KR102266100B1 - Quantum dot - resin composite and optical sheet using the same - Google Patents

Abstract

The present invention relates to a polythiol-ene resin composite containing quantum dot (QD) nanoparticles and an optical sheet using the same, and in particular, an optical material layer of quantum dot nanoparticles dispersed in a polythiol-ene resin matrix and the same It relates to an optical sheet.

Description

Quantum dot resin composite and optical sheet using same {QUANTUM DOT - RESIN COMPOSITE AND OPTICAL SHEET USING THE SAME}

The present invention relates to a polythiol-ene resin composite containing quantum dot (QD) nanoparticles and an optical sheet using the same, and in particular, an optical material layer of quantum dot nanoparticles dispersed in a polythiol-ene resin matrix and the same It relates to an optical sheet.

In the development of an optical sheet using an organic light-emitting diode (Organic Light Electronic Diode) or quantum dot nanomaterial, it is essential to block contact with moisture and oxygen as much as possible by stacking a barrier film on the upper and lower portions of the optical sheet. to be.

For this purpose, mainly by depositing a thin film of an inorganic material such as _{alumina (Al 2} O ₃ ) or silica (SiO ₂ ) on a polymer film such as polyethylene terephthalate (PET), polyethylene sulfone (PES), or polyethylene naphthalate (PEN). The formed gas barrier film (gas barrier film) is being applied.

The inorganic material deposition layer on the gas barrier film has a strong hydrophilic property intrinsically, and when a polymer or organic material layer is formed thereon, delamination can easily occur at the interface. This delamination may cause moisture and oxygen penetration through the interface when manufacturing a quantum dot composite optical sheet molded part, causing light emitting device defects.

Quantum dot nanoparticles are easily decomposed by moisture or oxygen and their quantum efficiency can be rapidly reduced, so efforts are being made to stabilize quantum dot nanoparticles from moisture or oxygen, etc., and dispersing quantum dot nanoparticles in a polymer matrix resin Thus, some optical sheet parts having a barrier film on one or both surfaces of the optical sheet are being commercialized.

Quantum dot nanoparticles provide different light absorption and emission (photoluminescence, PL) properties depending on the particle size. As the particle size decreases, an effective energy bandgap increases and a PL spectrum shifted to a blue wavelength region is generated. Because of the size-dependent optical properties of quantum dot nanoparticles, QDs have attracted great interest in many display and lighting applications. In general, quantum dot particles are capped with an organic ligand (ligand) on the surface, and generally encapsulated in a polymer matrix, protected from the influence of moisture or oxygen.

In the specification of the present invention, the reaction of a thiol compound and an alkene compound is a thiol-ene reaction (Charles E. Hoyle and Christopher N. Bowman., Angew. Chem. Int. Ed. (2010) Vol. 49). , pp. 1540-1573), and the thiol-ene reaction is usually performed by reacting an alkene compound of Formula 1 with a thiol compound of Formula 2 in a molar ratio of a functional group of about 1:1 to form a polyether having a thioether bond. A thiol-ene polymer chain is produced and a cured composition having a sufficient degree of crosslinking is obtained.

In addition, the polythiol-ene polymer matrix has attracted great attention for optical applications due to its high flexibility, transparency, adhesion to substrates, and excellent gas barrier properties.

Japanese Patent Laid-Open No. 2004-277660 discloses a thermosetting composition using a thiol-ene reaction by a thermal polymerization initiator, and the possibility of application in the fields of coatings such as paints, molding agents, adhesives and inks is described. have. However, in the Japanese Patent Application Laid-Open, a copolymer of an acrylate compound and a thiol-ene cured product using a thiol compound are described, but in the acrylate compound, a homopolymer reaction of the acrylate itself with the thiol-ene reaction product is performed. Since it progresses, it may not become a uniform composition, but the elasticity and flexibility of hardened|cured material may become inadequate.

In addition, Japanese Patent Laid-Open No. 2000-102933 describes a photocurable resin composition for a lens sheet, and discloses a technology related to a thiol-ene cured product by UV curing of an allyl compound and a thiol compound. An allyl compound having a molecular weight is used, and a thiol-ene cured product for an allyl oligomer having a large molecular weight is not disclosed. When such a thiol-ene compound is used, a cured product capable of satisfying sufficient bending resistance, adhesion to a substrate, storage stability, and barrier properties is insufficient.

Japanese Patent Laid-Open No. 2015-217359 discloses a siloxane compound partially modified by acryloxy and/or epoxy functional groups to form a film including quantum dots. In the case of such a modified siloxane compound, the dispersibility of quantum dots is improved, but there are disadvantages in that adhesion to the substrate and resistance to bending are insufficient.

Japanese Patent Laid-Open No. 2016-059931 discloses a composition for an optical material containing a polythiol compound, and discloses an epoxythiopropylsulfide-based compound for improving transparency and weather resistance. In the invention of the Japanese Patent Laid-Open, the curable composition has good barrier performance against moisture or air, but lacks flex resistance and flexibility, so that it is insufficient for film or sheet molding.

Accordingly, there is a significant demand in the related industry for a material that satisfies all of the above physical properties required for a molding such as an optical sheet.

Japanese Patent Laid-Open No. 2004-277660 Japanese Patent Laid-Open No. 2000-102933 Japanese Patent Laid-Open No. 2015-217359 Japanese Patent Laid-Open No. 2016-059931

The present invention, by selecting a specific alkene compound (or oligomer) and a thiol compound, excellent solvent resistance by UV curing and gas barrier (gas barrier) polythiol-ene resin and quantum dot resin composite comprising quantum dot nanoparticles aims to provide

Another object of the present invention is to provide an optical material layer in which the quantum dot resin composite is cured by irradiation with active energy rays.

Another object of the present invention is to provide an optical sheet in which the optical material layer is disposed between a pair of gas barrier base films.

The present invention may also have as its object to achieve these objects and other objects that can be easily derived by a person skilled in the art from the general description of the present specification in addition to the above clear objects.

