TWI675090B - Self emission type photosensitive resin composition, color filter manufactured using thereof and image display device having the same - Google Patents

Abstract

The present invention relates to a photosensitive resin composition, a color filter and an image display device including the photosensitive resin composition, and more particularly, the present invention relates to a photopolymerization initiator including a quantum dot, an antioxidant, a photopolymerizable compound, and the like. Agents, alkali-soluble resins, and solvents, and the antioxidant contains two or more compounds of different kinds selected from phenolic compounds, phosphorus compounds, and sulfur compounds, which can be produced, particularly after the hard-baking process. A photosensitive resin composition for a color filter that reduces the light-emitting properties of quantum dots and improves color reproducibility and brightness.

Description

Self-luminous photosensitive resin composition, color filter, and image display device

The present invention relates to a self-luminous photosensitive resin composition capable of maintaining luminous intensity without lowering light emission characteristics, a color filter and an image display device including the self-luminous photosensitive resin composition.

The display industry has rapidly changed from a cathode-ray tube (CRT) to a flat-panel display represented by a plasma display panel (PDP), an organic light-emitting diode (OLED), and a liquid-crystal display (LCD). Among them, LCDs are widely used in image display devices used in almost all industries due to their advantages such as thinness and lightness, excellent resolution, and low power consumption. It is expected that a larger market will be expanded in the future.

For LCD, the white light generated by the light source passes through the liquid crystal cell while adjusting the light transmittance, and the three primary colors from the red, green, and blue color filters are mixed to achieve full color.

The color filter is a thin film type optical component that extracts three colors of red, green, and blue from white light to form a fine pixel unit, and the size of one pixel is about tens to hundreds of microns. For the boundaries between pixels Partially shading, this color filter has a black matrix layer laminated on a transparent substrate in order to form a fixed pattern, and a plurality of colors (usually red (R), green (G)) are arranged in a predetermined order in order to form each pixel. And blue (B)).

Generally, a color filter is manufactured by coating three or more hue phases on a transparent substrate by a dyeing method, a plating method, a printing method, a pigment dispersion method, or the like. Recently, a pigment dispersion method using a pigment-dispersed photosensitive resin has become mainstream.

The pigment dispersion method, which is one of the methods for implementing a color filter, is performed by repeatedly coating a transparent substrate that provides a black matrix with a colorant and an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, an epoxy resin, a solvent, The photosensitive resin composition of other additives is a method of forming a colored film by exposing a pattern to be patterned, and then removing a non-exposed part with a solvent, followed by thermal curing. This pigment dispersion method is actively used in the manufacture of LCDs such as mobile phones, notebook computers, monitors, and televisions.

In recent years, a photosensitive resin composition for a color filter using a pigment dispersion method having various advantages is demanding not only excellent pattern characteristics and high color reproducibility, but also further improvement in performance such as high brightness and high contrast.

However, color reproduction is achieved by the light irradiated by the light source passing through the color filter, but since part of the light is absorbed by the color filter in this process, the light efficiency is reduced, and as a color filter, perfection is achieved through pigment characteristics There are fundamental limitations in color reproduction.

Accordingly, Korean Laid-Open Patent No. 10-2012-112188 (published on October 11, 2012) provides coloring for color filters with excellent flowability and stability Composition, and using a red composition with high brightness and contrast to form a color filter with good color characteristics and excellent heat resistance, a colorant (a), a resin (b) containing a benzimidazolone, A red coloring composition and a color filter for a color filter of the resin-type dispersant (c) and the solvent (d) having an acidic substituent. This prior art has a problem of reduced light efficiency.

The quantum dots emit light by a light source and are used to generate light in the visible and infrared regions. The quantum dots are smaller than the bulk exciton Bohr radius, and are small crystals of II-IV, III-V, IV-VI materials, which usually have a diameter of 1 nm to 20 nm. Due to the quantum confinement effect, the energy difference between the electronic states of the quantum dots is a function of both the composition and the physical size of the quantum dots. Therefore, the optical and electronic properties of the quantum dots can be adjusted and adjusted by changing the physical size of the quantum dots.

The quantum dot absorbs a wavelength shorter than the absorption onset wavelength, and emits light at the absorption onset wavelength. The bandwidth of the emission spectrum of quantum dots is related to temperature-dependent Doppler broadening, Heisenberg Uncertainty Principle, and the size distribution of quantum dots. In the provided quantum dots, the emission bandwidth of the quantum dots can be controlled by changing the size. Therefore, quantum dots can generate an unattainable color range with ordinary dyes and pigments.

However, quantum dots are essentially non-scattering particles due to the size of the nanoscale. Therefore, when light passes through a color filter including quantum dots, it has a very short optical path compared to the case of other dyes and pigments. Based on the insufficient thickness of the color filter, most of the light is absorbed by the quantum dots. To this end, it is proposed to adjust the thickness of color filters, increase the concentration of quantum dots, and introduce scattering particles. Methods, etc., but there is a problem in terms of color uniformity when adjusting thickness or density.

Korean Patent Publication No. 2009-0036373 discloses that by replacing a color filter of a liquid crystal display device with a light-emitting layer composed of quantum dot fluorescent light, the light-emitting efficiency can be improved and display quality can be improved. However, radicals generated in a hard baking process performed during the manufacture of a color filter oxidize the surface of the quantum dots, resulting in a problem that the light emitting characteristics are reduced.

Patent literature

Patent Document 1: Korean Published Patent No. 2010-0112188

Patent Document 2: Korean Published Patent No. 2009-0036373

For this reason, in the color filter using quantum dots, the applicant conducted a multi-angle study in order to maintain the luminous intensity without reducing the luminous characteristics, and confirmed that the use of antioxidants but the use of two or more different from each other In order to reduce the generation of free radicals, the antioxidant can maintain a high level of luminous intensity, thereby completing the present invention.

