JP7459003B2 - An ink composition, a pixel manufactured using the same, a color filter including the pixel, and an image display device including the color filter - Google Patents

Description

The present invention relates to an ink composition, a pixel manufactured using the ink composition, a color filter including the pixel, and an image display device equipped with the color filter.

Recently, inkjet printing has been preferred in view of process efficiency and economy. Inkjet printing is a non-impact printing technology in which ink droplets are jetted onto a substrate through a fine nozzle without contacting the nozzle with the substrate, and has process simplification and excellent economical effects.

However, when scattering particles or quantum dots are included in inkjet printing, problems arise due to aggregation phenomena of the scattering particles and/or quantum dots. Specifically, scattering particles and/or quantum dots are more prone to precipitation and aggregation phenomena than colorants used as pigments or dyes. Therefore, scattering particles and/or quantum dots often settle and aggregate, creating problems of clogging the nozzles of inkjet systems.

Therefore, a conventional technique such as the Republic of Korea Publication No. 10-2017-0084107 devises a method in which an ink composition is manufactured in a two-component type and mixed before use. However, when manufacturing in such a two-component type, the process is complicated and the product must be mixed immediately before use, which creates the problem that it is impossible to reuse it after mixing, reducing economic efficiency. . In addition, conventional compositions using acrylate resins have high viscosity, which causes nozzle clogging, and when only low-viscosity alkyl acrylate monomers are used for stable ejection, adhesion strength is significantly reduced. .

Therefore, the present invention has been made to solve the above problems.

Republic of Korea Publication No. 10-2017-0084107

The present invention is intended to improve the above-mentioned problems of the prior art, and significantly improves the phenomenon in which the ink composition tends to peel off from the lower substrate due to the brittle characteristics after the inkjet process. To provide an ink composition that has excellent adhesion, does not cause lifting or cracking of a manufactured coating film, has a low viscosity, and can be jetted continuously without the nozzle clogging phenomenon that frequently occurs in an inkjet process. With the goal.

The present invention provides an ink composition comprising scattering particles and a curable monomer, wherein the curable monomer contains one or more of compounds represented by Chemical Formula 1 and Chemical Formula 2 having two functional groups. An ink composition is provided.

(In the chemical formula 1, each R ₁ is independently hydrogen or a methyl group, and m is an integer from 1 to 15.)

(In the chemical formula 2, each R ₂ is independently hydrogen or a methyl group, and m is an integer from 1 to 15.)
The present invention also provides a light scattering pixel manufactured using the cured product of the above-described ink composition.

Furthermore, the present invention provides a color filter including the light scattering pixels described above.
Note that the present invention provides an image display device including the above-described color filter.

The present invention provides an ink composition that contains a curable monomer having a specific structure, which significantly improves the phenomenon in which the ink composition is prone to peeling from the underlying substrate due to its brittle characteristics after the inkjet process, has excellent adhesion, does not cause lifting or cracks in the coating film produced, and has low viscosity, allowing for continuous jetting without nozzle clogging, which frequently occurs during the inkjet process.

In addition, the ink composition has excellent viscosity stability with almost no change in viscosity even during long-term storage, and when applied to inkjet equipment, it can accurately eject ink at a specified position, minimizing inkjet misdirection.

The present invention relates to an ink composition containing scattering particles and/or quantum dots, which can achieve a significantly improved adhesion effect when introduced into an inkjet process, and in particular, a scattering powder having a modified surface. By using particles, viscosity stability can be ensured even during long-term storage, and the effect of minimizing erroneous inkjet bullets can be maximized.

Specifically, the present invention provides an ink composition containing scattering particles and a curable monomer, wherein the curable monomer is one or more selected from the group consisting of compounds represented by Chemical Formula 1 and Chemical Formula 2. The present invention relates to an ink composition comprising:

(In the chemical formula 1, each R ₁ is independently hydrogen or a methyl group, and m is an integer from 1 to 15.)

(In the chemical formula 2, each R ₂ is independently hydrogen or a methyl group, and m is an integer from 1 to 15.)
Scattering Particles In the present invention, the scattering particles play a role of improving the optical properties of the ink composition, and can be made of ordinary inorganic materials, preferably metal oxide particles having an average particle size of 50 to 1000 nm. It can contain things. The scattering particles are included in the composition in the form of a dispersion.

The metal oxides include Ti, 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, Sb, Sn, Zr, It may be an oxide containing one metal selected from the group consisting of Nb, Ce, Ta, In, and combinations thereof, but is not limited thereto. Specifically, the scattering particles include TiO ₂ , Al ₂ O ₃ , SiO ₂ , ZnO, ZrO ₂ , BaTiO ₃ , Ta ₂ O ₅ , Ti ₃ O ₅ , ITO, IZO, ATO, ZnO-Al, It can contain one or more metal oxides selected from the group consisting of Nb ₂ O ₃ , SnO, MgO, and combinations thereof, most preferably TiO ₂ .

In one embodiment, surface-treated TiO ₂ can be used as scattering particles, said TiO ₂ surface-treated with one or more components selected from Al, Si, Zr, Zn, and organic matter. is preferable, and in this case, it is more preferable that Al is included as an essential component among the surface treatment components. If necessary, a material surface-treated with a compound having an unsaturated bond such as acrylate can also be used. When an ink composition contains scattering particles, it may cause a decrease in continuous jetting properties and jetting mis-landing properties, but when using surface-modified scattering particles, while obtaining excellent optical properties effects, Continuous jetting performance and jetting erroneous landing characteristics can be improved.

In addition, in surface-treated TiO ₂ , the content ratio of TiO ₂ and surface treatment components may be 90:10 to 99:1 by weight, and most preferably 92:8 to 99:1. preferable. When the above weight ratio is satisfied, the viscosity stability is excellent even during long-term storage, and the effect of minimizing erroneous landing during inkjetting is achieved.

The scattering particles may have an average particle size of 50 to 1000 nm, preferably in the range of 100 to 500 nm. More preferably, the range is from 150 to 300 nm. When the size of the scattering particles satisfies the above-mentioned range, it can provide sufficient scattering effect of the light emitted from the quantum dots and the backlight (BLU), and can provide a uniform scattering effect without causing the problem of settling in the ink composition. This is preferable in that a coated surface can be obtained.

