KR102028583B1 - Photosensitive resin composition - Google Patents

Abstract

TECHNICAL FIELD The present invention relates to a photosensitive resin composition, and more specifically, to a photoluminescence quantum dot particle, a photopolymerizable compound, and a photopolymerization initiator, an alkali-soluble resin, and a solvent having a UV absorbance at a wavelength of 365 nm at a concentration of 0.001 mole of 0.1 or less, an alkali-soluble resin and a solvent And a photosensitive resin composition capable of producing a color filter with remarkably improved color reproducibility.

Description

Photosensitive Resin Composition {PHOTOSENSITIVE RESIN COMPOSITION}

The present invention relates to a photosensitive resin composition.

The color filter is a thin film type optical component that extracts three colors of red, green, blue, and white color from white light, and enables the pixel unit to have a pixel size of about tens to hundreds of micrometers. Such a color filter includes a black matrix layer formed in a predetermined pattern on a transparent substrate for shielding the boundary between each pixel, and a plurality of colors (typically, red (R) and green (G) to form each pixel. And a pixel portion in which three primary colors of blue (B) are arranged in a predetermined order. In general, color filters can be produced by coating three or more colors on a transparent substrate by a dyeing method, electrodeposition method, printing method, pigment dispersion method, etc. Recently, the pigment dispersion method using a pigment dispersion type photosensitive resin is mainly used in the mainstream. Achieve.

The pigment dispersion method, which is one of methods for implementing a color filter, coats a photosensitive resin composition including alkali colorant, alkali soluble resin, photopolymerization monomer, photopolymerization initiator, epoxy resin, solvent, and other additives on a transparent substrate provided with a black matrix. After exposing the pattern of the form to be formed, it is a method of forming a colored thin film by repeating a series of processes of removing the non-exposed areas with a solvent and thermally curing, and is active in manufacturing LCDs of mobile phones, laptops, monitors, and TVs. Is being applied. In recent years, in the photosensitive resin composition for color filters using pigment dispersion method having various advantages, not only excellent pattern characteristics but also high color reproducibility and improved performance such as high brightness and high contrast ratio are required.

However, color reproduction is realized by the light emitted from the light source passing through the color filter. In this process, a part of the light is absorbed by the color filter, and thus the light efficiency is lowered. There is a fundamental limitation.

Korean Patent Laid-Open No. 2012-112188 discloses a red color composition and a color filter for a color filter, but did not suggest an alternative to the problem.

Korean Laid-Open Patent No. 2012-112188

An object of this invention is to provide the photosensitive resin composition which can improve light efficiency and can manufacture the color filter excellent in color reproducibility.

In addition, an object of the present invention is to provide a color filter made of such a photosensitive resin composition and an image display device including the same.

1.Includes photoluminescence quantum dot particles, photopolymerizable compounds, photopolymerization initiators, alkali-soluble resins and solvents,

The photopolymerization initiator is a photosensitive resin composition, the UV absorbance of 365nm wavelength at 0.11 molar concentration is 0.1 or less.

2. The above 1, wherein the photoluminescence quantum dot particles have an average particle diameter of 1 to 40nm, the photosensitive resin composition.

3. In the above 1, wherein the photoluminescence quantum dot has a core-shell double structure, the average particle diameter of the core is 0.5 to 10nm, the average thickness of the shell is a photosensitive resin composition.

4. In the above 1, wherein the photoluminescence quantum dot particles are red quantum dot particles, green quantum dot particles or blue quantum dot particles, photosensitive resin composition.

5. In the above 1, wherein the photoluminescence quantum dot particles are II-VI group semiconductor compound; Group III-V semiconductor compounds; Group IV-VI semiconductor compounds; A Group IV element or a compound containing the same; Or a combination thereof.

6. In the above 1, the photopolymerization initiator is 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 4-methoxy-3.3'- dimethylbenzophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 1- [4- (2-hydroxyethoxy) -phenyl] -2- Hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1-1 {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2 -Methyl-propane-1-one, trimethyllopropane tris (3-mercaptopropionate), 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl- At least one member selected from the group consisting of phenyl) -butan-1-one and a compound represented by the following Chemical Formulas 2 to 12:

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

.

