate, or may be a site where the color conversion layer is located in a display device, etc., and is not particularly limited. The substrate may be glass, silicon (Si), silicon oxide (SiOx), or a polymer substrate. 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 self-luminous photosensitive resin composition, exposing, developing, and thermally curing it 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. In such cases, when applied to a display device, the emission light of the light source is not particularly limited, but a light source that emits blue light can be used in terms of better color reproduction.

According to another embodiment 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 such a case, the pattern layer further includes a transparent pattern layer that does not contain quantum dot particles.

In the case where only two color pattern layers are provided, a light source that emits light with a wavelength representing the remaining colors not included can be used. For example, when it includes a red pattern layer and a green pattern layer, a light source that emits blue light can 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 emits blue light as it is and appears blue.

The color conversion layer including the above-described substrate and pattern layer may further include partitions formed between each pattern, and may further include a black matrix. In addition, it may further include a protective film formed on the pattern layer of the color conversion layer.

display device

Additionally, the present invention provides a display device including the color conversion layer.

The color conversion layer of the present invention can be applied to various image display devices such as electroluminescence display devices, plasma display devices, and field emission display devices, as well as ordinary liquid crystal 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 such cases, when applied to a display device, the emission light of the light source is not particularly limited, but in terms of better color reproduction, a light source that emits blue light can be preferably used.

According to another embodiment of the present invention, the display device of the present invention may be provided with a color conversion layer that includes only two color pattern layers among a red pattern layer, a green pattern layer, and a blue pattern layer. In such a case, the color conversion layer further includes a transparent pattern layer that does not contain quantum dot particles.

In the case where only two color pattern layers are provided, a light source that emits light with a wavelength representing the remaining colors not included can be used. For example, when it includes a red pattern layer and a green pattern layer, a light source that emits blue light can 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 emits blue light as it is and appears blue.

The display device of the present invention has excellent light efficiency, exhibits high luminance, 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 for illustrating the present invention, and the present invention is not limited by the following examples and may be modified and changed in various ways. The scope of the present invention will be determined by the technical spirit of the claims described later. In addition, “%” and “part” indicating content below are based on weight, unless specifically stated.

Synthesis Example 1

According to a method known in the literature (J. Am. Soc., 4839 (1952)), a tetraazaporphyrin compound represented by Chemical Formula 1-1 was synthesized as follows.

50 parts by weight of metal-free octaphenyl tetraazaporphyrin and 1.5 parts by weight of aluminum oxide were refluxed for 1.5 hours in the presence of 25 parts by weight of o-dichlorobenzene as a solvent. When the reaction was completed, the reaction mixture was refluxed in a hot state. After completion of the reaction, the resulting solid was cooled to room temperature, washed with hot water and ethanol, and then extracted using chlorobenzene. Subsequently, the extract was crystallized to obtain pure aluminum octaphenyl tetraazaporphyrin.

Synthesis Example 2

Pure silicon octaphenyl tetraazaporphyrin 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 aluminum oxide.

Comparative Synthesis Example 1

Pure manganese octaphenyl tetraazaporphyrin represented by Chemical Formula 1-3 was obtained in the same manner as in Synthesis Example 1, except that anhydrous manganese was used instead of aluminum oxide.

Comparative Synthesis Example 2

Pure copper octaphenyl tetraazaporphyrin represented by Chemical Formula 1-4 was obtained in the same manner as in Synthesis Example 1, except that copper nitrate was used instead of aluminum oxide.

Synthesis Example 3

1,6,7,12-tetrachloroperylene tetracarboxylic acid dianhydride (0.11 mol) and 2,6-diisopropylaniline (0.44 mol) were added to 1 L of propionic acid, then heated and incubated at 140°C for 5 hours. The response was maintained. Afterwards, the reaction solution was cooled to room temperature, the precipitate was filtered under reduced pressure, and washed with methanol. The filter was dispersed in water, maintained for 30 minutes, filtered under reduced pressure, and dispersed again in methanol, maintained for 30 minutes, and then filtered under reduced pressure. The filtrate was dried to obtain an intermediate compound (INT) with a yield of 80.5%.

As a result of MS (Mass Spectrometric) measurement of the formed intermediate compound using a MALDI-TOF measuring device, it was confirmed that the molecular weight was 848.16.

