JP6663743B2 - Self-luminous photosensitive resin composition, color filter and image display device manufactured using the same - Google Patents

Description

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

  A color filter is a thin film type optical component that extracts three colors of red, green, and blue from white light and makes it possible in fine pixel units. The size of one pixel is several tens to several hundreds. It is on the order of micrometers. Such a color filter includes a black matrix layer formed in a pattern defined on a transparent substrate in order to shield a boundary portion between each pixel and a plurality of colors (usually red) to form each pixel. (R), green (G), and blue (B)) are arranged in a sequence in which pixel portions in which three primary colors are arranged in a predetermined procedure are sequentially stacked. Generally, a color filter can be manufactured by coating three or more hues on a transparent substrate by a dyeing method, an electrodeposition method, a printing method, a pigment dispersion method, and the like. The pigment dispersion method using a photosensitive resin is the mainstream.

  The pigment dispersion method, which is one of the methods for implementing a color filter, includes an alkali-soluble resin including a colorant on a transparent substrate provided with a black matrix, a photopolymerizable monomer, a photopolymerization initiator, After coating the photosensitive resin composition containing the epoxy resin, solvent and other additives, exposing the pattern of the form to be formed, removing the non-exposed area with a solvent, and repeating a series of steps of thermosetting. This is a method of forming a colored thin film, which is being actively applied to manufacture LCDs for mobile phones, notebook computers, monitors, televisions, and the like. In recent years, even in photosensitive resin compositions for color filters using the pigment dispersion method, which has various advantages, not only excellent pattern characteristics, but also improved performance such as high brightness and high contrast ratio with high color reproducibility. What is being requested is the current situation.

  However, color reproduction is realized by transmitting light emitted from a light source through a color filter.In this process, a part of the light is absorbed by the color filter, and the light efficiency is reduced. In addition, there is a fundamental limit that perfect color reproduction is not enough due to the pigment characteristics as a color filter.

  Patent Literature 1 discloses that by replacing a color filter of a liquid crystal display device with a light emitting layer made of a quantum dot phosphor, luminous efficiency can be improved and display quality can be improved. However, the surface of the quantum dots is oxidized due to radicals generated in a hard bake process performed during a color filter manufacturing process, and as a result, a problem that light emission characteristics are deteriorated occurs.

  Patent Document 2 includes a light source and a display panel on which light emitted from the light source is incident. The display panel includes a number of color conversion units, and the color conversion unit A display device including a number of wavelength converting particles for converting a wavelength and a number of color filter particles for absorbing light in a predetermined wavelength band with the light is disclosed.

  However, although the related art is similar in that quantum dots are included, there is no specific description of the content of the photosensitive resin composition, and only the display device having high color reproducibility and brightness is disclosed. Therefore, additional development for the photosensitive resin composition is required.

Korean Patent Publication No. 10-2009-0036373 Korean Patent Publication No. 10-2013-0000506

  The present invention has been made to solve the above-described problems, and has as its object to uniformly disperse quantum dot particles by including an alkali-soluble resin having a polymerizable unsaturated bond, to thereby provide a color filter. An object of the present invention is to provide a self-luminous photosensitive resin composition capable of producing an excellent color filter without problems such as a decrease in light efficiency and a poor photosensitive characteristic during the production process.

  It is another object of the present invention to provide a color filter manufactured using the light-emitting photosensitive resin composition as described above and an image display device including the same.

  The self-luminous photosensitive resin composition according to an embodiment of the present invention for achieving the above object includes an alkali-soluble resin, photoluminescent quantum dot particles, a photopolymerizable compound, a photopolymerization initiator, and a solvent, The soluble resin has a polymerizable unsaturated bond in its structure, and has an acrylic equivalent of 300 to 2,000 g / eq.

  In addition, the present invention is characterized by a color filter manufactured using the self-luminous photosensitive resin composition and an image display device including the same.

  As described above, the self-luminous photosensitive resin composition according to the present invention includes an alkali-soluble resin having an acryl equivalent of 300 to 2,000 g / eq, so that light efficiency is reduced and photosensitive characteristics are reduced during a hard baking process. There is an effect that a high-quality color filter excellent in luminance characteristics can be provided without a problem such as a defect of the color filter.

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

Hereinafter, the self-luminous photosensitive resin composition will be described in detail.
The alkali-soluble resin contained in the self-luminous photosensitive resin composition of the present invention serves to make a non-exposed portion of the photosensitive resin layer alkali-soluble and to make it removable, so that the exposed region remains. In addition, the alkali-soluble resin of the present invention has a polymerizable unsaturated bond, thereby effectively forming a protective layer around the surface of the quantum dot during the exposure step, and preventing the effects of high temperature and oxygen radicals in the POB process. High brightness can be maintained by maximally eliminating the brightness.

