KR20180025248A - Self emission type photosensitive resin composition, color filter using thereof and image display device having the same - Google Patents

Abstract

The present invention relates to a spontaneous emission photosensitive resin composition. More specifically, the present invention relates to a spontaneous emission photosensitive resin composition, a color filter produced by using the same, and an image display device. To this end, the spontaneous emission photosensitive resin composition is composed of a quantum dot, a photopolymerizable compound, a photopolymerization initiator, an alkali-soluble resin, and a solvent. The photopolymerizable compound contains a compound having 7-12 acrylic functional groups. By using the spontaneous emission photosensitive resin composition of the present invention, it is possible to create excellent color reproducibility by containing the quantum dots.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a self-luminous photosensitive resin composition, a color filter manufactured therefrom, and an image display device having the color filter,

The present invention relates to a self-luminescent photosensitive resin composition capable of realizing high image quality by securing excellent luminescence intensity and luminescent retention, a color filter manufactured therefrom, and an image display device.

The display industry has undergone drastic changes from cathode-ray tubes (CRTs) to flat panel displays such as plasma display panels (PDPs), organic light-emitting diodes (OLEDs), and liquid-crystal displays (LCDs). As an example, LCD has advantages such as thinness, lightness, excellent resolution and low power consumption, and is widely used as an image display device used in almost all industries.

Generally, the LCD achieves full color by mixing the three primary colors, in which the white light generated from the light source passes through the liquid crystal cell and the transmittance is controlled and transmitted through the red, green, and blue color filters. The color filter is manufactured by coating three or more colors on a transparent substrate by a pigment dispersion method, an electrodeposition method, a printing method, a dyeing method, a transfer method, an ink jet method or the like. In recent years, a pigment dispersion method using a pigment dispersion type photosensitive resin excellent in quality and performance is mainstream.

In the pigment dispersion method, a photosensitive resin composition including a colorant, an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, an epoxy resin, a solvent, and other additives is coated on a transparent substrate provided with a black matrix, And then the unexposed portions are removed with a solvent to form a colored thin film by repeating a series of processes such as thermosetting. Thus, the method is actively applied to manufacture LCDs for mobile phones, notebooks, monitors, TVs and the like.

In general, when a pigment dispersion method is used, dyes and pigments are used as colorants, which causes a problem of lowering the transmission efficiency of the light source. The color reproduction is realized when the light irradiated from the light source is transmitted through the color filter. As a result, the reduction of the transmission efficiency lowers the color reproducibility of the image display device, which makes it difficult to realize a high quality image. Korean Patent Laid-Open Publication No. 2012-0112188 discloses a red coloring composition and a color filter for a color filter, but fails to provide an alternative to the above problem.

The use of self-emitting quantum dots instead of dyes or pigments has been proposed, as it requires better performance as well as better pattern characteristics as well as more color representation, higher color gamut and higher brightness and higher contrast ratio. The quantum dots can be self-emitted by the light source and used to generate light in the visible and infrared regions. Quantum dots are materials with a crystal structure of a few nanometers in size, consisting of hundreds to thousands of atoms. Since the quantum dots are very small in size, when the size of the object becomes smaller than the nano-size, a quantum confinement effect, which is a phenomenon in which the energy band gap of the object becomes large, appears.

In general, the quantum dot has an advantage that the desired luminescence characteristics can be realized by adjusting the size and composition thereof. However, quantum dots have a problem in that the light efficiency decreases during the hard bake process and the luminescence retention rate is lowered, and a solution is needed to solve such problems.

Korean Patent Publication No. 2012-0112188

SUMMARY OF THE INVENTION The present invention has been made in order to solve the problems of the prior art,

Luminescent photosensitive resin composition which can emit self-luminescence including a quantum dot, thereby exhibiting excellent color reproducibility and securing high luminescence intensity and high retention ratio.

Another object of the present invention is to provide a color filter having excellent surface roughness using the self-luminescent photosensitive resin composition, and to provide an image display device capable of realizing a high-quality and vivid image quality.

Another object of the present invention is to provide a self-luminescent photosensitive resin composition which can provide excellent adhesion, heat resistance and chemical resistance, and can provide excellent self-luminescent pattern emission efficiency.

According to the present invention,

(A) a quantum dot, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) an alkali-soluble resin, and (E)

Wherein the photopolymerizable compound comprises a compound having 7 to 12 acrylic functional groups.

The present invention also provides a color filter made of the self-luminescent photosensitive resin composition and an image display device including the same.

By using the self-luminescent photosensitive resin composition of the present invention, it is possible to exhibit excellent color reproducibility and improve the viewing angle by including quantum dots, and to provide an effect of improving the light emission intensity and improving the light retention rate by improving heat resistance .

In addition, the present invention provides a color filter of excellent luminance manufactured using the self-luminous photosensitive resin composition, and the image display device provided with the color filter can secure a high optical efficiency and provide a vivid image quality.

In addition, the self-luminescent photosensitive resin composition of the present invention can provide excellent adhesion, heat resistance, and chemical resistance by including a specific cation resin in an alkali-soluble resin, and can provide excellent self-luminescent pattern emission efficiency.

Hereinafter, the components constituting the self-luminescent photosensitive resin composition of the present invention will be described in detail.

(A) Qdot

The quantum dot (A) contained in the self-luminescent photosensitive resin composition of the present invention is a nano-sized semiconductor material. The atoms form molecules, and the molecules form aggregates of small molecules called clusters to form nanoparticles. These nanoparticles are called quantum dots, especially when they have the characteristics of semiconductors. The quantum dots emit energy corresponding to the energy bandgap by themselves when they reach the excited state from the outside. That is, the self-luminescent photosensitive resin composition of the present invention can self-emit light by including such quantum dots.

Since the self-luminescent photosensitive resin composition of the present invention contains quantum dots as an essential component, light having a hue is spontaneously emitted, so that color reproducibility is better and light is emitted in all directions by spontaneous emission, thereby improving viewing angle . In addition, the overall light efficiency in the color filter can be increased.

In the present invention, the quantum dot (A) is not particularly limited as long as it can emit light by stimulation by light. For example, the II-VI semiconductor compound, the III-V semiconductor compound, the IV- Element or a compound containing the same may be used.

Wherein the II-VI group semiconductor compound is selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, and mixtures thereof; Trivalent compounds selected from the group consisting of CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe and mixtures thereof; And at least one element selected from the group consisting of CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, and mixtures thereof,

The III-V semiconductor compound is selected from the group consisting of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb and mixtures thereof. A trivalent compound selected from the group consisting of GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP and mixtures thereof; And a photoresist selected from the group consisting of GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, Or more,

The IV-VI semiconductor compound may be selected from the group consisting of SnS, SnSe, SnTe, PbS, PbSe, PbTe, and mixtures thereof. Ternary compounds selected from the group consisting of SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, and mixtures thereof; And a silicate compound selected from the group consisting of SnPbSSe, SnPbSeTe, SnPbSTe, and mixtures thereof,

The Group IV element or a compound containing the Group IV element is an elemental compound selected from the group consisting of Si, Ge, and mixtures thereof; And these elemental compounds selected from the group consisting of SiC, SiGe, and mixtures thereof.