Synthesis Example 4: Synthesis of compound of 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 of 4-fluorophenol (0.04 mol) dissolved in N-methylpyrrolidone (88.7 g) was added to the reaction solution at 120°C for 2 hours. After maintaining the reaction 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. Then, the reaction solution was cooled to room temperature and discharged into 3L of distilled water. The purple precipitate thus produced was filtered under reduced pressure and washed with methanol. The filtrate was re-dissolved in methylene chloride (MC), filtered through silica to remove impurities, and recrystallized with MeOH to obtain the compound of Chemical Formula 4-1 in a yield of 40.4%, and the molecular weight was confirmed to be 1198.29.

Synthesis Example 5: Synthesis of compound of 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 of 2,4-(tert-butyl)phenol (0.04 mol) dissolved in N-methylpyrrolidone (88.7 g) was added to the reaction solution at 120°C for 2 hours. After maintaining the reaction 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. Then, the reaction solution was cooled to room temperature and discharged into 3L of distilled water. The purple precipitate thus produced was filtered under reduced pressure and washed with methanol. The filtrate was re-dissolved in methylene chloride (MC), filtered through silica to remove impurities, and recrystallized with MeOH to obtain the compound of Chemical Formula 4-3 in a yield of 37.0%, and the molecular weight was confirmed to be 1236.37.

Synthesis Example 6: Synthesis of compound of 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 of 4-butylparaben (0.04 mol) dissolved in N-methylpyrrolidone (88.7 g) was added to the reaction solution at 120°C for 2 hours. After maintaining the reaction 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. Then, the reaction solution was cooled to room temperature and discharged into 3L of distilled water. The purple precipitate thus produced was filtered under reduced pressure and washed with methanol. The filtrate was re-dissolved in methylene chloride (MC), filtered through silica to remove impurities, and recrystallized with MeOH to obtain the compound of Chemical Formula 4-7 in a yield of 68.7%, and the molecular weight was confirmed to be 1280.35.

Synthesis Example 7: Synthesis of compounds of 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 of 4-(tert-butyl)phenol (0.04 mol) dissolved in N-methylpyrrolidone (88.7 g) was added to the reaction solution at 120°C for 2 hours. After maintaining the reaction 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. Then, the reaction solution was cooled to room temperature and discharged into 3L of distilled water. The purple precipitate thus produced was filtered under reduced pressure and washed with methanol. The filtrate was re-dissolved in methylene chloride (MC), filtered through silica to remove impurities, and recrystallized with MeOH to obtain the compound of Chemical Formula 4-10 in a yield of 56.5%, and the molecular weight was confirmed to be 1370.21.

Synthesis Example 8: Synthesis of compound of 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 of 3-(trifluoromethyl)phenol (0.04 mol) dissolved in N-methylpyrrolidone (88.7 g) was added to the reaction solution at 120°C for 2 hours. After maintaining the reaction 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. Then, the reaction solution was cooled to room temperature and discharged into 3L of distilled water. The purple precipitate thus produced was filtered under reduced pressure and washed with methanol. The filtrate was re-dissolved in methylene chloride (MC), filtered through silica to remove impurities, and recrystallized with MeOH to obtain the compound of Formula 4-12 in a yield of 40.5%, and the molecular weight was confirmed to be 1248.29.

Manufacturing example: binder resin

A flask equipped with a stirrer, thermometer reflux cooling pipe, dropping lot, and nitrogen introduction pipe was prepared. As a monomer dropping lot, 74.8 g (0.20 mol) of benzylmaleimide, 43.2 g (0.30 mol) of acrylic acid, 118.0 g (0.50 mol) of vinyl toluene, 4 g of t-butylperoxy-2-ethylhexanoate, and propylene glycol monomethyl. 40 g of ether acetate (PGMEA) was added and mixed with stirring, and as a chain transfer agent dropping tank, 6 g of n-dodecanethiol and 24 g of PGMEA were added and mixed with stirring. Afterwards, 395 g of PGMEA was introduced into the flask, the atmosphere inside the flask was changed from air to nitrogen, and the temperature of the flask was raised to 90°C while stirring. Next, dropping of the monomer and chain transfer agent was started from the dropping lot. The dropping was carried out for 2 hours while maintaining the temperature at 90℃. After 1 hour, the temperature was raised to 110℃ and maintained for 3 hours. Then, a gas introduction tube was introduced and a mixed gas of oxygen/nitrogen = 5/95 (v/v) was added. Bubbling started. 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 0.8 g of triethylamine were added into the flask and reacted at 110°C for 8 hours to obtain a binder resin with a solid acid value of 70 mgKOH/g. The weight average molecular weight in terms of polystyrene measured by GPC was 16,000, and the molecular weight distribution (Mw/Mn) was 2.3.

