PROCESS FOR THE PRODUCTION OF A LIGHT CONVERTER; LIGHT CONVERTER; LIGHTING DEVICE; AND LIQUID CRYSTA

专利摘要:
process for producing a light converter; light converter; lighting device; and liquid crystal display device The present invention provides a process for producing a light converter comprising a polymer matrix of siloxane with light converter nanoparticles incorporated therein, the process comprising (a) mixing (i) the converter nanoparticles of light having an outer surface grafted with graft binders and (ii) curable siloxane polymers, and (b) curing the curable siloxane polymers, thus producing the light converter; wherein the graft binders comprise siloxane graft binders having x1 structural elements of it, wherein at least one structural element of each siloxane graft binder comprises a side group having graft functionality; wherein the curable siloxane polymers have y1 structural elements of them; and where x1 is at least 20, where y1 is at least 2, and where x1/y1 >1.
公开号:BR112015009085B1
申请号:R112015009085-0
申请日:2013-10-23
公开日:2021-06-15
发明作者:Roelof Koole；Rifat Ata Mustafa Hikmet；Patrick John Baesjou；Mercel Rene Bohmer；Johan Lub
申请人:Lumileds Holding B.V.；
IPC主号:

专利说明:

FIELD OF THE INVENTION
[001] The invention relates to a process for the production of a polymer within the nanoparticles of the light converter incorporated in the polymer, a light converter thus obtained and a lighting unit comprising such a light converter (polymeric). HISTORY OF THE INVENTION
[002] The use of nanoparticles, such as quantum dots (QD), for lighting applications is known in the art. Document US20110240960, for example, describes a light emitting device comprising a light emitting source, a first quantum dot wavelength converter disposed above the light emitting source, the first dot wavelength converter comprising, a plurality of first quantum dots for generating wavelength converted light by wavelength converting light from the light emission source, a first dispersive means incorporating the first quantum dots dispersively therein, and a first sealant to seal the entire outer surface of the dispersive medium that incorporates the first quantum dots in a package.
[003] A first encapsulant is applied to encapsulate the entire outer surface of the first quantum dot wavelength converter. In addition, a second quantum dot wavelength converter is disposed above the first quantum dot wavelength converter, the second quantum dot wavelength converter comprising a plurality of second quantum dots for generating length converted light by converting the wavelength of light from the light emitting source, a second dispersive medium incorporating the second quantum dots dispersively there, in a second sealant to seal the entire outer surface of the second dispersive medium incorporating the second dots in a package, in which the first quantum dot wavelength converter, the second quantum dot wavelength converter, and the light emission source are moved away from each other. The second encapsulant is deposited on the entire outer surface of the second quantum dot wavelength converter and to encapsulate the entire outer surface of the second quantum dot wavelength converter. Also, the light emitting source is a light emitting diode or a laser diode.
[004] J.Mat. Chemistry C, vol. 1 (2012), p 86 to 94 describes bimodally grafted nanoparticles that are dispersed in siloxanes (abstract; scheme 1; page 90, upper left column; § 4). This document describes transparent luminescent silence nanocomposites filled with CdSe quantum dots grafted with a PMDS brush.
[005] The document US2010/276638A1 describes matrices doped with semiconductor nanocrystals. In certain embodiments, semiconductor nanocrystals are of a size and composition such that they absorb or emit light at particular wavelengths. Nanocrystals can comprise binders that allow mixing with various matrix materials so that a minimal amount of light is scattered across the matrices. Matrices are optionally formed from the binders. SUMMARY OF THE INVENTION
[006] Nanoparticles, such as quantum dots (QDs), have shown to be highly interesting in lighting applications. They could, for example, serve as an inorganic phosphor in converting blue light to other colors and have the advantage of a relatively narrow emission band and the advantage of the size-adjustable color of the QDs being able to obtain high quality pure white light.
[007] In order to use the QDs for LED applications, they need to be embedded in a suitable matrix. A QD powder (without matrix) is not desired because of both concentration and low process ability quenching effects of such pure QD powder. Until now, the incorporation of nanoparticles in many types of polymers seems to lead to aggregation of nanoparticles. Currently, acrylic matrices are mainly used as a matrix for QDs, but they are known for their poor stability towards high blue light fluxes. Silicones are considered the most preferred matrix for QDs because of the proven stability of silicones towards high blue fluxes (ie, their proven compatibility with LEDs).
[008] Silicones are currently used as a standard matrix/resin for many LED manufacturing processes. However, QDs often have a hydrophobic organic coating (in the form of binders, usually extending from the outer surface of the QD) that makes them incompatible with silicones: usually a cloudy mixture is obtained when QDs are mixed with silicones caused by agglomeration of the QDs . This is undesired because of concentration extinction effects, expected increased degradation effects, and an undesired processing pathway of these films that lead to spatial concentration variations. It can be said that there is no example of QDs (with coordination ligands) that are truly miscible with optional silicones.
[009] In summary, a more general way to improve the miscibility of QDs for optional silicones is highly desired. Therefore, it is an aspect of the invention to provide an alternative nanoparticle-polymeric system, especially a polymeric quantum dot system. Especially, it is an aspect of the invention to provide an alternative process for producing such a polymer with embedded nanoparticles. Furthermore, it is an aspect of the invention to provide an alternative light converter with nanoparticles incorporated therein. Still, it is another aspect to provide an alternative lighting unit comprising such a polymer with built-in QDs. Preferably, the alternative process and/or the alternative light converter and/or the alternative lighting unit at least partially obviates one or more of the drawbacks described above (and also others described below) of the prior art solutions.
[010] Surprisingly, the inventors have found among others that by exchanging the native QD ligands of the light converter nanoparticles for particular PDMS-type ligands, the QDs can become truly miscible with silicones and/or significantly improve miscibility with silicones under conditions specific are met. Furthermore, advantageously there is no need to use significant amounts of additional solvents such as hexane and acetone, or other solvents to obtain a well miscible system.
[011] Therefore, in a first aspect, the invention provides a process for the production of a light converter comprising a polymer matrix of siloxane with light converter nanoparticles (herein also referred to as "nanoparticles") incorporated therein, the process comprising: (a) mixing (i) the light converter nanoparticles having an outer surface grafted with graft binders and (ii) curable siloxane polymers, and (b) curing the curable siloxane polymers, thereby producing the converter light;- wherein the graft binders comprise siloxane having x1 Si structural elements, wherein at least one Si structural element of each siloxane graft binder comprises a side group having a graft functionality such as a side group selected from the group consisting of an amine comprising the side group or a carboxylic acid comprising the side group (although other functional groups are also possible, see below); - wherein the curable siloxane polymers have y1 structural elements of Si;- wherein x1 is especially at least 20, such as especially at least 40, even more especially at least 50, where y1 is especially at least 2, such as at least 7, as at least 10, and where x1/y1 ^ 0.8 > 1, as at least > 1.2.
[012] Nanoparticles are light converting nanoparticles, which can be specially configured to provide, upon excitation by UV and/or blue light, luminescence in at least part of the visible part of the spectrum. Therefore, these particles are also referred to here as light converter nanoparticles, of which the QDs (quantum dots) are a specific realization.
[013] Such a light converter, obtainable by the process described here, can show luminescence (when incorporated into the matrix of cured siloxane polymers) with a high yield and quantum stability. Furthermore, the light converter can be relatively temperature stable and/or photochemical and/or transparent. Furthermore, with this process, nanoparticles can be dispersed in the polymer in an even relative manner, without the substantial disadvantage of agglomeration.
[014] Therefore, in a further aspect, the invention also provides a light converter, obtainable by the process of the invention. Especially, the invention also provides the light convertor (per se) comprising a (cured) siloxane polymer (matrix) with light convertor nanoparticles incorporated herein, wherein: (a) the light convertor nanoparticles have an outer surface grafted with binders, and(b) the siloxane polymer matrix comprises crosslinked siloxane polymers;- wherein the binders comprise siloxane graft binders having x1 Si structural elements, wherein at least one Si structural element of each Si binder siloxane graft comprises a side group having a graft functionality (such as, for example, selected from the group consisting of an amine comprising side group or a carboxylic acid comprising side group); - wherein the curable siloxane polymers have y1 elements structural Si;- where x1 is especially at least 20, such as especially at least 40, even more especially at least 50, such as at least 80, where y1 is especially at least 2, such as at least 7, such as at least 10, and where x1/y1 > 1, such as at least > 1.2.