Further, the quantum dots may have a single homogeneous structure; A dual structure such as a core-shell structure, a gradient structure, or the like; Or a mixed structure thereof. For example, in the dual structure of the core-shell, the material forming each core and the shell may be made of the different semiconductor compounds mentioned above. More specifically, the core may include, but is not limited to, one or more materials selected from CdSe, CdS, ZnS, ZnSe, CdTe, CdSeTe, CdZnS, PbSe, AgInZnS and ZnO. The shell may include at least one material selected from CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, and HgSe, but is not limited thereto.

As the colored photosensitive resin composition used in the production of a typical color filter contains red, green and blue coloring agents for color implementation, the quantum dots of the present invention can be colored red, green, And quantum dots according to the present invention may be at least one kind selected from the above-mentioned red, green or blue quantum dots.

The quantum dot may be synthesized by a wet chemical process, a metal organic chemical vapor deposition (MOCVD) process, or a molecular beam epitaxy (MBE) process. The wet chemical process is a method of growing particles by adding a precursor material to an organic solvent. When crystals are grown, the organic solvent naturally coordinates to the surface of the quantum dot crystals to act as a dispersing agent to control crystal growth. Therefore, it is easier and less expensive to process nano-particles than the vapor deposition method such as the organic metal chemical vapor deposition or molecular beam epitaxy The growth of the particles can be controlled.

The content of the quantum dots (A) in the present invention is not particularly limited, but is preferably 3 to 80% by weight, more preferably 5 to 70% by weight, more preferably 5 to 70% by weight, based on the solid content in the self- More preferably from 20 to 40% by weight. If the content of the quantum dots is less than 3% by weight, the luminous efficiency may be insufficient. If the content of the quantum dots exceeds 80% by weight, the content of the other components is insufficient.

(B) Photopolymerization  compound

The photopolymerizable compound (B) contained in the self-luminescent photosensitive resin composition of the present invention is a compound that can be polymerized by an active radical, acid, or the like generated from a photopolymerization initiator (C) described later.

The self-luminescent photosensitive resin composition of the present invention is a photopolymerizable compound containing a compound having 7 to 12 acrylic functional groups, preferably a compound represented by the following formula (1).

[Chemical Formula 1]

이며,Wherein R is H or < RTI ID = 0.0 >

Lt;

n is an integer of 2 to 4;

When the compound of Formula 1 is included as a photopolymerizable compound, it may be more effective to increase the thermal stability of the quantum dot during the post-bake process during the color filter process so as to maintain the emission intensity high.

The compound represented by Formula 1 may be included in an amount of 5 to 100% by weight based on the total weight of the photopolymerizable compound, but is not limited thereto.

The photopolymerizable compound may further comprise a multifunctional monomer comprising from 1 to 6 unsaturated double bonds. More preferably, the polyfunctional monomer is an acrylate monomer having a carboxylic acid group as shown in the following formula (2), and a color filter having better light emission intensity and surface roughness characteristics than the case of using it may be produced.

(2)

이다. In the general formula (2), R ₃ to R ₅ are the same or different and each is OH, an alkyl group having 1 to 4 carbon atoms, an acrylate group, a methacrylate group or -OR ₇ . At least one of R ₃ to R ₅ is an acrylate group or a methacrylate group, and R ₇ is

to be.

Wherein R ₆ is -C (= O) CH ₂ CH ₂ C (= O) OH,

R ₈ and R ₉ are an acrylate group or a methacrylate group, and R ₁₀ is hydrogen, an acryloyl group, a methacryloyl group or -C (═O) CH ₂ CH ₂ C (═O) OH.

The multifunctional monomer having 1 to 6 unsaturated double bonds is preferably contained in an amount of 10 to 95% by weight, and more preferably 15 to 90% by weight based on the total weight of the photopolymerizable compound.

The photopolymerizable compound may further include monofunctional monomers, bifunctional monomers, and trifunctional or higher functional monomers in addition to the compounds described above.

Specific examples of the monofunctional monomer include, but are not limited to, nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl 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) , Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like, but are not limited thereto.

Specific examples of the trifunctional or higher functional polyfunctional monomer include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like, but are not limited thereto.

The photopolymerizable compound (B) is preferably contained in an amount of 5 to 70% by weight, more preferably 7 to 65% by weight based on the solid content in the self-luminescent photosensitive resin composition, more preferably 20 By weight to 50% by weight. When the content of the photopolymerizable compound is within the range of 5 to 70% by weight based on the above-mentioned criteria, it is preferable that the formation of the pixel trap is easy for the light source and the strength and smoothness of the pixel portion become good. If the content is less than 5% by weight, the degree of photo-curing due to light is lowered and the formation of a pixel pattern becomes difficult. When the content exceeds 70% by weight, peeling of the pattern may occur.

In particular, the compound having 7 to 12 acryl functional groups is contained in an amount of preferably 5 to 100% by weight, more preferably 10 to 95% by weight, and more preferably 60 to 80% by weight based on the total weight of the photopolymerizable compound %. When the content of the compound having 7 to 12 acrylic functional groups on the basis of the above criteria is 5 to 100% by weight, the quantum dots are prevented from being extinguished when baking at a high temperature during the color filter manufacturing process, So that the filter can be manufactured.

(C) a photopolymerization initiator

The photopolymerization initiator (C) contained in the self-luminescent photosensitive resin composition of the present invention initiates polymerization of the photopolymerizable compound (B) by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, And the like.

The photopolymerization initiator is not particularly limited as long as it is commonly used in the art within the scope of not impairing the object of the present invention. Specific examples of the photopolymerization initiator include triazine-based compounds, acetophenone-based compounds, nonimidazole-based compounds, and oxime-based compounds, but not limited thereto, and at least one selected therefrom can be used. The self-luminescent photosensitive resin composition containing the photopolymerization initiator described above has high sensitivity, and the pixel pixel of the color filter formed using this composition can have a good strength and patterning property of the pixel portion.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) (Trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) Bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) -Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- Azine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine and 2,4- Methyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- (4-methylthioxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2- 2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1-one, 1-one, and 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one. Further, a compound represented by the following formula (3) can be mentioned.

(3)

In Formula 3, R ₁ to R ₄ are each independently selected from the group consisting of hydrogen, halogen, OH, a phenyl group substituted with an alkyl group having 1 to 12 carbon atoms, a benzyl group substituted or unsubstituted with an alkyl group having 1 to 12 carbon atoms, Or a naphthyl group substituted or unsubstituted with an alkyl group having 1 to 12 carbon atoms.

Examples of the compound represented by the general formula (3) include 2-methyl-2-amino (4-morpholinophenyl) ethan- 1-one, 2-propyl-2-amino (4-morpholinophenyl) ethan- (4-morpholinophenyl) propane-1-one, 2-amino-2- 2-methyl-2-methylamino (4-morpholinophenyl) propane-1-one, 1-one, 2-methyl-2-dimethylamino (4-morpholinophenyl) propan- have.