  The alkali-soluble resin is not particularly limited as long as it has a polymerizable unsaturated bond in its structure. Specific examples of the monomer include 3- (acryloyloxy) -2-hydroxypropyl (Meth) acrylate, 2-methoxy-3-propene-2-oiloxy-propyl-2-methyl-2-propionate, 2-oxydanyl-3-propene-2-oiloxy-propyl-2-butanoate, 1,3 -Propanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, hydroquinone di (meth) acrylate, 1,4-phenylenedi (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate , 2-propenoyloxymethyl-2-propionate, triethylene glycol di (meth) Acrylate, tetraethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, bisphenol A di (meth) Acrylate, diurethane di (meth) acrylate, neopentyl glycol diacrylate and the like can be mentioned.

  The alkali-soluble resin may be used as a homopolymer, a copolymer with another unsaturated monomer, or a blend with a polymer polymerized with another unsaturated monomer. In this case, the copolymer may be in the form of an alternating copolymer, a random copolymer or a block copolymer, and is not particularly limited in the present invention.

  The type of the copolymerizable monomer is not particularly limited, and specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, Unsubstituted or substituted alkyl ester compounds of unsaturated carboxylic acids such as aminoethyl (meth) acrylate; cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl ( (Meth) acrylate, 2-isopropyl-5-methylcyclohexyl (meth) acrylate, cyclopentenyl (meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (Meth) acrylate, 2-isopropyl-5-methylcyclohexadienyl (meth) acrylate, isobornyl (meth) acrylate, tetrahydropyranyl (meth) acrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, tetrahydropyrenyl ( Unsaturated carboxylic acid ester compounds containing an alicyclic substituent such as meth) acrylate and tricyclodecyl methacrylate; monosaturated carboxylic acid ester compounds of glycols such as oligoethylene glycol monoalkyl (meth) acrylate; benzyl (meth) acrylate Carboxylic acid ester compounds having a substituent having an aromatic ring, such as phenoxy (meth) acrylate; aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyltoluene Carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate; vinyl cyanide compounds such as (meth) acrylonitrile and α-chloroacrylonitrile; maleimide compounds such as N-cyclohexylmaleimide, N-phenylmaleimide and N-benzylmaleimide; Is mentioned.

  In the present invention, the alkali-soluble resin preferably has a weight average molecular weight in terms of polystyrene of 3,000 to 100,000, more preferably 5,000 to 50,000. When the weight-average molecular weight of the alkali-soluble resin is within the above-mentioned range, it is difficult to reduce the film thickness of the exposed portion during development and the solubility of the unexposed portion tends to be good.

  The acid value of the alkali-soluble resin of the present invention is preferably in the range of 30 to 150 mgKOH / g based on the solid content. When the acid value is less than 30 mgKOH / g, the solubility in an alkali developing solution is low, and there is a possibility that a residue may be left on the substrate. When the acid value exceeds 150 mgKOH / g, pattern peeling may occur. Get higher.

  The molecular weight distribution of the alkali-soluble resin is preferably from 1.0 to 6.0, and more preferably from 1.5 to 4.0. If the molecular weight distribution of the alkali-soluble resin is within the above range, the developing property is excellent.

  The alkali-soluble resin of the present invention preferably has an acrylic equivalent of 300 to 2,000 g / eq, and more preferably 400 to 1,000 g / eq. When the alkali-soluble resin acrylic equivalent is within the above range, development that is quenched during the color filter step can be prevented. On the other hand, when the acrylic equivalent of the alkali-soluble resin exceeds 2,000 g / eq, the ability to effectively protect the quantum dots is insufficient. Although it is good in efficiency, it has a problem that it is peeled off without being dissolved at the time of development.

  The alkali-soluble resin of the present invention is preferably contained in a weight fraction of 5 to 80% by weight, more preferably 10 to 70% by weight, based on the solid content in the self-luminous photosensitive resin composition. preferable. When the content of the alkali-soluble resin is within the above range, the quantum dots can be easily dispersed, and the luminous efficiency can be kept high during the process.

The self-luminous photosensitive resin composition of the present invention contains photoluminescent quantum dot particles.
Quantum dots are nano-sized semiconductor materials. The atoms form molecules, and the molecules form aggregates of small molecules called clusters to form nanoparticles. When such nanoparticles have semiconductor properties in particular, they are called quantum dots. When the quantum dots receive energy from the outside and come to a floating state, the quantum dots themselves emit energy according to the corresponding energy band gap.

  The photosensitive resin composition of the present invention contains such photoluminescent quantum dot particles, and a color filter manufactured therefrom can emit light (photoluminescence) by light irradiation. In addition, since light having a hue is emitted, color reproducibility is further improved, and light is emitted in all directions by photoluminescence, so that the viewing angle can be improved.

  The quantum dot particle according to the present invention is not particularly limited as long as it is a quantum dot particle that can emit light upon stimulation by light. For example, a II-VI semiconductor compound; a III-V semiconductor compound; a IV-VI semiconductor compound; Compounds containing the same; and combinations thereof. These can be used alone or in combination of two or more.

