JP2021043446A - Light conversion ink composition, color filter, and image display device - Google Patents

Abstract

To provide a light conversion ink composition which can be effectively used when manufacturing color filters by an inject printing method.SOLUTION: A light conversion ink composition is provided, comprising quantum dots and a curable monomer. Each quantum dot has a ligand layer containing a carboxyl-substituted fluorene-based ligand having a specific structure formed on a surface thereof. The curable monomer contains a bifunctional (meth)acrylate having a specific structure.SELECTED DRAWING: None

Description

The present invention relates to a light conversion ink composition, a color filter, and an image display device. More specifically, the present invention is excellent in optical characteristics of quantum dots, can realize low viscosity, and can be realized in a continuous process. The present invention relates to a light conversion ink composition capable of ensuring excellent jetting characteristics without causing nozzle clogging, a color filter formed by using the light conversion ink composition, and an image display device including the color filter.

A color filter is a thin-film film-type optical component that extracts three types of colors, red, green, and blue from white light and functions them in minute pixel units. The size of one pixel is about tens to hundreds of μm. is there. Such a color filter has a black matrix layer formed in a predetermined pattern on a transparent substrate to block the boundary portion between each pixel, and a plurality of colors (usually red (usually, red) to form each pixel. It has a structure in which pixel portions formed by arranging the three primary colors (R), green (G), and blue (B)) in a predetermined order are laminated in order.

In recent years, as one of the methods for embodying a color filter, a pigment dispersion method using a pigment dispersion type photosensitive resin has been applied. However, when the pigment dispersion method is provided, a part of the light is absorbed by the color filter in the process of passing the light emitted from the light source through the color filter, so that the light efficiency is lowered and the light is included in the color filter. There is a problem that the color reproduction is deteriorated due to the characteristics of the pigment.

In particular, as color filters are used in various fields such as various image display devices, not only excellent pattern characteristics but also high brightness and high brightness / darkness ratio are required as well as high color reproduction. Has been done. Therefore, in order to solve such a problem, 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 the luminous efficiency can be improved and the display quality of the display device can be improved by replacing the existing color filter with a light emitting layer made of a quantum dot phosphor. ..

A photolithography method using a photosensitive resin composition containing such quantum dots is a method for producing a color filter by coating, exposure, development, and curing. This method is excellent in terms of the sophistication and reproducibility of the color filter, but it requires coating, exposure, developing, and curing processes for each color in order to form pixels, and the manufacturing process, It is difficult to manage the yield because the labor and cost are high and the number of control factors between processes is large.

In order to solve these problems, an inkjet method has been presented. The inkjet method is a technique in which a liquid ink is sprayed on a predetermined position defined by using an inkjet head (inkjet head) to realize an image in which each ink is colored. In the inkjet method, a plurality of colors including red, green, and blue can be colored at one time, and the manufacturing process, labor, and cost can be greatly reduced.

In recent years, with the demand for high color reproduction (color density compared to NTSC) in monitors, TVs, etc., it has been required to improve the emission brightness of quantum dots. In order to improve the emission brightness, there is a method of increasing the film thickness. However, in the quantum dot-containing ink composition having a high solvent content, there is a limit in increasing the film thickness. Further, when the content of the solvent is high, there is a problem that the solvent evaporates at the inlet of the nozzle and the solid ink is deposited, which causes the nozzle to be clogged during the progress of the continuous process. Therefore, there is a demand for a quantum dot-containing ink composition having a low solvent content or no solvent.

However, when the content of the solvent is lowered or the solvent is not contained, uniform dispersion becomes difficult, causing aggregation of the quantum dots, and the optical characteristics of the quantum dots are lowered or the viscosity is increased, resulting in jetting property. It may be defective.

One object of the present invention is to have excellent optical characteristics of quantum dots, to realize low viscosity, and to secure excellent jetting characteristics without causing nozzle clogging during the progress of a continuous process. It is to provide a light conversion ink composition.

Another object of the present invention is to provide a light conversion pixel containing 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 pixel.

Another object of the present invention is to provide an image display device including the color filter.

On the other hand, the present invention contains a quantum dot and a curable monomer, and the quantum dot has a ligand layer containing a compound represented by the following chemical formula 1 on the surface, and the curable monomer is a curable monomer. A photoconversion 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は、Ｃ_１〜Ｃ_６のアルキル基であり、
ｎは、０〜４の整数であり、
Ｚは、−ＣＨ_２−又は

In the above formula,
L is absent or is an alkylene group from _{C 1 to} C ₂₂ or an alkenylene group from _{C 4 to} C _22.
R is an alkyl group of _{C 1 to} C _{6 and}
n is an integer from 0 to 4 and
Z is -CH ₂ -or

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。

And
R ¹ is _{an alkylene group of C 1 to} C ₂₀ , a phenylene group or a cycloalkylene group of _{C 3 to} C _10.
R ² is a hydrogen or methyl group
m is an integer of 1 to 15.