Examples of the non-imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'- 4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole or an imidazole compound in which the phenyl group at the 4,4 ', 5,5' position is substituted with a carboalkoxy group. Among them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis 4,4 ', 5,5'-tetraphenylbiimidazole or 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl- Etc. may be used.

Examples of the oxime compounds include o-ethoxycarbonyl- alpha -oximimino-1-phenylpropan-1-one, 1- [9-ethyl-6- (2-methylbenzoyl) -9H- (Z) -2 - ((benzoyloxy) imino) -1- (4- (phenylthio) phenyl) octan-1-one, (E) -1- (((1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol- (((1- (6- (4 - ((2,2-dimethyl-1,3-dioxolan-4- yl) methoxy) -2-methylbenzoyl) -9- -Yl) ethyl) amino) oxy) ethanone, and commercially available products include, but are not limited to, OXE-01 and OXE-02 from BASF. Further, the following formulas (4) to (6) are exemplified.

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

Further, other photopolymerization initiators which are usually used may be further used within the range not impairing the effects of the present invention. Specific examples of the other photopolymerization initiators include benzoin compounds, benzophenone compounds, thioxanone compounds and anthracene compounds. These may be used alone or in combination of two or more.

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

Examples of the benzophenone compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and 4'-di (N, N'-dimethylamino) -benzophenone.

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

Examples of the anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, etc. .

Other photopolymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethyl anthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, Methyl phenylchloroxylate, and titanocene compounds.

The photopolymerization initiator (C) is preferably contained in an amount of 0.1 to 20% by weight, more preferably 1 to 10% by weight based on the solid content in the self-luminescent photosensitive resin composition of the present invention. When the content of the photopolymerization initiator is within the range of 0.1 to 20% by weight based on the above-mentioned criteria, the self-light-sensitive photosensitive resin composition is highly sensitized and the exposure time is shortened, so that productivity is improved and high resolution can be maintained. And the strength of the pixel portion formed by using the self-luminescent photosensitive resin composition of the present invention and the smoothness of the surface of the pixel portion can be improved.

On the other hand, in order to improve the sensitivity of the self-luminescent photosensitive resin composition of the present invention, the photopolymerization initiator (c) may be used in combination with the photopolymerization initiator (C). When the self-luminescent photosensitive resin composition of the present invention contains a photopolymerization initiator, the sensitivity is further increased and productivity can be improved when the color filter is formed using the composition.

As the photopolymerization initiation auxiliary (c1), for example, at least one compound selected from an amine compound and a carboxylic acid compound can be preferably used.

Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine; aliphatic amines such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl aminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'- Ethylamino) benzophenone, and the like, and it is more preferable to use an aromatic amine compound.

Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid , And aromatic heteroacetic acids such as dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

The photopolymerization initiator (c1) is preferably contained in an amount of 0.1 to 20% by weight, more preferably 1 to 10% by weight based on the solid content in the self-luminescent photosensitive resin composition. If the content of the photopolymerization initiator is within the above-mentioned range, the sensitivity efficiency of the self-luminescent photosensitive resin composition is further increased and the productivity of the color filter formed using the composition tends to be improved.

(D) an alkali-soluble resin

The alkali-soluble resin (D) contained in the self-luminescent photosensitive resin composition of the present invention is a component that imparts solubility to the alkali developing solution used in the developing process. That is, the non-exposed portion of the photosensitive resin layer formed by using the self-luminescent photosensitive resin composition can be rendered alkali soluble and the exposed portion can be left. In the present invention, any resin that can be dissolved in an alkaline developer is usable, Do.

The alkali-soluble resin can be produced by copolymerizing at least one selected from an unsaturated monomer having a carboxyl group and a monomer having an unsaturated bond copolymerizable therewith, but is not limited thereto.

As the unsaturated monomer having a carboxyl group, an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, or an unsaturated polycarboxylic acid can be used. Specific examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid,? -Chloroacrylic acid, cinnamic acid, and the like. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. The unsaturated dicarboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride, citraconic anhydride and the like. The unsaturated polycarboxylic acid may also be a mono (2-methacryloyloxyalkyl) ester thereof, for example, mono (2-acryloyloxyethyl) succinate, mono (2-methacryloyloxy Ethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl), and the like. The unsaturated polycarboxylic acid may be a mono (meth) acrylate of the both terminal dicarboxylic polymer. Examples thereof include? -Carboxypolycaprolactone monoacrylate and? -Carboxypolycaprolactone monomethacrylate. have. These unsaturated monomers having carboxyl groups may be used alone or in combination of two or more.

Of these compounds, acrylic acid and methacrylic acid may be more preferable because of their excellent copolymerization reactivity and solubility in developer.

The monomer having an unsaturated bond copolymerizable with the unsaturated monomer having a carboxyl group is not particularly limited as long as it contains an unsaturated double bond capable of polymerization.

Specific examples of the unsaturated carboxylic acid include unsaturated carboxylic acids such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) Unsubstituted or substituted alkyl ester compounds;

(Meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (Meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, mentadienyl (meth) acrylate, isobornyl An unsaturated carboxylic acid ester compound containing an alicyclic substituent group such as a phenanthryl (meth) acrylate, adamanthyl (meth) acrylate, norbornyl (meth) acrylate or pinenyl (meth) acrylate;

3-ethyloxetane, 3 - ((meth) acryloyloxymethyl) oxetane, 3 - ((meth) acryloyloxymethyl) Unsaturated carboxylic acid ester compounds containing thermosetting substituents such as oxetane and 3 - ((meth) acryloyloxymethyl) -2-trifluoromethyloxetane;

Mono-saturated carboxylic acid ester compounds of glycols such as oligoethylene glycol monoalkyl (meth) acrylate;

Unsaturated carboxylic acid ester compounds containing a substituent having an aromatic ring such as benzyl (meth) acrylate, phenoxy (meth) acrylate and the like;

Aromatic vinyl compounds such as styrene,? -Methylstyrene, and vinyltoluene;

Carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate, vinyl cyanide compounds such as (meth) acrylonitrile and? -Chloroacrylonitrile;

