JP7251984B2 - Self-luminous photosensitive resin composition, color conversion layer and display device manufactured using the same - Google Patents

Description

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

Recently, the display industry has undergone a rapid change from cathode-ray tubes (CRTs) to plasma display panels (PDPs), organic light-emitting diodes (OLEDs), and liquid-crystal displays (LCDs). has been achieved. Among them, LCDs are widely used as display devices in almost all industries, and their application range continues to expand.

In the LCD, the white light generated from the backlight unit passes through the liquid crystal cell, the transmittance of which is adjusted, and the three primary colors emitted through the color filters of red, green, and blue are mixed. Full color is achieved.

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

As a substitute for solving the above problems, researches on backlight units using LEDs (Light Emitting Diodes) are actively being conducted at present. When LEDs are used as backlight units, they can exceed 100% of the NTSC (National Television System Committee) color gamut specification to provide consumers with more vivid image quality.

Therefore, in order to improve the efficiency of the backlight source in the same industry, efforts are being made to improve the light efficiency by changing the materials and structures of color filters and LCD panels. Due to the limit of , it is difficult to satisfy both color reproducibility and luminance characteristics at the same time, and there is a problem that a certain level cannot be exceeded.

The problem of poor color reproducibility can be overcome by increasing the light efficiency of the color filters, either by increasing the thickness of the color filters or by adding a color conversion layer (or light conversion layer) laminated to or in close proximity thereto. A method of introducing the

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

US Pat. No. 5,300,002 discloses a display that includes a light conversion portion having at least one phosphor that converts incident light in the blue or ultraviolet wavelength band to light in a predetermined wavelength band. However, there is still a drawback that the fluorescence efficiency of the light conversion section is low.

Patent Literature 2 discloses a method for manufacturing a color conversion filter using an ink jet method, in which a color conversion layer can be formed at a desired position without separately forming partition walls. By itself, the fluorescence efficiency is low, and the use of an organic EL material has the problem of being insoluble in general solvents.

Korean Patent Publication No. 10-2012-0048218 Korean Patent Publication No. 10-2010-0056437

The present invention has been made to solve the above-described problems of the prior art, and includes a self-luminous photosensitive resin composition that can ensure excellent fluorescence efficiency characteristics by containing a specific tetraazaporphyrin-based compound, An object of the present invention is to provide a color conversion layer and a display device manufactured using this.

The present invention provides a self-luminous photosensitive resin composition comprising a dye; and a tetraazaporphyrin compound having aluminum (Al) or silicon (Si) as a central metal.

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

Furthermore, the present invention provides a display device including 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 compound having aluminum (Al) or silicon (Si) as a central metal. , excellent optical density (OD), fluorescence efficiency and luminous intensity.

FIG. 4 is a schematic diagram showing the role of a color conversion layer in a display device;

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

The color conversion layer is for improving the reduced light efficiency caused by the use of the color filter, and is located adjacent to the color filter (see FIG. 1), and red (R) and green (G) of the color filter. It consists of a fine pattern so as to correspond to the pattern. At this time, the fine pattern may be formed using a self-luminous photosensitive resin composition.

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

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

Each composition will be described below.

Tetraazaporphyrin-based compound The self-luminous photosensitive resin composition according to the present invention contains a tetraazaporphyrin-based compound having aluminum or silicon as a central metal, thereby exhibiting excellent optical density (O.D.). D.), fluorescence efficiency and luminous intensity characteristics can be ensured.

According to one embodiment of the present invention, the tetraazaporphyrin-based compound may be a compound represented by Formula 1 below.

（前記化学式１において、Ｒ^２６～Ｒ^３３は、それぞれ独立に、水素；非置換のフェニル基；炭素数１～８のアルキル基；炭素数１～８のアルコキシ基；ニトロ基；ハロゲン原子；シアノ基；炭素数１～８のアルキルアミノ基；炭素数１～８のアミノアルキル基；または炭素数１～８のアルコキシ基、炭素数１～８のアルキル基、ニトロ基、ハロゲン原子、炭素数１～８のアルキルアミノ基、炭素数１～８のアミノアルキル基、およびシアノ基の中から選択された１つ以上の置換基を有するフェニル基であり、
Ｍは、アンモニア、水、およびハロゲン原子の中から選択された１つ以上のリガンドを有するか、リガンドを有しないＡｌまたはＳｉである。）