Therefore, an object of the present invention is to provide a self-luminous photosensitive resin composition capable of maintaining light emission intensity even after a hard baking step.

Another object of the present invention is to provide an image display device capable of realizing high-quality vivid image quality by including a color filter containing the self-luminous resin composition.

In order to achieve the above object, a self-luminous photosensitive resin composition according to an embodiment of the present invention includes a quantum dot, an antioxidant, a photopolymerizable compound, a photopolymerization initiator, an alkali-soluble resin, and a solvent. The oxidizing agent includes two or more kinds of compounds different from each other selected from phenol-based compounds, phosphorus-based compounds, and sulfur-based compounds.

The antioxidant may be a combination of a phenolic compound and a phosphorus compound, a combination of a phenolic compound and a sulfur compound, a combination of a phosphorus compound and a sulfur compound, or a combination of a phenolic compound, a phosphorus compound and a sulfur compound.

The present invention is also characterized by a color filter manufactured from the self-luminous photosensitive resin composition and an image display device including the color filter.

The self-luminous photosensitive resin composition proposed in the present invention can solve the problem of a decrease in the luminous intensity of quantum dots that occurs after the conventional hard-baking process. That is, the aforementioned composition does not cause a significant reduction in luminous intensity after the hard baking step, and has a high luminous intensity maintenance ratio.

The color filter using the self-luminous photosensitive resin composition is excellent in fine pattern formation. The image display device incorporating the color filter maintains high brightness, ensures excellent color reproduction characteristics and high light efficiency, and can realize vivid colors. Quality.

FIG. 1 is a graph showing the luminous intensity and luminous intensity maintenance ratio (%) of the self-luminous photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 to 5.

detailed description

The present invention provides a self-color filter for an image display device. Luminescent photosensitive resin composition.

In particular, the present invention is characterized in that, in the composition of the color filter, quantum dots and antioxidants are necessary components, and two or more different kinds of antioxidants are mixed and used as the antioxidant. This solves the problem of lowering the luminous efficiency of the quantum dots that occurs after the conventional hard-baking process, and the overall light efficiency of the color filter can be improved by using the quantum dots. In addition, by manufacturing a pixel of a color filter from the self-luminous photosensitive resin composition, an advantage that a fine pattern can be easily formed is secured.

The self-luminous photosensitive resin composition of the present invention includes a quantum dot, an antioxidant, and a photopolymerizable compound, a photopolymerization initiator, an alkali-soluble resin, and a solvent.

Hereinafter, each component is demonstrated.

Quantum dots are nano-sized semiconductor substances. Atoms constitute molecules, and molecules form aggregates of small molecules called clusters to form nanoparticles. However, when such nanoparticles exhibit semiconductor characteristics, they are called quantum dots.

The quantum dot receives energy from the outside to reach a floating state, and releases energy based on its corresponding energy band gap.

The self-luminous photosensitive resin composition of the present invention contains such a quantum dot, and a color filter manufactured therefrom can emit light (photoluminescence) by irradiating light.

In an ordinary image display device including a color filter, white light passes through the color filter to realize color, but since a part of the light is absorbed by the color filter in this process, the light efficiency is reduced.

However, when the color filter manufactured from the self-luminous photosensitive resin composition of the present invention is included, the color filter emits light by the light of the light source. And can achieve more excellent light efficiency.

In addition, since light having a hue is emitted, color reproducibility is more excellent, and light is emitted in all directions by photoluminescence, so that the viewing angle can also be improved.

The quantum dot particle of the present invention is not particularly limited as long as it is a quantum dot particle that can emit light by light excitation. For example, a group II-IV semiconductor compound, a group III-V semiconductor compound, a group IV-VI semiconductor compound, or a group IV can be selected. Elements or compounds containing them, and combinations thereof. They can be used alone or in combination of two or more.

The aforementioned II-IV semiconductor compounds may be selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, and mixtures thereof; CdSeS, CdSeTe, CdSTe, ZnSeS Three-element compounds selected from the group consisting of ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HfZnSe, HgZnTe, and mixtures thereof; and CdZnSeS, CdZneS, CdZne In the group consisting of four-element compounds selected from the group consisting of CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, and mixtures thereof, the aforementioned III-V semiconductor compounds may be selected from the group consisting of GaN, GaP, GaAs, GaSb, AlN, AlP, Two-element compounds selected from the group consisting of AlAs, AlSb, InN, InP, InAs, InSb and their mixtures; GaNP, GaAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb Three-element compounds selected from the group consisting of, InPAs, InPSb, GaAlNP, and mixtures thereof; and GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, In the group consisting of four-element compounds selected from the group consisting of GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, and mixtures thereof, the aforementioned IV-VI semiconductor compounds may be selected from the group consisting of SnS, SnSe, and SnTe. Selected from the group consisting of PbS, PbSe, PbTe, and mixtures thereof; two-element compounds selected from the group consisting of SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, and mixtures thereof ; And in the group consisting of four-element compounds selected from the group consisting of SnPbSSe, SnPbSeTe, SnPbSTe, and mixtures thereof, the group IV element or a compound containing the same can be selected from the group consisting of Si, Ge, and mixtures thereof Elemental compounds; and two-element compounds selected from the group consisting of SiC, SiGe, and mixtures thereof.

In addition, the quantum dot particles may have a homogeneous single structure, a dual structure such as a core-shell, a gradient structure, or a mixed structure thereof.

In the dual structure of the core-shell, the substances constituting the core and the shell, respectively, may be composed of the aforementioned semiconductor compounds different from each other. For example, the aforementioned core may include a member selected from the group consisting of CdSe, CdS, ZnS, ZnSe, ZnTe, CdTe, CdSeTe, CdZnS, PbSe, HgInZnS, HgS, HgSe, HgTe, GaN, GaP, GaAs, InP, InS, and ZnO More than one substance, but not limited to this. The aforementioned shell may include one or more substances selected from the group consisting of CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, and HgSe, but is not limited thereto.

