KR20210087791A - Quantum dot optical film and quantum dot composition comprising therein - Google Patents

Abstract

The present invention relates to a quantum dot optical film and a quantum dot composition contained therein, wherein the quantum dot optical film comprises: a base film; a polymer matrix disposed on the base film; and a quantum dot-containing layer comprising a plurality of quantum dots dispersed in the polymer matrix, wherein the polymer matrix may include: a first photopolymerizable monomer having a carbon-carbon unsaturated bond at a terminal thereof; a second photopolymerizable monomer containing a thiol group at the terminal; and a cured product of the composition comprising at least one barrier material selected from a group consisting of halogen compounds and oxygen scavengers. The quantum dot optical film has excellent barrier properties even if a general optical film is used instead of a barrier film.

Description

Quantum dot optical film and quantum dot composition included therein {QUANTUM DOT OPTICAL FILM AND QUANTUM DOT COMPOSITION COMPRISING THEREIN}

The present invention relates to a quantum dot optical film and a quantum dot composition included therein, and more particularly, to a quantum dot optical film with improved barrier properties and a quantum dot composition included therein.

Quantum dots (QDs) are so-called semiconductor nanocrystals, which can emit light of different wavelengths for each particle size without changing the material type and can produce various colors, and have higher color purity and light stability than conventional light emitting materials. Because of its advantages, it is attracting attention as a next-generation light emitting device.

These quantum dots are dispersed in a polymer matrix and applied to a display in the form of a complex, playing a major role in realizing high luminance and high color reproduction of the display. However, unlike inorganic phosphors, quantum dots have a problem in that luminance decreases when exposed for a long time because they are vulnerable to external factors such as moisture or oxygen. Accordingly, in the prior art, a quantum dot optical film in which a barrier film including a barrier layer for preventing or removing moisture or oxygen is disposed on both sides of a polymer layer containing quantum dots was prepared. However, in the conventional quantum dot optical film, the deterioration of the edge portion occurred, and the manufacturing cost increased due to the high price of the barrier film, so both technical and economical aspects did not produce satisfactory results.

An object of the present invention is to provide a quantum dot optical film having excellent barrier properties even when a general optical film is used instead of a barrier film.

In order to achieve the above technical problem, the present invention is a base film; and disposed on one surface of the base film, a polymer matrix; and a quantum dot-containing layer including a plurality of quantum dots dispersed in the polymer matrix, wherein the polymer matrix includes: a first photopolymerizable monomer having a carbon-carbon unsaturated bond at a terminal thereof; a second photopolymerizable monomer containing a thiol group at the terminal; And it provides a quantum dot optical film comprising a cured product of a photocurable composition comprising one type of barrier material selected from the group consisting of halogen compounds and oxygen scavengers.

According to one example, the quantum dot optical film may not contain a barrier layer between the base film and the quantum dot-containing layer.

According to another example, the quantum dot-containing layer may include the polymer matrix and the plurality of quantum dots in a weight ratio of 70:30 to 99:1.

According to another example, the first photopolymerizable monomer and the second photopolymerizable monomer may be included in a weight ratio of 40:60 ~ 90:10.

According to another example, the first photopolymerizable monomer may include a trifunctional or less low-functionality (meth) acrylate monomer and a polyfunctional (meth) acrylate monomer of tetrafunctional or more.

According to another example, a mixing ratio of the low-functionality (meth)acrylate monomer and the polyfunctionality (meth)acrylate monomer may be 90:10 to 10:90 by weight.

According to another example, the low-functionality (meth)acrylate monomer may contain a trifunctional or less (meth)acrylate monomer having a weight average molecular weight (Mw) of 100 to 600 g/mol.

According to another example, the polyfunctional (meth)acrylate monomer may contain a tetrafunctional or more (meth)acrylate monomer having a weight average molecular weight (Mw) of 300 to 1000 g/mol.

According to another example, the content of the halogen compound may be 0.1 to 5 parts by weight based on 100 parts by weight of the quantum dot-containing layer.

According to another example, the content of the oxygen scavenger may be 0.1 to 5 parts by weight based on 100 parts by weight of the quantum dot-containing layer.

According to another example, a second base film disposed on the quantum dot-containing layer may be further included.

In addition, the present invention is a quantum dot; a first photopolymerizable monomer having a carbon-carbon unsaturated bond at the terminal; a second photopolymerizable monomer containing a thiol group at the terminal; And it provides a quantum dot composition comprising at least one barrier material selected from the group consisting of halogen compounds and oxygen scavengers.

According to an example, the composition, based on the total amount of the composition, 1 to 30% by weight of quantum dots; 40 to 80% by weight of a first photopolymerizable monomer; and 19 to 50% by weight of the second photopolymerizable monomer.

According to another example, the composition may further include an initiator.

According to another example, the composition may include 0.1 to 5 parts by weight of a halogen compound based on 100 parts by weight of the total content of the quantum dots, the first photopolymerizable monomer, the second photopolymerizable monomer and the initiator; and 0.1 to 5 parts by weight of an oxygen scavenger.

The quantum dot optical film according to the present invention has excellent barrier properties even when a general optical film is used instead of the barrier film, thereby extending the soft plate used for display applications.

1 is a cross-sectional view schematically showing a quantum dot optical film according to a first embodiment of the present invention.
2 is a cross-sectional view schematically showing a quantum dot optical film according to a second embodiment of the present invention.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated.

All terms (including technical and scientific terms) used in this specification may be used in the meaning commonly understood by those of ordinary skill in the art to which the present invention pertains, unless otherwise defined. In addition, terms defined in a commonly used dictionary are not to be interpreted ideally or excessively unless clearly specifically defined.

In addition, throughout the present specification, when a part "includes" a certain component, it means that other components may be further included, rather than excluding other components, unless otherwise stated. In addition, throughout the specification, "on" or "on" means that it includes not only the case where it is located above or below the target part, but also the case where there is another part in the middle, and the direction of gravity must be It does not mean that it is positioned above the reference.

In addition, in this specification, "(meth)acrylate" represents acrylate and methacrylate, "(meth)acryl" represents acryl and methacryl, and "(meth)acryloyl" represents acryloyl and methacryloyl.

In addition, in this specification, "monomer" and "monomer" have the same meaning. The monomer in this invention is distinguished from an oligomer and a polymer, and says the compound whose weight average molecular weight is 1,000 or less. In the present specification, the "polymerizable functional group" refers to a group involved in a polymerization reaction, such as a (meth)acrylate group.

<Quantum dot composition>

The quantum dot composition according to the present invention is a composition for forming a film (or sheet) containing quantum dots, and a layer containing a polymer matrix and a plurality of quantum dot (QD) particles dispersed in the polymer matrix (hereinafter, 'quantum dot-containing layer') It is a curable composition that forms

According to one example, the quantum dot composition of the present invention is a quantum dot; a first photopolymerizable monomer having a carbon-carbon unsaturated bond at the terminal; a second photopolymerizable monomer containing a thiol group at the terminal; and at least one barrier material selected from the group consisting of halogen compounds and oxygen scavengers. Optionally, it may further include photoinitiators and/or additives.

Hereinafter, the composition of the quantum dot composition according to the present invention will be described.

(a) quantum dots

In the quantum dot composition according to the present invention, quantum dots (Quantum Dot, QD) are nano-sized semiconductor materials, and may have different energy band gaps depending on the size and composition, and thus may emit light of various emission wavelengths.

These quantum dots have a homogeneous single-layer structure; multi-layer structures such as core-shell shapes, gradient structures, and the like; or a mixed structure thereof. When the shell is multi-layered, each layer may contain different components, for example (semi)metal oxides.

The quantum dot (QD) may be freely selected from a group II-VI compound, a group III-V compound, a group IV-VI compound, a group IV element, a group IV compound, and combinations thereof. When the quantum dot is in a core-shell form, the core and the shell may be freely configured from the components exemplified below, respectively.