In one embodiment of the present invention, the ligand layer may contain one or more compounds selected from the compounds represented by the following chemical formulas 1-1 to 1-8.

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 present invention, the quantum dots may be non-cadmium-based quantum dots.

In one embodiment of the present invention, the quantum dots have a core-shell structure including a core and a shell covering the core, and the cores are GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN. , InP, InAs, InSb, COLP, PLACS, PLACSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlPSa , GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, and InAlPSb, and the shell contains one or more selected from the group consisting of ZnSe, ZnS, and ZnTe. It's fine.

The light conversion ink composition according to one embodiment of the present invention may further contain scattered particles.

In one embodiment of the present invention, the scattered 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 scattered particles may be _{TiO 2.}

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

The light conversion ink composition according to the 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 the embodiment of the present invention may not contain a solvent.

On the other hand, the present invention provides a light conversion pixel containing 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 provided with the color filter.

The photoconverted ink composition according to the present invention contains quantum dots having a carboxy-substituted fluorene-based ligand having a specific structure on the surface as a colorant, and the carboxy-substituted fluorene-based ligand as a curable monomer. It contains a bifunctional (meth) acrylate with a specific structure that has excellent compatibility with ligands, has excellent optical characteristics of quantum dots, can realize low viscosity, and clogs nozzles as the continuous process progresses. It is possible to secure excellent jetting characteristics without causing it. Therefore, the light conversion ink composition according to the present invention can be effectively used when producing a color filter by an inkjet printing method.

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

Assuming that a member is located "above" another member in the present invention, this is not only when one member is in contact with another member, but also between both members and another member. Including the case where it exists.

When a component in the present invention is referred to as "contains" a component, this means that the other component may be further included rather than excluding the other component unless otherwise specified.

One embodiment of the present invention comprises a quantum dot (A) and a curable monomer (B), wherein the quantum dot (A) is coordinated with a carboxy-substituted fluorene-based ligand having a specific structure on the surface. The curable monomer (B) has a child layer, and relates to a photoconversion ink composition containing a bifunctional (meth) acrylate having a specific structure.

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

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は、Ｃ_１〜Ｃ_６のアルキル基であり、
ｎは、０〜４の整数であり、
Ｚは、−ＣＨ_２−又は

In the above formula,
L is absent or is an alkylene group from _{C 1 to} C ₂₂ or an alkenylene group from _{C 4 to} C _22.
R is an alkyl group of _{C 1 to} C _{6 and}
n is an integer from 0 to 4 and
Z is -CH ₂ -or

である。

Is.

_{The alkylene groups C 1 to} C ₂₂ used in the present specification mean linear or branched divalent hydrocarbons having 1 to 22 carbon atoms, for example, methylene, ethylene, n-propylene, i. Includes, but is not limited to, -propylene, n-butylene, n-heptylene, n-dodecylene and the like.

The C _{4 to} C ₂₂ alkenylene groups used herein are linear or branched divalent unsaturated hydrocarbons consisting of 4 to 22 carbon atoms with one or more carbon-carbon double bonds. Means, for example, buthenylene, pentenylene, hexenedylene, heptenylene, octenylene, nonenylene, desenylene, undesenilen, dodecenilen, tridecenylene, tetradecenylene, pentadecenylene, hexadecenylene, heptadecenylene, octatadecenelen, etc. Absent.

As used herein, _{the alkyl groups C 1 to} C ₆ mean linear or branched monovalent hydrocarbons consisting of 1 to 6 carbon atoms, for example, methyl, ethyl, n-propyl, i. Includes, but is not limited to, -propyl, n-butyl, i-butyl, t-butyl, n-pentyl, n-hexyl and the like.

As used herein, * means a bond.

Alkylene _group, an alkyl group of the alkenylene group and the _C 1 -C _6, a C 4 _{-C 22} of the _C 1 _{-C 22,} one or more hydrogen an alkyl group of _C 1 _{~C 6, C} 2 ~ C ₆ alkoxy 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 ~ C ₆ haloalkyl group, C ₁ ~ C ₆ alkoxy group, C ₁ ~ C ₆ thioalkoxy group, aryl group, acyl group, hydroxy, thio, halogen, amino, alkoxycarbonyl, carboxy, carbamoyl, It may be replaced with cyano, nitro, or the like.

Formula compound represented by 1 of the present invention, from the viewpoint of realization of compatibility and / or low viscosity of the quantum dots, or L is absent, alkylene group or a C ₄ -C ₂₀ in C ₁ -C ₂₀ compound alkenylene group, preferably either L is _absent, may be a compound which is an alkylene or alkenylene group of _C 4 _{-C 18} in C 1 _{-C 18.}

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 1-8 from the viewpoint of realizing compatibility of 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 the chemical formula 1 of the present invention is an organic ligand and can perform a role of stabilizing the quantum dots by being coordinated to the surface of the quantum dots.