The present invention is a quantum dot resin composite including quantum dots in polythiol-ene resin, wherein the quantum dot resin composite is

a compound of formula 1 having at least one polymerizable reactive alkenyl group,

a compound of formula 2 having at least one thiol group,

quantum dot (QD) nanoparticles, and

polymerization initiator

It is characterized by comprising:

[Formula 1]

during the meal,

R ₁ is a C6-C18 substituted or unsubstituted, alkyl group, cycloalkyl group, aryl group, saturated or unsaturated polycyclic group, cyanurate group, isocyanurate group, or a combination thereof ego,

R ₂ is H or methyl;

[Formula 2]

R ₃ -(SH) _n

during the meal,

R ₃ is an ester, amide, or urea bond having a C4-C18 substituted or unsubstituted, alkyl group, a cycloalkyl group, an aryl group, or a combination thereof;

n is an integer greater than or equal to 2;

In addition, the compound of Formula 1 may have one or more, or two or more polymerizable alkenyl groups.

And, the compound of Formula 1 may be an acryl or methacryl compound.

In addition, the compound of Formula 1 may be an oligomer.

In addition, the number average molecular weight of the compound of Formula 1 may be 500 to 20,000, or 500 to 15,000.

In addition, the refractive index of the compound of Formula 1 may be 1.43 to 1.54.

And, in the compound of Formula 1, R ₁ is a C7-C17 substituted or unsubstituted saturated or unsaturated polycyclic group, bicyclo[2,2,1]alkyl, or tricyclo[5,2,1,0] It may be a decane functional group.

In addition, the compound of Formula 1 is tricyclodecanedimethanol diacrylate, bis(phenolA)dimethacrylate, trimethylpropanetrimethacrylate, tris(2-hydroxyl) Ethyl) isocyanurate triacrylate (tris (2-hydroxyethyl) isocyanurate triacrylate), pentaerythritol tetraacrylate, isobornyl acrylate (isobonylacrylate), lauryl (meth) acrylate (laurylmethacrylate), 3, 5,5-trimethylcyclohexyl acrylate (3,5,5-trimethylcyclohexylacrylate), dodecylacrylate, tridecylacrylate, isodecylacrylate, or a mixture thereof.

In addition, the compound of Formula 2 may have 1 to 6, or 2 to 5 thiol groups.

And, the compound of Formula 2 is ethylene glycol bis (3-mercapto butyrate), 1,2-propylene glycol (3-mercapto butyrate), trimethylol propane tris (3-mercapto butyrate), ethylene glycol bis (2) -Mercaptoisobutyrate), 1,2-propylene glycol bis (2-mercaptoisobutyrate), trimethylolpropane tris (2-mercaptoisobutyrate), pentaerythritol tetrakis (3-mercaptopropionate) , pentaerythritol tetrakis (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H)-trione, 1,4-bis(3-mercaptobutyryloxy)butane, bisphenol A bis(3-mercaptobutyrate), triphenolmethanetris(3-mercaptobutyrate), or mixtures thereof have.

In addition, the quantum dot nanoparticles are CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, InP, InAs, GaN, GaP, GaAs, or a combination thereof may include a semiconductor nanocrystal having light-emitting properties.

In addition, the quantum dot nanoparticles may include semiconductor nanocrystals having a CdSe core and a ZnS shell, or an InP core and a ZnS shell structure.

In addition, the quantum dot nanoparticles may have a larger energy bandgap in the shell than the core.

And, the quantum dot nanoparticles may have a wavelength range of ultraviolet to infrared.

In addition, the quantum dot nanoparticles may have a quantum efficiency of 10% or more, 30% or more, 50% or more, 60% or more, 70% or more, or 90% or more.

In addition, the quantum dot nanoparticles may have a half-width of the emission wavelength spectrum of 45 nm or less, 40 nm or less, or 30 nm or less.

In addition, the polymerization initiator may be a photopolymerization initiator, a thermal polymerization initiator, or a mixture thereof.

In addition, the photopolymerization initiator may be an alkylphenone-based photopolymerization initiator, an α-aminoalkylketone-based photopolymerization initiator, a phosphineoxide-based photopolymerization initiator, or a mixture thereof.

And, the photopolymerization initiator is 1-hydroxycyclohexylphenylketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1 -one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4- (2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1 -one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholine- 4-ylphenyl)butan-1-one, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphineoxide, or a mixture thereof.

In addition, the quantum dot resin composite is

100 parts by weight of the compound of Formula 1,

8 to 20 parts by weight, 9 to 17 parts by weight, or 10 to 15 parts by weight of the compound of Formula 2;

0.5 to 1.5 parts by weight of quantum dot nanoparticles, 0.6 to 1.3 parts by weight, or 0.7 to 1.1 parts by weight, and

The photopolymerization initiator may include 0.01 to 5 parts by weight, 0.5 to 2 parts by weight, or 1.1 to 1.5 parts by weight.

In addition, the quantum dot resin composite may have a gas barrier property.

In addition, the monomer of the oligomer or polymer having the gas barrier property may be butadiene urethane acrylate, butadiene, isoprene, isobutylene, or a mixture thereof.

In addition, the number average molecular weight of the oligomer or polymer having the gas barrier property may be 1,000 to 40,000, or 2,000 to 10,000.

In addition, the quantum dot resin composite may further include a stabilizer.

In addition, the stabilizer is pyrogallol, 4-methoxy-1-naphthol, tert-butylcatechol, hydroquinone, gallic ester ( gallic ester), oxallic acid, phosphoric acid, tris (2,4-di-tert-butylphenyl) phosphite (Tris (2,4-di-tert-butylphenyl) phosphite), bis (2) ,4-di-tert-butylphenyl)pentaerythritol diphosphite (Bis(2,4-di-tert-butylphenyl)phentaerythritoldiphosphite), or a mixture thereof.

