KR102034463B1 - A wavelength conversion particle complex and Optical film comprising it - Google Patents

Abstract

The present application relates to a composite, a composition for an optical film comprising the same, an optical film, a manufacturing method and 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 be stably maintained for such a long time excellent properties. The optical film of the present application can be used in various lighting devices as well as in various applications including photovoltaic applications, light filters or light converters and the like.

Description

A wavelength conversion particle complex and optical film comprising it

The present application relates to a wavelength conversion particle composite, an optical film composition comprising the composite, an optical film, and use thereof.

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

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

In recent years, researches on lighting devices that emit white light using wavelength-converting particles, such as quantum dots, which vary in color of light emitted according to particle size, have been steadily being conducted. In particular, researches to increase the wavelength conversion efficiency of the quantum dot itself or the problem of efficiency reduction due to exposure to the gas such as oxygen, etc. have been actively conducted.

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

The present application, for example, for converting the wavelength conversion particle and the plasmon particles in one composite, to improve the wavelength conversion efficiency, and to provide an optical film having excellent optical properties for the wavelength conversion particle composite and an optical film comprising the same To provide a composition.

The present application also provides an optical film excellent in physical properties suitable for the film, for example, adhesion with other layers, durability or optical properties, and the like, through phase separation of the wavelength conversion layer.

The present application has been made to solve the above problems, wavelength conversion particles; Plasmon particles; And it relates to a composite comprising a ligand for binding the wavelength conversion particles and plasmon particles.

In one example, the ligand of the complex includes a first ligand bound to the surface of the wavelength conversion particle and a second ligand bound to the surface of the plasmon particle, wherein the first ligand and the second ligand are bonded to each other. It may be there.

The mutual bond between the first ligand and the second ligand may be a hydrogen bond or a hydrophobic interaction.

The present application also relates to a composition for an optical film comprising the composite. The composition for an optical film contains a polymeric resin or a composite with a first radically polymerizable compound.

In another example, the composition for an optical film may further include a second radically polymerizable compound phase-separated after polymerization with the first radically polymerizable compound.

The present application also relates to an optical film having a wavelength conversion layer comprising the composite.

In one example, the wavelength conversion layer of the optical film is a continuous phase matrix; And an emulsion region dispersed in the matrix, and the complex may be located in the matrix or emulsion region.

The present application also relates to a method for producing a composite comprising mixing a wavelength-modified particle surface-modified with a ligand and a plasmon particle surface-modified with a ligand.

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

The present application also relates to a lighting device and a display device including the optical film as described above.

The present application may provide a wavelength converting particle composite that may be included in an illumination device having a constant optical characteristic, for example, a light emission intensity and an improved wavelength conversion efficiency, using a plasmon resonance phenomenon.

In addition, the present application may provide an optical film having excellent physical properties suitable for the film, for example, adhesion with other layers, durability, or optical properties, through phase separation of the wavelength conversion layer.

1 and 2 are schematic diagrams of a composite including wavelength converting particles and plasmon 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.
5 and 6 are schematic diagrams of exemplary lighting devices.
7 shows the luminous efficiency of optical films according to Examples and Comparative Examples.

Hereinafter, the present application will be described in more detail with reference to Examples and drawings, but is only an embodiment limited to the gist of the present application. On the other hand, the present application is not limited to the process conditions presented in the following examples, it can be arbitrarily selected within the range of conditions necessary to achieve the purpose of the present application is apparent to those skilled in the art. Do.

The present application relates to a composite comprising wavelength converting particles, plasmon particles and ligands. The ligand may bind wavelength converting particles and plasmon particles.

In the present application, the term “wavelength converting particle” may mean a particle formed to absorb light having a predetermined wavelength and emit light having the same or different wavelength as the absorbed light.

In the present application, the term "plasmon particle" may refer to a particle capable of causing plasmon resonance.

The term "plasmon resonance" in the present application may refer to surface electromagnetic waves generated by the collective vibration of electrons occurring on the surface of the metal thin film when light having a specific wavelength is incident on the metal thin film.

That is, the composite of the present application includes a ligand that binds the wavelength converting particle and the plasmon particle to maintain the constant distance between the wavelength converting particle and the plasmon particle, thereby causing the wavelength caused by the surface electromagnetic wave generated by the plasmon resonance phenomenon described above. Excitation of the converted particles can be facilitated, the wavelength conversion efficiency of the optical film can be increased, and the light emission intensity can be kept constant.

The length of the ligand binding the wavelength converting particle and the plasmon particle is such that the generation of surface electromagnetic waves due to the plasmon resonance phenomenon and the generated surface electromagnetic waves promote excitation of the wavelength converting particle, thereby ultimately converting wavelengths and emitting light. There is no limit as long as the distance can increase the intensity. For example, the length of the ligand can be 100 to 1,000 nm.

In another example, the length of the ligand may be in the range of 200 to 800 nm or 300 to 700 nm.

Ligand binding the wavelength conversion particle and the plasmon particle may be included in the complex in a limitless form within the range that can achieve the above object.

In one example, the ligand of the complex may be in a state that includes at least one ligand at both ends that can be bonded to the surface of the wavelength conversion particle and the plasmon particle.

In another example, the ligand included in the complex may include a first ligand bound to the surface of the wavelength conversion particle and a second ligand bound to the surface of the plasmon particle. In addition, the first ligand and the second ligand may be mutually bound.

Specifically, as shown in FIG. 1, the complex of the present application includes a wavelength converting particle 100 having a first ligand 101 and a plasmon particle 200 having a second ligand 201. The first ligand 101 and the second ligand 201 may be in a mutually coupled state. The first ligand and the second ligand which are bonded to each other may be the same kind or different kinds of ligands.

For example, the first ligand and the second ligand may be each independently a molecule having an amine group (oleylamine, triethylamine, hexylamine, naphtylamine, etc.) or a polymer, a molecule having a carboxyl group (oleic acid, etc.) or a molecule having a thiol group (butanethiol, hexanethiol, dodecanethiol, etc.) or a polymer, a molecule having a pyridine group (pyridine, etc.) 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 ( alkyl ketones, etc.), molecules having a benzene ring (benzene, styrene, etc.) or polymers, molecules having a hydroxy group (butanol, hexanol, etc.) or polymers, or molecules having sulfone groups (such as sulfonic acid) or polymers that can be bonded to each other Or a polymer may be appropriately selected.

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

The composite of the present application may include wavelength converting particles. As described above, the wavelength conversion particle may mean a particle formed to absorb light having a predetermined wavelength and emit light having the same or different wavelength as the absorbed light.

The size of the wavelength converting particle is, for example, an average particle diameter of 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, 20 nm or less, or about It may be 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 conversion particles may be referred to as particles (hereinafter, referred to as green particles) capable of absorbing light of any wavelength within a range of 420 to 490 nm to emit light of any wavelength within a range of 490 to 580 nm. ) Or particles capable of absorbing light of any wavelength within the range of 420 to 490 nm to emit light of any wavelength within the range of 580 to 780 nm (hereinafter referred to as red particles).

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

That is, as shown in Figure 2, the complex of the present application, the wavelength conversion particle 100 having a first ligand 101 and the plasmon particle 200 having a second ligand 201, the wavelength conversion The particles are green particles and / or red particles, and may form a complex of plasmon particles and clusters via a ligand.