For example, the group II-VI compound may include a diatomic compound selected from the group consisting of CdO, CdS, CdSe, CdTe, ZnO, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, MgSe, MgS, and mixtures thereof; CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgZnTe, HgZnS, HgZnSe, HgZnTe, MgZnS, MgZnTe, MgZnS and mixtures thereof bovine compounds; and CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, and mixtures thereof.

In another example, the group III-V 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, and mixtures thereof; and GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, and mixtures thereof. have.

In another example, the group IV-VI compound is a binary 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 a quaternary compound selected from the group consisting of SnPbSSe, SnPbSeTe, SnPbSTe, and mixtures thereof.

In another example, the group IV element may be selected from the group consisting of Si, Ge, and mixtures thereof. The group IV compound may be a di-element compound selected from the group consisting of SiC, SiGe, and mixtures thereof.

The above-described binary, ternary or quaternary compound may be present in the particle at a uniform concentration, or may be present in the same particle as the concentration distribution is partially divided into different states. Also, one quantum dot may have a core/shell structure surrounding another quantum dot. The interface between the core and the shell may have a concentration gradient in which the concentration of the element present in the shell decreases toward the center.

A portion of the surface of the quantum dots may be substituted with an organic ligand. Such an organic ligand may be bound to the surface of the quantum dot to serve to stabilize the quantum dot. Non-limiting examples of organic ligands that can be used include, but are not limited to, C ₅ to C ₂₀ alkyl carboxylic acids, alkenyl carboxylic acids or alkynyl carboxylic acids; pyridine; mercapto alcohol; thiol; phosphine; phosphine oxide; primary amines; secondary amines; or a combination thereof. A method of substituting a part of the surface of the quantum dot with an organic ligand is not limited in the present invention, and a conventional method performed in the art may be used.

The form of the quantum dot is not particularly limited as long as it is a form generally used in the art. For example, spherical, rod-shaped, pyramid-shaped, disk-shaped, multi-arm, or cubic nanoparticles, nanotubes, nanowires, nanofibers, and nanoplatelet particles and the like can be used.

In addition, the size of the quantum dots is not particularly limited, and may be appropriately adjusted within a conventional range known in the art. As an example, the average particle diameter (D ₅₀ ) of the quantum dots may be about 2 to 10 nm. In this way, when the particle size of the quantum dots is controlled to be approximately in the range of about 2 to 10 nm, light of a desired color may be emitted. For example, when the particle size of the quantum dot core/shell containing InP is about 5 to 6 nm, light having a wavelength of about 520 to 550 nm can be emitted, while the particle size of the quantum dot core/shell containing InP is about In the case of 7 to 8 nm, light having a wavelength of about 620 to 640 may be emitted. For example, a non-cadmium (Cd)-based group III-V QD (eg, InP, InGaP, InZnP, GaN, GaAs, GaP) can be used as the blue-emitting quantum dot (QD).

In addition, the quantum dots may have a full width of half maximum (FWHM) of an emission wavelength spectrum of about 40 nm or less, and color purity or color reproducibility may be improved in this range. In addition, since the light emitted through the quantum dots is emitted in all directions, a wide viewing angle may be improved.

If necessary, the quantum dots may further include a polymer coating layer formed on a part or all of the surface. The polymer coating layer may include a polymer resin known in the art, such as a thermosetting polymer resin, a photocurable polymer resin, or a combination thereof. Specifically, it may be a resin selected from the group consisting of (meth)acrylic resins, urethane acrylate-based resins, and combinations thereof. The polymer constituting the polymer coating layer may include a functional resin that does not include a substituent or has at least one substituent selected from the group consisting of an acrylate group, an acryloyl group, a vinyl group, a thiol group, and combinations thereof.

In the present invention, the content of quantum dots may be appropriately adjusted within a range known in the art, for example, may be about 1 to 30% by weight based on the total amount of the quantum dot composition. Accordingly, the quantum dot-containing layer formed of the quantum dot composition of the present invention may include a polymer matrix and quantum dots in a weight ratio of 70:30 to 99:1.

(b) photopolymerizable monomers

In the quantum dot composition of the present invention, the photopolymerizable monomer is a component that forms a formulation in which quantum dots (QD) are dispersed, that is, a polymer matrix, and controls the overall crosslinking density of the polymer matrix to express the structure and general properties of the matrix. .

The photopolymerizable monomer according to the present invention may include a monomer having a carbon-carbon unsaturated bond at the terminal (hereinafter, 'first photopolymerizable monomer'); and a monomer containing a thiol group at the terminal (hereinafter, 'second photopolymerizable monomer'). As such, the present invention uses a mixture of the first photopolymerizable monomer and the second photopolymerizable monomer, unlike the case of using a monomer having a carbon-carbon unsaturated bond at the terminal alone, after photopolymerization, the quantum dot optical film is curled It is possible to prevent development and deterioration of barrier properties. In addition, in the present invention, unlike the case of using a monomer containing a thiol group at the terminal alone, it is possible to prevent the non-curing phenomenon after photopolymerization.

The first photopolymerizable monomer and the second photopolymerizable monomer are included in a weight ratio of 40:60 to 90:10. Accordingly, it is possible to improve the barrier properties of the quantum dot optical film without curling and non-curing of the quantum dot optical film after photopolymerization.

a) a first photopolymerizable monomer

In the quantum dot composition according to the present invention, the first photopolymerizable monomer is a component that forms a polymer matrix in which quantum dots (QD) are dispersed together with the second photopolymerizable monomer, and has flexibility and adhesiveness and adhesion with other materials can be improved

The first photopolymerizable monomer is a monomer having a carbon-carbon unsaturated bond at the terminal, specifically, having a carbon-carbon double bond or carbon-carbon triple bond at the terminal, and more specifically, a (meth)acrylate group at the terminal, acrylic It may have at least one of a loyl group, a methacryloyl group, an aryl group, and a vinyl group.

According to an example, the first photopolymerizable monomer may be a (meth)acrylate monomer.

The (meth) acrylate monomer includes a monofunctional acrylic monomer (f = 1), a bifunctional acrylic monomer (f = 2), depending on the number of polymerizable functional groups, such as (meth) acrylate groups, included in one molecule; It may be classified into a trifunctional acrylate monomer (f = 3) and a polyfunctional acrylate monomer having more than tetrafunctionality (f ≥ 4).

In the present invention, at least one (meth)acrylate monomer is used as the first photopolymerizable monomer, and specifically, a trifunctional or less functional (meth)acrylate monomer; and a polyfunctional (meth)acrylate monomer having a tetrafunctional or higher function may be mixed.

Here, the low-functionality (meth)acrylate monomer and the polyfunctionality (meth)acrylate monomer both contribute to forming a crosslinked structure through photocuring. In particular, the polyfunctional (meth)acrylate monomer containing at least 4 polymerizable functional groups forms a more dense and dense three-dimensional network crosslinking structure due to the number of functional groups included in the molecule, thereby forming a crosslinking density and glass transition of the matrix. A temperature (Tg) improvement effect can be realized. In consideration of these properties, a mixing ratio of the low-functionality (meth)acrylate monomer and the polyfunctionality (meth)acrylate monomer may be 90:10 to 10:90 by weight.

The low-functionality (meth)acrylate monomer may be used without limitation as long as it is a (meth)acrylate monomer containing 3 or less, specifically 2 to 3, photopolymerizable unsaturated groups in the molecule. According to an example, the low-functionality (meth)acrylate may include at least one of a bifunctional (meth)acrylate monomer and a trifunctional (meth)acrylate monomer, and specifically, a bifunctional (meth)acrylate monomer may include.

Examples of the bifunctional (meth)acrylate monomer usable in the present invention include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polyolefin glycol di(meth)acrylate, ethoxylated polypropylene glycol di( Meth)acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, 2-hydroxy-1,3-dimethacryloxypropane, dioxane glycol di(meth)acrylate, tricyclodecanedi Methanol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, glycerin di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth) ) acrylate, 1,10-decanediol di(meth)acrylate, neopentylglycol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate, 1,9-nonanediol Di(meth)acrylate, butylethylpropanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, and di(meth)acrylate having an aromatic ring, for example Examples thereof include, but are not limited to, ethoxylated bisphenol A di(meth)acrylate, propoxylated ethoxylated bisphenol A di(meth)acrylate, and ethoxylated bisphenol F di(meth)acrylate. These may be used alone or two or more of them may be used in combination.