And, the quantum dot resin composite may further include an additive selected from the group consisting of a UV stabilizer, an antioxidant, a light diffuser, and a mixture thereof.

On the other hand, the optical material layer of the present invention is characterized in that the quantum dot resin composite is cured by active energy ray irradiation.

And, the active energy ray may be ultraviolet rays.

And, the ultraviolet rays may be UVA of 320 to 390 nm or UVB of 395 to 445 nm.

And, the amount of energy provided by the active energy ray for curing may be 200 to 5,000 mJ/cm 2 , or 300 to 2,000 mJ/cm 2 .

And, the thickness of the optical material layer may be 20 to 200 ㎛, or 50 to 100 ㎛.

Meanwhile, the optical sheet of the present invention is characterized in that the optical material layer is disposed between a pair of gas barrier base films.

And, the gas barrier base film is polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polymethyl methacrylate (PMMA), polyimide (PI), polyether ether ketone (PEEK) , polyethylene (PE), a copolymer thereof, or a thin film coating of a metal oxide or nitride on one surface of the thermoplastic film including a mixture thereof.

In addition, an oxygen transmission rate (OTR) of the gas barrier base film may be less than ^{10 −1} cc/m ^{2 /day.}

In addition, a water vapor transmission rate (WVTR) of the gas barrier base film may be less than ^{10 −2} g/m ^{2 /day.}

In addition, the metal oxide or nitride may be silica (SiO ₂ ), alumina (Al ₂ O ₃ ), silicon oxynitride (SiO _x N), nano clay, or a mixture thereof.

In the optical sheet, in a life test at 60° C. and 90% humidity, the emission intensity of the emission wavelength spectrum after 1000 hours may be at least 80% of the peak emission intensity, or at least 90%.

And, the optical sheet is a gas barrier base film on one surface of the optical material layer slot die coating (slot die coating), gravure coating (gravue coating), spin coating (spin coating), ink-jet coating (ink-jet coating), Alternatively, it may be spray coated.

And, the optical sheet may be used for display or lighting.

The quantum dot resin composite of the present invention has superior light efficiency and color purity, high color gamut and color reproducibility compared to conventional phosphors by using quantum dots. In addition, due to the introduction of the thiol compound, it is easy to cure even with a small amount of addition, the effect of yellowing resistance is large, and the degree of crosslinking with the alkene compound is very high. For this reason, by blocking contact with moisture and oxygen as much as possible, excellent gas barrier properties are exhibited without using a high barrier inorganic material deposition layer, and the lifespan is also extended. Furthermore, the optical material layer using the quantum dot resin composite of the present invention has an advantage in that it has excellent solvent resistance by UV curing and exhibits high flexibility, transparency, adhesion properties to substrates, and light stability and storage stability.

According to the problem solving means of the present invention as described above, various effects including the following items can be expected. However, the present invention is not established only when exhibiting all of the following effects.

1 is a cross-sectional view of an exemplary article described herein.

Hereinafter, preferred embodiments of the present invention will be described in detail.

However, the present invention is not limited to the specific exemplary embodiments, since the following is only to be described in detail by exemplifying specific embodiments, and since the present invention may be variously changed and may have various forms. It should be understood that the present invention includes all modifications, equivalents and substitutes included in the spirit and scope of the present invention.

In addition, in the following description, many specific details such as specific components are described, which are provided to help a more general understanding of the present invention, and it is common in the art that the present invention can be practiced without these specific details. It will be self-evident to those who have the knowledge of And, in describing the present invention, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the gist of the present invention, the detailed description thereof will be omitted.

And, the terms used in the present application are only used to describe specific embodiments, and are not intended to limit the present invention. Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related art, and should not be interpreted in an ideal or excessively formal meaning unless explicitly defined in the present application. does not

In this application, the singular expression includes the plural expression unless the context clearly dictates otherwise.

In the present application, terms such as first and second may be used to describe various elements, but the elements should not be limited by the terms. The above terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, a first component may be referred to as a second component, and similarly, a second component may also be referred to as a first component.

In the present application, terms such as 'comprise', 'contain' or 'have' are intended to refer to the presence of a feature, component (or component), etc. described in the specification, but one or more other features or It does not mean that the component or the like is not present or cannot be added.

In this specification, the weight ratio is weight % (or parts by weight), and the temperature during the manufacturing process is room temperature. The compound represented by Formula 1 has at least one polymerizable reactive alkenyl group. Quantum dot (QD), which is a light emitting material, is well known in the art (for example, refer to US Patent Publication No. 2012/0113672), and in an embodiment of the present invention, the quantum dot material is manufactured by Nanosys (Nanosys). The supplied quantum dots were used.

Meanwhile, recent attempts have been made to obtain superior light efficiency and color purity compared to conventional phosphors by using semiconductor nanocrystals, so-called quantum dots, as a color down converting material for light emitting devices (LEDs). Light emitting semiconductor nanoparticles, such as CdSe or InP, are useful as quantum dot light emitting materials and are receiving great attention as display component materials having a high color gamut. For example, a diffusion film QDEF (quantum dot enhancement film), which is an optical sheet molded article using a quantum dot light emitting body, has been commercialized. In this product, the quantum dots are dispersed in a polymer matrix, which is placed between gas barrier films to protect the quantum dots from atmospheric components such as oxygen and moisture.

The theoretical quantum efficiency of QD is 100% and half band width is possible up to 40 nm or less, so color purity is high, so color reproducibility is expected to be greatly improved when QD is applied to light emitting devices of displays. However, QD nanoparticles have a problem that they are very vulnerable to moisture or oxygen, and when applied to a light emitting device, a reliable device can be developed only by securing a long lifespan. Many problems remain.

As a method for solving the above problem, it is essential to uniformly disperse the QDs in a polymer binding matrix having a gas barrier property and mold the QDs into a composite sheet.

On the other hand, in the production of the optical sheet protected by the gas barrier film as described above, in general, a polymer matrix resin containing quantum dot nanoparticles is applied on the lower base film, and then a gas barrier film is laminated on the applied resin, , to be manufactured into an optical sheet having a gas barrier film by curing the polymer matrix resin including the QD in a laminated state.