(In Chemical Formula 1, R ²⁶ to R ³³ are each independently hydrogen; an unsubstituted phenyl group; an alkyl group having 1 to 8 carbon atoms; an alkoxy group having 1 to 8 carbon atoms; a nitro group; a halogen atom; group; C1-8 alkylamino group; C1-8 aminoalkyl group; or C1-8 alkoxy group, C1-8 alkyl group, nitro group, halogen atom, C1 a phenyl group having one or more substituents selected from an alkylamino group having 1 to 8 carbon atoms, an aminoalkyl group having 1 to 8 carbon atoms, and a cyano group;
M is Al or Si with or without one or more ligands selected from among ammonia, water and halogen atoms. )

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 based on the total weight of the self-luminous photosensitive resin composition, and preferably 0.001 to 15% by weight. It is more preferably contained in an amount of 1 to 10% by weight. When the content of the tetraazaporphyrin-based compound is within the above range, excellent fluorescence efficiency can be obtained, and when the content of the tetraazaporphyrin-based compound exceeds the above range, the decrease in fluorescence and adverse effects on process performance are preferred. may affect

As used herein, "substituted or unsubstituted" means a halogen group, a nitrile group, a nitro group, a hydroxy group, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryloxy group, a thiol group, an alkylthio group, an arylthio group. , sulfoxy 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 substituted with one or more substituents selected from the group consisting of or without any substituents.

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

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

The dye may be a fluorescent dye, preferably a red fluorescent dye, more preferably a perylene bis-imide compound. can.

According to one embodiment of the present invention, the perylene bisimide-based compound may be a compound represented by Formula 2 below.

（前記化学式２において、Ｒ１およびＲ２は、それぞれ独立に、置換もしくは非置換のアリール基、置換もしくは非置換のヘテロ環基、または置換もしくは非置換の直鎖もしくは分枝鎖アルキル基であり、
Ｒ３、Ｒ４、Ｒ５およびＲ６は、それぞれ独立に、水素原子、ハロゲン原子、ヒドロキシ基、置換もしくは非置換の炭素数１～１０のアルコキシ基、置換もしくは非置換のフェノキシ基、置換もしくは非置換のチオフェノキシ基、または下記化学式３で表される置換基であり、かつＲ３、Ｒ４、Ｒ５およびＲ６がすべて同一ではない。）

(In the 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 hydroxy group, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted phenoxy group, a substituted or unsubstituted thio a phenoxy group or a substituent represented by the following chemical formula 3, and R3, R4, R5 and R6 are not all the same; )

（前記化学式３において、Ｘ１およびＸ５は、水素原子であり、
Ｘ２、Ｘ３およびＸ４は、それぞれ独立に、水素原子またはハロゲン原子であり、かつＸ２、Ｘ３およびＸ４のうちの少なくとも１つ以上は、ハロゲン原子であり、
Ｙは、酸素原子または硫黄原子である。）

(In the 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 or more of X2, X3 and X4 is a halogen atom,
Y is an oxygen atom or a sulfur atom. )

In addition, the compound represented by Formula 2 may be substituted with at least one halogen-substituted aryloxy group or thiophenoxy group.

The self-luminous photosensitive resin composition containing the perylene bisimide 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 asymmetrical substituent into the perylene bisimide-based compound to induce structural twisting, it is possible to increase the solubility in a solvent, resulting in excellent chemical, thermal and optical properties. It can exhibit stability and has a very beneficial effect on process applications.

According to another embodiment of the present invention, the perylene bisimide-based compound may be a compound represented by Formula 4 below.

（前記化学式４において、Ｒ１およびＲ２は、それぞれ独立に、置換もしくは非置換のアリール基、置換もしくは非置換のヘテロ環基、置換もしくは非置換の直鎖アルキル基、または置換もしくは非置換の分枝鎖アルキル基であり、
Ｒ１１、Ｒ１２、Ｒ１３およびＲ１４は、それぞれ独立に、ハロゲン原子、炭素数１～１０の直鎖または分枝鎖アルキル基、炭素数１～１０のハロアルキル基、ヒドロキシ基、炭素数１～１０のアルコキシ基、炭素数１～１０のエステル基、およびアミン基から選択される置換基であり、かつＲ１１、Ｒ１２、Ｒ１３およびＲ１４のうちの少なくとも１つは、残りと置換基の種類または置換基の位置が異なるものであり、
Ｙ_１、Ｙ_２、Ｙ_３およびＹ_４は、それぞれ独立に、酸素（Ｏ）原子または硫黄（Ｓ）原子であり、
ａ、ｂ、ｃおよびｄは、それぞれ独立に、１～５の整数である。）

