KR101999979B1 - A wavelength conversion particle complex and Optical film comprising it - Google Patents

Abstract

TECHNICAL FIELD The present invention relates to a composite, an optical film including the composite, a manufacturing method and a use thereof.
The present application can provide an optical film capable of providing an illumination device having excellent color purity and efficiency and excellent color characteristics.
The optical film of the present application can stably maintain such excellent properties for a long period of time. The optical film of the present application can be used for various applications including various lighting devices as well as photovoltaic applications, optical filters or optical converters.

Description

[0001] The present invention relates to a wavelength conversion particle composite and an optical film comprising the same,

The present application relates to a wavelength conversion particle composite, an optical film including the composite, an illumination device, and a display device including the same.

Lighting devices are used in a variety of applications. The lighting device may be, for example, a BLU of a display such as a liquid crystal display (LCD), a television, a computer, a mobile phone, a smart phone, a personal digital assistant (PDA), a gaming device, an electronic reading device, (Backlight Unit). In addition, the lighting device can be used for indoor or outdoor lighting, stage lighting, decorative lighting, accent lighting or museum lighting, and the like, and can also be used for horticulture or special wavelength lighting required for biology.

As a typical lighting device, for example, there is a device which is used as an LCD BLU or the like and which emits a white light by combining a phosphor such as a blue LED (Light Emitting Diode) and YAG (Yttrium aluminum garnet).

In recent years, researches on a lighting device emitting white light by using a wavelength conversion particle, for example, a quantum dot, in which the color of light emitted varies depending on the size of a particle, is progressing steadily. Particularly, there is a problem in that the efficiency is reduced due to exposure of the quantum dots to a gas such as oxygen, or studies for increasing the luminous efficiency of the quantum dots themselves are actively performed.

Korean Patent Publication No. 2011-0048397 Korean Patent Publication No. 2011-0038191

The present application provides a wavelength conversion particle composite and an optical film comprising the same, wherein the optical conversion film has improved luminescence intensity of the optical film including the wavelength converting particles, achieves high luminescence efficiency, and excellent optical characteristics.

The present application is conceived to solve the above-mentioned problems, and includes a wavelength converting particle; Scattering particles; And a ligand which binds the wavelength converting particles and the scattering particles.

In one example, the ligand of the complex comprises a first ligand bound to the surface of the wavelength converting particle and a second ligand bound to the surface of the scattering particle, wherein the first ligand and the second ligand are mutually coupled There may be something.

The mutual bonds of the first ligand and the second ligand may be a chemical bond such as a physical bond such as a hydrogen bond or a hydrophobic interaction.

The present application also relates to an optical film comprising the composite.

In one example, the optical film may comprise an emulsion region dispersed in a matrix that is a continuous phase, and may comprise a light emitting layer having the complex present in the continuous phase or emulsion region.

In another example, the emulsion region of the optical film may include an A region including a composite having first wavelength converting particles capable of absorbing light within a range of 420 nm to 490 nm and emitting light within a range of 490 nm to 580 nm, and / or And a B region including a complex having second wavelength conversion particles capable of absorbing light within a range of 420 nm to 490 nm and emitting light within a range of 580 nm to 780 nm.

The present application is also directed to a method of making a composite comprising the step of mixing wavelength-converting particles surface-modified with a ligand and surface-modified scattering particles with a ligand.

The present application also relates to a method for producing an optical film comprising the step of mixing a radically polymerizable compound with a wavelength converting particle surface-modified with a ligand and a scattering particle surface-modified with a ligand.

The present application also relates to a lighting device and a display device including such an optical film.

The present application relates to a wavelength conversion particle composite material capable of adjusting the probability that light incident on a light emitting layer is introduced into the wavelength conversion particle to control light characteristics of the light emitting layer, for example, Can be provided.

In addition, the present application can provide an optical film excellent in physical properties such as adhesiveness to other layers, durability, or optical characteristics through the phase separation structure of the light emitting layer.

Figures 1 and 2 are schematic diagrams of a composite comprising wavelength converting particles and scattering particles.
3 is a schematic diagram of a quantum dot of an exemplary Core-shell structure.
4 is an exemplary view of an optical film.
Figures 5 and 6 are schematic diagrams of an exemplary lighting device.
Figs. 7 and 8 show the results of evaluating the luminous efficiency QY of the optical films according to Examples and Comparative Examples.

Hereinafter, the present application will be described in more detail with reference to embodiments and drawings, but is merely an embodiment limited to the gist of the present application. It will be apparent to those skilled in the art that the present application is not limited to the process conditions set forth in the following examples, and may be arbitrarily selected within the range necessary for achieving the object of the present application .

The present application relates to composites comprising wavelength converting particles, scattering particles and ligands. The ligand may bind the wavelength converting particles and the scattering particles.

The term " wavelength converting particle " in the present application may mean particles formed by absorbing light of a predetermined wavelength and emitting light of the same or different wavelength as the absorbed light.

The term " scattering particles " in the present application refers to organic or inorganic particles having refractive indices different from those of the surrounding medium, for example, matrix and / or emulsion region, and having an appropriate size and capable of scattering, refracting, . ≪ / RTI >

That is, the composite of the present application includes a ligand for binding the wavelength converting particles and the scattering particles so that the wavelength converting particle and the scattering particle can maintain a certain distance, whereby light incident on the light emitting layer is introduced into the wavelength converting particle It is possible to provide an optical film which can be included in an illuminating device having excellent optical characteristics such as excellent color purity and efficiency and having excellent color characteristics by controlling the probability.

The length of the ligand for binding the wavelength converting particles and the scattering particles is limited by the distance that the light that is scattered, refracted or diffused through the scattering particles can be introduced into the wavelength converting particles to ultimately increase the light emitting efficiency and the luminescence intensity. There is no. For example, the length of the ligand may be from 5 nm to 100 nm, from 5 nm to 80 nm, from 5 nm to 60 nm, from 5 nm to 40 nm, or from 5 nm to 20 nm.

The ligand for binding the wavelength converting particle and the scattering particle may be included in the complex in an unlimited form to the extent that the above-mentioned object can be achieved.

In one example, the ligand of the complex may be in a state of containing at least one ligand at both ends that can bind to the surface of the wavelength converting particle and the scattering particle.

In another example, the ligand included in the complex may comprise a first ligand bonded to the surface of the wavelength converting particle and a second ligand bonded to the surface of the scattering particle. In addition, the first ligand and the second ligand may be mutually coupled.

Specifically, as shown in Fig. 1, the composite of the present application comprises scattering particles 200 comprising a wavelength converting particle 100 comprising a first ligand 101 and a second ligand 201 , The first ligand (101) and the second ligand (201) may be mutually bonded. The first ligand and the second ligand that are mutually bonded may be the same kind or may be different kinds of ligands.

For example, the first ligand and the second ligand may be independently selected from molecules having an amine group (oleylamine, triethylamine, hexylamine, naphtylamine, etc.) or polymers, molecules having a carboxyl group (oleic acid or the like) (triphenylphosphine, etc.), a molecule having a phosphine group (trioctylphosphine oxide, etc.), a molecule having a carbonyl group (e.g., butanethiol, hexanethiol, dodecanethiol, etc.) or a molecule having a pyridine group alkyl ketone, etc.), molecules capable of binding to each other among molecules having a benzene ring (benzene, styrene, etc.) or polymers, molecules having a hydroxyl group (butanol, hexanol, etc.), polymers, Or the polymer can be appropriately selected.

The first ligand and the second ligand may be linked to each other. The mutual bond may be a chemical bond such as a physical bond such as hydrogen bonding or a hydrophobic interaction.

The complexes of the present application may comprise wavelength converting particles. As described above, the wavelength converting particles may mean particles formed by absorbing light of a predetermined wavelength and emitting light having the same or different wavelengths as the absorbed light.

The size of the wavelength converting particle is, for example, about 100 nm or less, 90 nm or less, 80 nm or less, 70 nm or less, 60 nm or less, 50 nm or less, 40 nm or less, 30 nm or less, 15 nm or less, and the size of the particles may be different depending on the light of the wavelength to be emitted.

The shape of the wavelength conversion particle is not particularly limited, and may be spherical, ellipsoidal, polygonal or amorphous.

For example, the wavelength converting particles may be particles (hereinafter, referred to as green particles) capable of absorbing light of any wavelength within the range of 420 to 490 nm and emitting light of any wavelength within the range of 490 to 580 nm. ) And / or particles capable of absorbing light of any wavelength within the range of 420 to 490 nm and emitting light of any wavelength within the range of 580 to 780 nm (hereinafter referred to as red particles) .

For example, in order to obtain an optical film capable of emitting white light, the red particles and green particles may be included in the light emitting layer together at an appropriate ratio.

2, the complex of the present application comprises scattering particles 200 having wavelength conversion particles 100 having a first ligand 101 and a second ligand 201, The particles may be green particles and / or red particles, and may form a complex of scattering particles and clusters via ligands.

The wavelength converting particles can be used without any particular limitation as long as they exhibit such action. Representative examples of such particles include, but are not limited to, nanostructures called so-called Quantum Dots.