.

7. according to the above 1, 3 to 80% by weight of the photoluminescent quantum dot particles, 5 to 70% by weight of the photopolymerizable compound, 0.1 to 20% by weight of the photopolymerization initiator, 5 to 80% by weight of the alkali-soluble resin in the total weight of the solid content of the composition Including,

The photosensitive resin composition containing 60 to 90 weight% of a solvent in the total weight of a composition.

8. Color filter made of the photosensitive resin composition of any one of the above 1 to 7.

9. The color filter according to the above 8, comprising a red pattern layer containing red quantum dot particles, a green pattern layer containing green quantum dot particles, and a transparent pattern layer containing no quantum dot particles.

10. Image display device including the color filter of the above 8.

11. The light source according to the above 10, which emits blue light and

An image display device comprising a color filter comprising a red pattern layer containing red quantum dot particles, a green pattern layer containing green quantum dot particles, and a transparent pattern layer containing no quantum dot particles.

The photosensitive resin composition of this invention can produce the color filter by which light intensity was remarkably improved by light-emission by the light of a light source.

The photosensitive resin composition of this invention can manufacture the color filter by which color reproducibility was improved.

The photosensitive resin composition of this invention can form a fine pattern easily.

An image display device to which a color filter made of the photosensitive resin composition of the present invention is applied has a remarkably improved light efficiency and color reproducibility, and has a wide viewing angle.

The present invention includes a photoluminescence quantum dot particles, a photopolymerizable compound, a photopolymerization initiator having a UV absorbance of 0.1 nm or less at a wavelength of 0.001 at a concentration of 0.001 mole, an alkali-soluble resin and a solvent, thereby producing a color filter with remarkably improved brightness and color reproducibility. It relates to a photosensitive resin composition which can be made.

Hereinafter, the present invention will be described in detail.

<Photosensitive resin composition>

The photosensitive resin composition containing a quantum dot particle, a photopolymerizable compound, a photoinitiator, alkali-soluble resin, and a solvent.

Light luminescence Quantum dots  particle

The photosensitive resin composition of this invention contains photoluminescence quantum dot particle.

Quantum dots are nanoscale semiconductor materials. Atoms form molecules, and molecules form clusters of small molecules called clusters to form nanoparticles, which are called quantum dots, especially when they are semiconducting.

When a quantum dot reaches an excited state from the outside, the quantum dot emits energy according to a corresponding energy band gap.

The photosensitive resin composition of this invention contains such photoluminescence quantum dot particle, and the color filter manufactured from this can emit light (photoluminescence) by light irradiation.

In a typical image display apparatus including a color filter, white light is transmitted through the color filter to implement color. In this process, a part of the light is absorbed by the color filter, thereby degrading light efficiency.

However, in the case of including the color filter made of the photosensitive resin composition of the present invention, since the color filter emits light by the light of the light source, more excellent light efficiency can be realized.

In addition, since light having color is emitted, color reproducibility is more excellent, and light is emitted in all directions by photoluminescence, and thus viewing angle may be improved.

The quantum dot particle according to the present invention is not particularly limited as long as it is a quantum dot particle capable of emitting light by stimulation by light, for example, a group II-VI semiconductor compound; Group III-V semiconductor compounds; Group IV-VI semiconductor compounds; A Group IV element or a compound containing the same; And combinations thereof may be selected from the group. These can be used individually or in mixture of 2 or more types.

The II-VI semiconductor compound may be selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, and mixtures thereof; CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe And CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, and mixtures thereof, and the group III-V semiconductor compound , A binary element selected from the group consisting of GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, and mixtures thereof; Three-element compounds 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 an elemental compound selected from the group consisting of GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, and mixtures thereof. The group IV-VI semiconductor compound is a binary element selected from the group consisting of SnS, SnSe, SnTe, PbS, PbSe, PbTe, and mixtures thereof; A three-element compound selected from the group consisting of SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, and mixtures thereof; And SnPbSSe, SnPbSeTe, SnPbSTe, and an elemental compound selected from the group consisting of a mixture thereof, and the group IV element or the compound comprising the same is Si, Ge, and a mixture thereof. An element compound selected from; And a binary element compound selected from the group consisting of SiC, SiGe, and mixtures thereof.