(In the 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 branched is a chain alkyl group,
R11, R12, R13 and R14 each independently represents a halogen atom, a straight or branched chain alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a hydroxy group, or an alkoxy group having 1 to 10 carbon atoms. a substituent selected from a group, an ester group having 1 to 10 carbon atoms, and an amine group, and at least one of R11, R12, R13 and R14 is the type or position of the substituent with the rest are different and
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 1-5. )

In the compound represented by Formula 4, any one of R11, R12, R13 and R14 may be substituted at the para or meta position. The above R1 or R2 may be a substituent represented by Chemical Formula 5 below.

（前記化学式５において、Ｒ２１～Ｒ２５は、それぞれ独立に、水素原子、および置換もしくは非置換の炭素数１～５の直鎖または分枝鎖アルキル基から選択される置換基である。）

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

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

The content of the dye in the self-luminous photosensitive resin composition of the present invention is preferably 0.001 to 30% by weight, preferably 0.1 to 10% by weight, based on the total weight of the self-luminous photosensitive resin composition. % is more preferable. When the content of the dye is within the above range, it is advantageous in terms of fluorescence efficiency and processability. be.

Binder resin The binder resin contained in the self-luminous photosensitive resin composition of the present invention generally has reactivity by the action of light or heat and alkali solubility, and serves as a dispersion medium for the coloring material. works. The binder resin contained in the self-luminous photosensitive resin composition of the present invention acts as a binder resin for the dye and is a binder that is soluble in the alkaline developer used in the development step for the production of the color conversion layer. Any agent resin can be used.

Binder resins include, for example, copolymers of carboxyl group-containing monomers and other monomers copolymerizable with these monomers.

Examples of the carboxyl group-containing monomer include unsaturated polycarboxylic acids having one or more carboxyl groups in the molecule, such as unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated tricarboxylic acids. Saturated carboxylic acid and the like can be mentioned. 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 polycarboxylic acid may be an acid anhydride, and specific examples include maleic anhydride, itaconic anhydride, and citraconic anhydride. The unsaturated polycarboxylic acids may also be their mono(2-methacryloyloxyalkyl) esters, such as mono(2-acryloyloxyethyl) succinate, mono(2-methacryloyloxyethyl) succinate, Examples include mono(2-acryloyloxyethyl) phthalate, mono(2-methacryloyloxyethyl) phthalate, and the like. The unsaturated polycarboxylic acid may be a mono(meth)acrylate of a dicarboxy polymer at both ends thereof, such as ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. These carboxyl group-containing monomers can be used alone or in combination of two or more.

Examples of other monomers copolymerizable with the carboxyl group-containing monomer include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o -methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p - vinyl benzyl glycidyl ether, aromatic vinyl compounds such as indene; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate , n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2- Hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylates, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobol Nyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, adamantyl (meth)acrylate, norbornyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxy Unsaturated carboxylic acid esters such as propyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate , 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate. Carboxylic 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; vinyl methyl ether, vinyl ethyl ether , unsaturated ethers such as allyl glycidyl ether; acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinyl cyanide compounds such as vinylidene cyanide; acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide, Unsaturated amides such as N-2-hydroxyethyl methacrylamide; Unsaturated imides such as maleimide, benzylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide; Aliphatic conjugates such as 1,3-butadiene, isoprene, chloroprene Dienes; and polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, macromonomers having a monoacryloyl group or monomethacryloyl group at the end of the polymer molecular chain of polysiloxane Examples include body types. These monomers can be used either alone or in combination of two or more. In particular, bulky monomers such as monomers having a norbornyl skeleton, monomers having an adamantane skeleton, and monomers having a rosin skeleton are examples of other monomers copolymerizable with the carboxyl group-containing monomer. preferred because the body tends to lower the dielectric constant value.