As the wavelength converting particle, any one that exhibits such a function can be used without particular limitation. Representative examples of such particles include, but are not limited to, a nanostructure called a quantum dot.

Quantum dots that can be used in the present application can be formed using any suitable material, for example, an inorganic conductive or semiconducting material, as the inorganic material. Suitable semiconductor materials can be exemplified by Group II-VI, III-V, IV-VI and Group IV semiconductors. Specifically, Si, Ge, Sn, Se, Te, B, C (including diamond), P, BN, BP, BAs, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdSeZn, CdTe, HgS, HgSe, HgTe, BeS, BeSe, BeTe, MgS 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 suitable combinations of two or more of the above semiconductors may be illustrated, but are not limited thereto.

The quantum dots may have a core-shell structure. As shown in FIG. 3, the core-shell structure may include a core part 300 representing a center part of a quantum dot and a cell part 400 surrounding the core part 300. have.

Exemplary core-cell wavelength converting particles (core / cell) applicable in this application include, but are not limited to, CdSe / ZnS, InP / ZnS, PbSe / PbS, CdSe / CdS, CdTe / CdS or CdTe / ZnS, etc. It is not.

When the quantum dot has a core-shell sturucture, the cell part may be formed to be capable of binding to the terminal of the aforementioned ligand. In addition, the cell unit may be formed so that the above-described first ligand is 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, wherein the second cell portion is formed to be capable of binding to the terminal of the ligand. Alternatively, the first ligand may be formed to be bonded to the surface of the quantum dot.

In addition, the wavelength conversion particle may be a polymer particle made of an organic material. The type and size of the polymer particles made of the organic material may be used without limitation, for example, those of which the Republic of Korea Patent Publication No. 2014-0137676 is disclosed. When the wavelength conversion particle is a polymer particle of an organic material, the surface of the polymer particle may be formed to be bonded to the above-described ligand.

The wavelength converting particles can be prepared in any known manner. For example, U.S. Patent 6,225,198, U.S. Patent Publication 2002-0066401, U.S. Patent 6,207,229, U.S. Patent 6,322,901, U.S. Patent 6,949,206, U.S. Patent 7,572,393, U.S. Patent 7,767,865, U.S.A. A method of forming a quantum dot or the like is known from Patent No. 7,374,807 or US Pat. No. 6,861,155, 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 may be appropriately selected in consideration of desired light emission characteristics.

The wavelength converting particle may be one whose surface is modified to include one or more ligands or barriers. The ligand or barrier may be advantageous for improving the stability of the wavelength converting particles and protecting the wavelength converting particles from harmful external conditions including high temperature, high intensity, external gas or moisture, and the like. In addition, the ligand or barrier included in the wavelength converting particles binds to a ligand formed on the surface of the plasmon particles to maintain a constant distance between the wavelength converting particles and the plasmon particles, thereby causing wavelengths due to electromagnetic waves generated by plasmon resonance. Excitation of the conversion particles can be made easier.

In one example, the wavelength conversion particle may be a surface modified with a ligand.

As described above, the ligand formed through the surface modification of the wavelength converting particle can exhibit suitable properties on the surface of the wavelength converting particle, and can be combined with a ligand formed on the surface of the plasmon particle to increase the wavelength conversion efficiency. By acting, the formation method is known, and such a scheme can be applied without limitation in the present application. Such materials or methods are described, for example, in US Patent Publication No. 2008-0281010, US Publication No. 2008-0237540, US Publication No. 2010-0110728, US Publication No. 2008-0118755, US Patent No. 7,645,397 US Pat. No. 7,374,807, US Pat. No. 6,949,206, US Pat. No. 7,572,393, US Pat. No. 7,267,875, and the like, but are not limited thereto. In one example, the ligand is a molecule having an amine group (oleylamine, triethylamine, hexylamine, naphtylamine, etc.) or a polymer, a molecule having a carboxyl group (oleic acid, etc.) or a polymer, a molecule having a thiol group (butanethiol, hexanethiol, dodecanethiol, etc.) or Polymer, molecule having pyridine group (pyridine etc.) or polymer, molecule having phosphine group (triphenylphosphine etc.), molecule having phosphine group (trioctylphosphine oxide etc.), molecule having carbonyl group (alkyl ketone etc.), benzene ring Molecule (benzene, styrene, etc.) or a polymer, a molecule having a hydroxyl group (butanol, hexanol, etc.) or a polymer or a molecule having a sulfone group (Sulfonic acid, etc.) or a polymer, etc., the specific type of ligand is the surface of the plasmon particles Any of the molecules or polymers may be appropriately selected in consideration of the binding ability to the ligand formed in the.

The composite of the present application may comprise plasmon particles. Plasmon particles may refer to particles that can cause plasmon resonance as described above. The plasmon particle is to improve wavelength conversion efficiency by using a principle different from scattering particles and the like which can be added to improve wavelength conversion efficiency described later, that is, plasmon resonance phenomenon.

Plasmon particles, as described above, as long as the particles that can cause plasmon resonance phenomenon, the shape and material can be used without limitation.

For example, the plasmon particles may be in the shape of a spherical, oval, cylindrical, square, rectangular, rod, shaped tubular, pyramidal, triangular, plate or flat surface model.

For example, the plasmon particles may be particles of a core-shell structure having at least one metal particle core and an insulator cell covering the metal particle core.

The core of the plasmon particles is, for example, an alloy containing Ag (silver), Au (gold), Cu (copper), Al (aluminum), Pt (platinum), or any one of these metals as a main component (80% or more). It can be used, any one of the metals can be appropriately selected in consideration of the induction of plasmon resonance phenomenon according to the light source wavelength of the illumination device to emit white light.

As the material of the insulator, an insulator such as SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , PbO, B ₂ O ₃ , CaO, and BaO may be used for the cell of the plasmon particles.

When the plasmon particles are particles of a core-shell structure, the cell portion may be formed so that the ends of the ligands described above may be bonded. In addition, the cell unit may be formed so that the above-described second ligand is bound to the surface of the plasmon particle.

The size of the plasmon particle is not limited as long as the particle can induce plasmon resonance, thereby increasing the wavelength conversion efficiency of the wavelength conversion particle. For example, the plasmon particle may be a nano-dimension particle. The plasmon particles of the nano dimension may be, for example, spherical particles having a diameter in the range of 10 nm to 200 nm or 20 nm to 100 nm, but are not limited thereto.

In one example, the surface of the plasmon particle may be one whose surface is modified to include one or more ligands. The ligand binds to a ligand contained in a wavelength converting particle such as a quantum dot and maintains a constant distance between the plasmon particle and the wavelength converting particle, thereby causing excitation of the wavelength converting particle due to electromagnetic waves generated by plasmon resonance. It may be to play a role of making excitation more easily.