Acrylates such as glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, methyl glycidyl 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-methyloxetane, 3- (methacryloyloxymethyl) 3- (methacryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 3- 3- (methacryloyloxymethyl) -2,2-difluorooxetane, 3- (methacryloyloxymethyl) -2,2,4-trifluorooxetane, 3- 3- (methacryloyloxyethyl) -3-ethyloxetane, 2 (methacryloyloxyethyl) oxetane, 2- 3- (methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxy) (Methacryloyloxyethyl) -2-phenyloxetane, 2, 2-difluoro-3- (methacryloyloxyethyl) oxetane, 2- 3- (methacryloyloxyethyl) -2,2,4-trifluorooxetane, 3- (methacryloyloxyethyl) -2,2,4,4-tetrafluorooxetane, 3- (Acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- 3- (acryloyloxymethyl) -2-phenyloxetane, 3- (acryloyloxymethyl) -2-pentafluoroethyloxetane, 3- 3- (acryloyloxymethyl) -2,2-difluorooxetane, 3- (acryloyloxymethyl) -2,2,4-trifluorooxetane, 3- 3- (acryloyloxyethyl) -3-ethyloxetane, 2-ethyl-3- (acryloyloxyethyl) Oxyethyl) oxetane, 3- (acryloyloxyethyl) -2-t 2-pentafluoroethyloxetane, 3- (acryloyloxyethyl) -2-phenyloxetane, 2,2-difluoro-3 - (acryloyloxyethyl) oxetane, 3- (acryloyloxyethyl) -2,2,4-trifluorooxetane, 3- (acryloyloxyethyl) -2,2,4,4 (Meth) acrylate, 3,4-epoxytricyclodecan-8-yl (meth) acrylate, 3,4-epoxytricyclodecan- (Meth) acrylate, epoxylated dicyclopentanyloxyethyl (meth) acrylate (2- (3,4-epoxytricyclodecan-9-yloxy) An aliphatic polycyclic compound having an unsaturated bond with an epoxy group such as tricyclodecan-8-yloxy) ethyl (meth) acrylate and epoxidized dicyclopentanyloxyhexyl (meth) acrylate;

Epoxy compounds such as dicyclopentane, tricyclodecane, norbornane, isonorbornane, bicyclooctane, cyclononane, bicycloundecane, tricyclooctane, bicyclododecane, and tricyclododecane; N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N- Dicarbonylimide derivatives such as N-succinimidyl-3-maleimidepropionate and N- (9-acridinyl) maleimide, and the like.

The alkali-soluble resin particularly preferably contains a cationic binder resin containing at least one of the following chemical formulas (7) to (12) to improve the adhesiveness, heat resistance and chemical resistance of the self-luminescent photosensitive resin composition, : ≪ / RTI >

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

In the above formulas (7) to (12)

,

,

,

,

,

,

,

,

,

,

,

또는

이고,X and X 'are each independently a single _{bond, -CO-, -SO 2 -, -C} (CF 3) 2 -, -Si (CH 3) 2 -, -CH 2 -, -C (CH 3) 2 -, -O-,

,

,

,

,

,

,

,

,

,

,

,

or

ego,

Y is an acid anhydride residue and the acid anhydride residue is selected from the group consisting of maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylenedodomethylenetetrahydrophthalic anhydride, Or anhydrous methyl tetrahydrophthalic acid;

Z is an acid dianhydride moiety and the acid dianhydride moiety is anhydrous pyromellitic acid, benzophenonetetracarboxylic acid anhydride, biphenyltetracarboxylic acid anhydride, biphenyl ether tetracarboxylic acid anhydride, cyclohexyl acid anhydride, or cyclobutyric anhydride;

R 'is a ₂ H ₄ OH or -CH ₂ CH = CH ₂ a hydrogen atom, an ethyl group, a phenyl _{group, -C 2 H 4 Cl, -C} ,

R1, R1 ', R2, R2', R3, R3 ', R4, R4', R5, R5 ', R6 and R6' are each independently a hydrogen atom or a methyl group;

R7, R7 ', R8 and R8' are each independently a linear or branched alkylene group having 1 to 6 carbon atoms, and the alkylene group is an ester bond, a cycloalkylene group having 6 to 14 carbon atoms and an arylene group having 6 to 14 carbon atoms , ≪ / RTI >

R9, R9 ', R10, R10', R11, R11 ', R12 and R12' are each independently a hydrogen atom, a halogen atom or a straight or branched alkyl group having 1 to 5 carbon atoms;

m and n are integers satisfying 0? m? 30 and 0? n? 30, provided that m and n are not 0 at the same time;

P is

, A represents O, S, N, Si or Se, R13 and R14 independently represent hydrogen, a hydroxyl group, a thiol group, an amino group, a nitro group or a halogenated group;

a and b are integers from 1 to 6;

Ar 1 represents an aryl group having 5 to 15 carbon atoms.

The compound represented by any one of the above formulas (7) to (12) may be contained in an amount of 10 to 100% by weight, preferably 10 to 90% by weight, and more preferably 20 to 80% by weight, based on the total weight of the alkali- More preferable. When included in the above range, the adhesiveness, heat resistance, and chemical resistance of the self-luminescent photosensitive resin composition are improved, and the luminous efficiency of the self-luminescent pattern is improved.

The alkali-soluble resin (B) preferably further comprises an acrylic resin.

The alkali-soluble resin preferably has a weight average molecular weight in terms of polystyrene of 3,000 to 200,000 Da, more preferably 5,000 to 100,000 Da, in order to improve surface hardness for use as a color filter. Further, the molecular weight distribution, it is preferable (M _w / M _n) is from 1.5 to 6.0, more preferably in the range of 1.8 to 4.0. When the weight average molecular weight and the molecular weight distribution of the alkali-soluble resin are within the above-mentioned range, the hardness is improved, the residual film ratio is high, the solubility of the non-exposed portion in the developer is excellent, and the resolution can be improved.

The acid value of the alkali-soluble resin is preferably 20 to 200 mgKOH / g based on the solid content. The acid value is related to the solubility as a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the acrylic polymer. When the acid value of the resin is within the above range, the solubility in the developer is improved so that the non-exposed portion is easily dissolved and the sensitivity is increased, and consequently the pattern of the exposed portion remains during development, thereby improving the film remaining ratio.

The alkali-soluble resin (D) may be contained in an amount of preferably 5 to 80% by weight, more preferably 10 to 70% by weight based on the solid content in the self-luminescent photosensitive resin composition. When the content of the alkali-soluble resin (D) is within the above-mentioned range, solubility in a developing solution is sufficient, so that the absence of the non-pixel portion is improved, So that the pattern formation is facilitated.

(E) Solvent

The solvent (E) contained in the self-luminescent photosensitive resin composition of the present invention may be an organic solvent ordinarily used in the art without any particular limitation. Examples of the solvent include ethers, acetates, aromatic hydrocarbons, ketones, alcohols, and esters. One or more of these solvents can be selected and used, but the present invention is not limited thereto.

Specific examples of the ether solvents 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 dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether;

Propylene glycol dialkyl ethers such as propylene glycol monomethyl ether; And the like.

Examples of the acetate solvents include ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate;

Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monopropyl ether acetate;

Alkoxyalkyl acetates such as methoxybutyl acetate and methoxypentyl acetate; And the like.

Specific examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene.

Specific examples of the ketone solvent include methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone.

Specific examples of the alcohol solvents include ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin.

Specific examples of the ester solvent include esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate;

cyclic esters such as? -butyrolactone; And the like.

These solvents may be used alone or in combination of two or more.

Among the above-mentioned solvents (E), an organic solvent having a boiling point of 100 to 200 DEG C in terms of coatability and dryness is preferable, and alkylene glycol alkyl ether acetates; Ketones; Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; And the like. These solvents may be used alone or in combination of two or more.