Examples of the trifunctional (meth)acrylate monomer usable in the present invention include ethoxylated glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxy and trimethylolpropane tri(meth)acrylate and pentaerythritol tri(meth)acrylate.

The weight average molecular weight (Mw) of the low-functionality (meth)acrylate monomer is about 100 g/mol or more, and may specifically be about 100 to 600 g/mol.

As the polyfunctional (meth)acrylate monomer, a known (meth)acrylate monomer containing 4 or more, specifically 4 to 6, photopolymerizable unsaturated groups in a molecule may be used without limitation. According to one example, the polyfunctional (meth) acrylate monomer may include at least one of a tetrafunctional (meth) acrylate monomer and a pentafunctional (meth) acrylate monomer, and specifically, a tetrafunctional (meth) acrylate monomer can be

Non-limiting examples of the polyfunctional (meth)acrylate monomer usable in the present invention include pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acryl tetrafunctional (meth)acrylate monomers such as rate and the like; 5-functional (meth)acrylate monomers such as dipentaerythritol pentaacrylate, propionic acid-modified dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, propionic acid-modified dipentaerythritol pentamethacrylate; 6-functional (meth)acrylate monomers such as dipentaerythritol hexaacrylate, caprolactone-modified dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, caprolactone-modified dipentaerythritol hexamethacrylate, etc. There are, these may be used alone or two or more of them may be used in combination. According to one example, the polyfunctional (meth)acrylate monomer may be the same tetrafunctional (meth)acrylate monomer, specifically ditrimethylolpropane tetra(meth)acrylate.

The weight average molecular weight (Mw) of the polyfunctional (meth)acrylate monomer may be about 300 g/mol or more, specifically, about 300 to 1,000 g/mol.

In addition, the first photopolymerizable monomer of the present invention is carboxylic acid vinyl ester compounds such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, 3-butenoic acid, vinyl acetate, vinyl benzoate; alkenyl aromatic compounds such as styrene, alpha-methyl styrene, vinyl toluene, and vinyl benzyl methyl ether; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; One or more types of unsaturated amide compounds such as acrylamide and methacrylamide may be included. These monomers may be used alone or in combination with the above-mentioned (meth)acrylate monomers.

In the quantum dot composition of the present invention, the content of the first photopolymerizable monomer may be appropriately adjusted within a range known in the art in consideration of the structure and physical properties of the polymer matrix. For example, the content of the first photopolymerizable monomer may be about 40 to 80% by weight based on the total amount of the quantum dot composition (however, excluding the barrier material).

At this time, when the first photopolymerizable monomer contains a low-functionality (meth)acrylate and a polyfunctionality (meth)acrylate monomer, the content of the low-functionality (meth)acrylate monomer is the quantum dot composition (provided that the barrier material It may be about 20 to 60% by weight based on the total amount of the (excluding silver), and the content of the polyfunctional (meth)acrylate monomer is from about 10 to about the total amount of the quantum dot composition (except for the barrier material). 50% by weight. When the content of the polyfunctional (meth)acrylic monomer falls within the above range, the crosslinking structure and density of the matrix are improved by appropriately adjusting the viscosity and crosslinking density of the quantum dot composition, and the glass transition temperature (Tg) can be improved. .

b) a second photopolymerizable monomer

In the quantum dot composition of the present invention, the second photopolymerizable monomer is also a component that forms a polymer matrix, like the first photopolymerizable monomer, and controls the overall crosslinking density of the polymer matrix to express the structure and various physical properties of the polymer matrix. do.

The second photopolymerizable monomer is a compound containing a thiol group (-SH) at the terminal, specifically, one or more, more specifically, two or more (eg, 2 to 4) of thiol groups at the terminal. It may be a compound.

As the second photopolymerizable monomer usable in the present invention, any thiol-terminated compound in the art may be used without particular limitation, for example, a thiol-terminated polyester monomer, a thiol-terminated poly(meth)acrylate There are monomers and the like, but is not limited thereto. Here, the polyester is a compound including a plurality of ester groups in the molecular skeleton, and may include, for example, 2 to 4 ester groups. In addition, the polyacrylate monomer is a compound including a plurality of (meth)acrylate groups in the molecular skeleton, and may include, for example, 2 to 4 (meth)acrylate groups.

According to one example, the second photopolymerizable monomer may be a monomer represented by the following formula (1). However, the present invention is not limited thereto.

[Formula 1]

(In the above formula,

L ₁ is carbon, a C ₆ ~ C ₃₀ arylene group, a heteroarylene group having 5 to 30 nuclear atoms, a C ₃ ~ C ₃₀ cycloalkylene group, and a heterocycloalkylene group having 3 to 30 nuclear atoms. is selected from

Y _{1 To} Y _{4 Are} the same as or different from each other, and each independently selected from the group consisting _{of a direct bond (single bond), a C 1} ~ C ₃₀ alkylene group, and a C ₂ ~ C _{30 alkenylene group,}

At this time, at least one methylene (-CH _{2 -) in the C 1} ~ C ₃₀ alkylene group and the C ₂ ~ C ₃₀ alkenylene group is an ester (-C (= O) O-), an amide (-C (= O)NR-) (R is hydrogen or a C ₁ -C ₁₀ alkyl group), carbonyl (-C(=O)-), ether (-O-), sulfide (-S-) and sulfoxide (- S(=O)-) may be substituted or unsubstituted with one or more selected from the group consisting of,

R _{1 To} R ₄ are the same as or different from each other, and each independently a thiol group (-SH), hydrogen, halogen group, cyano group, nitro group, amino group, C ₁ ~ C ₃₀ alkyl group, C ₃ ~ C ₃₀ cyclo An alkyl group, a heterocycloalkyl group having 3 to 30 nuclear atoms, a C ₆ to C ₃₀ aryl group, a heteroaryl group having 3 to 30 nuclear atoms, a C ₆ to C ₃₀ alkoxy group and a hydroxyl group (-OH) is selected from

However _{, at least two of R 1} to R ₄ are thiol groups (-SH)).

Specifically, non-limiting examples of the second photopolymerizable monomer include pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate) [trimethylopropane tris (3-mercaptopropionate) ], pentaerythritol tetrakis(3-mercaptopropionate) [pentaerythritol tetrakis(3-mercaptopropionate)], pentaerythritol tetrakis(2-mercaptoacetate) [pentaerythritol tetrakis(2-mercaptoacetate)], dipenta Erythritol hexakis (3-mercaptopropionate), tris [2- (3-mercaptopropionyloxy) alkyl] isocyanurate (tris [2- (3-mercaptopropionyloxy) alkyl] isocyanurate), tris- [2-(3-mercaptopropionyloxy)-ethyl] isocyanurate (tris[2-(3-mercaptopropionyloxy)ethyl] isocyanutte), pentaerythritol tetrakis (pentaerythritol tetrakis) (3-mercaptobutylate), ethylene glycol bis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate) )) and the like, and these may be used alone or in combination of two or more.

In the quantum dot composition of the present invention, the content of the second photopolymerizable monomer may be appropriately adjusted within a range known in the art in consideration of the structure and physical properties of the polymer matrix. For example, the content of the second photopolymerizable monomer may be about 19 to 50% by weight based on the total amount of the quantum dot composition (provided that the barrier material is excluded).

(c) barrier material

In the quantum dot composition according to the present invention, the barrier material is a material that prevents substances such as moisture, humidity, and oxygen from being transferred into the optical film to deteriorate the quantum dots, and contains at least one of a halogen compound and an oxygen scavenger.

