JP2021113311A - Ink composition, pixel produced using the same, color filter including the pixel, and image display device provided with the color filter - Google Patents

Abstract

To provide an ink composition which improves the above-mentioned problem of a conventional art, significantly improves a phenomenon that is likely to cause peeling from a lower substrate from brittle characteristics of the ink composition after an inkjet step and is excellent in adhesion, prevents floating and cracking of a produced coated film, has low viscosity and enables continuous jetting without causing a nozzle clogging phenomenon frequently generated in an ink jetting step.SOLUTION: An ink composition contains scattered particles and a curable monomer. The curable monomer contains one or more compounds selected from a compound which has two functional groups and is represented by chemical formula 1 and chemical formula 2.SELECTED DRAWING: None

Description

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

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

However, when scattered particles or quantum dots are included in inkjet printing, a problem arises due to the aggregation phenomenon of scattered particles and / or quantum dots. Specifically, in the case of scattered particles and / or quantum dots, precipitation and aggregation phenomena are more likely to occur than colorants used as pigments or dyes. Therefore, scattered particles and / or quantum dots are often precipitated and agglomerated, causing problems that clog the nozzles of the inkjet system.

Therefore, in the prior art such as the Republic of Korea Publication No. 10-2017-0084107, a method of producing an ink composition in a two-component type and mixing and using the ink composition before use has been devised. However, in the case of manufacturing with such a two-component type, the process becomes complicated and the mixture must be mixed and used immediately before use, which causes a problem that it cannot be reused after mixing and the economic efficiency is lowered. .. Further, in the composition of the prior art using an acrylate resin, there is a problem that nozzle clogging occurs due to high viscosity, and if only an alkyl acrylate monomer having a low viscosity is used for stable ejection, the adhesive force is remarkably lowered. ..

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

Republic of Korea Publication No. 10-2017-0084107

The present invention is for improving the above-mentioned problems of the prior art, and the phenomenon that the ink composition is likely to be peeled off from the lower substrate is remarkably improved due to the brittle characteristics of the ink composition after the inkjet process. To provide an ink composition that has excellent adhesion, does not cause floating or cracking of the manufactured coating film, has low viscosity, and can be continuously jetted without the nozzle clogging phenomenon that frequently occurs in the ink jetting process. With the goal.

The present invention is an ink composition containing scattered particles and a curable monomer, wherein the curable monomer contains one or more of chemical formula 1 and a compound represented by chemical formula 2 having two functional groups. Provided is an ink composition which is a monomer.

(In the above chemical formula 1, R ₁ is an independent hydrogen or methyl group, and m is an integer of 1 to 15.)

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

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

In the present invention, by containing a curable monomer having a specific structure, the phenomenon that the ink composition is likely to be peeled off from the lower substrate is remarkably improved due to the brittle property of the ink composition after the inkjet process, and the adhesion is improved. It is excellent, does not cause floating or cracking of the produced coating film, has a low viscosity, and has an effect of providing an ink composition capable of continuously jetting without the nozzle clogging phenomenon that frequently occurs in the ink jetting process.

Furthermore, an ink composition that has almost no change in viscosity even during long-term storage, has excellent viscosity stability, can accurately eject ink to a specified position when applied to inkjet equipment, and can minimize ink jetting erroneous impact. Can be provided.

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

Specifically, the present invention is an ink composition containing scattered 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 above chemical formula 1, R ₁ is an independent hydrogen or methyl group, and m is an integer of 1 to 15.)

(In the above chemical formula 2, R ₂ is an independent hydrogen or methyl group, and m is an integer of 1 to 15.)
Scattered Particles In the present invention, the scattered particles play a role in improving the optical properties of the ink composition, and ordinary inorganic materials can be used, preferably metal oxidation having an average particle size of 50 to 1000 nm. Can include things. The scattered 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, but is not limited to, an oxide containing one metal selected from the group consisting of Nb, Ce, Ta, In, and combinations thereof. Specifically, as the scattered particles, 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, it is possible to use a TiO ₂ surface-treated as scattering particles, wherein the TiO ₂ is, Al, Si, Zr, Zn, and subjected to a surface treatment with one or more components selected from organic matter At this time, Al is more preferably contained as an essential component among the surface treatment components. If necessary, materials surface-treated with compounds having unsaturated bonds, such as acrylates, can also be used. When the ink composition contains scattered particles, it may cause deterioration of continuous jetting property and jetting mis-landing characteristics. However, when surface-modified scattered particles are used, excellent light characteristic effects can be obtained. It is possible to improve the continuous jetting property and the jetting mis-landing characteristic.

Further, in the surface-treated TiO ₂ , _{the content ratio of TiO 2} and the surface-treated component may be 90: 10 to 99: 1 by weight, and most preferably 92: 8 to 99: 1. preferable. When the weight ratio is satisfied, the viscosity stability is excellent even during long-term storage, and the effect of minimizing erroneous impact during ink jetting can be obtained.