In combination with a photosensitive resin used in the manufacture of ordinary color filters In order to achieve the hue, objects include colorants such as red, green, and blue. Similarly, photoluminescent quantum dot particles are also divided into red quantum dot particles, green quantum dot particles, and blue quantum dot particles. The quantum dot particles of the present invention may be red. Quantum dot particles, green quantum dot particles, or blue quantum dot particles.

The diameter of the quantum dot particles of the present invention is not particularly limited.

The aforementioned red, green, and blue quantum dot particles can be classified based on particle diameters, and the particle diameters become smaller in the order of red, green, and blue. Specifically, the particle size of the red quantum dot particles may be 5 nm to 10 nm, the particle size of the green quantum dot particles may be more than 3 nm to 5 nm, and the blue quantum dot particles may be 1 nm to 3 nm.

When light is irradiated, red quantum dot particles emit red light, green quantum dot particles emit green light, and blue quantum dot particles generate blue light.

The aforementioned quantum dots can be synthesized by a wet chemical process, an organometallic chemical deposition process, or a molecular beam epitaxy process. The wet chemical process is a method of growing a particle by placing a precursor substance in an organic solvent. During crystal growth, in order to allow the organic solvent to naturally dispose on the surface of the quantum dot crystals to act as a dispersant, thereby adjusting the crystal growth, the aforementioned vapor deposition methods such as organic metal chemical deposition (MOCVD) or molecular beam epitaxy (MBE) can be used to Simple and inexpensive process to control the growth of nanoparticles.

The content of the quantum dots of the present invention is not particularly limited, and may be 3 to 80% by weight, and preferably 5 to 70% by weight, relative to the total weight of the solid content of the self-luminous photosensitive resin composition. At this time, if the content is less than 3% by weight, the luminous efficiency is only a little, and if it exceeds 80% by weight, the content of other components is relatively insufficient, and there is a problem that it is difficult to form a pixel pattern.

Together with the aforementioned quantum dots, the antioxidant constituting a feature of the present invention is used to increase the luminous efficiency of the aforementioned quantum dots. The light irradiated by the light source enters the color filter at a critical angle. However, at this time, the incident light and the auto-emitted light emitted by the quantum dots and the free radicals meet at the same time when they meet with the radicals, and the desired level of luminous intensity cannot be obtained. This problem is further severe in the hard baking process. Therefore, in order to obtain a predetermined luminous intensity, even if each composition is designed, it is impossible to prevent a reduction in the luminous efficiency of the quantum dots generated in the manufacturing process.

For this reason, in the present invention, two or more antioxidants are used. However, by using different types of antioxidants in combination, it is possible to prevent the quantum dot light emission efficiency from being lowered due to the aforementioned free radical problem, and to make the color filter finally manufactured. The quantum dot's luminous intensity is maintained above a certain level.

The antioxidant may include two or more kinds selected from the group consisting of a phenol compound, a phosphorus compound, and a sulfur compound, and a phenol compound-phosphorus compound, a phenol compound-sulfur compound, and a phosphorus compound-sulfur may be used. Compound, or phenolic compound-phosphorus compound-sulfur compound. Such a combination of different types of antioxidants can further enhance the aforementioned effects, and can ensure more excellent effects than when two or more types of antioxidants of the same type are used alone or in combination.

The type of the phenolic antioxidant is not particularly limited, and specific examples include 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propanyloxy]- 1,1-dimethylethoxy] -2,4,8,10-tetraoxaspiro [5.5] undecane, pentaerythritol tetra [3- (3,5-di-tert-butyl-4-hydroxybenzene) Propyl) propionate], 1,3,5-trimethyl-2,4,6-tris (3 ', 5'-di-tert-butyl-4-hydroxybenzyl) benzene, triethylene glycol bis [ 3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-tert-butyl-3-methyl Phenol), tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethyl) Benzyl) isocyanurate, 1,6-hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2-thiodiimide Ethylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy -Hydrocinnamidine), 1,3,5-trimethyl-2,4,6-tri (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 2,4-bis ((octyl Thio) methyl] -O-cresol, 1,6-hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl [3 -(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 4,4'-butylene Bis (3-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5- Tris (4-hydroxybenzyl) benzene and tetrakis [methylene-3- (3,5'-di-tert-butyl-4'-hydroxyphenylpropionate)] methane and the like.

Among them, 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propanyloxy] -1,1 is preferable in terms of heat resistance and heat discoloration prevention. -Dimethylethoxy] -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,3,5-trimethyl-2,4,6-tri (3 ', 5 '-Di-tert-butyl-4-hydroxybenzyl) benzene, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], triethylene glycol bis [3- ( 3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-tert-butyl-3-methylphenol), tris (3,5- Di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate , 1,6-hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2-thiodiethylenebis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamidine), 1, 3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene and 2,4-bis [(octylthio) methyl] -O- Cresol and so on.

Commercially available products include Irganox 1010 (manufactured by BASF), Sumilizer BBM-S (manufactured by Sumitomo Chemical), ADK STAB AO-80 (manufactured by Adeka), Sumilizer GP (manufactured by Sumitomo Chemical), Irganox 1035 (manufactured by BASF), and the like.