Quantum dots that may be used in the present application may be formed using any suitable material, for example, an inorganic material, using an inorganic conducting or semi-conducting material. Suitable semiconductor materials include II-VI, III-V, IV-VI, and IV semiconductors. More specifically, it is possible to use Si, Ge, Sn, Se, Te, B, C (including diamond), P, BN, BP, BAs, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, ZnSe, ZnTe, CdS, CdSe, CdSeZn, CdTe, HgS, HgSe, HgTe, BeS, BeSe, BeTe, MgS, InS, InSb, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, ZnO, ZnS, MgSe, GeS, GeSe, GeTe, SnS, SnSe, SnTe, PbO, PbS, PbSe, PbTe, CuF, CuCl, CuBr, CuI, Si 3 N 4, Ge 3 N 4, Al 2 O 3, (Al, Ga, In ₂ (S, Se, Te) ₃ , Al ₂ CO and two or more of these semiconductors may be exemplified, but are not limited thereto.

The quantum dot may have a core-shell structure. As shown in FIG. 3, the core-shell structure may include a core portion 300 indicating a central portion of a quantum dot, and a cell portion 400 surrounding the core portion 300. have.

More specifically, the quantum dots (core / shell) of the core-shell structure include CdSe / ZnS, InP / ZnS, PbSe / PbS, CdSe / CdS, CdTe / CdS or CdTe / ZnS , But is not limited thereto.

When the quantum dot has a core-shell sturucture, the cell portion may be formed so as to be capable of binding with the end of the above-mentioned ligand. Further, the cell portion may be formed such that the first ligand described above can be bonded to the surface of the quantum dot.

 In one example, the cell portion of the quantum dot may include a first cell portion immediately surrounding the core and a second cell portion surrounding the first cell portion, and the second cell portion may be formed to be able to engage with the terminal end of the ligand Or the first ligand may be formed so as to be bonded to the surface of the quantum dot.

Further, the wavelength conversion particles may be polymer particles composed of an organic material. The kind and size of the polymer particles made of the organic material can be used without limitation as disclosed in, for example, Korean Patent Laid-Open Publication No. 2014-0137676. When the wavelength converting particle is a polymer particle of an organic material, the surface of the polymer particle may be formed so as to be capable of bonding with the above-mentioned ligand.

The wavelength converting particles can be produced in any known manner. For example, U.S. Patent No. 6,225,198, U.S. Patent Publication No. 2002-0066401, U.S. Patent No. 6,207,229, U.S. Patent No. 6,322,901, U.S. Patent No. 6,949,206, U.S. Patent No. 7,572,393, U.S. Patent No. 7,267,865, Patent No. 7,374,807 or U.S. Patent No. 6,861,155 discloses a method of forming quantum dots and the like, and various other known methods may be applied to the present application.

The specific kind of the wavelength conversion particle is not particularly limited, and can be appropriately selected in consideration of the desired light emission characteristics.

The wavelength converting particle may be one whose surface has been modified to include one or more ligands or barriers. The ligand or barrier may be advantageous to improve the stability of the wavelength converting particle and to protect the wavelength converting particle from harmful external conditions including high temperature, high intensity, external gas or moisture. Further, the ligand or barrier contained in the wavelength converting particle can be combined with the ligand formed on the surface of the scattering particle, so that the distance between the wavelength converting particle and the scattering particle can be kept constant.

In one example, the wavelength converting particles may be surface-modified with a ligand.

As described above, the ligand formed through the surface modification of the wavelength converting particles can exhibit characteristics suitable for the surface of the wavelength converting particle, and can be combined with the ligand formed on the surface of the scattering particle to increase the luminous efficiency , And the method of formation thereof is known, and such a method can be applied without limitation in the present application. Such materials and methods are disclosed, for example, in U.S. Patent Publication No. 2008-0281010, U.S. Patent Publication No. 2008-0237540, U.S. Patent Publication No. 2010-0110728, U.S. Patent Application No. 2008-0118755, U.S. Patent No. 7,645,397 U.S. Patent No. 7,374,807, U.S. Patent No. 6,949,206, U.S. Patent No. 7,572,393, U.S. Patent No. 7,267,875, and the like, but are not limited thereto. In one example, the ligand may be a molecule having an amine group (oleylamine, triethylamine, hexylamine, naphtylamine, etc.) or a polymer, a molecule having a carboxyl group (oleic acid or the like), a polymer having a thiol group (butanethiol, hexanethiol, dodecanethiol, etc.) A molecule having a phosphine group (e.g., triphenylphosphine), a molecule having an oxidized phosphine group (such as trioctylphosphine oxide), a molecule having a carbonyl group (such as alkyl ketone), a polymer having a benzene ring (Such as benzene, styrene, etc.) or a polymer, a molecule having a hydroxyl group (butanol, hexanol, etc.) or a molecule having a polymer or sulfone group (such as a sulfonic acid) or a polymer. Any one of the above-mentioned molecules or polymers can be appropriately selected in consideration of the binding ability with the ligand formed on the substrate.

The complexes of the present application may comprise scattering particles. Scattering particles mean organic or inorganic particles that have a refractive index different from that of the surrounding medium, e. G., The matrix or emulsion region as described above, and that have an appropriate size to scatter, refract, or diffuse the incident light .

The shape and material of the scattering particles are not limited as long as they can achieve the above-mentioned object of increasing the luminous efficiency, and known scattering particles can be adopted and used.

For example, the scattering particles may be in the shape of a sphere, an ellipse, a cylinder, a square, a rectangle, a rod, a tube, a pyramid, a triangle, a plate or a flat surface model.

For example, the scattering particles may be particles having an absolute value of the difference in refractive index between the surrounding medium, for example, the light emitting layer, of 0.2 or more or 0.4 or more. The upper limit of the absolute value of the difference in refractive index is not particularly limited, and may be, for example, about 0.8 or less or about 0.7 or less.

The scattering particles may have a mean particle diameter of, for example, 100 nm or more, 100 nm or more, 100 nm to 20,000 nm, 100 nm to 15,000 nm, 100 nm to 10,000 nm, 100 nm to 5,000 nm, nm to 500 nm. The scattering particle may have a shape such as a sphere, an ellipse, a polyhedron or an amorphous shape, but the shape is not particularly limited.

The scattering particles include, for example, polystyrene or a derivative thereof; An acrylic resin or a derivative thereof; Silicone resins or derivatives thereof; Or an organic material such as a novolak resin or a derivative thereof, or an inorganic material such as silica, alumina, titanium oxide or zirconium oxide.

That is, the scattering particles include polystyrene or a derivative thereof; An acrylic resin or a derivative thereof; Silicone resins or derivatives thereof; And any one of organic materials selected from the group consisting of a novolac resin or a derivative thereof, or an inorganic material selected from the group consisting of titanium oxide, metal oxide, aluminum oxide, glass beads, and silica glass . The scattering particles may include only one of the above materials, or may be formed to include two or more of the above materials. For example, as the scattering particles, hollow particles such as hollow silica or particles having a core / shell structure can be used.

In one example, the surface of the scattering particle can be modified so that the surface can be bound to the end of the ligand, or the surface can be modified such that more than one ligand can be attached. The ligand binds with a ligand contained in the wavelength conversion particle such as a quantum dot to maintain a constant distance between the scattering particle and the wavelength conversion particle, thereby ultimately increasing the luminous efficiency of the optical film.

For example, when a scattering particle is a core-shell structure, a ligand capable of binding to a cell portion of a scattering particle is used as a ligand. A method of forming a structure including a ligand can be used. X is a scattering particle bonding group capable of binding to the cell portion of the scattering particles, Y is a linking group, and Z may be a functional group.

X capable of binding to the cell portion of the scattering particles may be a molecule having an amine group (oleylamine, triethylamine, hexylamine, naphtylamine or the like) or a polymer, a molecule having a carboxyl group (such as oleic acid) or a polymer or a molecule having a thiol group (pyridine) or a polymer, a molecule having a phosphine group (e.g., triphenylphosphine), a molecule having an oxidized phosphine group (e.g., trioctylphosphine oxide), a molecule having a carbonyl group (Benzene, styrene, etc.) or a polymer, a molecule having a hydroxyl group (butanol, hexanol, etc.) or a molecule having a polymer or sulfone group (such as a sulfonic acid) , An external ligand structure including a linking group and a functional group can be formed on the surface of the scattering particles.

In an external ligand having a structure of X-Y-Z, Y can be appropriately selected in consideration of the dispersion characteristics of a hydrophobic or hydrophilic solvent such as, for example, a carbon chain of a single bond or a carbon body of an aromatic ring bond.

In an external ligand having a structure of XYZ, Z is a functional group which forms an outermost angle of scattering particles equal to or different from binding unit X capable of binding to the cell portion, and is capable of binding with ligands of the wavelength converting particles (Oleanamine, triethylamine, hexylamine, naphtylamine, etc.) or a polymer, a molecule having a carboxyl group (such as oleic acid) or a polymer or a molecule having a thiol group (such as butanethiol, hexanethiol or dodecanethiol) A molecule having a pyridine group (such as pyridine) or a polymer, a molecule having a phosphine group (such as triphenylphosphine), a molecule having a phosphine group (such as trioctylphosphine oxide), a molecule having a carbonyl group (such as alkyl ketone) benzene, styrene, etc.) or a polymer, a molecule having a hydroxyl group (butanol, hexanol, etc.), a molecule having a polymer or sulfone group (such as a sulfonic acid) Here there is included in the wavelength converting particles have appropriate molecular or polymer, depending on the type of ligand may be selected such that.

