KR102153629B1 - A light conversion ink composition, a color filter manufactured by using thereof and an image display device using the same - Google Patents

Abstract

The present invention relates to a light conversion ink composition comprising quantum dots, scattering particles, a monomer, and an antioxidant, and not comprising a solvent, wherein the monomer includes a compound represented by chemical formula 1, and the antioxidant includes at least one of the compounds represented by chemical formulas 2 to 5, to a light conversion pixel comprising a cured product thereof, to a color filter comprising the light conversion pixel, and to an image display device comprising the color filter. In addition, the light conversion ink composition is with excellent flatness.

Description

A light conversion ink composition, a color filter manufactured by using the same, and an image display device including the same {A light conversion ink composition, a color filter manufactured by using thereof and an image display device using the same}

The present invention relates to a photo-conversion ink composition, a color filter, and a display device, and more particularly, a photo-conversion ink composition that has excellent optical properties and dispersibility of quantum dots without a solvent, and is capable of realizing a low viscosity, and a color formed using the same It relates to a filter and an image display apparatus including the color filter.

A color filter is a thin film-type optical component that extracts three colors of red, green, and blue from white light and enables it in a fine pixel unit, and the size of one pixel is about tens to hundreds of micrometers. Such a color filter includes a black matrix layer formed in a predetermined pattern on a transparent substrate to block light at the boundary between each pixel, and a plurality of colors (typically red (R), green (G) and a plurality of colors) to form each pixel. It has a structure in which pixel portions in which three primary colors of blue (B) are arranged in a predetermined order are sequentially stacked.

Recently, as one of the methods of implementing a color filter, a pigment dispersion method using a pigment dispersion type photosensitive resin has been applied. However, a part of the light is absorbed by the color filter while the light irradiated from the light source passes through the color filter. There is a problem in that the efficiency is deteriorated and color reproduction is deteriorated due to the characteristics of the pigment included in the color filter.

In particular, as color filters are used in various fields including various image display devices, not only excellent pattern characteristics but also high color reproduction rates and excellent high luminance and high contrast ratio performance are required. To solve this problem, quantum dots are used. A method of manufacturing a color filter using the self-luminous photosensitive resin composition including the present invention has been proposed. For example, Korean Patent Application Publication No. 10-2009-0036373 discloses that the display quality of a display device can be improved by improving luminous efficiency by replacing the existing color filter with a light emitting layer made of a quantum dot phosphor.

The photolithography method using a photosensitive resin composition including such quantum dots is a method of forming a color filter by coating, exposure, development, and curing. Although it is excellent in terms of sophistication and reproducibility of the color filter, each color is applied to each color to form a pixel. On the other hand, the processes of coating, exposure, development, and curing are each required, which increases the manufacturing process, time and cost, and increases the control factor between processes, making it difficult to manage the yield.

In order to solve these problems, an inkjet method has been proposed. This inkjet method is a technology in which liquid ink is sprayed at a predetermined position partitioned using an inkjet head to realize an image in which each ink is colored, and a plurality of colors including red, green, and blue are colored at once. So that the manufacturing process, time and cost can be greatly reduced.

Recently, as a high color gamut (color density compared to NTSC) is required in monitors and TVs, it is necessary to improve the light emission luminance of quantum dots. In order to improve the light emission luminance, there is a method of increasing the film thickness. However, as an ink composition including quantum dots and a solvent, there is a limit to thickening the film thickness. Accordingly, there is a demand for a non-solvent type ink composition containing quantum dots that does not contain a solvent.

On the other hand, when the quantum dots are prepared as a solvent-free composition, it is difficult to uniformly disperse the quantum dots, causing agglomeration of the quantum dots, resulting in a decrease in optical properties of the quantum dots or an increase in viscosity, resulting in poor jetting properties.

Accordingly, there is an urgent need to develop a photo-conversion ink composition capable of achieving excellent optical properties and dispersibility of quantum dots and realizing low viscosity without a solvent.

Republic of Korea Patent Publication No. 10-2009-0036373

An object of the present invention is to provide a photo-conversion ink composition having excellent optical properties, dispersibility and film residual rate of quantum dots without a solvent, and excellent flatness by implementing a low viscosity.

Another object of the present invention is to provide a photoconversion pixel including a cured product of the photoconversion ink composition, a color filter including the photoconversion pixel, and an image display device including the color filter.

In order to achieve the above object, the present invention is a photoconversion ink composition comprising quantum dots, scattering particles, monomers and antioxidants, and does not include a solvent, wherein the monomer comprises a compound represented by the following formula (1), and the oxidation The inhibitor provides a light conversion ink composition comprising at least one of the compounds represented by the following Chemical Formulas 2 to 5.

[Formula 1]

(In Formula 1,

A ¹ is a hydrogen atom or a methyl group,

A ² is a C1 to C20 alkylene group, a phenylene group or a C3 to C10 cycloalkylene group,

m is an integer from 1 to 15.)

[Formula 2]

(In Formula 2, R ₁ is a C1 to C10 alkylene group,

R ₂ to R ₁₃ are each independently a hydrogen atom or a C1 to C20 alkyl group.)

[Formula 3]

(In Formula 3, R ₂₁ to R ₂₉ are each independently a hydrogen atom or a C1 to C20 alkyl group.)

[Formula 4]

(In Formula 4, R ₃₁ and R ₃₂ are each independently a C1 to C10 alkylene group,

R ₃₃ to R ₃₆ are each independently a hydrogen atom or a C1 to C20 alkyl group.)

[Formula 5]

(In Formula 5, R ₄₁ , R ₄₂ , R ₄₇ and R ₄₈ are each independently a C1 to C10 alkylene group,

R ₄₃ to R ₄₆ and R ₄₉ to R ₅₂ are each independently a hydrogen atom or a C1 to C20 alkyl group.)