In the present invention, the content of the solvent is not particularly limited, and may be included in an amount sufficient to satisfy 100 wt% of the self-luminescent photosensitive resin composition. Preferably 60 to 90% by weight, and more preferably 70 to 85% by weight based on the total weight of the self-emitting photosensitive resin composition. When the content of the solvent (E) is within the above-mentioned range, when the solvent (E) is applied by a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater It is possible to provide an effect of canceling.

(F) Gold oxide

Self-luminous photosensitive resin composition of the present invention are _{Al 2 O 3, SiO 2,} ZnO, ZrO 2, BaTiO 3, TiO 2, Ta 2 O 5, Ti 3 O 5, ITO, IZO, ATO, ZnO-Al, Nb 2 O ₃ , SnO, and MgO. The metal oxide may further include one or more metal oxides selected from the group consisting of O ₃ , SnO, and MgO.

When the self-emission photosensitive resin composition further includes a metal oxide, it is preferable that the light efficiency of the color filter can be increased by increasing the path of light spontaneously emitted from the quantum dots through the scattering particles.

The metal oxide may be contained in an amount of preferably 0.1 to 50% by weight, more preferably 0.3 to 30% by weight based on the solid content in the self-light-sensitive photosensitive resin composition.

<Color filter>

Further, the present invention provides a color filter made of the above-mentioned self-luminescent photosensitive resin composition.

When the color filter of the present invention is applied to an image display device, since it emits light by the light source, a higher optical efficiency can be realized. Further, since the light having the color is emitted by itself, the color reproducibility is better and the light is emitted in all directions by the self-luminescence, thereby also providing the effect of improving the viewing angle.

The color filter includes a substrate and a pattern layer formed on the substrate. The substrate may be a substrate of a color filter itself, or may be a portion where a color filter is placed on a display device or the like, and is not particularly limited. The substrate may be, for example, glass, silicon (Si), silicon oxide (SiO _x ), or a polymer substrate. Specifically, the polymer substrate may be polyethersulfone (PES) or polycarbonate (PC).

The pattern layer may be a layer containing the self-luminescent photosensitive resin composition of the present invention, and may be a layer formed by applying the self-luminescent photosensitive resin composition and exposing, developing and thermally curing the self-luminescent photosensitive resin composition in a predetermined pattern.

The pattern layer formed of the self-luminescent photosensitive resin composition may include a red pattern layer containing red quantum dots, a green pattern layer containing green quantum dots, and a blue pattern layer containing blue quantum dots. During the 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, the emitted light of the light source is not particularly limited when applied to an image display apparatus, but a light source that emits blue light in terms of better color reproducibility can be used.

In addition, the pattern layer may include only a pattern layer of two colors selected from a red pattern layer, a green pattern layer, and a blue pattern layer. In such a case, the pattern layer may further include a transparent pattern layer not containing a quantum dot.

In the case where only the pattern layer of two colors is provided, a light source that emits light having a wavelength that represents the remaining color that is not included can be used. For example, when a red pattern layer and a green pattern layer are included, a light source that emits blue light can be used. In such a case, the red quantum dot emits red light and the green quantum dot emits green light, and the transparent pattern layer transmits blue light as it is and exhibits blue color.

The color filter including the substrate and the pattern layer described above may further include a partition wall formed between each pattern, and may further include a black matrix. Further, it may further comprise a protective film formed on the pattern layer of the color filter.

<Image Display Device>

The present invention also provides an image display device including the color filter. The color filter is applicable to various image display devices such as an electroluminescence display device, a plasma display device, a field emission display device, and the like, as well as a normal liquid crystal display device.

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

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the following examples illustrate the present invention and the present invention is not limited by the following examples, and various modifications and changes may be made. The scope of the present invention will be determined by the technical idea of the following claims.

< Manufacturing example >

Manufacturing example  One. CdSe (core)/ ZnS (Shell) Structure of Green Quantum Dots A-1

CdO (0.4 mmol), zinc acetate (4 mmol) and oleic acid (5.5 mL) were added to the reactor together with 1-Octadecene (20 mL) and heated to 150 ° C. Lt; / RTI &gt; The reaction was then left under vacuum at 100 mTorr for 20 minutes to remove the acetic acid formed by the displacement of oleic acid into zinc.

Then, a transparent mixture was obtained by applying heat at 310 DEG C, and after maintaining the temperature at 310 DEG C for 20 minutes, 0.4 mmol of Se powder and 2.3 mmol of S powder were dissolved in 3 mL of trioctylphosphine, and Se And S solution were rapidly injected into a reactor containing Cd (OA) ₂ and Zn (OA) ₂ solutions. The resulting mixture was grown at 310 ° C for 5 minutes, and growth was stopped using an ice bath.

Thereafter, the precipitates were precipitated with ethanol, and the quantum dots were separated using a centrifugal separator. The excess impurities were washed with chloroform and ethanol to obtain particles having a core particle diameter and a shell thickness of 3 to 5 nm, which were stabilized with oleic acid And a quantum dot particle A-1 of a distributed CdSe (core) / ZnS (shell) structure was obtained.

Manufacturing example  2. Synthesis of alkali-soluble resin (D-1)

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was provided with 45 parts by weight of N -benzylmaleimide, 45 parts by weight of methacrylic acid, 10 parts by weight of tricyclodecyl methacrylate, 4 parts by weight of butylperoxy-2-ethylhexanoate and 40 parts by weight of propylene glycol monomethyl ether acetate (hereinafter, also referred to as &quot; PGMEA &quot;) were charged and stirred to prepare a monomer dropping funnel. 6 parts by weight and PGMEA (24 parts by weight), and the mixture was stirred to prepare a chain transfer agent dropwise. Then, 395 parts by weight of PGMEA was introduced into the flask, the atmosphere in the flask was replaced with nitrogen in air, and the temperature of the flask was raised to 90 DEG C while stirring. Then, the monomer and the chain transfer agent were added dropwise from the dropping funnel. The mixture was heated for 2 hours while keeping the temperature at 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 obtain a mixed gas of oxygen / nitrogen = 5 / Bubbling was started.

Then, 10 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 a flask, The reaction was continued, and then cooled to room temperature to obtain Resin D-1 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.

Manufacturing example  3: Synthesis of alkali-soluble resin (D-2)

 (1) 138 g of bisphenol epoxy compound 9,9'-bis (4-glycyloxyphenyl) fluorene (Hear chem), 54 g of 2-carboxyethyl acrylate, 1.4 g of benzyltriethylammonium chloride 1 g of triphenylphosphine (Aldrich), 128 g of propylene glycol methyl ethyl acetate (Daicel Chemical Co.) and 0.5 g of hydroquinone were charged, and the mixture was heated to 120 ° C and maintained at that temperature for 12 hours to obtain a compound represented by the following formula Were synthesized.