The type of the phosphorus-based antioxidant is not particularly limited, and specific examples include 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa -3,9-Diphosphaspiro [5.5] undecane (3,9- (2,6- -tert- -4- ) -2,4,8,10- -3,9- [5.5] ), Diisodecyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, 2,4,8,10-tetrakis (1,1-dimethylethyl) ) -6-[(2-ethylhexyl) oxy] -12H-dibenzo [d, g] [1,3,2] dioxophosphoheptyl (2,2'- (4,6- -t- 1- )(2- ) ), 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenzo [d, f] [1,3,2] Dioxphosphathene, triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, 4,4'-butylene bis (3 -Methyl-6-tert-butylphenylbistridecyl) phosphite, octadecyl phosphite, tris (nonylphenyl) phosphite, 9,10-dihydro-9-oxyl Hetero-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-tert-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene- 10-oxide, 10-decoxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris (2,4-di-tert-butylphenyl) phosphite Cyclic neopentane tetrayl bis (2,4-di-tert-butylphenyl) phosphite, cyclic neopentane tetrayl bis (2,6-di-tert-butylphenyl) phosphite, 2 , 2-methylenebis (4,6-di-tert-butylphenyl) octylphosphite, tris (2,4-di-tert-butylphenyl) phosphite, 4,4 '-[1, 1'-biphenyl] ylidene diphosphonic acid-tetra [2,4-di-tert-butylphenyl] ester ( (2,4- -t- ) [1,1- ] -4,4'- ), Bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl phosphonate and the like.

Among these phosphorus-based antioxidants, 2,4,8,10-tetra (1,1-dimethylethyl) -6-[(2-ethylhexyl) oxy] is preferred in terms of heat resistance and heat discoloration prevention. -12H-dibenzo [d, g] [1,3,2] dioxphosphathene, 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2 , 4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane and 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propane Oxy] -2,4,8,10-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxophosphoheptaline and the like.

The type of the sulfur-based antioxidant is not particularly limited, and specific examples include 2,2-bis ({[3- (dodecylthio) propanyl] oxy} methyl) -1,3-propanediyl -Bis [3- (dodecylthio) propionate] (2,2- ({[3- ( ) ] } ) -1,3- - [3- ( ) ]), 2-mercaptobenzimidazole, 3,3'-thiodipropionate didodecyl ester, 3,3'-thiodipropionate ditetradecyl ester, 3,3'-sulfur Dioctadecyl dipropionate, pentaerythritol tetrakis (3-dodecylthiopropionate), 2-mercaptobenzimidazole and the like.

Among these sulfur-based antioxidants, 2,2-bis ({[3- (dodecylthio) propylamidino] oxy} methyl) -1,3-propane is preferred in terms of heat resistance and heat discoloration prevention. Diyl-bis [3- (dodecylthio) propionate], 2-mercaptobenzimidazole, and the like.

The antioxidant is a solid with respect to the self-luminous photosensitive resin composition The total weight of the ingredients may be 0.1 to 10% by weight, preferably 0.5 to 5% by weight. At this time, if the content is less than the aforementioned range, the aforementioned effect cannot be ensured, that is, the suppression effect of the reduction of the luminous efficiency of the quantum dots after the hard-baking process. Conversely, if the content exceeds the aforementioned range, it may be due to the Pattern disconnection occurs, so it is appropriately used within the aforementioned range.

Along with the quantum dot and the antioxidant, the self-luminous photosensitive resin composition of the present invention further contains a photopolymerizable compound, a photopolymerization initiator, an alkali-soluble resin, and a solvent.

Hereinafter, each component will be described in detail.

The photopolymerizable compound of the present invention is a polymerizable compound by the action of light or a photopolymerization initiator described later, and examples thereof include monofunctional monomers, difunctional monomers, and other polyfunctional monomers. They can be used alone or in combination of two or more.

Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropylacrylate, 2-ethylhexylcarbitol acrylate, and acrylic-2. -Hydroxyethyl, N-vinylpyrrolidone and the like. Specific examples of the difunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and Ethylene glycol di (meth) acrylate, bisphenol A (acryloxyethyl) ether, 3-methyl-pentanediol di (meth) acrylate, propylene glycol dimethacrylate, polyurethane (formaldehyde) Group) acrylate and the like.

Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, and propoxylated trimethylol Propane tri (meth) acrylate, pentaerythritol Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol pentaacrylate succinate monoester, and the like.

The content of the photopolymerizable compound of the present invention is not particularly limited, and is, for example, 5 to 70% by weight, and preferably 7 to 45% by weight based on the total weight of the solid content of the self-luminous photosensitive resin composition. When it is within the aforementioned range, a pixel pattern is easily formed, and the pattern can be prevented from peeling.

The photopolymerization initiator of the present invention is not particularly limited, and may be, for example, one or more compounds selected from the group consisting of triazine-based compounds, acetophenone-based compounds, biimidazole-based compounds, oxime compounds, and combinations thereof.

The self-luminous photosensitive resin composition containing the aforementioned photopolymerization initiator has high sensitivity, and the pixel portion of a pixel formed using the composition has good strength and patternability. In addition, when a photopolymerization initiator is used in combination with a photopolymerization initiator, the sensitivity of the self-luminous photosensitive resin composition containing them is further improved, and productivity when forming a color filter using the composition is improved.

The type of the triazine compound is not particularly limited, and specifically, 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-piperyl-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) vinyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan -2-yl) ethylene Group] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) vinyl] -1, 3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) vinyl] -1,3,5-triazine and the like.

The type of the acetophenone compound is not particularly limited, and specific examples thereof include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, and acetophenone dimethyl ketal. , 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4 -Methylthiophenyl) -2-morpholinylpropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one, 2 -Hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1-one, 2- (4-methylbenzyl) -2- (dimethylamino)- 1- (4-morpholinophenyl) butane-1-one and the like. In addition, a compound represented by the following Chemical Formula 1 may be mentioned.

(Wherein R ₁ to R ₄ each independently represent hydrogen, halogen, hydroxyl, phenyl substituted or unsubstituted by alkyl having 1 to 12 carbons, and substituted or unsubstituted by alkyl having 1 to 12 carbons Benzyl, or naphthyl substituted or unsubstituted by alkyl having 1 to 12 carbons.)

