Source: http://www.google.ca/patents/US9303153
Timestamp: 2017-11-24 04:10:00
Document Index: 343049037

Matched Legal Cases: ['Application No. 61', 'Application No. 60', 'Application No. 10', 'Application No. 2010', 'Application No. 2010', 'Application No. 2012', 'Application No. 2012', 'Application No. 2010', 'Application No. 13', 'Application No. 2010', 'Application No. 13', 'Application No. 2010']

Patent US9303153 - Formulations including nanoparticles - Google Patents
The present invention relates to a formulation comprising a medium, one or more stabilizers, and one or more particles comprising nanoparticles included within a host material. In certain embodiments, a stabilizer comprises a HALS stabilizer. In certain embodiments, a stabilizer comprises a UVA stabilizer....http://www.google.ca/patents/US9303153?utm_source=gb-gplus-sharePatent US9303153 - Formulations including nanoparticles
Publication number US9303153 B2
Application number US 13/414,463
Also published as US20120256134, US20160355730, WO2011031876A1
Publication number 13414463, 414463, US 9303153 B2, US 9303153B2, US-B2-9303153, US9303153 B2, US9303153B2
Patent Citations (248), Non-Patent Citations (56), Referenced by (1), Classifications (22), Legal Events (4)
US 9303153 B2
1. A formulation comprising a medium, two or more stabilizers, and one or more particles comprising nanoparticles included within a host material, wherein at least a portion of the nanoparticles include a core comprising a first semiconductor material and a shell disposed over at least a portion of an outer surface of the core, the shell comprising a second semiconductor material, and wherein the two or more stabilizers include a HALS stabilizer and a UVA stabilizer.
2. A formulation in accordance with claim 1 wherein the particle has at least one dimension in the range from about 0.01 μm to about 100 μm.
3. A formulation in accordance with claim 1 wherein the particle includes at least about 0.001 weight percent nanoparticles.
4. A formulation in accordance with claim 1 wherein the particle includes from about 0.001 to about 25 weight percent nanoparticles.
5. A formulation in accordance with claim 1 wherein the host material comprises a polymer.
6. A formulation in accordance with claim 1 wherein the host material comprises a wax.
7. A formulation in accordance with claim 1 wherein at least a portion of the nanoparticles have light-emissive properties and wherein the host material is optically transparent.
8. A formulation in accordance with claim 7 wherein the host material is optically transparent to excitation light used to optically excite the nanoparticles.
9. A formulation in accordance with claim 7 wherein the host material is optically transparent to light emitted from the light-emissive nanoparticles.
10. A formulation in accordance with claim 7 wherein the host material is optically transparent to light emitted from the light-emissive nanoparticles.
11. A formulation in accordance with claim 1 wherein at least a portion of the nanoparticles includes one or more ligands attached to an outer surface thereof.
12. A powder comprising a formulation in accordance with claim 1 in a particulate form.
13. A powder in accordance with claim 12 wherein two or more populations of particles are included in the powder and wherein at least one population of particles includes nanoparticles that emit light at a wavelength that is distinct from that emitted by nanoparticles included in another population of particles.
14. A formulation in accordance with claim 1 wherein the medium comprises a liquid medium.
15. A formulation in accordance with claim 1 wherein the particles are present in the formulation in an amount of at least about 0.1 weight percent based on the weight of the medium.
16. A formulation in accordance with claim 1 wherein the particles are present in the formulation in an amount of at least about 0.1 to about 75 weight percent based on the weight of the medium.
17. A formulation in accordance with claim 1 wherein the particles are present in the formulation in an amount of at least about 0.1 to about 25 weight percent based on the weight of the medium.
18. A formulation in accordance with claim 1 wherein the particles are present in the formulation in an amount of at least about 0.1 to about 10 weight percent based on the weight of the medium.
19. A formulation in accordance with claim 1 wherein the particles are present in the formulation in an amount of at least about 0.1 to about 5 weight percent based on the weight of the medium.
20. A formulation in accordance with claim 1 wherein the medium comprises monomers, polymers, resins, and/or other film forming compositions.
21. A formulation in accordance with claim 1 wherein the formulation further includes one or more additives.
22. A formulation in accordance with claim 21 wherein the one or more additives comprise a colorant, a scatterer, a binder, a surfactant, and/or a mixture of one or more thereof.
23. A composition comprising a powder in accordance with claim 12.
24. A composition in accordance with claim 23 wherein the powder is dispersed in a second host material.
25. A composition in accordance with claim 24 wherein the second host material comprises a monomer.
26. A composition in accordance with claim 24 wherein the second host material comprises a resin.
27. A composition in accordance with claim 24 wherein the second host material comprises a polymer.
28. A formulation in accordance with claim 1 wherein the host material comprises polyacrylate.
29. A formulation in accordance with claim 1 wherein the host material comprises an inorganic material.
30. A formulation in accordance with claim 1 wherein the nanoparticles have light-emissive properties.
31. A formulation in accordance with claim 1 wherein the formulation includes the HALS stabilizer in an amount from about 0.1 to about 5 weight percent.
32. A formulation in accordance with claim 1 wherein the formulation includes the UVA stabilizer in an amount from about 0.1 to about 5 weight percent.
33. A formulation in accordance with claim 1 wherein the formulation includes the HALS stabilizer in an amount from about 0.1 to about 2 weight percent.
34. A formulation in accordance with claim 1 wherein the formulation includes the UVA stabilizer in an amount from about 0.1 to about 2 weight percent.
35. A formulation in accordance with claim 31 wherein the formulation includes the UVA stabilizer in an amount from about 0.1 to about 5 weight percent.
36. A formulation in accordance with claim 33 wherein the formulation includes the UVA stabilizer in an amount from about 0.1 to about 2 weight percent.
This application is a continuation of commonly owned International Application No. PCT/US2010/048291 filed 9 Sep. 2010, which was published in the English language as PCT Publication No. WO 2011/031876 A1 on 17 Mar. 2011, which International Application claims priority to U.S. Application No. 61/240,937 filed 9 Sep. 2009. Each of the foregoing is hereby incorporated herein by reference in its entirety.
A formulation can include from about 0.1 to about 5, and preferably about 0.1 to about 2, weight percent of a stabilizer.
A formulation can include more than one stabilizer. In such case, each stabilizer can be included in an amount from about 0.1 to about 5, and preferably about 0.1 to about 2 weight percent.
In certain embodiments, the particles have at least one dimension in the range from about 0.01 μm to about 100 μm. In certain embodiments, the particle has at least one dimension in the range from about 0.01 μm to about 50 μm.
Examples of polymers and resins include, for example and without limitation, polyethylene, polypropylene, polystyrene, polyethylene oxide, polysiloxane, polyphenylene, polythiophene, poly(phenylene-vinylene), polysilane, polyethylene terephthalate and poly(phenylene-ethynylene), polymethylmethacrylate, polylaurylmethacrylate, polycarbonate, epoxy, and other epoxies. Other polymers and resins can be readily ascertained by one of ordinary skill in the relevant art.