The binder resin of the present invention preferably has an acid value in the range of 20 to 200 (mgKOH/g). If the acid value is within the above range, the solubility in the developer is improved, the non-exposed portion is easily dissolved, and the sensitivity is increased. ) can be improved.

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

In addition, the polystyrene equivalent weight average molecular weight (hereinafter simply referred to as "weight average molecular weight") measured by gel permeation chromatography (GPC; tetrahydrofuran is used as an elution solvent) is 3,000 to 200,000, preferably 5,000 to A 100,000 binder resin is 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 the non-exposed portion in the developer is excellent, and the resolution tends to be improved, which is preferable.

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

The content of the binder resin of the present invention is generally 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, and residue is less likely to occur on the substrate in the non-pixel portion during development, and film reduction in the pixel portion of the exposed portion is less likely to occur during development. Therefore, it is preferable because it tends to have good omission properties in non-pixel portions.

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 comprises a monofunctional monomer, Examples include bifunctional monomers and other polyfunctional monomers.

Specific examples of monofunctional monomers include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate and N-vinylpyrrolidone.

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, bisphenol Bis(acryloyloxyethyl)ether of A, 3-methylpentanediol di(meth)acrylate and the like.

Specific examples of other polyfunctional monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol. hexa(meth)acrylate and the like. Among these, polyfunctional monomers having two or more functionalities are preferably used.

The photopolymerizable compound is generally 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, the strength and smoothness of the pixel portion tend to be improved, which is preferable.

Photopolymerization initiator The photopolymerization initiator used in the present invention preferably contains an acetophenone compound. Examples of acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)butan-1-one, oligomers of 2-hydroxy-2-methyl[4-(1-methylvinyl)phenyl]propan-1-one, preferably 2-benzyl-2 -dimethylamino-1-(4-morpholinophenyl)butan-1-one and the like. In addition, photopolymerization initiators other than the acetophenone-based initiators can be used in combination. Examples of photopolymerization initiators other than acetophenone-based photoinitiators include active radical generators that generate active radicals upon irradiation with light, sensitizers, acid generators, and the like. Examples of active radical generators include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and triazine-based compounds. Benzoin-based compounds include, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoisobutyl ether. Examples of benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3',4,4'-tetra(t-butylperoxycarbonyl ) benzophenone, 2,4,6-trimethylbenzophenone, and the like. Thioxanthone compounds include, for example, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like. Examples of triazine compounds include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4- methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6 -[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]- 1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis( trichloromethyl)-6-[2-(3,4dimethoxyphenyl)ethenyl]-1,3,5-triazine and the like. Examples of the active radical generator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2′-bis(o-chlorophenyl)-4,4′,5,5′-tetraphenyl-1,2 '-Biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compounds and the like can be used. Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexa Onium salts such as fluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylates, benzoin tosylates, etc. is mentioned. As active radical generators, some of the above compounds generate acid at the same time as 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 wt. %, preferably 1 to 30% by weight. When the content of the photopolymerization initiator is within the above range, the sensitivity of the self-luminous photosensitive resin composition is increased, and the strength of the pixel portion formed using this composition and the smoothness of the surface of the pixel portion are improved. It is preferred because it tends to be better.

Furthermore, in the present invention, a photopolymerization initiation aid can be used. A photopolymerization initiation aid is sometimes used in combination with a photopolymerization initiator, and is a compound used to promote polymerization of a photopolymerizable compound initiated by the photopolymerization initiator. Examples of photopolymerization initiation aids include amine-based compounds, alkoxyanthracene-based compounds, and thioxanthone-based compounds. Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylaminoethyl benzoate. , 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl p-toluidine, 4,4'-bis(dimethylamino)benzphenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4, 4′-bis(ethylmethylamino)benzophenone and the like, and 4,4′-bis(diethylamino)benzophenone is particularly preferred. Examples of alkoxyanthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. . Thioxanthone compounds include, for example, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like. Such photopolymerization initiation aids may be used alone or in combination.

In addition, a commercially available photopolymerization initiation aid can be used, and examples of commercially available photopolymerization initiation aids include the trade name "EAB-F" [manufacturer: Hodogaya Chemical Industry Co., Ltd.]. be done.

