JP7404199B2 - Photoconversion ink composition, color filter, and image display device - Google Patents

Description

The present invention relates to a light conversion ink composition, a color filter, and an image display device, and more specifically, the present invention relates to a light conversion ink composition, a color filter, and an image display device. The present invention relates to a light conversion ink composition that can ensure excellent jetting characteristics without causing nozzle clogging, a color filter formed using the same, and an image display device equipped with the color filter.

A color filter is a thin film type optical component that extracts the three colors red, green, and blue from white light and functions in minute pixel units. be. Such color filters include a black matrix layer formed in a predetermined pattern on a transparent substrate to block light at the boundary between each pixel, and a black matrix layer formed in a predetermined pattern on a transparent substrate to block light at the boundary between each pixel. The pixel portion has a structure in which pixel portions are formed by arranging the three primary colors of R), green (G), and blue (B)) in a predetermined order and are sequentially stacked.

In recent years, a pigment dispersion method using a pigment-dispersed photosensitive resin has been applied as one of the methods for realizing color filters. However, when using the pigment dispersion method, part of the light emitted from the light source is absorbed by the color filter during the process of passing through the color filter, reducing light efficiency. A problem has arisen in that color reproduction is degraded due to the characteristics of the pigments used.

In particular, as color filters are used in a variety of fields including various image display devices, they are required not only to have excellent pattern characteristics but also to have high color reproduction, high brightness, and high contrast ratio. It is being In order to solve these problems, a method for manufacturing a color filter using a self-luminous photosensitive resin composition containing quantum dots has been proposed. For example, Korean Patent Publication No. 10-2009-0036373 discloses that by replacing an existing color filter with a light-emitting layer made of quantum dot phosphor, the luminous efficiency can be improved and the display quality of a display device can be improved. .

A photolithography method using a photosensitive resin composition containing such quantum dots is a method of producing a color filter by coating, exposing, developing, and curing. Although this method is superior in terms of sophistication and reproducibility of the color filter, it requires coating, exposure, development, and curing processes for each color to form a pixel, and the manufacturing process, This increases labor and cost, and increases the number of control factors between processes, making it difficult to manage yield.

Inkjet methods have been proposed to solve these problems. The inkjet method is a technique that uses an inkjet head to spray liquid ink onto predetermined sections, thereby creating an image colored by each ink. The inkjet method allows multiple colors, including red, green, and blue, to be colored at once, greatly reducing manufacturing processes, labor, and costs.

In recent years, with the demand for high color reproducibility (NTSC contrast color density) for monitors, TVs, etc., it has become necessary to improve the luminance of quantum dots. In order to improve such luminance, there is a method of increasing the film thickness. However, with a quantum dot-containing ink composition having a high solvent content, there is a limit to increasing the film thickness. Furthermore, when the content of the solvent is high, the solvent evaporates at the inlet of the nozzle and solid ink is deposited, resulting in nozzle clogging during continuous processes. Therefore, there is a need for quantum dot-containing ink compositions with low or no solvent content.

However, if the content of the solvent is reduced or no solvent is included, uniform dispersion becomes difficult and causes aggregation of the quantum dots, which reduces the optical properties of the quantum dots and increases the viscosity, resulting in poor jetting properties. It may become defective.

One object of the present invention is to provide quantum dots with excellent optical properties, to realize low viscosity, and to ensure excellent jetting properties without causing nozzle clogging during continuous processes. An object of the present invention is to provide a light conversion ink composition.

Another object of the present invention is to provide a light conversion pixel including a cured product of the light conversion ink composition.

Another object of the present invention is to provide a color filter including the light conversion pixels.

Yet another object of the present invention is to provide an image display device equipped with the color filter.

On the other hand, the present invention includes a quantum dot and a curable monomer, the quantum dot has a ligand layer containing a compound represented by the following chemical formula 1 on the surface, and the curable monomer includes: A light conversion ink composition containing a compound represented by the following chemical formula 2 is provided.

前記式中、
Ｌは、存在しないか、Ｃ_１～Ｃ_２２のアルキレン基又はＣ_４～Ｃ_２２のアルケニレン基であり、
Ｒ^１は、Ｃ_１～Ｃ_２０のアルキレン基、フェニレン基又はＣ_３～Ｃ_１０のシクロアルキレン基であり、
Ｒ^２は、水素又はメチル基であり、
ｍは、１～１５の整数である。

In the above formula,
L is absent or is a C ₁ -C ₂₂ alkylene group or a C ₄ -C ₂₂ alkenylene group,
R ¹ is a C ₁ to C ₂₀ alkylene group, a phenylene group, or a C ₃ to C ₁₀ cycloalkylene group,
R ² is hydrogen or a methyl group,
m is an integer from 1 to 15.

In one embodiment of the present invention, the ligand layer may include one or more compounds selected from compounds represented by the following chemical formulas 1-1 to 1-5.

本発明の一実施形態において、前記量子ドットは、非カドミウム系量子ドットであってよい。

In one embodiment of the invention, the quantum dots may be non-cadmium based quantum dots.

In one embodiment of the invention, the quantum dot has a core-shell structure including a core and a shell covering the core, and the core is GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN. , InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNS b, GaAlPAs, GaAlPSb, GaInNPs, GaInNAs , GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, and InAlPSb, and the shell includes one or more selected from the group consisting of ZnSe, ZnS, and ZnTe. That's fine.

The light conversion ink composition according to one embodiment of the invention may further include scattering particles.

In one embodiment of the invention, the scattering particles are Al ₂ O ₃ , SiO ₂ , ZnO, ZrO 2 , BaTiO ₃ , TiO _{2 ,} Ta ₂ O ₅ , Ti ₃ O ₅ , ITO, IZO, ATO, ZnO- It may contain one or more selected from the group consisting of Al, Nb ₂ O ₃ , SnO, and MgO.

In one embodiment of the invention, the scattering particles may be _TiO2 .

The photoconversion ink composition according to one embodiment of the present invention may further include a photopolymerization initiator.

The light conversion ink composition according to one embodiment of the present invention may contain a solvent in an amount of 20% by weight or less based on 100% by weight of the total composition.

The light conversion ink composition according to one embodiment of the present invention may be solvent-free.

On the other hand, the present invention provides a light conversion pixel including a cured product of the light conversion ink composition.

On the other hand, the present invention provides a color filter including the light conversion pixel.

On the other hand, the present invention provides an image display device equipped with the color filter.