  The II-VI group semiconductor compound is a two-element compound selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe and a mixture thereof; CdSeS, CdSeTe, CdSTe, ZnSeS , ZnSe, CdZnSe, and CdZnSe selected from the group consisting of CdZnSe and CdZnSe selected from the group consisting of ZnCe, CdZnSe, and CdZnSe selected from the group consisting of ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnSe, HgZnSe, and mixtures thereof. Four elements selected from the group consisting of CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe and mixtures thereof The group III-V semiconductor compound may be selected from the group consisting of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, and mixtures thereof. A two-element compound selected from the group consisting of: GANP, GaNAs, GANSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, and a mixture thereof. Tri-element compound; and GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNS , InAlPAs, InAlPSb, and mixtures thereof. The IV-VI semiconductor compound may be selected from the group consisting of quaternary compounds selected from the group consisting of SnS, SnSe, SnTe, PbS, PbSe, PbTe, and the like. Binary compounds selected from the group consisting of these mixtures; SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, ternary compounds selected from the group consisting of SnPbSe, SnPbTe, and mixtures thereof; and SnPbSSe, SnPbSe. , SnPbSTe and a mixture thereof, and the group IV element or the compound containing the same may be selected from the group consisting of Si, Ge and a mixture thereof. Is And a two-element compound selected from the group consisting of SiC, SiGe, and mixtures thereof.

  The quantum dot particles may have a homogenous single structure; a double structure such as a core-shell, a gradient structure, or the like; or a mixed structure thereof.

  In the core-shell dual structure, the material forming each core and shell may be made of the above-mentioned different semiconductor compounds. For example, the core may include one or more materials selected from the group consisting of CdSe, CdS, ZnS, ZnSe, CdTe, CdSeTe, CdZnS, PbSe, AgInZnS, and ZnO, but are not limited thereto. is not. The shell may include, but is not limited to, one or more materials selected from the group consisting of CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, and HgSe.

  Photoluminescent quantum dot particles, such as a colored photosensitive resin composition used in the manufacture of a normal color filter, to include a red, green, and blue colorant in order to embody the hue, the red quantum dot particles , Green and blue quantum dot particles, and the quantum dot particles according to the present invention may be red, green or blue quantum dot particles.

  Quantum dot particles can be synthesized by a wet chemical process, a metal organic chemical vapor deposition process, or a molecular beam epitaxy process.

  The wet chemistry process is a method of growing particles by putting a precursor substance in an organic solvent. When the crystal grows, the organic solvent is naturally coordinated on the surface of the quantum dot crystal and acts as a dispersant to control the growth of the crystal. Therefore, metal organic chemical vapor deposition (MOCVD). The growth of nanoparticles can be controlled through an easier and less expensive process than a vapor deposition method such as molecular beam epitaxy (MBE) or molecular beam epitaxy (MBE).

  The content of the photoluminescent quantum dot particles according to the present invention is not particularly limited. For example, the content of the photoluminescent quantum dot particles is preferably 3 to 80% by weight based on the total weight of the solid content of the self-luminous photosensitive resin composition, and is preferably 5 to 70%. More preferably, it is contained by weight. When the content of the quantum dot particles is less than the above range, the luminous efficiency may be very weak. Is difficult to form.

  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 light and a photopolymerization initiator described below, and is a monofunctional monomer or a bifunctional monomer. And other polyfunctional monomers.

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

  Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and bisphenol. Bis (acryloyloxyethyl) ether of A, 3-methylpentanediol di (meth) acrylate and the like can be mentioned.

  Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol Hexa (meth) acrylate and the like. Of these, bifunctional or higher polyfunctional monomers are preferably used.

  The photopolymerizable compound is preferably contained in an amount of 5 to 50% by mass, more preferably 7 to 45% by mass, based on the solid content in the self-luminous photosensitive resin composition. When the photopolymerizable compound is contained within the above range, the strength and smoothness of the pixel portion can be improved.

  The photopolymerization initiator contained in the self-luminous photosensitive resin composition of the present invention is not limited, and is at least one selected from the group consisting of triazine compounds, acetophenone compounds, biimidazole compounds, and oxime compounds. Is a compound of The self-luminous photosensitive resin composition containing the above-described photopolymerization initiator has high sensitivity, and a pixel pixel formed using the composition has good strength and patternability of the pixel portion.

  Also, if a photopolymerization initiator is used in combination with the photopolymerization initiator, the self-luminous photosensitive resin composition containing these becomes more sensitive, and when a color filter is formed using this composition. This is preferable because the productivity of the compound improves.

  Examples of the triazine-based compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- (4-methoxy). Naphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-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, such as 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, and 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- And oligomers of (4-morpholinophenyl) butan-1-one and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one. Further, a compound represented by the following chemical formula 1 may be mentioned.

[Chemical formula 1]

In Formula 1, R _{1 to} R ₄ are each independently the same or different;

  A hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group substituted or unsubstituted with a C1-C12 alkyl group, a benzyl group substituted or unsubstituted with a C1-C12 alkyl group, or a C1-C12 group; Represents a naphthyl group substituted or unsubstituted by an alkyl group.