When the scattering particles are particles of a core-shell structure, the cell portion may be formed so that the ends of the above-mentioned ligands can be bonded. Further, the cell portion may be formed so that the above-mentioned second ligand can be bonded to the surface of the scattering particles.

The present application relates to an optical film comprising such a composite. The term " optical film " in the present application may refer to a film used in an optical apparatus for various purposes. For example, the optical film may mean a film formed to absorb light of a predetermined wavelength and emit light having the same or different wavelength as the absorbed light.

The optical film of the present application may include a complex comprising a wavelength converting particle, a scattering particle, and a ligand for binding the wavelength converting particle and the scattering particle.

The optical film of the present application may include a light emitting layer. The light-emitting layer may include the above-mentioned wavelength converting particles, scattering particles, and a composite comprising the wavelength converting particles and the ligand binding the scattering particles. The term " light-emitting layer " in the present application may mean a layer formed so as to absorb light from a light source described later and emit light of the same or different wavelength as the light from the light source.

In one example, the light emitting layer may comprise two regions that are phase separated from each other. It will be appreciated that the term "phase separated regions" in the present application are separated from each other as regions formed by two regions that do not mix with each other, such as regions that are relatively hydrophobic and regions that are relatively hydrophilic And the like. Hereinafter, for convenience of explanation, any one of the two regions of the light-emitting layer that are phase-separated may be referred to as a first region, and the other region may be referred to as a second region.

In one example, the first region among the first region and the second region of the light emitting layer may be a hydrophilic region, and the second region may be a hydrophobic region. In the present application, hydrophilicity and hydrophobicity for distinguishing the first and second regions are relative to each other. An absolute criterion for hydrophilicity and hydrophobicity is that the two regions are distinguished from each other in the light-emitting layer, It is not.

The ratio of the hydrophilic first region to the hydrophobic second region in the light emitting layer is not particularly limited. For example, the ratio can be selected in consideration of the ratio of the wavelength conversion particles to be included in the light emitting layer, the adhesion with other layers such as the barrier layer, and the physical properties required for film formation. For example, the light emitting layer may include 100 parts by weight of the first region and 10 to 100 parts by weight of the second region. In another example, the light emitting layer may include 50 to 95 parts by weight of the first region and 5 to 50 parts by weight of the second region. Alternatively, the light-emitting layer may include 50 to 95 parts by weight of the second region and 5 to 50 parts by weight of the first region.

In the present application, the term "parts by weight" means the weight ratios between the components unless otherwise specified.

In the above, the weights of the first and second regions may be the sum of the weights of all the components included in the regions.

The light emitting layer may be formed by polymerizing a radical polymerizing compound, for example, a mixture of a hydrophilic polymerizable composition and a hydrophobic polymerizable composition. In this case, the weight of each of the above regions means the weight of the hydrophilic polymerizable composition or the hydrophobic polymerizable composition, or the weight of the hydrophilic polymerizable compound and the hydrophobic polymerizable compound contained in each of the polymerizable compositions .

In the above, the hydrophilic polymerizable composition means a composition comprising a hydrophilic polymerizable compound, and the hydrophobic polymerizable composition may mean a composition comprising a hydrophobic polymerizable compound.

In the present application, the criterion for distinguishing the hydrophilicity and hydrophobicity of the hydrophilic polymerizable compound from that of the hydrophobic polymerizable compound is that, for example, when the two compounds are relatively hydrophilic or hydrophobic and mixed with each other, the above-mentioned phase-separated regions are formed The present invention is not limited thereto. In one example, the distinction between hydrophilicity and hydrophobicity can be performed by a so-called solubility parameter. In this application, the solubility parameter refers to the solubility parameter of a homopolymer formed by the polymerization of the hydrophilic or hydrophobic polymerizable compound, thereby determining the degree of hydrophilicity and hydrophobicity of the compound. The manner of obtaining the solubility parameter is not particularly limited and may be in accordance with a method known in the art. For example, the parameter may be calculated or obtained according to a method known in the art as a so-called Hansen solubility parameter (HSP). The hydrophobic polymerizable compound in the present application may mean a radically polymerizable compound having a solubility parameter of less than about 10 (cal / cm < ³ >) ^1/2 , and the hydrophilic polymerizable compound may have a parameter of about 10 (cal / cm < ³ >) ^1/2 or more.

The solubility parameter of a polymer in which the hydrophobic polymeric compound formed is ³ (cal / cm 3) ^1/2 or ^{more, 4 (cal / cm 3)} 1/2 or more, or about 5 (cal / cm ³⁾ in another example ^{1 / 2 or} more. The solubility parameter of a polymer in which the hydrophilic polymeric compound is formed in another example about 11 (cal / cm ³⁾ over ^{1/2, 12 (cal / cm 3} ) over ^{1/2, 13 (cal / cm 3} ) 1 / ² or more, 14 (cal / cm ³ ) ^1/2 or more, or 15 (cal / cm ³ ) ^{1/2 or} more. The solubility parameter of a polymer in which the hydrophilic polymeric compound is formed from about 40 (cal / cm ^{3) 1/2} or less, about 35 (cal / cm ^{3) 1/2} or less, or about 30 (cal / cm ³⁾ in another example Can be less than ^1/2 . The difference in solubility parameters of the hydrophobic and hydrophilic compounds can be controlled for the implementation of a suitable phase separation structure or emulsion structure. In one example of the difference between the solubility parameter of a polymer formed by the hydrophilic and hydrophobic polymeric compound or each of 5 (cal / cm ^{3) 1/2} or more, 6 (cal / cm ^{3) 1/2} or more, 7 (cal / cm ³ ) ^1/2 or more or about 8 (cal / cm ³ ) ^{1/2 or} more. The difference is a value obtained by subtracting a small value from a large value among the solubility parameters. The upper limit of the difference is not particularly limited. The greater the difference in solubility parameter, the more appropriate phase separation structure or emulsion structure can be formed. The upper limit of the difference may be, for example, 30 (cal / cm ³ ) ^1/2 or less, 25 (cal / cm ³ ) ^1/2 or less, or about 20 (cal / cm ³ ) ^1/2 or less.

In the case where the physical properties described in the present application vary depending on the temperature, the physical properties may mean physical properties at room temperature. As used herein, the term ambient temperature refers to a natural, unheated or non-warmed temperature, for example, any temperature within the range of about 10 ° C to 30 ° C, or about 23 ° C or about 25 ° C.

The first region and the second region may be randomly distributed to form a cluster to confirm that the two regions are divided in the light emitting layer.

In one example, the light emitting layer may be in the form of an emulsion.

The term emulsion-type layer in the present application means that any one of two or more phases that are not intermixed with each other (e.g., the first and second regions) may form a continuous phase in the layer And the other region is a dispersed phase dispersed in the continuous phase. The term " dispersed phase " The continuous phase and the dispersed phase may be solid phase, semi-solid phase or liquid phase, respectively, and may be the same phase or different phase. Emulsions are commonly used for two or more liquid phases that do not intermingle with each other, but the term emulsion in this application does not necessarily mean only the emulsion formed by two or more liquid phases.

In one example, the emissive layer comprises a matrix forming the continuous phase and may comprise an emulsion region that is a dispersed phase dispersed within the matrix. The complex may also be included in the continuous phase or in the emulsion region. In this case, the matrix is any one of the above-described first and second regions (for example, the first region), and the emulsion region as the dispersed phase is the region of the other of the first and second regions Region).

The emulsion region may be in the form of particles. That is, the emulsion regions may be dispersed within the matrix in the form of particles. In this case, the particle shape of the emulsion region is not particularly limited, and may be roughly spherical, ellipsoidal, polygonal or amorphous. The average diameter of the particle shape may be in the range of about 1 탆 to 200 탆, in the range of about 1 탆 to 50 탆, or in the range of about 50 탆 to 200 탆. The size of the particle shape can be controlled by controlling the ratio of the material forming the matrix and the emulsion region, or by using a surfactant or the like.

The ratio of the matrix and the emulsion region in the light emitting layer is. For example, the ratio can be selected in consideration of the ratio of the wavelength conversion particles to be included in the light emitting layer, the adhesion with other layers such as the barrier layer, the production efficiency of the emulsion structure as the phase separation structure, or the physical properties required for film formation . For example, the light emitting layer may comprise from 5 to 40 parts by weight of the emulsion region relative to 100 parts by weight of the matrix. The ratio of the emulsion region may be 10 parts by weight or more or 15 parts by weight or more based on 100 parts by weight of the matrix. The ratio of the emulsion region may be 35 parts by weight or less based on 100 parts by weight of the matrix. The ratio of the weight of the matrix and the emulsion region in the above is the ratio of the weight of each region itself or the sum of the weights of all the components contained in the region or the ratio of the main component or the weight of the material used for forming each of the regions It can mean the ratio. For example, the matrix and the emulsion region may each include polymerized units of a hydrophilic and hydrophobic polymerizable compound described below, and the ratio of the weight may be a ratio between the polymerized units.