The light conversion ink composition according to the present invention contains quantum dots having a thiol-substituted fluorene-based ligand with a specific structure on the surface as a colorant, and the thiol-substituted fluorene-based ligand as a curable monomer. Contains bifunctional (meth)acrylate with a specific structure that has excellent compatibility with ligands, making it possible to achieve excellent optical properties of quantum dots, low viscosity, and prevent nozzle clogging during continuous processes. It is possible to ensure excellent jetting characteristics without causing any problems. Therefore, the light conversion ink composition according to the present invention can be effectively used when manufacturing a color filter using an inkjet printing method.

The present invention will be explained in more detail below.

In the present invention, when we say that a certain member is located ``above'' another member, this does not mean only when a certain member is in contact with another member, but also when there is another member between the two members. Including cases where it exists.

In the present invention, when a part is said to "include" a certain component, unless otherwise specified, this means that the part does not exclude other components, but may further include other components.

One embodiment of the present invention includes a quantum dot (A) and a curable monomer (B), and the quantum dot (A) has a coordination structure containing a thiol-substituted fluorene-based ligand with a specific structure on its surface. The photoconversion ink composition has a sublayer, and the curable monomer (B) includes a bifunctional (meth)acrylate having a specific structure.

[Quantum dot (A)]
In one embodiment of the present invention, the quantum dot has a ligand layer containing a compound represented by the following chemical formula 1 on its surface.

前記式中、
Ｌは、存在しないか、Ｃ_１～Ｃ_２２のアルキレン基又はＣ_４～Ｃ_２２のアルケニレン基である。

In the above formula,
L is absent or is a C ₁ -C ₂₂ alkylene group or a C ₄ -C ₂₂ alkenylene group.

The C ₁ -C ₂₂ alkylene group used herein means a linear or branched divalent hydrocarbon having 1 to 22 carbon atoms, such as methylene, ethylene, n-propylene, i - including, but not limited to, propylene, n-butylene, n-heptylene, n-dodecylene, and the like.

The C ₄ -C ₂₂ alkenylene group used herein refers to a linear or branched divalent unsaturated hydrocarbon having 4 to 22 carbon atoms and one or more carbon-carbon double bonds. and includes, but is not limited to, butenylene, pentenylene, hexenylene, heptenylene, octenylene, nonenylene, decenylene, undecenylene, dodecenylene, tridecenylene, tetradecenylene, pentadecenylene, hexadecenylene, heptadecenylene, octadecenylene, etc. do not have.

The C ₁ -C ₂₂ alkylene group and the C ₄ -C ₂₂ alkenylene group include a C ₁ -C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, a C ₂ -C ₆ alkynyl group, C ₃ to C ₁₀ cycloalkyl group, C ₃ to C ₁₀ heterocycloalkyl group, C ₃ to C ₁₀ heterocycloalkyloxy group, C ₁ to C ₆ haloalkyl group, C ₁ to It may be substituted with a C ₆ alkoxy group, a C ₁ -C ₆ thioalkoxy group, an aryl group, an acyl group, hydroxy, thio, halogen, amino, alkoxycarbonyl, carboxy, carbamoyl, cyano, nitro, and the like.

In view of the compatibility of quantum dots and/or low viscosity, the compound represented by the chemical formula 1 of the present invention may have no L, a C ₁ to C ₂₀ alkylene group, or a C ₄ to C ₂₀ alkylene group. It may be a compound which is an alkenylene group, preferably a compound in which L is absent or is a C ₁ -C ₁₈ alkylene group or a C ₄ -C ₁₈ alkenylene group.

In one embodiment of the present invention, the compound represented by the chemical formula 1 is selected from the compounds represented by the following chemical formulas 1-1 to 1-5 in terms of compatibility with quantum dots and low viscosity. It may be one or more compounds.

本発明の前記化学式１で表される化合物は有機配位子であって量子ドットの表面に配位結合されて量子ドットを安定化させる役割を遂行することができる。

The compound represented by Formula 1 of the present invention is an organic ligand, and can serve to stabilize the quantum dots by being coordinately bonded to the surface of the quantum dots.

The compound represented by Formula 1 has a thiol group, and the thiol group may be bonded to the surface of the quantum dot. In the case of a thiol group, the bonding force with the quantum dot surface is superior to that of a ligand layer compound such as carboxylic acid, which is included in ordinary quantum dots. As a result, the compound represented by the chemical formula 1 suppresses quenching due to surface defects such as dangling bonds of quantum dots and quenching due to surface oxidation, and improves the optical characteristics (emission characteristics) and reliability of quantum dots. It has the advantage of improving sex.

Conventionally produced quantum dots generally have a ligand layer on their surface, and the ligand layer immediately after production is composed of oleic acid, lauric acid, etc. obtain. In this case, compared to the quantum dots of the present invention containing the compound represented by the chemical formula 1 as a ligand layer, non-bonding defects on the surface of the quantum dots due to weaker bonding force between the ligand layer and the quantum dots The surface protection effect may be reduced. In addition, in the case of oleic acid, it is easily dispersed in aliphatic hydrocarbon solvents such as n-hexane and aromatic hydrocarbon solvents such as benzene, which are highly volatile organic compounds (VOCs). It has poor dispersibility in solvents such as propylene glycol monomethyl ether acetate (PGMEA).

The compound represented by the chemical formula 1 has superior thiol binding strength compared to oleic acid containing carboxylic acid and can protect the quantum dot surface more reliably, and has a bulky structure of fluorene groups. can improve compatibility with surrounding materials.

Therefore, by including the compound represented by the chemical formula 1 in the ligand layer, the quantum dot of the present invention can exhibit excellent oxidation stability, suppress a decrease in quantum efficiency, and improve reliability. can be improved.

In addition, the quantum dots according to the present invention can exhibit good dispersibility with only the curable monomer described below even if the content of a solvent is low or does not contain a solvent, and when applied to an ink composition, it has a low viscosity. It becomes possible to achieve this, and it is also possible to ensure excellent jetting characteristics without causing nozzle clogging during the progression of continuous processes.

In one embodiment of the present invention, the quantum dot according to the present invention includes a compound represented by the chemical formula 1 in the ligand layer, and oleic acid, lauric acid, 2-( It may further contain one or more of 2-methoxyethoxy)acetic acid, 2-[2-(2-methoxyethoxy)ethoxy]acetic acid, succinic acid mono-[2-(2-methoxy-ethoxy)-ethyl]ester, and the like.

In one embodiment of the present invention, the quantum dots may refer to nano-sized semiconductor materials. Atoms make up molecules, and molecules make up clusters of small molecules to make nanoparticles, and when such nanoparticles exhibit semiconductor properties, they are called quantum dots. When the quantum dot receives energy from the outside and enters an excited state, it emits energy according to its own energy band gap. For example, by including such quantum dots, the light conversion ink composition of the present invention can photoconvert incident blue light into green light and red light.