In addition, the present invention provides a photo-conversion pixel including a cured product of the photo-conversion ink composition.

In addition, the present invention provides a color filter including the light conversion pixel.

Further, the present invention provides an image display device including the color filter.

The photoconversion ink composition according to the present invention does not contain a solvent, contains quantum dots, and contains an antioxidant, so that wrinkles do not occur and have excellent flatness coating properties, and excellent optical properties and dispersibility of quantum dots, It provides an effect that can implement low viscosity.

In addition, the present invention provides a photoconversion pixel having excellent brightness and light retention by using the photoconversion ink composition.

Therefore, the photoconversion ink composition according to the present invention can be effectively used to manufacture a color filter by inkjet printing.

1 is a diagram showing a criterion for evaluating the degree of occurrence of wrinkles in a coating film in the present invention.

The present invention is a photoconversion ink composition comprising quantum dots, scattering particles, monomers, and antioxidants, and does not contain a solvent, wherein the monomer comprises a compound represented by Formula 1, and the antioxidant is represented by Formulas 2 to 5 A photoconversion ink composition comprising at least one of the compounds to be used, a photoconversion pixel prepared using the same, and a color filter including the photoconversion pixel, wherein the photoconversion ink composition according to the present invention comprises a solvent By not doing this, it is possible to improve the luminance and light retention of the coating film produced by using the same, wrinkles do not occur, and the film residual rate after ink jetting is excellent.

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

<Light conversion ink composition>

Quantum dots

Quantum dots included in the photo-conversion ink composition of the present invention are nano-sized semiconductor materials. Atoms form molecules, and molecules form an aggregate of small molecules called clusters to form nanoparticles. When these nanoparticles have the characteristics of semiconductors, they are called quantum dots. These quantum dots have the characteristic of releasing energy corresponding to the energy band gap by themselves when they receive energy from the outside and reach an excited state. In short, since the photoconversion ink composition of the present invention includes such quantum dots, light conversion into green light and red light through an incident blue light source is possible.

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

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; A three-element compound selected from the group consisting of SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, and mixtures thereof; And SnPbSSe, SnPbSeTe, SnPbSTe, and may be one or more selected from the group consisting of a quaternary compound selected from the group consisting of mixtures thereof.

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

The quantum dot has a homogeneous single structure; A dual structure such as a core-shell structure and a gradient structure; Or it may be a mixed structure thereof. For example, in the dual structure of the core-shell, the material forming each core and the shell may be made of the above-mentioned different semiconductor compounds. More specifically, the core may include one or more materials selected from lnP, ZnS, ZnSe, PbSe, AgInZnS, and ZnO, but is not limited thereto. The shell may include at least one material selected from ZnSe, ZnS, ZnTe, PbS, TiO, SrSe, and HgSe, but is not limited thereto.

For example, the quantum dots of the 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 may be synthesized by a wet chemical process, metal organic chemical vapor deposition (MOCVD), or molecular beam epitaxy (MBE), but is not limited thereto. .

The quantum dots may include two or more quantum dots having different central excitation wavelengths for light conversion into green light and red light using an incident blue light source. At this time, the difference between the center excitation wavelengths of two or more types of quantum dots may be 50 nm or more.

The quantum dots may be included in an amount of 1 to 40 parts by weight, preferably 2 to 35 parts by weight, more preferably 5 to 30 parts by weight, based on 100 parts by weight of the solid content of the photo-conversion ink composition.

When the quantum dots are included within the above range, there is an advantage of excellent luminous efficiency and excellent reliability of the coating layer.

Scattering particles

The light conversion ink composition according to the present invention includes scattering particles.

The scattering particles may use a conventional inorganic material, and preferably include a metal oxide having an average particle diameter of 50 to 1000 nm. The metal oxides are Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Mo, Cs, Ba, La, Hf, W, Tl, Pb, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Ti, Sb, Sn, Zr, Nb, It may be an oxide containing one metal selected from the group consisting of Ce, Ta, In, and combinations thereof, but is not limited thereto. Specifically, Al ₂ O ₃ , SiO ₂ , ZnO, ZrO ₂ , BaTiO ₃ , TiO ₂ , Ta ₂ O ₅ , Ti ₃ O ₅ , ITO, IZO, ATO, ZnO-Al, Nb ₂ O ₃ , SnO, MgO and One selected from the group consisting of a combination thereof is possible. If necessary, a material treated with a compound having an unsaturated bond such as acrylate may be used. However, when the light conversion ink composition according to the present invention includes scattering particles, it is preferable to increase the overall light efficiency in the light conversion coating layer by increasing the path of light emitted from the quantum dots through the scattering particles.

The scattering particles may have an average particle diameter of 50 to 1000 nm, and preferably those in the range of 100 to 500 nm are used. At this time, if the particle size is too small, a sufficient scattering effect of the light emitted from the quantum dot cannot be expected, whereas if the particle size is too large, it may sink in the composition or obtain a surface of a uniform quality of the self-luminous layer, so it is appropriately adjusted within the above range. And use it.

The scattering particles may be included in an amount of 0.5 to 20 parts by weight, preferably 1 to 15 parts by weight, more preferably 2 to 10 parts by weight, based on 100 parts by weight of the total solid content of the light conversion ink composition.

When the scattering particles are included within the above range, it is preferable that the effect of increasing the light emission intensity can be maximized. If the scattering particles are included within the above range, it may be somewhat difficult to secure the desired luminous intensity, and if the scattering particles exceed the above range, the transmittance of blue irradiation light may be significantly lowered, resulting in a problem in color reproducibility. It is desirable to use it properly.

Monomer

The photoconversion ink composition according to the present invention contains a monomer.