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

The scattering particles are contained in an amount of 0.5 to 20% by weight, preferably 1 to 15% by weight, and more preferably 1 to 10% by weight based on the total weight of the ink composition.

When the scattering particles are within the above-mentioned range, the emitted light intensity increasing effect is maximized, the scattering effect is sufficient and the emitted light intensity can be secured, and the scattering characteristics exceed the threshold range to emit light. Blocking light is preferable in that it is possible to prevent the problem of reduced luminescence intensity.

Curable Monomer The ink composition of the present invention is characterized in that it contains one or more compounds represented by Chemical Formula 1 and Chemical Formula 2 as a curable monomer, and if necessary, In addition to the compound represented by, other curable monomers may be further included. By using the curable monomer according to the present invention in an ink composition, the adhesion to the base material can be improved, and continuous jetting properties and jetting erroneous impact properties that can be degraded by scattering particles can also be improved.

In the present invention, the curable monomer contains one or more of the compounds represented by Chemical Formula 1 and Chemical Formula 2 having two functional groups, so that an inkjet process is possible with low viscosity and no nozzle clogging, The jetted ink composition can have excellent adhesion to the base material.

When conventional alkyl acrylate monomers are used, the coating film itself becomes brittle and easily cracks, resulting in a significant decrease in adhesion to the underlying substrate, which ultimately leads to problems in the pixel or image surface device. Lifting and cracking occur between the ink layer and the lower base material, resulting in a decrease in the optical properties and transmittance of the quantum dots. Therefore, by including one or more of the compounds represented by Chemical Formula 1 and Chemical Formula 2, the present invention can have the effect of enabling an inkjet process with low viscosity and without nozzle clogging.

In the above formula 1, R ₁ is independently a hydrogen atom or a methyl group, and m is an integer of 1 to 15.

In Formula 2, each R ₂ is independently hydrogen or a methyl group, and m is an integer from 1 to 15.

Specific examples of the compound represented by Formula 1 include polyethylene glycol 200 di(meth)acrylate, polyethylene glycol 400 di(meth)acrylate, and polyethylene glycol 600. di(meta) ) acrylate (polyethylene glycol 600 diacrylate) and the like.

Specific examples of the compound represented by Chemical Formula 2 include dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol 100 di(meth)acrylate, polypropylene glycol 200 di(meth)acrylate, polypropylene glycol 400 di(meth)acrylate, and polypropylene glycol 700 di(meth)acrylate.

In addition, when the curable monomer further contains other curable monomers in addition to the compound represented by the chemical formula 1 and/or 2, based on the solid content of the entire curable monomer, the compound represented by the chemical formula 1 and/or 2 is The represented compounds may be present in an amount of 5 to 40% by weight, preferably 5 to 25% by weight. When the content is within the above range, viscosity stability can be improved during long-term storage, and erroneous landing during inkjetting can be reduced.

In the present invention, the curable monomer may further include a compound represented by the following chemical formula 3. By including the monofunctional monomer represented by the following chemical formula 3, the adhesion between the ink composition and the base material can be further improved after the inkjet process, and in the case of an ink composition containing quantum dots. , the effect of improving optical characteristics appears.

In the chemical formula 3, R ₃ is hydrogen or a methyl group, and A is -CH ₂ -CH ₂ -O- (ethylene oxide) or -CH ₂ -CH (CH ₃ ) -O- (propylene oxide). .

Examples of the compound represented by the chemical formula 3 include 2-(meth)acryloyloxyethyl succinate and Mono(2-acryloyloxyethyl) Succinate.

When the monofunctional monomer of Formula 3 is further included, it is included in an amount of 0.5 to 30% by weight based on the total weight of 100% of the curable monomer.

In the present invention, the curable monomer can further contain a hydroxyl group-containing (meth)acrylate, since it can further improve the adhesive properties with the base material.

The hydroxyl group-containing (meth)acrylate preferably has a hydroxyl value of 200 to 300 mgKOH/g and a viscosity of less than 50 cP. Specific examples of the hydroxyl group-containing (meth)acrylate include glycerol (meth)acrylate (eg, glycerol diacrylate).

When the hydroxyl group-containing (meth)acrylate is further included, it is included in an amount of 0.5 to 30% by weight based on the total 100% by weight of the curable monomer.

When the monomer of formula 3 and/or hydroxyl group-containing (meth)acrylate is further included, the pixels coated in the inkjet printing process can have improved adhesion properties without peeling or cracking from the substrate. When the monomer of formula 3 and/or hydroxyl group-containing (meth)acrylate is included in excess, curing may not be performed properly or adhesion may be slightly reduced, and the increase in viscosity due to the increase in content may reduce jetting properties, so when included, it is preferable that it is included within the above-mentioned range.

The curable monomer is contained in an amount of 40 to 98% based on 100% by weight of the total ink composition, more specifically, in the case of an ink composition containing quantum dots, it is contained in an amount of 40 to 70% by weight, preferably 50 to 98% by weight. In the case of an ink composition containing only scattering particles without quantum dots, the content is 80 to 95% by weight.

When the curable monomer is contained within the above range, there is an advantage that it is preferable in terms of continuous jetting without nozzle clogging and adhesion of pixel portions in the inkjet printing process. In addition, if the content falls within the above range, the adhesion of the pixel area will decrease slightly, which can prevent the problem of cracking or peeling of the coating after the inkjet process, and the content of quantum dots and/or scattering particles can be reduced. This is preferable because it can also solve the problem that the optical properties and transmittance of the coating film may be slightly lowered due to a decrease in the amount of light.

Quantum dots The quantum dots are not particularly limited as long as they can emit light by stimulation with light, but are preferably non-cadmium-based, and one or more selected from II-VI group semiconductor compounds, III-V group semiconductor compounds, IV-VI group semiconductor compounds, and IV group elements or compounds containing the same can be used. The II-VI group semiconductor compounds are bi-element compounds selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, and mixtures thereof; CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, and ternary compounds selected from the group consisting of HgZnS, HgZnSe, HgZnTe, and mixtures thereof; and quaternary compounds selected from the group consisting of CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, and mixtures thereof. The solid compound may be one or more selected from the group consisting of two-element compounds selected from the group consisting of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, and mixtures thereof; three-element compounds selected from the group consisting of GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, and mixtures thereof; and four-element compounds selected from the group consisting of GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, and mixtures thereof.