[015] As these light converters can be well applied in lighting devices, the invention provides in a further aspect, a lighting device comprising:- a light source configured to generate light from the light source (i.e., light source light), - a light converter obtainable by the process as defined herein and/or as defined per se, configured to convert at least part of the light source light into visible light from the converter.
[016] In a still further aspect, the invention also provides a liquid crystal display device comprising one or more backlighting units, wherein the one or more backlighting units comprise one or more lighting devices as defined on here.
[017] The term light converter refers to a system that is configured to convert light of a first wavelength into light of a second wavelength. Especially, UV and/or blue light (excitation wavelength) can be (at least partially) converted to visible light (of a wavelength longer than the excitation wavelength). This will be further elucidated below; first, some aspects concerning siloxane polymer, graft binders and curable siloxane polymers are described, as well as realizations of a process to obtain the light converter.
[018] Silicones, more precisely called siloxanes or polymerized or polymerizable polysiloxanes, are organic-inorganic polymers mixed with the chemical formula [(R1,R2)SiO]n (not taking into account the terminal groups), where R is such a group as, for example, hydrogen, hydrocarbon or fluorocarbon, especially methyl, ethyl, or phenyl. Especially, one or more R groups of one or more structural elements of Si comprise one or more of hydrocarbon and fluorocarbon. One or more of these side groups can also have cross-linking functionality, such as a vinyl group.
[019] These polymerized siloxanes or polysiloxanes materials consist of an inorganic oxygen-silicon structure (—Si-O-Si-O-Si-O—) with organic side groups attached to the silicon atoms, which are four coordinates. As the side groups R can in principle be different, instead of the formula [(R2)SiO]n also the formula [(R1,R2)SiO]n (not taking into account the end groups) can be applied. Note that here x1 and y1 are applied to the number of Si elements in the siloxane structure for the graft binders and siloxane (curable) polymers (which form the host material), respectively.
[020] The fact that here only R, or more precisely, R1,R2 are mentioned, does not exclude that different structural elements of Si can comprise the same side groups, but also more than two different types of side groups can be understood by silicone . Therefore, R can, for example, among others, be selected from the group consisting of methyl, phenyl, etc. Also halogens, mainly chlorine, are possible as the R-side compound. In addition, [R2SiO], or [-Si(R)2-O-] refers to the silicone unit or silicone characterizing group (ie, group which features a silicone).
[021] A siloxane is any chemical compound composed of units of the form R2SiO, where R is, for example, among others, a hydrogen atom, a hydrocarbon group, or one or more R2SiO units combined with a terminal group. Siloxanes can have branched or unbranched structures consisting of alternating silicon and -Si-O-Si-O- oxygen atoms with R side chains attached to the silicon atoms. Polymerized siloxanes with organic side chains (R ± H) are commonly known as silicones or as polysiloxanes. Here, these are also referred to as "siloxanes" or "siloxane polymers". Representative examples are [SiO(CH3)2]n (polydimethylsiloxane) and [SiO(C6H5)2]n(polydiphenylsiloxane). These compounds can be seen as a hybrid of both organic and inorganic compounds. Organic side chains confer hydrophobic properties, while the -Si-O-Si-O- structure is purely inorganic. As indicated above, the Si elements in the structure are also denoted here as Si structural elements. A siloxane [R2SiO]n comprises n Si structural elements. Therefore, any siloxane R2SiO characterization portion provides a silicon structural element ( which has two side groups). Note that, for example, PDMS is CH3[Si(CH3)2O]nSi(CH3)3, has n+1 Si elements, so in fact n+1 Si structural elements. Such a siloxane would be used as a graft binder , x1=n+1; such siloxane would be used as siloxane polymer to cure, y1=n+1. Furthermore, PDMS (see formula) has n-1 non-terminal Si structural elements.
[022] By varying the -Si-O- chain lengths, side groups, and crosslinking silicones can be synthesized with a wide variety of properties and compositions. They can range in consistency from liquid to gel to rubber to hard plastic.
[023] The most common siloxane is linear polydimethylsiloxane (PDMS; see above), a silicone oil. The second broadest group of silicone materials is based on silicone resins, which are formed by the branched and cage-like oligosiloxanes.
[024] Here, especially linear siloxanes are used as curable siloxane polymers and/or siloxane graft binders. However, also non-linear siloxanes can be used as curable siloxane polymers and/or siloxane graft binders. Also, as the siloxanes are cured, the light converter will typically be a solid light converter (solid polymeric light converter). Nevertheless, the light converter can, in one embodiment, be flexible.
[025] As indicated above, graft binders comprise siloxane graft binders having x1 Si structural elements; especially, the graft binders are siloxane graft binders (having x1 Si structural elements). The term "graft binder" refers to a ligand that coordinates or is attached to the outer surface of a light converting nanoparticle (such particles are also elucidated below), such as quantum dots. Graft binders are, for example, known in the art, and are, for example, described in WO/2009/035657, WO/2010/014198 and WO/2008/063653 etc. Graft binders are sometimes also referred to as capping binders.
[026] Graft binders comprise siloxane molecules, which will generally have the commonly known side groups, but also have at least one side group that has graft functionality. The side group having a graft functionality can be selected from the group consisting of an amine and a carboxylic acid. For example, the amine can be -NH2 or COOH, but it can also be -R-NH2 or R-COOH, respectively, where R is a hydrocarbon, preferably comprising less than 20 carbon atoms. However, the side group having graft functionality may also comprise a phosphine, a phosphine oxide, a phosphate, a thiol, etc. (and in combinations of performing two or more of them). Therefore, graft binders are siloxane molecules, which will generally have the commonly known side groups, but also have at least one side group that has graft functionality selected from the group consisting of an amine, a carboxylic acid , a phosphine, a phosphine oxide, a phosphate, a thiol, even more especially an amine, a carboxylic acid, a phosphine, a phosphine oxide, and a phosphate. The linker may, in one embodiment, comprise a plurality of side groups which have a graft functionality which may comprise different types of such side groups (or which may all be identical). A structural element of Si can also comprise two side groups that have a grafting functionality. The term “side group that has graft functionality” refers to a side group (not an end group) that has the ability to graft onto a luminescent nanoparticle, as described here. Therefore, the side group that has graft functionality provides siloxane with its grafting ability (and thus graft binder functionality).
[027] Therefore, especially the side group is a side group of a non-terminal Si structural element (see also below). The amine can be grafted as an amine onto the outer surface of the luminescent nanoparticle; the carboxylic acid can be grafted as a carboxylate to the luminescent nanoparticle. In particular, it appears that the functional groups should be specially arranged as side groups and not as end groups. Therefore, especially graft binders comprise siloxane molecules that have end groups that do not comprise a group selected from the group consisting of an amine, a carboxylic acid, a phosphine, a phosphine oxide, a phosphate, and a thiol; that is, having no end groups that (substantially) have graft functionality. Graft binders especially have side groups with graft functionality for the semiconductor quantum dots indicated here, especially the CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe nanoparticles , ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeS, CdZnSeT, GanSe, CdZnSe, CdZnSTe , AlN, AlP, AlAs, InN, InP, InAs, GaNP, GaNAs, GaPAs, AlNP, AlNAs, AlPAs, InNP, InNAs, InPAs, GaAlNP, GaAlNAs, GaAlPAs, GaInNP, GaInNAs, GaInPAs, InAlNP, InAlNAs, and InAlPAs indicated here, especially the sulfides, tellurides and selenides.
[028] Side groups that have graft functionality can be arranged anywhere in the siloxane structure of the graft binder. Assuming linear siloxane with x1 silicon structural units, then especially the one (or more) side group(s) that has (have) a functional group are found between 20 to 80% of the length of the structure. Assuming, for example, that the structure comprising 50 structural elements of Si, especially the side group having graft functionality is found in Si No. 10, or Si No. 40 or between (with Nos. 1 and 50 being end groups ).
[029] There is at least one such side group, although optionally there may be more than one side group that has a graft functionality such as selected from the group consisting of an amine and a carboxylic acid, or others such as a phosphine, an oxide of phosphine, a phosphate, a thiol. The number of such side groups which have a grafting functionality may depend on the chain length of the siloxane grafting binder, but especially does not exceed the number of 10. Therefore, especially not more than up to 10 Si structural elements (not being terminal Si structural elements) of each siloxane graft linker comprise a side group having graft functionality. Especially not more than 10 Si structural elements (not being terminal Si structural elements) of each siloxane graft binder comprise a side group (having a graft functionality) selected from the group consisting of a side group comprising amine, a group a side group comprising carboxylic acid, a side group comprising phosphine, a side group comprising phosphine oxide, a side group comprising phosphate, and a side group comprising thiol. When more than one sidegroup that has a grafting functionality is present, especially the percentage of the sidegroups that have a grafting functionality is equal to or less than 5% by mol (of all structural sidegroups R1,R, no more 5% comprises such a functional group), even more especially the percentage of the side groups which have a graft functionality is equal to or less than 2.5% by mol. Hence, assuming, for example, 22 Si structural elements (thus including two terminal Si structural elements), there are 40 side groups available; when 5% of them would have graft functionality, this would imply that up to two lateral groups would have graft functionality; the others would not have graft functionality, such as methyl, phenyl, etc. That plurality (p) of side groups having graft functionality can be distributed over p/2-p silicone structural units.