In certain preferred embodiments, the nanoparticles comprise semiconductor nanocrystals. (Semiconductor nanocrystals are also referred to herein as quantum dots.)
In accordance with another aspect of the present invention, there is provided a powder obtainable from a formulation in accordance with the invention.
In certain embodiments, the powder has a predetermined particle size distribution. A predetermined particles size distribution can be achieved by screening or by other techniques readily ascertainable by one of ordinary skill in the relevant art.
In certain embodiments, the particle size distribution is selected based on the intended end-use application. Such particle size distribution can be readily ascertained by one of ordinary skill in the relevant art.
In accordance with another aspect of the present invention, there is provided a raw batch formulation useful for making a particle. The raw batch formulation comprises from about 0.001 to about 25 weight percent quantum dots, photoinitiator, up to about 25 weight percent cross-linking agent, and one or more monomers.
Preferably, the raw batch formulation further includes a liquid medium and from about 0.01 to about 5 weight percent surfactant based on the weight of the liquid medium.
The present invention relates to a formulation comprising a medium, one or more stabilizers, and one or more particles comprising nanoparticles included within a host material. The present invention also relates to powders, compositions, films, and coatings including or prepared from a formulation taught herein, uses of the foregoing, and methods and a raw batch formulation and particle obtainable therefrom.
In certain embodiments, the polyvinyl alcohol compound comprises polyvinyl alcohol (PVA).
In certain embodiments, the polyvinyl alcohol compound comprises poly(ethylenevinyl) alcohol (EVA).
The poly(ethylenevinyl) alcohol can optionally include one or more substituent groups, which can be the same or different.
In certain embodiments, the coating comprises polyvinylidene dichloride.
The polyvinylidene dichloride can optionally include one or more substituent groups, which can be the same or different.
Examples of polymers and resins include, for example and without limitation, polyethylene, polypropylene, polystyrene, polyethylene oxide, polysiloxane, polyphenylene, polythiophene, poly(phenylene-vinylene), polysilane, polyethylene terephthalate and poly(phenylene-ethynylene), polymethylmethacrylate, polylaurylmethacrylate, polycarbonate, epoxy, and other epoxies.
Other polymers and resins can be readily ascertained by one of ordinary skill in the relevant art.
Additional examples of monomers include, but are not limited to, allyl methacrylate, benzyl methylacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, butyl acrylate, n-butyl methacrylate, ethyl methacrylate, 2-ethyl hexyl acrylate, 1,6-hexanediol dimethacrylate, 4-hydroxybutyl acrylate, hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, isobutyl methacrylate, lauryl methacrylate, methacrylic acid, methyl acrylate, 2,2,3,3,4,4,5,5-octafluoropentyl acrylate, pentaerythritol triacrylate, 2,2,2-trifluoroethyl 2-methylacrylate, trimethylolpropane triacrylate, acrylamide n,n,-methylene-bisacryl-amide phenyl acrylate, and divinyl benzene.
For those monomers that are photo-polymerizable, a photoinitiator species can be included with the monomer to enable the polymerization process. (A photoiniator species may also be referred to herein as a photosensitizer.) Effectively any chemical that can produce free-radicals in a fluidic monomer as a result of illumination absorption can be employed as the photoinitiator species. There are in general two classes of photoinitiators. In the first class, the chemical undergoes unimolecular bond cleavage to yield free radicals. Examples of such photoinitiators include benzoin ethers, benzil ketals, a-dialkoxy-acetophenones, a-amino-alkylphenones, and acylphosphine oxides. the second class of photoinitiators is characterized by a bimolecular reaction where the photoinitiator reacts with a coinitiator to form free radicals. Examples of such are benzophenones/amines, thioxanthones/amines, and titanocenes (vis light).
A non-exhaustive listing of examples of photoinitiators that may be useful with a photo-polymerizable monomer for particle preparation include the following from CIBA: IRGACURE 184 (1-hydroxy-cyclohexyl-phenyl-ketone), DAROCUR 1173 (2-hydroxy-2-methyl-1-phenyl-1-propanone), IRGACURE 2959 (2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone), DAROCUR MBF (methylbenzoylformate), IRGACURE 754 (oxy-phenyl-acetic acid 2-[2 oxo-2 phenyl-acetoxy-ethoxy]-ethyl ester and oxy-phenyl-acetic 2-[2-hydroxy-ethoxy]-ethyl ester), IRGACURE 651 Alpha, (alpha-dimethoxy-alpha-phenylacetophenone), IRGACURE 369 (2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone), IRGACURE 907 (2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone), DAROCUR TPO (diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide), IRGACURE 819 (phosphine oxide, phenyl bis(BAPO)(2,4,6-trimethylbenzoyl)), IRGACURE 784 (bis(eta 5-2,4-cyclopentadien-1-yl)Bis[2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl]titanium), IRGACURE 250 (iodonium, (4-methylphenyl)[4-(2-methylpropyl)phenyl]-hexafluorophosphate(1-)).
When used, a photoinitiator is included in at least an amount effective to enable the polymerization process.
Examples of host materials for inclusion in particles also include hydrocarbon wax, which is available in different molecular weight versions. Low molecular weight versions are called paraffin wax. Fischer-Tropsch wax is an example of a medium molecular weight version. Polyethylene wax is an example of a high molecular weight version. Melting points can range from 50° C. to 130° C. Straight chain hydrocarbon waxes will be very compatible with nanoparticles including one or more ligands comprising a straight chain alkane ligand. Above certain molecular weight, these waxes are insoluble in most solvents. Lower molecular weight chains are preferred host materials for nanoparticles comprising semiconductor nanocrystals. (Higher molecular weight chains can be more brittle which can make particle size reduction easier.) The index of refraction of these waxes generally is in a range from 1.51 to 1.54, similar to the 1.49 value for PMMA. It is uncolored to milky white. While polyethylene wax is less than an optimum O2 barrier, in certain uses it may be preferred because it is not biodegradable and it may be resistant to the liquids and/or components included in the formulation.
In certain embodiments of the present invention, a particle comprises a host material including nanoparticles dispersed therein. In certain embodiments, the nanoparticles are dispersed throughout the host material. In certain embodiments, the nanoparticles are substantially uniformly dispersed throughout the host material. In certain embodiments, the nanoparticles are dispersed throughout the particle. In certain embodiments, the nanoparticles are substantially uniformly dispersed throughout the particle.
In certain embodiments, a formulation can optionally include one or more additives, including, but not limited to, colorants, scatterers, binders, surfactants, defoaming agents, UV absorbers, etc., and/or mixtures of one or more of the foregoing.
In certain embodiments, a formulation of the invention can be used in a paint.
In certain embodiments, a formulation of the invention can be used in an ink.