Halogen compounds are substances containing halogens known in the art (eg, F, Cl, Br, I, etc.), and because they can prevent the penetration of oxygen and moisture, effectively delay or prevent oxidative damage of quantum dots can do. Because of these halogen compounds, the quantum dot optical film of the present invention has excellent barrier properties even if a separate barrier layer is not included between the base film and the quantum dot-containing layer. In addition, the quantum dot optical film of the present invention may have excellent barrier properties under high temperature conditions as well as high temperature and high humidity conditions.

Examples of the halogen compound may be at least one of a halide and an oxyhalide, specifically, may be at least one of an inorganic halide and an inorganic oxyhalide, and more specifically may be an inorganic halide.

Here, the inorganic halide is a conventional compound in which at least one metal and at least one halogen atom are ionically bonded, for example, ZnCl ₂ , ZnBr ₂ , ZnI _{2 There} are zinc (Zn)-based halides such as ZnI 2 . However, it is not particularly limited thereto. In addition, the inorganic oxyhalide (oxyhalide, oxohalide) is a compound in which an oxygen atom and a halogen atom are each bonded to a metal (M) in a single molecule, and may be, for example, a zirconium (Zr)-based oxyhalide such _{as ZrOCl 2 .} The above-mentioned components may be used alone, or two or more of them may be used in combination.

For example, the halogen compound may be a compound represented by the following Chemical Formula 2, but is not limited thereto.

[Formula 2]

MO _a X _b

(In the above formula,

M is a metal selected from the group consisting of alkali metals, alkaline earth metals, transition metals and post-transition metals, specifically Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, It may be one or more metals selected from the group consisting of Al, Zn, Zr, In and Pb, and more specifically, may be one or more metals selected from the group consisting of Na, Mg, Zn, In and Pb, and more Specifically, it may be Zn,

X is a halogen selected from the group consisting of F, Cl, Br, and I;

a is an integer from 0 to 2,

b is an integer from 1 to 3).

In the present invention, since the oxygen scavenger can remove (or absorb) oxygen in the quantum dot optical film, it is possible to effectively delay or prevent the oxidative damage of the quantum dot. Because of this oxygen scavenger, the quantum dot optical film of the present invention has excellent barrier properties even if it does not include a separate barrier layer between the base film and the quantum dot-containing layer. In addition, the quantum dot optical film of the present invention may have excellent barrier properties under high temperature conditions as well as high temperature and high humidity conditions.

As the oxygen scavenger usable in the present invention, any material that removes or absorbs oxygen in the art can be used without limitation, for example, morpholine, titanium dioxide, paraben, C ₁ ~ C ₆ alkyl paraben, sodium sulfite (sodium sulfite), sodium bisulfite (sodium bisulfite), triphenyl phosphine, ascorbic acid derivatives, thiourea derivatives, and the like, but are not limited thereto. These may be used alone or in combination of two or more.

In the quantum dot composition of the present invention, the content of the barrier material may be about 0.1 to 10 parts by weight based on 100 parts by weight of the total amount of the quantum dot composition (except for the barrier material). If the content of the barrier material is less than about 0.1 parts by weight, the barrier properties of the quantum dot-containing layer itself may be reduced, while if the content of the barrier material exceeds about 10 parts by weight, the optical properties of the quantum dot optical film will be lowered. can

For example, when the barrier material contains a halogen compound alone, the content of the halogen compound may be about 0.1 to 5 parts by weight based on 100 parts by weight of the total amount of the quantum dot composition (except for the barrier material). As another example, when the barrier material contains the oxygen scavenger alone, the content of the oxygen scavenger may be about 0.1 to 5 parts by weight based on 100 parts by weight of the total amount of the quantum dot composition (except for the barrier material). As another example, when the barrier material contains both a halogen compound and an oxygen scavenger, their total content may be about 0.2 to 10 parts by weight based on 100 parts by weight of the total amount of the quantum dot composition (except for the barrier material). In this case, the mixing ratio of the halogen compound and the oxygen scavenger may be 1: 0.5 to 2 weight ratio.

(d) initiator

The quantum dot composition according to the present invention may further include an initiator if necessary. The initiator is not particularly limited as long as it is capable of generating radicals in the art, and examples thereof include a photoinitiator or a thermal initiator.

According to one example, the quantum dot composition of the present invention may further include at least one selected from the group consisting of a photoinitiator and a thermal initiator.

The photoinitiator is a component that is excited by a light source such as ultraviolet (UV) light to initiate photopolymerization, and a conventional photopolymerization photoinitiator in the art may be used without limitation. For example, an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, a triazine-based compound, an oxime-based compound, and the like may be used.

Non-limiting examples of usable photoinitiators, Irgacure 184, Irgacure 369, Irgacure 651, Irgacure 819, Irgacure 907, benzion alkyl ether (Benzionalkylether), benzophenone (Benzophenone), benzyl dimethyl catal (Benzyl dimethyl kata), hydride Hydroxycyclohexyl phenylacetone, Chloroacetophenone, 1,1-Dichloro acetophenone, Diethoxy acetophenone, Hydroxyacetophenone (diethoxyaceto) Phenone (Hydroxy Acetophenone), 2-chlorothioxanthone (2-Choro thioxanthone), 2-ETAQ (2-EthylAnthraquinone), 1-Hydroxy-cyclohexyl-phenyl-ketone (1-Hydroxy-cyclohexyl-phenyl-ketone) , 2-hydroxy-2-methyl-1-phenyl-1-propanone (2-Hydroxy-2-methyl-1-phenyl-1-propanone), 2-hydroxy-1-[4- (2-hydroxyl) Roxyethoxy)phenyl]-2-methyl-1-propanone (2-Hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone), methylbenzoylformate, etc. These may be used alone or in combination of two or more.

The thermal initiator generates radicals by a predetermined heat to initiate polymerization, and any conventional thermal polymerization initiator known in the art may be used without limitation.

The thermal initiator may have a use temperature of about 35 °C or higher, specifically about 35-100 °C. When a thermal initiator having such a use temperature is used, thermal curing may proceed simultaneously due to heat generated during photocuring according to UV irradiation. Therefore, the curing reaction of the composition can be sufficiently performed even to the light-shielding portion (shaded area, shaded area) through which ultraviolet light cannot be transmitted without additional heating.

Possible thermal initiators in the present invention include azo-based compounds, peroxide-based compounds, hydroperoxide-based compounds, hydrazide-based compounds, imidazole-based compounds, and/or radicals under heating conditions. Other thermal initiator(s) capable of releasing Specifically, there are azonitrile, azo ester, azo amide, organic peroxide, inorganic peroxide, organic hydroperoxide, inorganic hydroperoxide, or mixtures thereof.

Specific examples include benzoyl peroxide, di-t-amyl peroxide, t-butyl peroxy benzoate, di-cumyl peroxide, t-amyl hydroperoxide and t-butyl hydroperoxide, 2,5-dimethyl- 2,5-di-(t-butylperoxy)hexyne-3) [2,5-Di(tert-butylperoxy)-2,5-dimethyl-3-hexyne], 2,5-dimethyl-2,5 -di-(tert-butylperoxy)hexane [2,5-Bis(tert-butylperoxy)-2,5-dimethylhexane], DuPont's VAZO compound [eg, VAZO 52 (2,2') -azobis (2,4-dimethylpentanenitrile)), bazo 64 (2,2'-azobis (2-methylpropanenitrile)), bazo 67 (2,2'-azobis (2-methylbutanenitrile) )), Vazo 88 (2,2'-azobis(cyclohexanecarbonitrile)), etc.], but is not limited thereto.

The content of the initiator may be appropriately adjusted within a range known in the art. As an example, based on the total weight of the quantum dot composition may be about 0.1 to 5 parts by weight. When the content of the initiator falls within the above-described range, the photopolymerization reaction may be sufficiently performed without deterioration of the physical properties of the matrix.

(e) Optionally, the quantum dot composition according to the present invention is at least one additive known in the art (eg, light scattering agent, solvent, dispersant, etc. ) may be further included without limitation. In this case, the content of the additive may be appropriately adjusted within a range known in the art.