The complex containing the wavelength converting particles may be contained in the matrix or the emulsion region. In one example, the wavelength converting particle may be contained in only one of the matrix and the emulsion region, and may not be substantially contained in the other region. In the present application, the fact that the wavelength conversion particles are not substantially contained in any region means that the weight ratio of the wavelength conversion particles contained in the corresponding region to the wavelength conversion particles included in the light emitting layer is 10 , Not more than 9%, not more than 8%, not more than 7%, not more than 6%, not more than 5%, not more than 4%, not more than 3%, not more than 2%, not more than 1%, not more than 0.5% or not more than 0.1% .

In one example, the complex comprising the wavelength converting particles may be substantially contained in the emulsion region in the matrix and the emulsion region. In this case, the matrix may be substantially free of complex. Therefore, in the above case, the proportion of the complex containing the wavelength converting particles contained in the emulsion region is 90% by weight or more, 91% by weight or more, 92% by weight or more, At least 93% by weight, at least 94% by weight, at least 95% by weight, at least 96% by weight, at least 97% by weight, at least 98% by weight, at least 99% by weight, at least 99.5% by weight or at least 99.9% by weight.

Any one of the matrix and the emulsion region may contain a hydrophilic polymer and the other region may include a hydrophobic polymer. In the hydrophilic polymer is the HSP (Hansen solubility parameter) is 10 (cal / cm ^{3) 1/2} or more means the polymer, and the hydrophobic polymer is less than the HSP 10 (cal / cm ^{3) 1/2} the polymer, as described above It can mean. The solubility parameter of the hydrophobic polymer may be 3 (cal / cm ³ ) ^1/2 or more, 4 (cal / cm ³ ) ^1/2 or more, or about 5 (cal / cm ³ ) ^{1/2 or} more in another example. The solubility parameters of the hydrophilic polymer is from about 11 (cal / cm ^{3) 1/2} or more in another example, 12 (cal / cm ^{3) 1/2} or more, 13 (cal / cm ^{3) 1/2} or more, 14 (cal / cm ³ ) ^1/2 or more or 15 (cal / cm ³ ) ^{1/2 or} more. The solubility parameters of the hydrophilic polymer is from about 40 (cal / cm ^{3) 1/2} or less, about 35 (cal / cm ^{3) 1/2} or less, or about 30 (cal / cm ^{3) 1/2} can be less than in other examples . The difference in solubility parameters of the hydrophobic and hydrophilic polymers can be controlled for the implementation of a suitable phase separation structure or emulsion structure. In one example the difference between the solubility parameters of the hydrophilic and hydrophobic polymer is 5 (cal / cm ^{3) 1/2} or higher, 6 (cal / cm ³⁾ than ^{1/2, 7 (cal / cm 3} ) least ^1/2 Or about 8 (cal / cm ³ ) ^{1/2 or} more. The difference is a value obtained by subtracting a small value from a large value among the solubility parameters. The upper limit of the difference is not particularly limited. The greater the difference in solubility parameter, the more appropriate phase separation structure or emulsion structure can be formed. The upper limit of the difference may be, for example, 30 (cal / cm ³ ) ^1/2 or less, 25 (cal / cm ³ ) ^1/2 or less, or about 20 (cal / cm ³ ) ^1/2 or less. In one example, the matrix may comprise a hydrophilic polymer and the emulsion region may comprise a hydrophobic polymer.

The first region or the matrix may be formed by polymerizing a hydrophilic polymerizable compound. For example, the first region or matrix may be a compound of Formula 1; A compound of Formula 2 below; A compound of Formula 3; A compound of formula (4); Nitrogen-containing radically polymerizable compounds; And a radical polymerizable compound including (meth) acrylic acid or a salt thereof. The term "polymerized unit of a given compound" in the present application may mean a state in which the predetermined compound is polymerized in a skeleton such as a main chain or side chain of a polymer formed by polymerizing the predetermined compound.

[Chemical Formula 1]

 (2)

(3)

 [Chemical Formula 4]

In the general formulas (1) to (4), Q is independently hydrogen or an alkyl group, U is independently an alkylene group, A is independently an alkylene group which may be substituted with a hydroxyl group, and Z is hydrogen, an alkoxy group, Is a hydrocarbon group, X is a hydroxyl group or a cyano group, and m and n are arbitrary numbers, for example, a positive integer.

The term "alkyl group" in the present application may mean an alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms, unless otherwise specified. The alkyl group may be linear, branched or cyclic. In addition, the alkyl group may be optionally substituted with one or more substituents.

The term "alkylene group" in the present application may mean an alkylene group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms unless otherwise specified. The alkylene group may be linear, branched or cyclic. The alkylene group may optionally be substituted with one or more substituents.

The term "epoxy group" in the present application means, unless otherwise specified, a cyclic ether having three ring atoms or a compound containing such a cyclic ether or a monovalent residue derived therefrom have. As the epoxy group, a glycidyl group, an epoxy alkyl group, a glycidoxyalkyl group or an alicyclic epoxy group can be exemplified. The alicyclic epoxy group may be a monovalent residue derived from a compound containing a structure containing an aliphatic hydrocarbon ring structure and having a structure in which two carbon atoms forming the aliphatic hydrocarbon ring also form an epoxy group. As the alicyclic epoxy group, an alicyclic epoxy group having 6 to 12 carbon atoms can be exemplified, and for example, 3,4-epoxycyclohexylethyl group and the like can be exemplified.

The term "alkoxy group" in the present application may mean an alkoxy group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms, unless otherwise specified. The alkoxy group may be linear, branched or cyclic. In addition, the alkoxy group may be optionally substituted with one or more substituents.

Unless otherwise specified, the term " monovalent hydrocarbon group " in the present application may mean a monovalent residue derived from a compound consisting of carbon and hydrogen or a derivative of such a compound. For example, the monovalent hydrocarbon group may contain from 1 to 25 carbon atoms. As the monovalent hydrocarbon group, an alkyl group, an alkenyl group, an alkynyl group or an aryl group can be exemplified.

Examples of the substituent which may optionally be substituted in the alkyl group, alkoxy group, alkylene group, epoxy group or monovalent hydrocarbon group in the present application include halogen, glycidyl, epoxyalkyl, glycidoxyalkyl or halogen such as hydroxy, But are not limited to, an epoxy group such as an alicyclic epoxy group, an acryloyl group, a methacryloyl group, an isocyanate group, a thiol group or a monovalent hydrocarbon group.

In the general formulas (1), (2) and (4), m and n are arbitrary numbers and can be, for example, independently in the range of 1 to 20, 1 to 16 or 1 to 12.

Examples of the nitrogen-containing radical polymerizable compound include an amide group-containing radical polymerizing compound, an amino group-containing radical polymerizing compound, an imide group-containing radical polymerizing compound, or a cyano group-containing radical polymerizing compound Etc. may be used. Examples of the amide group-containing radical polymerizable compound include (meth) acrylamide or N, N-dimethyl (meth) acrylamide, N, (Meth) acrylamide, N, N'-methylenebis (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, Acrylamide, N-vinylpyrrolidone, N-vinylcaprolactam or (meth) acryloylmorpholine. Examples of the amino group-containing radical polymerizable compound include aminoethyl (meth) acrylate, N-dimethylaminoethyl (meth) acrylate or N, N-dimethylaminopropyl (meth) acrylate. Examples of the imide group-containing radical polymerizable compound include N-isopropylmaleimide, N- Hexyl maleimide or itaconimide The like can be illustrated, and a cyano group-containing radical polymerizable, but as the compound, can be a nitrile such as acrylonitrile or methacrylonitrile, exemplified by acrylonitrile, but is not limited thereto.

As the salt of (meth) acrylic acid, for example, a salt with an alkali metal such as lithium, sodium, and potassium or a salt with an alkaline earth metal such as magnesium, calcium, strontium, and barium is exemplified But is not limited thereto.

The first region or matrix can be formed, for example, by polymerizing a hydrophilic polymerizable composition comprising a hydrophilic polymerizable compound and a radical initiator. Thus, the first region or matrix may be a polymer of the hydrophilic polymerizable composition.

The kind of the hydrophilic polymerizable compound is not particularly limited, and for example, the compounds described above can be used.

The kind of the radical initiator contained in the hydrophilic polymerizable composition is not particularly limited. As the initiator, a radical thermal initiator or a photo initiator capable of generating radicals to induce polymerization reaction by application of heat or irradiation of light can be used.

