KR102519941B1 - Light Conversion Resin Composition, Light Conversion Sheet and Display Device - Google Patents

Abstract

The present invention provides a light conversion resin composition comprising quantum dots and a curable resin, wherein the quantum dots have a ligand layer containing a thiocarboxylic acid compound on the surface, and the curable resin comprises a cardo-based resin. do. The light conversion resin composition according to the present invention can be effectively applied to the manufacture of a light conversion sheet that realizes white light with excellent light reliability and high color reproducibility by ensuring sufficient stability of quantum dots.

Description

Light conversion resin composition, light conversion sheet and image display device {Light Conversion Resin Composition, Light Conversion Sheet and Display Device}

The present invention relates to a photoconversion resin composition, a photoconversion sheet, and an image display device, and more particularly, to a photoconversion resin composition having excellent optical reliability by ensuring the stability of quantum dots, a photoconversion sheet formed using the same, and the photoconversion It relates to an image display device having a sheet.

A non-emissive display device such as a liquid crystal display implements an image based on the principle of allowing external light to pass through a display panel including a color filter. At this time, the external light means light supplied from the backlight unit (BLU), and cold cathode fluorescent lamps (CCFLs) and flat fluorescent lamps (FFLs) have been mainly used as light sources. Recently, it has many advantages such as excellent color reproducibility, lifespan of more than 50,000 hours and low power consumption, and is being replaced by light emitting diode (LED), which is recognized as an environmentally friendly light source because it does not use mercury. .

As an example of a plan to increase the color reproducibility of a recent liquid crystal display device, a liquid crystal display using a blue LED instead of a normal white LED and having a light conversion sheet including quantum dots as a separate light conversion means. A device has been proposed [see Korean Patent Publication No. 2014-0056490].

The light conversion sheet functions to implement white light with a high color gamut by including a light conversion layer in which red quantum dots or green quantum dots are dispersed in a resin having a refractive index. . The white light having a high color reproducibility refers to light in which light wavelengths corresponding to red, green, and blue light are sufficiently included.

On the other hand, quantum dots are usually prepared by a wet chemical process, and organic ligands such as oleic acid are generally used to impart stability to the produced quantum dots [Refer to Korean Patent Registration No. 10-1447238].

However, when a light conversion resin composition is prepared by mixing quantum dots containing an organic ligand such as oleic acid with a curable resin in order to apply them to a light conversion sheet, the stability of the quantum dots deteriorates, resulting in a decrease in optical properties, resulting in a decrease in color gamut. There is a problem in that it is difficult to implement high white light.

Therefore, there is a demand for development of a light conversion resin composition having sufficient stability of quantum dots and excellent light reliability.

Republic of Korea Patent Publication No. 2014-0056490 Republic of Korea Patent No. 10-1447238

One object of the present invention is to provide a light conversion resin composition having excellent optical reliability by ensuring sufficient stability of quantum dots.

Another object of the present invention is to provide a light conversion sheet formed using the light conversion resin composition.

Another object of the present invention is to provide an image display device having the light conversion sheet.

On the other hand, the present invention is a light conversion resin composition comprising quantum dots and a curable resin, wherein the quantum dots have a ligand layer including a thiocarboxylic acid compound of Formula 1 on the surface, and the curable resin includes a cardo-based resin. It provides a light conversion resin composition that does.

[Formula 1]

In the above formula,

R ^a is a C ₁ -C ₃ alkylene group;

R ^b is a C ₄ -C ₂₂ alkyl group or a C ₄ -C ₂₂ alkenyl group.

In one embodiment of the present invention, the thiocarboxylic acid compound of Chemical Formula 1 may be a compound represented by any one of Chemical Formulas 2 to 5 below.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In the above formula,

R ^b is a C ₄ -C ₂₂ alkyl group or a C ₄ -C ₂₂ alkenyl group.

In one embodiment of the present invention, R ^b may be a C ₁₀ -C ₁₄ alkyl group or a C ₁₀ -C ₁₄ alkenyl group.

In one embodiment of the present invention, the thiocarboxylic acid compound of Chemical Formula 1 may be a compound represented by any one of Chemical Formulas 6 to 9 below.

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

In one embodiment of the present invention, the quantum dot has a core-shell structure including a core and a shell covering the core, and the core is InP, InZnP, InGaP, CdSe, CdS, CdTe, ZnS, ZnSe, ZnTe, CdSeTe, CdZnS, CdSeS, PbSe, PbS, PbTe, AgInZnS, HgS, HgSe, HgTe, GaN, GaP, GaAs, InGaN InAs, and ZnO, wherein the shell includes ZnS, ZnSe, ZnTe, ZnO, CdS, CdSe , CdTe, CdO, InP, InS, GaP, GaN, GaO, InZnP, InGaP, InGaN, InZnSCdSe, PbS, TiO, may include one or more of SrSe and HgSe.

In one embodiment of the present invention, the quantum dot includes a first quantum dot and a second quantum dot having different central emission wavelengths (λmax), and the difference between the central emission wavelengths of the first quantum dot and the second quantum dot may be 60 nm or more.

In one embodiment of the present invention, the cardo-based resin may include at least one repeating unit of Formulas 10 to 15 below.

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

In the above formula,

,

,

,

,

,

,

,

,

,

,

,

또는

이고,X and X' are each independently a single bond, -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-,

,

,

,

,

,

,

,

,

,

,

,

or

ego,

Y is an acid anhydride residue,

Z is an acid dianhydride moiety;

R''' is a hydrogen atom, an ethyl group, a phenyl group, -C ₂ H ₄ Cl, -C ₂ H ₄ OH or -CH ₂ CH=CH ₂ ;

R1, R1', R2, R2', R3, R3', R4, R4', R5, R5', R6 and R6' are each independently a hydrogen atom or a methyl group;

R7, R7', R8 and R8' are each independently a C ₁ -C ₆ alkylene group, and the alkylene group is interposed with or without at least one of an ester bond, a C ₆ -C ₁₄ cycloalkylene group and an arylene group, ,

R9, R9', R10, R10', R11, R11', R12 and R12' are each independently a hydrogen atom, a halogen atom or a C ₁ -C ₆ alkyl group,

m and n are each independently an integer from 1 to 30;

,

,

,

또는

이고,P is each independently

,

,

,

or

ego,

R13 and R14 are each independently a hydrogen atom, a hydroxyl group, a thiol group, an amino group, a nitro group or a halogen atom;

Ar1 is each independently an aryl group,

Y' is an acid anhydride residue,

Z' is an acid dianhydride moiety;

A is O, S, NR''', Si(R''') ₂ or Se;

a and b are each independently an integer from 1 to 6,

p and q are each independently an integer of 1 to 30;

In one embodiment of the present invention, the acid anhydrides are maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride and methyl anhydride. It may be selected from the group consisting of tetrahydrophthalic acid.

In one embodiment of the present invention, the acid dianhydride may be selected from the group consisting of pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and biphenylethertetracarboxylic dianhydride.

In one embodiment of the present invention, the light conversion resin composition may further include a thermosetting agent.

In one embodiment of the present invention, the heat curing agent may include a thiol compound represented by Formula 16 below.

[Formula 16]

In the above formula,

R ^s is hydrogen or a C ₁ -C ₁₂ alkyl group;

R ^p is a C ₁ -C ₁₂ alkylene group,

R ^q is a t-valent aliphatic hydrocarbon group with or without a hetero atom;

t is an integer from 2 to 4.

In one embodiment of the present invention, R ^q may be trivalent trimethylpropane, divalent n-butane, tetravalent tetramethylmethane or trivalent triethylisocyanurate.

In one embodiment of the present invention, the thiol compound of Formula 16 may be a compound represented by any one of Formulas 17 to 24 below.

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

[Formula 22]

[Formula 23]

[Formula 24]

On the other hand, the present invention provides a light conversion sheet formed using the light conversion resin composition.

On the other hand, the present invention provides an image display device characterized in that the light conversion sheet is provided.

The light conversion resin composition according to the present invention can be effectively applied to the manufacture of a light conversion sheet that realizes white light with excellent light reliability and high color reproducibility by ensuring sufficient stability of quantum dots.

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

One embodiment of the present invention relates to a light conversion resin composition including a quantum dot (A) and a curable resin (B).

quantum dot (A)

In one embodiment of the present invention, the quantum dot has a ligand layer containing a thiocarboxylic acid compound of Formula 1 on the surface.

[Formula 1]

In the above formula,

R ^a is a C ₁ -C ₃ alkylene group;

R ^b is a C ₄ -C ₂₂ alkyl group or a C ₄ -C ₂₂ alkenyl group.

As used herein, the C ₁ -C ₃ alkylene group refers to a straight-chain or branched divalent hydrocarbon having 1 to 3 carbon atoms, and includes, for example, methylene, ethylene, n-propylene, i-propylene, etc. but is not limited thereto.

As used herein, the C ₄ -C ₂₂ alkyl group refers to a straight-chain or branched hydrocarbon having 4 to 22 carbon atoms, and examples thereof include n-butyl, i-butyl, t-butyl, pentyl, hexyl, and heptyl. , octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosanil, docosanil, and the like.

As used herein, the C ₄ -C ₂₂ alkenyl group refers to a straight-chain or branched unsaturated hydrocarbon having 4 to 22 carbon atoms and having at least one carbon-carbon double bond, for example, butenyl, pentenyl, hex cenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicocenyl , dococenyl, and the like, but are not limited thereto.

In one embodiment of the present invention, the thiocarboxylic acid compound of Chemical Formula 1 may be a compound represented by any one of Chemical Formulas 2 to 5 below.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In the above formula,

R ^b is a C ₄ -C ₂₂ alkyl group or a C ₄ -C ₂₂ alkenyl group.

