KR20180036053A - Self emission type photosensitive resin composition, color filter and image display device produced using the same - Google Patents

Abstract

A spontaneous photosensitive resin composition according to the present invention comprises: quantum dot; a phosphate dispersing agent; and a solvent. The spontaneous photosensitive resin composition according to the present invention is advantageous in that fine pixels can be easily formed by including a specific dispersant and deterioration of light efficiency or defective photosensitivity can be prevented.

Description

TECHNICAL FIELD [0001] The present invention relates to a self-luminescent photosensitive resin composition, a color filter manufactured using the same, and an image display device using the self-luminescent photosensitive resin composition.

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

A color filter is a thin film type optical component that extracts three colors of red, green, and blue in white light and makes it possible in fine pixel units. The size of one pixel is several tens to several hundreds of micrometers. Such a color filter has a black matrix layer formed in a predetermined pattern on a transparent substrate so as to shield a boundary portion between each pixel and a plurality of colors (typically red (R), green (G) and Blue (B)) are arranged in a predetermined order in this order.

In recent years, as a method of implementing a color filter, a pigment dispersion method using a pigment dispersion type photosensitive resin has been applied. However, in a process in which light emitted from a light source passes through a color filter, a part of light is absorbed by a color filter, The efficiency is lowered and the color reproduction is deteriorated due to the characteristics of the pigment contained in the color filter.

Particularly, since color filters are used in various fields including various image display devices, they are required not only to have excellent pattern characteristics but also to have high color reproducibility and excellent performance such as high luminance and high contrast ratio. In order to solve such problems, A method of manufacturing a color filter using the self-luminescent photosensitive resin composition has been proposed.

Korean Patent Laid-Open Publication No. 2013-0000506 relates to a display device, comprising: a plurality of wavelength conversion particles for converting a wavelength of light; And a color conversion section including a plurality of color filter particles that absorb light of a predetermined wavelength band in the light.

However, in order to produce a color filter or display device including quantum dots, it is necessary to disperse the quantum dot particles evenly, so that it is common to incorporate a dispersant into the self-luminescent photosensitive resin composition together. However, when a conventional dispersant is included, In addition, when an excess amount is used for dispersion of fine particles of several tens of nm or less, the quality of the pixel pixel deteriorates due to a decrease in the curing property.

Therefore, development of a self-luminescent photosensitive resin composition capable of producing an excellent color filter with no problem of deterioration in light efficiency or defective photosensitive property while uniformly dispersing quantum dot particles is required.

Korean Patent Publication No. 2013-0000506 (Mar.

It is an object of the present invention to provide a self-luminescent photosensitive resin composition capable of preventing a decrease in light efficiency or a defective photosensitive property.

The present invention also provides a color filter and an image display device manufactured using the self-light-sensitive photosensitive resin composition described above.

In order to accomplish the above object, the present invention provides a self-luminescent photosensitive resin composition comprising: a quantum dot; Phosphoric acid dispersant; And a solvent.

Further, the present invention provides a color filter including the above-mentioned self-luminescent photosensitive resin composition cured product and an image display apparatus including the same.

The self-luminescent photosensitive resin composition according to the present invention is advantageous in that formation of fine pixel pixels is easy by incorporating a specific dispersant and deterioration of light efficiency or defective photosensitivity can be prevented.

Further, the color filter and the image display device using the self-luminescent photosensitive resin composition of the present invention are advantageous in light efficiency and low defective photosensitivity.

Hereinafter, the present invention will be described in more detail.

When a member is referred to as being " on "another member in the present invention, this includes not only when a member is in contact with another member but also when another member exists between the two members.

Whenever a part is referred to as "including " an element in the present invention, it is to be understood that it may include other elements as well, without departing from the other elements unless specifically stated otherwise.

< Self-luminous  Photosensitive resin composition>

An aspect of the present invention relates to a quantum dot device comprising: a quantum dot; Phosphoric acid dispersant; And a solvent.

Qdot

The self-luminescent photosensitive resin composition according to the present invention comprises a photoluminescence quantum dot.

The quantum dot may be referred to as a nano-sized semiconductor material. The atoms form molecules, and the molecules form aggregates of small molecules called clusters to form nanoparticles. When these nanoparticles are semiconductor, they are called quantum dots. The quantum dots emit energy according to the corresponding energy band gap of the quantum dots when the quantum dots reach the excited state from the outside.

The color filter made of the self-luminescent photosensitive resin composition according to the present invention may emit light (luminescence) by light irradiation by including the quantum dot, specifically, a quantum dot.