The scattered particles can have an average particle size of 50 to 1000 nm, and preferably those in the range of 100 to 500 nm are used. More preferably, it is in the range of 150 to 300 nm. When the size of the scattered particles satisfies the above range, it is possible to provide a sufficient scattering effect of the light emitted from the quantum dots or the backlight (BLU), and it is uniform without causing the problem of sinking in the ink composition. It is preferable in that the surface of the coating film can be obtained.

In the present invention, the average particle size may be a number average particle size, and is 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 as an arithmetic mean value.

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

When the scattered particles are included in the above-mentioned range, the effect of increasing the emission intensity is maximized, the scattering effect is sufficient, the emission intensity can be secured, and the scattering characteristics are emitted beyond the threshold range. By blocking the light, it is preferable in that the problem of a decrease in emission intensity can be prevented.

Curable Monomer The ink composition of the present invention is characterized by containing at least one of the compounds represented by Chemical Formula 1 and Chemical Formula 2 as a curable monomer, and Chemical Formula 1 and / or 2 as required. In addition to the compound represented by, other curable monomers may be further contained. By using the curable monomer according to the present invention in the ink composition, the adhesion to the substrate can be improved, and the continuous jetting property and the jetting mis-landing property, which can be lowered by the scattered 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 the inkjet process can be performed with low viscosity and without nozzle clogging. It is possible to have an excellent adhesion effect between the jetted ink composition and the base material.

When a conventional alkyl acrylate monomer is used, the coating film itself is brittle and cracks well, causing a problem that the adhesion to the lower substrate is significantly reduced. Lifting and cracking between the ink layers with the lower base material occur, resulting in a decrease in the optical characteristics and transmittance of the quantum dots. Therefore, the present invention can have an effect that the inkjet process can be performed with low viscosity and without nozzle clogging by containing one or more of the compounds represented by the chemical formulas 1 and 2.

In the chemical formula 1, R ₁ is an independent hydrogen or methyl group, and m is an integer of 1 to 15.

In the chemical formula 2, R ₂ is an independent hydrogen or methyl group, and m is an integer of 1 to 15.

Specific examples of the compound represented by the chemical formula 1 include polyethylene glycol 200 di (meth) acrylate (polyethylene glycol 200 diacrylate), polyethylene glycol 400 di (meth) acrylate (polyethylene glycol 400 diacrylate), and polyethylene glycol 600 di (meth). ) Acrylate (polyethylene glycol 600 diacrylate) and the like can be mentioned.

Specific examples of the compound represented by the chemical formula 2 include dipropylene glycol di (meth) acrylate (Dipropylene glycol diacrylate), tripropylene glycol di (meth) acrylate (Tripropylene glycol diacrylate), and polypropylene glycol 100 di (meth) acrylate. , Polypropylene glycol 200 di (meth) acrylate, polypropylene glycol 400 di (meth) acrylate, polypropylene glycol 700 di (meth) acrylate and the like.

When the curable monomer further contains other curable monomers in addition to the compounds represented by the chemical formulas 1 and / or 2, the chemical formulas 1 and / or 2 are used based on the solid content of the overall curable monomer. The compound represented may be contained in an amount of 5 to 40% by weight, preferably 5 to 25% by weight. When it is included in the content range, the viscosity stability can be improved during long-term storage, and erroneous impact during ink jetting can be reduced.

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

In the chemical formula 3, R ₃ is a 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-acryloyl ethyl) succinate (Mono (2-acryloyloxyethyl) Succinate).

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

In the present invention, the curable monomer can further contain a hydroxyl group-containing (meth) acrylate from the viewpoint that the adhesion property with the substrate can be further improved.

The hydroxyl group-containing (meth) acrylate is more preferably when the hydroxyl value is 200 to 300 mgKOH / g and the viscosity is less than 50 cP. Specific examples of the hydroxyl group-containing (meth) acrylate include glycerol (meth) acrylate (for example, Glycerol dialcrylate).

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

When the monomer of Chemical Formula 3 and / or the hydroxyl group-containing (meth) acrylate is further contained, the pixel coated in the inkjet printing step can improve the property of excellent adhesion without peeling or cracking from the substrate. .. If the monomer and / or hydroxyl group-containing (meth) acrylate of Chemical Formula 3 is excessively contained, curing may not be performed properly, or rather the adhesion may be slightly reduced. When it is contained, it is preferably contained within the above-mentioned range because the tingling property can be reduced.

The curable monomer is contained in an amount of 40 to 98% based on 100% by weight of the total amount of the ink composition, and more specifically, in the case of an ink composition containing quantum dots, 40 to 70% by weight, preferably 50 to 50% by weight. In the case of an ink composition containing 60% by weight and containing only scattered particles without containing quantum dots, it is contained in an amount of 80 to 95% by weight.