The IV-VI group semiconductor compound is 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, A ternary compound selected from the group consisting of SnPbSe, SnPbTe, and a mixture thereof; and one or more types selected from the group consisting of a quaternary compound selected from the group consisting of SnPbSSe, SnPbSeTe, SnPbSTe, and a mixture thereof. It may be.

The Group IV element or a compound containing the same consists of an elemental compound selected from the group consisting of Si, Ge, and a mixture thereof; and a binary compound selected from the group consisting of SiC, SiGe, and a mixture thereof. It may be one or more selected from the group, but is not limited thereto.

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

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

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

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). Yes, but limited to It's not something you can do. Preferably, quantum dots with better optical properties can be obtained by synthesizing by a wet chemical process.

The wet chemical process is a method of growing particles by adding a precursor material to an organic solvent. When the crystal grows, the organic solvent is naturally coordinated to the surface of the quantum dot crystal and plays the role of a dispersing agent to control the crystal growth. It is preferable to manufacture the quantum dots using the wet chemical process because the growth of nanoparticles can be controlled by a process that is easier and cheaper than the wet chemical process.

When producing quantum dots using a wet chemical process, organic ligands are used to prevent quantum dot aggregation and control the particle size of quantum dots to nanoscale levels. As such an organic ligand, oleic acid can generally be used.

In one embodiment of the present invention, the quantum dots may have a ligand layer containing a polyethylene glycol compound. More specifically, the polyethylene glycol compound may be represented by the structures of the following chemical formulas 4a to 4c and 5a.

In one embodiment of the present invention, the quantum dot has on its surface a ligand layer containing one or more of the compounds represented by the following chemical formulas 4a to 4c and chemical formula 5a.

In the chemical formulas 4a to 4c,
R' and R'' are each independently a hydrogen atom; a carboxyl group; a phenyl group; or a C1-C20 alkyl group substituted or unsubstituted with a thiol group,
R' and R'' are not at the same time a hydrogen atom; a phenyl group; or an unsubstituted C1-C20 alkyl group,
R ^a is a substituted or unsubstituted C1-C22 alkyl group, or a substituted or unsubstituted C4-C22 alkenyl group,
n is an integer from 1 to 20,
p and q are each independently an integer of 1 to 100,
r is an integer from 1 to 10.

Further, in one embodiment, the quantum dot of the present invention may include a ligand layer having a structure represented by the following chemical formula 5a.

In the chemical formula 5a, R ^c is a substituted or unsubstituted C1-C22 alkyl group, or a substituted or unsubstituted C4-C22 alkenyl group,
R ^d is a substituted or unsubstituted C1-C22 alkylene group, a substituted or unsubstituted C3-C8 cycloalkylene group, or a substituted or unsubstituted C6-C14 arylene group,
A and B are each independently a single bond, a substituted or unsubstituted C1-C22 alkylene group, -O-, -NR ^e -, or -S-,
X is a carboxyl group, a phosphoric acid group, a thiol group, an amine group, a tetrazole group, an imidazole group, a pyridine group, or a lipoamide group,
R ^e is a substituted or unsubstituted C1-C22 alkyl group, or a substituted or unsubstituted C4-C22 alkenyl group,
u is an integer from 1 to 100.

The C1-C20 alkyl group used herein means a linear or branched monovalent hydrocarbon having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, Isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 2 -Methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2 -propylpentyl, n-nonyl, 2,2-dimethylheptyl, n-decyl, n-undecyl, and the like, but are not limited to these.

The C1-C22 alkyl group used herein means a linear or branched monovalent hydrocarbon having 1 to 22 carbon atoms, such as methyl, ethyl, n-propyl, Isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 2 -Methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2 -propylpentyl, n-nonyl, 2,2-dimethylheptyl, n-decyl, n-undecyl, n-docosanyl, and the like, but are not limited to these.

The C4-C22 alkenyl group used herein refers to a linear or branched monovalent unsaturated hydrocarbon having 4 to 22 carbon atoms and having one or more carbon-carbon double bonds. Examples thereof include, but are not limited to, butenylene, pentenylene, hexenylene, heptenylene, octenylene, nonenylene, decenylene, undecenylene, dodecenylene, tridecenylene, tetradecenylene, pentadecenylene, hexadecenylene, heptadecenylene, octadecenylene, and the like.

The C1-C20 alkyl group, C1-C22 alkyl group, and C4-C22 alkenyl group may have one or more hydrogens substituted with a C1-C6 alkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C3-C10 cycloalkyl group, a C3-C10 heterocycloalkyl group, a C3-C10 heterocycloalkyloxy group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 thioalkoxy group, an aryl group, an acyl group, a hydroxyl group, a thio (thio), a halogen group, an amino, an alkoxycarbonyl group, a carboxyl group, a carbamoyl group, a cyano group, a nitro group, or the like.

In the compound represented by the chemical formula 4a of the present invention, R' is a C1-C20 alkyl group substituted with a thiol group or not substituted with a thiol group, from the viewpoint of optical properties and dispersibility of quantum dots and realization of low viscosity. and R'' may be a carboxyl group.

In one embodiment of the present invention, specific examples of the compound represented by the chemical formula 4a include 2-(2-methoxyethoxy)acetic acid (WAKO), 2-[2-(2-methoxyethoxy)ethoxy]acetic acid (WAKO), {2-[2-(carboxymethoxy)ethoxy]ethoxy}acetic acid (WAKO), 2-[2-(benzyloxy)ethoxy]acetic acid, (2-(carboxymethoxy)ethoxy)acetic acid (WAKO) Examples include, but are not limited to, (2-butoxyethoxy)acetic acid (WAKO), carboxy-EG6-undecanethiol, and the like.

In terms of realizing the optical properties and dispersibility of quantum dots and low viscosity, the compound represented by Chemical Formula 4b of the present invention may be a compound in which R ^a is a C1-C22 alkyl group or a C4-C20 alkenyl group, and p is an integer from 1 to 50. In particular, if p in Chemical Formula 4b exceeds the above range, it may affect the viscosity of the light conversion ink composition.

The compound represented by Formula 4b has a thiol group, and the thiol group can be bonded to the surface of the quantum dot. In the case of a thiol group, it has excellent bonding strength with the surface of quantum dots compared to the ligand layer compounds of ordinary quantum dots such as carboxylic acids, and has excellent bonding strength with the surface of quantum dots such as quenching due to surface defects such as dangling bonds of quantum dots. It has the advantage of suppressing quenching due to oxidation and improving optical characteristics (emission characteristics) and reliability.