In one embodiment of the present invention, R ^b may be a C ₁₀ -C ₁₄ alkyl group or a C ₁₀ -C ₁₄ alkenyl group.

In one embodiment of the present invention, the thiocarboxylic acid compound of Chemical Formula 1 may be a compound represented by any one of Chemical Formulas 6 to 9 below.

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

In one embodiment of the present invention, the thiocarboxylic acid compound of Chemical Formula 1 may play a role of stabilizing the quantum dot by being coordinated to the surface of the quantum dot as an organic ligand. Since the thiocarboxylic acid compound of Chemical Formula 1 has both a carboxylic acid and a mercapto (sulfur) group as polar functional groups, and has better binding force with quantum dots than oleic acid, even after the light conversion resin composition containing these quantum dots is coated on a substrate Excellent light-emitting properties and excellent photostability can be obtained in a high-temperature, high-humidity environment.

The thiocarboxylic acid compound of Chemical Formula 1 may cover 5% or more of the total surface area of the quantum dots.

In this case, the content of the thiocarboxylic acid compound of Chemical Formula 1 may be 0.1 to 10 moles per mole of the quantum dots.

The ligand layer including the thiocarboxylic acid compound of Chemical Formula 1 may have a thickness of 0.1 nm to 2 nm, for example, 0.5 nm to 1.5 nm.

In one embodiment of the present invention, the quantum dot may refer to a nano-sized semiconductor material. Atoms form molecules, and molecules form a collection of small molecules called clusters to form nanoparticles. When these nanoparticles have semiconductor properties, they are called quantum dots. When the quantum dot reaches an excited state by receiving energy from the outside, energy is emitted according to an energy bandgap corresponding to the quantum dot itself. Accordingly, the photoconversion resin composition of the present invention includes such quantum dots, so that light conversion into green and red light is possible through incident blue light.

The quantum dot is not particularly limited as long as it is a quantum dot particle capable of emitting light when stimulated by light or electricity. For example, II-VI group semiconductor compounds; Group III-V semiconductor compounds; Group IV-VI semiconductor compounds; Group IV elements or compounds containing them; And it may be selected from the group consisting of combinations thereof, which may be used alone or in combination of two or more.

Specifically, the II-VI group semiconductor compound is a binary element compound selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, and mixtures thereof; CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, and mixtures thereof; and CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, and a quaternary compound selected from the group consisting of mixtures thereof, but is not limited thereto.

The group III-V semiconductor compound is a binary element 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 it may be selected from the group consisting of quaternary compounds selected from the group consisting of GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, and mixtures thereof. It is not limited.

The group IV-VI semiconductor compound is a binary element compound selected from the group consisting of SnS, SnSe, SnTe, PbS, PbSe, PbTe, and mixtures thereof; a ternary 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 at least one selected from the group consisting of quaternary compounds selected from the group consisting of mixtures thereof, but is not limited thereto either.

Although not limited thereto, the group IV element or a compound containing the same may be an element selected from the group consisting of Si, Ge, and mixtures thereof; And it may be selected from the group consisting of a binary element compound selected from the group consisting of SiC, SiGe, and mixtures thereof.

The quantum dot has a homogeneous unitary structure; dual structures such as core-shell and gradient structures; or a mixture thereof. Preferably, the quantum dots may have a core-shell structure including a core and a shell covering the core.

Specifically, in the core-shell dual structure, materials constituting the respective cores and shells may be formed of different semiconductor compounds mentioned above. For example, the core may include InP, InZnP, InGaP, CdSe, CdS, CdTe, ZnS, ZnSe, ZnTe, CdSeTe, CdZnS, CdSeS, PbSe, PbS, PbTe, AgInZnS, HgS, HgSe, HgTe, GaN, GaP, GaAs, InGaN It includes at least one of InAs and ZnO, and the shell is ZnS, ZnSe, ZnTe, ZnO, CdS, CdSe, CdTe, CdO, InP, InS, GaP, GaN, GaO, InZnP, InGaP, InGaN, InZnSCdSe, PbS, It may include one or more of TiO, SrSe, and HgSe, but is not limited thereto.

The quantum dots may be synthesized by a wet chemical process, a metal organic chemical vapor deposition (MOCVD) process, or a molecular beam epitaxy (MBE) process, but are not limited thereto. , Preferably, it is possible to obtain quantum dots having excellent optical properties when synthesized by a wet chemical process.

The wet chemical process is a method of growing particles by putting a precursor material in an organic solvent. When the crystal grows, the organic solvent is naturally coordinated on the surface of the quantum dot crystal and acts as a dispersant to control the growth of the crystal, so it is easier and cheaper than vapor deposition methods such as organometallic chemical vapor deposition or molecular beam epitaxy to produce nano Since the growth of the particles can be controlled, it is preferred to prepare the quantum dots using the wet chemical process.

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

In one embodiment of the present invention, the oleic acid used in the manufacturing process of the quantum dots is replaced by the thiocarboxylic acid compound of Formula 1 by a ligand exchange method.

In the ligand exchange, an organic ligand to be exchanged, that is, a thiocarboxylic acid compound of Formula 1 is added to a dispersion containing quantum dots having an original organic ligand, that is, oleic acid, and stirred at room temperature to 200° C. for 30 minutes to 3 hours. It can be carried out by obtaining a quantum dot to which the thiocarboxylic acid compound of Formula 1 is bonded. If necessary, a process of separating and purifying the quantum dots to which the thiocarboxylic acid compound of Formula 1 is bonded may be additionally performed.

As described above, the quantum dot according to an embodiment of the present invention can be produced by an organic ligand exchange method under a simple stirring process at room temperature, and thus has the advantage of being mass-produced.

In addition, the quantum dot according to an embodiment of the present invention can maintain a quantum efficiency of 80% or more compared to the initial quantum efficiency even after 10 days, so that it can be stably stored for a long period of time and commercialized for various purposes.

The quantum dots may include two or more types having different central emission wavelengths. Specifically, the quantum dot may include a first quantum dot and a second quantum dot having different central emission wavelengths (λmax). At this time, the difference between the central emission wavelengths of the first quantum dots and the second quantum dots may be 50 nm or more, preferably 60 nm or more, and more preferably 70 nm or more.

For example, the quantum dots may include a green first quantum dot having a central emission wavelength of 510 nm to 550 nm and a red second quantum dot having a central emission wavelength of 610 nm to 650 nm. If the central emission wavelength of the first quantum dot is less than 510 nm or exceeds 550 nm, the green expression of the image display device may be insufficient, and if the central emission wavelength of the second quantum dot is less than 610 nm or exceeds 650 nm, image display Red expression of the device may be insufficient, and accordingly, a problem of poor color reproducibility may be caused.

The green first quantum dot having a central emission wavelength of 510 nm to 550 nm and the red second quantum dot having a central emission wavelength of 610 nm to 650 nm may respectively implement green light emission and red light emission by incident blue light.

The quantum dots may be included in an amount of 1 to 60% by weight, preferably 2 to 50% by weight, based on 100% by weight of the total solid content in the light conversion resin composition. When the content of the quantum dots is within the above range, there are advantages in that the luminous efficiency is excellent and the reliability of the light conversion layer is excellent. If the content of the quantum dots is less than 1% by weight, light conversion efficiency may be insufficient, and if it exceeds 60% by weight, relatively blue light may not reach the top of the coating film, and light emitting properties may be deteriorated.

Curable Resin (B)

In one embodiment of the present invention, the curable resin (B) has reactivity by the action of light or heat, and acts as a dispersion medium for quantum dots and a binder resin.

The curable resin (B) includes a cardo-based resin. The cardo-based resin is not limited as long as it can be used as a support for the light conversion layer, but may preferably include at least one repeating unit of Chemical Formulas 10 to 15 below.

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

In the above formula,

,

,

,

,

,

,

,

,

,

,

,

또는

이고,X and X' are each independently a single bond, -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-,

,

,

,

,

,

,

,

,

,

,

,

or

ego,

Y is an acid anhydride residue,

Z is an acid dianhydride moiety;

R''' is a hydrogen atom, an ethyl group, a phenyl group, -C ₂ H ₄ Cl, -C ₂ H ₄ OH or -CH ₂ CH=CH ₂ ;

R1, R1', R2, R2', R3, R3', R4, R4', R5, R5', R6 and R6' are each independently a hydrogen atom or a methyl group;

R7, R7', R8 and R8' are each independently a C ₁ -C ₆ alkylene group, and the alkylene group is interposed with or without at least one of an ester bond, a C ₆ -C ₁₄ cycloalkylene group and an arylene group, ,

R9, R9', R10, R10', R11, R11', R12 and R12' are each independently a hydrogen atom, a halogen atom or a C ₁ -C ₆ alkyl group,

m and n are each independently an integer from 1 to 30;

,

,

,

또는

이고,P is each independently

,

,

,

or

ego,

R13 and R14 are each independently a hydrogen atom, a hydroxyl group, a thiol group, an amino group, a nitro group or a halogen atom;

Ar1 is each independently an aryl group,

Y' is an acid anhydride residue,

Z' is an acid dianhydride moiety;

A is O, S, NR''', Si(R''') ₂ or Se;

a and b are each independently an integer from 1 to 6,

p and q are each independently an integer of 1 to 30;

As used herein, the C ₁ -C ₆ alkylene group refers to a straight-chain or branched divalent hydrocarbon having 1 to 6 carbon atoms, and includes, for example, methylene, ethylene, propylene, butylene, etc., but is limited thereto. it is not going to be

As used herein, the C ₆ -C ₁₄ cycloalkylene group refers to a simple or fused cyclic divalent hydrocarbon having 6 to 14 carbon atoms, and examples thereof include cyclohexylene, cycloheptylene, and cyclooctylene. but is not limited thereto.