Quantum dot particles are homogeneous single structures; Dual structures such as core-shell, gradient structures, and the like; Or a mixed structure thereof.

In the dual structure of the core-shell, the material constituting 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 is not limited thereto. The shell may include one or more materials selected from the group consisting of CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, and HgSe, but is not limited thereto.

The diameter of the quantum dot particles according to the present invention is not particularly limited, for example, the average particle diameter may be 1 to 40nm. In the dual structure of the core-shell, the average particle diameter of the core may be 0.5 to 10 nm, and the average thickness of the shell may be 0.5 to 30 nm. When the average particle diameter and thickness are in the above range, the composition may have excellent dispersibility in the composition, and may be used to prepare a color filter by implementing color by light irradiation.

As the colored photosensitive resin composition used in the manufacture of conventional color filters includes colorants of red, green, and blue for color realization, photoluminescence quantum dot particles may be classified into red quantum dot particles, green quantum dot particles, and blue quantum dot particles. In addition, the quantum dot particles according to the present invention may be red quantum dot particles, green quantum dot particles or blue quantum dot particles.

The red, green, and blue quantum dot particles may be classified according to particle size, and the particle diameters of red, green, and blue become smaller in the order of red, green, and blue. Specifically, the red quantum dot particles may have a particle diameter of 5 nm or more and 10 nm or less, the green quantum dot particles may be more than 3 nm and 5 nm or less, and the blue quantum dot particles may be 1 nm or more and 3 nm or less.

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

Quantum dot particles can be synthesized by a wet chemical process, an organometallic chemical vapor deposition process, or a molecular beam epitaxy process. The wet chemical process is a method of growing particles by adding a precursor material to an organic solvent. As the crystal grows, the organic solvent naturally coordinates the surface of the quantum dot crystal and acts as a dispersant, thereby controlling the growth of the crystal. Therefore, organic metal chemical vapor deposition (MOCVD) or molecular beam epitaxy (MBE) It is easier and cheaper to control nanoparticle growth than vapor deposition such as epitaxy.

The content of the quantum dot particles according to the present invention is not particularly limited, and may be included, for example, in an amount of 3 to 80% by weight, preferably 5 to 70% by weight, based on the total weight of the solid content of the photosensitive resin composition. If the content is less than 3% by weight, the luminous efficiency may be insignificant. If the content is more than 80% by weight, the content of the relatively different composition may be insufficient to form a pixel pattern.

Photopolymerizable  compound

The photopolymerizable compound which concerns on this invention is a compound which can superpose | polymerize by the action of the photoinitiator mentioned later, A monofunctional monomer, a bifunctional monomer, another polyfunctional monomer, etc. are mentioned. These can be used individually or in mixture of 2 or more types.

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

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, Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, etc. are mentioned.

Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and pentaerythritol tree. (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol Hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, the dipentaerythritol (poly) acrylate which has a hydroxyl group like Formula 1 below, etc. are mentioned.

[Formula 1]

(Wherein R is a hydrogen atom or acryloyl group having 2 to 6 carbon atoms).

The content of the photopolymerizable compound according to the present invention is not particularly limited, and may be included, for example, in the range of 5 to 70% by weight, preferably 10 to 60% by weight, of the total weight of the photosensitive resin composition solids. When the content is less than 5% by weight, the degree of photocuring may be lowered, so that formation of the pixel pattern may be difficult. When the content is more than 70% by weight, the pattern may be peeled off.

Photopolymerization Initiator

The photopolymerization initiator according to the present invention has a UV absorbance of 365 nm wavelength at 0.001 molar concentration of 0 to 0.1 or less. If the UV absorbance of 365 nm wavelength is more than 0.1 at 0.001 molar concentration, it is not easy to form a fine pattern, and the photoluminescence intensity of the color filter formed from the composition of the present invention is lowered, thereby realizing a display device having sufficient luminance. none.