In a typical image display device including a color filter, white light is transmitted through the color filter to realize color. In this process, a part of light is absorbed by the color filter, so that the light efficiency is lowered. However, in the case of including the color filter made of the self-luminescent photosensitive resin composition according to the present invention, since the color filter is self-luminescent by the light of the light source, more excellent light efficiency can be realized, The color reproducibility is better and light is emitted in all directions due to the optical luminescence, so that there is an advantage that the viewing angle can also be improved.

And is not particularly limited as long as it is a quantum dot particle capable of emitting light by stimulation by light. For example, II-VI group semiconductor compounds; III-V semiconductor compound; Group IV-VI semiconductor compounds; Group IV elements or compounds containing them; And combinations thereof, and they may be used singly or in combination of two or more.

Specifically, 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 a silane compound 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 photonic 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 IV-VI group semiconductor compound is selected from the group consisting of SnS, SnSe, SnTe, PbS, PbSe, PbTe, and mixtures thereof; A triple compound selected from the group consisting of SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, and mixtures thereof; And a silane compound selected from the group consisting of SnPbSSe, SnPbSeTe, SnPbSTe, and mixtures thereof. However, the present invention is not limited thereto.

Although not limited thereto, the Group IV element or the compound containing it may be 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.

The quantum dot has a single homogeneous structure; A dual structure such as a core-shell, gradient structure or the like; Or a mixed structure thereof.

Specifically, 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. For example, the core may include, but is not limited to, one or more materials selected from the group consisting of CdSe, CdS, ZnS, ZnSe, CdTe, CdSeTe, CdZnS, PbSe, AgInZnS and ZnO. The shell may include at least one material selected from the group consisting of CdSe, ZnSe, ZnS, ZnTe, CdTe, PbS, TiO, SrSe, and HgSe.

The colored photosensitive resin composition used in the production of a typical color filter may be classified into an optical luminescence quantum dot quantum dot, a rust quantum dot, and a blue quantum dot, as well as including red, green, and blue colorants for color implementation. In short, the quantum dot according to the present invention may be an energetic quantum dot emitting red light, a rust quantum dot emitting green light, or a blue quantum dot emitting blue light.

The quantum dot may be synthesized by, but not limited to, a wet chemical process, a metal organic chemical vapor deposition (MOCVD) process, or a molecular beam epitaxy process (MBE) process .

In the wet chemical process, a precursor material is added to an organic solvent to grow particles. When the crystal grows, the organic solvent is naturally coordinated on the surface of the quantum dot crystal to act as a dispersing agent to control the crystal growth. Therefore, it is easier and cheaper to process the nano-particles than the vapor deposition method such as the organic metal chemical vapor deposition process or the molecular beam epitaxy It is preferable to produce the quantum dot according to the present invention by using the wet chemical process.

The quantum dot may be contained in an amount of 3 to 80 parts by weight, preferably 5 to 70 parts by weight, and more preferably 8 to 65 parts by weight based on 100 parts by weight of the total solid content of the self-emission photosensitive resin composition. When the quantum dot is included within the above range, it is possible to provide a self-emitting photosensitive resin composition having excellent photosensitivity. When the quantum dots are included in the range below the above range, the photosensitive properties may be somewhat lowered. In the case where the quantum dots are included in the above range, the quantities of constituents such as alkali soluble resins and photopolymerizable compounds, , There is a problem that the production of the color filter may be somewhat difficult. Therefore, it is preferable that the color filter is included within the above range.

The quantum dot may be contained in the self-luminescent photosensitive resin composition after preparing a quantum dot dispersion by mixing a dispersant and a solvent to be described later.

Phosphate dispersant

The self-luminescent photosensitive resin composition according to the present invention includes a phosphoric acid-based dispersant.

In one embodiment of the present invention, the phosphate dispersing agent further contains an ester group in one molecule.

Specifically, the phosphoric acid-based dispersant may include a phosphate ester compound. The phosphate dispersant may include a form in which a hydrogen atom of a hydroxy group or a hydroxyl group existing in phosphate ester ((HO) ₂ PO (OR)) or phosphoric acid (H ₃ PO ₄ ) is substituted or unsubstituted with another functional group. For example, the phosphoric acid-based dispersant may be expressed in the form of (H ₂ PO ₃ -), but is not limited thereto. In the present invention, the "phosphoric acid-based or phosphate ester-based" may include at least one selected from the group consisting of a phosphorous acid derivative, a phosphoric acid derivative, a phosphonic acid derivative and a phosphinic acid derivative.