The method for forming a ligand on the surface of the plasmon particles is well known, and the type of ligand may be appropriately selected in consideration of the kind of ligand that may be included in the above-described wavelength converting particle. In one example, the ligand is a molecule having an amine group (oleylamine, triethylamine, hexylamine, naphtylamine, etc.) or a polymer, a molecule having a carboxyl group (oleic acid, etc.) or a polymer, a molecule having a thiol group (butanethiol, hexanethiol, dodecanethiol, etc.) or Polymer, molecule having pyridine group (pyridine etc.) or polymer, molecule having phosphine group (triphenylphosphine etc.), molecule having phosphine group (trioctylphosphine oxide etc.), molecule having carbonyl group (alkyl ketone etc.), benzene ring Molecule (benzene, styrene, etc.) or a polymer, a molecule having a hydroxyl group (butanol, hexanol, etc.) or a polymer or a molecule having a sulfone group (Sulfonic acid, etc.) or a polymer, etc., the specific type of ligand is a light emitting nanoparticle Any of the molecules or polymers may be appropriately selected in consideration of the binding ability with the ligand formed.

The present application also relates to a composition for an optical film comprising the composite as described above.

The term "optical film" in the present application may mean a film used in an optical device for various uses. For example, the optical film may mean a film formed to absorb light having a predetermined wavelength and emit light having the same or different wavelength as the absorbed light.

The composition for an optical film of the present application has a composite including a wavelength converting particle and a plasmon particle in a state of being maintained at a short distance through a ligand, thereby maximizing plasmon resonance and ultimately improving wavelength conversion efficiency. It can be used to provide an optical film that can be.

The composition for an optical film of the present application may also include other factors that may adversely affect the wavelength converting particles by mainly including the composite in either of two regions that may be phase separated from each other, which may be formed by polymerization of the composition. It can be controlled effectively.

The composition for an optical film of this application is a polymer resin or a 1st radically polymerizable compound; And complexes. In addition, the composite is a wavelength conversion particle; Plasmon particles; And ligands for binding the wavelength converting particles and the plasmon particles.

The polymer resin or the first radically polymerizable compound may be selected as a main component for forming the wavelength conversion layer formed from the composition, in consideration of mixing properties with the composite and particle dispersibility. have.

In one example, the polymer resin may have a solubility parameter of less than 10 (cal / cm ³ ) ^1/2 .

Thus, a resin having a solubility parameter of less than 10 (cal / cm ³ ) ^1/2 may be referred to as a hydrophobic polymer resin. The manner of obtaining the solubility parameter is not particularly limited and may be in accordance with methods 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).

When the hydrophobic polymer resin is used as the polymer resin, the dispersibility of the wavelength converting particles and the composite thereof, and the like can be adequately ensured, and it can be effective to achieve the desired wavelength conversion efficiency.

The type of the polymer resin is one having the above-described solubility parameter range, and for example, acrylic, silicone, hydrocarbon polymer or urethane resin may be exemplified, but is not limited thereto.

In one example, the polymer resin may be polybutadiene, polyisobutylene, polyethylene, polypropylene, poly (1-decene), polystyrene, 1-octadecene, 1-nonadecene, cis-2-methyl-octadecene, Or a hydrocarbon polymer such as 1-heptadecene, 1-hexadecene, 1-pentadecene, 1-tetradecene, 1-tridecene, 1-undecene or 1-dodecene. As such, when the hydrocarbon polymer is used as the hydrophobic polymer resin, dispersion of the wavelength particles and stability under high temperature and high humidity conditions can be effectively ensured.

The composition for optical films can contain a 1st radically polymerizable compound.

The first radically polymerizable compound may be a polymerizable monomer, an oligomer, or a polymer as a main agent of the wavelength conversion layer.

In one example, the first radically polymerizable compound may have a solubility parameter of less than 10 (cal / cm ³ ) ^1/2 of a single polymer. That is, the first radically polymerizable compound may be a hydrophobic polymerizable compound. As described above, when the hydrophobic polymerizable compound is polymerized to form the wavelength conversion layer, dispersibility and stability of the wavelength conversion particle and the composite thereof can be achieved. In another example, the solubility parameter of the first radically polymerizable compound is 3 (cal / cm ³ ) ^1/2 or more, 4 (cal / cm ³ ) ^1/2 or more or about 5 (cal / cm ³ ) ^1/2 It may be abnormal.

The first radically polymerizable compound may satisfy any of the above-described solubility parameter ranges and may be, for example, any one selected from the group consisting of a compound of Formula 1, a compound of Formula 2, and a compound of Formula 3 .

 [Formula 1]

 [Formula 2]

 [Formula 3]

In Formulas 1 to 3, Q is each independently hydrogen or an alkyl group, U is independently an alkylene group, an alkenylene group or an alkynylene group or an arylene group, and B is a straight or branched chain alkyl group having 5 or more carbon atoms or an alicyclic hydrocarbon And 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 any number.

 In the present application, the term "alkyl group" 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.

In the present application, the term "alkylene group" 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. In addition, the alkylene group may be optionally substituted with one or more substituents.

In the present application, the term "alkenylene group or alkynylene group" 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, unless otherwise specified. Or an alkynylene group. The alkenylene group or alkynylene group may be linear, branched 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 refer to a divalent moiety derived from a compound or a derivative thereof including a structure in which benzene or two or more benzenes are condensed or bonded, unless otherwise specified. The arylene group may have a structure containing, for example, benzene, naphthalene or fluorene.

The term "aryl group" in the present application may refer to a monovalent moiety derived from a compound or a derivative thereof including a structure in which a benzene ring or a structure in which two or more benzene rings are condensed or bonded, unless otherwise specified. The range of the aryl group may include a functional group commonly referred to as an aryl group as well as a so-called aralkyl group or an arylalkyl group. 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 aryl group include phenyl group, phenoxy group, phenoxyphenyl group, phenoxybenzyl group, dichlorophenyl, chlorophenyl, phenylethyl group, phenylpropyl group, benzyl group, tolyl group, xylyl group or naphthyl group. Can be. In addition, the aryl group may be optionally substituted with one or more substituents.

Examples of the substituent that may be optionally substituted with the alkyl group, alkylene group, alkenylene group, alkynylene group, arylene group or aryl group in the present application include a halogen, alkyl group or aryloxy group such as hydroxy group, chlorine or fluorine, etc. It may be, but is not limited thereto.

In one example, Q of Formula 1 is hydrogen or an alkyl group, and B may be a straight or branched chain alkyl group or alicyclic hydrocarbon group having 5 or more carbon atoms.

In Formula 1, B may be a straight or branched chain alkyl group having 5 or more carbon atoms, 7 or more carbon atoms, or 9 or more carbon atoms. As such, a compound containing a relatively long chain alkyl group is known as a relatively nonpolar compound. The upper limit of the carbon number 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, in another example, 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, and examples of such hydrocarbon group include cyclohexyl group or iso Bornyl group and the like can be exemplified. Thus, the compound which has alicyclic hydrocarbon group is known as a relatively nonpolar compound.

In one example, Q in formula 2 is hydrogen or an alkyl group, and U may be an alkenylene group, an alkynylene group or an arylene group.

In one example, in formula (3), Q is hydrogen or an alkyl group, U is an alkylene 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, and Ar is an aryl group , n can be any number, for example a positive integer in the range of 1 to 20, 1 to 16 or 1 to 12.

The composition for an optical film of the present application may further include a second radically polymerizable compound which is phase-separated after polymerization with the first radically polymerizable compound.

As such, when the optical film is formed from a composition comprising two compounds which are phase-separated after polymerization, and the wavelength conversion particles are positioned only in a region where one of the two compounds is polymerized, It is possible to more effectively control other factors that may adversely affect the physical properties of the wavelength conversion particles such as an initiator or a crosslinking agent to provide an excellent optical film.