Azo compounds such as 2,2-azobis-2,4-dimethylvaleronitrile (V-65, Wako), 2,2-azobisisobutyronitrile (V-60, Azo type initiators such as 2,2-azobis-2-methylbutyronitrile (V-59, Wako); (Peroyl NPP, NOF), diisopropyl peroxydicarbonate (Peroyl IPP, NOF), bis-4-butylcyclohexyl peroxydicarbonate (Peroyl TCP, NOF (Peroyl EEP, NOF), diethoxyhexyl peroxydicarbonate (peroyl OPP, NOF), hexyl peroxydicarbonate (Perhexyl ND, NOF), diethoxyethyl peroxydicarbonate ), Dimethoxybutylperoxy dicarbonate (Peroyl MBP, NOF), bis (3-methoxy-3-methoxybutyl) peroxy dicarbonate (Peroyl SOP, NOF), hexyl peroxypivalate (Perflux, NOF), trimethylhexanoyl peroxide (Peroyl 355, NOF), amyl peroxypivalate (Luperox 546M75, Atofina), butyl peroxypivalate (Peroxy compound); (Luperox 610M75, Atofina), amyl peroxyneodecanoate (Luperox 546M75, Atofina) or butyl peroxyneodecanoate (Luperox 10M75, available from Atofina Peroxy dicarbonate compounds such as a)); Acyl peroxides such as 3,5,5-trimethylhexanoyl peroxide or dibenzoyl peroxide; Ketone peroxide; Dialkyl peroxides; Peroxyketals; Or peroxide initiators such as hydroperoxide and the like.

As the photoinitiator, benzoin, hydroxy ketone, amino ketone or phosphine oxide photoinitiators may be used. Specific examples thereof include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy 2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, benzophenone , p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methyl anthraquinone, 2-ethyl anthraquinone, 2- Thioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethylketal, acetophenone dimethylketal, p- Ester, ol Methyl-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone] and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide can be used. But is not limited to.

As the initiator, for example, a hydroxyketone compound, a water-dispersible hydroxyketone compound, an amino ketone compound, or an aqueous dispersion amino ketone compound may be used as the initiator, which exhibits high solubility in the hydrophilic component of the initiator , But is not limited thereto.

The radical initiator may be contained in the hydrophilic polymerizable composition in the range of, for example, 0.1 to 10 parts by weight based on 100 parts by weight of the hydrophilic polymerizable composition forming the light emitting layer. Such a ratio can be changed, for example, in consideration of the physical properties and polymerization efficiency of the film.

For example, considering the film property and the like, if necessary, the hydrophilic polymerizable composition may further include a crosslinking agent. As the crosslinking agent, for example, a compound having two or more radically polymerizable groups can be used.

As the compound which can be used as a crosslinking agent, a polyfunctional acrylate can be exemplified. The polyfunctional acrylate may mean a compound containing two or more acryloyl groups or methacryloyl groups.

Examples of the polyfunctional acrylate include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (Meth) acrylate, neopentylglycol adipate di (meth) acrylate, hydroxyl puivalic acid neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) Acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified di (meth) acrylate, di (meth) acryloxy ethyl isocyanurate, allyl cyclohexyl di ) Acrylate, tricyclodecane dimethanol (meth) acrylate, dimethylol dicyclopentanedi (meth) acrylate, ethylene oxide modified hexahydrophthalic acid di (meth) acrylate, tricyclo (Meth) acrylate, neopentyl glycol-modified trimethylpropane di (meth) acrylate, adamantane di (meth) acrylate or 9,9-bis [4- Ethoxy) phenyl] fluorene and the like; (Meth) acrylates such as trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri Trifunctional acrylates such as modified trimethylolpropane tri (meth) acrylate, trifunctional urethane (meth) acrylate or tris (meth) acryloxyethylisocyanurate; Tetrafunctional acrylates such as diglycerin tetra (meth) acrylate or pentaerythritol tetra (meth) acrylate; Pentafunctional acrylates such as propionic acid-modified dipentaerythritol penta (meth) acrylate; And dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate or urethane (meth) acrylate (e.g., an isocyanate monomer and trimethylolpropane tri Hexafunctional acrylates such as a reaction product) can be used. As the polyfunctional acrylate, urethane acrylate, epoxy acrylate, polyester acrylate or polyether acrylate can also be used as a compound called so-called photocurable oligomer in the industry. Of these compounds, one or more suitable types may be selected and used.

As the crosslinking agent, crosslinking agents such as the above-mentioned polyfunctional acrylates can be crosslinked by a thermal curing reaction such as known isocyanate crosslinking agents, epoxy crosslinking agents, aziridine crosslinking agents or metal chelate crosslinking agents, A component capable of implementing the structure may also be used.

The crosslinking agent may be contained in the hydrophilic polymerizable composition in the range of, for example, 10 parts by weight to 50 parts by weight based on 100 parts by weight of the hydrophilic polymerizable composition. The ratio of the cross-linking agent may be changed in consideration of, for example, physical properties of the film.

The hydrophilic polymerizable composition may further include other necessary components in addition to the above-described components. Further, the manner of forming the first region or matrix using the hydrophilic polymerizable composition will be described later.

The second region or the emulsion region can also be formed by polymerizing a radically polymerizable compound, for example, by polymerizing the hydrophobic polymerizable compound. The radical polymerizable compound capable of forming the second region or the emulsion region is not particularly limited. For example, the second region or the emulsion region may be a compound represented by any one of the following formulas (5) to And may include polymerized units.

[Chemical Formula 5]

 [Chemical Formula 6]

 (7)

In the formulas (5) to (7), each Q is independently hydrogen or an alkyl group,

B is a linear or branched alkyl or alicyclic hydrocarbon group having 5 or more carbon atoms, Y is a carbon atom, an oxygen atom or a sulfur atom, X is an oxygen atom, an oxygen atom or a sulfur atom, An atom, a sulfur atom or an alkylene group, Ar is an aryl group, and n is an arbitrary number.

The term " alkenylene group or alkynylene group " in the present application means an alkenylene group having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms, Or an alkynylene group. The alkenylene group or alkynylene group may be straight-chain, branched-chain or cyclic. In addition, the alkenylene group or alkynylene group may be optionally substituted with one or more substituents.

The term " arylene group " in the present application may mean a divalent moiety derived from a compound or derivative thereof containing a structure in which benzene or two or more benzenes are condensed or bonded, unless otherwise specified. The arylene group may have a structure including, for example, benzene, naphthalene or fluorene.

The term " aryl group " in the present application may mean a monovalent residue derived from a compound or derivative containing a benzene ring or a structure in which two or more benzene rings are condensed or bonded, unless otherwise specified. The aryl group may be, for example, an aryl group having 6 to 25 carbon atoms, 6 to 21 carbon atoms, 6 to 18 carbon atoms, or 6 to 12 carbon atoms.

Examples of the substituent which may optionally be substituted in the alkenylene group, alkynylene group, arylene group or aryl group in the present application include a halogen, an alkyl group or an aryloxy group such as a hydroxyl group, chlorine or fluorine, But is not limited to.

In one example, Q in Chemical Formula 5 is hydrogen or an alkyl group, and B may be a linear or branched alkyl group having 5 or more carbon atoms or an alicyclic hydrocarbon group. In Formula 5, B may be a linear or branched alkyl group having 5 or more carbon atoms, 7 or more carbon atoms, or 9 or more carbon atoms. Such relatively long chain alkyl group containing compounds are known to be relatively nonpolar compounds. The upper limit of the number of carbon atoms of the linear or branched alkyl group is not particularly limited. For example, the alkyl group may be an alkyl group having 20 or less carbon atoms. In another embodiment, B may be an alicyclic hydrocarbon group, for example, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, 3 to 16 carbon atoms, or 6 to 12 carbon atoms. Examples of such hydrocarbon groups include cyclohexyl group or iso Boronyl group and the like can be exemplified. The compound having an alicyclic hydrocarbon group is known as a relatively nonpolar compound.

In one example, Q in formula (6) is hydrogen or an alkyl group, and U may be an alkenylene, alkynylene or arylene group.

In one example, Q is hydrogen or an alkyl group, U is an alkylene group, Y is an oxygen atom or a sulfur atom, X is an oxygen atom, a sulfur atom or an alkylene group, Ar is an aryl group, May be any positive number, for example a positive integer within the range of 1 to 20, 1 to 16, or 1 to 12.

The second region or the emulsion region can be formed, for example, by polymerizing a hydrophobic polymerizable composition comprising a hydrophobic polymerizable compound and a radical initiator. Accordingly, the second region or the emulsion region may be a polymer of the hydrophobic polymerizable composition.

The kind of the hydrophobic polymerizable compound contained in the hydrophobic polymerizable composition is not particularly limited, and a compound known as a so-called non-polar monomer in the industry can be used. For example, the above-mentioned compounds can be used as the above-mentioned compounds.

The kind of the radical initiator contained in the hydrophobic polymerizable composition is not particularly limited. For example, an appropriate type of initiator described in the item of hydrophilic polymerizable compound described above can be selected and used.

The radical initiator may be included in the hydrophobic polymerizable composition in an amount of, for example, 5 parts by weight or less based on 100 parts by weight of the hydrophobic polymerizable composition. Such a weight ratio can be changed, for example, in consideration of the physical properties and polymerization efficiency of the film.

Considering film properties and the like, if necessary, the hydrophobic polymerizable composition may further include a crosslinking agent. As the crosslinking agent, for example, suitable components may be selected from among the components described in the item of the hydrophilic polymerizable composition without any particular limitation.