The self-luminescent photosensitive composition according to the present invention has the advantage of suppressing the deterioration of light efficiency and defective photosensitivity due to the phosphoric acid-based dispersing agent.

In another embodiment of the present invention, the phosphate dispersant may further include a polyether moiety in one molecule.

Specifically, the phosphoric acid-based dispersant may contain an ester group and a polyether moiety in one molecule.

In the present invention, "poly-" refers to a compound composed of a large number of repeating units, wherein the "polyether moiety" and the "polyester moiety" each have a repeating unit having an ether group or an ester group of 1 to 20 As shown in FIG. Preferably, in the present invention, the repeating unit may be composed of 5 to 20, more preferably 10 to 20, and in this case, there is an advantage of excellent compatibility.

When the phosphoric acid-based dispersant further contains a polyether moiety in one molecule, there is an advantage that compatibility with an alkali-soluble resin to be described later is improved, and the phosphate dispersant further contains an ester group or a polyester moiety in one molecule There is an advantage that the compatibility with the alkali-soluble resin and the dissolution property with respect to the alkali developer are improved. If the phosphoric acid-based dispersant further contains a phosphoric acid group in one molecule, it can act as a protective layer through adsorption on the surfaces of the quantum dots and has an advantage of deagglomerating the quantum dots.

Preferably, the phosphoric acid-based dispersant according to the present invention may contain a polyether moiety, an ester moiety, and a phosphoric acid moiety in one molecule. In this case, the quantum dots are deagglomerated to reduce the dispersed particle size, and the compatibility with the alkali- It is most preferable because it has a dissolution property for a developer and is advantageous for pattern formation.

In another embodiment of the present invention, the phosphoric acid-based dispersant may be contained in an amount of 1 to 300 parts by weight, preferably 3 to 250 parts by weight, more preferably 5 to 200 parts by weight per 100 parts by weight of the total solid content of the quantum dots &Lt; / RTI &gt; When the phosphate dispersant is included in the range of 100 parts by weight of the entire quantum solid part, the deaggregation effect of the quantum dot is excellent and the precipitation phenomenon due to the polarity difference in the self light- , And can serve as a protective layer of quantum dots in a color filter manufacturing process.

If the amount of the phosphoric acid-based dispersant is less than the above-mentioned range, the deagglomeration effect of the quantum dot may be somewhat lowered. When the amount exceeds the above range, the development characteristics of the self-emission photosensitive resin composition may be somewhat deteriorated. .

Examples of the phosphoric acid-based dispersant include Disperbyk-110, 111, 180, 192, 103, and 106, and they may be used alone or in combination.

solvent

The solvent to be contained in the self-luminescent photosensitive resin composition of the present invention is not particularly limited, and may include organic solvents commonly used in the art.

Specific examples of the solvent include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Diethylene glycol dialkyl ethers such as diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; 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; 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; and cyclic esters such as? -butyrolactone.

The solvent is preferably an organic solvent having a boiling point of 100 ° C to 200 ° C in the solvent in terms of coating property and drying property, more preferably an alkylene glycol alkyl ether acetate, a ketone, a 3-ethoxypropionic acid Ethyl, and 3-methoxypropionate, and more preferred examples thereof include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, 3- Methyl propoxypropionate, and the like. These solvents may be used alone or in combination of two or more.

The solvent may be included in an amount of 25 to 95 parts by weight, specifically 30 to 90 parts by weight, based on 100 parts by weight of the entire self-light-sensitive photosensitive resin composition, but is not limited thereto.

However, when the content of the solvent is within the above range, the coating property becomes good when applied with a coating apparatus such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater) . When the content of the solvent is less than the above range, the coating property may be somewhat lowered, and the process may be somewhat difficult. When the content is above the range, the performance of the color filter formed of the self-luminescent photosensitive resin composition may be somewhat deteriorated Problems can arise.

When the quantum dot according to the present invention is contained in the self-emitting photosensitive resin composition in the form of a quantum dot dispersion, a part of the solvent may be contained in the quantum dot dispersion. In this case, the solvent may be a non-polar solvent such as toluene, hexane, xylene, cyclohexane or chloroform.

In still another embodiment of the present invention, the self-luminescent photosensitive resin composition may further include at least one member selected from the group consisting of an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and an additive.

Alkali-soluble resin

The self-luminescent photosensitive resin composition according to the present invention may contain an alkali-soluble resin.