  The type of the compound represented by Formula 1 is not particularly limited, but specifically, 2-methyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-ethyl-2-one Amino (4-morpholinophenyl) ethane-1-one, 2-propyl-2-amino (4-morpholinophenyl) ethane-1-one, 2-butyl-2-amino (4-morpholinophenyl) ethane-1-one , 2-methyl-2-amino (4-morpholinophenyl) propan-1-one, 2-methyl-2-amino (4-morpholinophenyl) butan-1-one, 2-ethyl-2-amino (4-morpholino) Phenyl) propan-1-one, 2-ethyl-2-amino (4-morpholinophenyl) butan-1-one, 2-methyl-2-methylamino (4-morpholinophenyl) pro Down-1-one, 2-methyl-2-dimethylamino (4-morpholinophenyl) propane-1-one, such as 2-methyl-2-diethylamino (4-morpholinophenyl) propane-1-one and the like.

  Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (alkoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, an imidazole compound in which the phenyl group at the 4,4', 5,5 'position is substituted by a carboalkoxy group Is mentioned. Of these, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5 5,5'-Tetraphenylbiimidazole is preferably used.

The oxime compound has the following chemical formula.

  In addition, as long as the effects of the present invention are not impaired, other photopolymerization initiators commonly used in this field may be further included. Examples of other photopolymerization initiators include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and anthracene-based compounds. These may be used alone or in combination of two or more.

  Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

  Examples of the benzophenone-based compound include, for example, benzophenone, methyl o-benzoylbenzene, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenylsulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) ) Benzophenone, 2,4,6-trimethylbenzophenone, 4,4'-di (N, N'-dimethylamino) -benzophenone and the like.

  Examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

  Examples of the anthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like.

  In addition, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compounds, etc. Other photopolymerization initiators can be mentioned.

  In addition, as the photopolymerization initiation auxiliary that can be used in combination with the photopolymerization initiator in the present invention, one or more compounds selected from the group consisting of an amine compound, a carboxylic acid compound, and the like can be preferably used. .

  Specific examples of the amine compound among the photopolymerization initiation aids include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine; methyl 4-dimethylaminobenzene, ethyl 4-dimethylaminobenzene, Isoamyl dimethylaminobenzene, 2-ethylhexyl 4-dimethylaminobenzene, 2-dimethylaminoethyl benzene, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (alias: Michler's ketone), 4 And aromatic amine compounds such as 4′-bis (diethylamino) benzophenone. As the amine compound, an aromatic amine compound is preferably used.

  Carboxylic acid compounds include, for example, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N -Aromatic heteroacetic acids such as phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid.

  The content of the photopolymerization initiator in the self-luminous photosensitive resin composition of the present invention is preferably 0.1 to 20% by mass, and more preferably 1 to 10% by mass based on the total solid components. More preferred. When the use amount of the photopolymerization initiator is within the above range, the self-emission type photosensitive resin composition is highly sensitive, and the strength of the pixel portion and the smoothness on the surface of the pixel portion are excellent. ing.

  Further, the amount of the photopolymerization initiation auxiliary agent used is preferably from 0.1 to 20% by mass, more preferably from 1 to 10% by mass, based on the above criteria. When the amount of the photopolymerization initiation auxiliary agent is within the above range, the sensitivity efficiency of the self-luminous photosensitive resin composition is further increased, and the productivity of a color filter formed using this composition is improved. Can be improved.

  The solvent contained in the self-luminous photosensitive resin composition of the present invention is not particularly limited, and may be an organic solvent generally 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 diethyl ether, diethylene glycol dipropyl ether, diethylene glycol Diethylene glycol dialkyl ethers such as dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol dialkyl ethers such as propylene glycol monomethyl ether; propylene glycol monomethyl ether acetate; Alkylene glycol alkyl ether acetates such as pyrene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate; aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; methyl ethyl ketone, acetone and methyl Ketones such as amyl ketone, methyl isobutyl ketone and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin; esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate Cyclic esters such as γ-butyrolactone; and the like. These can be used alone or in combination of two or more.

  Since the viscosity of the solvent may vary depending on the coating method and apparatus, the concentration of the self-luminous photosensitive resin composition having the composition described above may be 10 to 50% by weight, preferably 10 to 30% by weight. The solvent content is adjusted appropriately to obtain.

  The content of the solvent according to the present invention is not particularly limited, and may be, for example, 60 to 90% by weight, and preferably 70 to 85% by weight based on the total weight of the self-luminous photosensitive resin composition. be able to. When the solvent is contained within the above range, the coatability is good.

The present invention also provides a color filter manufactured using the self-luminous photosensitive resin composition.
When the color filter of the present invention is applied to an image display device, the color filter emits light by the light of the light source of the image display device, so that excellent light efficiency can be realized. Further, since light having a hue is emitted, color reproducibility is excellent, and light is emitted in all directions by photoluminescence, so that the viewing angle can be improved.

  More specifically, in a normal image display device including a color filter, white light is transmitted through the color filter to realize color, and in this process, a part of the light is absorbed by the color filter, so that the light efficiency is reduced. May be. However, when a color filter manufactured using the self-luminous photosensitive resin composition of the present invention is included, the color filter itself emits light by the light of the light source, so that excellent light efficiency can be realized.