The type of the compound represented by the aforementioned Chemical Formula 1 is not particularly limited, and specific examples thereof include 2-methyl-2-amino (4-morpholinophenyl) ethane-1-one and 2-ethyl-2-amino (4 -Morpholinophenyl) ethane-1-one, 2-propyl-2-amino (4-morpholinophenyl) ethane-1-one, 2-butyl-2-amino (4-? Phenolinophenyl) ethane-1-one, 2-methyl-2-amino (4-morpholinophenyl) propane-1-one, 2-methyl-2-amino- (4-morpholino Phenyl) butane-1-one, 2-ethyl-2-amino (4-morpholinophenyl) propane -1-one, 2-ethyl-2-amino (4-morpholinophenyl) butane-1-one, 2-methyl-2-methylamino- (4-morpholinophenyl) propane -1-one, 2-methyl-2-dimethylamino- (4-morpholinophenyl) propane-1-one, 2-methyl-2-diethylamino (4-morpholinyl ) Propane-1-one and the like.

The type of the biimidazole compound is not particularly limited, and specific examples include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5 ' -Tetrakis (alkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (trialkoxyphenyl) biimidazole, 4, An imidazole compound in which the phenyl group at the 4 ', 5, 5' position is replaced with an alkoxycarbonyl group. Among these, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3-dichlorobenzene) are preferably used. Group) -4,4 ', 5,5'-tetraphenylbiimidazole.

The type of the oxime compound is not particularly limited, and specific examples include compounds represented by the following Chemical Formula 2, Chemical Formula 3, and Chemical Formula 4.

[Chemical Formula 3]

Examples of commercially available products include Irgacure-907 from BASF.

In addition, in the self-luminous photosensitive resin composition of the present invention, other commonly used photopolymerization initiators may be additionally used within a range that does not impair the object of the present invention. Examples of other photopolymerization initiators include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and anthracene-based compounds. These can be used individually or in combination of 2 or more types.

The type of the benzoin-based compound is not particularly limited, and specific examples thereof include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like.

The type of the benzophenone compound is not particularly limited, and specific examples thereof include benzophenone, o-benzoyl benzoate, 4-phenylbenzophenone, and 4-benzophenone-4'- Methyldiphenyl sulfide, 3,3 ', 4,4'-tetrakis (t-butylperoxycarbonyl) Benzophenone, 2,4,6-trimethylbenzophenone, 4,4'-bis (N, N'-dimethylamino) benzophenone, etc.

The type of thioxanthone compounds is not particularly limited, and specific examples include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4. -Propoxythioxanthone and the like.

The type of the anthracene compound is not particularly limited, and specific examples include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2- Ethyl-9,10-diethoxyanthracene and the like.

In addition, 2,4,6-trimethylbenzylidene diphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10- Phenanthrenequinone, camphorquinone, methyl phenylacetate, titanocene compound, etc. are used as other photopolymerization initiators.

The content of the photopolymerization initiator of the present invention is not particularly limited, and may be, for example, 0.1 to 20% by weight, and preferably 1 to 10% by weight based on the total weight of the solid content of the self-luminous photosensitive resin composition. When the content of the photopolymerization initiator is within the aforementioned range, the self-luminous photosensitive resin composition is highly sensitive, and the strength of the pixel portion or the smoothness of the surface of the pixel portion is good.

In addition, when the content of the photopolymerization initiator is within the aforementioned range, the sensitivity and efficiency of the self-luminous photosensitive resin composition are further improved, and the productivity of a color filter formed using the composition can be improved.

Furthermore, the self-luminous photosensitive resin composition of the present invention may further include a photopolymerization initiation aid that can be used in combination with a photopolymerization initiator. In this case, the sensitivity and efficiency of the composition are further improved, and the productivity of a color filter formed using the composition can be improved. In this case, as long as the type of photopolymerization initiation aid is a photopolymerization initiation aid commonly used in the art, The agent is not particularly limited, and a specific compound selected from the group consisting of an amine compound, a carboxylic acid compound, and the like can be specifically used.

Specific examples of the amine compound in the photopolymerization initiation aid include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, and 4-dimethyl Ethyl aminobenzoate, 4-dimethylaminobenzoate isoamyl, 2-dimethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethyl Aromatic amine compounds such as p-toluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as mignonone), 4,4'-bis (diethylamino) benzophenone. The amine compound is an aromatic amine compound.

Specific examples of the carboxylic acid compound in the photopolymerization initiation aid include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, and dimethylphenylthio Acetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthalene Aromatic heteroacetic acids such as glycine and naphthyloxyacetic acid.

The content of the photopolymerization initiation adjuvant of the present invention is not particularly limited, and may be, for example, 0.1 to 20% by weight, and preferably 1 to 10% by weight based on the total weight of the solid content of the self-luminous photosensitive resin composition. When the content of the photopolymerization initiation aid is within the aforementioned range, the self-luminous photosensitive resin composition is highly sensitive, and the strength of the pixel portion or the smoothness of the surface of the pixel portion is good.

In addition, when the content of the photopolymerization initiation aid is in the aforementioned range, the sensitivity efficiency of the self-luminous photosensitive resin composition is further increased, and the productivity of a color filter formed using the composition can be improved.

The alkali-soluble resin has a carboxyl group-containing ethylenically unsaturated monomer and is polymerized. The alkali-soluble resin provides solubility to an alkaline developing solution used in a development processing step when forming a pattern.

There are no particular restrictions on carboxy-containing ethylenically unsaturated monomers, and examples include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as fumaric acid, mesaconic acid, and their anhydrides; ω-carboxy polycaproic acid Mono (meth) acrylate and the like of a polymer having a carboxyl group and a hydroxyl group at both ends, such as lactone mono (meth) acrylate, are preferably acrylic acid and methacrylic acid. These can be used individually or in mixture of 2 or more types.