When these photopolymerization initiation aids are used, the amount used is usually 10.0 mol or less, preferably 0.01 to 5.0 mol, per 1 mol of the photopolymerization initiator. When the amount of the photopolymerization initiation aid used is within the above range, the sensitivity of the self-luminous photosensitive resin composition tends to be further increased, and the productivity of the color conversion layer formed using this composition tends to be improved. so preferred.

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 thereof include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol di Diethylene glycol dialkyl ethers such as butyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl Alkylene glycol alkyl ether acetates such as acetate, aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene, ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone, ethanol, propanol, butanol, hexanol , cyclohexanol, ethylene glycol and glycerin, esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and cyclic esters such as γ-butyrolactone.

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

The content of the solvent in the self-luminous photosensitive resin composition of the present invention is generally 60-90% by weight, preferably 70-85% 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, the coatability is improved when coated with a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (also referred to as a die coater), or an inkjet. It is preferred because it tends to

Other Additives The self-luminous photosensitive resin composition of the present invention may contain fillers, other polymer compounds, pigment dispersants, adhesion promoters, antioxidants, ultraviolet absorbers, coagulants, if necessary. Additives such as inhibitors may also be included.

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

Specific examples of other polymer compounds include curable resins such as epoxy resins and maleimide resins, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ethers, polyfluoroalkyl acrylates, polyesters, and polyurethanes. etc.

As the pigment dispersant, a commercially available surfactant can be used, and examples thereof include silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, and amphoteric surfactants. . These can be used individually or in combination of 2 or more types, respectively. Examples of surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines. There are other product names such as KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tokem Products), MEGAFAC ( Dainippon Ink and Chemicals Co., Ltd.), Flourad (manufactured by Sumitomo 3M), Asahi guard, Surflon (manufactured by Asahi Glass Co., Ltd.), SOLSPERSE (manufactured by Asahi Glass Co., Ltd.) Zeneca Co., Ltd.), EFKA (manufactured by EFKA Chemicals), PB821 (manufactured by Ajinomoto Co., Inc.), and the like.

Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-amino ethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-ethoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like.

Specific examples of the antioxidant include 2,2′-thiobis(4-methyl-6-t-butylphenol), 2,6-di-<81>t-butyl-4-methylphenol, and the like. be done. Specific examples of UV absorbers include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole and alkoxybenzophenone. Specific examples of the aggregation inhibitor include sodium polyacrylate and the like.

The self-luminous photosensitive resin composition of the present invention can be produced, for example, by the following method. The dye is premixed with a solvent to dissolve. At this time, if necessary, a pigment dispersant is used, and part or all of the binder resin may be blended. The resulting dispersion (hereinafter sometimes referred to as millbase) contains the remainder of the binder resin, the photopolymerizable compound, and the photopolymerization initiator, other components used as necessary, and additional A desired self-luminous photosensitive resin composition can be obtained by further adding a solvent to a predetermined concentration.

Color conversion layer The present invention also provides a color conversion layer made of the self-luminous photosensitive resin composition.

When the color conversion layer of the present invention is applied to a display device, the display device emits light by the light from the light source, so that superior light efficiency can be achieved. 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 be improved.

More specifically, in a typical display device including a color conversion layer, white light is transmitted through the color conversion layer to achieve colors. Light efficiency may decrease. However, when the color conversion layer is made of the self-luminous photosensitive resin composition of the present invention, the color conversion layer emits light by itself according to the light from the light source, thereby achieving better light efficiency.

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

The substrate is not particularly limited and may be the substrate of the color conversion layer itself or the portion where the color conversion layer is located in a display device or the like. 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). and so on.

The pattern layer is a layer containing the self-luminous photosensitive resin composition of the present invention, and is a layer formed by applying the self-luminous photosensitive resin composition, exposing it in a predetermined pattern, developing and heat-curing it. good too.

The pattern layer formed of the self-luminous photosensitive resin composition includes 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. be prepared. When irradiated with light, the red patterned layer emits red light, the green patterned layer emits green light, and the blue patterned layer emits blue light. In that case, the emitted light of the light source is not particularly limited when applied to the display device, but a light source that emits blue light can be used in terms of better color reproducibility.

According to another embodiment of the present invention, the patterned layers may comprise only patterned layers of two colors among a red patterned layer, a green patterned layer and a blue patterned layer. In that case, the pattern layer further comprises a transparent pattern layer containing no quantum dot particles.