Device: HLC-8120GPC (manufactured by Tosoh Corporation)

Column: TSK-GELG4000HXL + TSK-GELG2000HXL (serial connection)

Column temperature: 40℃

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0 mL/min

Injection volume: 50 μl

Detector: RI

Measured sample concentration: 0.6% by mass (solvent = tetrahydrofuran)

Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Co., Ltd.)

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

Examples 1 to 6 and Comparative Examples 1 to 3

Self-luminous photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 to 3 were prepared according to the composition and content shown in Table 1 below.

(Unit: parts by weight) Furtherance Example Comparative example One 2 3 4 5 6 One 2 3 tetraazaporphyrin TAP-1 0.4 0.4 0.4 0.4 0.4 TAP-2 0.4 TAP-3 0.4 TAP-4 0.4 dyes A-1 0.4 0.4 0.4 0.4 0.4 A-2 0.4 A-3 0.4 A-4 0.4 A-5 0.4 Binder Resin B 8.3 8.3 8.3 8.3 8.3 8.3 8.3 8.3 8.3 Photopolymerizable Compound C 8.45 8.45 8.45 8.45 8.45 8.45 8.45 8.45 8.45 photopolymerization initiator D-1 0.83 0.83 0.83 0.83 0.83 0.83 0.83 0.83 0.83 D-2 0.33 0.33 0.33 0.33 0.33 0.33 0.33 0.33 0.33 Solvent E 81.29 81.29 81.29 81.29 81.29 81.29 81.69 81.29 81.29

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: Binder resin of production example

C: Dipentaerythritol hexaacrylate (Kayarad DPHA: manufactured by Nippon Kayaku Co., Ltd.)

D-1: 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one (Irgacure 369; manufactured by Ciba Specialty Chemical)

D-2: 4,4'-bis(dimethylamino)benzphenone (EAB-F; manufactured by Hodogaya Chemical Co., Ltd.)

E: Propylene glycol monomethyl ether acetate (PGMEA)

Color conversion layer manufacturing example

A color conversion layer was prepared using the self-luminous photosensitive resin composition prepared in Examples 1 to 6 and Comparative Examples 1 to 3. That is, each self-luminous photosensitive resin composition was applied on a glass substrate by spin coating, then 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 onto the thin film. At this time, the ultraviolet light source was irradiated with an exposure dose of 40 mJ/cm2 (365 nm) under an atmospheric atmosphere using an ultra-high pressure mercury lamp (product name: USH-250D) manufactured by Ushio Denki Co., Ltd., and no special optical filter was used. The ultraviolet irradiated thin film was developed in a KOH aqueous developing solution of pH 12.5 using a spray developer for 60 seconds and then heated in a heating oven at 220°C for 20 minutes to prepare a pattern. The film thickness of the self-luminous color conversion layer pattern prepared above was 3.0 μm. The thickness of the color conversion layer can be variously controlled up to 500㎛.

Experimental example: Measurement of luminous intensity

The self-luminous color patterns with a thickness of 3.0 ㎛ prepared using the self-luminous photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 to 3 were measured using a quantum efficiency meter (QE-1000, manufactured by Otsuka Corporation), respectively. Photo Luminescence (PL) of the coated substrate was measured and listed in Table 2 below. It can be judged that the higher the measured luminescence intensity, the better the fluorescence efficiency characteristics.

division Luminous intensity (λ _max : 620) Example 1 4,500 Example 2 5,500 Example 3 4,700 Example 4 5,000 Example 5 5,100 Example 6 5,700 Comparative Example 1 3,000 Comparative Example 2 10 Comparative Example 3 150

Referring to Table 2, since Examples 1 to 6 have higher luminescence intensity values than Comparative Examples 1 to 3, the color conversion layer manufactured using the self-luminous photosensitive resin composition according to Examples 1 to 6 It can be seen that the fluorescence efficiency is superior to Comparative Examples 1 to 3.