The monomer may include a compound represented by Formula 1 below.

[Formula 1]

In Formula 1, A ¹ may be a hydrogen atom or a methyl group.

In addition, in Formula 1, A ² may be a C1 to C20 alkylene group, a phenylene group, or a C3 to C10 cycloalkylene group, preferably a C1 to C20 alkylene group, more preferably a C1 to C10 alkyl It could be Rengi.

In addition, in Formula 1, m may be an integer of 1 to 15, preferably an integer of 1 to 10.

The C1 to C20 alkylene group refers to a straight-chain or branched divalent hydrocarbon consisting of 1 to 20 carbon atoms, for example methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, and the like are included, but are not limited thereto.

The C3 to C10 cycloalkylene group refers to a simple or fused cyclic divalent hydrocarbon consisting of 3 to 10 carbon atoms, and includes, for example, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, etc. It does not become.

The C1 to C20 alkylene group, phenylene group, and C3 to C10 cycloalkylene group are one or more hydrogens of a C1 to C6 alkyl group, a C2 to C6 alkenyl group, a C2 to C6 alkynyl group, a C3 to C10 Cycloalkyl group, C3 to C10 heterocycloalkyl group, C3 to C10 heterocycloalkyloxy group, C1 to C6 haloalkyl group, C1 to C6 alkoxy group, C1 to C6 thioalkoxy group, aryl group, acyl group, hydroxy group , A thio group, a halogen group, an amino group, an alkoxycarbonyl group, a carboxyl group, a carbamoyl group, a cyano group, a nitro group, and the like.

The photoconversion ink composition according to the present invention is characterized in that it is a solvent-free type that does not contain a solvent. In order to implement such a solvent-free type of ink composition, not only can the quantum dots be excellently dispersed by using a monomer containing the compound represented by Formula 1, but also the problem of lowering the jetting property caused by including a solvent and It is possible to improve the defect problem.

The monomer may be characterized by using a low-viscosity monomer having a viscosity of 3 to 50 cP, and in this case, it is more preferable because the strength and smoothness of the pixel portion can be improved.

The monomer may be included in an amount of 20 to 90 parts by weight, preferably 25 to 85 parts by weight, more preferably 30 to 80 parts by weight, based on 100 parts by weight of the total solid content of the photoconversion ink composition.

When the monomer is included within the above range, there is a desirable advantage in terms of strength and smoothness of the pixel portion. If the monomer is contained within the above range, the intensity of the pixel portion may be slightly lowered, and if the monomer is contained beyond the above range, the smoothness may be slightly lowered. Therefore, it is preferable to be included within the above range.

Antioxidant

The photo-conversion ink composition according to the present invention contains an antioxidant.

The antioxidant can effectively inhibit and prevent the reduction of luminous efficiency due to reaction of the radicals with the quantum dots by trapping radicals generated by heat during post-baking.Since the radical trapping effect is excellent, a sufficient effect can be expected even when used in a small amount. I can.

The antioxidant may include one or more of the compounds represented by the following Chemical Formulas 2 to 5.

[Formula 2]

(In Formula 2, R ₁ is a C1 to C10 alkylene group,

R ₂ to R ₁₃ are each independently a hydrogen atom or a C1 to C20 alkyl group.)

[Formula 3]

(In Formula 3, R ₂₁ to R ₂₉ are each independently a hydrogen atom or a C1 to C20 alkyl group.)

[Formula 4]

(In Formula 4, R ₃₁ and R ₃₂ are each independently a C1 to C10 alkylene group,

R ₃₃ to R ₃₆ are each independently a hydrogen atom or a C1 to C20 alkyl group.)

[Formula 5]

(In Formula 5, R ₄₁ , R ₄₂ , R ₄₇ and R ₄₈ are each independently a C1 to C10 alkylene group,

R ₄₃ to R ₄₆ and R ₄₉ to R ₅₂ are each independently a hydrogen atom or a C1 to C20 alkyl group.)

The C1 to C20 alkyl group means a straight-chain or branched monovalent hydrocarbon consisting of 1 to 20 carbon atoms, for example 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, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but are not limited thereto.

The acidic antioxidant may further include at least one selected from a phosphorus antioxidant and a sulfur antioxidant.

The phosphorus antioxidant is 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5] Can, diisodecylpentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, 2,2'-methylenebis (4,6-di-t-butyl-1- Phenyloxy)(2-ethylhexyloxy)phosphorus, 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t -Butyldibenz[d,f][1,3,2]dioxaphosphine, triphenylphosphite, diphenylisodecylphosphite, phenyldiisodecylphosphite, 4,4'-butylidene-bis (3-Methyl-6-t-butylphenylditridecyl) phosphite, octadecyl phosphite, tris(nonylphenyl) phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-) 10-oxide, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy Cy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris(2,4-di-t-butylphenyl)phosphite, cyclic neopentanetetraylbis(2, 4-di-t-butylphenyl)phosphite, cyclic neopentanetetraylbis(2,6-di-t-butylphenyl)phosphite, 2,2-methylenebis(4,6-di-t-butyl Phenyl) octylphosphite, tris(2,4-di-t-butylphenyl)phosphite, tetrakis(2,4-di-t-butylphenyl)[1,1-biphenyl]-4,4'di Ilbisphosphonite, bis[2,4-bis(1,1-dimethylethyl)-6-methylphenyl]ethyl ester, phosphonic acid, etc. are mentioned.

In terms of heat resistance and heat discoloration prevention among the phosphorus antioxidants, 2,2'-methylenebis(4,6-di-t-butyl-1-phenyloxy)(2-ethylhexyloxy)phosphorus, 3,9 -Bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane and 6-[3-( 3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenz[d,f][1,3,2]dioxaphosphepine And the like are preferred.