The alkali-soluble resin of the present invention may be a resin that further contains at least one other monomer copolymerizable with the monomer and is polymerized, and examples thereof include styrene, vinyltoluene, methylstyrene, p-chlorostyrene, and o-methyl Oxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl Aromatic vinyl compounds such as glycidyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, indene; N-cyclohexylmaleimide, N-benzylmaleimide , N-phenylmaleimide, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, N-ortho Methylphenylmaleimide, N-m-methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-substituted-maleimide-based compounds such as N-m-methoxyphenylmaleimide and N-p-methoxyphenylmaleimide; methyl (meth) acrylate, (methyl) ) Ethyl acrylate, ( N-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tertiary (meth) acrylate Butyl esters, etc. Alkyl acrylates; cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclic (meth) acrylate [5.2.1.02 , 6] cycloaliphatic (meth) acrylates such as decane-8-yl ester, 2-dicyclopentyloxyethyl (meth) acrylate, isobornyl (meth) acrylate; (methyl ) Aryl (meth) acrylates such as phenyl acrylate and benzyl (meth) acrylate; 3- (methacryloxymethyl) oxetane, 3- (methacrylic acid) ) -3-ethyloxetane, 3- (methacryloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloxymethyl) 2-phenyloxetane, 2- (methacryloxymethyl) oxetane, 2- (methacryloxymethyl) -4-trifluoromethyloxe Unsaturated oxetane compounds such as cyclobutane. These compounds can be used individually or in combination of 2 or more types.

In this specification, (meth) acrylate means an acrylate or a methacrylate.

The content of the alkali-soluble resin of the present invention is not particularly limited. For example, it may be 5 to 80% by weight, and preferably 10 to 70% by weight, relative to the total weight of the solid content of the self-luminous photosensitive resin composition. When the content is within the above range, the solubility in the developing solution is sufficient, and a pattern is easily formed. This prevents the film of the pixel portion of the exposed portion from being reduced during development, and the peeling property of the non-pixel portion becomes good.

The solvent in the present invention is not particularly limited, and may be an organic solvent commonly used in the art.

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 dialkyl ethers such as diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; methyl cellosolve acetate, ethyl solvent Fiber glycol acetates such as cellulose acetate; propylene glycol dialkyl ethers such as propylene glycol monomethyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate Alkylene glycol alkyl ether acetates such as butyl methoxyacetate and pentyl methoxyacetate; aromatic hydrocarbons such as benzene, toluene, xylene, xylene; methyl ethyl ketone, acetone, Ketones such as methylpentyl ketone, methyl isobutyl ketone, cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol; 3-ethoxy Ester such as ethyl propionate and methyl 3-methoxypropionate; Cyclic esters such as γ-butyrolactone. These can be used alone or in combination of two or more.

The solvent content in the present invention is not particularly limited, and it is used in a content that can sufficiently dissolve or disperse the aforementioned solid components (ie, quantum dots, antioxidants, photopolymerizable compounds, photopolymerization initiators, and alkali-soluble resins). It can be considered to control the content of the coating process for coating. As an example, the solvent may be used in an amount of 10 to 80 parts by weight based on 1 part by weight of the solid content so that the entire self-luminous photosensitive resin composition has a concentration of 10 to 80% by weight. In the embodiment of the present invention, the content of the solvent is adjusted to satisfy a concentration of 20% by weight.

The present invention provides a color filter manufactured using the aforementioned self-luminous photosensitive resin composition.

When the color filter of the present invention is applied to an image display device, it emits light using light from a light source of the display device, so that it can achieve more excellent light efficiency. In addition, since it is light emitted from light having a hue, the color reproducibility is more excellent. Since light is emitted in all directions by photoluminescence, the viewing angle can be improved and the brightness characteristics are excellent.

The color filter includes a substrate and a pattern layer formed on an upper portion of the substrate.

The substrate is not particularly limited as long as it is a substrate of the color filter itself or a substrate located at a portion of the color filter such as a display device. The substrate may be glass, silicon, silicon oxide (SiOx), or a polymer base, and the polymer substrate may be polyether fluorene (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 photosensitive resin composition, exposing it to a predetermined pattern, developing, and thermally curing it.

The pattern layer formed using the aforementioned 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 the 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 this case, when applied to an image display device, the light emitted from the light source is not particularly limited, but a blue light-emitting light source can be preferably used in terms of more excellent brightness and color reproducibility.

According to other embodiments of the present invention, the aforementioned pattern layer further includes a transparent pattern layer that does not include a red pattern layer, a green pattern layer, and quantum dot particles. In the case where the pattern layer includes only two hue, a light source that emits light having a wavelength indicating the remaining hue that it does not include may be used. For example, when a red pattern layer and a green pattern layer are included, a light source emitting blue light may be used. At this time, the red quantum dot particles emit red light, the green quantum dot particles emit green light, and the transparent pattern layer directly transmits blue light to display blue light.

The color filter including a substrate and a pattern layer may further include a partition wall formed between the patterns, and may further include a black matrix. In addition, a protective film formed on an upper portion of the pattern layer of the color filter may be further included.

In addition, the present invention provides an image display device including the aforementioned color filter.

The color filter 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 image display device of the present invention may include a color filter having a red pattern layer containing red quantum dot particles, a green pattern layer containing green quantum dot particles, and a blue pattern layer containing blue quantum dot particles. In this case, when applied to an image display device, the light emitted from the light source is not particularly limited, but a blue light-emitting light source can be preferably used in terms of more excellent color reproducibility.

According to another embodiment of the present invention, the image display device of the present invention further includes a color filter having a pattern layer having only two hues of a red pattern layer, a green pattern layer, and a blue pattern layer. At this time, the aforementioned filter may further include a transparent pattern layer containing no quantum dot particles.