Claims (12)

dyes; and a tetraazaporphyrin-based compound having aluminum (Al) or silicon (Si) as a central metal,
A self-luminous photosensitive resin composition, characterized in that the tetraazaporphyrin-based compound is a compound represented by the following formula (1):
[Formula 1]

(In Formula 1, R ²⁶ to R ³³ are each independently an unsubstituted phenyl group,
M is Al or Si with one or more ligands selected from ammonia, water, and halogen atoms, or without a ligand.)
delete The self-luminous photosensitive resin composition of 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 of 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 perylene bisimide-based compound is a compound represented by the following formula (2).
[Formula 2]

(In 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 straight-chain or branched-chain alkyl group,
R3, R4, R5 and R6 are each independently a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted phenoxy group, a substituted or unsubstituted thiophenoxy group, or Although the substituents are represented by the following formula (3), R3, R4, R5 and R6 are not all the same.
The substituents that the aryl group, heterocyclic group, straight or branched chain alkyl group, alkoxy group, phenoxy group or thiophenoxy group may have are halogen group, nitrile group, nitro group, hydroxy group, alkyl group, cycloalkyl group, alkenyl group, alkoxy group. group, aryloxy group, thiol group, alkylthio group, arylthio group, sulfoxy group, alkylsulfoxy group, arylsulfoxy group, silyl group, boron group, arylamine group, aralkylamine group, alkylamine group, aryl group, It is one or more selected from the group consisting of an arylalkyl group, an arylalkenyl group, a heterocyclic group, and an acetylene group.)
[Formula 3]

(In Formula 3, X1 and X5 are hydrogen atoms,
X2, X3 and X4 are each independently a hydrogen atom or a halogen atom, but at least one of X2,
Y is an oxygen atom or a sulfur atom.)
The self-luminous photosensitive resin composition according to claim 5, wherein the perylene bisimide-based compound is a compound represented by the following formula (4).
[Formula 4]

(In Formula 4, R1 and R2 are each independently a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted straight-chain alkyl group, or a substituted or unsubstituted branched-chain alkyl group. ,
R11, R12, R13, and R14 are each independently a halogen atom, a straight-chain or branched alkyl group with 1 to 10 carbon atoms, a haloalkyl group with 1 to 10 carbon atoms, a hydroxy group, an alkoxy group with 1 to 10 carbon atoms, and an ester group with 1 to 10 carbon atoms. and a substituent selected from an amine group, wherein at least one of R11, R12, R13 and R14 is different from the others in type or position of the substituent,
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 integers from 1 to 5.
Substituents that the aryl group, heterocyclic group, straight or branched chain alkyl group, alkoxy group, phenoxy group or thiophenoxy group may have are halogen group, nitrile group, nitro group, hydroxy group, alkyl group, cycloalkyl group, alkenyl group, alkoxy group. group, aryloxy group, thiol group, alkylthio group, arylthio group, sulfoxy group, alkylsulfoxy group, arylsulfoxy group, silyl group, boron group, arylamine group, aralkylamine group, alkylamine group, aryl group, It is one or more selected from the group consisting of an arylalkyl group, an arylalkenyl group, a heterocyclic group, and an acetylene group.)
The self-luminescent photosensitive resin composition according to claim 1, wherein the self-luminescent photosensitive resin composition is used to form a color conversion layer.
The self-luminescent photosensitive resin composition of claim 1, further comprising a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.
The method of claim 9, comprising: 5 to 85% by weight of binder resin based on the total weight of solids of the self-luminous photosensitive resin composition; and 5 to 50% by weight of a photopolymerizable compound,
Containing 0.1 to 40% by weight of a photopolymerization initiator based on the total solid weight of the binder resin and the photopolymerizable compound,
0.001 to 15% by weight of a tetraazaporphyrin-based compound based on the total weight of the self-luminous photosensitive resin composition; 0.001 to 30% by weight of dye; and 60 to 90% by weight of a solvent.
A color conversion layer, characterized in that it is manufactured from the self-luminous photosensitive resin composition according to any one of claims 1 to 10.
A display device comprising the color conversion layer of claim 11.