The sulfur-based antioxidant is 2,2-bis({[3-(dodecylthio)propionyl]oxy}methyl)-1,3-propanediyl-bis[3-(dodecylthio)propionate], 2 -Mercaptobenzimidazole, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate , Pentaerythrityl-tetrakis(3-laurylthiopropionate), 2-mercaptobenzimidazole, and the like.

In terms of heat resistance and heat discoloration prevention among the sulfur-based antioxidants, 2,2-bis({[3(dodecylthio)propionyl]oxy}methyl)-1,3-propanediyl-bis[3-(dodecylthio ) Propionate], 2-mercaptobenzimidazole, and the like are preferable.

The antioxidant may be included in an amount of 1 to 15 parts by weight, preferably 2 to 10 parts by weight, more preferably 2 to 8 parts by weight, based on 100 parts by weight of the total solid content of the photo-conversion ink composition.

When the antioxidant is included within the above range, it is advantageous in terms of solving the problem of lowering luminous efficiency. When the antioxidant is included below the above range, there is a problem in that the effect as described above, that is, the effect of suppressing the reduction in the luminous efficiency of the quantum dot after the hard bake process cannot be secured, and when it is included in the above range, thermal curing is performed. There is a problem that is not completely achieved.

Photoinitiator

The photo-conversion ink composition of the present invention may further include a photo initiator. The photoinitiator serves to initiate a radical reaction of the photoconversion ink composition, causing curing and improving sensitivity. The photoinitiator is a photoinitiator generally used in the photoconversion ink composition, and acetophenone-based, benzophenone-based, triazine-based, thioxanthone-based, oxime-based, benzoin-based, biimidazole-based compound and the like can be used.

Examples of acetophenone-based compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, and 2-hydroxy-1-[4-(2 -Hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1- One, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl[4-(1-methylvinyl)phenyl]propane-1- And oligomers of on, preferably 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one.

In addition, photoinitiators other than the acetophenone type may be used in combination. Photoinitiators other than the acetophenone type include an active radical generator, a sensitizer, and an acid generator that generate active radicals by irradiation with light.

As an active radical generator, a benzoin type compound, a benzophenone type compound, a thioxanthone type compound, a triazine type compound, etc. are mentioned, for example. Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzo isobutyl ether. As a benzophenone compound, for example, benzophenone, o-benzoyl benzoate methyl, 4-phenylzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra( t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc. are mentioned. As a thioxanthone compound, for example, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, 1-chloro- 4-propoxy oxanthone, etc. are mentioned. As a triazine-based compound, for example, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl) -6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-tri Azine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl )-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino- 2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4dimethoxyphenyl)ethenyl]-1,3,5 -Triazine, etc. are mentioned.

Examples of the active radical generator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2,-bis(o-chlorophenyl)-4,4', 5,5'-tetra Phenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene Compounds and the like can be used. Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-acetoxyphenyldimethylsulfonium p-toluenesulfonium Nate, 4-acetoxyphenylmethylbenzylsulfoniumhexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfoniumhexafluoroantimonate, diphenyliodonium p-toluenesulfonate, Onium salts, such as diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, benzointosylate, etc. are mentioned. In addition, among the above compounds as an active radical generator, some compounds that generate an acid at the same time as the active radical are used. For example, a triazine-based photoinitiator is also used as an acid generator.

The photoinitiator may be included in an amount of 0.01 to 20% by weight, preferably 0.5 to 15% by weight, based on the total weight of the solid content of the photo-conversion ink composition. When a photoinitiator is included within the above range, the pattern formation is good and the photoconversion ink composition is highly sensitive, so that the strength of the pixel portion formed using the composition and the smoothness on the surface of the pixel portion tend to be good, which is preferable. Do.

Further, in the present invention, a photopolymerization initiation aid can be used. The photopolymerization initiation aid may be used in combination with a photoinitiator, and is a compound used to accelerate polymerization of a photopolymerizable compound in which polymerization was initiated by a photoinitiator.

The photopolymerization initiation aid may preferably be one or more compounds selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group, but is not limited thereto.

Specifically, examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyl diethanolamine, and triisopropanolamine; And 4-dimethylaminobenzoic acid methyl, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid isoamyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N,N-dimethylparatoluidine, 4 , 4'-bis(dimethylamino)benzophenone (common name: Michler's ketone), 4,4'-bis(diethylamino)benzophenone, and other aromatic amine compounds can be used, among which an aromatic amine compound is used. It is desirable.

The carboxylic acid compound is preferably an aromatic heteroacetic acid, specifically phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, And chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, and the like.

Specific examples of the organic sulfur compound having a thiol group include 9-mercaptofluorene, 2-mercaptobenzothiazole, 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3- Mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropanetris (3-mercaptopropionate), pentaerythritol tetra Kiss (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercapto) Propionate) etc. are mentioned.

The photopolymerization initiation aid can be appropriately added and used within a range that does not impair the effects of the present invention.

Even if these photoinitiators are used alone or in combination of a plurality of them, there is no problem. Moreover, what is marketed can be used as a photoinitiation auxiliary agent, and as a commercially available photoinitiation auxiliary agent, a brand name "EAB-F" [manufacturer: Hodogaya Chemical Industry Co., Ltd.] etc. are mentioned, for example.

In the case of using these photopolymerization initiation aids, the amount of the photoinitiator is generally 10 mol or less, preferably 0.01 to 5 mol per 1 mol of the photoinitiator. If it is in the above range, the sensitivity of the photoconversion ink composition is further increased, and the productivity of the photoconversion pixel formed using this composition tends to be improved, which is preferable.

additive

The photoconversion ink composition according to the present invention may further include additives as needed.

The additive may include at least one selected from the group consisting of dispersants, surfactants, fillers, hardeners, and adhesion promoters.