In one embodiment of the invention, the quantum dots may be non-cadmium based quantum dots.

The non-cadmium-based quantum dots are not particularly limited as long as they are quantum dot particles that can emit light when stimulated by light. For example, it is selected from the group consisting of II-VI group semiconductor compounds; III-V group semiconductor compounds; IV-VI group semiconductor compounds; group IV elements or compounds containing them; and combinations thereof; They may be used alone or in combination of two or more.

Specifically, the II-VI group semiconductor compound is a binary compound selected from the group consisting of ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, and mixtures thereof; ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe. , HgSTe, HgZnS, HgZnSe, HgZnTe, and mixtures thereof; and quaternary compounds selected from the group consisting of HgZnSeS, HgZnSeTe, HgZnSTe, and mixtures thereof. However, it is not limited to these.

The III-V group semiconductor compound is a binary compound selected from the group consisting of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, and mixtures thereof; GaNP, GaNAs , GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, and mixtures thereof; and GaAlNAs, GaAlNSb, GaAlPA s, It may be selected from the group consisting of a four-element compound selected from the group consisting of GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, and mixtures thereof, but these It is not limited.

The IV-VI group semiconductor compound is a binary compound selected from the group consisting of SnS, SnSe, SnTe, PbS, PbSe, PbTe, and mixtures thereof; SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe. , SnPbTe, and mixtures thereof; and one or more compounds selected from the group consisting of four element compounds selected from the group consisting of SnPbSSe, SnPbSeTe, SnPbSTe, and mixtures thereof. However, it is not limited to these as well.

Although not limited to these, the Group IV element or the compound containing the same is an element selected from the group consisting of Si, Ge, and a mixture thereof; and an element selected from the group consisting of SiC, SiGe, and a mixture thereof. It may be selected from the group consisting of selected two-element compounds.

The quantum dots may have a homogeneous single structure; a dual structure such as a core-shell, a gradient structure, etc.; or a mixed structure thereof. Preferably, the quantum dot may have a core-shell structure including a core and a shell covering the core.

Specifically, in the core-shell dual structure, the materials forming each core and shell may be made of the different semiconductor compounds described above. For example, the core may include GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNPs, InNAs, InNSb, InPAs, InPSb, GaAlNPs, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNPs, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNPs, InAlNAs, I One or more selected from the group consisting of nAlNSb, InAlPAs, and InAlPSb The shell may include one or more selected from the group consisting of ZnSe, ZnS, and ZnTe, but is not limited thereto.

Preferably, the core-shell quantum dots include InP/ZnS, InP/ZnSe, InP/GaP/ZnS, InP/ZnSe/ZnS, InP/ZnSeTe/ZnS, and InP/MnSe/ZnS.

The quantum dots are synthesized by a wet chemical process, a metal organic chemical vapor deposition process (MOCVD), or a molecular beam epitaxy process (MBE). may have been done, but these However, it is preferable to synthesize quantum dots by a wet chemical process, since quantum dots with better optical properties can be obtained.

The wet chemical process is a method of growing particles by adding a precursor material to an organic solvent. In the wet chemical process, when the crystal grows, the organic solvent naturally coordinates to the surface of the quantum dot crystal and acts as a dispersing agent to regulate the crystal growth. The growth of nanoparticles can be controlled by a process that is easier and cheaper than vapor phase deposition methods such as molecular beam epitaxy. Therefore, it is preferable to manufacture the quantum dots using the wet chemical process.

When producing quantum dots by a wet chemical process, organic ligands are used to suppress aggregation of quantum dots and control the particle size of quantum dots to the nano-level. As such an organic ligand, oleic acid may generally be used.

In one embodiment of the present invention, the oleic acid used in the manufacturing process of the quantum dots is replaced with a thiol-substituted fluorene-based compound represented by Formula 1 using a ligand exchange method.

The above-mentioned ligand exchange is performed by adding the organic ligand to be exchanged, that is, a thiol-substituted fluorene compound represented by Chemical Formula 1, to a dispersion containing quantum dots having the original organic ligand, that is, oleic acid. This may be carried out by stirring this at room temperature to 200° C. for 30 minutes to 3 hours to obtain quantum dots to which the thiol-substituted fluorene compound represented by Chemical Formula 1 is bonded. If necessary, a step of separating and purifying the quantum dots to which the thiol-substituted fluorene compound represented by Formula 1 is bonded may be further performed.

The quantum dots may be included in an amount of 1 to 60% by weight, preferably 5 to 50% by weight, based on 100% by weight of the entire photoconversion ink composition. When the quantum dots are contained within the above range, there are advantages that the luminous efficiency is excellent and the reliability of the coating layer is excellent. If the quantum dots are contained in an amount less than the above range, the light conversion efficiency may be insignificant, and if it exceeds the above range, the viscosity of the light conversion ink composition may increase, resulting in a decrease in jetting properties. This may occur.

[Curable monomer (B)]
In one embodiment of the present invention, the curable monomer (B) includes a compound represented by the following chemical formula 2.

前記式中、
Ｒ^１は、Ｃ_１～Ｃ_２０のアルキレン基、フェニレン基又はＣ_３～Ｃ_１０のシクロアルキレン基であり、
Ｒ^２は、水素又はメチル基であり、
ｍは、１～１５の整数である。

In the above formula,
R ¹ is a C ₁ to C ₂₀ alkylene group, a phenylene group, or a C ₃ to C ₁₀ cycloalkylene group,
R ² is hydrogen or a methyl group,
m is an integer from 1 to 15.

The C ₁ -C ₂₀ alkylene group used herein means a linear or branched divalent hydrocarbon having 1 to 20 carbon atoms, such as methylene, ethylene, n-propylene, isocarbon, etc. Examples include, but are not limited to, propylene, n-butylene, isobutylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, and the like.

The C ₃ to C ₁₀ cycloalkylene group used herein means a monocyclic or fused cyclic divalent hydrocarbon having 3 to 10 carbon atoms, such as cyclopropylene, cyclobutylene, cyclo These include, but are not limited to, pentylene, cyclohexylene, and the like.