The color filter includes a substrate and a pattern layer formed on the substrate.
The substrate may be the color filter itself, or may be a part of the display device where the color filter is located, and is not particularly limited. The substrate may be glass, silicone (Si), silicone oxide (SiO _x ), or a polymer substrate, and the polymer substrate may be polyethersulfone (PES) or polycarbonate (PC). Can be

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

  The pattern layer formed of the self-luminous photosensitive resin composition contains a red pattern layer containing red quantum dot particles, a green pattern layer containing green quantum dot particles, and a blue quantum dot particle. A blue pattern layer may be provided. Upon light irradiation, the red pattern layer emits red light, the green pattern layer emits green light, and the blue pattern layer emits blue light.

  In such a case, when applied to an image display device, the emission light of the light source is not particularly limited, but from the aspect of excellent color reproducibility, a light source that emits blue light can be used.

  According to another embodiment of the present invention, the pattern layer may include only two types of pattern layers of a red pattern layer, a green pattern layer, and a blue pattern layer. In such a case, the pattern layer further includes a transparent pattern layer containing no quantum dot particles.

  When only two types of pattern layers are provided, a light source that emits light having a wavelength indicating the remaining hues that are not included may be used. For example, when a red pattern layer and a green pattern layer are included, a light source that emits blue light may be used. In such a case, the red quantum dot particles emit red light, the green quantum dot particles emit green light, and the transparent pattern layer transmits blue light as it is to show blue.

  The color filter including the substrate and the pattern layer may further include a partition formed between the patterns, and may further include a black matrix. The color filter may further include a protective layer formed on the pattern layer of the color filter.

Further, the present invention provides an image display device including the color filter.
The color filter of the present invention can be applied not only to a general liquid crystal display device but also to various image display devices such as an electroluminescent display device, a plasma display device, and a field emission display device.

  The image display device of the present invention includes a color filter including a red pattern layer containing red quantum dot particles, a green pattern layer containing green quantum dot particles, and a blue pattern layer containing blue quantum dot particles. can do. In such a case, when applied to an image display device, the emission light of the light source is not particularly limited. However, from the aspect of excellent color reproducibility, a light source that emits blue light can be preferably used.

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

  When only two types of pattern layers are provided, a light source that emits light having a wavelength indicating the remaining hues that are not included may be used. For example, when a red pattern layer and a green pattern layer are included, a light source that emits blue light may be used. In such a case, the red quantum dot particles emit red light, the green quantum dot particles emit green light, and the transparent pattern layer transmits blue light as it is to show blue.

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

  Hereinafter, the present invention will be described in detail with reference to examples. However, the following examples are for describing the present invention more specifically, and the scope of the present invention is not limited by the following examples. The following embodiments can be appropriately modified and changed by those skilled in the art within the scope of the present invention.

Production Example 1. Synthesis of Photoluminescence Green Quantum Dot Particle A with CdSe (Core) / ZnS (Shell) Structure CdO (0.4 mmol), zinc acetate (Zinc acetate) (4 mmol), oleic acid (Oleic acid) (5.5 mL) Was placed in a reactor together with 1-octadecene (20 mL) and heated to 150 ° C. to react. Thereafter, the reaction was left under a vacuum of 100 mTorr for 20 minutes in order to remove acetic acid generated by replacing oleic acid with zinc. Then, a clear mixture was obtained by applying heat of 310 ° C., and the mixture was maintained at 310 ° C. for 20 minutes. Then, 0.4 mmol of Se powder and 2.3 mmol of S powder were mixed with 3 mL of trioctylphosphine. Was quickly injected into the reactor containing the Cd (OA) ₂ and Zn (OA) ₂ solutions. The resulting mixture was grown at 310 ° C. for 5 minutes and then stopped using an ice bath. Then, the quantum dots are precipitated using ethanol and separated using a centrifugal separator. Excess impurities are washed using chloroform and ethanol to remove the core particles stabilized with oleic acid. Quantum dot particles A having a CdSe (core) / ZnS (shell) structure in which particles having a sum of diameter and shell thickness of 3 to 5 nm were distributed were obtained.

Production Example 2-1. A flask equipped with a stirrer for synthesizing the alkali-soluble resin (D1), a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was prepared. On the other hand, N-benzylmaleimide 40 parts by weight, tricyclodecyl methacrylate 10 parts by weight, acrylic After adding 50 parts by weight of acid, 4 parts by weight of meta-t-butylperoxy-2-ethylhexanoate, 20 parts by weight of propylene glycol monomethyl ether acetate (hereinafter, referred to as “PGMEA”), and 20 parts by weight of propylene glycol monomethyl ether, A monomer dropping funnel was prepared by stirring and mixing, and 6 parts by weight of n-dodecanethiol and 24 parts by weight of PGMEA were added and mixed by stirring to prepare a dropping funnel for a chain transfer agent.

  Thereafter, 395 parts by weight of PGMEA was introduced into the flask, the atmosphere in the flask was replaced with nitrogen from air, and then the temperature of the flask was raised to 90 ° C. while stirring. Subsequently, dropping of the monomer and the chain transfer agent from the dropping funnel was started. The dripping proceeds for 2 hours while maintaining 90 ° C., and after 1 hour, the temperature is raised to 110 ° C. and maintained for 3 hours, and then, while cooling to room temperature, the solid content is 29.1% by weight, the weight average molecular weight is 10, Resin D1 having an acid number of 140 mgKOH / g was obtained.