However, the present invention includes a photopolymerization initiator having a UV absorbance of 0.1 nm or less at a concentration of 0.001 mole, which can easily form a fine pattern and significantly improve the luminance by maximizing the photoluminescence intensity of the photoluminescence quantum dot particles. can do. This means that when the UV absorbance is above 0.1, the photopolymerization initiator competitively absorbs photoluminescent quantum dot particles and UV, and the amount of UV absorbance of the photoluminescent quantum dot particles decreases, so that the luminous efficiency is lowered. It is believed that the particles absorb a much larger amount of UV than the photopolymerization initiator to improve the luminous efficiency.

Specifically, in view of the luminous efficiency of the photoluminescent quantum dot particles, the UV absorbance of 365 nm wavelength is preferably closer to 0 at 0.001 molar concentration of the photopolymerization initiator, and the absorbance is preferably closer to 0.1 in terms of fine pattern formation. The photopolymerization initiator according to the present invention may have a UV absorbance of 365 nm at a concentration of 0.001 molar concentration of 0 or more to 0.1 or less.

The photopolymerization initiator according to the present invention is not particularly limited as long as it has absorbance in the above range, and for example, acetophenone-based compound, polyfunctional thiol-based compound, biimidazole-based compound, oxime-based compound, and tria having absorbance in the above range. A true compound, etc. are mentioned. These can be used individually or in mixture of 2 or more types.

Specific examples of photopolymerization initiators having a UV absorbance of 0.1 nm or less at a concentration of 0.001 mole of 0.1 or less include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and 4-methoxy. -3.3'-dimethylbenzophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexyl-phenyl-ketone, 1- [4- (2-hydroxye Methoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1-1 {4- [4- (2-hydroxy-2-methyl-propionyl) -Benzyl] -phenyl} -2-methyl-propane-1-one, trimethyllopropane tris (3-mercaptopropionate), 2-dimethylamino-2- (4-methyl-benzyl) -1- (4 -Morpholin-4-yl-phenyl) -butan-1-one, the compound represented by following formula (2)-12, etc. are mentioned. These can be used individually or in mixture of 2 or more types.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

.

.

In addition, the photosensitive resin composition of this invention can also use together another photoinitiator etc. which are normally used in the field within the range which does not impair the objective of this invention. For example, a benzoin compound, a benzophenone type compound, a thioxanthone type compound, an anthracene type compound, etc. are mentioned. These can be used individually or in mixture of 2 or more types.

As a benzoin type compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example.

As a benzophenone type compound, for example, benzophenone, methyl 0- benzoyl benzoate, 4-phenyl benzophenone, 4-benzoyl-4'- methyl diphenyl sulfide, 3, 3 ', 4, 4'- tetra ( tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4,4'-di (N, N'-dimethylamino) -benzophenone, etc. are mentioned.

As a thioxanthone type compound, 2-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxy thioxanthone, etc. are mentioned, for example. Can be mentioned.

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. Can be mentioned.

Other 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylclioxylic acid Methyl, a titanocene compound, etc. can be illustrated further.

In addition, the photosensitive resin composition of the present invention may further include a photopolymerization initiation aid. In such cases the composition can be made even more sensitive.

Examples of the photopolymerization initiation aid include an amine compound and a carboxylic acid compound. These can be used individually or in mixture of 2 or more types.

Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoic acid and 4-dimethylamino 2-ethylhexyl benzoic acid, 2-dimethylaminoethyl benzoic acid, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (common name: Michler's ketone), 4,4'-bis (diethyl Aromatic amine compounds, such as amino) benzophenone, are mentioned, Preferably it can be an aromatic amine compound.

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

The content of the photopolymerization initiator according to the present invention is not particularly limited, and may be included, for example, in an amount of 0.1 to 20% by weight, preferably 0.5 to 15% by weight, based on the total weight of the solid content of the photosensitive resin composition. When the content is in the range of 0.1 to 20% by weight, the composition is highly sensitive, so that formation of a fine pixel pattern is easy.