When the curable monomer is contained in the above range, there is an advantage that it is preferable in terms of continuous jetting without nozzle clogging and adhesion of the pixel portion in the inkjet printing step. Further, when it is included in the above-mentioned range, it is possible to prevent the problem that the adhesion of the pixel portion is slightly lowered and the coating film is cracked or peeled off after the inkjet process, and the content of quantum dots and / or scattered particles is contained. It is preferable because it is possible to improve the problem that the light property and the transmittance of the coating film may be slightly lowered due to the decrease in the amount of light.

Quantum dots The quantum dots are not particularly limited as long as they can emit light when stimulated by light, but are preferably non-cadmium-based, and are preferably II-VI group semiconductor compounds, III-V group semiconductor compounds, and IV-VI group semiconductors. One or more selected from the compound, the group IV element, or the compound containing the compound can be used. The group II-VI semiconductor compound is a two-element compound selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, and mixtures thereof; ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSte, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, HgZnS, HgZnSe, HgZnTe It may be one or more selected from the group consisting of four element compounds selected from the group consisting of CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, and a mixture thereof, and may be one or more of the group III-V semiconductors. The 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; A three-element compound selected from the group consisting of GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, and mixtures thereof; It may be one or more selected from the group consisting of four element compounds selected from the group consisting of GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, and mixtures thereof.

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, PbSTe, SnPbS, A three-element compound selected from the group consisting of SnPbSe, SnPbTe, and a mixture thereof; and one or more selected from a group consisting of a four-element 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 comprises an element compound selected from the group consisting of Si, Ge, and a mixture thereof; and a two-element compound selected from the group consisting of SiC, SiGe, and a mixture thereof. It may be, but is not limited to, one or more selected from the group.

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

For example, the quantum dots having a core-shell structure 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 a wet chemical process, a metalorganic chemical vapor deposition (MOCVD, metalorganic chemical vapor deposition), or a molecular beam epitaxy (MBE, molecular beam epitaxy). It's not something.

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 can be synthesized by a wet chemical process, a metalorganic chemical vapor deposition (MOCVD, metalorganic chemical vapor deposition), or a molecular beam epitaxy (MBE, molecular beam epitaxy). It's not something. Preferably, it is possible to obtain quantum dots having more excellent optical characteristics by synthesizing them by a wet chemical process.

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

When quantum dots are produced by a wet chemical process, organic ligands are used to prevent quantum dot aggregation and control the particle size of the quantum dots to the nano level. 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-based compound. More specifically, the polyethylene glycol-based 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 dots have a ligand layer on the surface 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 independent C1-C20 alkyl groups substituted or unsubstituted with hydrogen atoms; carboxyl groups; phenyl groups; or thiol groups, respectively.
R'and R'are at the same time not a hydrogen atom; a phenyl group; or an unsubstituted alkyl group of C1-C20.
^Ra is a substituted or unsubstituted C1-C22 alkyl group or a substituted or unsubstituted C4-C22 alkenyl group.
n is an integer of 1 to 20
p and q are independently integers of 1 to 100, respectively.
r is an integer from 1 to 10.

Further, in one embodiment, the quantum dots of the present invention may include a ligand layer containing the structure of the following chemical formula 5a.

In the chemical formula 5a, ^Rc 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 independently single-bonded, substituted or unsubstituted C1-C22 alkylene groups, -O-, -NR ^e- , or -S-, respectively.
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.
^Re 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.

As used herein, the alkyl group of C1-C20 means a linear or branched monovalent hydrocarbon consisting of 1 to 20 carbon atoms, for example, methyl, ethyl, n-propyl, etc. 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 Includes, but is not limited to, -propylpentyl, n-nonyl, 2,2-dimethylheptyl, n-decyl, n-undecyl and the like.

As used herein, the alkyl group of C1-C22 means a linear or branched monovalent hydrocarbon consisting of 1 to 22 carbon atoms, for example, methyl, ethyl, n-propyl, etc. 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 Includes, but is not limited to, -propylpentyl, n-nonyl, 2,2-dimethylheptyl, n-decyl, n-undecyl, n-docosanyl and the like.

The alkenyl group of C4-C22 used herein is a linear or branched monovalent unsaturated hydrocarbon consisting of 4 to 22 carbon atoms with one or more carbon-carbon double bonds. Means, for example, buthenylene, pentenylene, hexenylene, heptenylene, octeneylene, nonenylene, desenylene, undesenilen, dodeceneylene, tridecenylene, tetradecenylene, pentadecenylene, hexadecenylene, heptadecenylene, octadecenylene, etc.

The alkyl group of C1-C20, the alkyl group of C1-C22, and the alkoxy group of C4-C22 have one or more hydrogens of the alkyl group of C1-C6, the alkoxy group of C2-C6, and the alkoxy group of C2-C6. Alkinyl group, C3-C10 cycloalkyl group, C3-C10 heterocycloalkyl group, C3-C10 heterocycloalkyloxy group, C1-C6 haloalkyl group, C1-C6 alkoxy group, C1-C6 thioalkoxy group It may be substituted with a group, an aryl group, an acyl group, hydroxy, thio, halogen, amino, alkoxycarbonyl, carboxy, carbamoyl, cyano, nitro and the like.