The arylene group used herein includes both divalent aromatic groups, heteroaromatic groups, and partially reduced derivatives thereof. The aromatic group is a 5- to 15-membered simple or fused ring, and the heteroaromatic group refers to an aromatic group containing at least one oxygen, sulfur, or nitrogen. Examples of representative arylene groups include phenylene, naphthylene, pyridinylene, furanylene, thiophenylene, indolylene, quinolinylene, imidazolinylene ( imidazolinylene), oxazolylene, thiazolylene, tetrahydronaphthylene, etc., but are not limited thereto.

As used herein, the C ₁ -C ₆ alkyl group refers to a straight-chain or branched monovalent hydrocarbon having 1 to 6 carbon atoms, and examples thereof include methyl, ethyl, n-propyl, i-propyl, and n-butyl. , i-butyl, t-butyl, n-pentyl, n-hexyl, and the like, but are not limited thereto.

Aryl groups as used herein include both aromatic groups, heteroaromatic groups, and partially reduced derivatives thereof. The aromatic group is a 5- to 15-membered simple or fused ring, and the heteroaromatic group refers to an aromatic group containing at least one oxygen, sulfur, or nitrogen. Representative examples of aryl groups include phenyl, naphthyl, pyridinyl, furanyl, thiophenyl, indolyl, quinolinyl, imidazolinyl, oxazolyl, thiazolyl, tetrahydronaphthyl, etc., but are not limited thereto.

The acid anhydride residue used herein may be obtained by reacting a bisphenol epoxy acrylate compound, which is a synthetic intermediate of the cardo-based resin of the present invention, with an acid anhydride. The acid anhydride into which the acid anhydride residue can be introduced is not particularly limited, and examples thereof include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylendomethylenetetrahydrophthalic anhydride. , chlorendic acid anhydride, methyltetrahydrophthalic anhydride, and the like. These acid anhydrides may be used alone or in combination of two or more.

The acid dianhydride residue used herein can be obtained by reacting acid dianhydride with a bisphenol epoxy acrylate compound, which is a synthesis intermediate of the cardo-based resin of the present invention. The acid dianhydride capable of introducing an acid dianhydride residue is not particularly limited, and examples thereof include pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and biphenylethertetracar. A boxylic acid dianhydride etc. are mentioned. These acid dianhydrides may be used alone or in combination of two or more.

In the present specification, the acid dianhydride refers to a compound containing two acid anhydride groups in a molecule.

The light conversion resin composition according to the present invention includes a cardo-based resin including at least one repeating unit of Formulas 10 to 15, so that reliability between processes is improved and outgas generation is minimized so that afterimages do not occur during panel operation. It has the advantage of being able to impart high-quality image quality, excellent heat resistance, chemical resistance, durability and reliability with excellent antireflection effect.

The method for producing the cardo-based resin is not particularly limited. For example, the cardo-based resin is synthesized by reacting a bisphenol compound and an epoxy compound to synthesize a bisphenol epoxy compound, reacting the synthesized bisphenol epoxy compound with an acrylate compound to synthesize a bisphenol epoxy acrylate compound, and then synthesizing a bisphenol epoxy acrylate compound It can be prepared by reacting with an acid anhydride, an acid dianhydride or a mixture thereof.

The light conversion resin composition according to the present invention may further mix and use an acrylic resin in addition to the cardo-based resin as a curable resin.

Examples of the acrylic resin include a carboxyl group-containing monomer and a copolymer with another monomer copolymerizable therewith.

Examples of the carboxyl group-containing monomer include unsaturated carboxylic acids such as unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated polycarboxylic acids having two or more carboxyl groups in a molecule such as unsaturated tricarboxylic acids. can be heard Here, examples of unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid. As unsaturated dicarboxylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid etc. are mentioned, for example. An acid anhydride may be sufficient as an unsaturated polyhydric carboxylic acid, and maleic acid anhydride, itaconic acid anhydride, a citraconic acid anhydride, etc. are mentioned specifically. In addition, the unsaturated polyhydric carboxylic acid may be its mono(2-methacryloyloxyalkyl) ester, for example, mono(2-methacryloyloxyethyl) succinate, mono(2-methacryloyloxyethyl) succinate ), phthalic acid mono(2-acryloyloxyethyl), phthalic acid mono(2-methacryloyloxyethyl), and the like. The unsaturated polyhydric carboxylic acid may be a mono(meth)acrylate of a dicarboxylic polymer at both terminals thereof, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. . These carboxyl group-containing monomers can be used individually or in mixture of 2 or more types, respectively.

Examples of other monomers copolymerizable with the carboxyl group-containing monomer include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, and m-methoxystyrene. Toxy styrene, p-methoxy styrene, o-vinylbenzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p- Aromatic vinyl compounds, such as vinyl benzyl glycidyl ether and indene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxy Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxy hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate Rate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl meth acrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxy diethylene glycol acrylate, methoxy diethylene glycol methacrylate, methoxy triethylene glycol acrylate, methoxy triethylene glycol methacrylate Rate, methoxy propylene glycol acrylate, methoxy propylene glycol methacrylate, methoxy dipropylene glycol acrylate, methoxy dipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl Acrylate, dicyclopentadienyl methacrylate, adamantyl (meth)acrylate, norbornyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3- unsaturated carboxylic acid esters such as phenoxypropyl methacrylate, glycerol monoacrylate, and glycerol monomethacrylate; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethyl Unsaturated carboxyl such as aminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate, etc. acid aminoalkyl esters; unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and vinylidene cyanide; unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethyl acrylamide, and N-2-hydroxyethyl methacrylamide; Maleimide, benzylmaleimide, N-phenylmaleimide. unsaturated imides such as N-cyclohexylmaleimide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; and polystyrene, polymethylacrylate, polymethylmethacrylate, poly-n-butylacrylate, poly-n-butylmethacrylate, and a monoacryloyl group or monomethacryloyl group at the end of the polymer molecular chain of polysiloxane. The macromonomers which have, etc. are mentioned. These monomers can be used individually or in mixture of 2 or more types, respectively.

The weight average molecular weight in terms of polystyrene (hereinafter simply referred to as 'weight average molecular weight') measured by gel permeation chromatography (GPC; using tetrahydrofuran as an elution solvent) of the curable resin is 2,000 g/mol to 200,000 g/mol. , preferably from 3,000 g/mol to 100,000 g/mol. When the weight average molecular weight is within the above range, the hardness of the coating is improved, and deterioration of light emitting characteristics of the quantum dots due to external environments can be prevented, which is preferable.

The molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) of the curable resin is preferably from 1.0 to 6.0, and more preferably from 1.5 to 6.0. A molecular weight distribution of 1.5 to 6.0 is preferable because reliability is excellent.

The curable resin (B) may be included in an amount of 40 to 99% by weight, preferably 50 to 98% by weight, based on 100% by weight of the total solid content in the light conversion resin composition. When the content of the curable resin is within the above range, the formation of a light conversion layer and the protective properties of quantum dots are good, which is advantageous in improving light emitting properties and reliability. When the content of the curable resin is less than 40% by weight, the reliability of the light conversion layer may deteriorate, and when it exceeds 99% by weight, light emitting properties may not be sufficient.

When the curable resin further includes an acrylic resin in addition to the cardo-based resin, the acrylic resin may be used in an amount of 10 to 800 parts by weight, preferably 15 to 600 parts by weight, based on 100 parts by weight of the cardo-based resin. When used in the above range, it is advantageous in terms of improving heat resistance and luminance.

heat curing agent (C)

The light conversion resin composition according to the present invention may further include a heat curing agent (C).

In one embodiment of the present invention, the heat curing agent may include a thiol compound.

The thiol compound can prevent oxidation and discoloration of quantum dots during a high-temperature process, and can be expected to have an effect of preventing light efficiency from deteriorating during long-term blue light resistance evaluation.

The thermosetting agent may include a thiol compound represented by Chemical Formula 16 below.

[Formula 16]

In the above formula,

R ^s is hydrogen or a C ₁ -C ₁₂ alkyl group;

R ^p is a C ₁ -C ₁₂ alkylene group,

R ^q is a t-valent aliphatic hydrocarbon group with or without a hetero atom;

t is an integer from 2 to 4.

As used herein, the C ₁ -C ₁₂ alkyl group refers to a straight-chain or branched monovalent hydrocarbon having 1 to 12 carbon atoms, and examples thereof include methyl, ethyl, n-propyl, i-propyl, and n-butyl. , i-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and the like, but are not limited thereto.

As used herein, the C ₁ -C ₁₂ alkylene group refers to a straight-chain or branched divalent hydrocarbon having 1 to 12 carbon atoms, and examples thereof include methylene, ethylene, propylene, butylene, pentylene, and hexylene. , heptylene, and the like, but are not limited thereto.

In one embodiment of the present invention, R ^q may be trivalent trimethylpropane, divalent n-butane, tetravalent tetramethylmethane or trivalent triethylisocyanurate.

Specifically, the thiol compound of Chemical Formula 16 may be a compound represented by any one of Chemical Formulas 17 to 24 below.

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

[Formula 22]

[Formula 23]

[Formula 24]

The heat curing agent (C) may be included in an amount of 5 to 40% by weight, more preferably 10 to 30% by weight based on 100% by weight of the total solid content in the light conversion resin composition. After thermal curing within the above range, resistance to blue light is excellent. If the content of the heat curing agent is less than 5% by weight, it is difficult to expect the effect of improving light resistance, and if it exceeds 40% by weight, the hardness of the cured film is lowered, so that damage to the coating film such as scratches may easily occur.

thermal polymerization Resin (D)

The light conversion resin composition according to the present invention may further include a thermal polymerization resin (D).