Examples of polymers and resins include, for example and without limitation, polyethylene, polypropylene, polystyrene, polyethylene oxide, polysiloxane, polyphenylene, polythiophene, poly(phenylene-vinylene), polysilane, polyethylene terephthalate poly(phenylene-ethynylene), polymethylmethacrylate, polylaurylmethacrylate, polycarbonate, epoxy, and other epoxies.
A particle can be obtained, for example, by dispersing quantum dots in a mixture of one or more monomers and a photoinitiator. Concentrations of quantum dots in the monomer(s) and the amount of photoiniator can be as described herein. The mixture can further include a cross-linker. (A cross-linker can be included in an amount up to about 25 percent by weight; in certain embodiments cross-linker can be included in an amount from about 15-20 weight percent.) The mixture further can include a surfactant (e.g., from about 0.01 to about 5 weight percent based on the water or other solvent to be used). The mixture can then be dispersed in water and/or other polar organic solvent with high shear, e.g., using a rotor-stator, disperser to generate microspheres. The microspheres are then quickly photo-polymerized (e.g., under UV) to generate solid, cross-linked microspheres containing the quantum dots. The microspheres can then be isolated.
In one example, quantum dots are dispersed in a mixture of acrylic monomers and cross-linking agents with a photosensitizer (also referred to herein as a photoinitiator) and a surfactant.
When the organic group is substituted, it may contain any functional group. Examples include, but are not limited to, OR, COR, COOR, OCOR, COONa, COOK, COO−NR4 +, halogen, CN, NR2, SO3H, SO3Na, SO3K, SO3 −NR4 +, NR(COR), CONR2, NO2, PO3H2, PO3HNa, PO3Na2, N═NR, NR3 +X−, and PR3 +X−. R can independently be hydrogen, C1-C.20 alkyl (branched or unbranched) or aryl. The integer n can range, e.g., from 1-8 and preferably from 2-4. The anion X− can be a halide or an anion that can be derived from a mineral or organic acid.
For example, the semiconductor nanocrystal can include a core having the formula MX, where M can be cadmium, zinc, magnesium, mercury, aluminum, gallium, indium, thallium, or mixtures thereof, and X can be oxygen, sulfur, selenium, tellurium, nitrogen, phosphorus, arsenic, antimony, or mixtures thereof. Examples of materials suitable for use as semiconductor nanocrystal cores include, but are not limited to, ZnO, ZnS, ZnSe, ZnTe, CdO, CdS, CdSe, CdTe, MgS, MgSe, GaAs, GaN, GaP, GaSe, GaSb, HgO, HgS, HgSe, HgTe, InAs, InN, InP, InSb, AlAs, AlN, AlP, AlSb, TlN, TlP, TlAs, TlSb, PbO, PbS, PbSe, PbTe, Ge, Si, an alloy including any of the foregoing, and/or a mixture including any of the foregoing, including ternary and quaternary mixtures or alloys.
The process of controlled growth and annealing of the semiconductor nanocrystals in the coordinating solvent that follows nucleation can also result in uniform surface derivatization and regular core structures. As the size distribution sharpens, the temperature can be raised to maintain steady growth. By adding more M donor or X donor, the growth period can be shortened. The M donor can be an inorganic compound, an organometallic compound, or elemental metal. For example, M can be cadmium, zinc, magnesium, mercury, aluminum, gallium, indium or thallium. The X donor is a compound capable of reacting with the M donor to form a material with the general formula MX. For example, the X donor can be a chalcogenide donor or a pnictide donor, such as a phosphine chalcogenide, a bis(silyl)chalcogenide, dioxygen, an ammonium salt, or a tris(silyl)pnictide. Suitable X donors include dioxygen, bis(trimethylsilyl)selenide ((TMS)2Se), trialkyl phosphine selenides such as (tri-noctylphosphine)selenide (TOPSe) or (tri-n-butylphosphine)selenide (TBPSe), trialkyl phosphine tellurides such as (tri-n-octylphosphine)telluride (TOPTe) or hexapropylphosphorustriamide telluride (HPPTTe), bis(trimethylsilyl)telluride ((TMS)2Te), bis(trimethylsilyl)sulfide ((TMS)2S), a trialkyl phosphine sulfide such as (tri-noctylphosphine)sulfide (TOPS), an ammonium salt such as an ammonium halide (e.g., NH4Cl), tris(trimethylsilyl)phosphide ((TMS)3P), tris(trimethylsilyl)arsenide ((TMS)3As), or tris(trimethylsilyl)antimonide ((TMS)3Sb). In certain embodiments, the M donor and the X donor can be moieties within the same molecule.
A coordinating solvent can help control the growth of the semiconductor nanocrystal. The coordinating solvent is a compound having a donor lone pair that, for example, has a lone electron pair available to coordinate to a surface of the growing semiconductor nanocrystal. Solvent coordination can stabilize the growing semiconductor nanocrystal. Examples of coordinating solvents include alkyl phosphines, alkyl phosphine oxides, alkyl phosphonic acids, or alkyl phosphinic acids, however, other coordinating solvents, such as pyridines, furans, and amines may also be suitable for the semiconductor nanocrystal production. Additional examples of suitable coordinating solvents include pyridine, tri-n-octyl phosphine (TOP), tri-n-octyl phosphine oxide (TOPO) and trishydroxylpropylphosphine (tHPP), tributylphosphine, tri(dodecyl)phosphine, dibutyl-phosphite, tributyl phosphite, trioctadecyl phosphite, trilauryl phosphite, tris(tridecyl)phosphite, triisodecyl phosphite, bis(2-ethylhexyl)phosphate, tris(tridecyl)phosphate, hexadecylamine, oleylamine, octadecylamine, bis(2-ethylhexyl)amine, octylamine, dioctylamine, trioctylamine, dodecylamine/laurylamine, didodecylamine tridodecylamine, hexadecylamine, dioctadecylamine, trioctadecylamine, phenylphosphonic acid, hexylphosphonic acid, tetradecylphosphonic acid, octylphosphonic acid, octadecylphosphonic acid, propylenediphosphonic acid, phenylphosphonic acid, aminohexylphosphonic acid, dioctyl ether, diphenyl ether, methyl myristate, octyl octanoate, and hexyl octanoate. In certain embodiments, technical grade TOPO can be used.
In certain embodiments, semiconductor nanocrystals can alternatively be prepared with use of non-coordinating solvent(s).
For example, a dispersion of the capped semiconductor nanocrystal can be treated with a coordinating organic compound, such as pyridine, to produce crystallites which disperse readily in pyridine, methanol, and aromatics but no longer disperse in aliphatic solvents. Such a surface exchange process can be carried out with any compound capable of coordinating to or bonding with the outer surface of the semiconductor nanocrystal, including, for example, phosphines, thiols, amities and phosphates. The semiconductor nanocrystal can be exposed to short chain polymers which exhibit an affinity for the surface and which terminate in a moiety having an affinity for a liquid medium in which the semiconductor nanocrystal is suspended or dispersed. Such affinity improves the stability of the suspension and discourages flocculation of the semiconductor nanocrystal.