If only patterned layers of two colors are provided, a light source that emits light at wavelengths indicative of the remaining colors not included can be used. For example, when including a red patterned layer and a green patterned layer, a light source that emits blue light can be used. In that 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, showing blue.

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

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 can comprise a color conversion layer including a red patterned layer containing red quantum dot particles, a green patterned layer containing green quantum dot particles, and a blue patterned layer containing blue quantum dot particles. . In that case, the emitted light of the light source is not particularly limited when applied to the display device, but from the viewpoint of better color reproducibility, 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 also comprise a color conversion layer comprising only two colored pattern layers of the red patterned layer, the green patterned layer and the blue patterned layer. . In that case, the color conversion layer further comprises a transparent pattern layer containing no quantum dot particles.

If only patterned layers of two colors are provided, a light source that emits light at wavelengths indicative of the remaining colors not included can be used. For example, when including a red patterned layer and a green patterned layer, a light source that emits blue light can be used. In that case, the red quantum dot particles emit red light, the green quantum dot particles emit green light, and the transparent pattern layer transmits blue light as it is, showing blue.

INDUSTRIAL APPLICABILITY 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 intended to illustrate the present invention, and the present invention is not limited by the following examples, and can be variously modified and changed. The scope of the present invention is determined by the technical ideas of the claims to be described later. Further, hereinafter, "%" and "parts" indicating contents are based on weight unless otherwise specified.

Synthesis example 1
A tetraazaporphyrin compound represented by the following chemical formula 1-1 was synthesized by a method known in the literature (J. Am. Soc., 4839 (1952)).

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

Synthesis example 2
A pure silicon octaphenyltetraazaporphyrin 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 octaphenyltetraazaporphyrin 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-Tetrachloroperylenetetracarboxylic acid dianhydride (0.11 mol) and 2,6-diisopropylaniline (0.44 mol) were added to 1 L of propionic acid, and the temperature was raised to 140° C. for 5 hours. Maintained time response. After that, the reaction solution was cooled to room temperature, and the precipitate was filtered under reduced pressure and washed with water with methanol. The filter media were dispersed in water, maintained for 30 minutes, filtered under reduced pressure, dispersed again in methanol, maintained for 30 minutes, and filtered under reduced pressure. The filter cake was dried to obtain the intermediate compound (INT) in 80.5% yield.

As a result of MS (Mass Spectrometric) measurement using a MALDI-TOF measurement device, the intermediate compound thus formed was found to have a molecular weight of 848.16.

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

Potassium carbonate (0.04 mol) was added to a solution of the intermediate compound (0.04 mol) synthesized in Synthesis Example 3 and N-methylpyrrolidone (266.1 g), 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. After that, the reaction solution was cooled to room temperature and discharged into 3 L of distilled water. The purple precipitate thus produced was filtered under reduced pressure and washed with water with methanol. After redissolving the filtered body in methylene chloride (MC), impurities were removed by silica filtration, and recrystallization was carried out with MeOH to obtain the compound of formula 4-1 with a yield of 40.4%. , the molecular weight was confirmed to be 1198.29.

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

Potassium carbonate (0.04 mol) was added to a solution of the intermediate compound (0.04 mol) synthesized in Synthesis Example 3 and N-methylpyrrolidone (266.1 g), 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. After that, the reaction solution was cooled to room temperature and discharged into 3 L of distilled water. The purple precipitate thus produced was filtered under reduced pressure and washed with water with methanol. After redissolving the filtered body in methylene chloride (MC), impurities were removed by silica filtration, and recrystallization was carried out with MeOH to obtain the compound of formula 4-3 with a yield of 37.0%. , the molecular weight was confirmed to be 1236.37.

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

Potassium carbonate (0.04 mol) was added to a solution of the intermediate compound (0.04 mol) synthesized in Synthesis Example 3 and N-methylpyrrolidone (266.1 g), 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. After that, the reaction solution was cooled to room temperature and discharged into 3 L of distilled water. The purple precipitate thus produced was filtered under reduced pressure and washed with water with methanol. After redissolving the filtered body in methylene chloride (MC), impurities were removed by silica filtration, and recrystallization was carried out with MeOH to obtain the compound of formula 4-7 with a yield of 68.7%. , molecular weight of 1280.35.