The crosslinking agent may be contained in the hydrophobic polymerizable composition in an amount of, for example, 50 parts by weight or less, or 10 parts by weight to 50 parts by weight, based on 100 parts by weight of the hydrophobic polymerizable composition. The weight ratio of the crosslinking agent may be changed in consideration of, for example, physical properties of the film, influence on other components contained in the polymerizable compound, and the like.

The hydrophobic polymerizable composition may further include other components if necessary. The method of forming the second region or the emulsion region using the hydrophobic polymerizable composition will be described later.

In one example, the light emitting layer may comprise a complex comprising a wavelength converting particle. The complex may be contained in the emulsion region of the light emitting layer, and may not be substantially contained in the matrix of the continuous phase. When the total weight of the complex contained in the light emitting layer including the emulsion region and the matrix is 100%, the fact that the complex is not included in any region in the present application means that the weight of the complex contained in the region When the ratio is 10% or less, 9% or less, 8% or less, 7% or less, 6% or less, 5% or less, 4% or less, 3% or less, 2% or less, 1% or less, 0.5% or less or 0.1% . ≪ / RTI >

By forming two regions phase-separated in the light-emitting layer and substantially positioning the complex containing the wavelength-converted particles in only one of the two regions, physical properties suitable for film formation can be ensured, It is advantageous to ensure adhesion between the light emitting layer and another layer such as a layer and other factors that may adversely affect physical properties of the nanoparticle such as an initiator and a crosslinking agent in a region where the wavelength converting particles exist in the formation of the optical film So that a film having excellent durability can be formed.

The wavelength converting particles contained in the complex of the emulsion region may be the above-mentioned green particles and / or red particles. In one example, the light emitting layer may contain green particles and red particles at the same time. The green particles and the red particles are included in the emulsion region of the light emitting layer and may not be substantially contained in the matrix of the continuous phase.

On the other hand, the green particles and the red particles contained in the emulsion region can be present in the A region or the B region, respectively, in a state of being complexed with the scattering particles via the ligand.

The A region may include a complex having green particles and may not include a complex having substantially red particles. The B region may include a complex having red particles, and a complex having green particles. It may mean an area that does not substantially contain it. For example, it may mean that the composite excluding the complex having the green particles in the A region is contained at a ratio of 10% by weight or less relative to the entire composite present in the A region.

That is, the emulsion region of the present application has an A region including a composite having first wavelength converting particles capable of absorbing light within a range of 420 nm to 490 nm and emitting light within a range of 490 nm to 580 nm, and / And a second wavelength converting particle capable of absorbing light within the wavelength range of 580 nm to 780 nm and emitting light within the range of 580 nm to 780 nm. The first wavelength conversion particle may mean the above-mentioned green particle, and the second wavelength conversion particle may mean the above-mentioned red particle.

The ratio of the wavelength converting particles in the light emitting layer is not particularly limited and may be selected in an appropriate range in consideration of, for example, desired optical characteristics. In one example, the wavelength converting particles may be included in the light emitting layer or the radical polymerizing compound in the range of 0.05 to 20 parts by weight based on 100 parts by weight of the radical polymerizing compound forming the light emitting layer or the light emitting layer, but the present invention is not limited thereto.

In one example, the light emitting layer may comprise a complex comprising scattering particles. Composites comprising scattering particles may be contained within the emulsion region or matrix. In one example, the composite comprising the scattering particles may be included only in the emulsion region, and may not be substantially contained in the other regions.

The scattering particles may have a refractive index that is lower or higher than the surrounding medium, for example, the matrix and / or emulsion region, and the absolute value of the refractive index difference with the matrix and / or emulsion region is at least 0.2 or at least 0.4. . The upper limit of the absolute value of the refractive index difference is not particularly limited, and may be, for example, about 0.8 or less or about 0.7 or less.

The ratio of the scattering particles in the light emitting layer is not particularly limited, and may be selected in an appropriate range in consideration of, for example, desired optical characteristics. In one example, the scattering particles may be included in the light emitting layer or the radical polymerizing compound in the range of 0.05 to 10 parts by weight or 0.05 to 5 parts by weight based on 100 parts by weight of the radical polymerizing compound forming the light emitting layer or the light emitting layer, But is not limited thereto.

The wavelength converting particles and the scattering particles of the present application may be contained in a state suitable for improving the luminous efficiency of the optical film, for example, in a state where the wavelength converting particles and the scattering particles form a complex through the ligand, have.

The light emitting layer may contain other components in addition to the above-mentioned components. Examples of other components that the luminescent layer may contain include, but are not limited to, amphipathic nanoparticles described below and the like.

In one example, the light emitting layer may comprise amphipathic nanoparticles. The term amphipathic nanoparticles in this application may refer to nano-sized particles that include both hydrophilic and hydrophobic properties, for example, what are termed surfactants in the so-called industry.

Amphipathic nanoparticles may be present, for example, at the interface between the first region or matrix and the second region or emulsion region. The amphiphilic nanoparticles can increase the stability of the two regions phase-separated in the light emitting layer.

In one example, the amphiphilic nanoparticles positioned at the boundary between the two regions may have different refractive indices from those of the two regions. When the amphipathic nanoparticles are positioned at the boundaries between the two regions, the efficiency of generating white light can be further increased, for example, by scattering or diffusing light by the nanoparticles.

The degree of difference in refractive index between the nanoparticles and the two regions may be set in an appropriate range in consideration of scattering or diffusing effects of the desired light, and the specific range thereof is not particularly limited. For example, the absolute value of the difference in refractive index between the nanoparticles and the matrix and the absolute value of the difference in refractive index between the nanoparticles and the emulsion region may each be in the range of 0.01 to 1.5 or 0.05 to 0.5. The refractive index of the nanoparticles is not particularly limited as long as it satisfies the above range, and may be in the range of 1.0 to 2.0, for example. The term refractive index in the present application is a value measured for light having a wavelength of about 550 nm unless otherwise specified.

In one example, the amphiphilic nanoparticle may comprise a cell portion comprising a nanocore portion and an amphipathic compound surrounding the core portion. In the above, the amphipathic compound is a compound which simultaneously contains a hydrophilic part and a hydrophobic part. For example, when the core portion is hydrophobic, the minority portion of the amphipathic nanoparticle in the cell portion faces the core and the hydrophilic portion is disposed outward to form amphipathic nanoparticles as a whole, and conversely, when the core portion is hydrophilic The hydrophilic portion of the amphipathic nanoparticle in the cell portion may be directed to the core and the minority portion may be disposed externally to form amphipathic nanoparticles as a whole. In the above, the core portion may have an average particle size within a range of, for example, about 10 nm to 1,000 nm, but is not particularly limited as long as it can be changed according to purposes. Core portion, for example, Au, Ag, Cu, Pt, Pd, Ni, metal particles such as Mn or Zn, SiO _2, Al ₂ O _3, TiO _2, ZnO, NiO, CuO, MnO _2, MgO, Oxide particles such as SrO or CaO, or particles made of polymers such as PMMA (polymethacrylate) or PS (polystyrene) can be used.

Triton X-114 (CAS No. 9036-19-5), Triton X-100 (CAS No. 92046-34-9), Brij-58 (CAS No. 92046-34-9), amphoteric compounds of the cell portion. : 9004-95-9), octyl glucoside (CAS No .: 29836-26-8), octylthio glucoside (CAS No .: 85618-21-9), decaethylene glycol monodecyl ether decaethylene glycol monododecyl ether, CAS No .: 9002-92-0), N-decanoyl-N-methylglucamine (CAS No .: 85261-20-7), decyl maltopyrano N-dodecyl maltoside (CAS No .: 69227-93-6), nonaethylene glycol monododecyl ether (CAS No .: 82494-09-5), decyl maltopyranoside , CAS No .: 3055-99-0), N-nonanoyl-N-methylglucamine (CAS No .: 85261-19-4), octaethylene glycol monododecyl ether (CAS No .: 3055-98-9), span 20 (Span 20, CAS No .: 1338-39-2), polyvinylpyrrole Money (polyvinylpyrrolidone, CAS No .: 9003-39-8) or Synperonic F108 (PEO-b-PPO-b-PEO, CAS No .: 9003-11-06), etc. can be used, but are not limited thereto.

The amphiphilic nanoparticle may contain the amphiphilic compound in a range that can ensure the stability of the first region or matrix and the second region or the emulsion region described above. For example, the ratio of the amphipathic compound in the amphiphilic nanoparticles may range from about 5 parts by weight to about 30 parts by weight based on 100 parts by weight of the amphipathic nanoparticles comprising the core and the shell, The range may be changed.

The method of incorporating the amphiphilic nanoparticles into the light emitting layer, for example, a method of positioning the amphiphilic nanoparticles at the boundary between the two regions is not particularly limited. For example, in the manufacturing process of the light emitting layer, A method of blending amphiphilic nanoparticles can be used.

The ratio of the amphiphilic nanoparticles in the light emitting layer can be selected in consideration of, for example, the stability of the two regions that are phase-separated. In one example, the amphiphilic nanoparticles may be contained in the light emitting layer or the radical polymerizable compound in the range of 1 to 10 parts by weight based on 100 parts by weight of the radical polymerizing compound forming the light emitting layer or the light emitting layer.