Alkali soluble resin

Alkali-soluble resins are polymerized including an ethylenically unsaturated monomer having a carboxyl group. It is a component which provides solubility to the alkaline developing solution used at the developing process process at the time of forming a pattern.

The ethylenically unsaturated monomer which has a carboxyl group is not specifically limited, For example, Monocarboxylic acids, such as acrylic acid, methacrylic acid, a crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid and anhydrides thereof; and mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both terminals, such as? -carboxypolycaprolactone mono (meth) acrylate, and preferably acrylic acid and methacrylic acid. These can be used individually or in mixture of 2 or more types.

Alkali-soluble resin according to the present invention may be polymerized further comprising at least one other monomer copolymerizable with the monomer. For example, styrene, vinyltoluene, methyl styrene, p-chlorostyrene, o-methoxy styrene, m-methoxy styrene, p-methoxy styrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p- Aromatic vinyl compounds such as vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether; N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm N-substituted maleimide compounds such as -methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, and Np-methoxyphenylmaleimide; Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth) acrylates such as sec-butyl (meth) acrylate and t-butyl (meth) acrylate; Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6] decane-8-yl (meth) acrylate, 2- Alicyclic (meth) acrylates such as dicyclopentanyloxyethyl (meth) acrylate and isobornyl (meth) acrylate; Aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, etc. And unsaturated oxetane compounds. These can be used individually or in mixture of 2 or more types.

As used herein, (meth) acrylate means acrylate or methacrylate.

The content of the alkali-soluble resin according to the present invention is not particularly limited, and for example, may be included in 5 to 80% by weight, preferably 10 to 70% by weight of the total weight of the photosensitive resin composition solids. When the content of the alkali-soluble resin is in the range of 5 to 80% by weight, the solubility in the developing solution is sufficient, so that pattern formation is easy, and the film reduction of the pixel portion of the exposed portion is prevented at the time of development, so that the non-pixel portion has good omission. .

solvent

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

Specific examples include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol 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; Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxy butyl acetate, and methoxy pentyl acetate; Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone; 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; Etc. can be mentioned. These can be used individually or in mixture of 2 or more types.

The content of the solvent according to the present invention is not particularly limited, for example, may be included in 60 to 90% by weight of the total weight of the photosensitive resin composition, preferably may be included in 70 to 85% by weight. When the content of the solvent is in the range of 60 to 90% by weight, the applicability may be good.

<Color filter>

In addition, the present invention provides a color filter made of the photosensitive resin composition.

When the color filter of the present invention is applied to an image display device, since the light is emitted by the light of the display device light source, it is possible to implement more excellent light efficiency. In addition, since light having color is emitted, color reproducibility is more excellent, and light is emitted in all directions by photoluminescence, and thus viewing angle may be improved.

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

The substrate may be a substrate of the color filter itself, or may be a portion where the color filter is positioned in a display device or the like, and is not particularly limited. The substrate may be glass, silicon (Si), silicon oxide (SiO _x ), or a polymer substrate, and the polymer substrate may be polyethersulfone (PES) or polycarbonate (PC).

The pattern layer is a layer including the photosensitive resin composition of the present invention, and may be a layer formed by applying the photosensitive resin composition and exposing, developing and thermosetting in a predetermined pattern.

The pattern layer formed of the photosensitive resin composition may include a red pattern layer containing red quantum dot particles, a green pattern layer containing green quantum dot particles, and a blue pattern layer containing blue quantum dot particles. In 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 emission light of the light source is not particularly limited when applied to the image display device, but in view of better luminance and color reproducibility, a light source that emits blue light can be preferably used.

According to another embodiment of the present invention, the pattern layer includes a red pattern layer, a green pattern layer, and a transparent pattern layer containing no quantum dot particles. In such a case, a light source emitting blue light may be used as a light source of the image display apparatus including the same. At this time, the red pattern layer emits red light, the green pattern layer emits green light, and the transparent pattern layer exhibits blue light as it is transmitted through as it is.