The C ₁ to C ₂₀ alkylene group, phenylene group, and C ₃ to C ₁₀ cycloalkylene group include a C ₁ to C ₆ alkyl group, a C ₂ to C ₆ alkenyl group in which one or more hydrogen atoms are group, C ₂ to C ₆ alkynyl group, C ₃ to C ₁₀ cycloalkyl group, C ₃ to C ₁₀ heterocycloalkyl group, C ₃ to C ₁₀ heterocycloalkyloxy group, C ₁ to C ₆ Haloalkyl group, C1 _{- C6} alkoxy group, _C1 - _C6 thioalkoxy group, aryl group, acyl group, hydroxy, thio, halogen, amino, alkoxycarbonyl, carboxy, carbamoyl, cyano, nitro, etc. may be replaced with

In one embodiment of the invention, R ¹ may be a C ₁ -C ₂₀ alkylene group, preferably a C ₁ -C ₁₂ alkylene group, as described above. When R ¹ is a C ₁ to C ₂₀ alkylene group, jetting properties can be improved due to excellent dispersibility of scattering particles even without a solvent, and coating film hardness and surface properties can be improved.

In one embodiment of the invention, m is an integer from 1 to 15, preferably from 1 to 5, as described above. If m exceeds the above range, the viscosity of the photoconversion ink composition may increase.

Specific examples of the compound represented by Formula 2 include 1,6-hexanediol diacrylate, 1,9-bisacryloyloxynonane, and tripropylene glycol diacrylate.

The compound represented by the chemical formula 2 has excellent compatibility with the thiol-substituted fluorene ligand represented by the chemical formula 1 and improves the dispersibility of quantum dots, so that the compound has a low solvent content or It is possible to realize a low-viscosity light-converting ink composition with excellent optical properties even without a solvent. Therefore, the light conversion ink composition according to the present invention can be effectively used when manufacturing a color filter using an inkjet printing method.

In addition to the polymerizable compound represented by the chemical formula 2, the light conversion ink composition according to the present invention may further contain a trifunctional or higher, preferably tetrafunctional or higher, polyfunctional monomer. Examples of the polyfunctional monomer include trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, and pentaerythritol tri(meth)acrylate. Acrylate, Pentaerythritol Tetra(meth)acrylate, Ethoxylated Pentaerythritol Tetra(meth)acrylate, Dipentaerythritol Penta(meth)acrylate, Dipentaerythritol Hexa(meth)acrylate, Ethoxylated Dipentaerythritol Hexa(meth)acrylate , propoxylated dipentaerythritol hexa(meth)acrylate, dipentaerythritol (poly)acrylate, and the like are preferably used.

The polyfunctional monomer may be included in an amount of 30% by weight or less based on 100% by weight of the entire curable monomer. If the polyfunctional monomer is contained in an amount exceeding 30% by weight based on 100% by weight of the entire curable monomer, jetting failure may occur due to an increase in viscosity.

The curable monomer (B) may be contained in an amount of 20 to 90% by weight, preferably 30 to 80% by weight, based on 100% by weight of the entire photoconversion ink composition. When the curable monomer is contained within the above range, there is an advantage that it is preferable in terms of strength and smoothness of the pixel portion. If the curable monomer is contained in an amount less than the above range, the strength of the pixel portion may decrease slightly, and if the curable monomer is contained in an amount exceeding the above range, the light conversion efficiency may decrease. It is preferably included within the above range.

[Scattering particles (C)]
The light conversion ink composition according to one embodiment of the present invention may further include scattering particles (C).

The scattering particles serve to increase the overall optical efficiency by increasing the number of paths of light emitted from the quantum dots.

As the material for the scattering particles, ordinary inorganic materials may be used, preferably metal oxides.

The metal oxides include Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Mo, Cs, Ba, La, Hf, W, Tl, Pb, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Ti, Sb, Sn, Zr, It may be an oxide containing one or more metals selected from the group consisting of Nb, Ce, Ta, In, and combinations thereof, but is not limited thereto.

Specifically, the scattering particles include Al ₂ O ₃ , SiO ₂ , ZnO, ZrO ₂ , BaTiO ₃ , TiO ₂ , Ta ₂ O ₅ , Ti ₃ O ₅ , ITO, IZO, ATO, ZnO-Al, Nb ₂ It may contain one or more selected from the group consisting of O ₃ , SnO, and MgO, and TiO ₂ is preferred from the viewpoint of light conversion efficiency characteristics.

If necessary, the scattering particles may be made of a material whose surface has been treated with a compound having an unsaturated bond such as acrylate.

The scattering particles may have an average particle size of from 50 to 1000 nm, preferably from 100 to 500 nm, more preferably from 150 to 300 nm. At this time, if the particle size is too small, a sufficient scattering effect of the light emitted from the quantum dots cannot be expected; on the other hand, if the particles are too large, they may sink into the composition and cause a uniform scattering effect. Since it is not possible to obtain a surface of the light conversion layer of high quality, the amount is adjusted appropriately within the above range.

In the present invention, the average particle size may refer to the number average particle size, and can be determined from images observed using a field emission scanning electron microscope (FE-SEM) or a transmission electron microscope (TEM), for example. Specifically, the value can be obtained by extracting several samples from the observed images of FE-SEM or TEM, measuring the diameters of these samples, and taking the arithmetic average value.

The scattering particles may be contained in an amount of 1 to 150% by weight, preferably 5 to 100% by weight, based on 100% by weight of the quantum dots. It is preferable that the scattering particles are contained within the above range because the effect of increasing the luminescence intensity is maximized. If the amount of the scattering particles is less than the above range, the scattering effect may be insufficient and it may be difficult to secure the desired emission intensity, and if it exceeds the above range, the scattering properties will exceed the critical range. By blocking the emitted light in this way, the intensity of the emitted light may decrease.

[Photopolymerization initiator (D)]
The photoconversion ink composition according to one embodiment of the present invention may further include a photopolymerization initiator (D).

In one embodiment of the present invention, the photopolymerization initiator (D) may be used without particular limitation as long as it can polymerize the curable monomer. In particular, the photopolymerization initiator (D) may be an acetophenone compound, a benzophenone compound, a triazine compound, a biimidazole compound, or an oxime compound from the viewpoint of polymerization properties, initiation efficiency, absorption wavelength, availability, price, etc. It is preferable to use one or more compounds selected from the group consisting of , and thioxanthone compounds.

The photopolymerization initiator (D) may be contained in an amount of 0.01 to 20% by weight, preferably 0.5 to 15% by weight, based on 100% by weight of the entire photoconversion ink composition. When the photopolymerization initiator is contained within the above range, the photoconversion ink composition becomes highly sensitive and the exposure time is shortened, which improves productivity, which is preferable. Further, there is an advantage that the strength of the pixel portion formed using the light conversion ink composition according to the present invention and the smoothness of the surface of the pixel portion are improved.