The alkali-soluble resin can make the unexposed portion of the color filter made of the self-light-sensitive photosensitive resin composition become alkali-soluble and can remove the alkali-soluble resin, and can perform the role of retaining the exposed region. When the self-luminescent photosensitive resin composition contains the alkali-soluble resin, the quantum dots may be uniformly dispersed in the composition, and the quantum dots may be protected during the process to maintain the luminance.

The alkali-soluble resin according to the present invention may be selected from those having an acid value of 50 to 200 (KOH mg / g). The above-mentioned "acid value" relates to the solubility as a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the acrylic polymer. If the acid value of the alkali-soluble resin is less than the above-mentioned range, it may be difficult to secure a sufficient developing rate. If the acid value exceeds the above range, the adhesion with the substrate tends to be reduced and the pattern tends to be short- There may arise a problem in which the temperature of the gas is increased.

Further, in order to improve the surface hardness of the alkali-soluble resin for use as a color filter, the molecular weight and molecular weight distribution (Mw / Mn) may be limited. Preferably a weight average molecular weight of 1,000 to 100,000, preferably 3,000 to 50,000, and a molecular weight distribution of 1.5 to 6.0, preferably 1.8 to 4.0. The alkali-soluble resin having the above molecular weight and molecular weight distribution in the above range can be improved in hardness as mentioned above, and has a high residual film ratio as well as excellent solubility in the non-exposed portion in the developer and can improve resolution.

The alkali-soluble resin includes at least one selected from the group consisting of a copolymer of a carboxyl group-containing unsaturated monomer, a copolymer of a monomer having a copolymerizable unsaturated bond and a combination thereof.

The carboxyl group-containing unsaturated monomer may be an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, or an unsaturated tricarboxylic acid. 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 polycarboxylic 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, succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl ), Phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl), and the like. The unsaturated polycarboxylic acid may be mono (meth) acrylate of the dicarboxylic polymer of both ends thereof, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate . These carboxyl group-containing monomers may be used alone or in combination of two or more.

The monomer copolymerizable with the carboxyl group-containing unsaturated monomer may be an aromatic vinyl compound, an unsaturated carboxylic acid ester compound, an unsaturated carboxylic acid aminoalkyl ester compound, an unsaturated carboxylic acid glycidyl ester compound, a carboxylic acid vinyl ester compound, An aliphatic conjugated diene compound, a macromonomer having a monoacryloyl group or monomethacryloyl group at the end of the molecular chain, a vulcanizable monomer, and a combination thereof in the group consisting of an ether compound, a vinyl cyanide compound, an unsaturated imide compound, an aliphatic conjugated diene compound, One selected paper is available.

More specifically, the copolymerizable monomer is selected from the group consisting of styrene,? -Methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m- Vinylbenzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl Aromatic vinyl compounds such as ether and indene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, Acrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl Methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxy diethylene glycol acrylate, methoxy diethylene glycol methacrylate, methoxy triethylene glycol acrylate, methoxy triethylene glycol methacrylate Acrylate, methoxypropylene glycol methacrylate, methoxypropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadiene Acrylate, dicyclopentadienyl methacrylate, adamantyl (meth) acrylate, (Meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate and the like Unsaturated carboxylic acid esters; Aminoethyl methacrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2- Unsaturated carboxylates such as methyl acrylate, ethyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, Acid amino alkyl ester compounds; Unsaturated carboxylic acid glycidyl ester compounds such as glycidyl acrylate and glycidyl methacrylate; Carboxylic acid vinyl ester compounds such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; Unsaturated ether compounds such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile,? -Chloroacrylonitrile, and vinylidene cyanide; Unsaturated amides such as acrylamide, methacrylamide,? -Chloroacrylamide, N-2-hydroxyethyl acrylamide and N-2-hydroxyethyl methacrylamide; Unsaturated imide compounds such as maleimide, benzylmaleimide, N-phenylmaleimide and N-cyclohexylmaleimide; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; And a monoacryloyl group or monomethacryloyl group at the end of the polymer molecular chain of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, Macromonomers; A bulky monomer such as a monomer having a norbornyl skeleton, a monomer having an adamantane skeleton, or a monomer having a rosin skeleton which can lower the relative dielectric constant can be used.

The alkali-soluble resin may be included in an amount of 5 to 80 parts by weight, specifically 10 to 70 parts by weight, more specifically 15 to 60 parts by weight, based on 100 parts by weight of the solid component of the self-emission photosensitive resin composition.