Generally, manufactured quantum dots have a ligand layer on the surface, and the ligand layer immediately after production is composed of oleic acid, lauric acid, and the like. obtain. In this case, as compared with the quantum dots of the present invention containing the compound represented by the chemical formula 1 as the ligand layer, due to non-bonding defects on the quantum dot surface due to a weaker bonding force between the ligand layer and the quantum dots. The surface protection effect may be reduced. Further, in the case of oleic acid, it is easily dispersed in an aliphatic hydrocarbon solvent such as n-hexane, which is a highly volatile compound (VOC), and an aromatic hydrocarbon solvent such as benzene. Poor dispersibility in solvents such as propylene glycol monomethyl ether acetate (PGMEA).

The quantum dots according to the present invention are applied to various application fields because the ligand layer contains the compound represented by the chemical formula 1 and the compatibility with peripheral materials is improved by introducing a bulky fluorene group. You get the advantage of being able to.

As a result, the quantum dots of the present invention can exhibit excellent oxidative stability, can suppress a decrease in quantum efficiency, and can improve reliability.

Further, the quantum dots according to the present invention can exhibit good dispersibility even if the content of the solvent is low or the curable monomer described later alone does not contain the solvent, and the quantum dots have a low viscosity when applied to an ink composition. It is possible to realize excellent jetting characteristics without causing nozzle clogging during the progress of a continuous process.

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

In one embodiment of the present invention, the quantum dots may refer to nano-sized semiconductor materials. Atoms form molecules, and molecules form an aggregate of small molecules called clusters to form nanoparticles. When such nanoparticles exhibit semiconductor characteristics, they are called quantum dots. When the quantum dot receives energy from the outside and becomes an excited state, the quantum dot itself emits energy corresponding to the corresponding energy band gap. For example, the light conversion ink composition of the present invention can convert incident blue light into green light and red light by including such quantum dots.

In one embodiment of the present 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 group II-VI semiconductor compounds; group III-V semiconductor compounds; group IV-VI semiconductor compounds; group IV elements or compounds containing them; and combinations thereof. It may be used alone or in combination of two or more.

Specifically, the II-VI group semiconductor compound is a two-element compound selected from the group consisting of ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, and mixtures thereof; ZnSeS, ZnSeTe, ZnSTe, HgSeS, and HgSeTe. , HgSte, HgZnS, HgZnSe, HgZnTe, and a three-element compound selected from the group consisting of a mixture thereof; However, the present invention is not limited to these.

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

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

Although not limited to these, the Group IV element or a compound containing the same is an element selected from the group consisting of Si, Ge, and a mixture thereof; and 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, gradient structure, or a mixed structure thereof. Preferably, the quantum dots may have a core-shell structure that includes a core and a shell that covers the core.

Specifically, in the core-shell dual structure, the substance forming each core and shell may be composed of the above-mentioned different semiconductor compounds. For example, the cores include GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, PLAP, PLGAs, VMwareSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, GaInPAs, GaInPSb, InAlNP, InAlNAs The shell may include, but is not limited to, one or more selected from the group consisting of ZnSe, ZnS, and ZnTe.

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

The quantum dots may be synthesized by a wet chemical process, a metalorganic chemical vapor deposition (MOCVD, metallic chemical vapor deposition), or a molecular beam epitaxy (MBE, molecular beam epitaxy). However, it is preferable to synthesize by a wet chemical process because quantum dots having more excellent optical characteristics can be obtained.

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

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

In one embodiment of the present invention, the oleic acid used in the process of producing the quantum dots is replaced by a carboxy-substituted fluorene compound represented by the chemical formula 1 by a ligand exchange method.

In the ligand exchange, the organic ligand to be exchanged, that is, the carboxy-substituted fluorene compound represented by Chemical Formula 1 is added to the dispersion liquid containing the original organic ligand, that is, the quantum dot having oleic acid. Then, this may be carried out by stirring at room temperature to 200 ° C. for 30 minutes to 3 hours to obtain quantum dots to which a carboxy-substituted fluorene compound represented by Chemical Formula 1 is bonded. If necessary, a process of separating and purifying the quantum dots to which the carboxy-substituted fluorene compound represented by the chemical formula 1 is bonded may be further performed.

The quantum dots may be contained in the range of 1 to 60% by weight, preferably 5 to 50% by weight, based on 100% by weight of the entire light conversion ink composition. When the quantum dots are included in the 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 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 increases and the jetting property deteriorates. May occur.