The photopolymerization initiator (D) may further contain a photopolymerization initiation aid (d1) in order to improve the sensitivity of the photoconversion ink composition according to the present invention. When the photopolymerization initiation auxiliary agent is included, there is an advantage that sensitivity is further increased and productivity is improved.

The photopolymerization initiation aid (d1) may preferably be one or more compounds selected from the group consisting of amine compounds, carboxylic acid compounds, and organic yellow compounds having a thiol group, but is not limited thereto. It's not something you can do.

Specific examples of amine compounds include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzoate. -Dimethylaminobenzoate 2-ethylhexyl, 2-dimethylaminoethyl benzoate, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino) ) Aromatic amine compounds such as benzophenone may be mentioned, and preferably aromatic amine compounds may be used.

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

The photopolymerization initiation aid (d1) may be added as appropriate to the extent that the effects of the present invention are not impaired.

[Additive (E)]
In addition to the above-mentioned components, the light conversion ink composition according to an embodiment of the present invention may further contain additives such as a surfactant and an adhesion promoter in order to improve coating film flatness and adhesion.

When the light conversion ink composition according to the present invention contains the surfactant, there is an advantage that the flatness of the coating film can be improved. For example, the surfactants include BM-1000, BM-1100 (manufactured by BM Chemie), Florado FC-135/FC-170C/FC-430 (manufactured by Sumitomo 3M), and SH-28PA/-190. Fluorine surfactants such as /-8400/SZ-6032 (manufactured by Toray Silicone Co., Ltd.) may be used, but are not limited thereto.

The adhesion promoter may be added to improve adhesion to the substrate, and is a reaction promoter selected from the group consisting of a carboxyl group, a (meth)acryloyl group, an isocyanate group, an epoxy group, and a combination thereof. The silane coupling agent may include, but is not limited to, a silane coupling agent having a chemical substituent.

In addition, the light conversion ink composition according to the present invention may further contain additives such as an antioxidant, an ultraviolet absorber, and an anti-aggregation agent within a range that does not impair the effects of the present invention. Those skilled in the art can add and use them as appropriate without impairing the effects of the present invention.

The additive is 0.05 to 10% by weight, specifically 0.1 to 10% by weight, more specifically 0.1 to 5% by weight, based on 100% by weight of the entire light conversion ink composition. However, it is not limited to these ranges.

The light conversion ink composition according to one embodiment of the present invention may contain a solvent in an amount of 20% by weight or less based on 100% by weight of the total composition.

Preferably, the light conversion ink composition according to one embodiment of the present invention may be a solvent-free type that does not contain a solvent from the viewpoint of continuous processability.

As the solvent, ether or ester solvents, aliphatic saturated hydrocarbon solvents, halogenated hydrocarbon solvents, aromatic hydrocarbon solvents, etc. may be used. For example, the solvent includes ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol. Diethylene glycol dialkyl ethers such as dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether acetate (PGMEA), ethylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl Alkylene glycol alkyl ether acetates such as 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, ethanol, and propanol. , alcohols such as butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin, esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and cyclic esters such as γ-butyrolactone.

The light conversion ink composition according to an embodiment of the present invention has excellent optical properties and dispersibility of quantum dots, and can realize low viscosity even if the content of the solvent is as low as 20% by weight or less. In addition, the light conversion ink composition according to an embodiment of the present invention has a low solvent content of 20% by weight or less, and no nozzle clogging due to evaporation of the solvent at the nozzle inlet does not occur, which is advantageous for continuous processes. It is.

Further, the light conversion ink composition according to an embodiment of the present invention does not substantially contain a resin component, and even if it does contain it, it is contained within 0.5% by weight based on 100% by weight of the entire light conversion ink composition. . The light conversion ink composition according to one embodiment of the present invention can realize low viscosity because it does not contain a resin component, and has excellent nozzle jetting characteristics of the ink.

One embodiment of the present invention relates to a light conversion pixel including a cured product of the above-described light conversion ink composition.

Moreover, one embodiment of the present invention relates to a color filter including the above-mentioned light conversion pixels.
A pattern forming method of a light conversion ink composition according to the present invention includes the steps of applying the above-mentioned light conversion ink composition to a predetermined area by an inkjet method, and curing the applied light conversion ink composition. Become.

First, the photoconversion ink composition according to the present invention is injected into an inkjet sprayer to print on a predetermined area of a substrate.

The substrate is not particularly limited, and examples include substrates with flat surfaces such as glass substrates, silicon substrates, polycarbonate substrates, polyester substrates, aromatic polyamide substrates, polyamideimide substrates, polyimide substrates, Al substrates, and GaAs substrates. It will be done. These substrates may be subjected to pretreatment such as chemical treatment with chemicals such as a silane coupling agent, plasma treatment, ion plating treatment, sputtering treatment, gas phase reaction treatment, and vacuum deposition treatment. When a silicon substrate or the like is used as the substrate, a charge coupled device (CCD), a thin film transistor (TFT), etc. may be formed on the surface of the silicon substrate or the like. Additionally, a partition matrix may be formed.

In order to form an appropriate phase on a substrate when ejected from a piezo inkjet head, which is an example of an inkjet ejector, properties such as viscosity, fluidity, and quantum dot particles must be balanced with the inkjet head. . Although the piezo inkjet head used in the present invention is not particularly limited, it ejects ink having a droplet size of about 10 to 100 pL, preferably about 20 to 40 pL.

The viscosity of the light conversion ink composition according to the present invention is preferably adjusted to a range of about 3 to 65 cP, more preferably 7 to 60 cP.

A color filter according to an embodiment of the present invention includes a colored pattern layer formed by the pattern forming method. That is, the color filter is characterized by including a colored pattern layer formed by applying the above-described light conversion ink composition on a substrate in a predetermined pattern and then curing the composition. The configuration and manufacturing method of the color filter are well known in the technical field, so detailed explanation will be omitted.

One embodiment of the present invention relates to an image display device equipped with the above-mentioned color filter.

The color filter according to the present invention is applicable not only to ordinary liquid crystal displays (LCDs), but also to electroluminescent displays (ELs), plasma display devices (PDPs), field emission displays (FEDs), organic light emitting devices (OLEDs), etc. It is applicable to various image display devices.

The image display device according to the present invention includes a configuration known in the technical field, except that it includes the color filter described above.

Hereinafter, the present invention will be explained more specifically using Examples, Comparative Examples, and Experimental Examples. It should be noted that these Examples, Comparative Examples, and Experimental Examples are merely for explaining the present invention, and it is obvious to those skilled in the art that the scope of the present invention is not limited thereto.