The dispersant is added for deaggregation and stability maintenance of quantum dots and scattering particles, and may be used without limitation, which is generally used in the art. Specific examples of the dispersant include cationic, anionic, nonionic, and amphoteric And surfactants such as polyester-based and polyamine-based, and these can be used alone or in combination of two or more.

Specific examples of the cationic surfactant include amine salts or quaternary ammonium salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride.

Specific examples of the anionic surfactant include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, and Alkyl aryl sulfonates, such as sodium dodecyl naphthalene sulfonate, etc. are mentioned.

Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene/oxypropylene block copolymers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, and polyoxyethylene alkylamine.

In addition, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes and polyethyleneimines are listed. have.

In addition, the dispersant preferably includes an acrylate-based dispersant (hereinafter, an acrylate-based dispersant) including butyl methacrylate (BMA) or N,N-dimethylaminoethyl methacrylate (DMAEMA). Commercially available products of the acrylate-based dispersant include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, or DISPER BYK-2150, and the acrylate-based dispersants are used alone or in combination of two or more. I can.

In addition to the acrylate-based dispersant, the dispersant may be a resin type dispersant. As the dispersant of the other resin type, a known dispersant of a resin type, in particular, a polycarboxylic acid ester typified by polyurethane and polyacrylate, an unsaturated polyamide, a polycarboxylic acid, a (partially) amine salt of a polycarboxylic acid , Ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long chain polyaminoamide phosphate salts, esters of hydroxyl group-containing polycarboxylic acids and modified products thereof, or free carboxyl groups An oily dispersant such as an amide or a salt thereof formed by reaction of a polyester having a poly(lower alkyleneimine); Water-soluble resins or water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinyl pyrrolidone; Polyester; Modified polyacrylate; Adducts of ethylene oxide/propylene oxide; And phosphate esters.

Commercially available products of the above other resin type dispersants include cationic resin dispersants, for example, BYK Chemie's brand names: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK -164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; BASF's brand names: EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA- 4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; Trade names of Lubirzol: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10; Kawaken Fine Chemical's trade names: Hinoact T-6000, Hinoact T-7000, Hinoact T-8000; Ajinomoto's brand names: AJISPUR PB-821, Ajisper PB-822, Ajisper PB-823; Kyoeisha Chemical Co., Ltd. trade names: FLORENE DOPA-17HF, Florene DOPA-15BHF, Floren DOPA-33, Florene DOPA-44, and the like.

In addition to the above acrylate-based dispersants, other resin-type dispersants may be used alone or in combination of two or more, or may be used in combination with an acrylate-based dispersant.

The dispersant may be included in an amount of 0.1 to 5 parts by weight, preferably 0.2 to 3 parts by weight, based on 100 parts by weight of the solid content of the photo-conversion ink composition.

When the dispersant is included within the above range, it is preferable because it has excellent dispersibility of quantum dots and scattering particles and is easy to maintain low viscosity.

Specific examples of the surfactants include silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, amphoteric surfactants, and the like, and these can be used alone or in combination of two or more.

Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, In addition to polyethyleneimines, brand names are F-554 (manufactured by DIC Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyei Chemical Co., Ltd.), Ftop (manufactured by Tochem Products) , MegaPak (manufactured by Dai Nippon Ink Chemical Industry Co., Ltd.), Florade (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Saffron (above, manufactured by Asahi Glass Co., Ltd.), Sor Spas (manufactured by Geneva Co., Ltd.) ), EFKA (manufactured by EFKACHEMICALS), PB821 (manufactured by Ajinomoto Co., Ltd.), and the like.

Glass, silica, alumina, etc. may be used as the filler, and specific examples of the other polymer compounds include curable resins such as epoxy resin and maleimide resin; And thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane.

The curing agent is used to increase deep curing and mechanical strength, and specific examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound.

Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, noblock epoxy resin, other aromatic epoxy resins, alicyclic epoxy resins, Glycidyl ester resins, glycidylamine resins, or brominated derivatives of such epoxy resins, aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and brominated derivatives thereof, butadiene (co)polymer epoxides, isoprene (co ) Polymer epoxidation, glycidyl (meth)acrylate (co)polymer, triglycidyl isocyanurate, etc. are mentioned.

Specific examples of the oxetane compound in the curing agent include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane. The curing agent may be used in combination with a curing agent and a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound.

Examples of the curing auxiliary compound include polyvalent carboxylic acids, polyvalent carboxylic anhydrides, and acid generators. The carboxylic anhydrides may be commercially available as an epoxy resin curing agent. As the epoxy resin curing agent, for example, a brand name (Adeka Hadona EH-700) (manufactured by Adeka Industries Co., Ltd.), a brand name (Rikashido HH) (manufactured by Shin Nippon Ewha Corporation), and a brand name (MH-700) ( Shin Nippon Ewha Co., Ltd.) and the like. The curing agent exemplified above may be used alone or in combination of two or more.

As the adhesion promoter, a silane-based compound is preferable, and specifically, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)- 3-Aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-gly Cydoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxy Propyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, etc. are mentioned.

The above additives may be appropriately added and used by a person skilled in the art within a range that does not impair the effects of the present invention. For example, the additive may be used in an amount of 0.01 to 10 parts by weight, preferably 0.01 to 8 parts by weight, more preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the solid content of the photo-conversion ink composition, but is not limited thereto.

<Light conversion pixel and color filter>

The photoconversion pixel according to the present invention includes a cured product of the photoconversion ink composition described above. In addition, the color filter according to the present invention includes the photo-conversion pixel.

A method of forming a pattern of a photo-conversion ink composition according to the present invention includes the steps of applying the above-described photo-conversion ink composition to a predetermined area by an ink jet method and curing the applied photo-conversion ink composition.