In one example, the composition for an optical film of the present application may form a hydrophilic region and a hydrophobic region that is phase separated from the hydrophilic region after polymerization, wherein the regions are respectively the second radical polymerizable compound and the first radical polymerizable. It may be a region formed by the compound.

Hereinafter, a region formed by polymerization of the first radically polymerizable compound may be referred to as a hydrophobic region or an emulsion region, and a region formed by polymerization of the second radically polymerizable compound may be referred to as a hydrophilic region or a matrix.

Specifically, the composition for an optical film of the present application may include, in addition to the first radically polymerizable compound, a second radically polymerizable compound which is phase-separated after the polymerization with the first radically polymerizable compound.

The term "phase-separated" means that when the composition for an optical film forms a wavelength conversion layer through a polymerization process or the like described later, regions which are phase-separated in the wavelength conversion layer, for example, relatively hydrophobic regions And two regions that are not mixed with each other, such as relatively hydrophilic regions, are separated from each other.

In one example, the second radically polymerizable compound may have a solubility parameter of a single polymer of 10 (cal / cm ³ ) ^1/2 or more. The solubility parameter of the second radically polymerizable compound is, in another example, about 11 (cal / cm ³ ) ^1/2 or more, 12 (cal / cm ³ ) ^1/2 or more, 13 (cal / cm ³ ) ^1/2 or more , At least 14 (cal / cm ³ ) ^1/2 or at least 15 (cal / cm ³ ) ^1/2 . The solubility parameter of the radically polymerizable compound is, in another example, 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 or less. Can be.

In a specific example, the second radically polymerizable compound may be a compound of Formula 4; A compound of formula 5; A compound of formula 6; A compound of formula (7); Nitrogen-containing radically polymerizable compounds; And it may be any one selected from the group consisting of (meth) acrylic acid or a radical polymerizable compound comprising a salt thereof.

 [Formula 4]

 [Formula 5]

 [Formula 6]

 [Formula 7]

In Formulas 4 to 7, each Q is independently hydrogen or an alkyl group, each U is independently an alkylene group, each independently is an alkylene group which may be substituted with a hydroxy group, and Z is hydrogen, an alkoxy group, an epoxy group or a monovalent group. A hydrocarbon group, X is a hydroxy group or a cyano group, and m and n are any number.

In the present application, the term "epoxy group", unless otherwise specified, may mean a cyclic ether having three ring constituent atoms or a compound containing the cyclic ether or a monovalent moiety derived therefrom. have. Examples of the epoxy group include glycidyl group, epoxyalkyl group, glycidoxyalkyl group or alicyclic epoxy group. In the above, the alicyclic epoxy group may mean a monovalent moiety derived from a compound containing an aliphatic hydrocarbon ring structure, wherein the two carbon atoms forming the aliphatic hydrocarbon ring also include an epoxy group. As the alicyclic epoxy group, an alicyclic epoxy group having 6 to 12 carbon atoms can be exemplified, for example, a 3,4-epoxycyclohexylethyl group or the like can be exemplified.

In the present application, the term "alkoxy group" 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.

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

In the present application, substituents that may be optionally substituted with the epoxy group, alkoxy group or monovalent hydrocarbon group include a hydroxy group; Halogen such as chlorine or fluorine; Epoxy groups such as glycidyl groups, epoxyalkyl groups, glycidoxyalkyl groups or alicyclic epoxy groups; Acryloyl group; Methacryloyl group; Isocyanate group; Thiol group; Aryloxy group; Or a monovalent hydrocarbon group may be exemplified, but is not limited thereto.

In Formulas 4, 5, and 6, m and n may be any numbers, and for example, may be independently 1 to 20, 1 to 16, or 1 to 12, respectively.

As said nitrogen-containing radically polymerizable compound, for example, an amide group-containing radically polymerizable compound, an amino group-containing radically polymerizable compound, an imide group-containing radically polymerizable compound, or a cyano group-containing radically polymerizable compound Etc. can be used. As said amide group-containing radically polymerizable compound, it is (meth) acrylamide or N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth), for example. Acrylamide, N-methylol (meth) acrylamide, diacetone (meth) acrylamide, N-vinylacetoamide, N, N'-methylenebis (meth) acrylamide, N, N-dimethylaminopropyl (meth) ) Acrylamide, N-vinylpyrrolidone, N-vinylcaprolactam or (meth) acryloyl morpholine and the like can be exemplified, and examples of the amino group-containing radically polymerizable compound include aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, etc. can be illustrated, As an imide group containing radically polymerizable compound, N-isopropyl maleimide, N-cyclo Hexylmaleimide or itacone 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 salts of (meth) acrylic acid, for example, salts of (meth) acrylic acid with alkali metals including lithium, sodium, and potassium, or salts with alkaline earth metals including magnesium, calcium, strontium and barium, and the like. This may be illustrated, but is not limited thereto.

The first radically polymerizable compound and the second radically polymerizable compound may form an emulsion region and a matrix of the wavelength conversion layer, respectively, after polymerization.

The difference in solubility parameters of the first radically polymerizable compound and the second radically polymerizable compound can be controlled to implement an appropriate phase separation structure of the optical film.

In one example, the difference between the solubility parameters of the first radically polymerizable compound and the second radically polymerizable compound is 5 (cal / cm ³ ) ^1/2 or more, 6 (cal / cm ³ ) ^1/2 or more, 7 ( cal / cm ³ ) ^1/2 or greater, or about 8 (cal / cm ³ ) ^{1/2 or} greater. The difference is the value of the solubility parameter minus the small value. The upper limit of the difference is not particularly limited. The greater the difference in solubility parameters, the more suitable phase separation structures 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.

When the first radically polymerizable compound and the second radically polymerizable compound are included in the composition together with the wavelength converting particles, the wavelength converting layer formed from the composition is phase-separated after polymerization to form respective regions, and the wavelength converting particles Is located in the region formed by the first radically polymerizable compound or the region formed by the second radically polymerizable compound, and the desired dispersibility and stability of the wavelength conversion particles can be achieved.

The ratio of the first radically polymerizable compound and the second radically polymerizable compound in the composition is not particularly limited.

For example, the composition for an optical film may include 100 parts by weight to 1,000 parts by weight of the second radically polymerizable compound with respect to 100 parts by weight of the first radically polymerizable compound.

In another example, the composition for an optical film includes 5 to 50 parts by weight of the first radically polymerizable compound and 50 to 95 parts by weight of the second radically polymerizable compound, or 50 to 95 parts by weight of the first radically polymerizable compound and the second 5 to 50 parts by weight of the radical polymerizable compound. The term weight part in the present application means a weight ratio between components, unless otherwise specified.

Composites included in the composition for an optical film of the present application is a wavelength conversion particle; Plasmon particles; And ligands for binding the wavelength converting particles and the plasmon particles.

In one example, the composite may be included in a hydrophilic region or a hydrophobic region formed by polymerization of the composition for an optical film of the present application.

Specifically, the composite may be included in the hydrophobic region formed by polymerization of the composition for an optical film of the present application, and may not be substantially included in the hydrophilic region.