The present invention provides a polythiol-ene composite comprising quantum dots, wherein the polythiol-ene composite is a compound of Formula 1 having at least one polymerizable reactive alkenyl group, at least one or more By using the compound of Formula 2 having a thiol group, quantum dot (QD) nanoparticles, and a polymerization initiator, adhesion to a substrate and moisture resistance are superior to those of conventionally known thiol-ene reaction products, and a barrier ) to provide a cured composition with improved properties, leading to the completion of the present invention:

[Formula 1]

during the meal,

R ₁ is a C6-C18 substituted or unsubstituted, alkyl group, cycloalkyl group, aryl group, saturated or unsaturated polycyclic group, cyanurate group, isocyanurate group, or a combination thereof ego,

R ₂ is H or methyl;

[Formula 2]

R ₃ -(SH) _n

during the meal,

R ₃ is an ester, amide, or urea bond having a C4-C18 substituted or unsubstituted, alkyl group, a cycloalkyl group, an aryl group, or a combination thereof;

n is an integer greater than or equal to 2;

In a preferred embodiment of the present invention, the compound of Formula 1 has an aliphatic, alicyclic or aromatic ring structure and one or more, or two or more polymerizable reactive alkenyl groups in the molecule, and preferably has a number average molecular weight. This is an oligomer of 500 to 20,000 or 500 to 15,000. The reactive alkenyl group is, for example, an ethylenically unsaturated group, and the compound of Formula 1 is preferably an acrylic or methacrylic compound such as allyl (meth)acrylate, and has a refractive index value in the range of 1.43 to 1.54. .

Preferably, R ₁ comprises a C7-C17 substituted or unsubstituted saturated or unsaturated polycyclic group, bicyclo[2,2,1]alkyl, or tricyclo[5,2,1,0]decane functional group. do. Particularly preferred compounds of formula 1 are tricyclodecanedimethanol diacrylate, bis(phenolA)dimethacrylate, trimethylolpropanetrimethacrylate, and tris(2-hydroxyethyl). ) isocyanurate triacrylate (tris(2-hydroxyethyl)isocyanuratetriacrylate), pentaerythritoltetraacrylate, isobornylacrylate, lauryl (meth)acrylate, 3 , 5,5-trimethylcyclohexyl acrylate (3,5,5-trimethylcyclohexylacrylate), dodecyl acrylate (dodecylacrylate), tridecyl acrylate (tridecylacrylate), isodecyl acrylate (isodecylacrylate) such as reactive monomer compounds However, the alkene compound used in the present invention is not limited thereto.

In one embodiment of the present invention, the polythiol-ene resin matrix is a cured reaction product of at least one polythiol and at least one polyalkene, and it is preferable that both the polythiol and the polyalkene have at least two reactive functional groups. In particular, the polythiol compound of Formula 2 has 1 to 6, or 2 to 5 thiol groups.

The quantum dot resin composite is

100 parts by weight of the compound of Formula 1,

8 to 20 parts by weight, 9 to 17 parts by weight, or 10 to 15 parts by weight of the compound of Formula 2;

0.5 to 1.5 parts by weight of quantum dot nanoparticles, 0.6 to 1.3 parts by weight, or 0.7 to 1.1 parts by weight.

As used in the Examples herein, a polythiol-ene composite is the curing of at least one polythiol having at least two thiol groups and at least one polyalkene compound having at least two alkenyl groups. The polyalkene may be present as a partially uncured mixture with acrylate oligomers and/or (meth)acrylate monomers.

Specific examples of the thiol compound of Formula 2 used in the present invention include ethylene glycol bis(3-mercaptobutyrate), 1,2-propylene glycol (3-mercaptobutyrate), and trimethylolpropane tris(3-mercaptobutyrate). butyrate), ethylene glycol bis (2-mercaptoisobutyrate), 1,2-propylene glycol bis (2-mercaptoisobutyrate) or trimethylolpropane tris (2-mercaptoisobutyrate), pentaerythritol tetrakis ( 3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1 , 4-bis(3-mercaptobutyryloxy)butane, bisphenol A bis(3-mercaptobutyrate), triphenolmethanetris(3-mercaptobutyrate), etc. are mentioned, The thiol compound used in the present invention is not limited to these.

The thiol compound is easy to cure even with a small amount of addition, and the effect of yellowing resistance obtained by the present invention is large, and the degree of crosslinking with the polyalgen compound is very high. -mercaptopropionator), pentaerythritol tetrakis (3-mercaptobutylate), 1,3,5-tris (3-mercaptobutyloxyethyl)-1,3,5-triazine-2, It is more preferable to use 4,6(1H,3H,5H)-trione or 1,4-bis(3-mercaptobutyryloxy)butane.

In the present invention, the amount of polythiol used may be 8 to 20 parts by weight, 9 to 17 parts by weight, or 10 to 15 parts by weight based on 100 parts by weight of the thiol-ene complex composition. If the amount of the thiol compound used is less than the above range, the thiol-ene reaction with the alkene compound of Formula 1 is not sufficient and sufficient polymeric crosslinking cannot be obtained in the polythiol-ene matrix, Conversely, when the above range is exceeded, the reactivity of the thiol-ene polymer composition is too high, so that it is difficult to manufacture an optical sheet or film that is a cured molding.

The thiol compound of formula (2) used in the present invention can be easily obtained as a commercial product.

The commercially available thiol compounds include pentaerythritol tetrakis (3-mercaptopropionator) (Thiocure PETMP, Brunobock), pentaerythritol tetrakis (3-mercaptobutylate) (Karenz MT™PE1, Showa Denko). ), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (Karenz MT™NR1, Showa Denko) and others.