In the case where the pattern layer includes only two hue, a light source that emits light having a wavelength indicating the remaining hue that it does not include may be used. For example, when a red pattern layer and a green pattern layer are included, a light source emitting blue light may be used. At this time, the red quantum dot particles emit red light, the green quantum dot particles emit green light, and the transparent pattern layer directly transmits blue light to display blue light.

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

In the following, preferred embodiments are provided to understand the present invention, but these embodiments are only used to illustrate the present invention, and do not limit the scope of the scope of the attached patent application. Obviously, those skilled in the art can use the scope and technology of the present invention. Various modifications and changes are made to the embodiment within the scope of the idea, and such changes and modifications naturally also belong to the scope of the attached patent application.

Production Example 1: Synthesis of Green Quantum Dots (A) with CdSe (Core) / ZnS (Shell) Structure

CdO (0.4 mmol), zinc acetate (4 mmol), and oleic acid (5.5 mL) were put into a reactor together with 1-octadecene (20 mL), and the reaction was heated at 150 ° C.

Thereafter, in order to remove the acetic acid produced by the substitution of zinc with oleic acid, the aforementioned reaction product was left under a vacuum of 100 mTorr for 20 minutes. Then, after heating to 310 ° C to obtain a transparent mixture, the mixture was maintained at 310 ° C for 20 minutes, and 0.4 mmol of Se powder and 2.3 mmol of S powder were dissolved in 3 mL of trioctylphosphine Se and The S solution was quickly injected into the reactor into which the Cd (OA) 2 (Cadmium oleate) and Zn (OA) 2 (Zinc oleate) solutions had been placed.

After the mixture thus obtained was allowed to grow at 310 ° C for 5 minutes, the growth was stopped in an ice bath.

After that, it was precipitated with ethanol, and the quantum dots were separated by a centrifugal separator. The excess impurities were washed with chloroform and ethanol, and stabilized with oleic acid to obtain a CdSe (core) with a particle size and a core distribution of 3 to 5 nm in total. Quantum dot A of ZnS (shell) structure.

Production Example 2: Synthesis of alkali-soluble resin

A flask having a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube was prepared. On the other hand, 45 parts by weight of N-benzylmaleimide, 45 parts by weight of methacrylic acid, and 10 parts by weight were added. Tricyclodecyl methacrylate, 4 parts by weight of tert-butyl peroxy-2-ethylhexanoate, and 40 parts by weight of propylene glycol monomethyl ether acetate (hereinafter, referred to as "PGMEA") A monomer dropping funnel was prepared by stirring and mixing, and 6 parts by weight of n-dodecyl glycol and 24 parts by weight of PGMEA were added and stirred to prepare a chain transfer agent dropping funnel.

Thereafter, 395 parts by weight of PGMEA was introduced into the flask, and the atmosphere in the flask was changed from air to nitrogen, and then the temperature of the flask was raised to 90 ° C. while stirring. Next, the monomer and the chain transfer agent were dropped from the dropping funnel. The dripping was performed for 2 hours while maintaining 90 ° C. After 1 hour, the temperature was raised to 110 ° C and maintained for 3 hours. Then, a gas introduction tube was introduced to start foaming of a mixed gas of oxygen / nitrogen = 5/95 (v / v).

Next, 10 parts by weight of glycidyl methacrylate, 0.4 parts by weight of 2,2′-methylenebis (4-methyl-6-tert-butylphenol), and 0.8 parts by weight of triethyl were added to the flask. The amine was reacted at 110 ° C. for 8 hours, and then cooled to room temperature to obtain an alkali-soluble resin having a solid content of 29.1% by weight, a weight average molecular weight of 32,000, and an acid value of 114 mgKOH / g.

Examples and Comparative Examples

(1) Production of self-luminous photosensitive resin composition

As described in the following Tables 1 to 3, after each component is mixed separately, the total solid content is 100% by weight, and it is diluted to 20% by weight with a solvent of propylene glycol monomethyl ether acetate, and then fully stirred To obtain a self-luminous photosensitive resin composition.

(2) Manufacturing of color filters

The self-luminous materials produced in the foregoing Examples 1 to 10 and Comparative Examples 1 to 5 were used The photosensitive resin composition produced a color filter.

That is, after each of the light-emitting photosensitive resin compositions described above was coated on a glass substrate by a spin coating method, it was placed on a hot plate and kept at a temperature of 100 ° C. for 3 minutes to form a thin film.

Next, a test photomask having a light-transmitting pattern having a length of 20 mm × 20 mm square and a line width / space pattern of 1 μm to 100 μm was placed on the film, and the interval between the test photomask and the test photomask was set to 100 μm. UV.

At this time, the ultra-high-pressure mercury lamp (trade name USH-250D) manufactured by USHIO Electric Co., Ltd. was used as the ultraviolet light source, and the light was irradiated with an exposure amount (365 nm) of 200 mJ / cm2 in an atmospheric atmosphere without using a special filter. The ultraviolet-irradiated film was immersed in a KOH aqueous solution developing solution having a pH of 10.5 for 80 seconds, and developed.

The thin-film-coated glass plate was washed with distilled water, sprayed with nitrogen and dried, and heated in a heating furnace at 150 ° C. for 10 minutes to produce a color filter. The thickness of the produced self-luminous color filter was 3.0 μm.

Experimental example

1: Measurement of luminous intensity

In the color filter forming the aforementioned self-luminous pixels, a 365 nm Tube-type 4W UV irradiator (VL-4LC, VILBER LOURMAT) was used to measure a light conversion area on a pattern portion formed by a 20 mm × 20 mm square pattern, and spectroscopic analysis was used. The meter (Ocean Optics) measures the luminous intensity of Examples 1 to 10 and Comparative Examples 1 to 5 in a region of 550 nm. The higher the measured luminous intensity, it can be judged that more excellent self-luminous characteristics are exhibited.