In one embodiment of the present invention, the compound represented by chemical formula 4b may be one or more compounds selected from the compounds represented by the following chemical formulas 4-1 to 4-6 in terms of the optical properties and dispersibility of the quantum dots and realization of low viscosity.

In the compound represented by the chemical formula 4c of the present invention, q is an integer of 1 to 50, and r is an integer of 1 to 8, from the viewpoint of optical properties and dispersibility of quantum dots and realization of low viscosity. It may be a certain compound. In particular, in the chemical formula 4c, when q and r exceed the above ranges, the viscosity of the light conversion ink composition may be affected.

The compound represented by Formula 4c has a thiol group, and the thiol group can be bonded to the surface of the quantum dot. In the case of a thiol group, it has excellent bonding strength with the surface of quantum dots compared to the ligand layer compounds of ordinary quantum dots such as carboxylic acids, and has excellent bonding strength with the surface of quantum dots such as quenching due to surface defects such as dangling bonds of quantum dots. It has the advantage of suppressing quenching due to oxidation and improving optical characteristics (emission characteristics) and reliability.

In one embodiment of the present invention, the compound represented by the chemical formula 4c is selected from the compounds represented by the following chemical formulas 4-7 to 4-12 from the viewpoint of optical properties and dispersibility of quantum dots and realization of low viscosity. It may be one or more compounds selected.

The compounds represented by the chemical formulas 4a to 4c of the present invention are organic ligands that are coordinately bonded to the surface of quantum dots to stabilize the quantum dots.

Typically, manufactured quantum dots have a ligand layer on their surface, and the ligand layer immediately after manufacturing may be made of oleic acid, lauric acid, or the like. In this case, due to the weaker bonding force with the quantum dots compared to when the quantum dots according to the present invention contain the compounds represented by the chemical formulas 4a to 4c as a ligand layer, the reason is due to non-bonding defects on the surface of the quantum dots. , the surface protection effect may be reduced. In addition, in the case of oleic acid, it is well dispersed in aliphatic hydrocarbon solvents such as n-hexane and aromatic hydrocarbon solvents such as benzene, which are highly volatile organic compounds (VOCs), but propylene It has poor dispersibility in solvents such as glycol methyl ether acetate (PGMEA). The quantum dots according to the present invention contain the compounds represented by the chemical formulas 4a to 4c as a ligand layer, have excellent dispersibility in a solvent such as PGMEA, and exhibit the effect of improving optical properties.

In addition, the quantum dots contain one or more polyethylene glycol-based ligands among the compounds represented by the chemical formulas 4a to 4c, and therefore have good dispersion properties even when using only the curable monomer described below without using a solvent. can be shown.

The compounds represented by the chemical formulas 4a to 4c may cover 5% or more of the total surface area of the quantum dots.

At this time, the content of the compounds represented by the chemical formulas 4a to 4c may be 0.1 to 10 mol per 1 mol of quantum dots.

The ligand layer containing the compounds represented by Formulas 4a to 4c may have a thickness of 0.1 nm to 2 nm, for example, 0.5 nm to 1.5 nm.

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

In one embodiment of the present invention, oleic acid used in the manufacturing process of the quantum dots is replaced with the ligands of Formulas 4a to 4c by a ligand exchange method.

The ligand exchange is carried out by adding the organic ligand to be exchanged, i.e., the compounds of formulae 4a to 4c, to a dispersion containing quantum dots having the original organic ligand, i.e., oleic acid, and stirring the mixture at room temperature to 200°C for 30 minutes to 3 hours to obtain quantum dots bound with the compounds of formulae 4a to 4c. If necessary, an additional process of isolating and purifying the quantum dots bound with the compounds of formulae 4a to 4c may be carried out.

When the quantum dots are additionally included, they are included in an amount of 1 to 60% by weight, preferably 5 to 50% by weight, based on 100% by weight of the total 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. When the quantum dots fall within the above range, it is preferable because the light conversion efficiency of green light and red light is excellent and the problem of increased viscosity of the ink composition and decreased jetting properties can be prevented.

Dispersant In the present invention, the dispersant means a dispersant that satisfies an acid value of 10 to 90 mgKOH/g and an amine value of 10 to 90 mgKOH/g. The dispersant of the present invention satisfies the acid value and the amine value at the same time, thereby effectively adhering the scattering particles and the monomer to the dispersant at the same time, thereby giving the ink composition excellent dispersibility.

More specifically, the dispersant included in the present invention may have an acid value of 10 to 90 mgKOH/g and an amine value of 10 to 90 mgKOH/g, or may have an acid value of 10 to 60 mgKOH/g and an amine value of 10. A range of ˜60 mgKOH/g is more preferable. When the dispersant satisfies the above-mentioned acid value and amine value at the same time, it is preferable because it can have the effect of significantly improving the phenomenon of clumping of scattering particles on the pixel surface in the inkjet process.

The present invention can include any type of dispersant as long as it satisfies the above-mentioned ranges of acid value and amine value. However, from the viewpoint of storage stability of the dispersion, it is more preferable to include a polyethylene (PE) or polyimine (PI)-based dispersant.

The dispersant is contained in an amount of 0.01 to 20% by weight, preferably 0.5 to 15% by weight, and more preferably 0.5 to 10% by weight, based on the total weight of the ink composition.

Photopolymerization Initiator In the present invention, the photopolymerization initiator plays the role of initiating a radical reaction in the ink composition, causing curing, and improving sensitivity. The initiator is a photopolymerization initiator commonly used in self-luminous compositions, such as acetophenone-based, benzophenone-based, triazine-based, thioxanthone-based, oxime-based, benzoin-based, biimidazole-based compounds, etc. I can do it.

Furthermore, in the present invention, a photopolymerization initiation aid can be used. A photopolymerization initiation aid is a compound that may be used in combination with a photoinitiator, and is used to accelerate the polymerization of a photopolymerizable compound whose polymerization has been initiated by the photoinitiator. Examples of the photopolymerization initiation aid include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, carboxylic acid compounds, and sulfonic acid compounds.

Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylaminoethyl benzoate. , 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4 Examples include '-bis(ethylmethylamino)benzophenone, among which 4,4'-bis(diethylamino)benzophenone is preferred.