The thiol-ene resin composite composition of the present invention preferably further comprises a photopolymerization initiator and/or a thermal polymerization initiator. Examples of the photopolymerization initiator include an alkylphenone-based photopolymerization initiator, an α-aminoalkylketone-based photopolymerization initiator, and a phosphineoxide-based photopolymerization initiator. More specifically, as an alkylphenone-based photopolymerization initiator, 1-hydroxycyclohexylphenylketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-hydroxy-2- Methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy- 1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one; and the like. As an α-aminoalkylketone-based photopolymerization initiator, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino -1-(4-morpholinophenyl)-1-butanone, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)butan-1-one, etc. can be heard Examples of the phosphineoxide-based photopolymerization initiator include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide etc. are mentioned, You may mix and add 2 or more types of these photoinitiators.

In the present invention, the polythiol-ene resin may be cured by irradiation with active energy rays, for example, ultraviolet rays. The thiol-ene composition may be exposed to any form of visible or UV radiation, but is preferably exposed to UVA radiation in the wavelength range of 320 to 390 nm or UVB radiation in the wavelength range of 395 to 445 nm. The thiol-ene resin composition described in the specification of the present invention is cured by irradiation with a sufficient amount of ultraviolet rays, and the amount of energy required for curing may be 200 to 5,000 mJ/cm 2 or 300 to 2,000 mJ/cm 2 .

In the present invention, the photopolymerization initiator is commercially available Ciba-Geigy's Irgacure 819 (Irgacure 819), Darocur 1173 (Darocur 1173), Irgacure 651 (Irgacure 651), Irgacure 184 (Irgacure184), and/or Lucem TPO from BASF.

In the present invention, the amount of the photopolymerization initiator used may be 0.01 to 5 parts by weight, 0.5 to 2 parts by weight, or 1.1 to 1.5 parts by weight, per 100 parts by weight of the compound of Formula 1 above. If the amount of the photopolymerization initiator used is less than the above range, sufficient curability may not be obtained. Conversely, if it exceeds the above range, the reactivity of the composition becomes too high, the storage stability of the thiol-ene composition becomes insufficient, and the physical properties of the thiol-ene resin composite In some cases, this is not preferable.

In the present invention, quantum dots are commercially available (eg, Nanosys, Inc.) and are typically provided in a dispersed state in a liquid organic ligand material. In some embodiments, the quantum dots comprise CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, InP, InAs, GaN, GaP, GaAs, or combinations thereof.

Quantum dots also comprise a core-shell structure, said structure comprising a core of a desired semiconductor nanoparticle, and at least one shell of additional material providing the desired stability and surface chemical or optoelectronic properties ( shell) has In one embodiment, the quantum dots have a CdSe core and a ZnS shell. In another embodiment, the structure is an InP core ZnS shell. The semiconductor nanocrystals have a larger energy band gap than that of the core and the material constituting the shell, and thus may have a structure in which the quantum confinement effect is effectively exhibited.

In this case, the quantum dot semiconductor nanocrystal may have a wavelength range of ultraviolet to infrared. The semiconductor nanocrystals may have a quantum efficiency of about 10% or greater, such as about 30% or greater, about 50% or greater, about 60% or greater, about 70% or greater, or about 90% or greater. In addition, the half width of the emission wavelength spectrum of the quantum dot nanoparticles may be designed to be wide or narrow depending on the application field, and the semiconductor nanocrystal may have a narrow spectrum in order to improve color purity or color reproducibility in a display. The semiconductor nanocrystal may have a half maximum width of the emission wavelength spectrum of about 45 nm or less, for example, about 40 nm or less, or about 30 nm or less. Within the above range, color purity or color reproducibility of the device may be improved.

The quantum dot resin composite of the present invention includes 0.5 to 1.5 parts by weight, 0.6 to 1.3 parts by weight, or 0.7 to 1.1 parts by weight of quantum dot nanoparticles per 100 parts by weight of the compound of Formula 1 above.

In an embodiment of the present invention, a cured molding (sheet or film) comprising quantum dot nanoparticles and a polythiol-ene resin matrix is 60 ° C., in a temperature/humidity lifetime test of 90%, the emission wavelength spectrum after 1000 hours The emission intensity is at least 80%, or even at least 90% of the peak emission intensity, and also shows high stability as a result of gas barrier property evaluation. In particular, the UV-cured molding of the polythiol-ene composite of the present invention provides a quantum dot resin composite having high barrier properties with little or no loss of luminous emission efficiency. For example, a cured molded article (sheet or film) can typically be produced without using a high-barrier inorganic-deposited plastic substrate, and can exhibit high light stability in the polythiol-ene resin composite.

Preferably, in one embodiment of the present invention, the polythiol-ene composite matrix including quantum dots is a butadiene urethane acrylate oligomer with other additive compounds that can further improve gas barrier performance. oligomer), polybutadiene, isoprene, or polyisobutylene resin compounds may be further included. The barrier improving additive is a low molecular weight liquid compound having a number average molecular weight in the range of 1,000 to 40,000 or 2,000 to 10,000, and may be blended with the poly alkene compound in the polythiol-ene polymer composition.

Preferably, the butadiene urethane acrylate oligomer is a commercially available product "CN9001NS" (Sartomer), polybutadiene is a "polyvest 110" product from Evonik GmH, and isoprene is a liquid product from Kuraray It is a product of "LIR-410", which is a liquid isoprene rubber.

In an embodiment of the present invention, the oligomer or polymer having the gas barrier property is in a range that does not impair the coating viscosity of the thiol-ene polymer composite composition, and is 2 to 40 parts by weight or 5 to 40 parts by weight based on 100 parts by weight of the compound of Formula 1 30 parts by weight may be added.

In addition, the polythiol-ene polymer composite matrix can reduce defects in the polymer structure that can be generated by UV irradiation, and has a barrier property that minimizes penetration of water and/or oxygen. It was confirmed that the sheet or film molding having the polythiol-ene polymer composite matrix including quantum dots described herein exhibits greatly improved barrier properties and storage stability.