Other examples of ligands include benzylphosphonic acid, benzylphosphonic acid including at least one substituent group on the ring of the benzyl group, a conjugate base of such acids, and mixtures including one or more of the foregoing. In certain embodiments, a ligand comprises 4-hydroxybenzylphosphonic acid, a conjugate base of the acid, or a mixture of the foregoing. In certain embodiments, a ligand comprises 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, a conjugate base of the acid, or a mixture of the foregoing.
The emission from a nanoparticle capable of emitting light (e.g., a semiconductor nanocrystal) can be a narrow Gaussian emission band that can be tuned through the complete wavelength range of the ultraviolet, visible, NIR (700 nm-1400 nm), or infra-red regions of the spectrum by varying the size of the nanoparticle, the composition of the nanoparticle, or both. For example, a semiconductor nanocrystal comprising CdSe can be tuned in the visible region; a semiconductor nanocrystal comprising InAs can be tuned in the infra-red region. The narrow size distribution of a population of nanoparticles capable of emitting light (e.g., semiconductor nanocrystals) can result in emission of light in a narrow spectral range. The population can be monodisperse preferably exhibits less than a 15% rms (root-mean-square) deviation in diameter of such nanoparticles, more preferably less than 10%, most preferably less than 5%. Spectral emissions in a narrow range of no greater than about 75 nm, preferably 60 nm, more preferably 40 nm, and most preferably 30 nm full width at half max (FWHM) for such nanoparticles that emit in the visible can be observed. IR-emitting nanoparticles can have a FWHM of no greater than 150 nm, or no greater than 100 nm. Expressed in terms of the energy of the emission, the emission can have a FWHM of no greater than 0.05 eV, or no greater than 0.03 eV. The breadth of the emission decreases as the dispersity of the light-emitting nanoparticle diameters decreases.
Other materials, techniques, methods, applications, and information that may be useful with the present invention are described in, International Application No. PCT/US2007/24320, filed Nov. 21, 2007, of Clough, et al., for “Nanocrystals Including A Group IIIa Element And A Group Va Element, Method, Composition, Device And Other Products” which published as WO2008/133660; International Application No. PCT/US2007/24305, filed Nov. 21, 2007, of Breen, et al., for “Blue Light Emitting Semiconductor Nanocrystal And Compositions And Devices Including Same” which published as WO2008/063652; International Application No. PCT/US2007/24306, filed Nov. 21, 2007, of Ramprasad, for “Semiconductor Nanocrystal And Compositions And Devices Including Same” which published as WO2008/063653; International Application No. PCT/US2007/013152, filed Jun. 4, 2007, of Coe-Sullivan, et al., for “Light-Emitting Devices And Displays With Improved Performance” which published as WO2007/143197; International Application No. PCT/US2007/24750, of Coe-Sullivan, et al., filed Dec. 3, 2007 “Improved Composites And Devices Including Nanoparticles” which published as WO2008/070028; International Application No. PCT/US2007/24310, filed Nov. 21, 2007, of Kazlas, et al., for “Light-Emitting Devices And Displays With Improved Performance” which published as WO2008/063653; International Application No. PCT/US2007/003677, filed Feb. 14, 2007, of Bulovic, et al., for “Solid State Lighting Devices Including Semiconductor Nanocrystals & Methods”, U.S. patent application Ser. No. 12/283,609, filed 12 Sep. 2008, of Coe-Sullivan et al., for “Compositions, Optical Component, System Including an Optical Component, Devices, and Other Products”, and U.S. Patent Application No. 60/949,306, filed 12 Jul. 2007, of Linton, et al., for “Compositions, Methods For Depositing Nanomaterial, Methods For Fabricating A Device, And Methods For Fabricating An Array Of Devices, U.S. Pat. No. 7,229,690, issued 12 Jun. 2007, of Chan, et al., for “Microspheres Including Nanoparticles”, U.S. Pat. No. 7,449,237, issued 11 Nov. 2008, of Chan, et al., for “Microspheres Including Nanoparticles in the Peripheral Region”, International Application No. PCT/US2009/01372, filed 4 Mar. 2009, of John R. Linton, et al, for “Particles Including Nanoparticles, Uses Thereof, and Methods”, CIBA TINUVIN 5000 Series product brochure entitled “High value light stabilizer blends for coatings” (c-August 2009, printed in Switzerland), Ciba Tinuvin 1130 product brochure—Coating Effects Segment (Edition: 15.12.97 Basle), Ciba Tinuvin 477 DW product brochure—Ciba Specialty Chemicals—Coating Effects Segment (Edition 02:05.05, Basle—Copyright 2005 Ciba Specialty Chemicals Inc.), G. J. M. Fechine, et al, “Evaluation of poly(ethylene terephthalate) photostabilisation using FTIR spectrometry of evolved carbon dioxide”, Polymer Degradation and Stability 94 (2009) 234-239, PAN Jiangquing and CUI Song, “Study on the Photolysis Mechanism of Polyester From Succinic Acid and N-β-Hydroxyethyl 2,2,6,6-tetramethyl-4 hydroxy piperidine (Tinuvin-622), Chinese Journal of Polymer Science, Vol. 6, No. 4 (1988), and O. Meszaros, et al., “Photooxidation of poly[methyl](phenyl)silylene] and effect of photostabilizers”, Polymer Degradation and Stability 91 (2006) 573-578. The disclosures of each of the foregoing listed publications and documents are hereby incorporated herein by reference in their entireties.
Preparation of particles including InP/ZnS Quantum Dots with Octadecylphosphonic Acid (ODPA) and Decylamine ligands in LMA/EGDA acrylic microcapsule via emulsion photopolymerization using Tween 80 as dispersant and using stabilizers.
Microcapsule Preparation:
QD Concentration 21 mg/mL
QD solution used 7 mL
inorganic in QD 59.6% TGA
LMA density 0.872 g/cc
LMA charged 6.88 mL
EGDA density 1.05 g/cc
EGDA charged 1.39 mL
Photosensitizer 0.28 g
HALS charged 0.08 g
Triazine Charged 0.04 g
QD (inorganic) 0.147 g 1.77%
Deionized water is used. Lauryl methacrylate (Aldrich Chemical, 96% lot #08118DE) and ethylene glycol diacrylate (Aldrich Chemical, 98% lot #15017PD) are purified by passage through a short plug of activated Alumina in order to remove polymerization inhibitors. After passage through the column, the monomers are kept in a sealed, amber glass vial, refrigerated and used within 24 hours. Tween 80 (Aldrich Chemical, SigmaUltra lot #037KO1551), photoinitiator 4,4′-bis(N,N-diethylamino)benzophenone (DEABP), photostabilizer Bis(1-octyloxy-2,2,6,6-tatramethyl-4-piperidyl)sebacate (HALS-3) and UV absorber 2-4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol (“Tinuvin 1577) are obtained from Aldrich and are used without further purification. All other solvents are reagent grade and used without further purification.