Quantum dot composition according to the present invention, quantum dots (QD); at least one photopolymerizable monomer; and a barrier material, and optionally the photoinitiator and/or other additives may be prepared by mixing and stirring according to conventional methods known in the art.

For a specific example, the quantum dot composition of the present invention, based on the total amount of the quantum dot and the photopolymerizable monomer, about 1 to 30% by weight of the quantum dot; about 40-80% by weight of a first photopolymerizable monomer; and about 19 to 50% by weight of the second photopolymerizable monomer, and about 0.2 to 10 parts by weight of a barrier material based on 100 parts by weight, which is the total amount of the quantum dots and the photopolymerizable monomer.

For a more specific embodiment, the quantum dot composition of the present invention, based on the total amount of the quantum dot and the photopolymerizable monomer, about 1 to 30% by weight of the quantum dot; about 40-80% by weight of a first photopolymerizable monomer; and about 19 to 50% by weight of a second photopolymerizable monomer, and based on 100 parts by weight of the quantum dot and the photopolymerizable monomer, about 0.1 to 5 parts by weight of a halogen compound and more than about 0.1 to 5 parts by weight of oxygen Removers may be included.

<Quantum dot optical film>

According to an embodiment of the present invention, a photocured material of the above-described quantum dot composition, that is, a quantum dot-containing layer provides a quantum dot optical film.

Figure 1 is a cross-sectional view schematically showing a quantum dot optical film according to a first embodiment of the present invention, Figure 2 is a cross-sectional view schematically showing a quantum dot optical film according to a second embodiment of the present invention.

1 and 2, the quantum dot optical film (100A, 100B) of the present invention is a base film (110); and a quantum dot-containing layer 120 disposed on one surface of the base film 110 and including a polymer matrix 121, and a plurality of quantum dots 122 dispersed in the polymer matrix 121. and optionally, a second base film 130 disposed on the quantum dot-containing layer 120 may be further included.

Hereinafter, with reference to FIG. 1, a quantum dot optical film 100A according to a first embodiment of the present invention will be described. However, content overlapping with the quantum dot composition described above will be omitted.

(1) base film

In the quantum dot optical film 100A of the present invention, the base film 110 is a light-transmitting film, and while supporting the quantum dot-containing layer, it is possible to prevent contamination of the quantum dot-containing layer from foreign substances in the external environment.

The base film 110 usable in the present invention may be used without limitation as long as it is a conventional light-transmitting film known in the art. According to one example, the light-transmitting film may have a light transmittance of about 70 to 100% at a wavelength of about 380 to 780 nm.

Examples of the material of the light-transmitting film include polyesters such as polyethylene naphthalate, polycarbonate, cycloolefine polymer, polyethylene terephthalate (PET), and the like; polyolefine, polysulfone, polyimide, silicone, polystyrene, polyacryl, polyvinylchloride, and the like, but is not limited thereto. These may be used alone or two or more of them may be used in combination.

The base film 110 may be a single layer or a multilayer type in which two or more resin films are laminated.

The thickness of the base film 110 is not particularly limited, and may be appropriately adjusted within a typical thickness range used in the display field. For example, it may be about 10 to 200 μm.

On the other hand, the quantum dot optical film 100A of the present invention may not include a separate barrier layer that is a single or multilayer inorganic coating layer that blocks moisture and/or oxygen between the above-described base film 110 and the quantum dot-containing layer. have. For example, a separate barrier layer is not coated on the surface of the base film 100A of the present invention.

(2) quantum dot-containing layer

In the quantum dot optical film 100A of the present invention, the quantum dot-containing layer 120 is a portion disposed on one surface of the base film 110 and includes a photocured material of the quantum dot composition.

Specifically, the quantum dot-containing layer 120 includes a polymer matrix 121 and a plurality of quantum dots 122 dispersed in the polymer matrix 121 .

Here, the description of the quantum dot 122 is the same as that described in the quantum dot in the aforementioned quantum dot composition, and thus will be omitted.

The polymer matrix 121 is impregnated with a plurality of quantum dots 122 . That is, the plurality of quantum dot particles 122 may be interspersed in the polymer matrix 121 , or some quantum dot particles 122 may be disposed on the surface of the matrix.

The polymer matrix 121 includes the remaining portion except for the quantum dots in the photocured material of the quantum dot composition. Specifically, the polymer matrix 121 may include a first photopolymerizable monomer having a carbon-carbon unsaturated bond at the terminal; a second photopolymerizable monomer containing a thiol group at the terminal; and a cured product of a curable composition for forming a polymer matrix including at least one barrier material selected from the group consisting of halogen compounds and oxygen scavengers. In this case, the ratio (mixing ratio) of the first photopolymerizable monomer and the second photopolymerizable monomer may be 40:60 to 90:10 by weight.

According to an example, the polymer matrix 121 may include (a) a polymer resin including a first repeating unit derived from the first photopolymerizable monomer and/or a second repeating unit derived from the second photopolymerizable monomer; and (b) at least one barrier material selected from the group consisting of halogen compounds and oxygen scavengers. Here, the polymer resin is a first polymer resin containing the first repeating unit, a second polymer resin containing the second repeating unit, and a third polymer resin containing the first repeating unit and the second repeating unit. It may be two or more selected from the group consisting of, or the third polymer resin. In this case, the first and second polymer resins are homopolymers, and the third polymer resin is a random copolymer, a block copolymer, an alternating copolymer, or a graft copolymer. ) can be

Specifically, the polymer matrix 121 may include a trifunctional or less functional (meth)acrylate monomer (eg, a bifunctional (meth)acrylate monomer); tetrafunctional or higher polyfunctional (meth)acrylate monomers (eg, tetrafunctional (meth)acrylate monomers); thiol-terminated polyester monomers; And it may be a cured product of a composition comprising one type of barrier material selected from the group consisting of halogen compounds and oxygen scavengers. In this case, the low-functionality (meth) acrylate monomer is a trifunctional or less (meth) acrylate monomer having a weight average molecular weight (Mw) of about 100 to 600 g/mol (specifically, a bifunctional (meth) acrylate monomer), and the polyfunctional (meth)acrylate monomer is a tetrafunctional or more (meth)acrylate monomer having a weight average molecular weight (Mw) of about 300 to 1000 g/mol (specifically, tetrafunctional (meth)) acrylate monomer). The mixing ratio of the low-functionality (meth)acrylate monomer and the polyfunctionality (meth)acrylate monomer may be 90:10 to 10:90 by weight.

Since the description of the barrier material is the same as described in the barrier material part in the above-described quantum dot composition, it will be omitted.

In the quantum dot-containing layer 120 , the ratio of the polymer matrix 121 and the plurality of quantum dots 122 may be appropriately adjusted within a common range known in the art. For example, the polymer matrix 121 and the plurality of quantum dots 122 may be included in a weight ratio of 70:30 to 99:1.

The thickness of the quantum dot-containing layer 120 is not particularly limited, but if the thickness of the quantum dot-containing layer is too thick, a problem may occur when applied (assembled) to a display, and when the thickness is too thin, between the quantum dots 122 Because there is no regular interval, entanglement may occur, or the surface of the quantum dots 122 may be exposed, thereby reducing the barrier properties of the film. Accordingly, the thickness of the quantum dot-containing layer 120 may be about 20 nm to 100 μm.

Hereinafter, a quantum dot optical film 100B according to a second embodiment of the present invention shown in FIG. 2 will be described.

As shown in Figure 2, the quantum dot optical film (100B) of the present invention is a first base film (110); A quantum dot-containing layer 120 disposed on one surface of the first base film 110 and including a polymer matrix 121 and a plurality of quantum dots 122 dispersed in the polymer matrix 121 . ; and a second base film 130 disposed on the quantum dot-containing layer 120 .

Since the first base film 110 and the quantum dot-containing layer 120 usable in the present invention are the same as those described in the base film and quantum dot-containing layer portion of the first embodiment, they will be omitted.