The polythiol-ene resin composite including the quantum dots of the present invention may include a stabilizer, a UV stabilizer, an antioxidant, and a light diffusing agent for improving the light emitting properties of the sheet molding.

The stabilizer is pyrogallol, 4-methoxy-1-naphthol, tert-butylcatechol, hydroquinone, gallic ester ), oxalic acid, phosphoric acid, tris (2,4-di-tert-butylphenyl) phosphite (Tris (2,4-di-tert-butylphenyl) phosphite), bis (2,4) -di-tert-butylphenyl)pentaerythritol diphosphite (Bis(2,4-di-tert-butylphenyl)phentaerythritoldiphosphite), or a mixture thereof.

Meanwhile, the optical sheet of the present invention includes a base film having a gas barrier property on the surface of the optical material layer obtained by curing the quantum dot resin composite, which is a polythiol-ene composite including quantum dot nanoparticles. Preferably, the base film is polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polymethyl methacrylate (PMMA), polyimide (PI), polyether ether ketone (PEEK), a thermoplastic film comprising polyethylene (PE), or a combination thereof. The barrier plastic base film is a metal oxide or nitride, preferably silica (SiO ₂ ), alumina (Al ₂ O ₃ ), silicon oxynitride (SiO _x N), nano clay (nano clay), or their The mixture may be a thin film coated on the base film.

Preferably, the gas barrier film has an oxygen transmission rate (OTR) of ^{less than 10 −1} cc/m ² /day and a water vapor transmission rate (WVTR) of less than ^{10 −2} g/m ^{2 /day} to be. In the present invention, the barrier base film is an alumina (Al ₂ O ₃ ) vapor deposition film (thickness: 12 μm, IB-PET) manufactured by Dai Nippon Printing Co., Ltd. of Japan.

In an embodiment of the present invention, the thickness of the optical material layer obtained by curing the polythiol-ene resin composite including the quantum dots is 20 to 200 μm or 50 to 100 μm. Preferably, the optical material layer of the present invention is prepared by UV curing a composite composition prepared by mixing reactive polyalkenes, polythiols, quantum dots, photopolymerization initiators and other optional additives. Preferably, the polythiol-ene resin composite is prepared by a conventional coating method, such as slot die coating, gravure coating, spin coating, ink-jet coating, or spraying. It is coated on a barrier base film by spray coating. Preferably, curing is initiated by exposing the polythiol-ene resin composite to ultraviolet irradiation or heat, preferably ultraviolet rays, and a thiol-ene composite optical sheet or optical film molded article is obtained.

The exemplary optical sheet or optical film molding described herein can be used in displays, LED lights, and light guides. In the present invention, the quantum dot device that can be used in the backlight of a liquid crystal display or an optical sheet using the same can be used by using the characteristics of the quantum dot.

Hereinafter, specific examples of the present invention will be presented. However, the examples described below are only for specifically illustrating or explaining the invention, and the scope of the present invention is not limited.

Example

Example 1: Preparation of an optical sheet using a quantum dot resin composite (1)

Tricyclodecane dimethanol diacrylate (TCDDA) 40 g, ethoxylated(2)bisphenolA dimethacrylate (EBPADA) 25 g, trimethylpropane triacrylate ( trimethylpropane triacrylate, TMPTA) 10 g, laurylmethacrylate (LMA) 10 g, butadiene urethane acrylate oligomer (BUA) 5 g, pentaerythritol tetrakis (3-mercaptobutyrate) ( 10 g of pentaerythritol tetrakis (3-mecaptobutylate, MTPE1), and 0.5 g of Irgacure 184 (BASF) as a photopolymerization initiator, 0.5 g of Irgacure TPO (BASF), 0.05 g of pyrogallol as an antioxidant, Irgafos 168 (BASF) g) 0.1 g was mixed and vacuum defoamed to prepare a thiol-ene resin composition.

0.7 g of InP/ZnS semiconductor nanocrystal quantum dots (QD) (Nanosys) dispersed in isobornylmethacrylate was added to the thiol-ene resin composition and stirred and mixed in a mixing device under a nitrogen atmosphere, the present invention A quantum dot resin composite composition was obtained.

The quantum dot resin composite composition was applied on a gas barrier base film (thickness: 12 μm, IB-PET film, DNP) and photocured for about 10 seconds through a UV exposure machine (500 mJ/cm 2 ), so that the light emitting layer had a thickness of 100 μm An optical sheet molded article of the present invention was obtained.

Example 2: Preparation of optical sheet using quantum dot resin composite (2)

Tricyclodecane dimethanol diacrylate (TCDDA) 56 g, trimethylpropane triacrylate (TMPTA) 14 g, lauryl methacrylate (LMA) 10 g, butadiene urethane acrylate oligomer (butadiene urethane acrylate oligomer, BUA) 10 g, pentaerythritol tetrakis (3-mercaptobutyrate) (pentaerythritol tetrakis (3-mecaptobutylate, MTPE1) 10 g, and Irgacure 184 (BASF) 0.5 g as a photopolymerization initiator), 0.5 g of Irgacure TPO (BASF), 0.05 g of pyrogallol as an antioxidant, and 0.1 g of Irgafos 168 (BASF) were mixed and vacuum defoamed to prepare a thiol-ene resin composition.

0.7 g of InP/ZnS semiconductor nanocrystal quantum dots (QD) (Nanosys) dispersed in isobornylmethacrylate was added to the thiol-ene resin composition and stirred and mixed in a mixing device under a nitrogen atmosphere, the present invention A quantum dot resin composite composition was obtained.

The quantum dot resin composite composition was applied on a gas barrier base film (thickness: 12 μm, IB-PET film, DNP) and photocured for about 10 seconds through a UV exposure machine (500 mJ/cm 2 ), so that the light emitting layer had a thickness of 100 μm An optical sheet molded article of the present invention was obtained.