First, the photoconversion ink composition of the present invention is injected into an inkjet sprayer and printed on a predetermined area of a substrate. The substrate is not particularly limited, and for example, a substrate having a flat surface such as a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, a polyamideimide substrate, a polyimide substrate, an Al substrate, a GaAs substrate, etc. Can be mentioned. 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 coupled device (CCD), a thin film transistor (TFT), or the like may be formed on the surface of the silicon substrate or the like. Further, a partition wall matrix may be formed.

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

The viscosity of the photoconversion ink composition of the present invention is suitably about 3 to 30 cP, and more preferably is adjusted in the range of 7 to 20 cP.

A color filter according to an embodiment of the present invention includes a colored pattern layer formed by the pattern forming method. That is, the color filter is characterized in that it includes a colored pattern layer formed by applying the above-described photo-conversion ink composition on a substrate in a predetermined pattern and then curing it. Since the configuration and manufacturing method of the color filter are well known in the art, detailed descriptions are omitted.

<Image display device>

An image display device according to the present invention includes the above-described color filter.

The color filter of the present invention is not only a conventional liquid crystal display (LCD), but also various images such as an electroluminescent display (EL), a plasma display (PDP), a field emission display (FED), and an organic light-emitting device (OLED). Applicable to display devices.

The image display device of the present invention includes a configuration known in the art, except for including the color filter described above.

Hereinafter, the present invention will be described in more detail based on Examples, but the embodiments of the present invention disclosed below are illustrative only, and the scope of the present invention is not limited to these embodiments. The scope of the present invention is indicated in the claims, and furthermore, it contains the meanings equivalent to the claims recorded and all modifications within the scope. In addition, in the following Examples and Comparative Examples, "%" and "parts" indicating content are based on mass unless otherwise noted.

Synthesis Example: Synthesis of quantum dots

Synthesis Example 1: Synthesis of quantum dot (Q-1)

Indium acetate (Indium acetate) 0.4mmol (0.058g), palmitic acid (palmitic acid) 0.6mmol (0.15g) and 1-octadecene (octadecene) 20mL was put into a reactor and heated to 120 ℃ under vacuum. After 1 hour, the atmosphere in the reactor was converted to nitrogen. After heating to 280° C., a mixed solution of tris(trimethylsilyl)phosphine (TMS3P) 0.2 mmol (58 μL) and trioctylphosphine 1.0 mL was rapidly injected and reacted for 1 minute.

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 reactor was heated to 280°C. 2 ml of the previously synthesized InP core solution was added, and then 4.8 mmol of selenium (Se/TOP) in trioctylphosphine was added, and the final mixture was reacted for 2 hours. Ethanol was added to the reaction solution quickly cooled to room temperature, and the precipitate obtained by centrifugation was filtered under reduced pressure and dried under reduced pressure to form an InP/ZnSe core-shell.

Then, 2.4 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, and then 4.8 mmol of sulfur (S/TOP) in trioctylphosphine was added, and the final mixture was reacted for 2 hours. Ethanol was added to the reaction solution rapidly cooled to room temperature, and the precipitate obtained by centrifugation was filtered under reduced pressure and dried under reduced pressure to obtain a precipitate having an InP/ZnSe/ZnS core-shell structure. The maximum emission peak of the photoluminescence spectrum of the obtained nano quantum dots was 535 nm.

5 mL of the previously obtained quantum dot solution was put into a centrifuge tube, and 20 mL of ethanol was added to precipitate. The supernatant was discarded through centrifugation, and 2 mL of chloroform was added to the precipitate to disperse the quantum dots, and 0.50 g of (2-butoxyethoxy) acetic acid was added and reacted for an hour while heating at 60° C. under a nitrogen atmosphere.

Then, 25 mL of n-hexane was added to the reaction product to precipitate the quantum dots, followed by centrifugation to obtain quantum dots (Q-1).

Preparation Example: Preparation of scattering particle dispersion and quantum dot dispersion

Preparation Example 1: Preparation of scattering particle dispersion (S-1)

TiO ₂ (Ishihara Corporation CR-63) 70.0 parts by weight as scattering particles, 4.0 parts by weight of DISPERBYK-2001 (manufactured by BYK Corporation) as a dispersant, and 26 parts by weight of low viscosity monomer 1,6-hexanediol diacrylate as a diluent A dispersion of scattering particles (S-1) was prepared by mixing and dispersing for 12 hours by a bead mill.

Preparation Example 2: Preparation of quantum dot dispersion (A-1)

47.6 parts by weight of quantum dots (Q-1), 4.8 parts by weight of DISPERBYK-2001 (manufactured by BYK) as a dispersant and 47.6 parts by weight of low viscosity monomer 1,6-hexanediol diacrylate as a diluent were mixed and heated to 60°C for 4 hours During the reaction, a quantum dot dispersion (A-1) was prepared.

Preparation Example 3: Preparation of quantum dot dispersion (A-2)

23.4 parts by weight of quantum dots (Q-1), 3.8 parts by weight of DISPERBYK-2001 (manufactured by BYK) as a dispersant and 72.8 parts by weight of PGEMA as a solvent were mixed and reacted at room temperature for 2 hours to prepare a quantum dot dispersion (A-2). .

Examples and Comparative Examples: Preparation of light conversion ink composition

Light conversion ink compositions of Examples 1 to 6 and Comparative Examples 1 to 5 were prepared using the components and contents (parts by weight) of Table 1 below.