Synthesis Example 7: Synthesis of Compounds of Chemical Formulas 4-10

Potassium carbonate (0.04 mol) was added to a solution of the intermediate compound (0.04 mol) synthesized in Synthesis Example 3 and N-methylpyrrolidone (266.1 g), 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. After that, the reaction solution was cooled to room temperature and discharged into 3 L of distilled water. The purple precipitate thus produced was filtered under reduced pressure and washed with water with methanol. After redissolving the filtered body in methylene chloride (MC), impurities were removed by silica filtration, and recrystallization was carried out with MeOH to obtain the compound of formula 4-10 with a yield of 56.5%. , molecular weight was determined to be 1370.21.

Synthesis Example 8: Synthesis of Compound of Chemical Formula 4-12

Potassium carbonate (0.04 mol) was added to a solution of the intermediate compound (0.04 mol) synthesized in Synthesis Example 3 and N-methylpyrrolidone (266.1 g), 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. After that, the reaction solution was cooled to room temperature and discharged into 3 L of distilled water. The purple precipitate thus produced was filtered under reduced pressure and washed with water with methanol. After redissolving the filtered body in methylene chloride (MC), impurities were removed by silica filtration, and recrystallization was carried out with MeOH to obtain the compound of formula 4-12 with a yield of 40.5%. , the molecular weight was confirmed to be 1248.29.

Preparation Example: Binder Resin A flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet was prepared. As a monomer dropping funnel, 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, t-butylperoxy-2-ethylhexa After adding 4 g of noate and 40 g of propylene glycol monomethyl ether acetate (PGMEA), stirring and mixing were prepared, and 6 g of n-dodecanethiol and 24 g of PGMEA were added and stirred and mixed to prepare a chain transfer agent dropping tank. After that, 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, the dropping of the monomer and the chain transfer agent was started from the dropping funnel. The dropping was continued for 2 hours while maintaining the temperature at 90° C. After 1 hour, the temperature was raised to 110° C. and maintained for 3 hours. v) Started bubbling of the gas mixture. Next, 28.4 g of glycidyl methacrylate [(0.10 mol), (33 mol % with respect to the carboxyl group of acrylic acid used in this reaction)], 2,2'-methylenebis(4-methyl-6-t -butylphenol) and 0.8 g of triethylamine were put into a flask and reacted at 110° C. for 8 hours to obtain a binder resin having a solid content acid value of 70 mgKOH/g. The polystyrene equivalent weight average molecular weight measured by GPC was 16,000, and the molecular weight distribution (Mw/Mn) was 2.3.

Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column: TSK-GELG4000HXL + TSK-GELG2000HXL (series connection)
Column temperature: 40°C
Mobile phase solvent: Tetrahydrofuran Flow rate: 1.0 ml/min Injection volume: 50 μl
Detector: RI
Measurement sample concentration: 0.6% by mass (solvent = tetrahydrofuran)
Calibration standard material: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

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

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

ＴＡＰ－１：合成例１
ＴＡＰ－２：合成例２
ＴＡＰ－３：比較合成例１
ＴＡＰ－４：比較合成例２
Ａ－１：合成例４
Ａ－２：合成例５
Ａ－３：合成例６
Ａ－４：合成例７
Ａ－５：合成例８
Ｂ：製造例の結合剤樹脂
Ｃ：ジペンタエリスリトールヘキサアクリレート（Ｋａｙａｒａｄ ＤＰＨＡ：日本化薬（株）製造）
Ｄ－１：２－ベンジル－２－ジメチルアミノ－１－（４－モルホリノフェニル）ブタン－１－オン（Ｉｒｇａｃｕｒｅ３６９；Ｃｉｂａ Ｓｐｅｃｉａｌｔｙ Ｃｈｅｍｉｃａｌ社製造）
Ｄ－２：４，４’－ビス（ジメチルアミノ）ベンズフェノン（ＥＡＢ－Ｆ；保土谷化学（株）製造）
Ｅ：プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）

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)