Colloidal InP/ZnS core/shell quantum dots including Octadecylphosphonic Acid (ODPA) and Decylamine ligands are dispersed in toluene (7 mL, 21 mg/mL on inorganic basis; 147 mg total inorganics); the quantum dots have an emissionmax=620 nm, quantum yield=68%, absorbance=589 nm, and FWHM=56 nm.
89 mL of deionized water is charged to the beaker. To this is added Tween 80 (178 mg, 0.2% w/v) which is initially mixed for 30 minutes to dissolve and then cooled to 6° C. by setting the circulating bath temperature to a 2° C. setpoint. Once the temperature is reached, the monomer/QD solution is added subsurface via syringe creating a suspension of red colored beads. The IKA T25 rotor-stator is then immersed in the suspension and sheared at low speed (8000 rpm) until oil phase on top of reaction solution disappears and is incorporated into emulsion. Rotor stator is allowed to run for 10 minutes at low-medium speed making sure that air entrainment is minimized. After 10 minutes, the rotor-stator is shut off and the lamp is connected to power supply and quickly placed in the quartz photo well. Lamp is ignited and allowed to run for exactly 20 minutes. At the end of 30 minutes, power to the lamp is shut off. Rose colored and cloudy but no visible particles are observed.
Preparation of particles including InP/ZnS Quantum Dots with Octadecylphosphonic Acid (ODPA) and Decylamine ligands in LMA/EGDA acrylic microcapsule matrix via emulsion photopolymerization using Tween 80 as dispersant and using stabilizers.
Deionized water is used. Lauryl methacrylate (Aldrich Chemical, 96% lot #08118DE) and ethylene glycol diacrylate (Aldrich Chemical, 98% lot #15017PD) are purified by passage through a short plug of activated Alumina in order to remove polymerization inhibitors. After passage through the column, the monomers are kept in a sealed, amber glass vial, refrigerated and used within 24 hours. Tween 80 (Aldrich Chemical, SigmaUltra lot #037KO1551), Esacure KTO 46 photoinitator (Sartomer, lot #2008050005)), photostabilizer Bis(1-octyloxy-2,2,6,6-tatramethyl-4-piperidyl)sebacate (HALS-3) and UV absorber 2-4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol (Tinuvin 1577) are obtained from Aldrich and are used without further purification. All other solvents are reagent grade and used without further purification.
LMA charged 4 mL
EGDA charged 1 mL
Photosensitizer 0.23 g
HALS charged 0.039 g
Triazine Charged 0.03 g
QD (inorganic) 0.147 g 2.79%
QD with Organic ligands 0.247 g 4.68%
LMA 3.488 g 66.17%
A 50 mL Schlenk flask equipped with a septum and stir bar is placed under nitrogen by vacuum/refilling 3×. InP quantum dots in toluene (7 mL, 21 mg/mL on inorganic basis; 147 mg total inorganics) are added via syringe followed by monomer/stabilizer solution. Vacuum is applied until all of the hexane solvent is removed as indicated by system pressure dropping below 500 mtorr. KTO-46 photoinitiator (280 mg) is then added to the lauryl acrylate/quantum dot solution and well mixed using a magnetic stirrer.
90 mL of deionized water is charged to the beaker. To this is added Tween 80 (215 mg, 0.2% w/v) which is initially mixed for 30 minutes to dissolve and then cooled to 6° C. by setting the circulating bath temperature to a 2° C. setpoint. Once the temperature is reached, the monomer/QD solution is added subsurface via syringe creating a suspension of red colored beads. The IKA T25 rotor-stator is then immersed in the suspension and sheared at low speed (8000 rpm) until oil phase on top of reaction solution disappears and is incorporated into emulsion. Rotor stator is allowed to run for 1 minute at low-medium speed making sure that air entrainment is minimized. After 1 minute, the rotor-stator is shut off and the lamp is connected to power supply and quickly placed in the quartz photo well along with a Pyrex filter sleeve. Lamp is ignited and allowed to run for exactly 15 minutes. At the end of 15 minutes, power to the lamp is shut off. Solution is rose colored and cloudy but no visible particles are observed.
Material is checked under a microscope, microemulsion droplets can be seen with no obvious coalescence. Observed through a rhodamine filter, they show strong red emission as seen in FIG. 1:
To test for polymerization, slide is placed on a 120° C. hot plate until all liquid is evaporated. Spheres persisted as seen in FIG. 2.
The reaction suspension is divided equally into two 200 mL glass centrifuge tubes and 50 mL of methanol is added to each. Tubes are mixed by inversion and centrifuged for 15 minutes at 4,000 rpm. Methanol layer is decanted and washing step is repeated with additional 1×50 mL MeOH, 2×50 mL hexanes for each tube. Hexane saturated final paste is transferred to a round bottomed flask and solvent is removed in vacuo for 5 hours. Dry solid is transferred to a sample jar for storage. Yield 95% theoretical.
Deionized water is used. Lauryl methacrylate (Aldrich Chemical, 96% lot #08118DE) and ethylene glycol diacrylate (Aldrich Chemical, 98% lot #15017PD) are purified by passage through a short plug of activated Alumina in order to remove polymerization inhibitors. After passage through the column, the monomers are kept in a sealed, amber glass vial, refrigerated and used within 24 hours. Esacure KTO 46 photoinitator (Sartomer, lot #2008050005) and Tween 80 (Aldrich Chemical, SigmaUltra lot #037KO1551) are used without further purification. All other solvents are reagent grade and used without further purification.
Quantum dot/monomer preparation. A 50 mL Schlenk flask equipped with rubber septum and magnetic stirrer is charged with lauryl acrylate (6.08 g, 6.88 mL) and Ethylene glycol diacrylate (1.52 g, 1.39 mL). InP quantum dots in toluene (7 mL, 21 mg/mL on inorganic basis; 147 mg total inorganics) are added via syringe and vacuum is continued until all of the toluene solvent is removed as indicated by system pressure dropping below 500 mtorr. Esacure KTO-46 photoinitiator (0.28 g) is then added to the lauryl acrylate/quantum dot solution and well mixed using a magnetic stirrer.
89 mL of deionized water is charged to the beaker. To this is added Tween 80 (178 mg, 0.2% w/v) which is initially mixed for 30 minutes to dissolve and then cooled to 6° C. by setting the circulating bath temperature to a 2° C. setpoint. Once the temperature is reached, the monomer/QD solution is added subsurface via syringe creating a suspension of red colored beads. The IKA T25 rotor-stator is then immersed in the suspension and sheared at low speed (8000 rpm) until oil phase on top of reaction solution disappears and is incorporated into emulsion. Rotor stator is allowed to run for 10 minutes at low-medium speed making sure that air entrainment is minimized. After 10 minutes, the rotor-stator is shut off and the lamp is connected to power supply and quickly placed in the quartz photo well. Lamp is ignited and allowed to run for exactly 20 minutes. At the end of 20 minutes, power to the lamp is shut off. Rose colored and cloudy but no visible particles can be seen.