[Curable Monomer (B)]
In one embodiment of the present invention, the curable monomer (B) contains 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 _{an alkylene group of C 1 to} C ₂₀ , a phenylene group or a cycloalkylene group of _{C 3 to} C _10.
R ² is a hydrogen or methyl group
m is an integer of 1 to 15.

As used herein, _{the alkylene group C 1 to} C ₂₀ means a linear or branched divalent hydrocarbon consisting of 1 to 20 carbon atoms, for example, methylene, ethylene, n-propylene, iso. Includes, but is not limited to, propylene, n-butylene, isobutylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene and the like.

_{The cycloalkylene groups C 3 to} C ₁₀ used herein mean monocyclic or fused cyclic divalent hydrocarbons consisting of 3 to 10 carbon atoms, such as cyclopropylene, cyclobutylene, and cyclo. Includes, but is not limited to, pentylene, cyclohexylene, and the like.

The alkylene group of C _{1 to} C ₂₀ , the phenylene group, and _{the cycloalkylene group of C 3 to} C ₁₀ have one or more hydrogens _{of the alkyl group of C 1 to} C ₆ , and the alkoxy group of C _{2 to} C ₆ . _group, an alkynyl group of C 2 -C _6, cycloalkyl group C 3 _{-C 10 heterocycloalkyl group,} heterocycloalkyl group of C 3 _{-C 10} in C 3 _{-C 10,} of C 1 -C ₆ Haloalkyl groups, C _{1 to} C ₆ alkoxy groups, C _{1 to} C ₆ thioalkoxy groups, aryl groups, acyl groups, hydroxy, thio, halogen, amino, alkoxycarbonyl, carboxy, carbamoyl, cyano, nitro, etc. May be replaced with.

In one embodiment of the invention, R ¹ _{may be an alkylene group of C 1 to} C ₂₀ as described above, preferably an alkylene group of C _{1 to} C ₁₂ . When R ¹ is _{an alkylene group of C 1 to} C ₂₀ , the jetting property can be improved by excellent dispersibility of scattered particles even without a solvent, and the coating film hardness and surface characteristics can be improved.

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

Specific examples of the compound represented by the chemical formula 2 include 1,6-hexanediol diacrylate, 1,9-bisacryloyl oxynonane, and tripropylene glycol diacrylate.

The compound represented by the chemical formula 2 has excellent compatibility with the carboxy-substituted fluorene-based ligand represented by the chemical formula 1 and improves the dispersibility of the quantum dots, whereby the solvent content is low or It enables the realization of a low-viscosity photoconversion ink composition having excellent light characteristics even without a solvent. Therefore, the light conversion ink composition according to the present invention can be effectively used when producing a color filter by an inkjet printing method.

The photoconverted ink composition according to the present invention may further contain a polyfunctional monomer having trifunctionality or higher, preferably tetrafunctionality or higher, in addition to the polymerizable compound represented by the chemical formula 2. Examples of the polyfunctional monomer include trimethylolpropoxyl propanetri (meth) acrylate, ethoxylated trimethylol propanetri (meth) acrylate, propoxylated trimethylol propanetri (meth) acrylate, and pentaerythritol tri (meth). Acrylate, pentaerythritol tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate , Propoxylated dipentaerytritor hexa (meth) acrylate, dipentaerytritor (poly) acrylate and the like are preferably used.

The polyfunctional monomer may be contained 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 of more than 30% by weight with respect to 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 the range of 20 to 90% by weight, preferably 30 to 80% by weight, based on 100% by weight of the entire light conversion 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 less than the above range, the strength of the pixel portion may be slightly lowered, and if the curable monomer is contained in excess of the above range, the light conversion efficiency may be lowered. It is preferably contained within the above range.

[Scattered particles (C)]
The light conversion ink composition according to one embodiment of the present invention may further contain scattered particles (C).

The scattered particles serve to increase the path of light emitted from the quantum dots and increase the overall light efficiency.

As the material of the scattered particles, an ordinary inorganic material may be used, and a metal oxide may be preferably used.

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 scattered 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-Al, Nb _2. It may contain one or more selected from the group consisting of _{O 3 , SnO, and MgO, and TiO 2} is preferable from the viewpoint of the characteristics of light conversion efficiency.

If necessary, the scattered particles may be made of a material surface-treated with a compound having an unsaturated bond such as acrylate.

The scattered particles may have an average particle size of 50 to 1000 nm, preferably in the range of 100 to 500 nm, more preferably 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, and conversely, if the particle size is too large, it sinks in the composition and is uniform. Since it is not possible to obtain a high-quality light conversion layer surface, it is used after being appropriately adjusted within the above range.

In the present invention, the average particle size may be a number average particle size, and can be obtained from, for example, an image observed by a field emission scanning electron microscope (FE-SEM) or a transmission electron microscope (TEM). Specifically, some samples can be extracted from the observation image of FE-SEM or TEM, and the diameters of these samples can be measured and obtained from the arithmetic mean value.