[Synthesis Example 1: Synthesis of InP/ZnS core-shell quantum dots]
0.05839 g of indium acetate, 0.12019 g of oleic acid, and 10 mL of 1-octadecene (ODE) were placed in a 3-neck flask. The flask was degassed for 30 minutes at 110° C. and 100 mTorr while stirring, and then heated at 270° C. under an inert gas until the solution became transparent.

Prepare 0.025054 g of tris(trimethylsilyl)phosphine as a phosphorus (P) precursor, stir it in 0.5 mL of 1-octadecene and 0.5 mL of tri-n-octylphosphine, and add this to 270 g of phosphine under an inert gas. Immediately inject into the flask heated at °C. After reacting for 1 hour, the reaction was terminated by quickly cooling. Then, when the temperature of the flask reached 100°C, 10 mL of toluene was injected and then transferred to a 50 mL centrifuge tube. After adding 10 mL of ethanol, it was purified twice using precipitation and redispersion method. Purified InP core nanoparticles were stored after being dispersed in 1-octadecene.

Put 3.669 g of zinc acetate, 20 mL of oleic acid, and 20 mL of 1-octadecene into a three-necked flask, and after degassing for 30 minutes at 110°C and 100 mTorr while stirring, the solution becomes clear. A clear precursor solution in the form of zinc oleate was obtained by heating at a temperature of 270° C. under an inert gas until the temperature reached 60° C. and cooling to 60° C.

Put 0.6412 g of sulfur and 10 mL of tri-n-octylphosphine into a three-necked flask, heat at a temperature of 80°C while stirring in an inert gas atmosphere until the solution becomes transparent, and then cool to room temperature. : An S-form S precursor solution was obtained.

The previously prepared InP core nanoparticle solution was placed in a separate three-necked flask, the temperature of the flask was adjusted to 300° C., and 0.6 mL of the previously prepared zinc precursor solution was quickly injected using a syringe. Then, 0.3 mL of the previously prepared S precursor solution was injected into the flask at a rate of 2 mL/hr using a syringe pump. After the injection was completed, the reaction was allowed to proceed for another 3 hours, and then quickly cooled to terminate the reaction. When the temperature of the flask reached 100°C, 10 mL of toluene was injected and then transferred to a 50 mL centrifuge tube. After adding 10 mL of ethanol, it was purified twice using precipitation and redispersion method. The purified InP/ZnS core-shell nanoparticles were dispersed in n-chloroform and then stored. The solid content was adjusted to 30% by weight. The maximum emission wavelength was 525 nm.

[Synthesis Example 2: Synthesis of InP/ZnSe/ZnS core-shell quantum dots]
0.4 mmol (0.058 g) of indium acetate, 0.6 mmol (0.15 g) of palmitic acid, and 20 mL of 1-octadecene were placed in a reactor and heated at 120°C under vacuum. Heated. One hour later, the atmosphere in the reactor was replaced with nitrogen. After heating at 280° C., a mixed solution of 0.2 mmol (58 μl) of tris(trimethylsilyl)phosphine (TMS ₃ P) and 1.0 mL of trioctylphosphine was quickly injected and reacted for 0.5 minutes.

Then, 2.4 mmol (0.448 g) of zinc acetate, 4.8 mmol of oleic acid, and 20 mL of trioctylamine were placed in the reactor and heated at 120° C. under vacuum. After 1 hour, the atmosphere inside the reactor was replaced with nitrogen, and the temperature of the reactor was raised to 280°C. After adding 2 mL of the previously synthesized InP core solution and then 4.8 mmol of selenium in trioctylphosphine (Se/TOP), the final mixture was allowed to react for 2 hours. Ethanol was added to the reaction solution that was quickly cooled to room temperature, and the precipitate obtained by centrifugation was filtered under reduced pressure and dried under reduced pressure to form an InP/ZnSe core-shell.

Then, 2.4 mmol (0.448 g) of zinc acetate, 4.8 mmol of oleic acid, and 20 mL of trioctylamine were placed in the reactor and heated at 120° C. under vacuum. After 1 hour, the atmosphere inside the reactor was replaced with nitrogen, and the temperature of the reactor was raised to 280°C. After charging 2 mL of previously synthesized InP/ZnSe core-shell solution followed by 4.8 mmol of sulfur in trioctylphosphine (S/TOP), the final mixture was allowed to react for 2 hours. Ethanol was added to the reaction solution that was quickly cooled to room temperature, and the precipitate obtained by centrifugation was filtered under reduced pressure and dried under reduced pressure to obtain quantum dots with an InP/ZnSe/ZnS core-shell structure, which were then dispersed in chloroform. . The solid content was adjusted to 30% by weight. The maximum emission wavelength was 520 nm.

[Manufacture of ligand-substituted quantum dots]
[Production Example 1: Ligand-substituted quantum dot A-1]
5 mL of the quantum dot solution obtained in Synthesis Example 1 was placed in a centrifuge tube, and 20 mL of ethanol was added thereto for precipitation. The upper layer liquid was discarded by centrifugation, 3 mL of chloroform was added to the precipitate to disperse the quantum dots, and 2.50 g of 9-mercaptofluorene (manufactured by TCI) represented by the following chemical formula 1-1 was added. The reaction was allowed to proceed for 1 hour while heating at 60° C. under a nitrogen atmosphere.

Next, 25 mL of n-hexane was added to the reaction mixture to precipitate the quantum dots, and then centrifugation was performed to separate the precipitate. After drying for 1 hour, quantum dots A-1 were obtained.

[Production Example 2: Ligand-substituted quantum dot A-2]
Except that 4-(9H-fluoren-9-yl)-butane-1-thiol (manufactured by TCI) represented by the following chemical formula 1-2 was used instead of the ligand used in Production Example 1. Quantum dots A-2 were obtained in the same manner as in Production Example 1.

［製造例３：配位子置換量子ドットＡ－３］
合成例２で得られた量子ドット溶液５ｍＬを遠心分離チューブに入れ、エタノール２０ｍＬを入れて沈澱させた。遠心分離によって上層液は捨て、沈殿物に３ｍＬのクロロホルムを入れて量子ドットを分散させた後、３．００ｇの前記化学式１－１で表される９－メルカプトフルオレン（ＴＣＩ社製）を入れ、窒素雰囲気下、６０℃で加熱しながら１時間反応させた。

[Production Example 3: Ligand-substituted quantum dot A-3]
5 mL of the quantum dot solution obtained in Synthesis Example 2 was placed in a centrifuge tube, and 20 mL of ethanol was added thereto for precipitation. The upper layer liquid was discarded by centrifugation, 3 mL of chloroform was added to the precipitate to disperse the quantum dots, and 3.00 g of 9-mercaptofluorene (manufactured by TCI) represented by the chemical formula 1-1 was added. The reaction was allowed to proceed for 1 hour while heating at 60° C. under a nitrogen atmosphere.