After hard-baking at 230 ° C for 60 minutes, the hard-baking was measured. The luminous intensity after the luminous intensity was compared with that of Comparative Example 4 in which an antioxidant was introduced, and is shown in Table 4 and FIG. 1.

Furthermore, the luminous intensities without using an antioxidant and the average luminous intensities of the examples using one, two, or three kinds were compared based on one antioxidant, and are shown in Table 5.

As can be seen from Tables 4 to 5 and FIG. 1, in the case of Comparative Example 1 without the addition of an antioxidant, the luminous intensity was very low, which was 67.7%, compared to Comparative Example 4 using one kind. In the cases of Comparative Examples 2 to 5 in which an antioxidant was mixed, the luminous intensity maintenance rate was similar. Therefore, it can be confirmed that the luminous intensity and the maintenance ratio can be improved by the presence or absence of an antioxidant.

In addition, it was confirmed that the compositions of Examples 1 to 10 in which two or more kinds of antioxidants different from each other were mixed were significantly superior in light emission intensity compared to the case where one kind of antioxidant was used.

Specifically, compared with the average luminous intensity of Comparative Examples 1 to 4, it was confirmed that the luminous intensity of the composition without the antioxidant was decreased by 69.2%, and the luminous intensity of the two or more compositions different from each other was increased by 115.2. %, The luminous intensity of the three compositions was increased by 122.0%.

Claims (9)

A self-luminous photosensitive resin composition, comprising a quantum dot, an antioxidant, a photopolymerizable compound, a photopolymerization initiator, an alkali-soluble resin, and a solvent. The antioxidant includes a phenolic compound, a phosphorus compound, and Two or more compounds of different types selected from the sulfur compounds, and the content of the antioxidant in the composition is 0.1 to 10% by weight of the antioxidant relative to the total weight of the solid content of the composition. The self-luminous photosensitive resin composition according to claim 1, wherein the antioxidant is a combination of a phenol compound and a phosphorus compound, a combination of a phenol compound and a sulfur compound, a combination of a phosphorus compound and a sulfur compound, or A phenolic compound, a phosphorus compound, and a sulfur compound are used in combination. The self-luminous photosensitive resin composition according to claim 1, wherein the phenolic compound is selected from the group consisting of 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylbenzene) Propyl) propanyloxy] -1,1-dimethylethoxy] -2,4,8,10-tetraoxaspiro [5.5] undecane, pentaerythritol tetra [3- (3,5-di Tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris (3 ', 5'-di-tert-butyl-4-hydroxybenzyl) Benzene, triethylene glycol bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-tert-butyl-3- Methylphenol), tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6- Dimethylbenzyl) isocyanurate, 1,6-hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2-thio Diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-tert-butyl-4hydroxy-hydrocinnamonate) Amine), 1,3,5-trimethyl-2,4,6-tri (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 2,4-bis ((octylthio) methyl Yl] -O-cresol, 1,6-hexanediol bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 4,4'-butylenebis (3 -Methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris (4- One or more of the group consisting of hydroxybenzyl) benzene and tetrakis [methylene-3- (3,5'-di-t-butyl-4'-hydroxyphenylpropionate)] methane. The self-luminous photosensitive resin composition according to claim 1, wherein the phosphorus compound is selected from the group consisting of 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4 , 8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, diisodecyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diimide Phosphate, 2,4,8,10-tetra (1,1-dimethylethyl) -6-[(2-ethylhexyl) oxy] -12H-dibenzo [d, g] [1, 3,2] Dioxoheteroheptin, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyl Dibenzo [d, f] [1,3,2] dioxophosphoheptanine, triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, 4 , 4'-butylenebis (3-methyl-6-tert-butylphenylbistridecyl) phosphite, octadecylphosphite, tris (nonylphenyl) phosphite, 9 , 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-tert-butyl-4-hydroxybenzyl) -9,10-dihydro-9- Oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris (2,4- Di-tert-butylphenyl) phosphite, cyclic neopentane tetrayl bis (2,4-di-tert-butylphenyl) phosphite, cyclic neopentane tetrayl bis (2,6-di-tert-butyl) Butylphenyl) phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octylphosphite, tris (2,4-di-tert-butylphenyl) phosphite Ester, 4,4 '-[1,1'-biphenyl] subunit diphosphonic acid-tetra [2,4-di-tert-butylphenyl] ester, phosphonate bis [2,4-bis (1, One or more of the group consisting of 1-dimethylethyl) -6-methylphenyl] ethyl ester. The self-luminous photosensitive resin composition according to claim 1, wherein the sulfur compound is selected from the group consisting of 2,2-bis ({[3- (dodecylthio) propanyl] oxy} methyl) -1,3-propanediyl-bis [3- (dodecylthio) propionate], 3,3'-thiodipropionate didodecyl, 3,3'-thiodi A group consisting of ditetradecyl propionate, dioctadecyl 3,3'-thiodipropionate, pentaerythritol tetrakis (3-dodecylthiopropionate) and 2-mercaptobenzimidazole More than one of them. The self-luminous photosensitive resin composition according to claim 1, wherein the quantum dot comprises a compound selected from the group consisting of a group II-IV semiconductor compound, a group III-V semiconductor compound, a group IV-VI semiconductor compound, and a group IV element or contains the IV One or more of the group consisting of a compound of a group element. The self-luminous photosensitive resin composition according to claim 1, wherein the total weight of the solid component of the composition includes: 3 to 80% by weight of quantum dots; 5 to 70% by weight of a photopolymerizable compound; 0.1 to 20% by weight % Photopolymerization initiator; and 5 ~ 80% by weight of alkali-soluble resin. A color filter manufactured using the self-luminous photosensitive resin composition according to any one of claims 1 to 7. An image display device, wherein the image display device package Include color filters as in claim 8.