The color filter including the substrate and the pattern layer as described above may further include a partition formed between each pattern, and may further include a black matrix. In addition, a protective film formed on the pattern layer of the color filter may be further included.

<Image display device>

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

The color filter of the present invention can be applied to various image display devices such as electroluminescent display devices, plasma display devices, field emission display devices, as well as ordinary liquid crystal display devices.

The image display apparatus of the present invention may include 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. In such a case, the emission light of the light source is not particularly limited when applied to the image display device, but in view of better color reproducibility, a light source that emits blue light may be preferably used.

According to another embodiment of the present invention, the image display apparatus of the present invention may include a color filter including a red pattern layer, a green pattern layer, and a transparent pattern layer containing no quantum dot particles.

In this case, a light source emitting blue light may be used as the light source. 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 shows blue light as it is transmitted.

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

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but these examples are merely illustrative of the present invention and are not intended to limit the scope of the appended claims, which are within the scope and spirit of the present invention. It is apparent to those skilled in the art that various changes and modifications can be made to the present invention, and such modifications and changes belong to the appended claims.

Production Example  One. CdSe (core)/ ZnS (Shell) structure Light luminescence  rust Quantum dots  Synthesis of Particle 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. Reacted. Thereafter, the reaction was allowed to stand for 20 minutes under vacuum of 100 mTorr to remove acetic acid produced by substitution of oleic acid with zinc. Then, 310 ° C. heat was applied to obtain a clear mixture. After maintaining 310 ° 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 S solution was rapidly injected into the reactor containing 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, precipitated with ethanol to separate the quantum dots using a centrifuge and the excess impurities washed with chloroform and ethanol, stabilized with oleic acid, the core particle diameter and the sum of the shell thickness of 3 to 5nm Quantum dot particles A-1 having CdSe (core) / ZnS (shell) structure in which they were distributed were obtained.

Production Example  2. Synthesis of Alkali Soluble Resin

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube was prepared, while 45 parts by weight of N-benzylmaleimide, 45 parts by weight of methacrylic acid, and 10 parts by weight of tricyclodecyl methacrylate, t -4 parts by weight of butyl peroxy-2-ethylhexanoate and 40 parts by weight of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) were added and stirred to prepare a monomer dropping lot, and 6 parts by weight of n-dodecanethiol, 24 parts by weight of PGMEA was added thereto, followed by stirring and mixing to prepare a lot of chain transfer agent dropping lot. Thereafter, 395 parts by weight of PGMEA was introduced into the flask, the atmosphere in the flask was changed to nitrogen from air, and the temperature of the flask was raised to 90 ° C. while stirring. Subsequently, dropping of the monomer and the chain transfer agent was started from the dropping lot. The dropwise addition was carried out for 2 hours while maintaining 90 ° C, and after 1 hour, the temperature was raised to 110 ° C and maintained for 3 hours, and then a gas introduction tube was introduced to bubble oxygen / nitrogen = 5/95 (v / v) mixed gas. The ring started. Subsequently, 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 added to the flask, followed by 8 hours at 110 ° C. The reaction was continued and an alkali-soluble resin having a solid content of 29.1 wt%, a weight average molecular weight of 32,000, and an acid value of 114 mgKOH / g was then cooled to room temperature.

Example  And Comparative example

(1) Preparation of Photosensitive Resin Composition

The composition (weight part) shown in following Table 1 was added, and it diluted with propylene glycol monomethyl ether acetate so that solid content might be 18 weight%, and stirred, and prepared the photosensitive resin composition.