When the alkali-soluble resin is contained within the above-mentioned range, the solubility in the developer is sufficient, the pattern formation is easy, and the reduction of the film thickness of the pixel portion of the exposed portion is prevented during development, so that the non-pixel portion is satisfactorily missed. If the alkali-soluble resin is contained in the range below the above-mentioned range, the non-pixel portion may be somewhat missed. If the alkali-soluble resin is contained in the above range, the solubility in the developer may be somewhat lowered and pattern formation may be somewhat difficult.

Photopolymerization  compound

The photopolymerizable compound contained in the self-luminescent photosensitive resin composition of the present invention is a compound capable of polymerizing under the action of light and a photopolymerization initiator described later, and examples thereof include monofunctional monomers, bifunctional monomers, and other polyfunctional monomers.

The type of the monofunctional monomer is not particularly limited, and examples thereof include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate N-vinylpyrrolidone, and the like.

The type of the bifunctional monomer is not particularly limited and examples thereof include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) Glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, and 3-methylpentanediol di (meth) acrylate.

The type of the polyfunctional monomer is not particularly limited and includes, for example, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (Meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. Of these, multifunctional monomers having two or more functional groups are preferably used.

Commercially available examples of the photopolymerizable compound include, but are not limited to, A9550 from Shin Nakamura Co., Ltd.

The photopolymerizable compound may be contained in an amount of 5 to 80 parts by weight, specifically 10 to 70 parts by weight, more specifically 15 to 60 parts by weight, based on 100 parts by weight of the entire self-light-sensitive photosensitive resin composition. When the photopolymerizable compound is included in the above range, it is advantageous in terms of strength and smoothness of the pixel portion.

When the photopolymerizable compound is contained in the range below the above range, the strength of the pixel portion may be somewhat lowered, and when the photopolymerizable compound is contained in the range exceeding the above range, the smoothness may be somewhat lowered. .

Light curing Initiator

The photopolymerization initiator according to the present invention can be used without particular limitation as long as it can polymerize the photopolymerizable compound. Particularly, from the viewpoints of polymerization characteristics, initiation efficiency, absorption wavelength, availability, and cost, the photopolymerization initiator is preferably used in combination with an acetophenone compound, a benzophenone compound, a triazine compound, a biimidazole compound, It is preferable to use at least one compound selected from the group consisting of compounds.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy- 1- [4- 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-methylcyclohexyl phenyl ketone, 2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1-one 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.

Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Specific examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6 - (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, (Trichloromethyl) -6- [2- (5-methylfuran-2- (4-methoxystyryl) -1,3,5-triazine, Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- ) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Specific examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbimidazole, 2,2'-bis (2,3- Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) , 2,2'-bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) Imidazole compounds in which 4'5,5'-tetraphenyl-1,2'-biimidazole or phenyl groups at 4,4 ', 5,5' positions are substituted by carboalkoxy groups. Among them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- , 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole is preferably used do.

Specific examples of the oxime compounds include o-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one and commercially available products such as Irgacure OXE 01 and OXE 02 from BASF.

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

The photopolymerization initiator may be added in an amount of 0.1 to 10 parts by weight, preferably 1 to 8 parts by weight, more preferably 3 to 5 parts by weight based on 100 parts by weight of the entire self-light-sensitive resin composition.

When the photopolymerization initiator is contained within the above range, the self-light-sensitive photosensitive resin composition is highly sensitized and the exposure time is shortened, so that the productivity is improved and the high resolution can be maintained. Further, there is an advantage that the strength of the pixel portion formed by using the self-luminescent photosensitive resin composition according to the present invention and the smoothness on the surface of the pixel portion are improved.

The photopolymerization initiator may further include a photopolymerization initiator in order to improve the sensitivity of the self-luminescent photosensitive resin composition. When the photopolymerization initiator is included, the sensitivity is further increased and the productivity is improved.

The photopolymerization initiation auxiliary may be, for example, at least one compound selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group, but is not limited thereto.

As the amine compound, an aromatic amine compound is preferably used. Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Dimethylaminobenzoic acid, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone ), 4,4'-bis (diethylamino) benzophenone, and the like.

The carboxylic acid compound is preferably an aromatic heteroacetic acid, and more specifically, it is preferably an aromatic heteroaromatic acid such as phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthio Acetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.

Specific examples of the organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -thione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexacis (3-mercaptopropionate), and tetraethylene glycol bis (3-mercaptopropionate) .