The compound represented by the chemical formula 4a of the present invention has an alkyl group of C1-C20 in which R'is substituted with a thiol group or not substituted from the viewpoint of optical properties and dispersibility of quantum dots and realization of low viscosity. And may be a compound in which R'' is 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) and 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) , (2-Butoxyethoxy) acetic acid (WAKO), carboxy-EG6-undecanethiol and the like, but are not limited thereto.

^{In the compound represented by the chemical formula 4b of the present invention, Ra} is an alkyl group of C1-C22 or an alkenyl group of C4-C20 from the viewpoints of optical properties and dispersibility of quantum dots and realization of low viscosity. , P may be a compound which is an integer of 1 to 50. In particular, in the chemical formula 4b, when p exceeds the above range, it may affect the viscosity of the photoconverted ink composition.

The compound represented by the chemical 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, the ligand layer compound of ordinary quantum dots such as carboxylic acid has excellent bonding force with the surface of the quantum dots, and quenching and surface due to surface defects such as dangling bonds of the quantum dots. It has the advantage of suppressing quenching due to oxidation and improving light characteristics (light emission characteristics) and reliability.

In one embodiment of the present invention, the compound represented by the chemical formula 4b is composed of 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 the realization of low viscosity. It may be one or more compounds of choice.

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 in terms of the optical properties and dispersibility of the quantum dots and the realization of low viscosity. It may be a compound. In particular, in the chemical formula 4c, when q and r exceed the above range, it may affect the viscosity of the photoconverted ink composition.

The compound represented by the chemical 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, the ligand layer compound of ordinary quantum dots such as carboxylic acid has excellent bonding force with the surface of the quantum dots, and quenching and surface due to surface defects such as dangling bonds of the quantum dots. It has the advantage of suppressing quenching due to oxidation and improving light characteristics (light emission characteristics) and reliability.

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

The compounds represented by the chemical formulas 4a to 4c of the present invention are organic ligands and can play a role of stabilizing the quantum dots by being coordinated to the surface of the quantum dots.

Generally, the produced quantum dots generally have a ligand layer on the surface, and the ligand layer immediately after production may be made of oleic acid, lauric acid, or the like. In this case, the reason is that the quantum dot according to the present invention has a weaker bonding force with the quantum dot, which is compared with the case where the compound represented by the chemical formulas 4a to 4c is contained as the ligand layer, due to the non-bonding defect on the surface of the quantum dot. , The surface protection effect may be reduced. Further, in the case of oleic acid, it is well 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, but propylene. 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 have an effect of improving optical characteristics.

Further, since the quantum dots contain one or more polyethylene glycol-based ligands among the compounds represented by the chemical formulas 4a to 4c, the dispersion characteristics are good even with the curable monomer described below without a solvent. Can be shown.

The compounds represented by the chemical formulas 4a to 4c may cover the surface of 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 with respect to 1 mol of the quantum dots.

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

In one embodiment of the invention, the quantum dots can 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 reaches an excited state, the quantum dot emits energy due to its own 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 oleic acid used in the process of producing the quantum dots is replaced with the ligands of the chemical formulas 4a to 4c by the ligand exchange method.

In the ligand exchange, the organic ligand to be exchanged, that is, the compound of the chemical formulas 4a to 4c is added to the dispersion liquid containing the original organic ligand, that is, the quantum dot having oleic acid, and this is added at room temperature to 200 ° C. at 30 ° C. This is done by stirring for minutes to 3 hours to obtain quantum dots to which the compounds of formulas 4a to 4c are bonded. If necessary, an additional step of separating and purifying the quantum dots to which the compounds of the chemical formulas 4a to 4c are bonded may be performed.

When the quantum dots are additionally contained, they are contained 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 included in the range, there are advantages that the luminous efficiency is excellent and the reliability of the coating layer is excellent. When the quantum dots are included in the above-mentioned range, it is preferable in that the light conversion efficiency of green light and red light is excellent, and the problem that the viscosity of the ink composition is high and the jetting property is lowered can be prevented.

Dispersant In the present invention, the dispersant means a dispersant satisfying 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 plays a role of effectively adhering the scattered particles and the monomer to the dispersant at the same time and imparting excellent dispersibility to the ink composition by simultaneously satisfying the acid value and the amine value.

More specifically, the dispersant contained 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, an acid value of 10 to 60 mgKOH / g and an amine value of 10. The range of ~ 60 mgKOH / g is more preferable. When the dispersant simultaneously satisfies the acid value and the amine value in the above range, it is preferable in that it can have an effect of remarkably improving the agglomeration phenomenon of scattered particles on the pixel surface in the inkjet process.

The present invention can be included in any type as long as it is a dispersant satisfying the acid value and amine value in the above range. However, from the viewpoint of storage stability of the dispersion, it is more preferable to include a Polyethylene (PE) or Polyethylene (PI) -based dispersant.