Production Example 2-2: Synthesis of alkali-soluble resin (D2) A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was prepared, while 40 parts by weight of N-benzylmaleimide and tricyclodecyl were prepared. 10 parts by weight of methacrylate, 50 parts by weight of acrylic acid, 4 parts by weight of meth-t-butylperoxy-2-ethylhexanoate, 20 parts by weight of propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA"), 20 parts by weight of propylene glycol monomethyl ether Then, the mixture was stirred and mixed to prepare a monomer dropping funnel, and 6 parts by weight of n-dodecanethiol and 24 parts by weight of PGMEA were added and mixed by stirring to prepare a dropping funnel for a chain transfer agent.

  Thereafter, 395 parts by weight of PGMEA was introduced into the flask, the atmosphere in the flask was replaced with nitrogen from air, and then the temperature of the flask was raised to 90 ° C. while stirring. Subsequently, dropping of the monomer and the chain transfer agent from the dropping funnel was started. The dripping proceeds for 2 hours while maintaining 90 ° C., and after 1 hour, the temperature is raised to 110 ° C. and maintained for 3 hours. Then, a gas introduction pipe is introduced, and oxygen / nitrogen = 5/95 (v / v). Bubbling of the mixed gas was started. Subsequently, 5 parts by weight of glycidyl methacrylate, 0.4 parts by weight of 2,2′-methylenebis (4-methyl-6-t-butylphenol), and 0.8 parts by weight of triethylamine were charged into the flask and the mixture was heated at 110 ° C. for 8 hours. The reaction was continued, and then, while cooling to room temperature, a resin D2 having a solid content of 29.1% by weight, a weight average molecular weight of 10,000, an acid value of 130 mgKOH / g, and an acrylic equivalent of 4300 g / eq was obtained.

Production Example 2-3: Synthesis of alkali-soluble resin (D3) A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was prepared, while 40 parts by weight of N-benzylmaleimide and tricyclodecyl were prepared. 10 parts by weight of methacrylate, 50 parts by weight of acrylic acid, 4 parts by weight of meth-t-butylperoxy-2-ethylhexanoate, 20 parts by weight of propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA"), 20 parts by weight of propylene glycol monomethyl ether Then, the mixture was stirred and mixed to prepare a monomer dropping funnel, and 6 parts by weight of n-dodecanethiol and 24 parts by weight of PGMEA were added and mixed by stirring to prepare a dropping funnel for a chain transfer agent.

  Thereafter, 395 parts by weight of PGMEA was introduced into the flask, the atmosphere in the flask was replaced with nitrogen from air, and then the temperature of the flask was raised to 90 ° C. while stirring. Subsequently, dropping of the monomer and the chain transfer agent from the dropping funnel was started. The dripping proceeds for 2 hours while maintaining 90 ° C., and after 1 hour, the temperature is raised to 110 ° C. and maintained for 3 hours. Then, a gas introduction pipe is introduced, and oxygen / nitrogen = 5/95 (v / v). Bubbling of the mixed gas was started. Subsequently, 15 parts by weight of glycidyl methacrylate, 0.4 parts by weight of 2,2′-methylenebis (4-methyl-6-t-butylphenol) and 0.8 parts by weight of triethylamine were charged into the flask, and the mixture was heated at 110 ° C. for 8 hours. The reaction was continued, and then, while cooling to room temperature, a resin D3 having a solid content of 29.1% by weight, a weight average molecular weight of 10,000, an acid value of 110 mgKOH / g, and an acrylic equivalent of 1450 g / eq was obtained.

Production Example 2-4: Synthesis of Alkali-Soluble Resin (D4) A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was prepared, while 40 parts by weight of N-benzylmaleimide and tricyclodecyl were prepared. 10 parts by weight of methacrylate, 50 parts by weight of acrylic acid, 4 parts by weight of meth-t-butylperoxy-2-ethylhexanoate, 20 parts by weight of propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA"), 20 parts by weight of propylene glycol monomethyl ether Then, the mixture was stirred and mixed to prepare a monomer dropping funnel, and 6 parts by weight of n-dodecanethiol and 24 parts by weight of PGMEA were added and mixed by stirring to prepare a dropping funnel for a chain transfer agent.

  Thereafter, 395 parts by weight of PGMEA was introduced into the flask, the atmosphere in the flask was replaced with nitrogen from air, and then the temperature of the flask was raised to 90 ° C. while stirring. Subsequently, dropping of the monomer and the chain transfer agent from the dropping funnel was started. The dripping proceeds for 2 hours while maintaining 90 ° C., and after 1 hour, the temperature is raised to 110 ° C. and maintained for 3 hours. Then, a gas introduction pipe is introduced, and oxygen / nitrogen = 5/95 (v / v). Bubbling of the mixed gas was started. Subsequently, 30 parts by weight of glycidyl methacrylate, 0.4 part by weight of 2,2′-methylenebis (4-methyl-6-t-butylphenol), and 0.8 part by weight of triethylamine were charged into the flask, and the mixture was heated at 110 ° C. for 8 hours. The reaction was continued, and then, while cooling to room temperature, a resin D4 having a solid content of 29.1% by weight, a weight average molecular weight of 10,000, an acid value of 85 mgKOH / g, and an acrylic equivalent of 725 g / eq was obtained.