(2) 60 g of the compound represented by the above formula (13), 11 g of biphenyltetracarboxylic dianhydride (Mitsubishi Gas), 3 g of tetrahydrophthalic anhydride (Aldrich), 3 g of propylene glycol methyl ethyl acetate ), And 0.1 g of N, N'-tetramethylammonium chloride were added, and the temperature was raised to 120 占 폚 and maintained for 2 hours to synthesize a compound represented by the following formula (14). The weight average molecular weight of the resin represented by the formula (14) was 5,400 g / mol.

[Chemical Formula 13]

[Chemical Formula 14]

Manufacturing example  4: Synthesis of alkali-soluble resin (D-3)

(1) 138 g of bisphenol epoxy compound 9,9'-bis (4-glycyloxyphenyl) fluorene (Hear chem), 54 g of mono-2-acryloyloxyethyl succinate, benzyltriethylammonium chloride 1 g of triphenylphosphine (Aldrich), 128 g of propylglycolmethylethylacetate (Daicel Chemical Co.) and 0.5 g of hydroquinone were charged, and the mixture was heated to 120 캜 and maintained at that temperature for 12 hours, Was synthesized.

(2) In a reactor, 60 g of the compound represented by the above formula (15), 11 g of biphenyltetracarboxylic dianhydride (Mitsubishi Gas), 3 g of tetrahydrophthalic anhydride (Aldrich), 3 g of propylglycolmethylethylacetate ) And 0.1 g of N, N'-tetramethylammonium chlorite were charged, and the mixture was heated to 120 ° C and maintained at that temperature for 2 hours to synthesize a compound represented by the following formula (16). The weight average molecular weight of the resin represented by the formula (16) was 5,400 g / mol.

[Chemical Formula 15]

[Chemical Formula 16]

Manufacturing example  5: Synthesis of alkali-soluble resin (D-4)

 (1) In order to synthesize the compound of formula (12), a 3,000 ml three-necked round-bottomed flask was charged with 3 ', 6'-dihydroxyspiro (fluorene-9,9 -xanthene and 0.4159 g of t-butylammonium bromide were mixed, and 2359 g of epichlorohydrin was added and reacted by heating at 90 DEG C. Analysis by liquid chromatography revealed that 3,6-dihydroxy spiro (fluorene- 9,9-xanthene) was completely consumed, the reaction mixture was cooled to 30 DEG C and slowly added with 50% NaOH aqueous solution (3 equivalents). When the epichlorohydrin was completely removed by analysis by liquid chromatography, the reaction product was extracted with dichloromethane three times After washing with water, the organic layer was dried over magnesium sulfate, and the dichloromethane was distilled off under reduced pressure, and recrystallization was performed using a dichloromethane / methanol mixture ratio of 50:50.

One equivalent of the thus synthesized epoxy compound, 0.004 equivalent of t-butylammonium bromide, 0.001 equivalent of 2,6-diisobutylphenol and 2.2 equivalents of acrylic acid were mixed and 24.89 g of solvent propylene glycol monomethyl ether acetate was added and mixed. The reaction solution was heated and dissolved at 90 to 100 ° C while air was blown at 25 ml / min. The reaction solution was completely dissolved by heating to 120 DEG C in a cloudy state. When the solution becomes transparent and the viscosity becomes high, the acid value is measured and stirred until the acid value becomes less than 1.0 mg KOH / g. It took 11 hours to reach the target price (0.8). After completion of the reaction, the temperature of the reactor was lowered to room temperature to obtain a colorless transparent compound.

[Chemical Formula 17]

(2) After adding 600 g of propylene glycol monomethyl ether acetate to 307.0 g of the compound of the formula (12) and dissolving, 78 g of biphenyltetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed and slowly heated to 110 ° C Lt; / RTI &gt; After disappearance of the acid anhydride group was confirmed, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 DEG C for 6 hours to polymerize with a cationic binder resin. The disappearance of the anhydride was confirmed by IR spectrum.

Manufacturing example  6: Synthesis of alkali-soluble resin (D-5)

(1) To synthesize the compound of formula (13), 4,4 '- (9H-xanthene-9,9-diyl) diphenol (4,4' - (9H-xanthene-9,9-diyl ) diphenol) and 0.4159 g of t-butylammonium bromide were mixed, 2359 g of epichlorohydrin was added, and the mixture was reacted by heating at 90 占 폚. (9H-xanthene-9,9-diyl) diphenol) was completely depleted, the reaction mixture was cooled to 30 ° C Cooled and slowly added 50% NaOH aqueous solution (3 eq.). When the epichlorohydrin was completely exhausted, the reaction mixture was extracted with dichloromethane and then washed three times. The organic layer was dried over magnesium sulfate, and the dichloromethane was distilled off under reduced pressure. The dichloromethane-methanol mixture ratio was 50:50 And recrystallized.

One equivalent of the thus synthesized epoxy compound, 0.004 equivalent of t-butylammonium bromide, 0.001 equivalent of 2,6-diisobutylphenol and 2.2 equivalents of acrylic acid were mixed and 24.89 g of solvent propylene glycol monomethyl ether acetate was added and mixed. The reaction solution was heated and dissolved at 90 to 100 ° C while air was blown at 25 ml / min. The reaction solution was completely dissolved by heating to 120 DEG C in a cloudy state. When the solution becomes transparent and the viscosity becomes high, the acid value is measured and stirred until the acid value becomes less than 1.0 mg KOH / g. It took 11 hours to reach the target price (0.8). After completion of the reaction, the temperature of the reactor was lowered to room temperature to obtain a colorless transparent compound.

[Chemical Formula 19]

(2) To 307.0 g of the compound of the formula (13), 600 g of propylene glycol monomethyl ether acetate was added and dissolved. 78 g of biphenyltetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed and slowly heated to a temperature of 110 to 115 DEG C Lt; / RTI &gt; After disappearance of the acid anhydride group was confirmed, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 DEG C for 6 hours to polymerize with a cationic binder resin. The disappearance of the anhydride was confirmed by IR spectrum.

Manufacturing example  7: Synthesis of alkali-soluble resin (D-6)

(1) A reflux condenser and a thermometer were set in a 3-neck flask, and then 42.5 g of 9,9-bisphenolfluorene was added and 220 mL of 2- (chloromethyl) oxirane was injected. After adding 100 mg of tetrabutylammonium bromide, the temperature was raised to 90 캜 while stirring was started. After confirming that the unreacted content was less than 0.3%, it was distilled under reduced pressure.

 After the temperature was lowered to 30 ° C, dichloromethane was added, and NaOH was slowly added. The product was confirmed to be 96% or more by a high performance liquid chromatography (HPLC) method, and 5% HCl was added dropwise to terminate the reaction. The reaction product was extracted and layered, and the organic layer was washed with water and neutralized. The organic layer was dried over MgSO4 and concentrated under reduced pressure using a rotary evaporator. Dichloromethane was added to the concentrated product, and methanol was added to the solution while the temperature was raised to 40 ° C. The solution temperature was lowered and stirred. The resulting solid was filtered, and then vacuum-dried at room temperature to obtain 52.7 g (yield 94%) of a white solid powder. The structure thereof was confirmed by 1H NMR.