The dispersant is contained in an amount of 0.01 to 20% by weight, preferably 0.5 to 15% by weight, 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 a role of initiating a radical reaction of an ink composition to cause curing and improve sensitivity. The initiator is a photopolymerization initiator generally used in self-luminous compositions, and acetophenone-based, benzophenone-based, triazine-based, thioxanthone-based, oxime-based, benzoin-based, biimidazole-based compounds and the like should be used. Can be done.

Further, in the present invention, a photopolymerization initiation aid can be used. The photopolymerization initiator is a compound that may be used in combination with a photoinitiator and is used to accelerate the polymerization of a photopolymerizable compound that has been initiated by the photoinitiator. Examples of the photopolymerization initiator 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 ′ -Bis (ethylmethylamino) benzophenone and the like can be mentioned, and among them, 4,4′-bis (diethylamino) benzophenone is preferable.

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

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. 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 initiator may be used alone or in combination of two or more without any problem. Further, a commercially available photopolymerization initiator can be used, and examples of the commercially available photopolymerization initiator include the trade name "EAB-F" [manufacturer: Hodogaya Chemical Co., Ltd.]. Be done.

When these photopolymerization initiators are used, the amount used is usually 10 mol or less, preferably 0.01 to 5 mol, per 1 mol of the photoinitiator. Within the above range, the sensitivity of the self-luminous composition tends to be higher, and the productivity of the photoconverted laminated base material formed by using this composition tends to be improved, which 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 in the above range, the pattern formation is improved, the self-luminous composition is made highly sensitive, the strength of the pixel portion formed by using this composition, and the surface of the pixel portion. It is preferable because the smoothness tends to be good.

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

When the 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 are F-554, BM-1000, BM-1100 (BM Chemie), Florard FC-135 / FC-170C / FC-430 (Sumitomo 3M Ltd.), SH-28PA /-. Fluorine-based surfactants such as 190 / -8400 / SZ-6032 (Toray Silicone Co., Ltd.) can be used, but the present invention is not limited thereto.

The adhesion accelerator can be added to enhance the adhesion to the substrate, and can be added as a reactive substituent selected from the group consisting of a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, and a combination thereof. A silane coupling agent having a silane coupling agent can be included, but the present invention is not limited thereto.

In addition to this, the 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. Similarly, those skilled in the art can appropriately add and use it as long as the effects of the present invention are not impaired.

When the additive is further contained, 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 total ink composition. By weight% can be used, but is not limited to this.

The ink composition of the present invention is most preferably solvent-free in terms of continuous processability. The solvent-free type in the present specification means that the ink composition solvent can be contained 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 the embodiment of the present invention is a solvent-free type, and even if the solvent content is as low as 5% by weight or less, the optical characteristics and dispersibility of the quantum dots are excellent, and the viscosity is low. Can be realized. Further, the ink composition according to the embodiment of the present invention has a low solvent content of 5% by weight or less, does not cause nozzle clogging due to evaporation of the solvent at the nozzle inlet, and is advantageous for continuous processes. be.

Further, the 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 total ink composition. The ink composition according to one embodiment of the present invention can achieve 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 pixel containing a cured product of the ink composition described above.
Moreover, one embodiment of the present invention relates to the above-mentioned color filter including pixels.

The method for forming a pattern of an ink composition according to the present invention includes a step of applying the above-mentioned ink composition to a predetermined region by an inkjet method and a step of curing the applied ink composition.

First, the ink composition of the present invention is injected into an inkjet injector and printed on a predetermined region of a substrate.

The substrate is not 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. .. These substrates can 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 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 can be formed on the surface of the silicon substrate or the like. Further, a partition matrix may be formed.

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

The viscosity of the ink composition of the present invention is appropriately about 3 to 30 cP, and more preferably formed in the range of 7 to 20 cP is most preferable in terms of improving jetting property.

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 ink composition to a predetermined pattern on a substrate and then curing the ink composition. The composition and manufacturing method of the color filter can be formed by a usual method.

One embodiment of the present invention relates to an image display device provided with the above-mentioned color filter.
The color filter of 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 of the present invention includes configurations known in the art, except that it includes the color filters described above.

Hereinafter, the present invention will be described in more detail with reference to Production Examples, Examples, Comparative Examples and Experimental Examples. 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.

Production Example 1: Synthesis of Ligand Substituted Quantum Dots (A-1) 0.4 mmol (0.058 g) of Indium Acetate, 0.6 mmol (0.15 g) of palmitic acid, and 1-octadecene ( 20 mL of 1-octadecene) was placed in a reactor and heated to 120 ° C. under vacuum. After 1 hour, the atmosphere in the reactor was switched 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 1 minute.

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 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 a reaction solution that had been rapidly cooled at room temperature, and the precipitate obtained by centrifugation was filtered under reduced pressure and then 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 a reactor and heated to 120 ° C. under vacuum. After 1 hour, the atmosphere in the reactor was switched to 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 a reaction solution that had been rapidly cooled at room temperature, and the precipitate obtained by centrifugation was filtered under reduced pressure and then dried under reduced pressure to disperse quantum dots having an InP / ZnSe / ZnS core-shell structure in chloroform.