In the present application, the composite is not substantially included, for example, based on the total weight of the composite included in the composition for an optical film, the weight ratio of the composite included in the corresponding region is 10% or less, 9% or less, It may mean a case of 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% or less.

The ratio in the composition for an optical film of a composite is not specifically limited, For example, it may be selected in an appropriate range in consideration of desired optical properties.

The complex may be included in the composition, for example, in a ratio of 0.05 to 35 parts by weight, 0.05 to 25 parts by weight or 0.05 to 15 parts by weight, 0.1 to 15 parts by weight or 0.5 to 15 parts by weight, relative to 100 parts by weight of the composition, It is not limited to this.

The composition for an optical film of the present application may include a radical initiator for polymerization of the radically polymerizable compound.

The kind of radical initiator contained in the composition for optical films of this application is not specifically limited. As the initiator, a radical thermal initiator or a photoinitiator capable of generating a radical so as to induce a polymerization reaction by application of heat or irradiation of light can be used.

As the thermal initiator, for example, 2,2-azobis-2,4-dimethylvaleronitrile (V-65, Wako), 2,2-azobisisobutyronitrile (V-60, Azo initiators such as Wako (manufactured) or 2,2-azobis-2-methylbutyronitrile (V-59, made by Wako); Dipropyl peroxydicarbonate (Peroyl NPP, NOF (product), diisopropyl peroxy dicarbonate (Peroyl IPP, NOF (product)), bis-4-butylcyclohexyl peroxy dicarbonate (Peroyl TCP, NOF (agent) )), Diethoxyethyl peroxy dicarbonate (Peroyl EEP, NOF (product)), diethoxyhexyl peroxy dicarbonate (Peroyl OPP, NOF agent), hexyl peroxy dicarbonate (Perhexyl ND, NOF agent) ), Dimethoxybutyl peroxy dicarbonate (Peroyl MBP, NOF (product)), bis (3-methoxy-3-methoxybutyl) peroxy dicarbonate (Peroyl SOP, NOF agent), hexyl peroxy pival Rate (Perhexyl PV, NOF), amyl peroxy pivalate (Luperox 546M75, Atofina), butyl peroxy pivalate (Perbutyl, NOF) or trimethylhexanoyl peroxide (Peroyl 355, NOF) Peroxy ester compounds such as (agent); Dimethyl hydroxybutyl peroxane neodecanoate (Luperox 610M75, Atofina), amyl peroxy neodecanoate (Luperox 546M75, Atofina) or butyl peroxy neodecanoate (Luperox 10M75, Atofina) Peroxy dicarbonate compounds such as; Acyl peroxides such as 3,5,5-trimethylhexanoyl peroxide or dibenzoyl peroxide; Ketone peroxide; Dialkyl peroxides; Peroxy ketal; Alternatively, one kind or two or more kinds of peroxide initiators such as hydroperoxide and the like can be used.

As the photoinitiator, a benzoin-based, hydroxy ketone-based, amino-ketone-based or phosphine oxide-based photoinitiator may be used. Specifically, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylamino acetophenone, 2,2-dimethoxy 2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl -1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, benzophenone , p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-aminoanthraquinone, 2- Methyl thioxanthone, 2-ethyl thioxanthone, 2-chloro thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal, p-dimethylamino benzoic acid Ester, ol And [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone] and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and the like can be used, but It is not limited.

The composition for optical films of this application can use suitably selecting what shows high solubility to a hydrophilic or hydrophobic component in the said initiator.

The content of the initiator in the composition for an optical film of the present application is not particularly limited, for example, the initiator may be included in the composition for an optical film in the range of 0.1% to 15% by weight relative to the total weight of the composition for the optical film, but is not limited thereto. It is not.

The composition for an optical film of the present application may further include a crosslinking agent, if necessary, in consideration of filming properties and the like. As a crosslinking agent, the compound which has two or more radically polymerizable groups can be used, for example.

As a compound which can be used as a crosslinking agent, polyfunctional acrylate can be illustrated. The multifunctional acrylate may mean a compound including 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, and polyethylene glycol di ( Meta) acrylate, neopentylglycol adipate di (meth) acrylate, hydroxyl puivalic acid neopentylglycol di (meth) acrylate, dicyclopentanyl di (meth) Acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified di (meth) acrylate, di (meth) acryloxy ethyl isocyanurate, allylated cyclohexyl di (meth) ) Acrylate, tricyclodecane dimethanol (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, ethylene oxide modified hexahydrophthalic acid di (meth) acrylate, tricyclo Candimethanol (meth) acrylate, neopentylglycol modified trimethylpropane di (meth) acrylate, adamantane di (meth) acrylate or 9,9-bis [4- (2-acryloyloxy Difunctional acrylates such as ethoxy) phenyl] fluorene and the like; Trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide Trifunctional acrylates such as modified trimethylolpropane tri (meth) acrylate, trifunctional urethane (meth) acrylate or tris (meth) acryloxyethyl isocyanurate; Tetrafunctional acrylates such as diglycerin tetra (meth) acrylate or pentaerythritol tetra (meth) acrylate; 5-functional 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 (ex. Isocyanate monomers and trimethylolpropane tri (meth) acrylate 6 functional acrylates, such as reactants), etc. can be used. Moreover, as a polyfunctional acrylate, urethane acrylate, an epoxy acrylate, polyester acrylate, a polyether acrylate, etc. can also be used as a compound called what is called photocurable oligomer in the industry. An appropriate kind can be selected and used out of the above compounds.

As the crosslinking agent, a component capable of realizing a crosslinking structure by a radical reaction such as the multifunctional acrylate, as well as, if necessary, crosslinking by a thermosetting reaction such as a known isocyanate crosslinking agent, epoxy crosslinking agent, aziridine crosslinking agent or metal chelate crosslinking agent Components that can implement the structure can also be used.

For example, the crosslinking agent may be included in the composition for an optical film in a range of 10% by weight to 50% by weight based on the total solid weight of the composition for an optical film of the present application, but is not limited thereto. Can be changed.

The composition for an optical film of the present application may further include other components in addition to the aforementioned components.

For example, the composition for an optical film of the present application may further include amphiphilic nanoparticles.

In the present application, the term "amphiphilic nanoparticles" may refer to particles of nano dimensions that include both hydrophilic and hydrophobic properties, and for example, may refer to what are called surfactants in the industry. have.

The ratio of the amphiphilic nanoparticles in the composition for an optical film of the present application may be, for example, in the range of 1% by weight to 10% by weight based on the total weight of the composition solid content for the optical film, but is not limited thereto. The above range may be appropriately modified in view of improvement of luminous efficiency.

The composition for an optical film may also contain scattering particles. The scattering particles included in the wavelength conversion layer may further improve the optical characteristics of the wavelength conversion layer described later by controlling the probability that light incident on the wavelength conversion layer is introduced into the wavelength conversion particle.

The term "scattering particles" in this application is any kind of material that has a different refractive index than the surrounding medium, for example the matrix or emulsion region described below, and has an appropriate size and can scatter, refract or diffuse incident light. May mean particles.