[030] Note that the terms “graft binder” or “siloxane graft binder” can also refer to a plurality of different types of graft binders. In one embodiment, these graft binders are substantially identical. However, in another embodiment, the graft binders can comprise a plurality of different graft binders. For example, they may differ in chain length (x1), and/or they may differ in side groups, and/or they may differ in side groups that have a graft functionality, and/or they may differ in the number of side groups which have a grafting functionality and/or may differ in the position of the side groups which have a grafting functionality (and/or differ in the type of the end groups). For example, siloxane graft binders can comprise a plurality of siloxane polymers, each having only one side group (amine), but in which the position of the side group (amine) is randomly distributed over the siloxane polymers.
[031] In general, curable siloxane polymers, or siloxane polymers (crosslinked) of the light converter (polymeric device) do not have one or more side groups that have a graft functionality selected from the group consisting of an amine and a carboxylic acid. Except for the side groups which have a graft functionality, information stated above with respect to siloxane graft binders substantially also applies to curable siloxane polymers.
[032] Except for the side groups which have a grafting functionality, information given above with respect to siloxane graft binders substantially also applies to curable siloxane polymers.
[033] The term "curable siloxane polymers" can also refer to a plurality of different types of curable siloxane polymers. In one embodiment, these curable siloxane polymers are substantially identical. However, in another embodiment, the curable siloxane polymers can comprise a plurality of different curable siloxane polymers. For example, they may differ in chain length (y1), and/or they may differ in (type of) sidegroups. Also, they may differ in the type of end group. Curable siloxane polymers can have end groups that are configured to form crosslinks upon curing. Note that additionally or alternatively, also one or more side groups per curable siloxane polymer can be configured to form a crosslink upon cure. For example, side groups can include a vinyl group (or a hydrogen group). As can be understood from the above, curable siloxane polymers can comprise end groups and/or side groups that are configured to form crosslinks upon curing.
[034] In a specific embodiment, x1 is at least 40, such as at least 50, especially at least 80. Better and/or more stable systems can then be obtained. In one embodiment, x1 is not greater than 2000, especially not greater than 1000, such as not greater than 800. In a specific embodiment, x1 is in the range of 40 to 1000, such as 40 to 800, such as 100 to 800. As per mentioned above, a combination of different graft binders can be applied; in such an example x1 is the mean value (weight).
[035] Furthermore, y1 is at least 7, such as especially at least 10, and especially not greater than 400, such as not greater than 200. As mentioned above, a combination of different curable siloxane polymers can be applied; in such an example y1 is the mean value (weight).
[036] Furthermore, good results can be obtained with x1/y1 ^ 0.80, but in general better results, in the sense of stability and/or transmission (of the light converter) are obtained when x1/y1 > 0.95, such as x1/y1>1,2.
[037] Especially, graft binders and curable siloxane polymers are chemically substantially identical. This could, for example, mean that both graft binders and curable siloxane polymers are polymethyl siloxanes or polyphenyl siloxanes or polymethylphenyl siloxanes (especially 50/50), with the graft binders having at least one side group that is a side group that has a grafting functionality.
[038] In a specific embodiment, at least 75%, especially 80%, even more especially 85%, even more especially at least 90%, such as especially at least 95% of the side groups of siloxane graft binders and polymers from Curable siloxane overlap in chemical identity. The overlap in chemical identity can be assessed by determining the percentages of specific side groups in the graft binders and curable siloxane polymers and counting the overlapping parts of the percentages. For example, in a hypothetical example, when a siloxane graft binder comprises 72% methyl and 25% phenyl side groups, and curable siloxane polymers comprise 66% methyl and 29% phenyl side groups, then the sum of the overlap percentages is 66% + 25% = 91%. Therefore, such siloxane graft binders and curable siloxane polymers are substantially identical chemicals.
[039] As indicated above, siloxane graft binders and/or curable siloxane polymers may comprise a plurality of different molecules, respectively. In such a case, average values are used. For example, suppose a first siloxane graft linker that has 74% methyl and 22% phenyl side groups and a second siloxane graft linker that has 70% methyl and 28% phenyl side groups, then the average percentages are 72% methyl and 25% phenyl.
[040] In a specific embodiment, at least 75%, especially 80%, even more especially 85%, even more especially at least 90%, such as especially at least 95% of the structural elements of Si (not including end groups) of the siloxane graft binders have methyl side groups, and especially at least 75%, especially 80%, even more especially 85%, even more especially at least 90%, such as especially at least 95% of Si structural elements (not including end groups) of siloxane polymers (curable) have methyl side groups. Therefore, in one embodiment, the siloxane polymer (matrix) (solid) and the siloxane graft binders comprise polydimethyl siloxane polymers. Assuming a siloxane comprising 10 silicon structural units (not including end groups), and 90% methyl side groups, 16 methyl side groups will be present.
[041] Especially, the siloxanes for both graft binder and curable siloxane polymers are 100% methyl side groups, or 50/50 methyl/phenyl side groups (with graft binders at least one side group is , however, a side group which has graft functionality, so such side group is not only methyl or phenyl, but alternatively or additionally comprises, for example, an amine or carboxylic acid).
[042] In yet another embodiment, at least 75%, especially 80%, even more especially 85%, even more especially at least 90%, such as especially at least 95% of the structural elements of Si (not including the end groups) of the siloxane graft binders have phenyl side groups and at least 75%, especially 80%, even more especially 85%, even more especially at least 90%, such as especially at least 95% of the structural elements of Si (not including end groups) of siloxane polymers have phenyl side groups.
[043] As will be clear, end groups may also comprise methyl, phenyl, or other groups, such as optionally groups that have cross-linking functionality.
[044] Quantum dots or luminescent nanoparticles, which are here indicated as light converter nanoparticles, may, for example, comprise semiconductor quantum dots of group II-VI compound selected from the group consisting of CdS, CdSe, CdTe, ZnS , ZnSe, ZnTe, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, HgSnTe, CdZdHg , CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe and HgZnSTe. In another embodiment, the luminescent nanoparticles may, for example, be group III-V compound semiconductor quantum dots selected from the group consisting of GaN, GaP, GaAs, AlN, AlP, AlAs, InN, InP, InAs, GaNP, GaNAs, GaPAs, AlNP, AlNAs, AlPAs, InNP, InNAs, InPAs, GaAlNP, GaAlNAs, GaAlPAs, GaInNP, GaInNAs, GaInPAs, InAlNP, InAlNAs, and InAlPAs. In yet another embodiment, the luminescent nanoparticles can, for example, be semiconductor quantum dots type chalcopyrite I-III-VI2 selected from the group consisting of CuInS2, CuInSe2, CuGaS2, CuGaSe2, AgInS2, AgInSe2, AgGaS2, and AgGaSe2. In yet another embodiment, the luminescent nanoparticles may, for example, be semiconductor quantum dots I-V-VI2, such as selected from the group consisting of LiAsSe2, NaAsSe2 and KAsSe2. In yet another embodiment, the luminescent nanoparticles can, for example, be semiconductor nanocrystals of a group IV-VI compound such as SbTe. In a specific embodiment, luminescent nanoparticles are selected from the group consisting of InP, CuInS2, CuInSe2, CdTe, CdSe, CdSeTe, AgInS2 and AgInSe2. In yet another embodiment, the luminescent nanoparticles can, for example, be one of the semiconductor nanocrystals of the compound of group II-VI, III-V, I-III-V and IV-VI selected from the materials described above with dopants inside, such as ZnSe:Mn, ZnS:Mn. The doping elements could be selected from Mn, Ag, Zn, Eu, S, P, Cu, Ce, Tb, Au, Pb, Tb, Sb, Sn and Tl. Here, luminescent nanoparticles based on luminescent material can also comprise different types of QDs, such as CdSe and ZnSe:Mn.