The maximum emission peak of the light emission 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 for precipitation. The upper layer liquid is discarded by centrifugation, 2 mL of chloroform is added to the precipitate to disperse the quantum dots, 0.50 g of (2-butoxyethoxy) acetic acid is added, and the mixture is heated to 60 ° C. under a nitrogen atmosphere. While reacting for 1 hour.

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

Production Example 2: Synthesis of Ligand-Substituted Quantum Dots (A-2) 0.4 mmol (0.058 g) of Indium Acetate, 0.6 mmol (0.15 g) of palmitic acid, and 1-octadecene ( 20 mL of 1-octadecene) was placed in a reactor and heated to 120 ° C. under vacuum. After 1 hour, the atmosphere in the reactor was switched 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 is rapidly injected, and after a reaction for 5 minutes, the reaction solution is prepared at room temperature. Chilled 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 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 and then lowered to room temperature to lower the InP / ZnSe core. -A shell was formed.

Then, 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 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 is added to a reaction solution that has been rapidly cooled at room temperature, and the precipitate obtained by centrifugation is filtered under reduced pressure and then dried under reduced pressure to obtain quantum dots having an InP / ZnSe / ZnS core-shell structure, which are then dispersed in chloroform. I let you.

The maximum emission peak of the light emission 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 for precipitation. The upper layer liquid is discarded by centrifugation, 2 mL of chloroform is added to the precipitate to disperse the quantum dots, 0.65 g of carboxy-EG6-undecanethiol is added, and the mixture is heated to 60 ° C. under a nitrogen atmosphere. It was allowed to react for 1 hour.

Next, 25 mL of n-hexane was added to the reaction product to precipitate the quantum dots, and then centrifugation was performed and the upper layer liquid was discarded to obtain a precipitate.

Production Example 3: Synthesis of Ligand-Substituted Quantum Dots (A-3) 0.4 mmol (0.058 g) of Indium Acetate, 0.6 mmol (0.15 g) of palmitic acid, and 1-octadecene ( 20 mL of octadecene) was placed in a reactor and heated to 120 ° C. under vacuum. After 1 hour, the atmosphere in the reactor was switched 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 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 to 120 ° C. under vacuum. After 1 hour, the atmosphere in the reactor was switched to 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 a reaction solution that had been rapidly cooled at room temperature, and the precipitate obtained by centrifugation was filtered under reduced pressure and then 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 to 120 ° C. under vacuum. After 1 hour, the atmosphere in the reactor was switched to 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 is added to a reaction solution that has been rapidly cooled at room temperature, and the precipitate obtained by centrifugation is filtered under reduced pressure and then dried under reduced pressure to obtain quantum dots having an InP / ZnSe / ZnS core-shell structure, which are then dispersed in chloroform. I let you. 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 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 1.00 g of mPEG5-SH (Futurechem) represented by the following chemical formula 4-1 is added. The reaction was carried out for 1 hour while heating at 60 ° C. under a nitrogen atmosphere.

Next, 25 mL of n-hexane was added to the reaction product to precipitate the quantum dots, and then centrifugation was performed and the upper layer liquid was discarded to obtain a precipitate.

Production Example 4: Synthesis of ligand-substituted quantum dots (A-4) Except that 3.00 g of the compound represented by the following chemical formula 4-7 was used in place of the 1.00 g of the ligand used in Production Example 3. , The same procedure as in Production Example 3 was carried out.

Production Example 5: Production of Scattered Particle Dispersion Liquid (C-1) _{TiO 2} (CR of Ishihara Co., Ltd. _{) surface-treated with TiO 2} as scattered particles and surface-treated components (Al, Si, and Organic) at a weight ratio of 97: 3. -63, 210 nm) 70.0 parts by weight, DISPERBYK-2001 (manufactured by BYK) 4.0 parts by weight as a dispersant, and 26 parts by weight of 1,6-hexanediol diacrylate through the monomer t were mixed by a bead mill for 12 hours. The dispersion produced a scattered particle dispersion (C-1).

Production Example 6: Production of Scattered Particle Dispersion Liquid (C-2) Instead of the scattered particles used in Production Example 5, TiO ₂ and the surface treatment component (Al) were surface-treated at a weight ratio of 95: 5 _{(TiO 2} ). A scattered particle dispersion (C-2) was produced in the same manner as in Production Example 5 except that CR-60 (210 nm) manufactured by Ishihara Co., Ltd. was used.

Production Example 7: Production of Scattered Particle Dispersion Liquid (C-3) Instead of the scattered particles used in Production Example 5, TiO ₂ and surface treatment components (Al, Zr, and Organic) are surface-treated at a weight ratio of 93: 7. A scattered particle dispersion (C-3) was produced in the same manner as in Production Example 5 except that the treated TiO _{2 (UT771, 250 nm of Ishihara Co., Ltd.) was used.}

Production Example 8: Production of Scattered Particle Dispersion Liquid (C-4) Instead of the scattered particles used in Production Example 5, TiO ₂ and surface treatment components (Al, Si, Zn, and Organic) have a weight ratio of 92: 8. A scattered particle dispersion (C-4) was produced in the same manner as in Production Example 5 except _{that TiO 2} (PF-742 of Ishihara Co., Ltd., 250 nm) surface-treated in the above was used.