The reaction solution is checked under microscope and 1-10 μm particles are seen which fluoresce under rhodamine filter.
A drop of solution is placed on 100° C. microscope slide and film is allowed to form and heat for 10 minutes. Capsules agglomerate but none burst. Capsules have polymerized.
The reaction mixture is divided and transferred into two 200 mL centrifuge bottles with a small amount of deionized water. The tubes are brought up to 200 mL with methanol and shaken to mix causing a loose flocculate to form and spun at 4000 rpm for 20 minutes. The solids are at the bottom of the tube (tan in color) with a clear layer above it. The clear methanol layer is decanted and the wash procedure is repeated for total of 2×150 mL methanol, 2×100 mL hexanes. The solids are finally transferred to a round bottom flask with a small amount of hexanes and placed on a vacuum line for 4 hours to remove all residual solvent. Tan powder fluoresces with a string red emission when illuminated with 365 nm light. The dried, tan solid is transferred to a jar for storage.
Yield 6.97 g dried solid (87%) based on theoretical 7.99 g
Deionized water is used. Lauryl methacrylate (Aldrich Chemical, 96% lot #08118DE) and ethylene glycol diacrylate (Aldrich Chemical, 98% lot #15017PD) are purified by passage through a short plug of activated alumina in order to remove polymerization inhibitors. After passage through the column, the monomers are kept in a sealed, amber glass vial, refrigerated and used within 24 hours. Tween 80 (Aldrich Chemical, SigmaUltra lot #037KO1551), Esacure KTO 46 photoinitator (Sartomer, lot #8908062588)), photostabilizer Bis(1-octyloxy-2,2,6,6-tatramethyl-4-piperidyl)sebacate (HALS-3) and UV absorber 2-4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol (Tinuvin 1577) are obtained from Aldrich and used without further purification. All other solvents are reagent grade and used without further purification.
Colloidal InP/ZnS core/shell quantum dots including Octadecylphosphonie Acid (ODPA) (PCI, Lot #807001N09) and Decylamine ligands are dispersed in toluene (22 mg/mL), and have emissionmax=621 nm, quantum yield=60%, absorbance=584 nm, FWHM=56 nm, inorganics 67%.
Quantum dot/monomer preparation. A 50 mL septum vial equipped magnetic stirrer is charged with lauryl acrylate, ethylene glycol diacrylate, and octadecylphosphonic acid (ODPA). The mixture is stirred overnight during which time all solids are dissolved/dispersed. (ODPA showed some cloudiness). Care is taken not to expose solution to light.
A 50 mL Schlenk flask equipped with a septum and stir bar is placed under nitrogen by vacuum/refilling 3× with inert gas. InP quantum dots in hexanes are added via syringe followed by slow addition of the monomer/stabilizer solution over about 3 minutes. Vacuum is applied until all of the hexane solvent is removed as indicated by system pressure dropping below 200 mtorr. KTO-46 photoinitiator is then added to the lauryl acrylate/quantum dot solution and well mixed using a magnetic stirrer for 3 minutes.
190 mL of deionized water is charged to the beaker. To this is added Tween 80 previously dissolved in 10 mL water overnight. The solution is then cooled to 6° C. by setting the circulating bath temperature to a 17° C. setpoint. Once the temperature is reached, the monomer/QD solution is added subsurface via syringe creating a suspension of red colored beads. The IKA T25 rotor-stator is then immersed in the suspension and sheared at low speed (8000 rpm) until oil phase on top of reaction solution disappears and is incorporated into emulsion. Rotor stator is allowed to run for 2 minutes at low-medium speed making sure that air entrainment is minimized. After 1 minute, the rotor-stator is shut off and the lamp is connected to power supply and quickly placed in the quartz photo well along with a Pyrex filter sleeve. Lamp is ignited and allowed to run for exactly 15 minutes. At the end of 15 minutes, power to the lamp is shut off. Solution is rose colored and cloudy but no visible particles can be seen.
Material is checked under a microscope, microemulsion droplets can be seen with no obvious coalescence. To test for polymerization, the slide is placed on a 120° C. hot plate until all liquid is evaporated. Persistent spheres is taken as evidence of polymerization.
In a similar fashion, the pink pellet is resuspended and washed with hexane (2×100 mL) and xylene (2×100 mL). After the final centrate removal, the pellet is resuspended in the appropriate vehicle (see, e.g., below) and stored on a septum topped amber vial.
The external photoluminescent (PL) quantum efficiency is generally measured using the method developed by Mello et al. (See Mello et al., Advanced Materials 9(3):230 (1997), which is hereby incorporated by reference in its entirety). The method uses a collimated 450 nm LED source, an integrating sphere and a spectrometer. Three measurements are taken. First, the LED directly illuminates the integrating sphere giving the spectrum labeled L1 below. Next, the PL sample is placed into the integrating sphere so that only diffuse LED light illuminates the sample giving the (L2+P2) spectrum below. Finally, the PL sample is placed into the integrating sphere so that the LED directly illuminates the sample (just off normal incidence) giving the (L3+P3) spectrum below. (See FIG. 3). After collecting the data, each spectral contribution (L's and P's) is computed. L1, L2 and L3 correspond to the sums of the LED spectra for each measurement and P2 and P3 are the sums associated with the PL spectra for 2nd and 3rd measurements. The following equation then gives the external PL quantum efficiency:
US7625501 17 May 2005 1 Dec 2009 Ifire Ip Corporation Color-converting photoluminescent film
US7674844 29 Apr 2009 9 Mar 2010 Nanoco Technologies Limited Labelled beads
US7723394 17 Nov 2003 25 May 2010 Los Alamos National Security, Llc Nanocrystal/sol-gel nanocomposites
US7867413 14 Mar 2007 11 Jan 2011 Lg Chem, Ltd. Ink for ink jet printing and method for preparing metal nanoparticles used therein
US8404347 26 Jan 2009 26 Mar 2013 Hong Kong Polytechnic University Method of synthesis of amphiphilic magnetic composite particles
US8420155 9 Jun 2011 16 Apr 2013 Indiana University Research And Technology Corporation Alloyed semiconductor quantum dots and concentration-gradient alloyed quantum dots, series comprising the same and methods related thereto