Examples of alkoxyanthracene-based compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, etc. . Examples of thioxanthone compounds include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

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

In the present invention, the photopolymerization initiators may be used alone or in combination without any problem. In addition, commercially available photopolymerization initiation aids can be used, and examples of commercially available photopolymerization initiation aids include the product name "EAB-F" [manufacturer: Hodogaya Chemical Industry Co., Ltd.]. It will be done.

When these photopolymerization initiation aids are used, the amount used is usually 10 mol or less, preferably 0.01 to 5 mol, per 1 mol of photoinitiator. If it is within the above range, the sensitivity of the self-luminous composition tends to be higher and the productivity of the light conversion laminated base material formed using this composition tends to be improved, so it is preferable.

The photopolymerization initiator is contained in an amount of 0.1 to 3.0% by weight, preferably 0.5 to 2.0% by weight, based on the total weight of the ink composition. When the photopolymerization initiator is contained within the above range, pattern formation becomes good, the self-luminous composition becomes highly sensitive, and the strength of the pixel part formed using this composition and the smoothness of the surface of this pixel part tend to be good, which is preferable.

Additives In addition to the above-mentioned components, the ink composition according to one embodiment of the present invention may also contain surfactants, silane coupling agents, adhesion promoters, etc. in order to improve the flatness or adhesion of the coating film. Additives may additionally be included.

When the ink composition according to the present invention contains the surfactant, it has the advantage of improving the flatness of the coating film. For example, the surfactant may be a fluorine-based surfactant such as F-554, BM-1000, BM-1100 (BM Chemie), Fluorad FC-135/FC-170C/FC-430 (Sumitomo 3M Limited), SH-28PA/-190/-8400/SZ-6032 (Toray Silicone Co., Ltd.), but is not limited to these.

The adhesion promoter can be added to enhance adhesion to the substrate, and can include, but is not limited to, a silane coupling agent having a reactive substituent selected from the group consisting of a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, and combinations thereof.

In addition, the ink composition according to the present invention may further contain additives such as antioxidants, ultraviolet absorbers, and anti-aggregation agents, as long as the effects of the present invention are not impaired. Similarly, the additives described above can be appropriately added and used by those skilled in the art, as long as the effects of the present invention are not impaired.

When the additive is further included, it may be used in an amount of 0.05 to 10 wt %, specifically 0.1 to 10 wt %, and more specifically 0.1 to 5 wt %, based on 100 wt % of the total ink composition, but is not limited thereto.

The ink composition of the present invention is most preferably solvent-free from the viewpoint of continuous processability. The term "solvent-free" as used herein means that the ink composition can contain a solvent in an amount of 5% by weight or less based on 100% by weight of the total composition. More specifically, it is more preferable that the ink composition of the present invention does not contain a solvent. Specifically, the ink composition according to one embodiment of the present invention is solvent-free, has excellent optical properties and dispersibility of quantum dots, and has low viscosity even when the solvent content is as low as 5% by weight or less. It is possible to realize Furthermore, the ink composition according to an embodiment of the present invention has a low solvent content of 5% 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. be.

Furthermore, the ink composition according to one 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 total ink composition. The ink composition according to one embodiment of the present invention can achieve low viscosity by not containing a resin component, and has excellent ink nozzle jetting characteristics.

One embodiment of the present invention relates to a pixel including a cured product of the above-described ink composition.
Moreover, one embodiment of the present invention relates to a color filter including the above-mentioned pixels.

A method for forming a pattern using an ink composition according to the present invention includes the steps of applying the above-described ink composition to a predetermined area using an inkjet method, and curing the applied ink composition.

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

The substrate is not 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, GaAs substrates, etc. . These substrates can be subjected to pretreatment such as chemical treatment with chemicals such as silane coupling agents, plasma treatment, ion plating treatment, sputtering treatment, gas phase reaction treatment, and vacuum evaporation treatment. When a silicon substrate or the like is used as the substrate, a charge coupled device (CCD), a thin film transistor (TFT), etc. can be formed on the surface of the silicon substrate or the like. Moreover, a partition matrix may be formed.

In order to form the appropriate phase on a substrate when ejected from a piezoelectric inkjet head, which is an example of an inkjet ejector, the properties of the viscosity, fluidity, quantum dot particles, etc. must be balanced with the inkjet head. The piezoelectric inkjet head used in the present invention ejects ink having a droplet size of about 10 to 100 pL, preferably about 20 to 40 pL, although there is no limitation thereto.

The viscosity of the ink composition of the present invention is suitably in the range of about 3 to 30 cP, more preferably in the range of 7 to 20 cP, from the viewpoint of improving jetting properties.

A color filter according to one 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 ink composition described above in a predetermined pattern on a substrate and then curing the composition. The color filter can be configured and manufactured by a conventional method.

One embodiment of the present invention relates to an image display device equipped with the above-mentioned color filter.
The color filter of the present invention can be applied not only to ordinary liquid crystal displays (LCDs), but also to electroluminescent displays (ELs), plasma displays (PDPs), field emission displays (FEDs), organic light emitting devices (OLEDs), etc. It is applicable to various image display devices.

The image display device of the present invention includes a configuration 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 the following manufacturing examples, examples, comparative examples, and experimental examples. These examples, comparative examples, and experimental examples are provided merely to illustrate the present invention, and the scope of the present invention is not limited thereto.

Production Example 1: Synthesis of Ligand Substituted Quantum Dots (A-1) Indium acetate 0.4 mmol (0.058 g), palmitic acid 0.6 mmol (0.15 g), and 1-octadecene ( 1-octadecene) was placed in the reactor and heated to 120° C. under vacuum. After 1 hour, the atmosphere in the reactor was changed to nitrogen. After heating to 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 1 minute.

2.4 mmol (0.448 g) zinc acetate, 4.8 mmol oleic acid, and 20 mL trioctylamine were placed in a reactor and heated to 120° C. under vacuum. After 1 hour, the atmosphere in the reactor was changed to nitrogen, and the temperature of the reactor was raised to 280°C. After adding 2 mL of 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 rapidly cooled at room temperature, and the resulting precipitate was centrifuged. The resulting precipitate 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 to 120° C. under vacuum. After 1 hour, the atmosphere in the reactor was changed to 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 at room temperature, and the precipitate obtained by centrifugation was filtered under reduced pressure and dried under reduced pressure to disperse quantum dots with an InP/ZnSe/ZnS core-shell structure in chloroform.