1) Quantum dot dispersion prepared in Preparation Example 2

2) Quantum dot dispersion prepared in Preparation Example 3

3) Quantum dots synthesized in Synthesis Example 1

4) 1,6-Hexanediol diacrylate (Sigma-Aldrich, Cas No. 13048-33-4)

5) Tetra(ethylene glycol) diacrylate (Sigma-Aldrich, Cas No. 17831-71-9)

6) KAYARAD DPHA (manufactured by Nippon Kayaku)

7) DISPERBYK-2001 (Big Chemie)

8) PGMEA

9) Scattering particle dispersion prepared in Preparation Example 1

10) Irganox 1010 (BASF company)

11) Sumilizer GP (Sumitomo Chemical)

12) Irganox 1035 (BASF company)

13) Sumilizer BBM-S (Sumitomo Chemical)

14) AO-503 (Adeka Corporation)

15) 9-Mercapto fluorene (Sigma-Aldrich Cas No. 19552-08-0)

16) Irgacure-907 (BASF company)

17) DETX-S, a thioxanthone-based compound (Nippon Kayaku)

18) Disperbyk-111 (Bicchemy, phosphoric acid-based dispersant)

19) F-554 (DIC Corporation)

Experimental example

<Production of light conversion coating layer>

Each photoconversion ink composition prepared in the above Examples and Comparative Examples was applied on a 5cmХ5cm glass substrate by spin coating, and then 1000mJ/cm using a 1kW high pressure mercury lamp containing all g, h, and i lines as an ultraviolet light source. After irradiation with ² , it was heated in a heating oven at 180° C. for 30 minutes to prepare a light conversion coating layer.

Experimental Example 1: Evaluation of brightness and light retention

After placing the light conversion coating layer prepared above on the top of a blue light source (XLamp XR-E LED, Royal blue 450, Cree Company) set to 450nm wavelength and illuminance 60 mW/cm ² , it is blocked from external light and air, The luminance was measured using a luminance meter (CAS140CT Spectrometer, Instrument Systems Co., Ltd.) at regular time intervals. In addition, the light retention was measured based on the initial luminance of the luminance measured at regular time intervals, and the luminance is shown in Table 2 below, and the light retention is shown in Table 3 below.

(Unit: lx) 0 hours 2 hours 4 hours 6 hours 18 hours 42 hours 82 hours Example 1 3518 3465 3455 3423 3409 3395 3346 Example 2 3687 3643 3621 3602 3587 3576 3558 Example 3 3351 3307 3287 3267 3254 3230 3200 Example 4 3810 3768 3745 3726 3707 3696 3688 Example 5 3495 3436 3425 3408 3397 3376 3327 Example 6 3703 3655 3636 3614 3599 3588 3577 Comparative Example 1 2087 1964 1916 1837 1743 1565 1478 Comparative Example 2 3405 3354 3337 3316 3303 3279 3235 Comparative Example 3 2215 2027 2002 1956 1894 1834 1770 Comparative Example 4 3235 3183 3167 3144 3138 3106 3067 Comparative Example 5 3594 3551 3526 3501 3486 3483 3436

(Unit: lx) 0 hours 2 hours 4 hours 6 hours 18 hours 42 hours 82 hours Example 1 100.0% 98.5% 98.2% 97.3% 96.9% 96.5% 95.1% Example 2 100.0% 98.8% 98.2% 97.7% 97.3% 97.0% 96.5% Example 3 100.0% 98.7% 98.1% 97.5% 97.1% 96.4% 95.5% Example 4 100.0% 98.9% 98.3% 97.8% 97.3% 97.0% 96.8% Example 5 100.0% 98.3% 98.0% 97.5% 97.2% 96.6% 95.2% Example 6 100.0% 98.7% 98.2% 97.6% 97.2% 96.9% 96.6% Comparative Example 1 100.0% 94.1% 91.8% 88.0% 83.5% 75.0% 70.8% Comparative Example 2 100.0% 98.5% 98.0% 97.4% 97.0% 96.3% 95.0% Comparative Example 3 100.0% 91.5% 90.4% 88.3% 85.5% 82.8% 79.9% Comparative Example 4 100.0% 98.4% 97.9% 97.2% 97.0% 96.0% 94.8% Comparative Example 5 100.0% 98.8% 98.1% 97.4% 97.0% 96.9% 95.6%

Experimental Example 2: Evaluation of coating film wrinkles

It was evaluated whether wrinkles occurred in the upper coating film of the light conversion coating layer prepared above. 1 is a diagram showing a criterion for evaluating whether the coating film is wrinkled. The wrinkles occurring on the coating film after exposure were observed with the naked eye to determine whether wrinkles occurred or not as'strong, weak or absent', and the results are shown in Table 4 below.

Experimental Example 3: Evaluation of residual film rate after ink jetting

Each of the photo-conversion ink compositions prepared in Examples and Comparative Examples was ink-jetted on a 15 µm partition wall and then cured by irradiating light with the photo-conversion coating layer, and the film thickness was first evaluated. Then, the film thickness was compared after heating in a heating oven at 180° C. for 30 minutes. At this time, the film thickness was measured using an inkjet drop analyzer (UJ 2400C, Unijet). The results are shown in Table 4 below.

Experimental Example 4: Viscosity Measurement

The viscosity of the photoconversion ink composition was measured using an R-type viscometer (VISCOMETER MODEL RE120L SYSTEM, manufactured by Toki Sangyo Corporation) at a rotational speed of 20 rpm and a temperature of 30°C. The results are shown in Table 4 below.

Experimental Example 5: Evaluation of flatness (film level difference) after ink jetting

Each of the photo-conversion ink compositions prepared in Examples and Comparative Examples was ink-jetted on a 15 µm partition wall, and then cured by irradiating light with the photo-conversion coating layer, followed by heating in a heating oven at 180° C. for 30 minutes to form a coating film. I did.