The light-emitting layer may further include, in addition to the above-mentioned components, additives such as an oxygen scavenger, a radical scavenger or an antioxidant in necessary amounts.

The optical film may further include a barrier layer on the light emitting layer. In one example, the optical film may include a barrier layer on one or both sides of the light emitting layer.

Such a barrier layer can protect the luminescent layer from conditions under high temperature conditions or in the presence of harmful external factors such as oxygen and moisture.

FIG. 4 shows a structure including an emission layer 500 and a barrier layer 600 disposed on both sides thereof as one exemplary optical film. The barrier layer may be formed of a material having good stability, for example, hydrophobic and free from yellowing even when exposed to light. In one example, in order to reduce the loss of light at the interface between the light emitting layer and the barrier layer, the barrier layer may be selected so as to have a refractive index generally similar to that of the light emitting layer.

The barrier layer may be, for example, a solid material, or a cured liquid, gel, or polymer, and may be selected from materials that are flexible or non-flexible depending upon the application. The type of the material forming the barrier layer is not particularly limited and may be selected from known materials including glass, polymer, oxide, nitride, and the like. The barrier layer may be, for example, glass; Polymers such as PET (poly (ethylene terephthalate)); Or an oxide or nitride such as silicon, titanium or aluminum, or a combination of two or more of the above, but is not limited thereto.

The barrier layer may be present on both surfaces of the light-emitting layer, or may exist only on either surface, as exemplarily shown in Fig. Further, the optical film may have a structure in which a barrier layer exists on both surfaces as well as on both sides, and the light emitting layer is entirely sealed by the barrier layer.

The present application also relates to a process for producing the above-described complexes.

In one example, the present application may be directed to a method of making a composite comprising including the step of mixing wavelength-converting particles surface-modified with a ligand and surface-modified scattering particles with a ligand. When the wavelength converting particles and the scattering particles surface-modified with the ligand are mixed as described above, the wavelength converting particles and the scattering particles can be in a state of being kept at a certain distance by being coupled through the ligand.

The wavelength conversion particles, the type of scattering particles and the configuration of the ligand that can be used in the method for producing the composite can be all the contents described in the above-mentioned composite material without limitation, and a method for modifying the surface of the wavelength converting particles and scattering particles, It is a notice.

Specifically, in the composite according to the present application, when the wavelength converting particle and the scattering particle surface-modified with the ligand are mixed with the radical polymerizing compound, the ligand contained in the surface of the wavelength converting particle and the scattering particle is mutually bonded, Hydrogen bonding, or the like, or hydrophobic interaction.

The present application also relates to an optical film, for example, a method for producing the aforementioned optical film. The method may include, for example, mixing the wavelength-converted particles surface-modified with a ligand and scattering particles surface-modified with a ligand with a radically polymerizable compound.

By simply mixing the surface-modified wavelength conversion particles and the scattering particles with the radical polymerizing compound as described above, the wavelength converting particles and the scattering particles are mutually bonded via the ligand to be contained in the light emitting layer at predetermined intervals, It becomes possible to produce a film.

The surface-modified wavelength converting particles and the scattering particles may be in a state of forming a complex before they are mixed with the radical polymerizing compound. In addition, the surface-modified wavelength converting particles and scattering particles may be mixed with a radical polymerizing compound and may form a complex due to a bond between the ligands.

By including the complex having the ligand for keeping the wavelength converting particles and the scattering particles at a predetermined distance in the light emitting layer as described above, it is possible to further increase the light emitting efficiency of the light emitting layer due to scattering, refraction, or diffusion of light by the scattering particles have.

In one example, the radically polymerizable compound can be a mixture of a hydrophilic polymerizable composition and a hydrophobic polymerizable composition.

The radically polymerizable compound may be prepared by separately preparing a hydrophilic or hydrophobic polymerizable composition and then mixing the components or mixing the components constituting the hydrophilic and hydrophobic polymerizable composition at once.

When the radically polymerizable compound is polymerized after mixing the surface of the ligand with the radically polymerizable compound, the phase separation occurs in the polymerization process, and the phase-separated continuous phase A light-emitting layer including a phase-change matrix and an emulsion region may be formed. By the phase separation structure as described above, physical properties suitable for film formation can be ensured, and it is advantageous to ensure adhesion between the other layer such as the barrier layer and the light emitting layer. In the formation of the optical film, Other factors that may adversely affect the physical properties of the nanoparticles, such as cross-linking agents and the like, can be more effectively controlled to form a film having excellent durability.

In one example, the emulsion region may comprise an A region and / or a B region, each containing different wavelength converting particles, as described above.

In one example, in order to obtain an emissive layer including the emulsion regions A and B, two hydrophobic polymerizable compositions containing the wavelength converting particles are separately prepared, and one hydrophobic polymerizable composition contains green particles And the other hydrophobic polymerizable composition is allowed to contain red particles, and then the two are mixed again and polymerized. Herein, the hydrophobic polymerizable composition containing green particles is referred to as a first hydrophobic polymerizable composition, and the hydrophobic polymerizable composition comprising red particles may be referred to as a second hydrophobic polymerizable composition.

That is, the hydrophobic polymerizable composition may include a first hydrophobic polymerizable composition containing first wavelength converting particles capable of absorbing light within a range of 420 nm to 490 nm and emitting light within a range of 490 nm to 580 nm, And a second wavelength converting particle capable of absorbing light and emitting light within a range of 580 nm to 780 nm.

The radically polymerizable compound capable of forming the light emitting layer of the present application can be produced by mixing the two hydrophobic polymerizable compositions different from each other with the hydrophilic polymerizable composition, and then mixing the two with each other.

For example, a hydrophilic polymerizable composition is mixed with a first hydrophobic polymerizable composition containing green particles to prepare a radically polymerizable compound A, and a hydrophilic polymerizable composition is mixed with a second hydrophobic polymerizable composition containing red particles To prepare a radical polymerizable compound B, and then the two are mixed again for polymerization.

The degree of hydrophilicity or hydrophobicity of each of the radically polymerizable compounds is not particularly limited and may be such that the phase separation structure described above can be formed when the composition is mixed.

The manner of forming the layer containing the radical polymerizing compound is not particularly limited. For example, the obtained mixture can be formed by coating on a suitable substrate by a known coating method.

The method of curing the layer formed in the above manner is not particularly limited. For example, it is possible to apply an appropriate range of heat to activate the initiator contained in each composition, or to apply electromagnetic waves such as ultraviolet rays . ≪ / RTI >

The method for producing an optical film of the present application may further include the step of forming a barrier layer after forming the light emitting layer through the above step, if necessary, or the curing step may be performed adjacent to the barrier layer.

The present application is also directed to a lighting device. Exemplary lighting devices may include a light source and the optical film. In one example, the light source and the optical film in the illumination device may be arranged so that the light emitted from the light source is incident on the optical film. When the light irradiated from the light source is incident on the optical film, a part of the incident light is not absorbed by the wavelength converting particles in the optical film but is emitted as it is, while the other part is absorbed by the wavelength converting particle Can be released. Part of the incident light or a part of the light emitted by the wavelength converting particles collides with the wavelength converting particle by a phenomenon such as scattering, refraction, or diffusion caused by scattering particles in the optical film, As shown in FIG. Accordingly, it is possible to control the color purity or color of the light emitted from the optical film by controlling the wavelength of the light emitted from the light source and the wavelength of the light emitted by the wavelength converting particles, thereby providing an optical film having increased luminous efficiency.

In one example, when the light emitting layer contains the above-mentioned red and green particles in an appropriate amount, and the light source is adjusted to emit blue light, white light may be emitted in the optical film.

The type of the light source included in the illumination device of the present application is not particularly limited, and an appropriate type can be selected in consideration of the type of the target light. In one example, the light source is a blue light source, and may be, for example, a light source capable of emitting light in a wavelength range of 420 to 490 nm.

5 and 6 illustrate an illumination device including a light source and an optical film as described above.

As shown in Figs. 5 and 6, the light source and the optical film in the illumination device can be arranged so that the light irradiated from the light source can be incident on the optical film. 5, the light source 700 is disposed below the optical film 800, so that the light emitted from the light source 700 in the upward direction can be incident on the optical film 800.

Fig. 6 shows a case where the light source 700 is disposed on the side of the optical film 800. Fig. When the light source 700 is disposed on the side of the optical film 800 as described above, light from the light source 700, such as a light guiding plate 900 and a reflection plate 1000, Other means may be included to enable the optical film 800 to be efficiently incident.

The example shown in Figs. 5 and 6 is one example of the illumination device of the present application, and the illumination device may have various known configurations and may additionally include various known configurations for this purpose.

The illumination device of the present application as described above can be used for various applications. A typical application to which the illumination apparatus of the present application may be applied is a display apparatus. For example, the illumination device can be used as a BLU (Backlight Unit) of a display device such as an LCD (Liquid Crystal Display).

In addition, the lighting device may be a backlight unit (BLU) of a display device such as a computer, a mobile phone, a smart phone, a personal digital assistant (PDA), a gaming device, an electronic reading device or a digital camera, , Stage lighting, decorative lighting, accent lighting or museum lighting, etc. In addition, it may be used in horticulture, special wavelength lighting required in biology, etc., but the application to which the lighting device can be applied is not limited to the above.