The maximum emission peak of the photoemission spectrum of the obtained nano-quantum dots was 535 nm, and 5 mL of the quantum dot solution was placed in a centrifuge tube, and 20 mL of ethanol was added thereto for precipitation. The upper layer was discarded by centrifugation, and 2 mL of chloroform was added to the precipitate to disperse the quantum dots. Then, 0.50 g of (2-butoxyethoxy)acetic acid was added, and the mixture was heated to 60°C under a nitrogen atmosphere. The reaction was allowed to proceed for 1 hour.

Next, 25 mL of n-hexane was added to the reaction mixture to precipitate the quantum dots, followed by centrifugation to obtain a precipitate.

Production Example 2: Synthesis of Ligand-Substituted Quantum Dots (A-2) Indium acetate 0.4 mmol (0.058 g), palmitic acid 0.6 mmol (0.15 g), and 1-octadecene ( 1-octadecene) was placed in the reactor and heated to 120° C. under vacuum. After 1 hour, the atmosphere in the reactor was changed to nitrogen. After heating to 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 after reacting for 5 minutes, the reaction solution was allowed to stand at room temperature. Cooled quickly. The maximum absorption wavelength was 560 to 590 nm.

2.4 mmol (0.448 g) of zinc acetate, 4.8 mmol of oleic acid, and 20 mL of trioctylamine were placed in a reactor and heated to 120°C under vacuum. After 1 hour, the atmosphere in the reactor was switched to nitrogen, and the reactor was heated to 280°C. 2 mL of the previously synthesized InP core solution was added, followed by 4.8 mmol of selenium in trioctylphosphine (Se/TOP), and the final mixture was reacted for 2 hours before being cooled to room temperature 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 to 120° C. under vacuum. After 1 hour, the atmosphere in the reactor was changed to 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 quickly cooled at room temperature, and the precipitate obtained by centrifugation was filtered under reduced pressure, dried under reduced pressure to obtain quantum dots with an InP/ZnSe/ZnS core-shell structure, and then dispersed in chloroform. I let it happen.

The maximum emission peak of the photoemission spectrum of the obtained nano-quantum dots was 635 nm, and 5 mL of the synthesized quantum dot solution was placed in a centrifuge tube, and 20 mL of ethanol was added thereto for precipitation. The upper layer was discarded by centrifugation, and 2 mL of chloroform was added to the precipitate to disperse the quantum dots. Then, 0.65 g of carboxy-EG6-undecanethiol was added, and the mixture was heated to 60°C under a nitrogen atmosphere. The reaction was allowed to proceed for 1 hour.

Next, 25 mL of n-hexane was added to the reaction mixture to precipitate the quantum dots, and then centrifugation was performed to discard the supernatant and obtain the precipitate.

Production Example 3: Synthesis of ligand-substituted quantum dots (A-3) Indium acetate 0.4 mmol (0.058 g), palmitic acid 0.6 mmol (0.15 g), and 1-octadecene ( octadecene) was placed in the reactor and heated to 120° C. under vacuum. After 1 hour, the atmosphere in the reactor was changed to nitrogen.

After heating to 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 min.

Next, 2.4 mmol of zinc acetate (0.448 g), 4.8 mmol of oleic acid, and 20 mL of trioctylamine were placed in a reactor and heated to 120°C under vacuum. After 1 hour, the atmosphere in the reactor was switched to nitrogen, and the reactor was heated to 280°C. 2 mL of the previously synthesized InP core solution was added, followed by 4.8 mmol of selenium in trioctylphosphine (Se/TOP), and the final mixture was reacted for 2 hours. Ethanol was added to the reaction solution, which 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 to 120° C. under vacuum. After 1 hour, the atmosphere in the reactor was changed to 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 quickly cooled at room temperature, and the precipitate obtained by centrifugation was filtered under reduced pressure, dried under reduced pressure to obtain quantum dots with an InP/ZnSe/ZnS core-shell structure, and then dispersed in chloroform. I let it happen. The solid content was adjusted to 10%. The maximum emission wavelength was 520 nm.

5 mL of the synthesized quantum dot solution was placed in a centrifugation tube, and 20 mL of ethanol was added thereto for precipitation. Discard the upper layer by centrifugation, add 3 mL of chloroform to the precipitate to disperse the quantum dots, and then add 1.00 g of mPEG5-SH (FutureChem) represented by the following chemical formula 4-1. The mixture was reacted for 1 hour under a nitrogen atmosphere while heating at 60°C.

Next, 25 mL of n-hexane was added to the reaction mixture to precipitate the quantum dots, followed by centrifugation and the upper layer was discarded to obtain a precipitate.

Preparation Example 4: Synthesis of ligand-substituted quantum dots (A-4) Preparation was carried out in the same manner as in Preparation Example 3, except that 3.00 g of a compound represented by the following chemical formula 4-7 was used instead of 1.00 g of the ligand used in Preparation Example 3.

Production Example 5: Production of scattering particle dispersion liquid (C-1) TiO ₂ (Ishihara Co., Ltd. CR) whose surface was treated with TiO ₂ and surface treatment components (Al, Si, and Organic) at a weight ratio of 97:3 was used as scattering particles. -63, 210 nm) 70.0 parts by weight, 4.0 parts by weight of DISPERBYK-2001 (manufactured by BYK) as a dispersant, and 26 parts by weight of 1,6-hexanediol diacrylate were mixed in a bead mill for 12 hours. A scattering particle dispersion (C-1) was produced by dispersing.

Production Example 6: Production of scattering particle dispersion (C-2) Instead of the scattering particles used in Production Example 5, TiO _{2 (} A scattering particle dispersion (C-2) was produced in the same manner as in Production Example 5, except that Ishihara Co., Ltd.'s CR-60, 210 nm) was used.

Production Example 7: Production of scattering particle dispersion (C-3) Instead of the scattering particles used in Production Example 5, TiO ₂ and surface treatment components (Al, Zr, and Organic) were added to the surface in a weight ratio of 93:7. A scattering particle dispersion (C-3) was produced in the same manner as in Production Example 5, except that treated TiO ₂ (UT771, 250 nm, manufactured by Ishihara Co., Ltd.) was used.