The film level difference between the thickest portion and the thinnest portion of the coating film was measured using a stylus profiler. However, when measuring the film thickness, the end part of the film, that is, the part in contact with the glass was excluded. The results are shown in Table 4 below.

wrinkle Film thickness change Viscosity
(mPa·s) Membrane level difference (㎛) After jetting After exposure-PoB Example 1 about 100% 94% 18 2.4 Example 2 about 100% 93% 18.5 2.25 Example 3 none 100% 94% 17.8 2.38 Example 4 none 100% 91% 15 2.3 Example 5 none 100% 90% 19 2.53 Example 6 none 100% 91% 20 2.11 Comparative Example 1 River 100% 95% 14 2.34 Comparative Example 2 about 100% 37% 3 2.31 Comparative Example 3 River 100% 39% 3 2.25 Comparative Example 4 none 100% 81% 16 2.41 Comparative Example 5 none 100% 96% Not measurable 5.5

Referring to Table 4, it can be seen that the light conversion ink compositions according to Examples 1 to 6 of the present invention exhibit excellent effects in luminance, light retention, coating wrinkles, residual film ratio after ink jetting, and flatness evaluation. .

On the other hand, in the case of the photoconversion ink compositions according to Comparative Examples 1 and 3 that do not contain an antioxidant, it can be confirmed that the luminance and light retention rate are lowered, and the wrinkles of the coating film are strongly generated, and a solvent is included in place of the monomer. In the case of Comparative Examples 2 and 3, it can be seen that the residual film rate is very low after ink jetting.

In addition, in the case of the photo-conversion ink composition according to Comparative Example 4 containing an antioxidant that does not correspond to the antioxidant of Formulas 2 to 5 of the present invention, it can be confirmed that the improvement of the residual film rate after ink jetting is insufficient.

Further, in the case of the photo-conversion ink composition according to Comparative Example 5 including a monomer not corresponding to the compound represented by Formula 1, it can be confirmed that the viscosity cannot be measured, and the flatness of the pixel after ink jetting is poor. That is, since the photo-conversion ink composition according to Comparative Example 5 containing a monomer having a viscosity of 50 cps or more has a too high viscosity, the difference in height of the coating film thickness is large when the coating film is manufactured by the ink jetting method, and thus overall pixel flatness is poor. It can be confirmed.

Therefore, the photoconversion ink composition according to the present invention does not contain a solvent, contains quantum dots as a colorant, and contains an antioxidant together, so that it can have a coating film property that does not cause wrinkles, and optical properties and dispersibility of quantum dots This excellent, low-viscosity implementation can provide an effect possible.

Claims (11)

As a photoconversion ink composition containing quantum dots, scattering particles, monomers, and antioxidants, and not containing a solvent,
The monomer is a low viscosity monomer having a viscosity of 3 to 50 cP, and includes a compound represented by the following formula (1),
The antioxidant is a photoconversion ink composition comprising at least one of the compounds represented by the following formulas 2 to 5.
[Formula 1]

(In Formula 1,
A ¹ is a hydrogen atom or a methyl group,
A ² is a C1 to C20 alkylene group, a phenylene group or a C3 to C10 cycloalkylene group,
m is an integer from 1 to 15.)
[Formula 2]

(In Formula 2, R ₁ is a C1 to C10 alkylene group,
R ₂ to R ₁₃ are each independently a hydrogen atom or a C1 to C20 alkyl group.)
[Formula 3]

(In Formula 3, R ₂₁ to R ₂₉ are each independently a hydrogen atom or a C1 to C20 alkyl group.)
[Formula 4]

(In Formula 4, R ₃₁ and R ₃₂ are each independently a C1 to C10 alkylene group,
R ₃₃ to R ₃₆ are each independently a hydrogen atom or a C1 to C20 alkyl group.)
[Formula 5]

(In Formula 5, R ₄₁ , R ₄₂ , R ₄₇ and R ₄₈ are each independently a C1 to C10 alkylene group,
R ₄₃ to R ₄₆ and R ₄₉ to R ₅₂ are each independently a hydrogen atom or a C1 to C20 alkyl group.)
The method according to claim 1,
The quantum dot is a photoconversion ink composition, characterized in that the non-cadmium-based.
The method according to claim 2,
The photoconversion ink composition, wherein the non-cadmium-based quantum dots include two or more types of quantum dots having an InP core.
The method according to claim 2,
The quantum dots include a core comprising at least one material selected from InP, ZnS, ZnSe, PbSe, AgInZnS and ZnO; And a shell comprising at least one material selected from ZnSe, ZnS, ZnTe, PbS, TiO, SrSe, and HgSe.
The method according to claim 1,
The quantum dot is a photoconversion ink composition, characterized in that the central excitation wavelength comprises two or more kinds of quantum dots having a difference of 50 nm or more from each other.
The method according to claim 1,
The scattering particles are Al ₂ O ₃ , SiO ₂ , ZnO, ZrO ₂ , BaTiO ₃ , TiO ₂ , Ta ₂ O ₅ , Ti ₃ O ₅ , ITO, IZO, ATO, ZnO-Al, Nb ₂ O ₃ , SnO, A photoconversion ink composition comprising at least one selected from the group consisting of MgO and combinations thereof.
The method according to claim 1,
Based on 100 parts by weight of the solid content of the photo-conversion ink composition,
1 to 40 parts by weight of the quantum dots,
0.5 to 20 parts by weight of the scattering particles,
20 to 90 parts by weight of the monomer and
A photoconversion ink composition comprising 1 to 15 parts by weight of the antioxidant.
The method according to claim 1,
The photo-conversion ink composition is a photo-conversion ink composition for improving wrinkles of a coating film formed by using the same.
A photoconversion pixel comprising a cured product of the photoconversion ink composition according to any one of claims 1 to 8.
A color filter comprising the photoconversion pixel according to claim 9.
An image display device comprising the color filter according to claim 10.

Images