The scattered particles may be contained in the range of 1 to 150% by weight, preferably 5 to 100% by weight, based on 100% by weight of the quantum dots. When the scattered particles are contained within the above range, the effect of increasing the emission intensity is maximized, which is preferable. If the scattered particles are contained in the range less than the above range, the scattering effect may be insufficient and it may be difficult to secure the emission intensity to be obtained, and if the scattering particles are exceeded in the above range, the scattering characteristics exceed the critical range. By blocking the light emitted in this way, the emission intensity may decrease.

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

In one embodiment of the present invention, the type of 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) is an acetophenone-based compound, a benzophenone-based compound, a triazine-based compound, a biimidazole-based compound, an oxime-based compound from the viewpoints of polymerization characteristics, starting efficiency, absorption wavelength, availability, price, and the like. , And one or more compounds selected from the group consisting of thioxanthone compounds are preferably used.

The photopolymerization initiator (D) may be contained in the range 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 is preferable because the productivity is improved. Further, there is an advantage that the strength of the pixel portion formed by using the light conversion ink composition according to the present invention and the smoothness on the surface of the pixel portion are improved.

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

As the photopolymerization initiation aid (d1), for example, one or more compounds selected from the group consisting of amine compounds, carboxylic acid compounds, and organic yellow compounds having a thiol group may be preferably used, but are limited thereto. It's not a thing.

Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4 -Dimethylamino 2-ethylhexyl benzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler ketone), 4,4'-bis (diethylamino) ) An aromatic amine compound such as benzophenone can be mentioned, and an aromatic amine compound may be preferable.

Specific examples of the carboxylic acid compound 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 appropriately added and used as long as the effects of the present invention are not impaired.

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

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), Florard FC-135 / FC-170C / FC-430 (manufactured by Sumitomo 3M Ltd.), SH-28PA / -190. Fluorine-based surfactants such as / -8400 / SZ-6032 (manufactured by Toray Silicone Co., Ltd.) may be used, but the present invention is not limited thereto.

The adhesion accelerator may be added to enhance the adhesion to the substrate, and is a reaction selected from the group consisting of a carboxyl group, a (meth) acryloyl group, an isocyanate group, an epoxy group, and a combination thereof. It may include, but is not limited to, a silane coupling agent having a sex 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 as long as the effects of the present invention are not impaired. Those skilled in the art can appropriately add and use the present invention as long as the effects of the present invention are not impaired.

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 photoconversion ink composition. It may be used in the range of, but is not limited to these.

The light conversion ink composition according to the 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 the 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, an ether or ester solvent, an aliphatic saturated hydrocarbon solvent, a halogenated hydrocarbon solvent, an aromatic hydrocarbon solvent and the like may be used. For example, 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 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 mesityrene, ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone, ethanol and propanol. , Butanol, hexanol, cyclohexanol, ethylene glycol, glycerin and other alcohols, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and the like, cyclic esters such as γ-butyrolactone and the like may be used.

The light conversion ink composition according to the embodiment of the present invention is excellent in the optical characteristics and dispersibility of quantum dots even if the content of the solvent is as low as 20% by weight or less, and low viscosity can be realized. Further, the light conversion ink composition according to the embodiment of the present invention has a low solvent content of 20% by weight or less and does not cause nozzle clogging due to evaporation of the solvent at the nozzle inlet, which is advantageous for continuous steps. Is.

Further, the light conversion ink composition according to the embodiment of the present invention does not substantially contain a resin component, and even if it contains the resin component, it is contained within 0.5% by weight with respect to 100% by weight of the whole light conversion ink composition. .. The light conversion ink composition according to the embodiment of the present invention can realize a low viscosity by not containing a resin component, and is excellent in nozzle jetting characteristics of ink.

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

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

First, the light conversion ink composition according to the present invention is injected into an inkjet injector and printed on a predetermined area of the substrate.

The substrate is not particularly limited, and examples thereof include substrates having a flat surface such as a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, a polyamide-imide substrate, a polyimide substrate, an Al substrate, and a GaAs substrate. Be done. These substrates may be subjected to pretreatment such as chemical treatment with a chemical such as a silane coupling agent, plasma treatment, ion plating treatment, sputtering treatment, gas phase reaction treatment, and vacuum vapor deposition treatment. When a silicon substrate or the like is used as the substrate, a charge coupling element (CCD), a thin film transistor (TFT), or the like may be formed on the surface of the silicon substrate or the like. In addition, a partition matrix may be formed.

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

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

The color filter according to the 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-mentioned light conversion ink composition on a substrate in a predetermined pattern and then curing the color filter. Since the structure and manufacturing method of the color filter are well known in the art, detailed description thereof will be omitted.