The thermal polymerization resin not only improves surface hardness and adhesion of the coating film, but also suppresses deterioration of quantum dots under high temperature and high humidity conditions, thereby increasing reliability.

The thermal polymerization resin may include at least one selected from the group consisting of a multifunctional alicyclic epoxy resin, a novolak epoxy resin, and a silane-modified epoxy resin.

The multifunctional alicyclic epoxy resin may include a compound represented by Formula 25 or 26 below.

[Formula 25]

In the above formula,

R is a C ₁ -C ₁₀ alkyl group,

d, e and f are each independently an integer of 1 to 20.

[Formula 26]

As used herein, the C ₁ -C ₁₀ alkyl group refers to a straight-chain or branched monovalent hydrocarbon having 1 to 10 carbon atoms, and examples thereof include methyl, ethyl, n-propyl, i-propyl, and n-butyl. , i-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and the like, but are not limited thereto.

Commercially available products of the polyfunctional alicyclic epoxy resin include "CEL-2021" from Daicel Kagaku Kogyo Co., Ltd., alicyclic solid epoxy resin "EHPE-3150", epoxidized polybutadiene "PB3600", flexible aliphatic epoxy Compound "CEL-2081", lactone-modified epoxy resin "PCL-G", etc. can be used. In addition, "Ceroxide 2000", "Epollide GT-3000", "GT-4000" of Daicel Kagaku Kogyo Co., Ltd. can be used, but is not limited thereto.

By using the polyfunctional alicyclic epoxy resin, not only the surface hardness and adhesion of the coating film are excellent, but also the deterioration of the quantum dots can be suppressed to improve reliability.

The novolak epoxy resin may include a compound represented by Chemical Formula 27 below.

[Formula 27]

In the above formula,

v is an integer from 1 to 20;

As a commercial product of the novolac epoxy resin, Sumi Epoxy ESCN 195XL (manufactured by Sumitomo Kagaku Kogyo Co., Ltd.) may be used, but is not limited thereto.

By using the novolak epoxy resin, not only the surface hardness and adhesion of the coating film are excellent, but also the deterioration of the quantum dots can be suppressed.

The silane-modified epoxy resin may be prepared by a dealcohol condensation reaction between a hydroxyl group-containing epoxy resin and an alkoxysilane.

The hydroxyl group-containing epoxy resin may include a compound represented by Formula 28 below.

[Formula 28]

In the above formula, x is an integer from 1 to 34.

The thermal polymeric resin (D) may be included in an amount of 1 to 50% by weight, preferably 5 to 40% by weight, based on 100% by weight of the total solid content in the light conversion resin composition. There is an advantage in that the surface hardness and adhesion of the coating film are improved within the above range.

Scattering Particles (E)

The light conversion resin composition according to the present invention may further include scattering particles (E). The scattering particles are a common inorganic material, for example, a metal oxide may be used.

The metal oxides include Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Mo, Cs, Ba, La, Hf, W, Tl, Pb, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Ti, Sb, Sn, Zr, Nb, It may be an oxide containing one type of 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 species selected from the group consisting of combinations thereof is possible. If necessary, a material surface-treated with a compound having an unsaturated bond such as acrylate may also be used.

When the light conversion resin composition according to the present invention includes scattering particles, it is preferable to increase the overall light efficiency in the light conversion 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 30 to 1000 nm, preferably 100 to 500 nm, more preferably 150 to 300 nm. At this time, if the particle size is too small, a sufficient scattering effect of the light emitted from the quantum dots cannot be expected. On the contrary, if the particle size is too large, it is not possible to sink in the composition or obtain a uniform quality surface of the light conversion layer.

The scattering particles (E) may be included in an amount of 0.5 to 20% by weight, preferably 1 to 15% by weight, based on 100% by weight of the total solid content in the light conversion resin composition. When the scattering particles are included within the above range, it is preferable that the effect of increasing the luminous intensity can be maximized. If the content of the scattering particles is less than 0.5% by weight, it may be difficult to obtain desired luminous intensity, and if it is more than 20% by weight, the transmittance of blue light is significantly reduced, resulting in problems with color reproducibility.

Solvent (F)

The solvent contained in the light conversion resin composition of the present invention usually includes one or two or more kinds.

As the solvent in the present invention, it is preferable to use a solvent having a solvent polarity in the range of 4 to 7 when used alone or in a mixture of two or more kinds. If the polarity is out of the above range, it may be a factor in deteriorating luminance characteristics of the light conversion resin composition. In addition, when two or more solvents are mixed, even if the polarity value of the mixed solvent satisfies the above range, if at least one solvent among the solvents constituting the mixed solvent does not satisfy the above polarity range, still This may cause a problem of luminance deterioration.

In addition, it is appropriate that the boiling point is in the range of 100 to 250°C, preferably 100 to 200°C, either alone or in a mixture of two or more. If the boiling point is less than 100 ° C, there is a risk of coating film uniformity and nozzle clogging due to a fast drying rate, and if the boiling point is higher than 250 ° C, there is a risk of reducing the coating hardness or staining due to a too slow drying rate.

Examples of solvents satisfying the polarity and/or boiling point include those listed in Table 1 below, but are not limited thereto.

solvent Polarity (δp )* Boiling point (℃) Dipropylene glycol methyl ether 4 190 Propylene glycol methyl ether acetate 5.6 146 Dipropylene glycol methyl ether acetate 4.9 209 Propylene glycol n-propyl ether 4.9 149 Propylene glycol n-butyl ether 4.2 171 Propylene glycol phenyl ether 5.3 243 Ethylene glycol monoethyl ether acetate 4.7 156 Diethylene glycol n-butyl ether 7 230 Ethylene glycol n-butyl ether acetate 4.5 192 Ethylene glycol hexyl ether 6.9 208 n-Butanol 5.7 117.7 isobutanol 5.7 107.9 2-methyl butanol 5.1 128.7 n-pentanol 4.5 137.9 n-propyl acetate 4.3 101.5 n-butyl propionate 5.4 144.7 n-pentyl propionate 5.1 165 n-propyl propionate 5.8 122.4 cyclohexanone 6.3 155.6 methyl isobutyl ketone 6.1 116.1

* Polarity in Table 1 means the value of polarity (δp) among the Hansen solubility parameters.

In the present invention, when the solvent is used alone and the boiling point is out of 100 to 200 ° C, two or more solvents may be mixed to use a mixed solvent having the boiling point range.

If necessary, the solvent according to the present invention is a halogenated hydrocarbon-based solvent in addition to the solvents exemplified above; aromatic hydrocarbon-based solvents; aliphatic saturated hydrocarbon-based solvents; Ether and ester solvents may be further included.

The halogenated hydrocarbon-based solvent may include, for example, chloroform, dichloromethane, chloromethane, carbon tetrachloride, dichloroethane, tetrachloroethane, and the like, but is not limited thereto.

The aromatic hydrocarbon-based solvent may include benzene, toluene, dichlorobenzene, xylene, and the like, but is not limited thereto.

The aliphatic saturated hydrocarbon-based solvent may include, but is not limited to, chain-shaped alkanes such as N-hexane, pentane, and heptane, cyclic alkanes such as cyclopentane and cyclohexane, and kerosene.

Specific examples of the ether and ester solvents include:

Diethyl carbonate, ethyl butyrate, ethyl isobutyrate, tert-butyl acetate, isopropyl propionate, methyl-3-methylbutanoate, propyl propionate, methyl 2-methyl butanoate, sec-butyl acetate , methyl pentanoate, isobutyl acetate, butyl acetate, methyl fibarate, sec-butyl propionate, n-butyl propionate, 2-methyl butyl acetate, ethyl 2-methylbutyrate, methyl 2-methylpentanoate , 2-pentyl acetate, neopentyl acetate, 3-methylbutan-2-yl acetate, isopropyl isobutyrate, propyl isobutyrate, ethyl isovalerate, methyl 3-methyl pentanoate, ethyl pentanoate, methyl 4- Methyl pentanoate, methyl hexanoate, isoamyl acetate, pentyl acetate, isopropyl butyrate, propyl butanoate, isobutyl propionate, 2,2-dimethyl butanoic acid methyl ester, ethyl pivalate, tert-amyl Acetate, tert-butyl propionate, methyl 3,3-dimethylbutyrate, diethylacetic acid methyl ester, 3-pentyl acetate, 2,3-dimethylbutanoic acid methyl ester, propyl 2-methylbutanoate, ethyl Hexanoate, isopropyl 2-methylbutanoate, isobutyl isobutanoate, 2-methylbutyl propionate, 2-hexyl acetate, 1-methylbutyl propanoate, methyl 2-ethyl-3-methylbutyrate , 3-methylpentyl 3-acetate, 3-hexyl acetate, 2,2-dimethyl-3-acetoxybutane, ethyl 2-methylpentanoate, sec-butyl butyrate, ethyl 3-methylpentanoate, ethyl 2, 3-Dimethylbutanoate, 2,3-dimethyl-2-butyl acetate, 2-ethylbutyl acetate, acetic acid-(2,2-dimethyl-butyl ester), 2,3-dimethylbutyl acetate, 3-methyl -1-pentyl acetate, 3,3-dimethylbutyl acetate, n-butyl isobutyrate, isopropyl pentanoate, butyl butyrate, amyl propionate, hexyl acetate, propyl 3-methylbutanoate, methyl heptanoate, Isopropyl 3-methylbutanoate, isobutyl butyrate, sec-butyl isobutyrate, propyl pentanoate, isoamyl propionate, ethyl 4-methylpentanoate, 4-methyl-1-pentyl acetate, methyl 5- Methylhexanoate, methyl 2-ethyl-2-methylbutyrate, 2,2-dimethyl-pentanoic acid methyl ester, ethyl 2,2-dimethylbutanoate, i-propyl pivalate, propyl 2,2-dimethylpro Panoate, 2,2-dimethyl-1-propanol propanoate, ethyl 3,3-dimethylbutanoate, 2-methyl-3-pentyl acetate, acetic acid-(2-methyl-pentyl ester), 4- Methyl-2-pentyl acetate, tert-butyl 2-methylpropanoate, 2,3-dimethyl-valeric acid methyl ester, 2-ethyl-valeric acid methyl ester, methyl-2-methylcaproate, 2-methyl Pentan-2-yl acetate, tert-butyl butyrate, 3-ethyl-valeric acid methyl ester, ethyl 2-ethylbutanoate, sec-amyl propionate, methyl 2,3,3-trimethyl butanoate, 3 ,3-dimethylpentanoic acid methyl ester, tert-amyl propanoate, methyl 2,4-dimethyl pentanoate, methyl 2,2,3-trimethylbutanoate, 3-methyl-pentyl-2-acetate, methyl 4,4-dimethylpentanoate, methyl 3,4-dimethylpentanoate, valeric acid isobutyl ester, 2-methylbutyl butanoate, valeric acid sec-butyl ester, 2-pentyl butanoate, 2 -Methylpropyl 2-methylbutanoate, n-butyl 2-methylbutanoate, isopentyl butanoate, isobutyl isopentanoate, 1-methyl pentyl propanoate, 1-methylhexyl acetate, 2-methyl -butyric acid sec-butyl ester, 2-methylpropanoic acid 2-methylbutyl ester, ethyl 3-methylhexanoate, ethyl 2-methylhexanoate, 1-heptyl acetate, methyl 3-methylheptanoate , 1,1,2,2-tetramethylpropyl acetate, 1-acetoxy-2,3,3-trimethylbutane, acetic acid-(2-ethyl-2-methyl-butyl ester), acetic acid-( 3,3-dimethyl-pentyl ester), acetic acid-(1,3,3-trimethyl-butyl ester), 2,4-dimethyl-3-acetoxypentane, acetic acid-(2-ethyl-3 -methyl-butyl ester), acetic acid-(3-methyl-hexyl ester), acetic acid-(4-methyl-hexyl ester), isobutyric acid-(1,2-dimethyl-propyl ester), 4 -methyl-valeric acid propyl ester, 4-methyl-hexanoic acid ethyl ester, methyl 5-methylheptanoate, isovaleric acid sec-butyl ester, isobutyric acid isopentyl ester, butyl pentanoate, propyl Hexanoate, Hexyl Propionate, Methyl Octanate, 5-Methylhexyl Acetate, Ethyl Isoamyl Acetate, Pentyl Butyrate, Ethyl Heptanoate, Isopropyl Hexanoate, Butyl 3-Methylbutanoate, 2-Ethyl- 3-methyl-valeric acid methyl ester, methyl 2-isopropyl-3-methylbutanoate, 2-ethyl-3-methyl-butyric acid ethyl ester, 2-ethyl-valeric acid ethyl ester, methyl 2- Ethylhexanoate, ethyl 2,4-dimethylpentanoate, methyl 2,5-dimethylhexanoate, acetic acid-(1-ethyl-3-methyl-butyl ester), 4-heptyl acetate, 4-methyl -2-pentyl propionate, 5-methylhexan-2-yl acetate, 2,2-diethyl-butyric acid methyl ester, acetic acid-(1,1-diethyl-propyl ester), 2,3 -Dimethyl-hexanoic acid methyl ester, 2-ethyl-2-methyl-valeric acid methyl ester, 2-ethyl-2-methylbutyric acid ethyl ester, ethyl 2,2-dimethylpentanoate, 2,2- Dimethyl-hexanoic acid methyl ester, 2,2-dimethyl-butyric acid propyl ester, pivalic acid tert-butyl ester, isobutyl pivalate, pivalic acid butyl ester, acetic acid-(1,2-dimethyl- pentyl ester), 2,4,4-trimethyl-valeric acid methyl ester, acetic acid-(1-ethyl-1-methyl-butyl ester), 3,3-dimethyl-valeric acid ethyl ester, isobutyric Acid tert-pentyl ester, tert-amyl butyrate, 3-acetoxy-2,2-dimethyl-pentane, propionic acid-(3,3-dimethyl-butyl ester), isopropyl 3,3-dimethylbutanoate , 3,3-dimethyl-butyric acid propyl ester, neopentyl 2-methylpropanoate, neopentyl butanoate, tert-butyl 3-methyl butanoate, tert-butyl pentanoate, 3,3,4 -trimethyl-valeric acid methyl ester, 4,5-dimethyl-hexanoic acid methyl ester, ethyl 4,4-dimethylpentanoate, 3,4-dimethyl-pentanoic acid ethyl ester, acetic acid-(1- isopropyl-butyl ester), 2-propyl 2-methylpentanoate, methyl 6-methylheptanoate, isopropyl 2-ethylbutyrate, 2-acetoxy-4-methyl-hexane, 2,2,3, 3-tetramethylbutanoate, 4-methyl-heptanoic acid methyl ester, methyl 4-ethylhexanoate, ethyl-2,3,3-trimethylbutanoate, 2,2-dimethyl-pentanol-(1 )-acetate, 2,4-dimethyl-2-pentyl acetate, 2-methyl-2-hexyl acetate, 4,4-dimethylpentyl acetate, pentyl isobutanoate, methyl 2-methylheptanoate, butane-2- 2,2-dimethylpropanoate, methyl 4,4-dimethylhexanoate, 2-propyl-pentanoic acid methyl ester, hexanoic acid-(2,4-dimethyl methyl ester), 2,2,3- Trimethylbutanoic acid ethyl ester, 2-methylhexyl acetate, methyl-3,4,4-trimethylpentanoate, propyl-2-ethylbutanoate, isopropyl 2,2-dimethylbutanoate, 3-ethyl- 4-methyl-pentanoic acid methyl ester, methyl 2,2,4-trimethylpentanoate, 2,3-dimethyl-3-pentylacetate, pentan-3-yl 2-methylpropanoate, 3-ethyl-3 -methyl-pentanoic acid methyl ester, methyl 3,4-dimethylhexanoate, ethyl-3-ethyl-pentanoate, methyl 2,2,3-trimethylpentanoate, methyl 2-ethyl-3,3- Dimethylpentanoate, pentan-3-yl butyrate, 4-methyl-3-hexyl acetate, 2-methyl-3-methylbutyl propanoic acid ester, 3-methoxy-1-pentyl propionate, 2-pentyl 2-methylpropanoate, tert-butyl 2-methylbutanoate, methyl 5,5-dimethylhexanoate, 3,3-dimethyl 2-butyl propionate, 1-ethyl butyl propanoate, 2-methyl -1-pentyl propanoate, n-propyl 2-methylbarerate, sec-amyl barerate, sec-butyl hexanoate, 2-methylbutyl isobarate, pentanoic acid 2-methylbutyl ester, 2,2 ,3-trimethyl-valeric acid ethyl ester, 1-methylhexyl propanoate, hexyl-2-butanoate, 2,2-dimethyl-3-hexylacetate, 2-methyl-1-butyl 2-methylbutano 8, 3-methylbutyl 2-methylbutanoate, methyl 2,6-dimethylheptanoate, 2-octyl acetate, 1-ethylhexyl acetate, acetic acid-(1-isopropyl-2,2-dimethyl- propyl ester), acetic acid-(2-ethyl-3,3-dimethyl-butyl ester), acetic acid-(2,2,3-trimethyl-pentyl ester), acetic acid-(2,2,3 ,3-Tetramethyl-butyl ester), acetic acid-(1,2,2,3-tetramethyl-butyl ester), acetic acid-(2-isopropyl-3-methyl-butyl ester), acetic Acid-(4-ethyl-hexyl ester), acetic acid-(2,2-diethyl-butyl ester), 3-methyl-valeric acid sec-butyl ester, isopentyl 3-methylbutanoate, isopropyl Heptanoate, 4-methyl-valeric acid isobutyl ester, 4-methyl-heptanoic acid ethyl ester, 3-methylbutyl pentanoate, butyl hexanoate, n-pentyl n-pentanoate, n-propyl Heptanoate, 5-methyl-heptanoic acid ethyl ester, ethyl 6-methylheptanoate, hexyl butyrate, octanoic acid ethyl ester, methyl 6-methyloctanoate, heptyl propionate, nonanoic acid methyl ester , 1-octyl acetate, 2,2,3,3-tetramethyl-butyric acid ethyl ester, acetic acid-(1-ethyl-2,2-dimethyl-butyl ester), acetic acid-(1-iso propyl-pentyl ester), acetic acid-(1,2-dimethyl-hexyl ester), 2-iso-propyl-3-methyl-butyric acid ethyl ester, propionic acid-(3,3-dimethyl-pentyl ester) ), acetic acid-(1-ethyl-3-methyl-pentyl ester), 2,3,5-trimethyl-hexanoic acid methyl ester, acetic acid-(1-ethyl-2-methyl-pentyl ester), Propionic acid-(1-ethyl-2,2-dimethyl-propyl ester), ethyl 2,2-diethylbutanoate, 2,2,3-trimethyl-butyric acid isopropyl ester, acetic acid-( 1-ethyl-3,3-dimethyl-butyl ester), butyl 2,2-dimethylbutyrate, 3-methyl-2-propyl-valeric acid methyl ester, 2-methyl-heptanoic acid ethyl ester, methyl 2-methyl Octanoate, butyric acid-(1,3-dimethyl-butyl ester), 3-ethyl-hexanoic acid ethyl ester, 2-ethyl-2-methyl-valeric acid ethyl ester, ethyl 3,5-dimethylhexa Noate, 3,3-dimethyl-valeric acid propyl ester, 2,2,4,4-tetramethyl-pentanoic acid methyl ester, ethyl 2,2-dimethyl-hexanoate, butyric acid-(2- ethyl-butyl ester), 2-ethyl-4-methyl-valeric acid ethyl ester, ethyl 2-propylpentanoate, methyl 2-propylhexanoate, ethyl 2-ethylhexanoate, acetic acid-(1 ,1-diethyl-butyl ester), 2,5-dimethyl-hexanoic acid ethyl ester, ethyl 4,5-dimethylhexanoate, acetic acid-(1-isobutyl-butyl ester), acetic acid- (1-ethyl-4-methyl-pentyl ester), acetic acid-(1-methyl-1-propyl-butyl ester), isovaleric acid tert-pentyl ester, 3-propyl-hexanoic acid methyl ester, 3 -Ethyl-heptanoic acid methyl ester, acetic acid-(1,1,4-trimethyl-pentyl ester), acetic acid-(1,5-dimethyl-hexyl ester), 3-methyl-heptanoic acid ethyl ester , 3,3,5-trimethyl-hexanoic acid methyl ester, 3,3-dimethyl-heptanoic acid methyl ester, 3,3-dimethyl-valeric acid isopropyl ester, 2-ethylhexyl acetate, ethyl 2,4 ,4-Trimethylpentanoate, Butyl Neopentanoate, Neopentyl Pivarate, Pivaric Acid Isopentyl Ester, 2-Ethyl-Butyric Acid Tert-Butyl Ester, 3,3-Dimethyl-Butyric Acid Sec-Butyl Ester, acetic acid-(1,4-dimethylbutyl)ester, sec-amyl isovarerate, 3-acetoxy-2,4-dimethylhexane, 3,3-diethyl-pentanoic acid methyl ester, methyl- 4,4-dimethylheptanoate, methyl 3,5,5-trimethylhexanoate, acetic acid 4-octyl ester, 3,5-dimethyl-heptanoic acid methyl ester, 1-acetoxy-4,4- Dimethyl-hexane, pentyl 3-methylbutanoate, 7-methyloctanoic acid methyl ester, 2-ethyl-heptanoic acid methyl ester, methyl 2,4-dimethylheptanoate, methyl 2,2-dimethyl heptano 8, pentyl 2,2-dimethylpropanoate, ethyl 2,3,4-trimethylbarerate, tert-butyl hexanoate, 3-acetoxy-2,5-dimethyl-hexane, 1,1,3, 3-tetramethylbutyl acetate, 2,2,4-trimethylpentyl acetate, methyl 2,2,3,3-tetramethylpentanoate, pentanoic acid-(2,2,3,4-tetramethyl-methyl ester ), 2-propyl-2-methyl-pentanoic acid methyl ester, 1,1-dimethylethyl 3,3-dimethylbutanoate, tert-butyl 4-methylpentanoate, 2-isopropyl-3,3- Dimethyl-butyric acid methyl ester, methyl 2-ethyl-2-methylhexanoate, ethyl 2-ethyl-3,3-dimethylbutanoate, hexyl isobutanoate, methyl-5,5-dimethylheptanoate , methyl-2,3,4-trimethylhexanoate, methyl 2,3-dimethyl-2-ethylpentanoate, 3-methyl octanoic acid methyl ester, 2,2-dimethylhexyl acetate, propylneoheptanoate , isopropyl 2-methylhexanoate, 2-propyl-pentyl-acetate, butyl 2-ethyl butyrate, 4-methyloctanoic acid methyl ester, 2-methylpentanoic acid-(1-methyl propyl ester), 2, 2,4-trimethyl-hexanoic acid methyl ester, hexanoic acid-(2,2,5-trimethyl-methyl ester), 4-methylpentyl isobutyrate, 3-methylpentyl butyrate, ethyl 3,3,4-trimethyl Pentanoate, pentanoic acid-(3,4,4-trimethyl-ethyl ester), tert-amyl fibarate, isobutyl 3,3-dimethylbutyrate, 1-isopropyl-1,2-dimethylpropyl acetate, ethyl 4-ethylhexanoate, methyl 2-ethyl-3,3-dimethylpentanoate, methyl 3,6-dimethylheptanoate, isobutyl hexanoate, 3,3,4,4-tetramethyl pentanoic acid Methyl ester, 2-methylvaleric butyl ester, pentyl 2-methylbutanoate, neopentyl 2-methylbutanoate, ethyl 3,3-dimethylhexanoate, 4-ethyl-3-hexyl acetate, 2,4 -Dimethylpentan-3-yl propionate, methyl neononanoate, methyl 4,4,5-trimethylhexanoate, methyl diisopropyl propionate, 1-methylethyl 4-methylhexanoate, butanoic Acid 1-ethylbutyl ester, 1-ethylpentyl propanoate, pentan-3-yl pentanoate, methyl 4-ethylheptanoate, pentan-3-yl 3-methylbutanoate, ethyl 5,5-dimethyl Hexanoate, 2-methyl-3-methylbutyl butanoic acid ester, neryl acetate and the like can be used.