Production Example 2-5: Synthesis of alkali-soluble resin (D5) A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was prepared, while 35 parts by weight of N-benzylmaleimide and tricyclodecyl were prepared. 10 parts by weight of methacrylate, 55 parts by weight of acrylic acid, 4 parts by weight of meth-t-butylperoxy-2-ethylhexanoate, 20 parts by weight of propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA"), 20 parts by weight of propylene glycol monomethyl ether Then, the mixture was stirred and mixed to prepare a monomer dropping funnel, and 6 parts by weight of n-dodecanethiol and 24 parts by weight of PGMEA were added and mixed by stirring to prepare a dropping funnel for a chain transfer agent.

  Thereafter, 395 parts by weight of PGMEA was introduced into the flask, the atmosphere in the flask was replaced with nitrogen from air, and then the temperature of the flask was raised to 90 ° C. while stirring. Subsequently, dropping of the monomer and the chain transfer agent from the dropping funnel was started. The dripping proceeds for 2 hours while maintaining 90 ° C., and after 1 hour, the temperature is raised to 110 ° C. and maintained for 3 hours. Then, a gas introduction pipe is introduced, and oxygen / nitrogen = 5/95 (v / v). Bubbling of the mixed gas was started. Subsequently, 50 parts by weight of glycidyl methacrylate, 0.4 parts by weight of 2,2′-methylenebis (4-methyl-6-t-butylphenol) and 0.8 parts by weight of triethylamine were charged into the flask, and the mixture was heated at 110 ° C. for 8 hours. The reaction was continued, and then, while cooling to room temperature, a resin D5 having a solid content of 29.1% by weight, a weight average molecular weight of 10,000, an acid value of 60 mg KOH / g, and an acrylic equivalent of 435 g / eq was obtained.

Production Example 2-6: Synthesis of alkali-soluble resin (D6) A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel, and a nitrogen inlet tube was prepared. On the other hand, 10 parts by weight of N-benzylmaleimide and tricyclodecyl were prepared. 10 parts by weight of methacrylate, 80 parts by weight of glycidyl methacrylate, 4 parts by weight of meth-t-butylperoxy-2-ethylhexanoate, 20 parts by weight of propylene glycol monomethyl ether acetate (hereinafter, referred to as “PGMEA”), 20 parts by weight of propylene glycol monomethyl ether Then, the mixture was stirred and mixed to prepare a monomer dropping funnel, and 6 parts by weight of n-dodecanethiol and 24 parts by weight of PGMEA were added and mixed by stirring to prepare a dropping funnel for a chain transfer agent.

  Thereafter, 395 parts by weight of PGMEA was introduced into the flask, the atmosphere in the flask was replaced with nitrogen from air, and then the temperature of the flask was raised to 90 ° C. while stirring. Subsequently, dropping of the monomer and the chain transfer agent from the dropping funnel was started. The dripping proceeds for 2 hours while maintaining 90 ° C., and after 1 hour, the temperature is raised to 110 ° C. and maintained for 3 hours. Then, a gas introduction pipe is introduced, and oxygen / nitrogen = 5/95 (v / v). Bubbling of the mixed gas was started. Subsequently, 85 parts by weight of acrylic acid, 0.4 parts by weight of 2,2′-methylenebis (4-methyl-6-t-butylphenol) and 0.8 parts by weight of triethylamine are charged into the flask, and the mixture is heated at 110 ° C. for 8 hours. The reaction was continued, and then, while cooling to room temperature, a resin D6 having a solid content of 29.1% by weight, a weight average molecular weight of 10,000, an acid value of 60 mg KOH / g, and an acrylic equivalent of 270 g / eq was obtained.

Examples 1 to 3 and Comparative Examples 1 to 3: Production of a self-luminous photosensitive resin composition As shown in Table 1 below, the components were mixed so that the total solid content was 20% by weight. After dilution with propylene glycol monomethyl ether acetate, the mixture was sufficiently stirred to obtain a self-luminous photosensitive resin composition.

Example of Manufacturing Color Filter (Glass Substrate) A color filter was manufactured using the self-luminous photosensitive resin compositions manufactured in Examples 1 to 3 and Comparative Examples 1 to 3. That is, each of the self-luminous photosensitive resin compositions is applied on a glass substrate by a spin coating method, and then placed on a heating plate and maintained at a temperature of 100 ° C. for 3 minutes to form a thin film. Was. Subsequently, a test photomask having a 20 mm × 20 mm square transmission pattern and a 1 μm to 100 μm line / space pattern on the thin film was placed on the thin film, and the distance between the test photomask and the test photomask was set to 100 μm, and ultraviolet rays were irradiated. .