. (2H), 2.87 (2H), 2.71 (2H), 2.71 (2H, 2H), 3.71 ).

(2) Synthesis of 3,3 '- ((9H-fluorene-9,9-diyl) bis (4,1-phenylene)) bis (oxy)) bis (1- (phenylthio) propan-2-ol).

 A reflux condenser and a thermometer were set in a 3-neck flask, and then a first-stage reaction product (1000 g), 524 g of thiophenol and 617 g of ethanol were added and stirred. 328 g of triethylamine was slowly added dropwise to the reaction solution. After confirming that the starting material disappeared by high performance liquid chromatography (HPLC) method, the reaction was terminated. After completion of the reaction, the ethanol was distilled off under reduced pressure. The organics were dissolved in dichloromethane, washed with water and then dichloromethane was removed by distillation under reduced pressure. The concentrated organic material was dissolved in ethyl acetate, ether solvent was added dropwise, and the mixture was stirred for 30 minutes. The compound was distilled under reduced pressure to obtain 945 g (yield: 64%) of pale yellow oil. Its structure was confirmed by 1H NMR.

2H NMR (CDCl3): 7.82 (2H), 7.38-6.72 (2H), 6.51 (4H), 4.00 (2H), 3.97 ).

(3) Synthesis of binder resin

After the reflux condenser and thermometer were set in a 3-neck flask, a solution of 3,3 '- ((9H-fluorene-9,9-diyl) bis (4,1- bis (oxy)) bis (1- (phenylthio) propan-2-ol) monomer was added and the temperature was elevated to 115 ° C. 31.1 g of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride was added dropwise at 115 DEG C, and the mixture was stirred at 115 DEG C for 6 hours. Phthalic anhydride (7.35 g) was added thereto, followed by further stirring for 2 hours, and the reaction was terminated. After cooling, a binder solution having a weight average molecular weight of 3,500 g / mol was obtained.

Production Example 8: Synthesis of alkali-soluble resin (D-7)

A reflux condenser and a thermometer were set in a 3-neck flask, and a solution of 3,3 '- ((9H-fluorene-9,9-diyl) bis bis (oxy)) bis (1- (phenylthio) propan-2-ol) monomer was added and the temperature was raised to 115 ° C. 21.1 g of pyromellitic dianhydride was added dropwise at 115 캜, and the mixture was stirred at 115 캜 for 6 hours. Phthalic anhydride (7.35 g) was added thereto, and the reaction was terminated after stirring for an additional 2 hours. After cooling, a binder solution having a weight average molecular weight of 4,500 g / mol was obtained.

&Lt; Examples and Comparative Examples &

Examples 1 to 13 and Comparative Examples 1 to 5. Production of self-luminescent photosensitive resin composition

Each of the components was mixed as shown in the following Table 1, diluted with propylene glycol monomethyl ether acetate so that the total solid content was 20% by weight, and sufficiently stirred to obtain a self-luminescent photosensitive resin composition.

week)

(A) Quantum dot

A-1: CdSe (core) / ZnS (shell) structure of Production Example 1 Quantum dots A-1

(B) a photopolymerizable compound

B-1: VISCOAT802, manufactured by Osaka Organic Chemicals, 8-functional photopolymerizable compound

B-2: UA-33H, 9-functional photopolymerizable compound manufactured by Shin Nakamura Chemical Co., Ltd.

B-3: U-10HA, manufactured by Shin Nakamura Chemical Co., Ltd., 10-functional photopolymerizable compound

B-4: TO-1382, Dong-A Synthetic Preparation, 5-Function Photopolymerizable Compound Containing Carboxylic Acid

B-5: TO-756, Dong-A Synthetic Preparation, Trifunctional Photopolymerizable Compound Containing Carboxylic Acid

B-6: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd., 6-functional photopolymerizable compound

B-7: EA-7420 / PGMAc, manufactured by Shin-Nakamura Chemical Co., Ltd., 13-functional photopolymerizable compound

B-8: U-15HA, manufactured by Shin Nakamura Chemical Co., Ltd., 15-functional photopolymerizable compound

(C) a photopolymerization initiator

C-1: Irgacure 907 (BASF)

(D) an alkali-soluble resin

D-1: An alkali-soluble resin of Production Example 2

D-2: An alkali-soluble resin of Production Example 3

D-3: An alkali-soluble resin of Production Example 4

D-4: An alkali-soluble resin of Production Example 5

D-5: The alkali-soluble resin of Production Example 6

D-6: An alkali-soluble resin of Production Example 7

D-7: An alkali-soluble resin of Production Example 8

<Color filter ( Glass substrate ) Manufacturing example >

A color filter was prepared using the self-luminescent photosensitive resin compositions prepared in Examples 1 to 13 and Comparative Examples 1 to 5. That is, each of the self-luminescent photosensitive resin compositions was coated on a glass substrate by spin coating, and then placed on a heating plate and maintained at a temperature of 100 ° C for 3 minutes to form a thin film. Then, a test photomask having a transmittance of 20 mm × 20 mm square and a line / space pattern of 1 μm to 100 μm was placed on the thin film and irradiated with ultraviolet rays at a distance of 100 μm from the test photomask. At this time, the ultraviolet light source was irradiated with light of 200 mJ / cm ² (365 nm) using an ultra-high pressure mercury lamp (trade name: USH-250D) manufactured by Ushio DENKI Co., Ltd., and no special optical filter was used. The thin film irradiated with ultraviolet rays was immersed in a KOH aqueous solution of pH 10.5 for 80 seconds. The glass plate coated with the thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 150 캜 for 10 minutes to prepare a color filter pattern. The film thickness of the self-emission color pattern prepared above was 3.0 mu m.

< Experimental Example >

Experimental Example  One. Self-luminous  The photosensitive resin composition Surface roughness  Measure

A self-emission color pattern substrate was prepared in the same manner as in the production of the color filter using the self-luminescent photosensitive resin compositions of Examples 1 to 13 and Comparative Examples 1 to 5, and the self-emission color pattern substrate was prepared using a surface roughness meter DEKTAK-6M ) Was used to measure the surface roughness of the pixel surface. The measured surface roughness results are shown in Table 2 below.

Normally, when the surface roughness of the pixel surface of the color filter is 100 nm or more, it is impossible to use the surface irregularity.

Experimental Example  2. Measurement of intensity and retention rate

The photo-converted regions were measured through a 365 nm tube type 4W UV illuminator (VL-4LC, VILBER LOURMAT) on the pattern portion formed in the pattern of 20 mm x 20 mm square among the color filters in which the self-luminescent pixels were formed. In Comparative Examples 1 to 5, the intensity of light in the 550 nm region was measured using a spectrum meter (manufactured by Ocean Optics). It can be judged that the higher the measured light intensity, the better the self-luminescence characteristics are, and the luminescence intensity measurement results are shown in Table 2 below.