One embodiment of the present invention relates to an image display device provided with the above-mentioned color filter.
The color filter according to the present invention includes not only a normal liquid crystal display device (LCD), but also a field emission display device (EL), a plasma display device (PDP), a field emission display device (FED), an organic light emitting element (OLED), and the like. It can be applied to various image display devices.

The image display device according to the present invention includes configurations known in the art, except that it includes the color filter described above.

Hereinafter, the present invention will be described in more detail with reference to Examples, Comparative Examples and Experimental Examples. It is obvious to those skilled in the art that these Examples, Comparative Examples and Experimental Examples are merely for explaining the present invention, and the scope of the present invention is not limited thereto.

[Synthesis Example 1: Synthesis of InP / ZnS core-shell quantum dots]
A three-necked flask (3-neck flask) was charged with 0.05839 g of indium acetate, 0.12019 g of oleic acid, and 10 mL of 1-octadecene (ODE). The flask was subjected to a degassing process at 110 ° C. under 100 mTorr for 30 minutes with stirring, and then heated at a temperature of 270 ° C. under an inert gas until the solution became transparent.

0.025054 g of tris (trimethylsilyl) phosphine was prepared as a phosphorus (P) precursor, placed in 0.5 mL of 1-octadecene and 0.5 mL of tri-n-octylphosphine and stirred, and this was stirred under an inert gas of 270. It was quickly poured into the flask heated at ° C. After reacting for 1 hour, it was cooled quickly to terminate the reaction. 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 the precipitation and redispersion method. The purified InP core nanoparticles were dispersed in 1-octadecene and then stored.

3.669 g of zinc acetate, 20 mL of oleic acid, and 20 mL of 1-octadecene are placed in a three-necked flask, and the solution becomes transparent after undergoing a 30-minute degassing process at 110 ° C. under 100 mTorr with stirring. It was heated to a temperature of 270 ° C. under an inert gas and then cooled to 60 ° C. to obtain a clear precursor solution in the form of zinc oleate.

Put 0.6412 g of sulfur and 10 mL of tri-n-octylphosphine in 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 to TOP. : An S-form S precursor solution was obtained.

A pre-prepared InP core nanoparticle solution was placed in a separate three-necked flask, the temperature of the flask was adjusted to 300 ° C., and then 0.6 mL of the pre-prepared zinc precursor solution was quickly injected using a syringe. Next, 0.3 mL of the S precursor solution prepared in advance was injected into the flask at a rate of 2 mL / hr using a syringe pump. The reaction was allowed to proceed for an additional 3 hours after the injection was completed and cooled quickly 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 the precipitation and redispersion method. The purified InP / ZnS core-shell structure 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: InP / ZnSe / ZnS Core-Shell Quantum Dot Synthesis]
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 the reactor at 120 ° C. under vacuum. It was heated. After 1 hour, 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 rapidly injected and reacted for 0.5 minutes.

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

[Manufacturing of ligand-substituted quantum dots]
[Production Example 1: Ligand Substitution 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 for precipitation. The upper layer liquid is discarded by centrifugation, 3 mL of chloroform is added to the precipitate to disperse the quantum dots, and then 2.50 g of 9H-fluorene-2-carboxylic acid represented by the following chemical formula 1-1 is added, and nitrogen is added. The reaction was carried out for 1 hour while heating at 60 ° C. in an atmosphere.

次いで、反応物に２５ｍＬのｎ−ヘキサンを入れて量子ドットを沈澱させた後、遠心分離を実施して沈殿物を分離してから、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−１を収得した。

Next, 25 mL of n-hexane was added to the reaction product to precipitate the quantum dots, and then centrifugation was performed to separate the precipitate, and then the temperature was 60 ° C. using a vacuum drying oven (manufactured by Yamato Co., Ltd., DP43). After drying for 1 hour, quantum dots A-1 were obtained.

[Production Example 2: Ligand Substitution Quantum Dot A-2]
Quantum dots were carried out in the same manner as in Production Example 1 except that 9H-fluorene-4-carboxylic acid represented by the following chemical formula 1-2 was used instead of the ligand used in Production Example 1. I got A-2.

［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９Ｈ−フルオレン−２−カルボン酸を入れ、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 Substitution 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 for precipitation. The upper layer liquid is discarded by centrifugation, 3 mL of chloroform is added to the precipitate to disperse the quantum dots, and then 3.00 g of 9H-fluorene-2-carboxylic acid represented by the chemical formula 1-1 is added to nitrogen. The reaction was carried out for 1 hour while heating at 60 ° C. in an atmosphere.

Next, 25 mL of n-hexane was added to the reaction product to precipitate the quantum dots, and then centrifugation was performed to separate the precipitate, and then the temperature was 60 ° C. using a vacuum drying oven (manufactured by Yamato Co., Ltd., DP43). After drying for 1 hour, quantum dots A-3 were obtained.