[045] It seems to be especially advantageous to use quantum dots II-VI. Hence, in one embodiment, semiconductor-based luminescent quantum dots comprise quantum dots II-VI, specially selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe , ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe and HgZnSTe also more specially selected from the group consisting of CdS, CdSe, CdSe/CdS and CdSe/CdS/ZnS.
[046] In one embodiment, QDs without Cd are applied. In a specific embodiment, the light converter nanoparticles comprise III-V QDs, more specifically quantum dots based on an InP, such as the InP-ZnS QDs of the core shell. Note that the terms "InP quantum dot" or "InP-based quantum dot" and similar terms may refer to "discovered" InP QDs, but also to core shell InP QDs, a shell in the InP core, such as a core shell InP-ZnS QDs, such as a rod point of InP-ZnS QDs.
[047] The luminescent nanoparticles (uncoated) can have dimensions in the range of about 2 to 50 nm, especially from 2 to 20 nm, such as from 5 to 15 nm; especially at least 90% of the nanoparticles have dimensions in the indicated ranges, respectively (i.e., for example, at least 90% of the nanoparticles have dimensions in the range 2 to 50 nm, or especially at least 90% of the nanoparticles have dimensions in the range from 5 to 15 nm). The term “dimensions” especially refers to one or more of length, width, diameter, depending on the shape of the nanoparticle.
[048] In some embodiments, the light converter nanoparticles have an average particle size in a range of about 1 to about 1000 nanometers (nm), and preferably in a range of about 1 to about 100 nm. In one embodiment, the nanoparticles have an average particle size in a range of about 1 to 50 nm, especially 1 to about 20 nm, and generally at least 1.5 nm, such as at least 2 nm. In one embodiment, the nanoparticles have an average particle size in a range from about 1 to about 20 nm.
[049] Typical spots are made of binary alloys such as cadmium selenide, cadmium sulfide, indium arsenide, and indium phosphide. However, the stitches can also be made from ternary alloys such as cadmium sulfide and selenide. These quantum dots can contain as many as 100 to 100,000 atoms within the quantum dot volume, with a diameter of 10 to 50 atoms. This corresponds to about 2 to 10 nanometers. For example, spherical particles such as CdSe, InP, or CuInSe2 with a diameter of about 3 nm can be provided. Luminescent (uncoated) nanoparticles can be shaped like spheres, cubes, rods, wires, disks, multipods, etc., with the size in a dimension of less than 10 nm. For example, CdSe nanorods with a length of 20 nm and a diameter of 4 nm can be provided. Therefore, in one embodiment, semiconductor-based luminescent quantum dots comprise core-shell quantum dots. In yet another embodiment, semiconductor-based luminescent quantum dots comprise rod dot nanoparticles. A combination of different types of particles can also be applied. For example, core shell particles and stick dots can be applied and/or combinations of two or more of the above-mentioned nanoparticles can be applied, such as CdS and CdSe. Here, the term “different types” can refer to different geometries as well as different types of semiconductor luminescent material. Therefore, a combination of two or more of the quantum dots (the ones indicated above) or luminescent nanoparticles can also be applied.
[050] An example, as derived from WO 2011/031871, of a method of manufacturing a semiconductor nanocrystal is a colloidal growth process. Colloidal growth occurs by injecting an M donor and an X donor in a hot coordinating solvent. An example of a preferred method for preparing monodisperse semiconductor nanocrystals comprises pyrolysis of organometallic reagents, such as dimethyl cadmium, injected into a hot coordinating solvent. This allows for discrete nucleation and results in the controlled growth of macroscopic quantities of semiconductor nanocrystals. The injection produces a core that can be grown in a controlled manner to form a semiconductor nanocrystal. The reaction mixture can be gently heated to cultivate and temper the semiconductor nanocrystal. Both the average size and size distribution of nanocrystal semiconductors in a sample are dependent on the growth temperature. The growth temperature necessary to maintain continuous growth with increasing average crystal size. The semiconductor nanocrystal is a member of a population of semiconductor nanocrystals. As a result of discrete nucleation and controlled growth, the population of semiconductor nanocrystals that can be obtained has a narrow, monodisperse diameter distribution. The monodisperse diameter distribution can also be referred to as a size. Preferably, a monodisperse population of particles includes a population of particles where at least about 60% of the particles in the population span a specific particle size range. A population of monodisperse particles preferably deviates less than 15% rms (root mean square) in diameter and more preferably less than 10% rms and most preferably less than 5%. In one embodiment, the nanoparticles may comprise semiconductor nanocrystals including a core comprising a first semiconductor material and a shell comprising a second semiconductor material, wherein the shell is disposed over at least a portion of a surface of the core. A semiconductor nanocrystal including a core and shell is also referred to as a “core/shell” semiconductor nanocrystal. For example, the semiconductor nanocrystal can include a core that has the formula MX, where M can be cadmium, zinc, magnesium, mercury, aluminum , gallium, indium, thallium or mixtures thereof, and X may be oxygen, sulfur, selenium, tellurium, nitrogen, phosphorus, arsenic, antimony or mixtures thereof. Examples of materials suitable for use as semiconductor nanocrystal cores include, among others, ZnO, ZnS, ZnSe, ZnTe, CdO, CdS, CdSe, CdTe, MgS, MgSe, GaAs, GaN, GaP, GaSe, GaSb, HgO, HgS, HgSe, HgTe, InAs, InN, InP, InSb, AlAs, AIN, AlP, AlSb, TIN, TIP, TlAs, TlSb, PbO, PbS, PbSe, PbTe, Ge, Si, an alloy including any of the above, and/or a mixture including any of the above, including ternary and quaternary mixtures or alloys.
[051] In one embodiment, nanoparticles can comprise semiconductor nanocrystals including a core comprising a first semiconductor material and a shell comprising a second semiconductor material, wherein the shell is disposed over at least a portion of a surface of the core. A semiconductor nanocrystal including a core and shell is also referred to as a “core/shell” semiconductor nanocrystal.
[052] For example, the semiconductor nanocrystal can include a core that has 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, among others, ZnO, ZnS, ZnSe, ZnTe, CdO, CdS, CdSe, CdTe, MgS, MgSe, GaAs, GaN, GaP, GaSe, GaSb, HgO, HgS, HgSe, HgTe, InAs,InN, InP, InSb, AlAs, AIN, AlP, AlSb, TIN, TIP, TlAs, TlSb,PbO, PbS, PbSe, PbTe, Ge, Si, an alloy including any of the above, and/or a mixture including any of the above, including ternary and quaternary mixtures or alloys.
[053] The shell may be a semiconductor material that has a composition that is the same or different from the composition of the core. The shell comprising a coating of a semiconductor material on a surface of the semiconductor nanocrystal of the core may include a Group IV element, a Group II-VI compound, a Group II-V compound, a Group III-VI compound, a Group III-V compound, a Group IV-VI compound, a Group I-III-VI compound, a Group II-IV-VI compound, a Group II-IV-V compound, alloys including any of the above, and/or mixtures including any of the above, including ternary and quaternary mixtures or alloys. Examples 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, AIN, AlP, AlSb, TIN, TIP, TlAs, TlSb, PbO, PbS, PbSe, PbTe, Ge, Si, an alloy including any of the above, and/or the mixture including any of the above. For example, ZnS, ZnSe or CdS coatings can be cultured on CdSe or CdTe semiconductor nanocrystals. A coating process is described, for example, in U.S. Patent 6,322,901. By adjusting the temperature of the reaction mixture during coating and monitoring the absorption spectrum of the core, coated materials that have high emission quantum efficiency and narrow size distributions can be obtained. The coating can comprise one or more layers. The coating comprises at least one semiconductor material that is the same or different from the core composition. Preferably, the coating has a thickness of from about one to about ten monolayers. A coating can also have a thickness greater than ten monolayers. In one embodiment, more than one coating can be included on a core.
[054] In one embodiment, the surrounding "wrapper" material may have a band opening greater than the band opening of the core material. In other embodiments, the surrounding wrapper material may have a strip opening smaller than the strip opening of the core material.
[055] In one embodiment, the shell may be chosen to have an atomic spacing proxied to that of the "core" substrate. In certain embodiments, the shell and core materials can have the same crystal structure.