In addition, ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dipropyl ether; alkylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate; alkoxyalkyl acetates such as methoxybutyl acetate and methoxypentyl acetate; ketones such as methyl isoamyl ketone, diisobutyl ketone, methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin; esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; and cyclic esters such as γ-butyrolactone.

The solvent (F) may be included in an amount of 45 to 95% by weight, preferably 50 to 90% by weight, based on 100% by weight of the total light conversion resin composition. When the solvent is contained within the above range, it is preferable because coating properties tend to be good when applied with a coating device such as a roll coater, spin coater, slit-and-spin coater, slit coater (sometimes referred to as a die coater), inkjet, or the like. .

Additive (G)

The light-changing resin composition according to the present invention may further include additives such as a surfactant, an adhesion promoter, an antioxidant, a UV absorber, and an aggregation inhibitor, if necessary.

Commercially available surfactants can be used as the surfactant, and examples thereof include surfactants such as silicone, fluorine, ester, cationic, anionic, nonionic, and amphoteric surfactants. These may be used alone or in combination of two or more.

Examples of the above surfactants 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, there are polyethylene imines, etc., and as trade names, KP (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products), Mega MEGAFAC (manufactured by Dainipbon Ink Kagaku Kogyo Co., Ltd.), Flourad (manufactured by Sumitomo 3M Co., Ltd.), Asahi guard, Surflon (manufactured by Asahi Glass Co., Ltd.), Sol SOLSPERSE (manufactured by Geneca Co., Ltd.), EFKA (manufactured by EFKA Chemicals), PB 821 (manufactured by Ajinomoto Co., Ltd.), and the like.

As said adhesion promoter, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2 -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyl Trimethoxysilane etc. are mentioned.

Specific examples of the antioxidant include 2,2'-thiobis(4-methyl-6-t-butylphenol) and 2,6-di-t-butyl-4-methylphenol.

Specific examples of the ultraviolet absorber include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole and alkoxybenzophenone.

Specifically as said aggregation inhibitor, sodium polyacrylate etc. are mentioned.

The additives may be appropriately added and used as needed within a range that does not impair the effects of the present invention. For example, the additive may be used in an amount of 0.05 to 10% by weight, preferably 0.1 to 10% by weight, and more preferably 0.1 to 5% by weight, based on 100% by weight of the total light-changing resin composition, but is not limited thereto.

One embodiment of the present invention relates to a light conversion sheet formed using the light conversion resin composition described above. A light conversion sheet according to an embodiment of the present invention is characterized in that it includes a light conversion layer formed by coating the light conversion resin composition described above on a substrate, drying it, and then curing it.

Glass may be used as the substrate.

The curing may be performed at 100 to 250°C, preferably 150 to 230°C, for 10 minutes to 1 hour, preferably 30 minutes.

The light conversion sheet according to the present invention can realize excellent light efficiency when applied to an image display device. In addition, color reproducibility is better because light with a color is emitted, and a viewing angle can be improved because light is emitted in all directions by photoluminescence.

In addition, compared to white light used in conventional image display devices, excellent color reproducibility can be obtained by significantly reducing the half width of emission wavelengths of blue, green, and red emitted.

Accordingly, one embodiment of the present invention relates to an image display device provided with the light conversion sheet described above.

The image display device of the present invention includes not only a normal liquid crystal display device, but also various image display devices such as an electroluminescence display device, a plasma display device, and a field emission display device.

Hereinafter, the present invention will be described in more detail by Examples, Comparative Examples and Experimental Examples. These Examples, Comparative Examples and Experimental Examples are only for explaining the present invention, and it is obvious to those skilled in the art that the scope of the present invention is not limited thereto.

synthesis example 1-1: InP / ZnSe / ZnS green quantum dot synthesis

4mmol (0.58g) of indium acetate, 6mmol (1.5g) of palmitic acid, and 200mL of 1-octadecene were put into a reactor and heated to 120°C under vacuum. After 1 hour, the atmosphere in the reactor was changed to nitrogen. After heating to 300 ° C., a mixed solution of 2 mmol (580 μl) of tris (trimethylsilyl) phosphine (TMS ₃ P) and 10 mL of trioctylphosphine was quickly injected and reacted for 1 minute to form an InP core.