Production Example 8: Production of scattering particle dispersion (C-4) Instead of the scattering particles used in Production Example 5, TiO ₂ and surface treatment components (Al, Si, Zn, and Organic) were used in a weight ratio of 92:8. A scattering particle dispersion (C-4) was produced in the same manner as in Production Example 5 above, except that TiO ₂ (PF-742, 250 nm, manufactured by Ishihara Co., Ltd.) surface-treated with was used.

Production Example 9: Production of scattering particle dispersion (C-5) Instead of the scattering particles used in Production Example 5, TiO was surface-treated with TiO ₂ and surface treatment components (Al and Si) at a weight ratio of 88:12. A scattering particle dispersion (C-5) was produced in the same manner as in Production Example 5, except that ₂ (S-305, 250 nm, manufactured by Ishihara Co., Ltd.) was used.

Production Example 10: Production of scattering particle dispersion (C-6) Except that pure TiO ₂ (PT-301, 270 nm, manufactured by Ishiharasha) without surface treatment was used instead of the scattering particles used in Production Example 5. For example, a scattering particle dispersion (C-6) was produced in the same manner as in Production Example 5 above.

Examples 1 to 90 and Comparative Examples 1 to 8: Production of ink compositions Ink compositions were produced by mixing the respective components in the compositions shown in Tables 1 to 8 below (% by weight).

*In Tables 1 to 8 above, "(B) content ratio" means the content (% by weight) of the compounds represented by chemical formulas 1 and 2, based on the solid content of the curable monomer (B). .

Quantum dots A-1 to A-4: Quantum dots produced in Production Examples 1 to 4, respectively. B-1: Polyethylene glycol 200 diacrylate (Shin-Nakamura Chemical Co., Ltd., A-200)
B-2: polyethylene glycol 400 diacrylate (Shin-Nakamura Chemical Co., Ltd., A-400)
B-3: polyethylene glycol 600 diacrylate (Shin-Nakamura Chemical Co., Ltd., A-600)
B-4: Polypropylene glycol 100 diacrylate (Shin-Nakamura Chemical Co., Ltd., APG-100)
B-5: Polypropylene glycol 200 diacrylate (Shin-Nakamura Chemical Co., Ltd., APG-200)
B-6: Polypropylene glycol 400 diacrylate (Shin-Nakamura Chemical Co., Ltd., APG-400)
B-7: Polypropylene glycol 700 diacrylate (Shin-Nakamura Chemical Co., Ltd., APG-700)
B-8: Mono(2-acryloyloxyethyl) Succinate (TCI) - Chemical formula 3
B-9: Glycerol diacrylate (Toagosei Co., Ltd., MT-3560)
B-10: 1,6-Haxanediol diacrylate (Shin-Nakamura Chemical Co., Ltd.)
B-11: 1,10-Decanediol diacrylate (Shin-Nakamura Chemical Co., Ltd.)
B-12: Propoxylated trimethylolpropane triacrylate (Shin-Nakamura Chemical Co., Ltd.)
C-1: Scattering particle dispersion liquid produced in Production Example 5-TiO ₂ (Ishihara Corporation, CR-63; particle size 210 nm; Al, Si, organic surface treatment 3%)
C-2: Scattering particle dispersion liquid produced in Production Example 6-TiO ₂ (Ishihara Corporation, CR-60; particle size 210 nm; Al surface treatment 5%)
C-3: Scattering particle dispersion liquid produced in Production Example 7-TiO ₂ (Ishihara Corporation, UT771; particle size 250 nm; Al, Zr, organic surface treatment 7%)
C-4: Scattering particle dispersion liquid produced in Production Example 8-TiO ₂ (Ishihara Corporation, PF-742; particle size 250 nm; Al, Si, Zn, organic surface treatment 8%)
C-5: Scattering particle dispersion liquid produced in Production Example 9-TiO ₂ (Ishihara Corporation, S-305; particle size 250 nm; Al, Si surface treatment 12%)
C-6: Scattering particle dispersion liquid produced in Production Example 10-TiO ₂ (Ishihara Corporation, PT-301; particle size 270 nm; surface treatment 0%)
Photopolymerization initiator (E): Irgacure OXE-01 (BASF)
F-1: Fluorine-based surfactant (F-554, DIC Corporation)
F-2: Silane coupling agent (NSC-02, NIC Corporation)
<Experimental Example>
Using the ink compositions prepared in the above examples and comparative examples, the viscosity and the number of continuous jetting were measured, and a coating layer having a thickness of 10 μm was prepared, and the light conversion efficiency and adhesion of the coating layer were measured. The results are shown in Tables 10 to 13 below.

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

The coating layer containing quantum dots was placed on top of a blue light source (XLamp XR-E LED, Royal blue 450, Cree), and the light conversion efficiency was measured using a luminance meter (CAS140CT Spectrometer, Instrument Systems) according to the following formula 1, and the results are shown in Tables 10 to 13 below.

The higher the light conversion efficiency (%), the better the brightness you can achieve.

(2) Viscosity The viscosity of the 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 25°C, and the results are shown in the table below. Shown in 10-13.

(3) Number of consecutive jettings After filling Unijet's inkjet printing equipment with the above ink composition, fixing the temperature of the jetting head at 40°C, ejecting ink for 1 minute, and leaving the jetting head for 30 minutes. The number of continuous jetting operations was evaluated by repeating the jetting until the nozzle became clogged and could no longer be ejected. The results are shown in Tables 10 to 13 below.

As the number of times of continuous jetting increases, better characteristics can be obtained in the continuous process.
(4) Measurement of Adhesion of Coating Layer The coating layer prepared using the ink composition was subjected to a Cross-Cut Adhesion Test according to the international standard (ASTM D3359).

Using a knife, make incisions in a lattice pattern while applying uniform force to the manufactured coating layer. Apply tape to the incision surface and rub until it is completely adhered. After 30 seconds, remove the edge of the tape. The tape was removed by pulling it at an angle of approximately 180 degrees, and the adhesion of the coating layer was evaluated according to the criteria shown in Table 9 below, and the results are shown in Tables 10 to 13 below.

(5) Viscosity stability evaluation The ink compositions of the above Examples and Comparative Examples were evaluated 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. The initial viscosity and viscosity were measured after one month of storage at room temperature and two weeks at 40°C. The viscosity stability was evaluated based on the viscosity change rate calculated based on the following evaluation criteria, and the results are shown in Tables 10 to 13 below.