[056] Examples of semiconductor nanocrystal (core) shell materials include, but are not limited to: red (eg (CdSe)ZnS (core)shell), green (eg (CdZnSe)CdZnS (core)shell, etc. ), and blue (eg (CdS)CdZnS (core)shell (see further, also above, for examples of specific light converter nanoparticles based on semiconductors. Therefore, the outer surface mentioned above may have the surface of a bare quantum dot (i.e., a QD not comprising another shell or coating) or may be the surface of a coated quantum dot, such as a core shell quantum dot (such as core shell or stick dot), that is. is, the (outer) surface of the envelope. The graft binder thus specially grafts onto the outer surface of the quantum dot, such as the outer surface of a stick-dot QD.
[057] Therefore, the above-mentioned outer surface may have the surface of a bare quantum dot (i.e., a QD not comprising another shell or coating) or it may be the surface of a coated quantum dot, such as a core shell quantum dot (such as core casing or stick point), ie the (outer) surface of the casing. The graft binder thus especially grafts onto the outer surface of the quantum dot, such as the outer surface of a stick-dot QD.
[058] Therefore, in a specific embodiment, the light converter nanoparticles are selected from the group consisting of core shell nanoparticles, with the cores and shells comprising one or more of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgSe, CdZnTe, CdZnTe, HgZ CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, GaN, GaP, GaAs, AlN, AlP, AlAs, InN, InP, InAs, GaNP, GaNAs, GaPAs, AlNP, AlNAs, AlPAs, InNP, InNAs, GasAlP, InPAs GaAlPAs, GaInNP, GaInNAs, GaInPAs, InAlNP, InAlNAs, and InAlPAs.
[059] In general, cores and shells comprise the same class of material, but essentially consist of different materials, such as a ZnS shell around a CdSe core, etc.
[060] Here, the term "solid polymer" is used, as to indicate that the polymeric end product of the process of the invention is not a liquid polymer or a solvent, but a tangible product (at room temperature (and atmospheric pressure)) in the shape of, for example, particles, a film, a plate, etc. Hence, in one embodiment, the light converter is selected from the group consisting of a coating, a self-supporting layer, and a plate; light converter which is thus especially solid at room temperature, especially even up to 100 °C, especially even up to 150 °C, especially even up to 200 °C). The light converter can be flexible or it can be rigid. Also, the light converter can be flat or curved (in one or two dimensions). Furthermore, optionally the light converter can comprise externally coupling structures on at least part of the external surface of the light converter.
[061] The process of the invention comprises at least two process elements, which will generally be executed consecutively, with the first process element preceding the second process element. The fact that two process elements are explicitly mentioned does not exclude the presence of one or more other process elements, which may be included in the process before the first process element, and/or between the first and second process elements , and/or after the second element of the process. For example, the process of the invention may also include an exchange of graft molecules existing on the quantum nanoparticle with graft molecules as defined in the present invention. This process can, furthermore, optionally include the removal of excess binders (ie, binders that are bound to the light converter nanoparticles).
[062] The first element of the process includes mixing the grafted nanoparticles (that is, the converter nanoparticles having an outer surface grafted with the graft binders) and the curable siloxane polymers. In general, this could be accelerated or optimized in the presence of a liquid in which the QDs can be dispersed and which is especially a solvent for curable siloxane polymers. Here, a solvent is considered as a solvent when, at room temperature, at least 0.1 gram/l of a species to be dissolved can be dissolved in the solvent. The solvent could be any common solvents, preferably non-polar, with preferably a boiling point of less than 120°C. For example, the solvent could be toluene, benzene, hexane, cyclohexane, etc. The solvent could be a polar solvent. For example, the solvent could be chloroform, acetone, acetone nitrile, ethyl acetate, petroleum ether, etc. Mixing can be done with conventional techniques. Optionally, the mixture can be heated.
[063] Healing can be done with techniques known in the art. As indicated above, to that end, at least part of the curable siloxane polymers may have reactive groups that are configured to form crosslinks upon curing. Healing can be assisted by a catalyst. In addition, the mixture can be heated and/or irradiated to initiate and/or propagate curing. Upon curing, a (solid) matrix or host for the grafted light converter nanoparticles is obtained (the latter being incorporated and distributed in the former).
[064] As suggested above, the process of the invention can provide a light converter (luminescent) comprising a polymer (solid) within the nanoparticles incorporated in the polymeric article of the light converter that has an outer surface grafted with graft molecules. As indicated above, the (luminescent) light converter can, for example, be transparent or translucent, especially substantially transparent. The process of the invention can lead in one embodiment to a product in which at least part of the graft binder is intertwined (through, for example, crosslinks) with siloxane polymer(s). The latter embodiment may be the case when graft binders may be able to react with curable (or cured) siloxane polymers. Therefore, in one embodiment, one or more graft binders may comprise functional groups that are configured to form crosslinks with especially the curable siloxane polymers (which form the host material or matrix). .
[065] The process of the invention can thus also provide the light converter defined herein (or light converter element) with light converter nanoparticles incorporated therein. Therefore, the light converter defined here (or light converter element), with light converter nanoparticles incorporated therein, is in one embodiment obtainable by the process as defined here. Therefore, as indicated above, in another aspect, the invention provides a light converter comprising a polymeric siloxane matrix with light converter nanoparticles incorporated therein, wherein: (a) the light converter nanoparticles have an outer surface grafted with graft binders, and(b) the siloxane polymer matrix comprises crosslinked siloxane polymers; graft binders comprise siloxane graft binders having x1 Si structural elements, wherein at least one Si structural element of each siloxane graft binder comprises a side group having a grafting functionality selected from the group consisting of a side group comprising amine or a side group comprising carboxylic acid;- wherein the curable siloxane polymers have y1 Si structural elements;- wherein x1 is especially at least 20 , such as especially at least 40, even more especially at least 50, where y1 is especially at least s 2, such as at least 7, such as at least 10, and where x1/y1 > 1, such as at least > 1.2.
[066] Especially, the light converter comprises 0.001 to 25% by weight of nanoparticles of the light converter with respect to the total weight of the light converter, such as 0.1 to 20% by weight, especially not more than 5% by weight, such as 0.1 to 2% by weight.
[067] Especially, the matrix of the cured (curable) siloxane polymers is transmissive for light having a wavelength selected from the range of 380 to 750 nm. For example, the matrix of cured (curable) siloxane polymers can be transmissive to blue, and/or green, and/or red light. Especially, the matrix of the cured (curable) siloxane polymers is transmissive for at least the entire range from 420 to 680 nm. Especially, the matrix of cured (curable) siloxane polymers has a light transmission in the range of 50 to 100%, especially in the range of 70 to 100%, for light generated by the light source of the lighting unit (see also below) and having a wavelength selected from the visible wavelength range. In this way, the matrix of cured (curable) siloxane polymers is transmissive to visible light from the lighting unit. The transmission or permeability of light can be determined by providing light at a specific wavelength with a first intensity for the material and in relation to the intensity of light at that wavelength measured after transmission through the material, for the first intensity of the light provided at that material-specific wavelength (see also E-208 and E-406 of CRC Handbook of Chemistry and Physics, 69th edition, 1088-1989). The light converter can be transparent or translucent, but it can be especially transparent. Especially, the light converter is substantially transparent and/or does not substantially scatter light. When the light converter is transparent, light from the light source may not be fully absorbed by the light converter. Especially when using blue light, this can be of interest, as blue light can be used to excite the light converter nanoparticles and can be used to provide a blue component (in white light). Therefore, especially curable siloxane polymers are required to provide a substantially transmissive matrix (or host) for the light converter nanoparticles.
[068] In addition, as cited above, the invention also provides a lighting unit comprising (i) a light source configured to generate a light from the light source and (ii) a light converter configured to convert at least part of the light from the light source to light from the converter, wherein the light converter comprises the solid polymer obtainable according to the process as defined herein or the light converter as defined herein. Therefore, in another aspect, the invention provides a lighting device comprising: - a light source configured to generate light from the light source, - a light converter obtainable by the process as defined herein or the light converter per se as defined here, set to convert at least some of the light from the light source into visible light from the converter.
[069] It may be advantageous, in view of efficiency and/or stability, to arrange the nanoparticles, or especially the light converter, at a non-zero distance, such as 0.5 to 50 mm, such as 1 to 50 mm, from of the light source. Therefore, in one embodiment, the light converter can be configured at a non-zero distance from the light source. For example, the light converter, or especially the luminescent material, can be applied to or can be comprised of a window of the lighting unit. In case the light source is configured to provide blue light, the luminescent material can be configured to convert only part of the light from the light source. The blue light from the light source and the light from the luminescent material of the nanoparticles from the light converter based on the luminescent material together can provide, in one realization, light from the white illumination unit. Therefore, in one embodiment, the light converter is configured at a non-zero distance from the light source. Note, however, that the invention is not limited to applications where the distance between the light converter and the light source is non-zero. The invention, and the specific embodiments described herein, can also be applied in other embodiments, where the light source and the light converter are in physical contact. In such cases, the light converter can be specially configured in physical contact with, for example, an LED mold.