In the present invention, the second base film 130 is a light-transmitting film, and is a portion disposed opposite to the first base film 110 . That is, the second base film 130 has a quantum dot-containing layer 120 interposed therebetween with the first base film.

The second base film 130 is the same as or different from the first base film 110 . Examples of the second base film 130 usable in the present invention, descriptions of thickness, etc. are the same as those described in the base film portion of the first embodiment, and thus will be omitted.

The quantum dot optical film (100A, 100B) of the present invention configured as described above is a first photopolymerizable monomer having a carbon-carbon unsaturated bond at the terminal and a second photopolymerizable monomer containing a thiol group at the terminal together with a halogen compound and It includes a quantum dot-containing layer 120 comprising a polymer matrix by mixing one or more barrier materials selected from the group consisting of oxygen scavengers. Thus, the quantum dot-containing layer of the present invention has a dense and dense three-dimensional network cross-linked structure, as well as includes a barrier material, so the quantum dot-containing layer blocks the penetration of substances such as moisture, humidity, oxygen, etc. deterioration can be prevented or delayed. In this way, the quantum dot optical film (100A, 100B) of the present invention is, unlike the conventional quantum dot optical film, even if it does not include a barrier layer between the general light-transmitting film and the quantum dot-containing layer, the barrier properties are excellent, so that the use of a display application article Soft plate can be extended (see Tables 1 to 3 below). In addition, the quantum dot optical films 100A and 100B of the present invention may have excellent barrier properties in high temperature conditions as well as high temperature and high humidity conditions (see Table 4 below).

According to an example, the quantum dot optical film of the present invention is about 50% or less, preferably about 20% or less, after irradiating light of a blue wavelength (about 450 nm) for about 300 hours at 25 ° C. have.

According to another example, after the quantum dot optical film of the present invention is left for about 500 hours at 60° C. and 95% and irradiated with light (450 nm) of a blue wavelength for about 100 hours, the amount of change in luminance compared to the maximum luminance is 50% or less, Preferably, it may be about 35% or less.

According to another example, the quantum dot optical film of the present invention is left under 60 ° C. for 500 hours and then irradiated with blue wavelength light (450 nm) for 100 hours, the change in luminance compared to the maximum luminance is about 30% or less, about 20% may be below.

Meanwhile, in the present invention, the above-described embodiments of FIGS. 1 and 2 are exemplarily described. However, it is also within the scope of the present invention to freely select and configure the number of each layer constituting the quantum dot optical film 100A, 100B and the order of their lamination according to the use. For example, the order of the respective layers 110 , 120 , 130 may be changed or other layers conventional in the art may be introduced to have a multi-layered structure rather than the exemplified structure.

Hereinafter, a method of manufacturing the quantum dot optical film 100A, 100B according to the present invention will be described. However, it is not limited only by the following manufacturing method, and the steps of each process may be modified or selectively mixed as needed.

The manufacturing method of the quantum dot optical film (100A) according to the present invention is (i) quantum dots; a first photopolymerizable monomer having a carbon-carbon unsaturated bond at the terminal; a second photopolymerizable monomer containing a thiol group at the terminal; at least one barrier material selected from the group consisting of halogen compounds and oxygen scavengers; Optionally preparing a quantum dot composition comprising a photoinitiator ('S10 step'); and (ii) applying the quantum dot composition on one side of the base film and curing the composition ('S20 step'). Optionally, before curing of the composition, the second base film may be disposed in contact with the coated surface of the composition. However, in the above-described manufacturing method according to the present invention, the steps of each process may be modified or selectively mixed as needed.

In the step (i), specific examples of the quantum dot composition, based on the total amount of the quantum dot and the photopolymerizable monomer, about 1 to 30% by weight of the quantum dot; about 40-80% by weight of a first photopolymerizable monomer; and about 19 to 50% by weight of a second photopolymerizable monomer, based on 100 parts by weight of the total amount of the quantum dots and the photopolymerizable monomer (or based on 100 parts by weight of the total amount of the quantum dots, the photopolymerizable monomer and the initiator) It may contain about 0.1 to 5 parts by weight of a halogen compound and about 0.1 to 5 parts by weight of an oxygen scavenger.

In step (ii), the quantum dot composition is applied on one surface of the first barrier film. In this case, the coating method is not particularly limited, and methods such as spray coating, roll coating, knife coating, spin coating, bar coating, flow coating, and dipping coating can be applied without limitation.

After such coating, by photo-curing the applied composition, a desired quantum dot optical film can be prepared. In this case, the photocuring conditions are not particularly limited, and may be appropriately adjusted within a range known in the art.

Optionally, before photo-curing of the composition, the composition coating layer forming surface of the base film and one surface of the second base film are disposed to face each other and combined, and then photo-curing may be performed. If necessary, it may be joined to have a certain thickness through a roll lamination process.

The quantum dot optical films 100A and 100B of the present invention configured as described above may be mounted on various display devices requiring quantum dots (QD).

For an embodiment of such a display device, a quantum dot optical film; a light source unit including a light source for generating light; and a light guide plate for guiding the light. Here, the backlight unit may further include an optical member and a reflective sheet.

According to another embodiment of the present invention, a display device including the above-described backlight unit is provided. The display may include a display panel and a backlight unit, and the display panel may be a liquid crystal display panel, an electrophoretic display panel, or an electrowetting display panel. In addition, as the configuration of the display device, those known in the art may be applied.

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited to the examples.

<Example 1>

1-1. Preparation of photocurable composition

30% by weight of hexanediol diacrylate (M200, miwon specialty chemical) and 25% by weight of ditrimethylolpropane tetraacrylate (M410, miwon specialty chemical) were mixed, and then 0.5 parts by weight of zinc chloride was added thereto. Crude liquid A was prepared. 25% by weight of quantum dots [green quantum dot (InP): red quantum dot (InP) = 2: 1 weight ratio] was added to the crude solution A and dispersed, and then 40% by weight of pentaerythritol tetrakis (3-mercapto) was added thereto Propionate) [pentaerythritol tetrakis (3-mercaptopropionate)] (4T, Bruno Bock) was dispersed to prepare a photocurable composition. Here, the content unit of zinc chloride is parts by weight, based on 100 parts by weight of the total amount of the remaining components except zinc chloride, and the content unit of the remaining components except zinc chloride is weight%, and the composition (except zinc chloride) ) was based on the total amount of

1-2. Preparation of quantum dot optical film

The photocurable composition obtained in Example 1-1 was coated on one side of a polyethylene terephthalate film (PET film) (thickness: 100 μm) as a base film to a thickness of 85 μm, and then the UV light amount was 80 mJ/cm 2 for 4 seconds. By light irradiation during curing to form a quantum dot-containing layer, a quantum dot optical film was prepared.

<Example 2>

2-1. Preparation of photocurable composition

A photocurable composition was prepared in the same manner as in Example 1-1, except that 0.5 parts by weight of indium chloride was used instead of 0.5 parts by weight of zinc chloride used in Example 1-1.

2-2. Preparation of quantum dot optical film

A quantum dot optical film was prepared in the same manner as in Example 1-2, except that the photocurable composition prepared in Example 2-1 was used instead of the photocurable composition used in Example 1-2.

<Example 3>

3-1. Preparation of photocurable composition

A photocurable composition was prepared in the same manner as in Example 1-1, except that 0.5 parts by weight of lead chloride was used instead of 0.5 parts by weight of zinc chloride used in Example 1-1.

3-2. Preparation of quantum dot optical film

A quantum dot optical film was prepared in the same manner as in Example 1-2, except that the photocurable composition prepared in Example 3-1 was used instead of the photocurable composition used in Example 1-2.

<Example 4>

4-1. Preparation of photocurable composition

A photocurable composition was prepared in the same manner as in Example 1-1, except that 0.5 parts by weight of zinc iodide was used instead of 0.5 parts by weight of zinc chloride used in Example 1-1.