[Production Example 4: Ligand Substitution Quantum Dot A-4]
Quantum dots were carried out in the same manner as in Production Example 3 except that 9H-fluorene-4-carboxylic acid represented by the chemical formula 1-2 was used instead of the ligand used in Production Example 3. Obtained A-4.

[Production Example 5: Ligand Substitution Quantum Dot A-5]
Quantum dots A-5 were obtained in the same manner as in Production Example 3 except that the 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 Substitution Quantum Dot A-6]
Quantum dots A-6 were obtained in the same manner as in Production Example 3 except that the 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 Substitution Quantum Dot A-7]
Quantum dots A-7 were obtained in the same manner as in Production Example 3 except that the compound represented by the following chemical formula 1-5 was used instead of the ligand used in Production Example 3.

［製造例８：配位子置換量子ドットＡ−８］
製造例３で用いた配位子の代わりに、下記化学式１−６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−８を収得した。

[Production Example 8: Ligand Substitution Quantum Dot A-8]
Quantum dots A-8 were obtained in the same manner as in Production Example 3 except that the compound represented by the following chemical formula 1-6 was used instead of the ligand used in Production Example 3.

［製造例９：配位子置換量子ドットＡ−９］
製造例３で用いた配位子の代わりに、下記化学式１−７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−９を収得した。

[Production Example 9: Ligand Substitution Quantum Dot A-9]
Quantum dots A-9 were obtained in the same manner as in Production Example 3 except that the compound represented by the following chemical formula 1-7 was used instead of the ligand used in Production Example 3.

［製造例１０：配位子置換量子ドットＡ−１０］
製造例３で用いた配位子の代わりに、下記化学式１−８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−１０を収得した。

[Production Example 10: Ligand Substitution Quantum Dot A-10]
Quantum dots A-10 were obtained in the same manner as in Production Example 3 except that the compound represented by the following chemical formula 1-8 was used instead of the ligand used in Production Example 3.

［製造例１１：配位子未置換量子ドットＡ−１１］
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−１１を収得した。

[Production Example 11: Ligand Unsubstituted Quantum Dots A-11]
5 mL of the quantum dot solution obtained in Synthesis Example 1 in which oleic acid was bound to the surface was placed in a centrifuge tube, and 20 mL of ethanol was added for precipitation. The upper layer liquid was discarded by centrifugation, and the precipitate was dried at 60 ° C. for 1 hour using a vacuum drying oven (manufactured by Yamato Co., Ltd., DP43) to obtain quantum dots A-11.

[Production Example 12: Ligand Unsubstituted Quantum Dots A-12]
5 mL of the quantum dot solution obtained in Synthesis Example 2 in which oleic acid was bound to the surface was placed in a centrifuge tube, and 20 mL of ethanol was added for precipitation. The upper layer liquid was discarded by centrifugation, and the precipitate was dried at 60 ° C. for 1 hour using a vacuum drying oven (manufactured by Yamato Co., Ltd., DP43) to obtain quantum dots A-12.

[Production Example 13: Ligand Substitution Quantum Dot A-13]
Quantum dots A-13 were obtained in the same manner as in Production Example 3 except that the 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]
Each component was mixed with the compositions shown in Tables 1 to 3 below to produce a light conversion ink composition (% by weight).

量子ドットＡ−１〜Ａ−１３：製造例１〜１３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：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−３：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 dot A-1 to A-13: Quantum dot curable monomer (B) produced in Production Examples 1 to 13.
B-1: 1,6-hexanediol diacrylate (manufactured by Sigma-Aldrich)
B-2: Tripropylene glycol diacrylate (manufactured by Sigma-Aldrich)
B-3: Dipentaerythritol hexaacrylate (A-9550, manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
Scattered particles (C): TiO ₂ (manufactured by Huntsman, TR-88, particle size 220 nm)
Photopolymerization Initiator (D): Irgacure OXE-01 (manufactured by BASF)
Additive (E): SH8400 (manufactured by Dow Corning Toray Silicone)
Solvent (F): Propylene glycol monomethyl ether acetate (PGMEA)
[Experimental example]
The viscosity and the number of continuous jettings were measured using the photoconversion ink compositions produced in the above Examples and Comparative Examples, a photoconversion coating layer having a thickness of 12 μm was produced, and the photoconversion efficiency was measured. 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 manufactured in Examples and Comparative Examples onto a 5 cm × 5 cm glass substrate by an inkjet method, g is used as an ultraviolet light source. ^{After irradiating at 1000 mJ / cm 2} using a 1 kW high-pressure mercury lamp containing all of h and i rays, the light conversion coating layer was produced by heating in a heating oven at 180 ° C. for 30 minutes.