[070] In a further embodiment, the light source comprises a solid state light source, such as a solid state light emitting device or solid state laser. The term light source can also refer to a plurality of light sources.
[071] As indicated above, the lighting device can be applied as a backlight unit in an LCD application. Therefore, the invention provides in a further aspect a liquid crystal display device comprising a backlighting unit, wherein the backlighting unit comprises one or more lighting devices as defined herein.
[072] In addition to the light converter nanoparticles, the light converter can comprise other host materials (particulates), such as, for example, one or more of an organic dye and reflective particles (non-luminescent), type TiO2. Such material(s) (particulate(s)) can be mixed with the light converter nanoparticles and curable siloxane polymers. Therefore, the expression "mixing (i) the light converter nanoparticles (herein also referred to as "nanoparticles") with an outer surface grafted with graft binders and (ii) curable siloxane polymers" can also refer to the "mixture (i) light converter nanoparticles (herein also referred to as "nanoparticles") with an outer surface grafted with graft binders and (ii) curable siloxane polymers, and optionally one or more other materials."
[073] The term white light here is known to the person skilled in the art. It especially refers to light that has a correlated color temperature (CCT) between about 2000 and 20000 K, especially 2700 to 20000 K, for general lighting especially in the range of about 2700 K and 6500 K, and for lighting purposes background especially in the range of about 7000K and 20000K, and especially within about 15 SDCM (color matching standard deviation) of BBL (blackbody location), especially within about 10 SDCM of BBL, still more especially within about 5 SDCM of BBL.
[074] The terms "violet light" or "violet emission" especially refer to light that has a wavelength in the range of about 380 to 440 nm. The terms “blue light” or “blue emission” especially refer to light that has a wavelength in the range of about 440 to 490 nm (including some shades of violet and cyan). The terms "green light" or "green emission" especially refer to light that has a wavelength in the range of about 490 to 560 nm. The terms "yellow light" or "yellow emission" especially refer to light that has a wavelength in the range of about 560 to 590 nm. The terms "orange light" or "orange emission" especially refer to light that has a wavelength in the range of about 590 to 620 nm. The terms "red light" or "red emission" especially refer to light that has a wavelength in the range of about 620 to 750 nm. The terms "visible light" or "visible emission" refer to light that has a wavelength in the range of about 380 to 750 nm.
[075] The term "substantially" herein, such as in "substantially all issue" or in "substantially consists", will be understood by the skilled artisan. The term "substantially" may also include accomplishments such as "entirely", "completely", "all", etc Therefore, in realizations the adjective substantially can also be removed. Where applicable, the term "substantially" may also refer to 90% or more, such as 95% or more, especially 99% or more, even more especially 99.5% or more, including 100%. The term "comprises" also includes realizations where the term "comprises" means "consists of".
[076] Furthermore, the terms first, second, third and similar in the description and in the claims are used to distinguish between similar elements and not necessarily to describe a sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of the invention described herein are capable of operating in other sequences described or illustrated herein.
[077] The devices here are among the others described during operation. As will be clear to the person skilled in the art, the invention is not limited to methods of operation or devices in operation.
[078] It should be noted that the above mentioned embodiments illustrate more than limit the invention, and that those skilled in the art will be able to design many alternative embodiments without departing from the scope of the appended claims. In the claims, any reference signs enclosed in parentheses shall not be construed as limiting the claim. The use of the verb “to understand” and its conjugations does not exclude the presence of elements or stages different from those mentioned in a claim. The article “a” or “an” that precedes an element does not exclude the presence of a plurality of such elements. This simple fact that certain measures are cited in mutually different dependent claims does not indicate that a combination of these measures cannot be used to advantage.
[079] The invention, furthermore, applies to a device comprising one or more of the characterization features described in the description and/or shown in the attached drawings. The invention, furthermore, belongs to a method or process comprising one or more of the characterization features described in the description and/or shown in the accompanying drawings.
[080] The various aspects discussed in this patent can be combined in order to provide additional advantages. In addition, some of the features may form the basis for one or more divisional applications. BRIEF DESCRIPTION OF THE DRAWINGS
[081] The embodiments of the invention will now be described, by way of example only, with reference to the accompanying schematic drawings, in which corresponding reference symbols indicate corresponding parts, and in which:
[082] Figures 1a to 1c schematically describe some aspects of the device(s) of the invention;
[083] Figures 2a to 2d schematically describe some additional aspects of the invention;
[084] Figures 3a to 3j schematically describe some additional aspects of siloxanes and some additional aspects of the invention.
[085] Drawings are not necessarily to scale.
[086] Figures 4a and 4b show TEM figures of QDs before and after the exchange of graft binders according to the invention, respectively.
[087] Figure 5 shows a photograph of a silicone gel comprising QDs after the exchange of graft binders according to the invention. DETAILED DESCRIPTION OF ACHIEVEMENTS
[088] Figure 1a schematically depicts a lighting device 1 comprising a light source 10 configured to generate light from the light source 11 and a light converter 100 configured to convert at least part of the light from the light source 11 m to visible light of the converter 121. Here, schematically only one light source 10 is described. However, more than one light source 10 may be present.
[089] The light converter has an upside 101 (part of an outer surface of the light converter), which is at least partially directed to the light source 10, and a downside 102 (part of an outer surface of the light converter). light), which faces away from light source 10 (in this transmissive configuration).
[090] The light converter 100 comprises a polymeric host material 110 with nanoparticles from the light converter 120 incorporated in the polymeric host material 110. These can be dots, rods, a combination thereof, etc. (see also above). The nanoparticles from the light converter 120 generate, upon excitation by light from the light source 11, visible light from the converter (and optionally also non-visible radiation, such as IR radiation). At least part of the light from the converter 121 escapes from the downside 102 as light from the lighting device 5. That light from the lighting device 5, of which at least part is in the visible part, at least contains part of the light from the converter 121, and may optionally also contain some remaining light from the light source 11.
[091] Figure 1a schematically describes the lighting device in operation.
[092] Figure 1b schematically describes another embodiment, in which the light converter 100 is encapsulated. A 400 package covers the light converter; this encapsulation can substantially block the oxygen carrier (and/or H2O) from the atmosphere to the light converter. This can add to the stability of the 120 light converter nanoparticles (and the polymeric host). The combination of light converter 100 and package 400 is also indicated here as a light converter unit 1100.
[093] Figure 1c schematically depicts one of the applications of the lighting unit 1, here in a liquid crystal display device 2, which comprises a background lighting unit 200 comprising one or more lighting units 1 (here, a lighting unit is described schematically), as well as an LCD panel 300, which can be illuminated with the lighting device light 5 of the lighting unit(s) 100 of the backlighting unit 200.
[094] The converter 100 can especially be arranged at a non-zero distance d from the light source 10, which can, for example, be a light-emitting diode, although the distance d can also be zero, for example, when the luminescent material 30 is applied in an LED array or embedded in a cone (silicone) in the LED array. The converter can optionally allow at least some of the light from the light source 11 to penetrate through the converter. In this way, descending from the converter, a combination of the converter light 121 and light from the light source 11 can be formulated. The downlight of the light converter is indicated on a lighting device light 5. The distance d can especially be in the range of 0.1 to 100 mm, especially 0.5 to 100 mm, such as 1 to 20 mm, as especially 1 to 50 mm, such as about 1 to 3 for applications close to the light source and 5 to 50 mm for more remote applications. Note, however, that the invention is not limited to applications where d>0. The invention, and the specific embodiments described herein, can also be applied in other embodiments with d=0. In such cases, the light converter can be specially configured in physical contact with the LED array.
[095] In addition to the ligand-grafted semiconductor 120 nanoparticles of the light converter, the light converter 100 may optionally also comprise other types of luminescent materials, for example, the color tone of the light from the lighting unit 5, to increase color rendering, color temperature tone, etc.
[096] The terms "ascending" and "descending" refer to an arrangement of items or resources relating to the propagation of light from a means of light generation (here especially the first light source), in which the relation of a first position within the light beam from the light generating means, a second position within the light beam near the light generating means is "upward", and a third position within the light beam is "downward".