division Quantum dots
Particle (A) Photopolymerizable
compound
(B) Photopolymerization Initiator
(C) Alkali soluble resin
(D) ingredient content ingredient content Example 1 a A-1 30 35 C-1 5 30 b A-2 30 35 C-1 5 30 Example 2 a A-1 30 35 C-2 5 30 b A-2 30 35 C-2 5 30 Example 3 a A-1 30 35 C-3 5 30 b A-2 30 35 C-3 5 30 Example 4 a A-1 30 35 C-4 5 30 b A-2 30 35 C-4 5 30 Example 5 a A-1 50 25 C-1 5 20 b A-2 50 25 C-1 5 20 Example 6 a A-1 30 25 C-1 20 25 b A-2 30 25 C-1 20 25 Example 7 a A-1 30 30 C-1 10 30 b A-2 30 30 C-1 10 30 Example 8 a A-1 30 25 C-1 22 23 b A-2 30 25 C-1 22 23 Comparative Example 1 a A-1 30 35 C-5 5 30 b A-2 30 35 C-5 5 30 Comparative Example 2 a A-1 30 35 C-6 5 30 b A-2 30 35 C-6 5 30 Comparative Example 3 a A-1 30 35 C-7 5 30 b A-2 30 35 C-7 5 30 Comparative Example 4 a A-1 30 35 C-8 5 30 b A-2 30 35 C-8 5 30 Comparative Example 5 a A-1 30 35 C-9 5 30 b A-2 30 35 C-9 5 30 A-1: Quantum dot particle of Preparation Example 1
^{A-2: Lumidot TM CdSe /} ZnS 640 ( red quantum dot particles, Aldrich)
B: dipentaerythritol hexaacrylate (KAYARAD DPHA, Nippon Kayakusa)
C-1: Irgacure-907 (BASF)
C-2: KAYACURE MBP (Midori Chemical)
C-3: TMMP (Sakai Chemical Co., Ltd.)
C-4: Irgacure-379 (BASF)
C-5: Irgacure-369 (BASF)
C-6: KAYACURE DET-X
C-7: Triazine-PP (BASF)
C-8: Irgacure OXE01 (BASF)
C-9: Irgacure OXE02 (BASF)
D: Alkali-soluble resin of Preparation Example 3

(2) Manufacture of color filters

After apply | coating the photosensitive resin composition of an Example and a comparative example on the glass substrate by the spin coating method, it put on the heating plate, hold | maintained at the temperature of 100 degreeC for 3 minutes, and formed the thin film. A test photomask having a 20 mm × 20 mm square transmission pattern and a line / space pattern of 1 to 100 μm was placed on the thin film, and ultraviolet rays were irradiated with a distance of 100 μm from the test photomask.

In this case, the ultraviolet light source was irradiated with an exposure amount (365 nm) of 200 mJ / cm ² under an atmosphere using an ultra high pressure mercury lamp (USH-250D) manufactured by Ushio Denki Co., Ltd., and no optical filter was used. Thereafter, the thin film was developed by soaking in an aqueous KOH solution having a pH of 10.5 for 80 seconds.

After washing with distilled water, the mixture was dried by blowing nitrogen gas and heated for 10 minutes in an oven at 150 ℃ to prepare a color filter. The thickness of the produced color pattern was 3.0 μm.

Experimental Example

(One) Photopolymerization  Absorbance Measurement of Initiator

Each photopolymerization initiator used in the examples and comparative examples was diluted with propylene glycol monomethyl ether acetate so that the concentration was 0.01 mol / liter, and then the absorbance at 365 nm was measured with an absorbance meter (UV-2550, Shimadzu). The results are shown in Table 2 below.

(2) evaluation of the formation of fine patterns

The width of the pattern of the pattern mask was measured by the OM device (ECLIPSE LV100POL, Nikon) by measuring the width of the pattern obtained through the line / space pattern mask having an opening width of 100 μm in the color filter manufactured by the compositions of Examples and Comparative Examples. The difference in widths was obtained and shown in Table 2.

A smaller difference between the width of the opening of the pattern mask and the width of the pattern indicates that a finer pattern can be formed.

If the absolute value of the difference is 20 µm or more, it is difficult to implement the fine pixel, and a negative value may cause process defects.