The photopolymerization initiator may be appropriately added in the range not impairing the scope of the present invention.

additive

The self-luminescent photosensitive resin composition according to the present invention may further include an additive such as an adhesion promoter and a surfactant in order to improve coatability or adhesion.

The adhesion promoter may include a silane coupling agent having a reactive substituent selected from the group consisting of a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, and a combination thereof, which may be added to improve adhesion with the substrate. But is not limited thereto. For example, the silane coupling agent may be at least one selected from the group consisting of trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatepropyltriethoxysilane,? -Glycidoxy Propyltrimethoxysilane, and? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc., these may be used singly or in combination of two or more kinds

When the self-luminescent photosensitive resin composition according to the present invention includes the above-mentioned surfactant, there is an advantage that the coating property can be improved. For example, the surfactant may be selected from the group consisting of BM-1000, BM-1100 (BM Chemie), Prolide FC-135 / FC-170C / FC-430 (Sumitomo 3M Co.), SH-28PA / -190 / SZ- Co., Ltd.) may be used, but the present invention is not limited thereto.

In addition, the self-luminescent photosensitive resin composition according to the present invention may further contain additives such as an antioxidant, an ultraviolet absorber and an antiflocculant to the extent that the effect of the present invention is not impaired, It can be appropriately added by a person skilled in the art. For example, the additive may be used in an amount of 0.05 to 10 parts by weight, specifically 0.1 to 10 parts by weight, more specifically 0.1 to 5 parts by weight, based on the total weight of the self-emission photosensitive resin composition, but is not limited thereto.

<Color filter>

Another aspect of the present invention relates to a color filter manufactured using the self-luminous photosensitive resin composition described above.

Since the color filter according to the present invention includes a phosphoric acid-based dispersant, the quantum dot particles are evenly dispersed, so that the light efficiency is excellent and the quality of the pixel pixel is excellent.

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

The substrate may be the substrate of the 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 glass, silicon (Si), silicon oxide (SiOx), or a polymer substrate, and 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, which is formed by applying the self-luminescent photosensitive resin composition and exposing, developing, and thermosetting the self-luminescent photosensitive resin composition in a predetermined pattern. The pattern layer may be formed by performing a method commonly known in the art.

The color filter including the substrate and the pattern layer as described above may further include a partition wall formed between each pattern, and may further include a black matrix, but is not limited thereto.

Further, the color filter may further include a protective film formed on the pattern layer of the color filter.

In another embodiment of the present invention, the color filter may include at least one selected from the group consisting of a red pattern layer, a green pattern layer, and a blue pattern layer. Specifically, the color filter may include at least one selected from the group consisting of a red pattern layer including an effective quantum dot, a green pattern layer including a rust quantum dot, and a blue pattern layer including a blue quantum dot according to the present invention . The red pattern layer, the green pattern layer, and the blue pattern layer may emit red light, green light, and blue light when irradiated with light, respectively. At this time, the emission light of the light source is not particularly limited, but blue light A light source that emits light can be used.

The color filter may include only a pattern layer of two colors of a red pattern layer, a green pattern layer, and a blue pattern layer, but is not limited thereto. However, if the color filter has only a pattern layer of two colors, the pattern layer may further include a transparent pattern layer not containing the quantum dot particles.

When the color filter includes only the pattern layer of the two colors, a light source that emits light having a wavelength other than the two colors may be used. For example, when the color filter includes a red pattern layer and a green pattern layer, a light source that emits blue light may be used. In this case, the red quantum dot emits red light and the green quantum dot emits green light. Blue light can be seen as blue light by the light source is transmitted as it is.

<Image Display Device>

Further, another aspect of the present invention relates to an image display apparatus including the color filter described above.

The color filter of the present invention is applicable not only to a general liquid crystal display device but also to various image display devices such as an electroluminescence display device, a plasma display device, and a field emission display device.

Since the image display apparatus according to the present invention includes a quantum dot and a phosphoric acid-based dispersing agent, it has an excellent light efficiency, exhibits a high luminance, has excellent color reproducibility, and has a wide viewing angle.

In another embodiment of the present invention, the image display apparatus may further include a light source for emitting blue light and a transparent pattern layer, the light source for emitting the blue light, have.

Hereinafter, the present invention will be described in detail by way of examples to illustrate the present invention. However, the embodiments according to the present disclosure can be modified in various other forms, and the scope of the present specification is not construed as being limited to the above-described embodiments. Embodiments of the present disclosure are provided to more fully describe the present disclosure to those of ordinary skill in the art. In the following, "%" and "part" representing the content are by weight unless otherwise specified.