[097] Figure 2a schematically describes a non-limiting number of examples of nanoparticles of the 120 light converter, here quantum dots (QDs). By way of example, (i) indicates a QD particle, which has a dot shape, with no additional layers. For example, this could be, for example, CdSe. Graft binders are not shown for clarity (see below). The QD example (ii) schematically describes a core shell system, by way of example, shell (core) of (CdSe)ZnS. The QD example (iii) schematically describes a point-to-stick QD system, for example, point-to-stick (CdS)ZnS (which is also a type of core shell QD). The light converter nanoparticles have an outer surface indicated with reference 127.
[098] Figure 2b schematically depicts a QD with graft binder 130. As can be seen, in this example, the side groups that have a graft functionality (the group is indicated with reference 131) are not end groups; the graft binders are attached to the outer surface 127 of the light converter nanoparticles. Therefore, graft binders can have (at least) two tails. Graft binders would have more than one side group having graft functionality, other (more complex) structures can be found. On the inset, a magnification is shown, with two tails on either side of the silicone structural element that supports the side group that has a graft functionality that attaches to the outer surface 127 of the light converting nanoparticle.
[099] Figure 2c very schematically depicts the situation before curing, where, for example, the light converter nanoparticles with graft binders bonded to the outer surface of the nanoparticles as well as uncured siloxane polymers, indicated with reference 330, are distributed in a liquid in the vessel, which is indicated with reference 300. The liquid is indicated with reference 31; it can be used to disperse the grafted nanoparticles 120; in addition, it can be applied to dissolve curable siloxane polymers.
[0100] After curing, such as by heating and in the presence of a catalyst (for clarity not described) in the mixture in the vessel, the cured system is obtained, i.e., the light converter, as schematically described in figure 2d . The cured siloxane polymers, now forming a silicone, are considered the polymeric 110 host material for the 120 light converter nanoparticles, such as QDs (see also above).
[0101] Figures 3a to 3h are discussed below during the experimental part.
[0102] Figure 3i very schematically depicts part of a siloxane polymer, with only 6 silicone structural elements described; the structural elements of Si 1 and 6 are end groups, with, for example, end groups R3'-R3' and end groups R4'-R4', respectively. Such end groups can comprise, for example, (one or more of) OH, methyl, phenyl, vinyl, hydrogen, etc. etc., as known in the art. Each (non-terminal) silicone structural element has two side groups, which may in principle all be different, but which may also all be the same, except that the graft binder has at least one side group having a graft functionality as defined above.
[0103] Figure 3j is shown to indicate how the chemical overlap can be determined. As indicated above, especially at least 75%, especially 80%, even more especially 85%, even more especially at least 90%, such as especially at least 95% of the side groups of siloxane graft binders and curable siloxane polymers if overlap in chemical identity. R3'-R3'', R4'-R4''', R5'-R5'' and R6'-R6''' are end groups, and are not considered when evaluating chemical overlap of side groups. Figure 3j schematically shows simple (but common) systems with only two different side groups. The graft binder has, by way of example, 4 non-terminal silicone structural elements (and two terminal Si structural elements); curable siloxane polymer 330 has, by way of example, 3 silicone structural elements (and two terminal Si structural elements). The graft linker has, by way of example, a side group that has graft functionality (FSG). In the table below, the overlap in chemical identity is shown. Note that in columns II and V only the number of non-terminal Si structural elements is given, as only these can provide side groups; the terminal Si structural elements have terminal groups.

[0104] So here the chemical overlap is 79.2%. In practice, the chemical overlap will generally be greater such as at least 90%. EXPERIMENTAL PART
[0105] Experimental results of quantum dots in silicones
[0106] Examples of binders with various sizes and functional groups
[0107] In the research for compatible systems with QD/silicone binder, up to 20 binders of different compositions/functionalities were investigated, and up to 10 different silicones. Roughly, binders can be classified as:
[0108] Short monofunctional siloxane (eg 3-aminopropylpentamethyldisiloxane, AB129258; ABCR supplier); see figure 3a;
[0109] Short bifunctional siloxane (for example 1,3-Bis(3-aminopropyl)tetramethyldisiloxane, AB 110832); see figure 3b;
[0110] PDMS functionalized at the end with amine or acid at both ends ("symmetrical", eg polydimethylsiloxane, aminopropyl terminated, AB111872); see figure. 3c;
[0111] PDMS functionalized at the end with amine or acid at one end ("asymmetric", eg, asymmetric monocarboxydecyl terminated polydimethylsiloxane, AB 252409); see figure 3d;
[0112] PDMS functionalized on the side with amine or acid (2 to 3% aminopropylmethylsiloxane) - dimethylsiloxane copolymer, AB109373); see figure 3e, with reference 131 referring to the side group which has a graft functionality.
[0113] In all cases, a small amount of QDs in toluene was added to 1 ml of the pure binder, which yielded very turbid mixtures, is almost all cases. The mixture was stirred for more than 12 hours at 100°C. In most cases, the pure QD-linker mixture became transparent within an hour, which provided evidence for linker change. After cooling, this mixture was directly added to various silicones, and the degree of mixture was determined by visual inspection of the obtained mixture. In contrast to the experiments in the other examples in this document, the QDs were not purified from excess ligands in the experiments described here. An overview of all tested ligands can be found in the table below. It was observed that only QDs with functionalized ligands on the side (the last category) yielded improved miscibility with the selected silicones. It was later found that binders very similar to AB109373 (AB109374, AB124359, AB116669 (the latter two are branched)) showed similar transparent mixtures. The common factor is that it involves PDMS chains with a medium (randomly distributed) amine group 1 in the side chain and with a molecular weight of ~5000-1000, corresponding to a viscosity of 100 to 300 cSt. An illustration of these molecules is given in Figures 3f and 3g.
[0114] It was observed that only QDs with functionalized ligands on the side (the last category) yielded improved miscibility with the selected silicones. It was later found that binders very similar to AB109373 (AB109374, AB124359, AB116669 (the latter two are branched)) showed similar transparent mixtures. The common factor is that it involves PDMS chains with a medium (randomly distributed) amine group 1 in the side chain and with a molecular weight of ~ 5000-1000, corresponding to a viscosity of 100 to 300 cSt. An illustration of these molecules is given in Figures 3f and 3g.
[0115] From the above experiments, it appears that short binders, and/or end functionalized binders did not show an improved miscibility with silicones. The effect of long versus short binders is explained in more detail below. For that purpose, two siloxane linkers functionalized at the long-chain end were tested again (AB109371 and 153374 with viscosity 100 and 1000 cSt respectively), but it was found that the linker exchange itself was not successful, i.e. , the QD-binder mixture did not become transparent over time.
[0116] In summary, the results clearly show that laterally functionalized siloxane ligands are preferred.
[0117] Chemical compatibility will be discussed in more detail below:



[0118] Persona synthesized ligand] Lysed with a carboxylic acid group, based on the AB109373 molecule
[0119] The above successful examples of linkers with functional groups in the side chain are based on amine functional groups. However, carboxylic acid side groups are known to be more preferred in view of the stability of QD. Furthermore, it is observed that excess amine binders inhibit the silicone curing reaction, while excess carboxylic acid binders do not. Thus, a molecule similar to, for example, AB109373, but with a carboxylic acid instead of an amine side group and with a viscosity of 100 to 300 cSt and similar molecular weight is more preferred. The molecule can be branched or unbranched. However, such molecules are not commercially available for the best of understanding. This molecule is therefore custom synthesized by the reaction of an anhydride moiety to the amine group of the AB109373 ligand. The reaction and the resulting carboxy ligand are shown in figure 3h (conversion of the AB109373 ligand to a carboxy-functionalized ligand by reaction with succinic anhydride).
[0120] Custom synthesized AB109373-COOH ligand was tested. Upon mixing CdSe quantum dots with the undiluted AB109373-COOH ligand, a low miscibility was again observed. However, the mixture becomes clear after just a few minutes at 100 °C. This higher reactivity may be due to the carboxylic acid group compared to an amine group, or the fact that the side chain is slightly longer. This is an important proof that also PDMS linkers with a carboxylic side chain group can be used.
[0121] This experiment was repeated with the binder AB109373-COOH diluted in a hydrocarbon solvent (dodecane), and again clear mixtures were obtained after heating to 100 °C, below a concentration of 1% by weight of the binder in the solvent . Typically binder concentrations of 5 to 10% by weight were used in the experiments.
[0122] This experiment was again repeated with InP quantum dots in a dilute AB109373-COOH binder solution (5% by weight of AB109373-COOH binder in a solvent). Again, a clear mixture was obtained after changing the binder.