4-2. Preparation of quantum dot optical film

A quantum dot optical film was prepared in the same manner as in Example 1-2, except that the photocurable composition prepared in Example 4-1 was used instead of the photocurable composition used in Example 1-2.

<Example 5>

5-1. Preparation of photocurable composition

A photocurable composition was prepared in the same manner as in Example 1-1, except that 0.3 parts by weight of zinc iodide was used instead of 0.5 parts by weight of zinc chloride used in Example 1-1.

5-2. Preparation of quantum dot optical film

A quantum dot optical film was prepared in the same manner as in Example 1-2, except that the photocurable composition prepared in Example 5-1 was used instead of the photocurable composition used in Example 1-2.

<Example 6>

6-1. Preparation of photocurable composition

A photocurable composition was prepared in the same manner as in Example 1-1, except that 1 part by weight of zinc iodide was used instead of 0.5 parts by weight of zinc chloride used in Example 1-1.

6-2. Preparation of quantum dot optical film

A quantum dot optical film was prepared in the same manner as in Example 1-2, except that the photocurable composition prepared in Example 6-1 was used instead of the photocurable composition used in Example 1-2.

<Example 7>

7-1. Preparation of photocurable composition

A photocurable composition was prepared in the same manner as in Example 1-1, except that 3 parts by weight of zinc iodide was used instead of 0.5 parts by weight of zinc chloride used in Example 1-1.

7-2. Preparation of quantum dot optical film

A quantum dot optical film was prepared in the same manner as in Example 1-2, except that the photocurable composition prepared in Example 7-1 was used instead of the photocurable composition used in Example 1-2.

<Example 8>

8-1. Preparation of photocurable composition

A photocurable composition was prepared in the same manner as in Example 1-1, except that 5 parts by weight of zinc iodide was used instead of 0.5 parts by weight of zinc chloride used in Example 1-1.

8-2. Preparation of quantum dot optical film

A quantum dot optical film was prepared in the same manner as in Example 1-2, except that the photocurable composition prepared in Example 8-1 was used instead of the photocurable composition used in Example 1-2.

<Example 9>

9-1. Preparation of photocurable composition

A photocurable composition was prepared in the same manner as in Example 1-1, except that 0.5 parts by weight of morpholine was used instead of 0.5 parts by weight of zinc chloride used in Example 1-1. Here, morpholine was used as an oxygen scavenger.

9-2. Preparation of quantum dot optical film

A quantum dot optical film was prepared in the same manner as in Example 1-2, except that the photocurable composition prepared in Example 9-1 was used instead of the photocurable composition used in Example 1-2.

<Example 10>

10-1. Preparation of photocurable composition

A photocurable composition was prepared in the same manner as in Example 1-1, except that 0.5 parts by weight of zinc iodide and 0.5 parts by weight of morpholine were used instead of 0.5 parts by weight of zinc chloride used in Example 1-1. prepared. Here, morpholine was used as an oxygen scavenger.

10-2. Preparation of quantum dot optical film

A quantum dot optical film was prepared in the same manner as in Example 1-2, except that the photocurable composition prepared in Example 10-1 was used instead of the photocurable composition used in Example 1-2.

<Comparative Example 1>

1-1. Preparation of photocurable composition

A photocurable composition was prepared in the same manner as in Example 1-1, except that 0.5 parts by weight of zinc chloride used in Example 1-1 was not used.

1-2. Preparation of quantum dot optical film

A quantum dot optical film was prepared in the same manner as in Example 1-2, except that the photocurable composition prepared in Comparative Example 1-1 was used instead of the photocurable composition used in Example 1-2.

<Experimental Example 1>

In order to confirm the barrier properties of the quantum dot optical film of the present invention according to the type of halogen compound, the measurement results are shown in Table 1 after the measurement as follows.

After exposing the quantum dot optical films of Examples 1 to 4 and Comparative Example 1 to light (450 nm) of a blue wavelength for 300 hours, the luminance (Lm) and color coordinates (Cx, Cy) of the quantum dot optical film for each time were calculated using an integrating sphere (PIMACS, Neolight IS500), and then the luminance and color coordinates of a specific time compared to the initial value were calculated according to Equations 1 to 3 below. At this time, before light irradiation, the initial luminance (Lm) and initial color coordinates (Cx, Cy) of the quantum dot optical film were set to 100% and 0.000, respectively.

[Equation 1]

(In the above formula,

Lm ₁ is the luminance value of the quantum dot optical film before light irradiation,

Lm ₂ is the luminance value of the quantum dot optical film after light irradiation for a specific time).

[Equation 2]

[Equation 3]

(In the above formula,

Cx1 and Cy1 are the initial color coordinates of the quantum dot optical film before light irradiation,

Cx2 and Cy2 are the color coordinates of the quantum dot optical film after light irradiation for a specific time).

As shown in Table 1, in the case of Comparative Example 1, when the light of the blue wavelength was irradiated for 300 hours, the decrease in luminance compared to the maximum luminance was -53% (47%-100%). On the other hand, when the blue wavelength light was irradiated for 300 hours, the amount of change (decrease width) of the luminance compared to the maximum luminance was -20% (91%-111%) in Example 1, -32% (74%) in Example 2 -106%), Example 3 was -52% (51%-103%), Example 4 was -26% (80%-106%), which was similar to or smaller than that of Comparative Example 1 .

Through this, although there is a difference in the brightness reduction width compared to the maximum brightness of the quantum dot optical film depending on the type of halogen compound, the quantum dot optical film of the present invention including a quantum dot-containing layer containing a halogen compound is oxidative when exposed to a blue wavelength. It was confirmed that damage can be effectively delayed/prevented.

<Experimental Example 2>

In order to confirm the barrier properties of the quantum dot optical film of the present invention according to the content of the halogen compound, the measurement results are shown in Table 2 below after measurement as follows.

After exposing the quantum dot optical film of Examples 5 to 8 to light (450 nm) of a blue wavelength for 468 hours, the luminance (Lm) and color coordinates (Cx, Cy) of the quantum dot optical film for each time were calculated using an integrating sphere (PIMACS, Neolight) IS500), and then, the luminance and color coordinates of a specific time compared to the initial value were calculated and shown according to Equations 1 to 3. At this time, before light irradiation, the initial luminance (Lm) and initial color coordinates (Cx, Cy) of the quantum dot optical film were set to 100% and 0.000, respectively.

As shown in Table 2, when the light of the blue wavelength was irradiated for 468 hours, the decrease in luminance compared to the maximum luminance was -63% (45%-108%) in Example 5, and -34% in Example 6 ( 68%-102%), Example 7 -54% (78%-132%), and Example 8 -91% (59-150%).

However, when the content of the halogen compound was more than 1 part by weight (Examples 7 to 8), the increase in luminance and color coordinates was large compared to the initial luminance and color coordinates when blue light was irradiated for 21 hours. Therefore, it was found that it is advantageous for the quantum dot-containing layer to include a halogen compound content of 1 part by weight or less for color implementation of the quantum dot optical film of the present invention.

<Experimental Example 3>

In order to check the barrier properties of the quantum dot optical film of the present invention according to the presence or absence of an oxygen scavenger and the mixed use of an oxygen scavenger and a halogen compound, the measurement results are shown in Table 3 after measurement as follows.

After exposing the quantum dot optical films of Examples 4, 9 and 10 to light (450 nm) of a blue wavelength for 378 hours, the luminance (Lm) and color coordinates (Cx, Cy) of the quantum dot optical film for each time were calculated using an integrating sphere (PIMACS) , Neolight IS500), and then the luminance and color coordinates of a specific time compared to the initial value were calculated and shown according to Equations 1 to 3. At this time, before light irradiation, the initial luminance (Lm) and initial color coordinates (Cx, Cy) of the quantum dot optical film were set to 100% and 0.000, respectively.

As shown in Table 3, when the light of the blue wavelength was irradiated for 378 hours, the decrease in luminance compared to the maximum luminance was -39% (67%-106%) in Example 4, and -32% in Example 9 ( 77-108%) and Example 10 -29% (82-111%).