24 mmol (4.48 g) of zinc acetate, 48 mmol of oleic acid and 200 mL of trioctylamine were then charged into the reactor and heated to 120° C. under vacuum. After 1 hour, the atmosphere in the reactor was changed to nitrogen, and the temperature of the reactor was raised to 280°C. 20 ml of the previously synthesized InP core solution was added, followed by 48 mmol of selenium (Se/TOP) in trioctylphosphine, and the final mixture was reacted for 90 minutes. 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 form an InP/ZnSe core-shell.

Then, 24 mmol (4.48 g) of zinc acetate, 48 mmol of oleic acid and 200 mL of trioctylamine were charged into the reactor and heated to 120° C. under vacuum. After 1 hour, the atmosphere in the reactor was changed to nitrogen, and the temperature of the reactor was raised to 280°C. 20 ml of the previously synthesized InP/ZnSe core-shell solution was added, followed by 48 mmol of sulfur (S/TOP) in trioctylphosphine, and the final mixture was reacted for 2 hours. After adding ethanol to the reaction solution rapidly cooled to room temperature, the precipitate obtained by centrifugation was filtered under reduced pressure and dried under reduced pressure to obtain quantum dots having an InP/ZnSe/ZnS core-shell structure, and then 100 mL of ethanol was added to precipitate and redisperse the method. was purified twice using The purified InP/ZnSe/ZnS core-shell structured green quantum dots were dispersed in 1-octadecene and then stored.

As a result of measuring the emission spectrum of the green quantum dots using QE-2100 (manufactured by Otsuka Co., Ltd.), the maximum emission peak was 530 nm and the half width was 38 nm.

synthesis example 1-2: InP / ZnS Red of quantum dots synthesis

2mmol (0.58g) of indium acetate, 6mmol (1.5g) of palmitic acid, and 100mL of 1-octadecene were put into a reactor and heated to 120°C under vacuum. After 1 hour, the atmosphere in the reactor was changed to nitrogen. After heating to 280 ° C., a mixed solution of tris (trimethylsilyl) phosphine (TMS ₃ P) 1 mmol (290 μl) and trioctylphosphine 5 mL was quickly injected and reacted for 15 minutes. Acetone was added to the reaction solution quickly cooled to room temperature, and the precipitate obtained by centrifugation was dispersed in toluene. The obtained InP semiconductor nanocrystals exhibited a maximum UV first absorption wavelength of 560 to 590 nm.

12 mmol (2.24 g) of zinc acetate, 24 mmol of oleic acid and 100 mL of trioctylamine were placed in a reactor and heated to 120° C. under vacuum. After 1 hour, the atmosphere in the reactor was changed to nitrogen, and the temperature of the reactor was raised to 280°C. 10 mL of the previously synthesized InP core solution was added, followed by 24 mmol of S (sulfur)/TOP (trioctylphosphine), and the final mixture was reacted for 2 hours. Ethanol was added to the reaction solution rapidly cooled to room temperature and centrifuged to obtain red quantum dots having an InP (core)/ZnS (shell) structure with an emission wavelength of 625 nm and a full width at half maximum of 40 nm.

synthesis example 2-1: Formula 6 ligand having InP / ZnSe / ZnS core-shell green quantum dot manufacturing

Into a solution in which 5 g of InP/ZnSe/ZnS quantum dots of Synthesis Example 1-1 having oleic acid bonded to the surface were dispersed in 50 ml of N-hexane, 2 g of a novel thiocarboxylic acid compound of Formula 6 was added and stirred for 30 minutes or more. . In this process, the new ligand replaced oleic acid on the surface of the quantum dots. Thereafter, 100 ml of ethanol was added to the mixed solution in which the quantum dot-novel ligand conjugate and the unreacted ligand were mixed to aggregate the quantum dot-novel ligand conjugate. The aggregated quantum dot-novel ligand conjugate was separated from oleic acid and unreacted ligands separated from the quantum dot through centrifugation (8000 rpm, 30 minutes). Then, the quantum dot-new ligand conjugate was dispersed in N-hexane at 30% by weight.

synthesis example 2-2: Formula 7 ligand having InP / ZnSe / ZnS core-shell green quantum dot manufacturing

Except for using the ligand of Chemical Formula 7 instead of the ligand of Chemical Formula 6, the same procedure as in Synthesis Example 2-1 was performed.

synthesis example 2-3: Formula 8 ligand having InP / ZnSe / ZnS core-shell green quantum dot manufacturing

Except for using the ligand of Chemical Formula 8 instead of the ligand of Chemical Formula 6, the same procedure as in Synthesis Example 2-1 was performed.

synthesis example 2-4: Formula 6 ligand having InP / ZnS core-shell red quantum dot manufacturing

Except for using the red quantum dots of Synthesis Example 1-2 instead of the green quantum dots of Synthesis Example 1-1, red quantum dots to which the ligand of Chemical Time 6 was applied were obtained in the same manner as in Synthesis Example 2-1.

synthesis example 2-5: ligand No exchange reaction InP / ZnSe / ZnS core-shell green quantum dot preparation

5 g of InP/ZnSe/ZnS green quantum dots of Synthesis Example 1-1 having oleic acid bonded to the surface were dispersed in 30% by weight of N-hexane.

synthesis example 2-6: ligand No exchange reaction InP / ZnS core-shell red quantum dot preparation

5 g of InP/ZnS red quantum dots of Synthesis Example 1-2 having oleic acid bonded to the surface were dispersed in 30% by weight of N-hexane.

synthesis example 2-7: Formula 29 ligand having InP / ZnSe / ZnS core-shell green quantum dot manufacturing

Except for using the ligand of Chemical Formula 29 instead of the ligand of Chemical Formula 6, the same procedure as in Synthesis Example 2-1 was performed.

[Formula 29]

synthesis example 3-1: Synthesis of curable resin

In a 3000 ml three-necked round flask, 364.4 g of 3,6'-dihydroxyspiro (fluorene-9,9-xantene) and 0.4159 t-butylammonium bromide were added. g was mixed, and 2359 g of epichlorohydrin was added and reacted by heating to 90°C. As analyzed by liquid chromatography, when 3,6'-dihydroxyspiro (fluorene-9,9-xanthene) was completely consumed, the mixture was cooled to 30° C. and 50% NaOH aqueous solution (3 equivalents) was slowly added thereto. When epichlorohydrin was completely exhausted as analyzed by liquid chromatography, it was extracted with dichloromethane, washed with water three times, and the organic layer was dried with magnesium sulfate. recrystallized.

After mixing 1 equivalent of the synthesized epoxy compound with 0.004 equivalent of t-butylammonium bromide, 0.001 equivalent of 2,6-diisobutylphenol, and 2.2 equivalent of acrylic acid, 24.89 g of the solvent propylene glycol monomethyl ether acetate was added and mixed. The reaction solution was heated and dissolved at 90 to 100°C while blowing air at 25 ml/min. In a cloudy state, the reaction solution was completely dissolved by heating to 120°C. When the solution became clear and the viscosity increased, the acid value was measured and stirred until the acid value was less than 1.0 mgKOH/g. It took 11 hours for the acid value to reach the target (0.8). After completion of the reaction, the temperature of the reactor was lowered to room temperature to obtain a colorless and transparent compound represented by Chemical Formula 30.

[Formula 30]

Thereafter, 600 g of propylene glycol monomethyl ether acetate was added to 307.0 g of the compound of Formula 30 and dissolved, and then 78 g of biphenyltetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed and the temperature was gradually raised to 4 at 110 to 115 ° C. reacted over time. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90° C. for 6 hours to polymerize the cardo-based resin. Disappearance of anhydride was confirmed by IR spectrum. The weight average molecular weight of the prepared cardo-based resin was 3,500 g/mol.

synthesis example 3-2: Synthesis of curable resin

A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet pipe was prepared, and on the other hand, 45 parts by weight of N-benzylmaleimide, 45 parts by weight of methacrylic acid, 10 parts by weight of tricyclodecyl methacrylate, 4 parts by weight of t-butylperoxy-2-ethylhexanoate and 40 parts by weight of propylene glycol monomethyl ether acetate were added, stirred and mixed to prepare a monomer dropping lot, and 6 parts by weight of n-dodecanethiol and propylene glycol monomethyl A chain transfer agent dropping lot was prepared by adding 24 parts by weight of ether acetate and mixing with stirring.

Thereafter, 395 parts by weight of propylene glycol monomethyl ether acetate was introduced into the flask, the atmosphere in the flask was changed from air to nitrogen, and the temperature of the flask was raised to 90° C. while stirring.

Subsequently, loading of the monomer and chain transfer agent from the loading lot was started. Dropping proceeded for 2 hours while maintaining 90 ° C. After 1 hour, the temperature was raised to 110 ° C and maintained for 3 hours. Then, a gas inlet pipe was introduced to bubble the oxygen / nitrogen = 5/95 (v / v) mixed gas. ring started.

Subsequently, 10 parts by weight of glycidyl methacrylate, 0.4 parts by weight of 2,2'-methylenebis(4-methyl-6-t-butylphenol), and 0.8 parts by weight of triethylamine were put into a flask and kept at 110°C for 8 hours. The reaction was continued, and then cooled to room temperature to obtain an acrylic resin having a solid content of 29.1% by weight, a weight average molecular weight of 32,000 g/mol, and an acid value of 114 mgKOH/g.