The hard bake was conducted at 230 캜 for 60 minutes to measure the light emission intensity before and after the hard bake, and the level at which the light emission efficiency was maintained was confirmed, and is shown in Table 2 below as the light emission intensity retention rate.

division Surface roughness
(nm) Intensity
(au) Luminescence intensity maintenance rate Example 1 98 66321 66.5% Example 2 95 61235 65.3% Example 3 96 62354 64.5% Example 4 40 66215 64.1% Example 5 51 65902 65.8% Example 6 44 61245 62.8% Example 7 46 62675 63.3% Example 8 15.3 79585 87.1% Example 9 14.5 73482 86.5% Example 10 23.9 74825 88.8% Example 11 26.2 79458 84.8% Example 12 18.1 85673 89.8% Example 13 16.7 81478 88.2% Example 14 10.5 78725 89.2% Example 15 12.3 80354 90.1% Example 16 11.7 81816 82.1% Comparative Example 1 21 53215 52.8% Comparative Example 2 25 54235 51.2% Comparative Example 3 198 21015 23.5%

As can be seen from the results of Table 2, the compositions of Examples 1 to 15 exhibited better surface roughness characteristics and luminescence intensities as compared with the compositions of Comparative Examples 1 to 5, It has been confirmed that a color filter having a high light emission intensity and a high light emission intensity retention ratio can be produced. Particularly, in Examples 8 to 15, it was confirmed that the surface roughness evaluation showed remarkably excellent results.

On the other hand, Comparative Example 3 exceeded 100 nm in the surface roughness evaluation to show not only poor results but also poor emission intensity and luminescence intensity retention.

Claims (16)

(A) a quantum dot, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) an alkali-soluble resin, and (E)
Wherein the photopolymerizable compound comprises a compound having 7 to 12 acrylic functional groups.
2. The compound according to claim 1, wherein the quantum dot is a II-VI group semiconductor compound; III-V semiconductor compound; Group IV-VI semiconductor compounds; And at least one member selected from Group IV elements or compounds containing the Group IV element.
The method according to claim 1,
Wherein the photopolymerizable compound comprises a compound represented by the following formula (1): &lt; EMI ID =
[Chemical Formula 1]

Wherein R is H or &lt; RTI ID = 0.0 &gt;

Lt;
n is an integer of 2 to 4;
The self-luminescent photosensitive resin composition according to 1 above, wherein the alkali-soluble resin comprises a cationic binder resin comprising at least one compound represented by any one of the following formulas (7) to (12)
(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

In the above formulas (7) to (12)
X and X 'are each independently a single _{bond, -CO-, -SO 2 -, -C} (CF 3) 2 -, -Si (CH 3) 2 -, -CH 2 -, -C (CH 3) 2 -, -O-,

,

,

,

,

,

,

,

,

,

,

,

or

ego,
Y is an acid anhydride residue and the acid anhydride residue is selected from the group consisting of maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylenedodomethylenetetrahydrophthalic anhydride, Or anhydrous methyl tetrahydrophthalic acid;
Z is an acid dianhydride moiety and the acid dianhydride moiety is anhydrous pyromellitic acid, benzophenonetetracarboxylic acid anhydride, biphenyltetracarboxylic acid anhydride, biphenyl ether tetracarboxylic acid anhydride, cyclohexyl acid anhydride, or cyclobutyric anhydride;
R 'is a ₂ H ₄ OH or -CH ₂ CH = CH ₂ a hydrogen atom, an ethyl group, a phenyl _{group, -C 2 H 4 Cl, -C} ,
R1, R1 ', R2, R2', R3, R3 ', R4, R4', R5, R5 ', R6 and R6' are each independently a hydrogen atom or a methyl group;
R7, R7 ', R8 and R8' are each independently a linear or branched alkylene group having 1 to 6 carbon atoms, and the alkylene group is an ester bond, a cycloalkylene group having 6 to 14 carbon atoms and an arylene group having 6 to 14 carbon atoms , &Lt; / RTI &gt;
R9, R9 ', R10, R10', R11, R11 ', R12 and R12' are each independently a hydrogen atom, a halogen atom or a straight or branched alkyl group having 1 to 5 carbon atoms;
m and n are integers satisfying 0? m? 30 and 0? n? 30, provided that m and n are not 0 at the same time;
P is

, A represents O, S, N, Si or Se, R13 and R14 independently represent hydrogen, a hydroxyl group, a thiol group, an amino group, a nitro group or a halogenated group;
a and b are integers from 1 to 6;
Ar 1 represents an aryl group having 5 to 15 carbon atoms.
The self-luminescent photosensitive resin composition according to claim 4, wherein the alkali-soluble resin (B) further comprises an acrylic resin.
According to the claim _{1, Al 2 O 3, SiO} 2, ZnO, ZrO 2, BaTiO 3, TiO 2, Ta 2 O 5, Ti 3 O 5, ITO, IZO, ATO, ZnO-Al, Nb 2 O 3, SnO, and MgO. The self-luminescent photosensitive resin composition according to claim 1, wherein the metal oxide is at least one selected from the group consisting of SnO and MgO.
The method according to claim 1,
With respect to the solid content in the composition,
3 to 80 wt% of a quantum dot;
5 to 70% by weight of photopolymerizable compound;
0.1 to 20% by weight of a photopolymerization initiator and
And 5 to 80% by weight of an alkali-soluble resin.
The composition of claim 1, wherein, relative to the total weight of the composition,
And 60 to 90% by weight of a solvent.
The method according to claim 1,
Wherein the photosensitive resin composition contains 5 to 100% by weight of the compound having 7 to 12 acrylic functional groups based on the total weight of the photopolymerizable compound.
The method of claim 3,
Wherein the compound represented by the formula (1) is contained in an amount of 5 to 100% by weight based on the total weight of the photopolymerizable compound.
The method according to claim 1,
Wherein the photopolymerizable compound further comprises a multifunctional monomer having 1 to 6 unsaturated double bonds.
The method of claim 11,
Wherein the multifunctional monomer is a compound represented by the following formula (2): &lt; EMI ID =
(2)

In Formula 2, R ₃ to R ₅ are the same or different and each is OH, an alkyl group having 1 to 4 carbon atoms, an acrylate group, a methacrylate group or -OR ₇ , and at least one of R ₃ to R ₅ is acryl acrylate group or a methacrylate group and, R ₇ is

And, wherein R ₆ is _{-C (= O) CH 2 CH} 2 C (= O) OH,
R ₈ and R ₉ are an acrylate group or a methacrylate group, and R ₁₀ is hydrogen, an acryloyl group, a methacryloyl group or -C (═O) CH ₂ CH ₂ C (═O) OH.
The method of claim 11,
Wherein the polyfunctional monomer is contained in an amount of 10 to 95% by weight based on the total weight of the photopolymerizable compound.
The method according to claim 1,
Wherein the quantum dot is at least one selected from a red quantum dot, a green quantum dot and a blue quantum dot.
A color filter produced by using the self-luminescent photosensitive resin composition according to any one of claims 1 to 14.
An image display device comprising the color filter of claim 15.