The manufactured light conversion coating layer is placed on top of a blue light source (XLamp XR-E LED, Royal blue 450, manufactured by Cree), and then a brightness measuring instrument (CAS140CT Spectrometer, manufactured by Instrument systems) is used. The optical conversion efficiency was measured by 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 photoconverted ink composition was measured using an R-type viscometer (VISCOMETER MODEL RE120L SYSTEM, manufactured by Toki Sangyo Co., Ltd.) under the conditions of a rotation speed of 20 rpm and a temperature of 30 ° C.

(3) Number of continuous jettings After filling the light conversion ink composition into an inkjet printing facility manufactured by Unijet, the temperature of the jetting head is fixed at 40 ° C., and then the ink is ejected for 1 minute, and then 30. The number of continuous jettings was evaluated by repeating leaving for a minute until ejection became impossible due to nozzle clogging of the jetting head portion.

As the number of continuous jettings increases, the characteristic that the continuous process is excellent can be obtained.

前記表４に表したように、本発明に係る特定構造のカルボキシ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。

As shown in Table 4, the photoconversion ink composition containing quantum dots containing a carboxy-substituted fluorene-based ligand having a specific structure according to the present invention and a bifunctional curable monomer has excellent photoconversion efficiency and excellent photoconversion efficiency. It was confirmed that the continuous jetting characteristic was exhibited four times or more.

On the other hand, the photoconverted ink composition of Comparative Example 4 containing no bifunctional curable monomer has too high a viscosity to allow ink jetting, and also contains a carboxy-substituted fluorene-based ligand having a specific structure. In the light conversion ink compositions of Comparative Examples 1 to 3 and 5, it can be confirmed that the light conversion efficiency is lowered and nozzle clogging occurs after being left for 2 or 3 times when evaluating the continuous jetting property. did it.

In particular, the light conversion ink compositions of Examples 1 to 12 containing no solvent were capable of ink jetting even after 5 times of continuous jetting without nozzle clogging, and even after 5 times of continuous jetting, the solvent was used. The light conversion ink compositions of Examples 13 to 14 containing the results showed that continuous jetting was possible up to 5 times or 4 times. Therefore, it was confirmed that the solvent-free type that does not contain a solvent has further improved continuous processability as compared with the solvent type that contains a solvent.

Further, the photoconverted ink composition of Example 3 further containing the hexafunctional curable monomer in addition to the bifunctional curable monomer has a higher viscosity than the photoconverted ink composition of Example 1 containing only the bifunctional curable monomer. Showed a rising result.

Although the specific parts of the present invention have been described in detail above, such a specific description is merely a suitable embodiment for those who have ordinary knowledge in the technical field to which the present invention belongs. It is clear that these do not limit the scope of the invention. Any person who has ordinary knowledge in the technical field to which the present invention belongs will be able to carry out various applications and modifications within the scope of the present invention based on the above contents.

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

Claims (13)

Contains quantum dots and curable monomers
The quantum dots have a ligand layer containing a compound represented by the following chemical formula 1 on the surface thereof.
The curable monomer is a photoconversion ink composition containing a compound represented by the following chemical formula 2.

In the above formula,
L is absent or is an alkylene group from _{C 1 to} C ₂₂ or an alkenylene group from _{C 4 to} C _22.
R is an alkyl group of _{C 1 to} C _{6 and}
n is an integer from 0 to 4 and
Z is -CH ₂ -or

And
R ¹ is _{an alkylene group of C 1 to} C ₂₀ , a phenylene group or a cycloalkylene group of _{C 3 to} C _10.
R ² is a hydrogen or methyl group
m is an integer of 1 to 15. The photoconverted ink composition according to claim 1, wherein the ligand layer contains one or more compounds selected from the compounds represented by the following chemical formulas 1-1 to 1-8.

The light conversion ink composition according to claim 1, wherein the quantum dots are non-cadmium-based quantum dots. The quantum dots have a core-shell structure that includes a core and a shell that covers the core.
The cores are GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, PLAP, GaNAs, VMwareSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InPSb
The light conversion ink composition according to claim 3, wherein the shell contains at least one selected from the group consisting of ZnSe, ZnS, and ZnTe. The light conversion ink composition according to claim 1, further comprising scattered particles. The scattered 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-Al, Nb ₂ O ₃ , SnO. The photoconverted ink composition according to claim 5, which comprises one or more selected from the group consisting of, and MgO. The light conversion ink composition according to claim 6, wherein the scattered particles are TiO _2. The photoconversion ink composition according to claim 1, further comprising a photopolymerization initiator. The light conversion ink composition according to claim 1, wherein the solvent is contained 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, which is characterized by containing no solvent. A light conversion pixel containing a cured product of the light conversion ink composition according to any one of claims 1 to 10. The color filter including the light conversion pixel according to claim 11. An image display device comprising the color filter according to claim 12.