US8440229 13 Aug 2008 14 May 2013 The Regents Of The University Of California Hollow silica nanospheres and methods of making same
US20020098217 29 Oct 2001 25 Jul 2002 Bertrand Piot Cosmetic composition comprising at least one fiber and at least one wax
US20050068154 21 Dec 2001 31 Mar 2005 Lutz Beste Method for identifying an individual module for short range wireless communication
US20050117868 1 Dec 2003 2 Jun 2005 Gang Chen Polymeric compositions comprising quantum dots, optical devices comprising these compositions and methods for preparing same
US20060083694 29 Apr 2005 20 Apr 2006 Cabot Corporation Multi-component particles comprising inorganic nanoparticles distributed in an organic matrix and processes for making and using same
US20060167147 24 Jan 2006 27 Jul 2006 Blue Membranes Gmbh Metal-containing composite materials
US20070087187 5 Oct 2006 19 Apr 2007 Ppg Industries Ohio, Inc. Nanostructured coatings and related methods
US20070087190 10 Aug 2004 19 Apr 2007 Kousuke Akiyama Oil-resistant sheet material
US20070197003 22 Sep 2005 23 Aug 2007 Brian Yen Flow method and reactor for manufacturing nanocrystals
US20080103250 21 Sep 2007 1 May 2008 Xerox Corporation Nanostructed particles, phase change inks including same and methods for making same
US20080115722 13 Dec 2007 22 May 2008 Massachusetts Institute Of Technology Flow method and reactor for manufacturing nanocrystals
US20080268249 21 Nov 2005 30 Oct 2008 Koiti Araki Stabilized Inorganic Nanoparticle, Stabilized Inorganic Nanoparticle Material, Method For Producing Stabilized Inorganic Nanoparticle, and Method For Using Stabilized Inorganic Nanoparticle
US20090143227 11 Jan 2006 4 Jun 2009 Nanosys, Inc. Porous substrates, articles, systems and compositions comprising nanofibers and methods of their use and production
US20110175250 15 Jan 2010 21 Jul 2011 Choon Sup Yoon Method of manufacturing flexible display substrate having low moisture and low oxygen permeability
US20110245533 28 Jan 2011 6 Oct 2011 Craig Breen Nanoparticle including multi-functional ligand and method
US20130075014 26 Nov 2012 28 Mar 2013 Nanosys, Inc. Methods for encapsulating nanocrystals and resulting compositions
CN101522557B 28 Feb 2007 20 Jun 2012 Lg化学株式会社 Ink for ink jet printing and method for preparing metal nanoparticles used therein
JP2008528722A Title not available
WO2006077256A1 23 Jan 2006 27 Jul 2006 Cinvention Ag Metal containing composite materials
WO2009014590A3 25 Jun 2008 30 Apr 2009 Qd Vision Inc Compositions and methods including depositing nanomaterial
WO2009014590A9 25 Jun 2008 19 Mar 2009 Qd Vision Inc Compositions and methods including depositing nanomaterial
WO2011031876A1 9 Sep 2010 17 Mar 2011 Qd Vision, Inc. Formulations including nanoparticles
1 Bin, X., et al., "High-quality CdTe Quantum Dots Synthesized in Liquid Paraffin Wax", ISSN, 2008 29. (2) Abstract.
2 Boev, V.I., et al., "Incorporation of CdTe nanoparticles from colloidal solution into optically clear ureasilicate matrix with preservation of quantum size effect", Solid State Sciences, vol. 8, (2006) pp. 50-58.
3 Budriene, S., et al "Preparation of Lipophillic Dye-Loaded (Vinyl Alcohol) Microcapsules and Their Characteristics", Chemija (Vilnius), 2002, T. 13, Nr. 2, 103-106.
4 Cameron, N.R., et al., "Non-Aqueous High Internal Phase Emulsions Preparation and Stability", J. Chem. Soc., Faraday Trans., 1996, 92(9), pp. 1543-1547.
5 Chatterjee, J., et al., "Synthesis of Polyethylene Magnetic Nanoparticles", European Cells and Materials, vol. 3, Suppl. 2, 2002 (pp. 98-101).
6 Ciba Tinuvin 1130 product brochure-Ciba Specialty Chemicals-Coating Effects Segment (Edition: 15.12.97 Basle).
7 Ciba Tinuvin 477 DW product brochure-Ciba Specialty Chemicals-Coating Effects Segment (Edition 02:05.05, Basle-Copyright 2005 Ciba Specialty Chemicals Inc.).
8 Ciba Tinuvin 5000 Series product brochure entitled "High value light stabilizer blends for coatings", Ciba, Inc., (c-Aug. 2009, printed in Switzerland).
9 Crespy, D., et al., "Making dry fertile: a practical tour of non-aqueous emulsions mini-emulsions, their preparation and some applications", Soft Matter, 2011, 7, pp. 11054-11064
10 Dabbousi et al., "(CdSe)ZnS Core-Shell Quantum Dots: Synthesis and Characterization of a Size Series of Highly Luminescent Nanocrystallites", J. Phys. Chem B. 101, pp. 9463-9475 (1997).
11 De Mello, J.C., et al., "An Improved Experimental Determination of External Photoluminescence Quantum Efficiency", Advanced Materials 9(3):230(1997).
12 Dubertret, B., et al. "In vivo Imaging of Quantum Dots Encapsulated in Phospholipid Micelles", Science vol. 298, Nov. 2002 (pp. 1759-1762).
13 European Supplemental Search Report mailed Dec. 8, 2014 in European Patent Application No. 10 816 085.4. EP10 816 085.4 is the European counterpart of copending U.S. Appl. No. 13/414,417.
14 Fechine, et al, "Evaluation of poly(ethylene terephthalate) photostabilisation using FTIR spectrometry of evolved carbon dioxide", Polymer Degradation and Stability 94 (2009) 234-239.
15 Garner, B., et al., "Electric Field Enhanced Photoluminescence of CdTe Quantum Dots Encapsulated in Poly (N-Isopropylacrylamide) Nano-Spheres", Optics Express vol. 16, No. 24, 19410-19418 (2008).
16 Iwamoto, "Production of Gold Nanoparticles-Polymer Composite by Quite Simple Method", Eur. Phys. J.D. 24, 365-367 (2003).
17 Jayaweera, P.V.V., et al., "Displacement Currents in Semiconductor Quantum Dots Embedded Dielectric Media: A Method for Room Temperature Photon Detection", Applied Physics Letters, 91 063114 (2007).
18 Kim, S., et al., "Oligomeric Ligands for Luminescent and Stable Nanocrystal Quantum Dots", J. Am. Chem. Soc., 2003, 125, pp. 14652-14653.
19 Klapper, et al., "Oil-in-Oil Emulsions: A Unique Tool for the Formation of Polymer Nanoparticles", Accounts of Chemical Research 2008, Vol, 41, No. 9, pp. 1190-1201.
20 Lee, J., et al,, "Full Color Emission from II-VI Semiconductor Quantum Dot-Polymer Composites", Advanced Materials, 2000, 12, No. 15, Aug. 2.
21 Machol, J.L., et al., "Optical studies of IV-VI quantum dots", Physica A vol. 207 (1994), pp. 427-434.
22 Meszaros, et al., "Photooxidation of poly[methyl](phenyl)silylene] and effect of photostabilizers", Polymer Degradation and Stability 91 (2006) 573-578.