Next, 25 mL of n-hexane was added to the reaction mixture to precipitate the quantum dots, and then centrifugation was performed to separate the precipitate. After drying for 1 hour, quantum dots A-3 were obtained.

[Production Example 4: Ligand-substituted quantum dot A-4]
Except that 4-(9H-fluoren-9-yl)-butane-1-thiol (manufactured by TCI) represented by the chemical formula 1-2 was used instead of the ligand used in Production Example 3. Quantum dots A-4 were obtained in the same manner as in Production Example 3.

[Production Example 5: Ligand-substituted quantum dot A-5]
Quantum dots A-5 were obtained in the same manner as in Production Example 3, except that a compound represented by the following chemical formula 1-3 was used instead of the ligand used in Production Example 3.

［製造例６：配位子置換量子ドットＡ－６］
製造例３で用いた配位子の代わりに、下記化学式１－４で表される化合物を用いたことを除いては、製造例３と同様に実施して量子ドットＡ－６を収得した。

[Production Example 6: Ligand-substituted quantum dot A-6]
Quantum dots A-6 were obtained in the same manner as in Production Example 3, except that a compound represented by the following chemical formula 1-4 was used instead of the ligand used in Production Example 3.

［製造例７：配位子置換量子ドットＡ－７］
製造例３で用いた配位子の代わりに、下記化学式１－５で表される化合物を用いたことを除いては、製造例３と同様に実施して量子ドットＡ－７を収得した。

[Production Example 7: Ligand-substituted quantum dot A-7]
Quantum dots A-7 were obtained in the same manner as in Production Example 3, except that a compound represented by the following chemical formula 1-5 was used instead of the ligand used in Production Example 3.

［製造例８：配位子未置換量子ドットＡ－８］
オレイン酸が表面に結合されている合成例１で得られた量子ドット溶液５ｍＬを遠心分離チューブに入れ、エタノール２０ｍＬを入れて沈澱させた。遠心分離によって上層液は捨て、沈殿物を減圧乾燥オーブン（ヤマト社製、ＤＰ４３）を用いて６０℃で１時間乾燥して、量子ドットＡ－８を収得した。

[Production Example 8: Ligand unsubstituted quantum dot A-8]
5 mL of the quantum dot solution obtained in Synthesis Example 1, in which oleic acid was bonded to the surface, was placed in a centrifuge tube, and 20 mL of ethanol was added thereto for precipitation. The upper layer was discarded by centrifugation, and the precipitate was dried at 60° C. for 1 hour using a vacuum drying oven (DP43, manufactured by Yamato) to obtain quantum dots A-8.

[Production Example 9: Ligand unsubstituted quantum dot A-9]
5 mL of the quantum dot solution obtained in Synthesis Example 2 in which oleic acid was bonded to the surface was placed in a centrifuge tube, and 20 mL of ethanol was added thereto for precipitation. The upper layer was discarded by centrifugation, and the precipitate was dried at 60° C. for 1 hour using a vacuum drying oven (DP43, manufactured by Yamato) to obtain quantum dots A-9.

[Production Example 10: Ligand-substituted quantum dot A-10]
Quantum dots A-10 were obtained in the same manner as in Production Example 3, except that a compound represented by the following chemical formula 3 was used instead of the ligand used in Production Example 3.

［実施例及び比較例：光変換インク組成物の製造］
下記の表１～表３の組成でそれぞれの成分を混合して光変換インク組成物を製造した（重量％）。

[Examples and Comparative Examples: Production of light conversion ink composition]
A light conversion ink composition was prepared by mixing the respective components according to the compositions shown in Tables 1 to 3 below (wt%).

量子ドットＡ－１～Ａ－１０：製造例１～１０で製造された量子ドット
硬化性モノマー（Ｂ）
Ｂ－１：１,６－ヘキサンジオールジアクリレート（シグマアルドリッチ社製）
Ｂ－２：１,９－ビスアクリロイルオキシノナン（ＴＣＩ社製）
Ｂ－３：トリプロピレングリコールジアクリレート（シグマアルドリッチ社製）
Ｂ－４：エトキシレイテッドペンタエリトリトールテトラアクリレート（ＡＴＭ－４Ｅ、新中村化学社製）
Ｂ－５：ジペンタエリトリトールヘキサアクリレート（Ａ－９５５０、新中村化学社製）
散乱粒子（Ｃ）：ＴｉＯ_２（ハンツマン社製、ＴＲ－８８、粒径２２０ｎｍ）
光重合開始剤（Ｄ）：Ｉｒｇａｃｕｒｅ ＯＸＥ－０１（ＢＡＳＦ社製）
添加剤（Ｅ）：ＳＨ８４００（ダウコーニング東レシリコーン社製）
溶剤（Ｆ）：プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）
［実験例］
前記実施例及び比較例で製造された光変換インク組成物を用いて粘度及び連続ジェッティング回数を測定し、１２μｍ厚みの光変換コーティング層を製造して光変換効率を測定し、その結果を下記表４に表した。

Quantum dots A-1 to A-10: Quantum dot curable monomers (B) produced in Production Examples 1 to 10
B-1: 1,6-hexanediol diacrylate (manufactured by Sigma-Aldrich)
B-2: 1,9-bisacryloyloxynonane (manufactured by TCI)
B-3: Tripropylene glycol diacrylate (manufactured by Sigma-Aldrich)
B-4: Ethoxylated pentaerythritol tetraacrylate (ATM-4E, manufactured by Shin Nakamura Chemical Co., Ltd.)
B-5: Dipentaerythritol hexaacrylate (A-9550, manufactured by Shin Nakamura Chemical Co., Ltd.)
Scattering particles (C): TiO ₂ (manufactured by Huntsman, TR-88, particle size 220 nm)
Photoinitiator (D): Irgacure OXE-01 (manufactured by BASF)
Additive (E): SH8400 (manufactured by Dow Corning Toray Silicone)
Solvent (F): Propylene glycol monomethyl ether acetate (PGMEA)
[Experiment example]
The viscosity and continuous jetting frequency were measured using the light conversion ink compositions prepared in the Examples and Comparative Examples, and the light conversion efficiency was measured by manufacturing a 12 μm thick light conversion coating layer, and the results are shown below. It is shown in Table 4.