Example 1 to 7 and comparative example 1 to 4

After mixing the respective components (unit: parts by weight) with the compositions shown in Tables 2 and 3 below, propylene glycol methyl ether acetate (PGMEA) was added as a solvent so that the solid content of the total light conversion resin composition was 30% by weight to light conversion A resin composition was prepared.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 quantum dot Synthesis Example 2-1 10 7 3 10 Synthesis Example 2-2 10 Synthesis Example 2-3 10 Synthesis Example 2-4 10 3 7 curable resin Synthesis Example 3-1 65 65 65 65 65 65 70 heat curing agent 10 10 10 10 10 10 thermal polymeric resin 10 10 10 10 10 10 15 scattering particles 5 5 5 5 5 5 5 Sum 100 100 100 100 100 100 100

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 quantum dot Synthesis Example 2-1 10 Synthesis Example 2-5 10 Synthesis Example 2-6 10 Synthesis Example 2-7 10 curable resin Synthesis Example 3-1 65 65 65 Synthesis Example 3-2 65 heat curing agent 10 10 10 10 thermal polymeric resin 10 10 10 10 scattering particles 5 5 5 5 Sum 100 100 100 100

Thermal curing agent: thiol compound of formula 17

Thermal polymeric resin: Sumi Epoxy ESCN 195XL (Sumitomo Kagaku Kogyo Co., Ltd.)

Scattering particles: TR-88 (TiO ₂ , 220 nm, manufactured by Huntsman)

Experimental example One:

After preparing a light conversion sheet as follows using the light conversion resin composition prepared in the above Examples and Comparative Examples, heat resistance and high temperature and high humidity resistance were evaluated as follows.

<Manufacture of light conversion sheet>

The light conversion resin composition was applied on a 5cm×5cm glass substrate by spin coating, then placed on a heating plate and maintained at a temperature of 100°C for 10 minutes to form a thin film, and then heated in a heating oven at 180°C for 30 minutes to form a light conversion layer. was manufactured. The thickness of the light conversion layer prepared above was 10 μm.

(1) heat resistance

After placing the light conversion sheet on top of a blue light source (XLamp XR-E LED, Royal blue 450 illuminance 3mW/cm ² , Cree Co.), the luminance was measured using a luminance meter (CAS140CT Spectrometer, Instrument systems Co.), and the same After heating the light conversion sheet in a heating oven at 230 ° C. for 30 minutes, the luminance was measured in the same manner as above, and the luminance retention after heating was calculated by Equation 1 below to evaluate heat resistance.

[Equation 1]

Luminance retention rate = (luminance after treatment at 230°C for 30 minutes)/(luminance before treatment at 230°C for 30 minutes) × 100

The results are shown in Table 4 below. At this time, it can be determined that the higher the numerical value, the better the heat resistance.

(2) resistance to high temperature and humidity

After placing the light conversion sheet on top of a blue light source (XLamp XR-E LED, Royal blue 450 illuminance 3mW/cm ² , Cree Co.), the luminance was measured using a luminance meter (CAS140CT Spectrometer, Instrument systems Co.), and the same After exposing the light conversion sheet in a high-temperature, high-humidity treatment device (TH-PE manufactured by Jeio Tech) for 250 hours at a temperature of 80 ° C and a humidity of 85%, the luminance was measured in the same way as above, and the luminance retention rate after the high-temperature and high-humidity treatment was calculated using the following formula The high temperature and high humidity resistance was evaluated by calculating with Equation 2.

[Equation 2]

Luminance retention rate = (temperature 80℃, humidity 85%, luminance after 250 hours treatment)/(temperature 80℃, humidity 85%, luminance before 250 hours treatment) × 100

The results are shown in Table 4 below. At this time, it can be determined that the higher the numerical value, the better the high temperature and high humidity resistance.

heat resistance resistance to high temperature and humidity Example 1 85% 95% Example 2 84% 93% Example 3 86% 94% Example 4 86% 93% Example 5 85% 95% Example 6 86% 96% Example 7 82% 90% Comparative Example 1 71% 84% Comparative Example 2 70% 82% Comparative Example 3 75% 86% Comparative Example 4 73% 79%

As shown in Table 4, the photoconversion sheets formed by the photoconversion resin compositions of Examples 1 to 7 including quantum dots having a thiocarboxylic acid compound ligand and a cardo-based resin according to the present invention were compared to Comparative Examples 1 to 4. It was confirmed that the heat resistance and high temperature and high humidity properties were more excellent.

Having described specific parts of the present invention in detail above, it is clear that these specific techniques are only preferred embodiments for those skilled in the art to which the present invention belongs, and the scope of the present invention is not limited thereto. do. Those skilled in the art to which the present invention pertains will be able to make various applications and modifications within the scope of the present invention based on the above information.

Accordingly, the substantial scope of the present invention will be defined by the appended claims and equivalents thereof.

Claims (15)

A light conversion resin composition comprising quantum dots and a curable resin,
The quantum dot has a ligand layer containing a thiocarboxylic acid compound of Formula 1 on the surface,
The quantum dot includes a first quantum dot and a second quantum dot having different central emission wavelengths (λmax), and the difference between the central emission wavelengths of the first quantum dot and the second quantum dot is 60 nm or more,
The curable resin is a light conversion resin composition comprising a cardo-based resin:
[Formula 1]

In the above formula,
R ^a is a C ₁ -C ₃ alkylene group;
R ^b is a C ₄ -C ₂₂ alkyl group or a C ₄ -C ₂₂ alkenyl group. The light conversion resin composition according to claim 1, wherein the thiocarboxylic acid compound of Formula 1 is a compound represented by any one of Formulas 2 to 5:
[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In the above formula,
R ^b is a C ₄ -C ₂₂ alkyl group or a C ₄ -C ₂₂ alkenyl group. The light conversion resin composition according to claim 1, wherein R ^b is a C ₁₀ -C ₁₄ alkyl group or a C ₁₀ -C ₁₄ alkenyl group. The light conversion resin composition according to claim 1, wherein the thiocarboxylic acid compound of Formula 1 is a compound represented by any one of Formulas 6 to 9:
[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

The method of claim 1, wherein the quantum dots have a core-shell structure including a core and a shell covering the core,
The core may include InP, InZnP, InGaP, CdSe, CdS, CdTe, ZnS, ZnSe, ZnTe, CdSeTe, CdZnS, CdSeS, PbSe, PbS, PbTe, AgInZnS, HgS, HgSe, HgTe, GaN, GaP, GaAs, InGaN InAs and Including one or more of ZnO,
The shell includes at least one of ZnS, ZnSe, ZnTe, ZnO, CdS, CdSe, CdTe, CdO, InP, InS, GaP, GaN, GaO, InZnP, InGaP, InGaN, InZnSCdSe, PbS, TiO, SrSe, and HgSe. A light conversion resin composition to do. delete The light conversion resin composition of claim 1, wherein the cardo-based resin includes at least one repeating unit of Formulas 10 to 15:
[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

In the above formula,
X and X' are each independently a single bond, -CO-, -SO ₂ -, -C(CF ₃ ) ₂ -, -Si(CH ₃ ) ₂ -, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-,

,

,

,

,

,

,

,

,

,

,

,

or

ego,
Y is an acid anhydride residue,
Z is an acid dianhydride moiety;
R''' is a hydrogen atom, an ethyl group, a phenyl group, -C ₂ H ₄ Cl, -C ₂ H ₄ OH or -CH ₂ CH=CH ₂ ;
R1, R1', R2, R2', R3, R3', R4, R4', R5, R5', R6 and R6' are each independently a hydrogen atom or a methyl group;
R7, R7', R8 and R8' are each independently a C ₁ -C ₆ alkylene group, and the alkylene group is interposed with or without at least one of an ester bond, a C ₆ -C ₁₄ cycloalkylene group and an arylene group, ,
R9, R9', R10, R10', R11, R11', R12 and R12' are each independently a hydrogen atom, a halogen atom or a C ₁ -C ₆ alkyl group,
m and n are each independently an integer from 1 to 30;
P is each independently

,

,

,

or

ego,
R13 and R14 are each independently a hydrogen atom, a hydroxyl group, a thiol group, an amino group, a nitro group or a halogen atom;
Ar1 is each independently an aryl group,
Y' is an acid anhydride residue,
Z' is an acid dianhydride moiety;
A is O, S, NR''', Si(R''') ₂ or Se;
a and b are each independently an integer from 1 to 6,
p and q are each independently an integer of 1 to 30; The acid anhydride of claim 7, wherein the acid anhydride is maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride and methyltetrahydrophthalic anhydride. A light conversion resin composition selected from the group consisting of phthalic acid. The light conversion resin composition according to claim 7, wherein the acid dianhydride is selected from the group consisting of pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride and biphenylethertetracarboxylic dianhydride. The light conversion resin composition according to claim 1, further comprising a heat curing agent. The light conversion resin composition of claim 10, wherein the thermosetting agent comprises a thiol compound represented by Formula 16:
[Formula 16]

In the above formula,
R ^s is hydrogen or a C ₁ -C ₁₂ alkyl group;
R ^p is a C ₁ -C ₁₂ alkylene group,
R ^q is a t-valent aliphatic hydrocarbon group with or without a hetero atom;
t is an integer from 2 to 4. The light conversion resin composition according to claim 11, wherein R ^q is trivalent trimethylpropane, divalent n-butane, tetravalent tetramethylmethane or trivalent triethylisocyanurate. The light conversion resin composition according to claim 11, wherein the thiol compound of Formula 16 is a compound represented by any one of Formulas 17 to 24:
[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

[Formula 22]

[Formula 23]

[Formula 24]

A light conversion sheet formed by using the light conversion resin composition according to any one of claims 1 to 5 and 7 to 13. An image display device comprising the light conversion sheet according to claim 14.