Preparation Example of Color Conversion Layer Using the self-luminous photosensitive resin compositions prepared in Examples 1-6 and Comparative Examples 1-3, color conversion layers were prepared. Specifically, each self-luminous photosensitive resin composition was applied onto a glass substrate by a spin coating method, placed on a heating plate, and maintained at a temperature of 100° C. for 3 minutes to form a thin film. Next, the thin film was irradiated with ultraviolet rays. At this time, an ultra-high pressure mercury lamp (trade name: USH-250D) manufactured by Ushio Inc. was used as the ultraviolet light source, and light was irradiated at an exposure amount of 40 mJ/cm ² (365 nm) in an air atmosphere. No filters were used. The UV-irradiated thin film was developed with a KOH aqueous solution developer of pH 12.5 for 60 seconds using a spray developer, and then heated in a heating oven at 220° C. for 20 minutes to form a pattern. The film thickness of the produced self-luminous color conversion layer pattern was 3.0 μm. The thickness of the color conversion layer can be variously controlled up to 500 μm.

Experimental Example: Measurement of Emission Intensity A self-luminous color pattern having a thickness of 3.0 μm produced using the self-luminous photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 to 3 was measured by quantum measurement. Using an efficiency measuring device (QE-1000, manufactured by Otsuka Co., Ltd.), luminescence (Photo Luminescence, PL) for each coated substrate was measured and shown in Table 2 below. It can be determined that the higher the measured emission intensity, the better the fluorescence efficiency characteristics.

Referring to Table 2, Examples 1 to 6 have higher luminous intensity than Comparative Examples 1 to 3. It can be seen that the fluorescence efficiency of the color conversion layer is superior to that of Comparative Examples 1-3.

Claims (7)

a dye; and a tetraazaporphyrin-based compound having aluminum (Al) or silicon (Si) as the central metal ,
The tetraazaporphyrin-based compound is a compound represented by the following chemical formula 1,
The self-luminous photosensitive resin composition , wherein the dye is a compound represented by Formula 2 below .

(In Chemical Formula 1, R ²⁶ to R ³³ are each independently hydrogen; an unsubstituted phenyl group; an alkyl group having 1 to 8 carbon atoms; an alkoxy group having 1 to 8 carbon atoms; a nitro group; a halogen atom; group; C1-8 alkylamino group; C1-8 aminoalkyl group; or C1-8 alkoxy group, C1-8 alkyl group, nitro group, halogen atom, C1 a phenyl group having one or more substituents selected from an alkylamino group having 1 to 8 carbon atoms, an aminoalkyl group having 1 to 8 carbon atoms, and a cyano group;
M is Al or Si with or without one or more ligands selected from among ammonia, water and halogen atoms. )

(In the 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 hydroxy group, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted phenoxy group, a substituted or unsubstituted thio a phenoxy group or a substituent represented by the following chemical formula 3, and R3, R4, R5 and R6 are not all the same; )

(In the 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 or more of X2, X3 and X4 is a halogen atom,
Y is an oxygen atom or a sulfur atom. ) The self-luminous photosensitive resin composition of claim 1 , wherein the dye is a compound represented by Formula 4 below.

(In the 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 branched is a chain alkyl group,
R11, R12, R13 and R14 each independently represents a halogen atom, a straight or branched chain alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a hydroxy group, or an alkoxy group having 1 to 10 carbon atoms. a substituent selected from a group, an ester group having 1 to 10 carbon atoms, and an amine group, and at least one of R11, R12, R13 and R14 is the type or position of the substituent with the rest are different and
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 1-5. ) 2. The self-luminous photosensitive resin composition according to claim 1, wherein the self-luminous photosensitive resin composition is used for forming a color conversion layer. The self-luminous photosensitive resin composition of claim 1, further comprising a binder resin, a photopolymerizable compound, a photoinitiator, and a solvent. 5 to 85% by weight of a binder resin; and 5 to 50% by weight of a photopolymerizable compound, based on the total solid weight of the self-luminous photosensitive resin composition
0.1 to 40% by weight of a photopolymerization initiator based on the total weight of the solid content of the binder resin and the photopolymerizable compound,
0.001 to 15% by weight of a tetraazaporphyrin compound; 0.001 to 30% by weight of a dye; and 60 to 90% by weight of a solvent, based on the total weight of the self-luminous photosensitive resin composition. The self-luminous photosensitive resin composition according to claim 4 . A color conversion layer produced from the self-luminous photosensitive resin composition according to any one of claims 1 to 5 . A display device comprising the color conversion layer according to claim 6 .

Images