(1) Production of light conversion coating layer and measurement of light conversion efficiency After applying each of the light conversion ink compositions produced in Examples and Comparative Examples onto a 5 cm x 5 cm glass substrate using an inkjet method, g After irradiating with 1000 mJ/cm ² using a 1 kW high-pressure mercury lamp containing , h, and i-rays, a light conversion coating layer was prepared by heating in a heating oven at 180° C. for 30 minutes.

The manufactured light conversion coating layer was placed on top of a blue light source (XLamp The light conversion efficiency was measured using the following mathematical formula 1.

The higher the light conversion efficiency (%), the better the brightness can be obtained.

（２）粘度
前記光変換インク組成物の粘度は、Ｒ型粘度計（ＶＩＳＣＯＭＥＴＥＲ ＭＯＤＥＬ ＲＥ１２０Ｌ ＳＹＳＴＥＭ、東機産業株式会社製）を用いて回転数２０ｒｐｍ、温度３０℃の条件で測定した。

(2) Viscosity The viscosity of the photoconversion ink composition was measured using an R-type viscometer (VISCOMETER MODEL RE120L SYSTEM, manufactured by Toki Sangyo Co., Ltd.) at a rotation speed of 20 rpm and a temperature of 30°C.

(3) Number of consecutive jettings After filling the photoconversion ink composition into the inkjet printing equipment manufactured by Unijet, the temperature of the jetting head was fixed at 40°C, the ink was ejected for 1 minute, and then 30 The number of times of continuous jetting was evaluated by repeatedly leaving the jet for 1 minute until jetting became impossible due to nozzle clogging in the jetting head.

As the number of times of continuous jetting increases, it is possible to obtain a characteristic that the continuous process is superior.

前記表４に表したように、本発明に係る特定構造のチオール置換されたフルオレン系配位子を含む量子ドット及び２官能硬化性モノマーを含む光変換インク組成物は、優れた光変換効率及び４回以上の連続ジェッティング特性を示すことを確認することができた。一方、２官能硬化性モノマーを含まない比較例４～５の光変換インク組成物は、粘度が高すぎてインクジェッティングが不可能であり、また、特定構造のチオール置換されたフルオレン系配位子を含まない比較例１～３及び６の光変換インク組成物は、光変換効率が低下し連続ジェッティング性の評価の際に、２回又は３回の放置後にノズル詰りが生じることを確認することができた。

As shown in Table 4 above, the light conversion ink composition containing quantum dots containing a thiol-substituted fluorene ligand with a specific structure and a bifunctional curable monomer according to the present invention has excellent light conversion efficiency and It was confirmed that continuous jetting characteristics were exhibited four times or more. On the other hand, the photoconversion ink compositions of Comparative Examples 4 and 5, which do not contain a bifunctional curable monomer, have too high a viscosity and cannot be inkjetted. It was confirmed that the light conversion ink compositions of Comparative Examples 1 to 3 and 6, which do not contain the above, had a reduced light conversion efficiency, and during evaluation of continuous jetting properties, nozzle clogging occurred after being left for two or three times. I was able to do that.

In particular, the photoconversion ink compositions of Examples 1 to 11, which did not contain a solvent, did not cause nozzle clogging even after five consecutive jettings, and inkjetting was possible even after five consecutive jettings. The photoconversion ink compositions of Examples 12 to 14 showed results that continuous jetting was possible up to 5 times or 4 times. Therefore, it was confirmed that the continuous processability of the solvent-free type that does not contain a solvent is further improved than that of the solvent-based type that does not contain a solvent.

In addition, the photoconversion ink compositions of Examples 4 and 5 further containing a tetrafunctional or hexafunctional curable monomer in addition to the bifunctional curable monomer are different from the photoconversion ink composition of Example 1 containing only a bifunctional curable monomer. The results showed that the viscosity increased compared to that of the solid.

Although specific parts of the present invention have been described in detail above, those with ordinary knowledge in the technical field to which the present invention pertains will understand that such specific descriptions are merely preferred embodiments. It is clear that the scope of the present invention is not limited by these. Those with ordinary knowledge in the technical field to which the present invention pertains will be able to make various applications and modifications within the scope of the present invention based on the above content.

Therefore, it can be said that the substantial scope of the invention is defined by the claims and their equivalents.

Claims (13)

Contains quantum dots and curable monomers,
The quantum dot has a ligand layer containing a compound represented by the following chemical formula 1 on the surface,
The curable monomer is a light conversion ink composition containing a compound represented by the following chemical formula 2.

In the above formula,
L is absent or is a C ₁ -C ₂₂ alkylene group or a C ₄ -C ₂₂ alkenylene group,
R ¹ is a C ₁ to C ₂₀ alkylene group, a phenylene group, or a C ₃ to C ₁₀ cycloalkylene group,
R ² is hydrogen or a methyl group,
m is an integer from 1 to 15. The light conversion ink composition according to claim 1, wherein the ligand layer contains one or more compounds selected from compounds represented by the following chemical formulas 1-1 to 1-5.

The photoconversion ink composition of claim 1, wherein the quantum dots are non-cadmium based quantum dots. The quantum dot has a core-shell structure including a core and a shell covering the core,
The core includes GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNPs, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNPs, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNPs, InAlNAs, InAlNS b, InAlPAs, and InAlPSb, including one or more selected from the group consisting of
The light conversion ink composition according to claim 3, wherein the shell contains one or more selected from the group consisting of ZnSe, ZnS, and ZnTe. The light conversion ink composition of claim 1, further comprising scattering particles. The scattering particles include Al ₂ O ₃ , SiO ₂ , ZnO, ZrO ₂ , BaTiO ₃ , TiO ₂ , Ta ₂ O ₅ , Ti ₃ O ₅ , ITO, IZO, ATO, ZnO-Al, Nb ₂ O ₃ , SnO The light conversion ink composition according to claim 5, comprising one or more selected from the group consisting of , and MgO. 7. The light conversion ink composition of claim 6, wherein the scattering particles are _TiO2 . The photoconversion ink composition according to claim 1, further comprising a photoinitiator. The light conversion ink composition according to claim 1, comprising a solvent in an amount of 20% by weight or less based on 100% by weight of the total composition. The light conversion ink composition according to claim 9, characterized in that it does not contain a solvent. A light conversion pixel comprising a cured product of the light conversion ink composition according to any one of claims 1 to 10. A color filter comprising the light conversion pixel according to claim 11. An image display device comprising the color filter according to claim 12.