Example 3: Preparation of optical sheet using quantum dot resin composite (3)

36 g of tricyclodecane dimethanol diacrylate (TCDDA), 10 g of ethoxylated(2)bisphenolA dimethacrylate (EBPADA), and trimethylpropane triacrylate (trimethylpropane triacrylate, TMPTA) 14 g, laurylmethacrylate (LMA) 10 g, polybutadiene (Polyvest 110, Evonik GmH) 20 g, pentaerythritol tetrakis (3-mercaptobutyrate) ( 10 g of pentaerythritol tetrakis (3-mecaptobutylate, MTPE1), and 0.5 g of Irgacure 184 (BASF) as a photopolymerization initiator, 0.5 g of Irgacure TPO (BASF), 0.05 g of pyrogallol as an antioxidant, Irgafos 168 (BASF) g) 0.1 g was mixed and vacuum defoamed to prepare a thiol-ene resin composition.

0.7 g of InP/ZnS semiconductor nanocrystal quantum dots (QD) (Nanosys) dispersed in isobornylmethacrylate was added to the thiol-ene resin composition and stirred and mixed in a mixing device under a nitrogen atmosphere, the present invention A quantum dot resin composite composition was obtained.

The quantum dot resin composite composition was applied on a gas barrier base film (thickness: 12 μm, IB-PET film, DNP) and photocured for about 10 seconds through a UV exposure machine (500 mJ/cm 2 ), so that the light emitting layer had a thickness of 100 μm An optical sheet molded article of the present invention was obtained.

Comparative Example 1: Preparation of optical sheet using quantum dot resin composite (4)

46 g of tricyclodecane dimethanol diacrylate (TCDDA) as a polyalkene compound, 1,3,5-triallyl-1,3,5-triazine-2,4,6-trione (1 ,3,5-triallyl-1,3,5-triazine-2,4,6-trione, TAIC, Nippon Kasei Chemical Co.) 20 g, trimethylpropane triacrylate (TMPTA) 18 g, lauryl meth 12 g of acrylate (laurylmethacrylate, LMA), 4 g of pentaerythritol tetrakis(3-mecaptobutylate, MTPE1), and 0.5 g of Irgacure 184 (BASF) as a photopolymerization initiator 0.5 g of TPO (BASF), 0.05 g of pyrogallol as an antioxidant, and 0.1 g of Irgafos 168 (BASF) were mixed and vacuum defoamed to prepare a thiol-ene resin composition.

0.7 g of InP/ZnS semiconductor nanocrystal quantum dots (QD) (Nanosys) dispersed in isobornylmethacrylate was added to the thiol-ene resin composition and stirred and mixed in a mixing device under a nitrogen atmosphere, the present invention A quantum dot resin composite composition was obtained.

The quantum dot resin composite composition was applied on a gas barrier base film (thickness: 12 μm, IB-PET film, DNP) and photocured for about 10 seconds through a UV exposure machine (500 mJ/cm 2 ), so that the light emitting layer had a thickness of 100 μm An optical sheet molded article of the present invention was obtained.

Comparative Example 2: Preparation of optical sheet using quantum dot resin composite (5)

56 g of tricyclodecane dimethanol diacrylate (TCDDA), 20 g of ethoxylated(2)bisphenolA dimethacrylate (EBPADA), 20 g of trimethylpropane triacrylate ( 4 g of trimethylpropane triacrylate, TMPTA), 10 g of laurylmethacrylate (LMA), 10 g of pentaerythritol tetrakis(3-mercaptobutyrate) (pentaerythritol tetrakis(3-mecaptobutylate, MTPE1), and a photoinitiator 0.5 g of Irgacure 184 (BASF), 0.5 g of Irgacure TPO (BASF), 0.05 g of pyrogallol as an antioxidant, 0.1 g of Irgafos 168 (BASF) were mixed and vacuum defoamed to obtain a thiol-ene resin composition Manufactured.

0.7 g of InP/ZnS semiconductor nanocrystal quantum dots (QD) (Nanosys) dispersed in isobornylmethacrylate was added to the thiol-ene resin composition and stirred and mixed in a mixing device under a nitrogen atmosphere, the present invention A quantum dot resin composite composition was obtained.

The quantum dot resin composite composition was applied to an optical polyethylene terephthalate (PET) base film (thickness: 12 μm, SKC, Korea) and photocured for about 10 seconds through a UV exposure machine (500 mJ/cm 2 ) so that the thickness of the light emitting layer was 100 An optical sheet molded article of the present invention having a size of μm was obtained.

The configuration of the quantum dot resin composite composition described in Examples 1 to 3 and Comparative Examples 1 and 2 is summarized in Table 1 below.

[Table 1]

In Table 1, the content of each component is weight % (or parts by weight), and the names of the abbreviations are as follows.

TCDDA: Tricyclodecane dimethanol diacrylate

EBPADA: Ethoxylated(2)bisphenolA diacrylate

TAIC: 1,3,5-Triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione

TMPTA: Trimethylpropane triacrylate

LMA: Lauryl methacrylate

BUA oligomer: Butadiene urethane acrylate oligomer (CN9001NS, Sartomer)

Polyvest 110: polybutadiene 110 (Evonik GmH)

MTPE1: Pentaerythritol tetrakis(3-mecaptobutylate) (Karenz MT™PE1, Showa Denko)

Irgacure 184, Irgacure TPO

pyrogallol, Irgafos 168

QD: Quantum dot (InP/ZnS, Nanosys Inc.)

IB-PET: Gas Barrier Film (IB Film, DNP)

Test Example: Long-term reliability evaluation experiment

The water vapor transmission rate (WVTR) of the optical sheets of Examples 1 to 3 and Comparative Examples 1 and 2 was measured according to JIS K7129B using Aquatran (Mocon Inc.).

In addition, the size of the optical sheet of Examples 1 to 3 and Comparative Examples 1 and 2 was 152 x 152 mm to prepare a reliability evaluation specimen, and the light was driven on a blue LED light source having a peak wavelength of 449 nm. Characteristics and luminance were measured. In addition, the optical sheet was driven at 60° C. and a relative humidity of 90%, and the luminance was measured over time to measure the change in optical properties of the manufactured optical sheet.