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

_{Production Example 10: Production of Scattered Particle Dispersion Liquid (C-6) Except that pure TiO 2} (Ishihara's PT-301, 270 nm) without surface treatment was used instead of the scattered particles used in Production Example 5. For example, a scattered particle dispersion (C-6) was produced in the same manner as in Production Example 5.

Examples 1 to 90 and Comparative Examples 1 to 8: Production of Ink Composition An ink composition was produced by mixing the respective components with 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 the chemical formulas 1 and 2 based on the solid content of the curable monomer (B). ..

Quantum dots A-1 to A-4: Quantum dots manufactured in Production Examples 1 to 4, respectively B-1: Polyethylene glycol 200 dialclylate (Shin-Nakamura Chemical Co., Ltd., A-200)
B-2: Polyethylene glycol 400 dialclylate (Shin-Nakamura Chemical Co., Ltd., A-400)
B-3: Polyethylene glycol 600 dialclylate (Shin-Nakamura Chemical Co., Ltd., A-600)
B-4: Polypropylene glycol 100 dialclylate (Shin-Nakamura Chemical Co., Ltd., APG-100)
B-5: Polypropylene glycol 200 dialclylate (Shin-Nakamura Chemical Co., Ltd., APG-200)
B-6: Polypropylene glycol 400 dialclylate (Shin-Nakamura Chemical Co., Ltd., APG-400)
B-7: Polypropylene glycol 700 dialclylate (Shin-Nakamura Chemical Co., Ltd., APG-700)
B-8: Mono (2-acrylolyloxyethyl) Succinate (TCI) -Chemical formula 3
B-9: Glycerol dialurate (Toagosei, MT-3560)
B-10: 1,6-Haxanediol dialurate (Shin-Nakamura Chemical Co., Ltd.)
B-11: 1,10-Decanediol dialurate (Shin-Nakamura Chemical Co., Ltd.)
B-12: Propoxylated trimethylolpropane triacrylate (Shin-Nakamura Chemical Co., Ltd.)
C-1: Scattered particle dispersion-TIO ₂ produced in Production Example 5 (Ishihara, CR-63; particle size 210 nm; Al, Si, Organic surface treatment 3%)
C-2: Scattered particle dispersion-TIO ₂ produced in Production Example 6 (Ishihara, CR-60; particle size 210 nm; Al surface treatment 5%)
C-3: Scattered particle dispersion-TiO ₂ produced in Production Example 7 (Ishihara, UT771; particle size 250 nm; Al, Zr, Organic surface treatment 7%)
C-4: Scattered particle dispersion-TIO ₂ produced in Production Example 8 (Ishihara, PF-742; particle size 250 nm; Al, Si, Zn, Organic surface treatment 8%)
C-5: Scattered particle dispersion-TIO ₂ produced in Production Example 9 (Ishihara, S-305; particle size 250 nm; Al, Si surface treatment 12%)
C-6: Scattered particle dispersion-TIO ₂ produced in Production Example 10 (Ishihara, 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)
<Experimental example>
The viscosity and the number of continuous jettings were measured using the ink compositions produced in the above Examples and Comparative Examples, a coating layer having a thickness of 10 μm was produced, and the light conversion efficiency and the 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 on a glass substrate of 5 cm × 5 cm by an inkjet method, g, h, as an ultraviolet light source, ^{A coating layer was produced by irradiating at 1000 mJ / cm 2} using a 1 kW high-pressure mercury lamp containing all i-rays and then heating in a heating oven at 180 ° C. for 30 minutes.

Of the manufactured coating layers, the coating layer containing the quantum dots was placed on top of a blue light source (XLamp XR-E LED, Royal blue 450, Cree), and then a brightness measuring instrument (CAS140CT Spectrometer), The optical conversion efficiency was measured using Equation 1 below using an instrument system), and the results are shown in Tables 10 to 13 below.

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

(2) Viscosity The viscosity of the ink composition was measured using an R-type viscometer (VISCOMETER MODEL RE120L SYSTEM, a product of Toki Sangyo Co., Ltd.) under the conditions of a rotation speed of 20 rpm and a temperature of 25 ° C., and the results are shown in the table below. 10 to 13 are shown.

(3) Number of continuous jettings After filling the ink composition in the inkjet printing equipment of Unijet, the temperature of the jetting head is fixed at 40 ° C., the ink is ejected for 1 minute, and the jetting head is left for 30 minutes. The number of continuous jettings was evaluated by repeating the process until the ink was not discharged due to the nozzle clogging of the portion, and the results are shown in Tables 10 to 13 below.