At this time, the ultraviolet light source is irradiated with light at a light exposure of 200 mJ / cm ² (365 nm) under the atmosphere using an ultra-high pressure mercury lamp (trade name: USH-250D) manufactured by Ushio Inc. No optical filters were used. The thin film irradiated with the ultraviolet rays was developed by immersing it in a KOH aqueous solution developing solution having a pH of 10.5 for 80 seconds. The glass plate provided with the thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 150 ° C. for 10 minutes to produce a color filter pattern. The film thickness of the self-luminous color pattern manufactured as described above was 3.0 μm.

Emission Intensity Measurement Light conversion is performed using a 365 nm Tube 4W UV irradiator (VL-4LC, VILBER LOURMAT) on a pattern portion formed of a 20 mm × 20 mm square pattern in the color filter in which the self-luminous pixels are formed. In Examples 1 to 3 and Comparative Examples 1 and 2, the emission intensity (Intensity) in the 550 nm region was measured using a spectrum meter (Ocean Optics). It can be determined that the higher the measured luminescence intensity (Intensity), the more excellent the self-luminous properties are exhibited. The measurement results of the luminescence intensity (Intensity) are shown in Table 2 below.

  Further, the hard bake was performed at 230 ° C. for 60 minutes, and the light emission intensity (Intensity) before the hard bake and the light emission intensity (Intensity) after the hard bake were measured to determine the level at which the light emission efficiency was maintained. After confirmation, the results are shown in Table 2 in terms of emission intensity maintenance ratio.

Measurement of development type of self-luminous photosensitive resin composition After applying the self-luminous photosensitive resin compositions of Examples 1 to 3 and Comparative Examples 1 to 3 on a glass substrate by a spin coating method, on a heating plate And kept at a temperature of 100 ° C. for 3 minutes to form a thin film, and then immersed in a KOH aqueous solution developing solution having a pH of 10.5 to develop the coated self-luminous photosensitive resin composition layer. It was confirmed whether the resulting form was a dissolved form or a peeled form, and the results are shown in Table 2 below.

  In the case of the dissolving form, the formation of the pixel pattern is good, but in the case of the peeling form, the formation of the pixel pattern is difficult and cannot be used.

  As can be seen from Table 2, in the case of Examples 1 to 3 and Comparative Example 3 using a resin having an acrylic equivalent of 2,000 g / eq or less, the emission intensity (Intensity) is superior to Comparative Examples 1 and 2, It can be confirmed that the emission intensity is maintained high even after the baking process at 230 ° C.

  In particular, in Examples 1 to 3 and Comparative Example 3, as the acrylic equivalent increases, the luminescence intensity (Intensity) and the retention rate increase together, so that the acrylic group in the structure is used as the protective layer for the quantum dots. It can be confirmed that it has the effect of suppressing development quenched during the process. However, in the case of Comparative Example 3 in which a resin having an acrylic equivalent of 300 g / eq or less was used, the emission intensity and the maintenance ratio were high, but the resin was peeled off during development, so that it was not suitable for pattern formation. Can be.

Claims (9)

Alkali-soluble resin, photoluminescent quantum dot particles, containing a photopolymerizable compound, a photopolymerization initiator and a solvent,
The self-luminous photosensitive resin composition, wherein the alkali-soluble resin has a polymerizable unsaturated bond in the structure, and has an acrylic equivalent of 435 to 725 g / eq.   Photoluminescence quantum dot particles 3 to 80% by weight, photopolymerizable compound 5 to 50% by weight, photopolymerization initiator 0.1 to The self-luminous photosensitive resin composition according to claim 1, comprising 20% by weight and 5 to 80% by weight of an alkali-soluble resin. The alkali-soluble resin,
3- (acryloyloxy) -2-hydroxypropyl (meth) acrylate, 2-methoxy-3-propene-2-oiloxy-propyl-2-methyl-2-propionate, 2-oxydanyl-3-propene-2-oil Oxy-propyl-2-butanoate, 1,3-propanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, hydroquinone di (meth) acrylate, 1,4-phenylenedi (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, 2-propenoyloxymethyl-2-propionate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) ) Acrylates 1,12- De cane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, bisphenol A di (meth) acrylate, Jiuretanji (meth) acrylate, a single containing one or more selected from the group consisting of neopentyl glycol diacrylate The self-luminous photosensitive resin composition according to claim 1 , which is a polymer of a monomer mixture .   The self-luminous photosensitive resin composition according to any one of claims 1 to 3, wherein the alkali-soluble resin has a weight average molecular weight in terms of polystyrene of 3,000 to 100,000.   The self-luminous photosensitive resin composition according to any one of claims 1 to 4, wherein the alkali-soluble resin has an acid value of 30 to 150 mgKOH / g.   The self-luminous photosensitive resin according to any one of claims 1 to 5, wherein the photoluminescence quantum dot particle is a red quantum dot particle, a green quantum dot particle, or a blue quantum dot particle. Composition.   The photoluminescent quantum dot particles are selected from the group consisting of II-VI semiconductor compounds; III-V semiconductor compounds; IV-VI semiconductor compounds; IV group elements or compounds containing the same; and combinations thereof. The self-luminous photosensitive resin composition according to claim 1, comprising one kind.   A color filter produced using the self-luminous photosensitive resin composition according to claim 1.   An image display device comprising the color filter according to claim 8.