Manufacturing example  One : CdSe (core)/ ZnS (Shell) Structure of Optical Luminescent Sintered Rat Quantum Dot Particle Synthesis

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 for 20 minutes, 0.4 mmol of Se powder and 2.3 mmol of S powder were dissolved in 3 mL of trioctylphosphine, S solution was rapidly injected into a reactor containing a solution of Cd (OA) ₂ and Zn (OA) ₂ . The resulting mixture was grown at 310 ° C for 5 minutes, and growth was stopped using an ice bath. Then, the precipitate was 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 size and shell thickness summed to 3 to 5 nm (CdSe (core) / ZnS (shell) structure distributed quantum dot particle A-1.

Manufacturing example  2: Synthesis of alkali-soluble resin

A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen-introducing 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 t-butylperoxy-2-ethylhexanoate and 40 parts by weight of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) were charged and stirred to prepare a monomer dropping tank. 6 parts by weight of n-dodecanethiol And 24 parts by weight of PGMEA were added and stirred to prepare a 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 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 allowed to stand at 90 DEG C for 2 hours each. After 1 hour, the temperature was elevated to 110, and the mixture was maintained for 3 hours. Then, a gas introduction tube was introduced to prepare a bubbling gas mixture of oxygen / nitrogen = 5 / . 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 an alkali-soluble resin having a solid content of 29.1% by weight, a weight average molecular weight of 32,000 and an acid value of 114 mgKOH / g.

Manufacturing example  3: Qdot  Preparation of dispersion

A quantum dot dispersion (A ') was prepared from the composition shown in Table 1 below.

A quantum dot dispersant Manufacturing example 3-1 3-2 3-3 3-4 3-5 3-6 3-7 3-8 3-9 3-10 3-11 The quantum dot (A-1) 20 20 20 20 20 20 - 20 20 20 - The quantum dot (A-2) - - - - - - 20 - - - 20 The dispersant (B-1) One 5 40 50 - - 5 - - - - Dispersant (B-2) - - - - 5 - - - - - - Dispersant (B-3) - - - - - 5 - - - - Dispersant (B-4) - - - - - - - - 5 - - Dispersant (B-5) - - - - - - - - - 5 - Solvent (C) 79 75 40 30 75 75 75 80 75 75 80 A-1: Quantum dot synthesized in Production Example 1
A-2: Nanosquare Quantum Dot NSQDs-HOS 535nm
B-1: Disperbyk-111 (Phosphoric acid dispersant, manufactured by Big Chemie)
B-2: Disperbyk-110 (phosphate-based dispersant, manufactured by Big Chemie)
B-3: Disperbyk-103 (Phosphoric acid dispersant, manufactured by Big Chemie)
B-4: Disperbyk-161 (a urethane dispersant manufactured by Big Chemie)
B-5: Disperbyk-2001 (acrylic dispersant, manufactured by Big Chemie)
C: chloroform

Example  1 to 7 and Comparative Example  1 to 4: Self-luminous  Preparation of Photosensitive Resin Composition

In Production Examples 3-1 to 3-11, alkali-soluble resins, a solvent, a photopolymerizable compound and a photopolymerization initiator were mixed with the compositions according to Tables 2 and 3, and the self-luminescence according to Examples 1 to 7 and Comparative Examples 1 to 4 To prepare a photosensitive resin composition.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 A quantum dot dispersant
(A ') Production example 3-1 40 - - - - - - Production example 3-2 - 40 - - - - - Production Example 3-3 - - 40 - - - - Production example 3-4 - - - 40 - - - Production Example 3-5 - - - - 40 - - Production Example 3-6 - - - - - 40 - Production Example 3-7 - - - - - - 40 Production Example 3-8 - - - - - - - Production Example 3-9 - - - - - - - Production Example 3-10 - - - - - - - Production Example 3-11 - - - - - - - The alkali-soluble resin (B ') 20 20 20 20 20 20 20 The solvent (C ') 15 15 15 15 15 15 15 The photopolymerizable compound (D ') 20 20 20 20 20 20 20 Photopolymerization initiator (E ') 5 5 5 5 5 5 5 A ': Quantum dot dispersion according to Production Example 3
B ': An alkali-soluble resin according to Production Example 2
C ': Propylene glycol monomethyl ether acetate (PGMEA)
D ': dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
E ': Irgacure-907 (BASF)