Hereinafter, the optical films and the like of the present application will be specifically described by way of examples and comparative examples, but the scope of the optical films and the like is not limited to the following examples.

Example  One.

Green PEG (PEG thiol) obtained by reacting the particles with a 1: 2 weight ratio of particles made of a ligand of an oleic acid and PEG thiol as a Quantum Dot particle for 4 hours in toluene, SiO ₂ nanoparticles having a diameter of about 20 nm and a surface hydroxyl group (Nissan) are mixed in a weight ratio of 1: 1, and the mixture is stirred in acetone for 6 hours. After the reaction, the precipitate obtained through a centrifuge (5000 rpm, 10 minutes) and a poly (ethyleneglycol) diacrylate (PEGDA, CAS No. 26570-48-9, solubility parameter (HSP) about ^{18 (cal / cm 3) 1/2} ), lauryl acrylate (LA, lauryl acrylate, CAS No .: 2156-97-0, solubility parameter (HSP): about 8 (cal / cm ^{3) 1/2} ), Bisfluorene diacrylate (CAS No. 161182-73-6, solubility parameter (HSP): about 8 to 9 (cal / cmcm ³ ) ^1/2 ), polyvinylpyrrolidone Were mixed in a weight ratio of 0.2: 9: 1: 1: 0.05 (precipitate: PEGDA: LA: BD: surfactant). Irgacure 2959 and Irgacure 907 as radical initiators were then mixed to a concentration of about 1% The mixture was then placed between two barrier films (i-components) spaced apart at regular intervals to a thickness of about 100 μm, Cured by irradiation with a line leading to radical polymerization wavelength conversion particle - to form a light emitting layer containing the scattering particles conjugate distance is approximately 10 to 100 nm between the wavelength converting particles and the scattering particles contained in the light emitting layer.

Comparative Example  One.

A poly (ethyleneglycol) diacrylate, CAS No. 26570-48-9, a solubility parameter (HSP) of about 18 (cal / cm ³ ) ^1/2 ), lauryl acrylate acrylate (LA, lauryl acrylate, CAS No .: 2156-97-0, solubility parameter (HSP): about ^{8 (cal / cm 3) 1/2} ), bis fluorene diacrylate (BD, bisfluorene diacrylate, CAS No : 161182-73-6, solubility parameter (HSP): about 8 to ^{9 (cal / cmcm 3) 1/2} ), green particles (Quantum Dot particles), SiO ₂ nanoparticles, and surfactant (polyvinylpyrrolidone) 9: 1: 1: 0.1: 0.1: 0.1 (PEGDA: LA: BD: green particles: SiO ₂ nanoparticles: surfactant). Irgacure 2959 and Irgacure 907 as radical initiators were then added at a concentration of about 1 wt% The mixture was stirred for about 6 hours to prepare a radical polymerizable mixture, and a light emitting layer was formed in the same manner as in Example 1 except that this mixture was used.

Test Example  - Evaluation of luminous efficiency

The light emission efficiency (Q.Y) according to the absorption spectrum (black line) and the emission spectrum (red line) of the luminescent film according to Example 1 and Comparative Example 1 were evaluated and shown in FIGS. As shown in FIGS. 7 and 8, it was confirmed that the luminescent efficiency of the luminescent film according to Example 1 (about 44%) and Comparative Example 1 (about 22%) was about twice as large.

100: Wavelength conversion particle
101: first ligand
200: scattering particles
201: Second ligand
300: core part
400:
500: light emitting layer
600: barrier layer
700: Light source
800: Optical film
900: light guide plate
1000: reflective layer

Claims (22)

Wavelength converting particles;
Scattering particles;
And a ligand for binding the wavelength converting particles and the scattering particles,
Wherein the ligand comprises a first ligand bonded to the surface of the wavelength converting particle and a second ligand bonded to the surface of the scattering particle, wherein the first ligand and the second ligand are mutually bonded by hydrogen bonding. The method according to claim 1,
Wherein the length of the ligand is from 5 nm to 100 nm. delete delete The method according to claim 1,
Wherein the wavelength converting particle is a quantum dot or a polymer particle. The method according to claim 1,
The scattering particles include polystyrene or a derivative thereof; An acrylic resin or a derivative thereof; Silicone resins or derivatives thereof; And any one of organic materials selected from the group consisting of novolac resins or derivatives thereof, or any inorganic material selected from the group consisting of metal oxides and glass beads. Wavelength converting particles;
Scattering particles; And
And a ligand which binds the wavelength converting particles and the scattering particles,
Wherein the ligand comprises a first ligand bonded to the surface of the wavelength converting particle and a second ligand bonded to the surface of the scattering particle, wherein the first ligand and the second ligand are mutually bonded by hydrogen bonding. 8. The method of claim 7,
An optical film comprising a light emitting layer comprising an emulsion region dispersed in a continuous phase matrix, the light emitting layer comprising the continuous phase or a complex present in the emulsion region. 9. The method of claim 8,
Wherein the light emitting layer comprises an emulsion region of 5 to 40 parts by weight based on 100 parts by weight of the matrix. 9. The method of claim 8,
Wherein the scattering particles have a refractive index difference of 0.2 or more with the matrix and / or the emulsion region. 9. The method of claim 8,
Wherein the matrix is a compound of formula 1; A compound of Formula 2 below; A compound of Formula 3; A compound of formula (4); Nitrogen-containing radically polymerizable compounds; And a radically polymerizable compound comprising (meth) acrylic acid or a salt thereof:
[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

In the general formulas (1) to (4), each Q is independently hydrogen or an alkyl group,
U is independently an alkylene group,
A is independently an alkylene group which may be substituted with a hydroxy group,
Z is hydrogen, an alkoxy group, an epoxy group or a monovalent hydrocarbon group,
X is a hydroxy group or a cyano group,
m and n are positive integers. 9. The method of claim 8,
Wherein the emulsion region comprises a polymerized unit of a radically polymerizable compound represented by any one of the following formulas (5) to (7):
[Chemical Formula 5]

[Chemical Formula 6]

(7)

In the formulas (5) to (7), each Q is independently hydrogen or an alkyl group,
U is independently an alkylene, alkenylene or alkynylene or an arylene group,
B is a linear or branched alkyl group having 5 or more carbon atoms or an alicyclic hydrocarbon group,
Y is an oxygen atom or a sulfur atom,
X is an oxygen atom, a sulfur atom or an alkylene group,
Ar is an aryl group,
and n is a positive integer in the range of 1 to 20. 9. The method of claim 8,
The emulsion region absorbs light within the range of 420 nm to 490 nm and / or the A region including the composite having the first wavelength conversion particle capable of absorbing light within the range of 420 nm to 490 nm and capable of emitting light within the range of 490 nm to 580 nm And a second wavelength converting particle capable of emitting light within a range of 580 nm to 780 nm. 9. The method of claim 8,
An optical film further comprising a barrier layer on the light emitting layer. A method for producing a composite according to claim 1, comprising mixing the wavelength-converted particles surface-modified with a ligand and scattering particles surface-modified with a ligand. 9. The method of producing an optical film according to claim 8, comprising the step of mixing the radically polymerizable compound with the wavelength converting particles surface-modified with the ligand and the scattering particles surface-modified with the ligand. 17. The method of claim 16,
Wherein the radical polymerizable compound is a mixture of a hydrophilic polymerizable compound and a hydrophobic polymerizable compound. 18. The method of claim 17,
The hydrophilic polymerizable compound is a compound represented by the following formula (1): A compound of Formula 2 below; A compound of Formula 3; A compound of formula (4); Nitrogen-containing radically polymerizable compounds; And a radically polymerizable compound comprising (meth) acrylic acid or a salt thereof.
[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

In the general formulas (1) to (4), each Q is independently hydrogen or an alkyl group,
U is independently an alkylene group,
A is independently an alkylene group which may be substituted with a hydroxy group,
Z is hydrogen, an alkoxy group, an epoxy group or a monovalent hydrocarbon group,
X is a hydroxy group or a cyano group,
m and n are positive integers. The method for producing an optical film according to claim 17, wherein the hydrophobic polymerizable compound is a radically polymerizable compound represented by any one of the following formulas (5) to (7)
[Chemical Formula 5]

[Chemical Formula 6]

(7)

In the formulas (5) to (7), each Q is independently hydrogen or an alkyl group,
U is independently an alkylene, alkenylene or alkynylene or an arylene group,
B is a linear or branched alkyl group having 5 or more carbon atoms or an alicyclic hydrocarbon group,
Y is a carbon atom, an oxygen atom or a sulfur atom,
X is an oxygen atom, a sulfur atom or an alkylene group,
Ar is an aryl group,
and n is a positive integer in the range of 1 to 20. Light source; And
9. The illumination device according to claim 8, wherein the light source and the optical film are disposed so that light from the light source can be incident on the optical film. 21. The method of claim 20,
Wherein the light source is capable of emitting light of a wavelength within a range of 420 nm to 490 nm. A display device comprising the lighting device of claim 21.

Images