The evaluation results of the above test examples are shown in Tables 2 and 3.

[Table 2] Measurement of Quantum Efficiency

Quantum dot (QD) thiol-ene in substantially the same manner as shown in Table 2, except that 10 wt% of the barrier improving additive is added to the quantum dot (QD)-containing polymer composition based on 100 wt% of the thiol-ene composition It is to obtain a composite composition and to manufacture a reliable quantum dot (QD) composite optical sheet.

[Table 3] Long-term reliability evaluation (60 ℃, 90% relative humidity, 1,000 hours elapsed)

According to the results of optical properties in Tables 2 and 3, in the case of the quantum dot resin composite of the present invention, it is possible to prepare an excellent quantum dot-containing optical sheet having a quantum efficiency (QE) of 90% or more. In addition, as shown in Table 3, the long-term reliability evaluation results of the molded quantum dot optical sheet confirmed that the quantum dot (QD) resin composites of Examples 1 to 3 could provide an optical sheet having excellent barrier performance and good luminous efficiency.

In the above, preferred embodiments of the present invention have been described, but the present invention is not limited to the specific embodiments described above, and those skilled in the art can implement various modifications without departing from the gist of the present invention. Of course it is possible. Therefore, the scope of the present invention should not be construed as being limited to the above embodiments, and should be defined by the claims and equivalents to the claims described below.

101, 102: gas barrier base film
100: quantum dot resin composite

Claims (12)

As a quantum dot resin composite including quantum dots in polythiol-ene resin, the quantum dot resin composite is
a compound of formula 1 having at least one polymerizable reactive alkenyl group,
a compound of formula 2 having at least one thiol group,
quantum dot (QD) nanoparticles, and
polymerization initiator
including,
[Formula 1]

during the meal,
R ₁ is a C6-C18 substituted or unsubstituted, alkyl group, cycloalkyl group, aryl group, saturated or unsaturated polycyclic group, cyanurate group, isocyanurate group, or a combination thereof ego,
R ₂ is H or methyl;
[Formula 2]
R ₃ -(SH) _n
during the meal,
R ₃ is an ester, amide, or urea bond having a C4-C18 substituted or unsubstituted, alkyl group, a cycloalkyl group, an aryl group, or a combination thereof;
n is an integer greater than or equal to 2,
The compound of Formula 1 is tricyclodecanedimethanol diacrylate, bis(phenolA)dimethacrylate, trimethylpropanetrimethacrylate, tris(2-hydroxyethyl) isocyanurate
Tris(2-hydroxyethyl)isocyanuratetriacrylate), pentaerythritoltetraacrylate, isobornylacrylate, lauryl(meth)acrylate, 3,5,5-trimethylcyclo Hexyl acrylate (3,5,5-trimethylcyclohexylacrylate), dodecylacrylate (dodecylacrylate), tridecylacrylate (tridecylacrylate), isodecylacrylate (isodecylacrylate), or a mixture thereof,
The compound of Formula 2 is ethylene glycol bis (3-mercapto butyrate), 1,2-propylene glycol (3-mercapto butyrate), trimethylol propane tris (3-mercapto butyrate), ethylene glycol bis (2-mercap) Toisobutyrate), 1,2-propylene glycol bis (2-mercaptoisobutyrate), trimethylolpropane tris (2-mercaptoisobutyrate), pentaerythritol tetrakis (3-mercaptopropionate), penta Erythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H) -trione, 1,4-bis(3-mercaptobutyryloxy)butane, bisphenol A bis(3-mercaptobutyrate), triphenolmethanetris(3-mercaptobutyrate), or a mixture thereof;
The quantum dot resin composite further comprises an oligomer or a polymer having the gas barrier properties,
The monomer of the oligomer or polymer having the gas barrier property is butadiene urethane acrylate, butadiene, isoprene, or a mixture thereof,
The number average molecular weight of the oligomer or polymer having the gas barrier property is 2,000 to 10,000, the quantum dot resin composite. delete delete The method according to claim 1,
The quantum dot nanoparticles are CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, InP, InAs, GaN, GaP, GaAs, or a combination thereof. . The method according to claim 1,
The quantum dot nanoparticles are CdSe core (core) and ZnS shell (shell), or InP core and the quantum dot resin composite, characterized in that it comprises a semiconductor nanocrystals having a ZnS shell structure. The method according to claim 1,
The quantum dot resin composite is
100 parts by weight of the compound of Formula 1,
8 to 20 parts by weight, 9 to 17 parts by weight, or 10 to 15 parts by weight of the compound of Formula 2;
0.5 to 1.5 parts by weight of quantum dot nanoparticles, 0.6 to 1.3 parts by weight, or 0.7 to 1.1 parts by weight, and
0.01 to 5 parts by weight, 0.5 to 2 parts by weight, or 1.1 to 1.5 parts by weight of the photopolymerization initiator, characterized in that it comprises a quantum dot resin composite. delete delete The method according to claim 1,
The quantum dot resin composite is characterized in that it further comprises a stabilizer, the quantum dot resin composite. 10. The method of claim 9,
The stabilizer is pyrogallol, 4-methoxy-1-naphthol, tert-butylcatechol, hydroquinone, gallic ester ), oxalic acid, phosphoric acid, tris (2,4-di-tert-butylphenyl) phosphite (Tris (2,4-di-tert-butylphenyl) phosphite), bis (2,4) -Di-tert-butylphenyl)pentaerythritol diphosphite (Bis(2,4-di-tert-butylphenyl)phentaerythritoldiphosphite), or a mixture thereof, characterized in that the quantum dot resin composite. An optical material layer wherein the quantum dot resin composite of any one of claims 1, 4 to 6, 9 or 10 is cured by irradiation with active energy rays. An optical sheet, wherein the optical material layer of claim 11 is disposed between a pair of gas barrier base films.

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