The scattering particles may, for example, have an average particle diameter of at least 100 nm, more than 100 nm, 100 nm to 20,000 nm, 100 nm to 15,000 nm, 100 nm to 10,000 nm, 100 nm to 5,000 nm, 100 nm to 1,000 nm or 100 nm to 500 nm. The scattering particles may have a shape such as spherical, elliptical, polyhedron or amorphous, but the shape is not particularly limited. As the scattering particles, for example, organic materials such as polystyrene or derivatives thereof, acrylic resins or derivatives thereof, silicone resins or derivatives thereof, or novolak resins or derivatives thereof, or silica, alumina, titanium oxide or zirconium oxide Particles comprising an inorganic material can be exemplified. The scattering particles may be formed of only one of the above materials or two or more of the above materials. For example, hollow particles such as hollow silica or core-cell structure particles may be used as scattering particles.

The ratio of the scattering particles in the wavelength conversion layer is not particularly limited, and for example, may be selected at an appropriate ratio in consideration of the path of light incident on the wavelength conversion layer.

The ratio of the scattering particles in the composition for an optical film of the present application may be, for example, in the range of 1% to 20% by weight based on the total weight of the composition solid content for the optical film, but is not limited thereto. The range may be appropriately modified in consideration of the improvement aspect of the above.

The composition for an optical film may further include additives such as an oxygen scavenger, a radical scavenger, an antioxidant, etc. in a required amount, in addition to the aforementioned components.

The present application also relates to an optical film.

The optical film of the present application may include a composite including a wavelength converting particle, a plasmon particle, and a ligand binding the wavelength converting particle and the plasmon particle, and the complex is included in the wavelength converting layer.

That is, the optical film of the present application includes a wavelength conversion layer, and the wavelength conversion layer includes a complex including the above-described wavelength conversion particles, plasmon particles, and a ligand binding the wavelength conversion particles and plasmon particles.

The term "wavelength conversion layer" of the present application may mean a layer formed so as to absorb light from a light source and emit light having a wavelength equal to or different from that of the light source.

The wavelength conversion layer may be formed from the composition for an optical film described above. When the composition for an optical film further includes not only the first radical polymerizable compound but also the second radical polymerizable compound, the wavelength conversion layer may be formed in a phase. Separation structures can be implemented.

In one example, the wavelength conversion layer may include two regions that are phase separated from each other. In the present application, it is confirmed that the terms "phase-separated regions" are separated from each other as regions formed by two regions that do not mix with each other, for example, relatively hydrophobic regions and relatively hydrophilic regions. It may mean areas formed in a state capable of.

That is, the wavelength conversion layer of the present application may include a first region and a second region that is phase-separated from the first region.

In one example, a first region may be a hydrophilic region, and a second region may be a hydrophobic region among the first region and the second region of the wavelength conversion layer. In the present application, hydrophilicity and hydrophobicity distinguishing the first and second regions are relative to each other, and an absolute criterion for hydrophilicity and hydrophobicity is that the two regions are separated from each other in the wavelength conversion layer. It is not particularly limited.

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

The wavelength conversion layer included in the optical film of the present application may be, for example, an emulsion type layer.

In the present application, the term “layer in emulsion form” means that any one of two or more phases (eg, the first and second regions) that are not mixed with each other is a continuous phase in the layer. ) And the other region may refer to a layer having a form dispersed in the continuous phase to form a dispersed phase. In the above, the continuous phase and the dispersed phase may be solid, semi-solid or liquid phase, respectively, and may be the same phase or different phases. Generally, emulsion is a term mainly used for two or more liquid phases which are not mixed with each other, but the term emulsion in the present application does not necessarily mean an emulsion formed by two or more liquid phases.

In one example, the wavelength conversion layer may include a matrix forming the continuous phase and an emulsion region that is a dispersed phase dispersed in the matrix, and the composite may be in the matrix or emulsion region. Can be located.

By placing the composite in the matrix or emulsion region of the wavelength conversion layer, the wavelength conversion efficiency and durability can be increased.

In one example, the composite may be included in the emulsion region in the wavelength conversion layer of the optical film.

The composite included in the emulsion region is, for example, 90% by weight, 91% by weight, 92% by weight, 93% by weight, 94% by weight, 95% by weight or more of the total composite included in the wavelength conversion layer. , At least 96 wt%, at least 97 wt%, at least 98 wt%, at least 99 wt%, at least 99.5 wt% or at least 99.9 wt%.

Forming two phase-separated regions within the wavelength conversion layer and substantially placing the composite only in one of the two regions, specifically in the emulsion region, ensures physical properties suitable for filming, which will be described later. It is advantageous to secure the adhesiveness between the wavelength converting layer and another layer such as a barrier layer, and other materials which may adversely affect the physical properties of the wavelength converting particles such as an initiator or a crosslinking agent in a region where the wavelength converting particles exist in the formation of the optical film. The factors can be controlled more effectively to form a durable film.

Specific types and physical properties of the wavelength conversion particles, the plasmon particles, and the composite constituting the composite are as described above.

The matrix or emulsion region included in the wavelength conversion layer of the optical film may be formed by the polymerization of the aforementioned first radically polymerizable compound or second radically polymerizable compound.

In one example, any one of the matrix and emulsion region included in the wavelength conversion layer may include polymerized units of the first radically polymerizable compound, and the other may include polymerized units of the second radically polymerizable compound.

The matrix included in the wavelength conversion layer of the optical film may be a continuous phase, for example, formed by polymerization of a second radically polymerizable compound.

In one example, the matrix included in the wavelength conversion layer is a compound of Formula 4 to 7; Nitrogen-containing radically polymerizable compounds; And (meth) acrylic acid or a polymerizable unit of any one compound selected from the group consisting of a radically polymerizable compound including a salt thereof.

The emulsion region included in the wavelength conversion layer of the optical film is dispersed in a continuous matrix, and may be, for example, in the form of particles.

In one example, the emulsion region may be in the form of particles having an average diameter in the range of 1 μm to 200 μm. In another example, the emulsion region may be in the form of particles having an average diameter in the range of about 1 μm to 50 μm or in the range of about 50 μm to 200 μm. The size of the particle form may be controlled by adjusting the proportion of the material forming the matrix and the emulsion region, or by using a surfactant or the like.

Such an emulsion region may be formed by, for example, polymerization of the aforementioned first radically polymerizable compound.

The emulsion region may include, for example, a composite, wherein the wavelength converting particles of the composite included in the emulsion region may be the green particles and / or red particles described above.

In one example, the wavelength converting particles in the emulsion region may comprise green particles and red particles at the same time, where each particle may be located in a different region from each other in the emulsion region.

Specifically, the emulsion region may be a region A having a first composite including first wavelength converting particles capable of absorbing light in the range of 420 nm to 490 nm and emitting light in the range of 490 nm to 580 nm and / or in the range of 420 nm to 490 nm. It may include a region B having a second composite including a second wavelength conversion particles capable of absorbing light within and emitting light in the range of 580 nm to 780 nm.

As such, when the first and second composites having two kinds of wavelength converting particles, such as green particles and red particles, are included in the emulsion region, the mutual interaction that may occur between the particles may be controlled by adjusting the region where the composites are located. By minimizing the operation, it is possible to increase the color purity.