As the number of continuous jettings increases, excellent characteristics can be obtained in the continuous process.
(4) Measurement of Adhesion of Coating Layer A cross-cut test (Cross-Cut Addition Test) according to an international standard (ASTM D3359) was carried out on a coating layer produced of the ink composition.

Using a knife (Knife), make cuts in a grid pattern while applying uniform force to the manufactured coating layer, then apply tape to the cut surface and rub it until it is completely attached, and after 30 seconds, remove the end of the tape. The tape was removed by pulling it close to an angle of 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 subjected to the conditions of a rotation speed of 20 rpm and a temperature of 30 ° C. using an R-type viscometer (VISCOMETER MODEL RE120L SYSTEM, manufactured by Toki Sangyo Co., Ltd.). , Initial viscosity and storage at room temperature for 1 month, and viscosity was measured after 2 weeks at 40 ° C. From the viscosity change rate calculated by this, the viscosity stability was evaluated according to the following evaluation criteria, and the results are shown in Tables 10 to 13 below.

<Viscosity stability evaluation criteria>
⊚: Viscosity change rate 103% or less ○: Viscosity change rate 103% excess 105% or less Δ: Viscosity change rate 105% excess 110% or less ×: Viscosity change rate 110% excess (6) Jetting erroneous impact evaluation After filling the ink compositions of 1 to 70 and Comparative Examples 1 to 25 into the inkjet printing equipment of Unijet, the temperature of the jetting head is fixed at 40 ° C., and then 30 drops of ink is ejected in a row on the substrate. Then, the viscosity at which the ejection was not performed at the designated position was confirmed, the jetting erroneous impact was evaluated according to the following evaluation criteria, and the results are shown in Tables 10 to 13.

<Jetting mis-landing evaluation criteria>
⊚: No erroneous landing ○: erroneous landing 1 droplet excess 3 drops or less △: erroneous landing 3 drops more than 5 drops

As can be confirmed from the above experimental results, Examples 1 to 90 containing a curable monomer having a specific chemical structural formula are excellent in jetting property, adhesion performance, viscosity stability and jetting mis-landing property. I was able to confirm that.

Specifically, 92 of TiO ₂ and the surface treatment component as scattering particles: 8-99: For Example 1 to 70 with TiO ₂ which is surface treated in a weight ratio range, the viscosity stability and / or jet It can be confirmed that the ting mis-landing property is further improved, and further, the content of the curable monomer of the chemical formulas 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 satisfying the content ratio, better viscosity stability and jetting mis-landing characteristics could be ensured.

Further, in the cases of Examples 31 to 33 and 35 to 38, it was confirmed that more excellent adhesion can be ensured by further containing the chemical formula 3 or the (meth) acrylate containing a hydroxide group.

On the other hand, in the cases of Comparative Examples 1 to 8, the jetting effect and the low viscosity could be obtained by containing only the monomer without containing the solvent, but the curable monomer of the chemical formula 1 and / or the chemical formula 2 of the present invention could be obtained. It was confirmed that the adhesion was significantly reduced by not including it.

Further, it was confirmed from the experimental results in Tables 10 to 13 that the jetting mis-landing property was improved when the surface-treated scattered particles were used or the curable monomer according to the present invention was used.

Claims (17)

An ink composition containing scattered particles and curable monomers.
The curable monomer contains one or more compounds selected from the group consisting of a compound having two functional groups and a compound represented by the chemical formula 2.

(In the above chemical formula 1, R ₁ is an independent hydrogen or methyl group, and m is an integer of 1 to 15.)

(In the above chemical formula 2, R ₂ is an independent hydrogen or methyl group, and m is an integer of 1 to 15.) The scattered 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, Nb ₂ O ₃ , SnO. The ink composition according to claim 1, which is one or more selected from the group consisting of, and MgO. The ink composition according to claim ₂ , wherein the scattered particles are TiO 2. The ink composition according to claim 3, wherein the TiO ₂ is surface-treated with one or more components selected from Al, Si, Zr, Zn, and an organic substance. The ink composition according to claim 4, wherein the weight ratio of the TiO _{2 to 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 quantum dots, a dispersant, a photopolymerization initiator, and an additive. The ink composition according to claim 6, wherein the quantum dots are non-cadmium-based quantum dots. The ink composition according to claim 6, wherein the quantum dots include a polyethylene glycol-based ligand layer. The ink composition according to claim 8, wherein the polyethylene glycol-based ligand layer contains one or more selected from the compounds represented by the chemical formulas 4a to 4c and the chemical formula 5a.

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

(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 independently single-bonded, substituted or unsubstituted C1-C22 alkylene groups, -O-, -NR ^e- , or -S-, respectively.
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.
^Re 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 curable monomer further contains a compound represented by the following chemical formula 3.

(In the above chemical formula 3, R ₃ is a 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. The ink composition according to claim 11, 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 the chemical formulas 1 and 2 is 5% by weight 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 produced by using the cured product of the ink composition according to any one of claims 1 to 14. The color filter including the light scattering pixel according to claim 15. An image display device including the color filter according to claim 16.