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 A quantum dot dispersant
(A ') Production example 3-1 - - - - Production example 3-2 - - - - Production Example 3-3 - - - - Production example 3-4 - - - - Production Example 3-5 - - - - Production Example 3-6 - - - - Production Example 3-7 - - - - Production Example 3-8 40 - - - Production Example 3-9 - 40 - - Production Example 3-10 - - 40 - Production Example 3-11 - - - 40 The alkali-soluble resin (B ') 20 20 20 20 20 The solvent (C ') 15 15 15 15 15 The photopolymerizable compound (D ') 20 20 20 20 20 Photopolymerization initiator (E ') 5 5 5 5 5 A ': Quantum dot dispersion according to Production Example 3
B ': An alkali-soluble resin according to Production Example 2
C ': Propylene glycol monomethyl ether acetate (PGMEA)
D ': dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
E ': Irgacure-907 (BASF)

Experimental Example

(1) Dispersion size measurement of the quantum dot dispersion and the self-luminescent photosensitive resin composition

The dispersion particle size was measured using ELSZ-2000ZS (manufactured by Otsuka Chemical Co., Ltd.), and it is shown in Table 4 below. Normally, when the quantum dot particles are aggregated, the dispersed particle size becomes large, thereby causing a problem that the luminescent properties are deteriorated.

(2) Measurement of developing type of self-luminescent photosensitive resin composition

The self-luminescent photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 to 4 were coated on a glass substrate by a spin coating method and then placed on a heating plate and maintained at a temperature of 100 ° C for 3 minutes to form a thin film. (0.04% KOH, 26 DEG C) in an aqueous solution developing solution to confirm that the form of the coated self-emitting photosensitive resin composition layer was a dissolved form or a peeled form, and is shown in Table 4 below.

In the case of the dissolving type, the formation of the pixel pattern is good, but in the case of the delamination form, the formation of the pixel pattern is difficult, and thus it can not be used.

(3) Intensity measurement

The photo-converted region was measured by a 365 nm type 4 W UV illuminator (VL-4LC, VILBER LOURMAT) on a pattern portion formed in a pattern of 20 mm × 20 mm square among the color filters having the self-luminous pixels, And measured using USB2000 + (manufactured by Ocean Optics Co., Ltd.).

It can be judged that the higher the intensity of the measured light is, the better the self-luminescence characteristic is exhibited.

Quantum dot dispersed dispersed particle size Photosensitive resin composition
Dispersed particle size Developability Emission intensity
(Light emitting area) Example 1 7 nm 8 nm Dissolution 5,371,429 Example 2 8 nm 7 nm Dissolution 5,556,548 Example 3 8 nm 7 nm Dissolution 5,050,252 Example 4 7 nm 7 nm Exfoliation 5,324,876 Example 5 9 nm 10 nm Dissolution 5,109,639 Example 6 8 nm 9 nm Dissolution 5,254,188 Example 7 10 nm 10 nm Dissolution 5,576,527 Comparative Example 1 8 nm 1,372 nm Dissolution 2,634,158 Comparative Example 2 11 nm 859 nm Dissolution 2,851,660 Comparative Example 3 13 nm 1,134 nm Dissolution 2,846,916 Comparative Example 4 9 nm 935 nm Dissolution 2,462,551

As can be seen in Table 4, the dispersion particle size of the self-emitting photosensitive resin composition containing the phosphoric acid-based dispersant according to the present invention was maintained similar to the dispersion particle size of the quantum dot dispersion body, The light emission intensity is greatly increased.

When the content of the phosphoric acid dispersant exceeds 200 parts by weight as in Examples 1 to 4, the emission intensity is excellent but the pattern formation is somewhat lowered as the developing property is changed to peeling.

Claims (8)

Quantum dot; Phosphoric acid dispersant; And a solvent. The method according to claim 1,
Wherein the phosphoric acid-based dispersant further contains an ester group in one molecule. 3. The method according to claim 1 or 2,
Wherein the phosphoric acid-based dispersant further contains a polyether moiety in one molecule. The method according to claim 1,
Wherein the phosphoric acid-based dispersant is 1 to 300 parts by weight based on 100 parts by weight of the total solid content of the quantum dots. The method according to claim 1,
An alkali-soluble resin, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and an additive. A color filter comprising a cured product of the self-luminescent photosensitive resin composition according to claim 1. The method according to claim 6,
Wherein the color filter includes at least one selected from the group consisting of a red pattern layer, a green pattern layer, and a blue pattern layer. An image display device comprising the color filter according to claim 6.