23 Mueller, W., et al. "Hydrophobic Shell Loading of Pb-b-PEO Vesicles", Macromolecules 2009 42, 357-361.
24 Murray, C. "Synthesis and Characterization of II-VI Quantum Dots and Their Assembly into 3-D Quantum Dot Superlattices", Thesis, Massachusetts Institute of Technology, Sep. 1995.
25 Murray, C. B., et al., "Synthesis and Characterization of Nearly Monodisperse CdE (E = S, Se, Te).Semiconductor Nanocrystallites", J. Am. Chem. Soc. 1993, 115, 8706.
26 Nikolic, M., Dissertation entitled Encapsulation of Nanoparticles within Poly(ethylene oxide) Shell, University of Hamburg 2007.
27 Office Action (Final) mailed Jan. 27, 2015 in copending U.S. Appl. No. 12/874,357.
28 Office Action (Final) mailed Jul. 3, 2013 in copending U.S. Appl. No. 12/727,941.
29 Office Action (first) dated Jun 3, 2013 in Chinese Patent Application No. 2010-80040045.1 CN2010-80040045 is the Chinese counterpart of copending U.S. Appl. No. 13/414,417.(Chinese language).
30 Office Action (first) dated Jun. 3, 2013 in Chinese Patent Application No. 2010-80040045.1 CN2010-80040045 is the Chinese counterpart of copending U.S. Appl. No. 13/414,417. (Engl. Transl.).
31 Office Action (first) dated Mar. 4, 2014 in Japanese Patent Application No. 2012-528899. JP2012-528899 is the Japanese counterpart of copending U.S. Appl. No. 13/414,417. (Engl. Transl.).
32 Office Action (first) dated Mar. 4, 2014 in Japanese Patent Application No. 2012-528899. JP2012-528899 is the Japanese counterpart of copending U.S. Appl. No. 13/414,417. (Japanese).
33 Office Action (Nonfinal) mailed Jan. 16, 2015 in copending U.S. Appl. No. 12/727,941.
34 Office Action (Nonfinal) mailed May 30, 2014 in copending U.S. Appl. No. 12/874,357.
35 Office Action (Nonfinal) mailed Oct. 8, 2014 in copending U.S. Appl. No. 13/414,417.
36 Office Action (Nonfinal) mailed Sep. 5, 2012 in copending U.S. Appl. No. 12/727,941.
37 Office Action (second) & Supplementary Search Report dated Apr. 28, 2014 in Chinese Patent Application No. 2010-800400451. CN2010-80040045 is the Chinese counterpart of copending Application No. 13/414417. (Chinese).
38 Office Action (second) & Supplementary Search Report dated Apr. 28, 2014 in Chinese Patent Application No. 2010-800400451. CN2010-80040045 is the Chinese counterpart of copending Application No. 13/414417. (Engl. Transl.).
39 Pan Jiangqing, et al., Study on the Photolysis Mechanism of Polyester From Succinic Acid and N-beta-Hydroxyethyl 2,2,6,6-tetramethyl-4 hydroxy piperidine (Tinuvin-622), Chinese Journal of Polymer Science, vol. 6, No. 4 (1988).
40 Pan Jiangqing, et al., Study on the Photolysis Mechanism of Polyester From Succinic Acid and N-β-Hydroxyethyl 2,2,6,6-tetramethyl-4 hydroxy piperidine (Tinuvin-622), Chinese Journal of Polymer Science, vol. 6, No. 4 (1988).
41 PCT International Search Report and Written Opinion mailed Nov. 8, 2010 in International Application No. PCT/US2010/048285 of QD Vision, Inc. (which is the patent of copending U.S. Appl. No. 13/414,417).
42 PCT International Search Report and Written Opinion mailed Oct. 22, 2010 in International Application No. PCT/US2010/48291 of QD Vision, Inc. (which is the parent of the present application).
43 PCT International Search Report and Written Opinion mailed Oct. 29, 2009 in International Application No. PCT/US2009/001372 of QD Vision, Inc. (which is the parent of copending U.S. Appl. No. 12/874,357).
44 Peter, W., et al., "Advancements in Novel Encapsulated Light Stabilizers for Waterborne Coatings", PCIMAG.com, Aug. 2008, pp. 44-50.
45 Petersen, et al., "Studies on Nonaqueous Emulsions", J. Soc. Cosmetic Chemists, 19, (1968), pp. 627-640.
46 Primary Search Report dated Jun. 3, 2013 in Chinese Patent Application No. 2010-80040045.1. CN2010-80040045 is the Chinese counterpart of copending U.S. Appl. No. 13/414,417. (Engl. Transl.).
47 Sakthivel, et al., "Non-aqueous emulsions: hydrocarbon-formamide systems", International Journal of Pharmaceutics, 214 (2001), pp. 43-48.
48 Sheng, et al., "In-Situ Encapsulation of Quantum Dots into Polymer Microspheres", Langmuir 2006, vol. 22, pp. 3782-3790.
49 Shojaei-Zadeh, S., et al., "Encapsulation of Multicolored Quantum Dots in Polystyrene Beads Using Microfluidic Devices", American Institute of Chemical Engineers, 2008 Annual Meeting-Conference.Proceedings, Engineering Sciences and Fundamentals.
50 Sipos, et al., "The Ultraviolet Absorption Spectra of Synthetic Bayer Liquors", J. Chem. Soc., Chem. Commun., (1994), pp. 2355-2356.
51 SpecialChem S.A., "Hindered Amine Stabilizers" web page for SpecialChem4Adhesives, Copyright 2010 (incomplete).
52 SpecialChem S.A., "Hindered Amine Stabilizers" web page for SpecialChem4Adhesives, Copyright 2014.
53 Thomas, V., et al., "Review on Polymer, Hydrogel and Microgel Metal Nanocomposites: a facile Nanotechnological Approach", Journal of Macromolecular Science, (2008) 45, 107-119.
54 Wang, et al., "Composite Photonic Crystals from Semiconductor Nanocrystal/Polyelectrolyte-Coated Colloidal Spheres", Chem. Mater., 15 (2003), pp. 2724-2729.
55 Ye, Xinyu, et al., "Zinc Sulfide Nanocrystals in Paraffin Liquid Open to Air: Preparation, Structure, and Mechanism", Chemistry Letters vol. 36, No. 11 (2007) 1376-1377.
56 Zwiller, V., et al., Quantum Optics With Single Quantum Dot Devices, New Journal of Physics, 6 (2004) 96.
US20160355730 * 4 Apr 2016 8 Dec 2016 Qd Vision, Inc. Formulations including nanoparticles
International Classification C08K9/10, C08K13/02
Cooperative Classification C08K5/3435, C08K13/02, C09D7/1241, C09K11/703, C08K5/3492, Y10S977/83, C09K11/025, C09D7/1225, Y10S977/834, C08F2220/1883, C09K11/02, B01J13/18, C09D5/24, C09D5/22, C08K9/10, B82Y20/00, C08K2201/001, C08F220/18, C08K2201/011, C08L33/00
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