The ratio of matrix and emulsion regions in the wavelength conversion layer is For example, the ratio of the wavelength conversion particles to be included in the wavelength conversion layer, the adhesion with other layers such as a barrier layer, the production efficiency of the emulsion structure which is a phase-separated structure, or the physical properties required for film formation are selected. Can be. For example, the wavelength conversion layer may include 5 to 40 parts by weight of the emulsion region relative to 100 parts by weight of the matrix. The proportion of the emulsion region may be at least 10 parts by weight or at least 15 parts by weight with respect to 100 parts by weight of the matrix. The ratio of the emulsion region may be 35 parts by weight or less with respect to 100 parts by weight of the matrix. In the above, the ratio of the weight of the matrix and the emulsion region is the ratio of the weight of each region itself, or the sum of the weights of all the components included in the region or the ratio of the main components or the weight of the material used to form the respective regions. It can mean a ratio.

The optical film of the present application may further include a barrier layer on the wavelength conversion layer. In one example, the optical film may further include a barrier layer on one or both sides of the wavelength conversion layer.

Such a barrier layer can protect the wavelength conversion layer from a high temperature condition or a condition in which harmful external factors such as oxygen and moisture exist.

4 illustrates a structure including a wavelength conversion layer 500 and a barrier layer 600 disposed on both sides as one exemplary optical film. For example, the barrier layer may be formed of a material having good stability, which is hydrophobic and does not cause yellowing even when exposed to light. In one example, the barrier layer may be selected to have a refractive index in a range similar to that of the wavelength conversion layer in order to reduce loss of light at an interface between the wavelength conversion layer and the barrier layer.

The barrier layer may be, for example, a solid material, or a cured liquid, gel, or polymer, and may be selected from flexible or inflexible materials, depending on the application. The kind of material for forming the barrier layer is not particularly limited and may be selected from known materials including glass, polymers, oxides or nitrides and the like. The barrier layer is, for example, glass; Polymers such as poly (ethylene terephtalate) (PET); 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 wavelength conversion layer, or only on one surface, as exemplarily shown in FIG. 4. In addition, the optical film may have a structure in which barrier layers exist on both surfaces as well as on the side surfaces thereof, and the wavelength conversion layer is entirely sealed by the barrier layer.

The present application also relates to a method for producing the above-described composite.

In one example, the present application may be directed to a method for preparing a composite comprising mixing a wavelength converting particle surface-modified with a ligand and a plasmon particle surface-modified with a ligand. When mixing the wavelength-converted particles and plasmon particles surface-modified with a ligand as described above, the wavelength-converting particles and plasmon particles may be in a state of maintaining a constant distance by binding through the ligand.

The composition of the wavelength conversion particles, plasmon particles and ligands that can be used in the method of manufacturing the composite may include without limitation all the contents described in the above-described complex, the surface modification method of the wavelength conversion particles and plasmon particles, and also It is known.

Specifically, in the composite according to the present application, when a wavelength-modified particle and a plasmon particle surface-modified with a ligand are mixed with a radically polymerizable compound, the ligand contained on the surface of the wavelength-converting particle and the plasmon particle is mutually bonded, for example, It may be formed by physical bonding such as hydrogen bonding or chemical bonding such as hydrophobic interaction.

The present application may also include mixing an optical film, such as a composite, with a polymer resin or a radically polymerizable compound. For example, the complex may be prepared by mixing a wavelength-converted particle surface-modified with a ligand and a plasmon particle surface-modified with a ligand; Plasmon particles and ligands that bind the wavelength converting particles to the plasmon particles.

By simply mixing the composite with the polymer resin or the radical polymerizable composition as described above, the composite is included in the wavelength conversion layer, thereby making it possible to produce an optical film having excellent optical properties.

In one example, the radically polymerizable composition may be a composition comprising a first radically polymerizable compound and a second radically polymerizable compound.

When the composite is mixed with the composition and then the mixture is polymerized, phase separation may occur during the polymerization process, and a wavelength conversion layer formed on the phase-separated matrix and emulsion regions of the aforementioned type may be formed.

According to the above method, since the wavelength conversion particles and the plasmon particles are formed at a predetermined distance from the wavelength conversion layer, the loss of electromagnetic waves generated by the plasmon resonance phenomenon can be minimized, and the wavelength conversion efficiency of the wavelength conversion particles is increased. You can. In addition, it is possible to secure physical properties suitable for film formation, to secure adhesion between the other layer such as a barrier layer and the wavelength conversion layer, and to provide an initiator, a crosslinking agent, or the like in a region where wavelength conversion particles are present at the time of forming the optical film. Other factors that may adversely affect the physical properties of the same nanoparticles can be more effectively controlled to form a film having excellent durability.

In one example, when the composite and the composition are mixed and then polymerized, a wavelength conversion layer having a continuous matrix and an emulsion region dispersed in the matrix may be formed, wherein the emulsion region may be formed as described above. Each may include an A region and a B region including different wavelength converting particles.

In order to obtain a wavelength conversion layer in which the emulsion region includes the A and B regions, two kinds of compositions including the first radically polymerizable compound including the wavelength conversion particles may be separately prepared, but one composition may include green particles. In another composition, the red particles may be included, and then a mixture of both of them may be polymerized.

The manner of forming the layer by mixing the composite and the composition is not particularly limited. For example, the resulting mixture can be formed by coating onto a suitable substrate in a known coating manner.

The method of curing the layer formed in the above manner is not particularly limited, for example, applying an appropriate range of heat to the extent that the initiator included in the composition is activated, or applying electromagnetic waves such as ultraviolet rays. It can be done in a way.

In the method of manufacturing the optical film of the present application, if necessary, after the wavelength conversion layer is formed through the above steps, a barrier layer may be additionally formed, or the polymerization process may be performed in a state adjacent to the barrier layer. .

The present application also relates to a lighting device. An exemplary lighting device may include a light source and the optical film. In one example, the light source and the optical film in the lighting device may be arranged to allow the light irradiated from the light source to enter the optical film. When the light irradiated from the light source is incident on the optical film, some of the incident light is not absorbed by the wavelength converting particles in the optical film and is emitted as it is, and another part is absorbed by the wavelength converting particles and then converted into light having a different wavelength. Can be released. In addition, some of the incident light or part of the light emitted by the wavelength converting particles collide with the plasmon particles in the optical film, and generate plasmon resonance, thereby facilitating excitation of the wavelength converting particles by electromagnetic waves. have. Accordingly, by adjusting the wavelength of the light emitted from the light source and the wavelength of the light emitted by the wavelength conversion particles, it is possible to adjust the color purity or color of the light emitted from the optical film, it is possible to provide an optical film with increased wavelength conversion efficiency. .

In one example, white light may be emitted from the optical film when the wavelength conversion layer contains the appropriate amounts of the above-mentioned red and green particles and the light source is adjusted to emit blue light.

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

5 and 6 are views exemplarily showing a lighting 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 may be arranged to allow light emitted from the light source to be incident on the optical film. In FIG. 5, the light source 700 is disposed under the optical film 800, and thus light irradiated from the light source 700 in the upward direction may be incident to the optical film 800.

6 is a case where the light source 700 is disposed on the side of the optical film 800. Although not essential, when the light source 700 is disposed on the side of the optical film 800 as described above, the light from the light source 700, such as the light guiding plate 900 or the reflecting plate 1000 is more visible. Other means may be included that allow for efficient incidence on the optical film 800.

5 and 6 is one example of the lighting device of the present application, in addition to the lighting device may have a variety of known forms, for this purpose may further include a variety of known configurations.