(3) emission intensity measurement

In the color filter manufactured by the compositions of the examples and the comparative examples, the light emitted by the photoluminescence was irradiated with light by a 365 nm tube type 4W UV irradiator (VL-4LC, VILBERLOURMAT) at a pattern portion of 20 mm x 20 mm. Quantum dots 640nm, green quantum dots 545nm) the intensity of the light (intensity) was measured by a spectrum meter (Ocean Optics), and are shown in Table 2 below.

It can be judged that the more the intensity | strength of the measured light demonstrates the outstanding photoluminescence characteristic.

division Absorbance of photopolymerization initiator
(0.001 mol / liter, 365nm) Pattern of mask
Opening width and
The difference in the width of the pattern
(Μm) a
Luminous intensity
(λ _{545 nm} ) b
Luminous intensity
(λ _{640 nm} ) Example 1 0.04 7 22,575 21,621 Example 2 0.06 6 20,180 20,317 Example 3 0.01 10 26,830 19,467 Example 4 0.1 9 18,110 19,680 Example 5 0.04 4 25,396 23,176 Example 6 0.04 19 19,947 18,433 Example 7 0.04 14 20,438 19,244 Example 8 0.04 22 18,376 17,989 Comparative Example 1 0.14 11 12,060 11,390 Comparative Example 2 0.46 -14 3,170 4,381 Comparative Example 3 1.52 9 5,690 4,920 Comparative Example 4 0.43 11 4,120 3,810 Comparative Example 5 0.34 14 4,570 4,310

Referring to Table 2, the compositions of Examples 1 to 8 including the photopolymerization initiator having a UV absorbance of 0.1 nm or less at a wavelength of 0.001 mole at 0.1 nm are less than the difference between the width of the opening of the pattern mask and the pattern to form a very fine pattern. Could. And it was confirmed that the intensity | strength of photoluminescence was very excellent, and showed high luminance.

However, the compositions of Comparative Examples 1 to 5 could not form fine patterns or had poor photoluminescence intensity.

Claims (11)

60 to 90% by weight of the solvent in the total weight of the composition,
3 to 80 wt% of photoluminescent quantum dot particles, 5 to 70 wt% of photopolymerizable compound, 0.1 to 20 wt% of photopolymerization initiator, and 5 to 80 wt% of alkali-soluble resin, based on the total weight of solids of the composition,
Said photoinitiator contains trimethylolpropane tris (3-mercaptopropionate) whose UV absorbance of 365 nm wavelength is 0.1 or less at 0.001 mol concentration, The photosensitive resin composition.
The photosensitive resin composition of Claim 1 whose particle | grains of the said photoluminescence quantum dot are 1-40 nm in average particle diameter.
The photosensitive resin composition of claim 1, wherein the photoluminescence quantum dot has a core-shell dual structure, and the average particle diameter of the core is 0.5 to 10 nm, and the average thickness of the shell is 0.5 to 30 nm.
The photosensitive resin composition according to claim 1, wherein the photoluminescent quantum dot particles are red quantum dot particles, green quantum dot particles, or blue quantum dot particles.
The method according to claim 1, wherein the photoluminescence quantum dot particles are a group II-VI semiconductor compound; Group III-V semiconductor compounds; Group IV-VI semiconductor compounds; A Group IV element or a compound containing the same; Or a combination thereof.
The method of claim 1, wherein the photopolymerization initiator is 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 4-methoxy-3.3'-dimethylbenzophenone, 2, 2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy 2-Methyl-1-propane-1-one, 2-hydroxy-1-1 {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl -Propan-1-one, 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one and represented by the following formulas 2 to 12 Further comprising at least one member selected from the group consisting of a photosensitive resin composition:
[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

.
delete The color filter manufactured from the photosensitive resin composition of any one of Claims 1-6.
The color filter according to claim 8, comprising a red pattern layer containing red quantum dot particles, a green pattern layer containing green quantum dot particles, and a transparent pattern layer containing no quantum dot particles.
An image display device comprising the color filter of claim 8.
The light source according to claim 10, which emits blue light and
An image display device comprising a color filter comprising a red pattern layer containing red quantum dot particles, a green pattern layer containing green quantum dot particles, and a transparent pattern layer containing no quantum dot particles.