As such, it was confirmed that the quantum dot optical film of the present invention in which the quantum dot-containing layer includes an oxygen scavenger and/or a halogen compound has excellent barrier properties.

<Experimental Example 4>

In order to confirm the barrier properties of the quantum dot optical film of the present invention under high temperature, high humidity and high temperature conditions, the measurement results are shown in Table 4 below after measurement as follows.

1) Reliability evaluation under high temperature and high humidity conditions

After exposing the quantum dot optical films of Example 10 and Comparative Example 1 for 526 hours under conditions of 60 ° C. and 95%, 526 hours after irradiating to blue wavelength light (450 nm) for 100 hours, the luminance of the quantum dot optical film (Lm) and color coordinates (Cx, Cy) were measured using an integrating sphere (PIMACS, Neolight IS500), and then the luminance and color coordinates of a specific time compared to the initial value were calculated and expressed according to Equations 1 to 3. At this time, before light irradiation, the initial luminance (Lm) and initial color coordinates (Cx, Cy) of the quantum dot optical film were set to 100% and 0.000, respectively.

2) Reliability evaluation under high temperature conditions

After exposing the quantum dot optical films of Example 10 and Comparative Example 1 for 526 hours under a condition of 60 ° C., after 526 hours, the luminance (Lm) of the quantum dot optical film after being irradiated to blue wavelength light (450 nm) for 100 hours and color coordinates (Cx, Cy) were measured using an integrating sphere (PIMACS, Neolight IS500), and then the luminance and color coordinates of a specific time compared to the initial value were calculated and expressed according to Equations 1 to 3. At this time, before light irradiation, the initial luminance (Lm) and initial color coordinates (Cx, Cy) of the quantum dot optical film were set to 100% and 0.000, respectively.

As shown in Table 4, the quantum dot optical film of Example 10 in which the quantum dot-containing layer contains both an oxygen scavenger and a halogen compound is compared to the quantum dot optical film of Comparative Example 1 in which the quantum dot-containing layer does not contain an oxygen scavenger and a halogen compound It was confirmed that the barrier properties were better under high-temperature, high-humidity and high-temperature conditions.

100A, 100B: quantum dot optical film;
110: a base film, a first base film,
120: quantum dot-containing layer,
121: polymer matrix,
122: quantum dots;
130: second base film

Claims (18)

base film; and
disposed on the base film, a polymer matrix; and a quantum dot-containing layer comprising a plurality of quantum dots dispersed in the polymer matrix.
including,
The polymer matrix may include a first photopolymerizable monomer having a carbon-carbon unsaturated bond at a terminal thereof; a second photopolymerizable monomer containing a thiol group at the terminal; and a cured product of a composition comprising one type of barrier material selected from the group consisting of halogen compounds and oxygen scavengers. According to claim 1,
wherein the quantum dot optical film does not contain a barrier layer between the base film and the quantum dot-containing layer. According to claim 1,
The quantum dot-containing layer is a quantum dot optical film comprising the polymer matrix and the plurality of quantum dots in a weight ratio of 70:30 to 99:1. According to claim 1,
Wherein the first photopolymerizable monomer and the second photopolymerizable monomer are included in a weight ratio of 40:60 to 90:10, quantum dot optical film. According to claim 1,
The first photopolymerizable monomer is trifunctional or less low-functionality (meth) acrylate monomers and tetrafunctional or more polyfunctional (meth) acrylate monomers, quantum dot optical film comprising a monomer. 6. The method of claim 5,
The mixing ratio of the low-functional (meth) acrylate monomer and the polyfunctional (meth) acrylate monomer is 90:10 to 10:90 by weight, a quantum dot optical film. 6. The method of claim 5,
The low functional (meth) acrylate monomer is a quantum dot optical film containing a trifunctional or less (meth) acrylate monomer having a weight average molecular weight (Mw) of 100 to 600 g / mol. 6. The method of claim 5,
The multifunctional (meth) acrylate monomer is a quantum dot optical film containing a (meth) acrylate monomer having a weight average molecular weight (Mw) of 300 to 1000 g/mol or more. The method of claim 1
The second photopolymerizable monomer is a compound represented by the following formula (1), quantum dot optical film:
[Formula 1]

(In the above formula,
L ₁ is carbon, a C ₆ ~ C ₃₀ arylene group, a heteroarylene group having 5 to 30 nuclear atoms, a C ₃ ~ C ₃₀ cycloalkylene group, and a heterocycloalkylene group having 3 to 30 nuclear atoms. is selected from
Y _{1 To} Y _{4 Are} the same as or different from each other, and each independently selected from the group consisting _{of a direct bond (single bond), a C 1} ~ C ₃₀ alkylene group, and a C ₂ ~ C _{30 alkenylene group,}
At this time, at least one methylene (-CH _{2 -) in the C 1} ~ C ₃₀ alkylene group and the C ₂ ~ C ₃₀ alkenylene group is an ester (-C (= O) O-), an amide (-C (= O)NR-) (R is hydrogen or a C ₁ -C ₁₀ alkyl group), carbonyl (-C(=O)-), ether (-O-), sulfide (-S-) and sulfoxide (- S(=O)-) may be substituted or unsubstituted with one or more selected from the group consisting of,
R _{1 To} R ₄ are the same as or different from each other, and each independently a thiol group (-SH), hydrogen, halogen group, cyano group, nitro group, amino group, C ₁ ~ C ₃₀ alkyl group, C ₃ ~ C ₃₀ cyclo An alkyl group, a heterocycloalkyl group having 3 to 30 nuclear atoms, a C ₆ to C ₃₀ aryl group, a heteroaryl group having 3 to 30 nuclear atoms, a C ₆ to C ₃₀ alkoxy group and a hydroxyl group (-OH) is selected from
However _{, at least two of R 1} to R ₄ are thiol groups (-SH)). According to claim 1,
The halogen compound is a compound represented by the following formula (2), quantum dot optical film:
[Formula 2]
MO _a X _b
(In the above formula,
M is a metal selected from the group consisting of alkali metals, alkaline earth metals, transition metals and post-transition metals,
X is a halogen selected from the group consisting of F, Cl, Br, and I;
a is an integer from 0 to 2,
b is an integer from 1 to 3). According to claim 1,
The content of the halogen compound is 0.1 to 5 parts by weight, based on 100 parts by weight of the quantum dot-containing layer, quantum dot optical film. According to claim 1,
The oxygen scavenger is morpholine, titanium dioxide, paraben, C1-C6 alkyl paraben, sodium sulfite, sodium bisulfite, triphenyl phosphine, ascorbic acid A quantum dot optical film comprising at least one selected from the group consisting of ascorbic acid derivatives, and thiourea derivatives. According to claim 1,
The content of the oxygen scavenger is 0.1 to 5 parts by weight, based on 100 parts by weight of the quantum dot-containing layer, the quantum dot optical film. According to claim 1,
Quantum dot optical film further comprising a second base film disposed on the quantum dot-containing layer. quantum dots;
a first photopolymerizable monomer having a carbon-carbon unsaturated bond at the terminal;
a second photopolymerizable monomer containing a thiol group at the terminal; and
At least one barrier material selected from the group consisting of halogen compounds and oxygen scavengers
A quantum dot composition comprising a. 16. The method of claim 15,
The composition, based on the total amount of the composition,
1 to 30% by weight of quantum dots;
40 to 80% by weight of a first photopolymerizable monomer; and
19 to 50% by weight of the second photopolymerizable monomer
A quantum dot composition comprising a. 16. The composition of claim 15, further comprising an initiator. 18. The method of claim 17,
The composition is based on 100 parts by weight of the total content of the quantum dots, the first photopolymerizable monomer, the second photopolymerizable monomer and the initiator,
0.1 to 5 parts by weight of a halogen compound; and
0.1 to 5 parts by weight of oxygen scavenger
A quantum dot composition comprising a.

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