The lighting device of the present application as described above can be used for various applications. A representative use of the lighting device of the present application is a display device. For example, the lighting device may be used as a backlight unit (BLU) of a display device such as a liquid crystal display (LCD).

In addition, the lighting device may be a backlight unit (BLU) of a display device such as a computer, a mobile phone, a smartphone, a personal digital assistant (PDA), a gaming device, an electronic reading device, or a digital camera, indoor or outdoor lighting. It may be used for stage lighting, decorative lighting, accent lighting, or museum lighting, and the like, but may also be used for horticulture or special wavelength lighting required in biology, but the use of the lighting apparatus is not limited thereto.

Hereinafter, although an optical film etc. of this application are demonstrated concretely through an Example and a comparative example, the range of the said optical film etc. is not restrict | limited to the following Example.

Example  One.

Green particles (Quantum Dot particles, which are made of ligands of oleic acid and the weight ratio of PEG thiol to 1: 2, are surfaced with polyethylene glycol thiol (PEG thiol) obtained by reacting for 4 hours by stirring in toluene). Modified particles) and plasmon particles (Ag nanoplate, CN Vision) having a diameter of about 20 nm and a hydroxyl group are mixed at a weight ratio of 1: 1 and stirred for 6 hours in acetone. Precipitate and poly (ethylene glycol) diacrylate (PEGDA, (poly (ethyleneglycol) diacrylate, CAS No .: 26570-48-9), solubility parameter (HSP) obtained through centrifuge (5000 rpm, 10 minutes) after the reaction. 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 (BD, bisfluorene diacrylate, CAS No .: 161182-73-6, solubility parameter (HSP): about 8 to 9 (cal / cmcm ³ ) ^1/2 ), surfactant (polyvinylpyrrolidone) Mix in a weight ratio of 0.2: 9: 1: 1: 0.05 (precipitate: PEGDA: LA: BD: surfactant), then mix Irgacure2959 and Irgacure907 as radical initiators each to a concentration of about 1% by weight, for 6 hours. The mixture was prepared by stirring to a degree, after which the mixture was placed at a thickness of about 100 μm between two barrier films (i-components) spaced at regular intervals, followed by ultraviolet. Radiation polymerization was induced to cure the radiation to form a light emitting layer including the wavelength converting particle-scattering particle composite, and the distance between the wavelength converting particle and the plasmon particle contained in the light emitting layer was about 100 to 1,000 nm.

Comparative example  One.

Poly (ethyleneglycol) diacrylate (PEGDA, (poly (ethyleneglycol) diacrylate, CAS No .: 26570-48-9, solubility parameter (HSP): about 18 (cal / cm ³ ) ^1/2 ), lauryl acrylic Rate (LA, lauryl acrylate, CAS No .: 2156-97-0, solubility parameter (HSP): about 8 (cal / cm ³ ) ^1/2 ), bisfluorene 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), plasmon particles (Ag nanoplate, CN Vision) and surfactant ( polyvinylpyrrolidone) was mixed at a weight ratio of 9: 1: 1: 0.1: 0.1: 0.1 (PEGDA: LA: BD: green particles: plasmon particles: surfactants), followed by Irgacure2959 and Irgacure907 as radical initiators, each having a concentration of about 1 The mixture was mixed to the weight%, stirred for about 6 hours to prepare a mixture, and a light emitting layer was formed in the same manner as in Example 1 except that the 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 optical films according to Example 1 and Comparative Example 1 was evaluated and shown in FIG. Specifically, as shown in FIG. 7, when the wavelength conversion particle and the plasmon particle are included in the wavelength conversion layer in a state in which a composite is formed, the plasmon particles are relatively included in the wavelength conversion layer. It was confirmed that exhibits high wavelength conversion efficiency.

100: wavelength conversion particle
101: first ligand
200: plasmon particles
201: second ligand
300 core part
400: cell part
500: wavelength conversion layer
600: barrier layer
700: light source
800: optical film
900 light guide plate
1000: reflective layer

Claims (23)

Continuous merchant matrix;
An emulsion region dispersed in the matrix; And
Having a wavelength conversion layer comprising a composite located in the matrix or emulsion region,
The composite film includes a wavelength converting particle, a plasmon particle, and a ligand binding the wavelength converting particle and the plasmon particle. The method of claim 1,
Ligand has an optical film length of 100 to 1,000 nm. The method of claim 1,
The ligand is an optical film comprising a first ligand bound to the surface of the wavelength conversion particle and a second ligand bound to the surface of the plasmon particle, wherein the first ligand and the second ligand are bonded to each other. The method of claim 3, wherein
An optical film, wherein the first ligand and the second ligand are mutually bonded by hydrogen bonding or hydrophobic interaction. The method of claim 1,
The wavelength conversion particle is an optical film which is a quantum dot or a polymer particle. The method of claim 1,
The plasmon particles are core cell type particles having at least one metal particle core and an insulator cell covering the metal particle core. delete delete delete delete delete delete The method of claim 1,
The ratio of the composite contained in an emulsion region is 90 weight% or more with respect to the total composite contained in a wavelength conversion layer. The method of claim 1,
The emulsion region is an optical film comprising a polymer unit, which is any one selected from the group consisting of a compound of Formula 1, a compound of Formula 2, and a compound of Formula 3:
[Formula 1]

[Formula 2]

[Formula 3]

In Chemical Formulas 1 to 3,
Each Q is independently hydrogen or an alkyl group,
Each U is independently an alkylene group, an alkenylene group or an alkynylene group or an arylene group,
B is a straight or branched chain 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,
n is 1 to 20. The method of claim 1,
The emulsion region is an optical film in the form of particles having an average diameter in the range of 1 μm to 200 μm. The method of claim 1,
The emulsion region absorbs light in the range of 420 nm to 490 nm and absorbs light in the A region and the region of 420 nm to 490 nm including a first composite having a first wavelength converting particle capable of emitting light in the range of 490 nm to 580 nm. An optical film comprising a B region comprising a second composite having a second wavelength converting particle capable of emitting light in the range of 580 nm to 780 nm. The method of claim 1,
The matrix is a compound of formula (4); A compound of formula 5; A compound of formula 6; A compound of formula (7); Nitrogen-containing radically polymerizable compounds; And a radically polymerizable compound comprising (meth) acrylic acid or a salt thereof. An optical film comprising any one of polymerized units selected from the group consisting of:
[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

In Formulas 4 to 7 each Q is independently hydrogen or an alkyl group,
Each U is independently an alkylene group,
A each independently represents 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 1-20. The method of claim 1,
An optical film further comprising a barrier layer on one or both sides of the wavelength conversion layer. delete A method of manufacturing the optical film of claim 1, comprising mixing a composite comprising a wavelength converting particle, a plasmon particle, and a ligand for binding the wavelength converting particle and the plasmon particle with a polymer resin or a radical polymerizable composition. The method of claim 20,
The radically polymerizable composition comprises a first radically polymerizable compound and a second radically polymerizable compound which is phase-separated after polymerization with the first radically polymerizable compound. An illuminating device comprising a light source and the optical film of claim 1, wherein the light source and the optical film are arranged to allow light from the light source to be incident on the optical film. A display device comprising the lighting device of claim 22.

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