<Viscosity stability evaluation criteria>
: Viscosity change rate is 103% or less. ◯: Viscosity change rate is more than 103% and less than 105%. △: Viscosity change rate is more than 105% and less than 110%. ×: Viscosity change rate is more than 110%. (6) Evaluation of Misdirected Jetting The ink compositions of Examples 1 to 70 and Comparative Examples 1 to 25 were filled into an inkjet printing device manufactured by Unijet Co., Ltd., and the temperature of the jetting head was fixed at 40° C., after which 30 droplets of ink were ejected onto a substrate in a line. Any droplets that were not ejected at the designated positions were confirmed, and misdirected jetting was evaluated according to the following evaluation criteria. The results are shown in Tables 10 to 13.

<Evaluation criteria for jetting misfire>
◎: No mishit bullets ○: Mishit bullets exceed 1 droplet and 3 droplets or less △: Mishit bullets exceed 3 droplets and 5 droplets or less ×: Mishit bullets exceed 5 droplets

As can be seen from the above experimental results, in the case of Examples 1 to 90, which contain a curable monomer having a specific chemical structure, it was confirmed that the jetting properties, adhesion performance, viscosity stability, and jetting mis-landing properties were excellent.

Specifically, in Examples 1 to 70, in which TiO ₂ was surface-treated as scattering particles with a weight ratio of TiO ₂ and a surface treatment component in the range of 92:8 to 99:1, viscosity stability and/or jet It can be confirmed that the mis-landing property is further improved, and further, when the content of the curable monomer of the chemical formula 1 and/or 2 of the present invention is 5 to 40% based on the solid content of the curable monomer. In the cases of Examples 57 to 70 that satisfied the content ratio, better viscosity stability and jetting erroneous impact properties were ensured.

In addition, in the case of Examples 31 to 33 and 35 to 38, it was confirmed that better adhesion could be ensured by further containing chemical formula 3 or a (meth)acrylate containing a hydroxyl group.

On the other hand, in the case of Comparative Examples 1 to 8, the jetting effect and low viscosity were achieved by containing only the monomer without containing a solvent, but the curable monomer of Chemical Formula 1 and/or Chemical Formula 2 of the present invention was used. It was confirmed that the adhesion force was significantly reduced by not including it.

In addition, the experimental results in Tables 10 to 13 confirmed that the jetting mislanding characteristics were improved when surface-treated scattering particles or the curable monomer according to the present invention were used.

Claims (12)

1. An ink composition comprising scattering particles , a curable monomer and quantum dots ,
The ink composition contains 0.5 to 20% by weight of the scattering particles and 40 to 98% by weight of the curable monomer, based on a total weight of 100% by weight of the ink composition;
the scattering particles are _TiO2 ,
_The TiO2 is surface-treated with one or more components selected from Al, Si, Zr, Zn, and organic substances;
The curable monomer includes one or more compounds selected from the group consisting of compounds represented by Chemical Formula 1 and Chemical Formula 2 having two functional groups,
the quantum dots include a polyethylene glycol-based ligand layer;
The ink composition, wherein the polyethylene glycol-based ligand layer contains one or more compounds selected from the group consisting of compounds represented by Chemical Formulae 4a to 4c and 5a .

(In the above Chemical Formula 1, R ₁ is independently a hydrogen atom or a methyl group, and m is an integer of 1 to 15.)

(In the above Chemical Formula 2, _R2 is independently hydrogen or a methyl group, and m is an integer of 1 to 15.)

(In the above chemical formulas 4a to 4c,
R' and R'' are each independently a hydrogen atom, a carboxyl group, a phenyl group, or a C1-C20 alkyl group which is unsubstituted or substituted with a thiol group, and R' and R'' are not simultaneously a hydrogen atom, a phenyl group, or an unsubstituted C1-C20 alkyl group;
R ^a is a substituted or unsubstituted C1-C22 alkyl group or a substituted or unsubstituted C4-C22 alkenyl group;
n is an integer from 1 to 20,
p and q each independently represent an integer from 1 to 100;
r is an integer from 1 to 10.

(In the above Chemical Formula 5a,
R ^c is a substituted or unsubstituted C1-C22 alkyl group or a substituted or unsubstituted C4-C22 alkenyl group;
R ^d is a substituted or unsubstituted C1-C22 alkylene group, a substituted or unsubstituted C3-C8 cycloalkylene group, or a substituted or unsubstituted C6-C14 arylene group;
A and B are each independently a single bond, a substituted or unsubstituted C1-C22 alkylene group, -O-, -NR ^e -, or -S-;
X is a carboxyl group, a phosphate group, a thiol group, an amine group, a tetrazole group, an imidazole group, a pyridine group, or a lipoamide group;
R ^e is a substituted or unsubstituted C1-C22 alkyl group or a substituted or unsubstituted C4-C22 alkenyl group;
u is an integer from 1 to 100. The ink composition according to claim 1 , wherein the weight ratio of the TiO ₂ and the surface treatment component is 92:8 to 99:1. The ink composition according to claim 1, wherein the ink composition further contains one or more selected from the group consisting of a dispersant , a photopolymerization initiator, and an additive. The ink composition according to claim 1 , wherein the quantum dots are non-cadmium quantum dots. The ink composition according to claim 1 , wherein the curable monomer further comprises a compound represented by the following Chemical Formula 3:

(In the above Chemical Formula 3, R ₃ is hydrogen or a methyl group, and A is —CH ₂ —CH ₂ —O— or —CH ₂ —CH(CH ₃ )—O—.) The ink composition according to claim 1, wherein the curable monomer further contains a hydroxyl group-containing (meth)acrylate. 7. The ink composition according to claim 6 , wherein the hydroxyl group-containing (meth)acrylate has a hydroxyl value of 200 to 300 mgKOH/g and a viscosity of less than 50 cP. The ink composition according to claim 1, wherein the content of the compounds represented by Chemical Formulas 1 and 2 is 5% to 40% by weight based on the solid content of the curable monomer. The ink composition according to claim 1, wherein the ink composition is a solvent-free type. A light scattering pixel manufactured using a cured product of the ink composition according to any one of claims 1 to 9 . A color filter comprising the light scattering pixels of claim 10 . An image display device comprising the color filter according to claim 11 .