[0123] Prior to blending into other silicones, the light convertor nanoparticle systems with graft binders (in toluene) were purified by substantially removing excess binder.
[0124] TEM in dry QDs with custom binder AB109373 in a grade evidence for binder change including wash procedure.
[0125] Figure 4a shows a TEM image of washed CdSe quantum dots, prepared following the method as described by Lim et al. (Advanced Materials, 2007, 19, p. 1927-1932), and dried on a TEM grid. Figure 4b shows a TEM image of CdSe quantum dots, from the same batch as shown in figure 4a, after switching the binder with the custom binder AB109373.
[0126] Figure 4a shows that the quantum dots before changing the ligand have an interparticle distance of about 1 nm. Figure 4b shows that the quantum dots, after bond exchange and formed into two-dimensional aggregates during the drying process, are placed far apart from each other having an interparticle distance of about 7 to 8 nm. The latter indicates that the thickness of the ligand layer at the quantum dots is around 3.5 nm. Typically, interparticle distances of 4 to 5 nm are observed.
[0127] A similar result was observed for CdSe quantum dots washed after the linker change where the linker was diluted with a solvent, in that case, a slightly shorter interparticle distance of about 3 nm was observed. The interparticle distance that is achieved may depend on the degree of ligand exchange, among others.
[0128] A similar result was observed when using the InP quantum dots after ligand exchange.
[0129] TEM of QDs without binder change in various silicones - evidence for large aggregates
[0130] If CdSe quantum dots, as prepared according to Lim et. al. (Advanced Materials, 2007, 19, p. 1927-1932), are mixed into silicones, frequent immediately strong flocculation is observed. Broad aggregates are formed and even if the layers appear transparent to the naked eye, microscopy reveals that aggregates are present.
[0131] Examples of long-linked QDs (x1=68) in siloxanes with various chain lengths, using purified QDs
[0132] Purified QDs redispersed in toluene could be mixed with pdms with low molecular weights to create stable dispersions. Dots could be dispersed in a pdms with a molecular weight of 1250, 2000, 3800 and 6000 (corresponding viscosities of 10, 20, 50 and 100 cSt or 17, 27, 50, 80 structural Si units)) to yield dispersions of do not scatter. At a 200 cSt (Mw 9430, y1=127) pdms, the sample was scattering.
[0133] Similar results were obtained with the CdSe quantum dots where lower ligand concentration was used during the ligand exchange.
[0134] Similar results were obtained with ligand-exchange InP quantum dots.
[0135] Examples of short-linked QDs in siloxanes with various chain lengths
[0136] QDs were modified with a short-end functionalized siloxane binder (terminated monoaminopropyl, AB 250914 with a viscosity of 7 to 14 cSt and Pm of 800 to 1100, x1=12)).
[0137] The linker change was successful, that is, the QD-linker mixture was transparent after the linker change (>12h at 100 °C). It was observed upon mixing, the QDs with the binder AB250914 remain totally transparent in the 10 cSt PDMS (y1=17) for about 30 seconds, after that it starts to flocculate gradually, and it eventually becomes turbid. This result was reproduced several times. It is interpreted as that the ligands are just below the threshold of being long enough to stabilize the QDs in the 10 cSt of PDMS. As a result, the mixture is initially stable, but slowly starts to flocculate over time. When mixed with 100 cSt, (y1=80), it yielded an immediately cloudy suspension, as expected.
[0138] Examples of long-bonded QDs with various types of siloxane groups.
[0139] To investigate the importance of chemical compatibility between the binder and siloxane polymer, QDs with custom AB109373-COOH binder (x1=68) were mixed with siloxane molecules with various side groups. An overview is given in the table below.
[0140] The results in the table below confirm once again that QDs with the binder AB109373-COOH form a transparent mixture with PDMS siloxane molecules up to a viscosity of 100 cSt (y1=80). However, when the same QDs with AB109373-COOH linkers are mixed with other siloxane molecules with multiple side chains. As learned from previous examples, QDs with AB109373-COOH binder will not yield clear mixtures with siloxane molecules with a viscosity much greater than 100 cSt. However, the table below shows that even for siloxanes with relatively low viscosity, these QDs with AB109373-COOH binder yield turbid mixtures. This indicates that the siloxane structure of the binder preferably chemically matches the structure of the siloxane polymer with which it is to be mixed. In this case, the AB109373-COOH binder has 100% dimethyl groups, so it disperses well into the 100% PDMS siloxanes. It is anticipated that in case the QDs need to be mixed with, for example, a phenylmethyl (50%) silicone, the ligands in the QDs would, for example, have a similar (50%) phenylmethyl siloxane structure.

[0141] Example of a curable composition using low molecular weight silicones
[0142] To prepare cured layers for composition the following was used:


[0143] The layers were prepared using silicone liquids from more concentrated QDs (CdSe) using dots redispersed in 100 μl of toluene, the dots (CdSe) having AB109373-COOH graft binders. The liquid was dropcasted onto 3*3 cm Eagle glass slides, pre-cleaned with isopropanol and acetone. The layers were cured for one hour at 150 °C resulting in a clear color film. A bulk gel was prepared by curing for 2 hours at 70 °C. Transparent layers and 5 mm thick bulk materials were obtained, as shown in figure 5, where the transparency of the material is demonstrated by placing on top of a part of the text where the word “encounter” is clearly visible. In another experiment, a bulk gel was prepared using identical CdSe QDs that were unmodified, that is, having no AB109373-COOH graft binders, and using an identical liquid silicone composition as indicated in the table directly above, in which the gel resulting mass appeared very turbid and having relatively large aggregates of quantum dots.

权利要求:
Claims (15)
[0001]
1. PROCESS FOR THE PRODUCTION OF A LIGHT CONVERTER (100), characterized in that it comprises a polymer matrix of siloxane with light converter nanoparticles (120) incorporated therein, the process comprising: (a) mixing (i) the converter nanoparticles of light having an outer surface grafted with graft binders and (ii) curable siloxane polymers, and (b) curing the curable siloxane polymers, thus producing the light converter (100);- wherein the graft binders comprise siloxane graft binders having x1 Si structural elements, wherein at least one Si structural element of each siloxane graft binder comprises a side group having a graft functionality selected from the group consisting of a side group comprising amine, a side group comprising carboxylic acid, a side group comprising phosphine, a side group comprising phosphine oxide, a side group comprising phosphate, and a side group comprising thiol-comprising side group, wherein the side group is a side group of a non-terminal Si structural element;- wherein the curable siloxane polymers have y1 Si structural elements;- wherein x1 is at least 20, wherein y1 is at least minus 2, and where x1/y1 > 1.
[0002]
Process according to claim 1, characterized in that x1 is at least 40 and x1 is not greater than 2000, where y1 is at least 7, and where y1 is not greater than 400.
[0003]
Process according to any one of the preceding claims, characterized in that the graft binders and curable siloxane polymers are substantially chemically identical.
[0004]
Process according to any one of the preceding claims, characterized in that at least 80% of the side groups having graft functionality of siloxane graft binders and curable siloxane polymers overlap in chemical identity.
[0005]
A process according to any one of the preceding claims, characterized in that at least 90% of the Si structural elements of the siloxane graft binders have methyl side groups and in that at least 90% of the Si structural elements of the siloxane polymers siloxane have methyl side groups.
[0006]
Process according to any one of the preceding claims, characterized in that both the graft binders and curable siloxane polymers are polymethyl siloxanes, or polyphenyl siloxanes, or polymethylphenyl siloxanes, and wherein x1/y1^1,2 .
[0007]
Process according to any one of the preceding claims, characterized in that x1 is at least 50, wherein no more than 10 Si structural elements are not terminal Si structural elements of each siloxane graft binder comprising the side group which has a graft functionality.
[0008]
8. Process according to any one of the preceding claims, characterized in that the light converter nanoparticles (120) are selected from the group consisting of core shell nanoparticles, the cores and shells comprising one or more of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, HgSnSe, CdZnHg CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, GaN, GaP, GaAs, AlN, AlP, AlAs, InN, InP, InAs, GaNP, AlPA, AlPAs InNAs, InPAs, GaAlNP, GaAlNAs, GaAlPAs, GaInNP, GaInNAs, GaInPAs, InAlNP, InAlNAs, and InAlPAs.
[0009]
9. LIGHT CONVERTER (100), characterized in that it comprises a polymeric matrix of siloxane with light converter nanoparticles (120) incorporated therein, wherein:- a) the light converter nanoparticles have an outer surface grafted with graft binders , and- b) the siloxane polymeric matrix comprises cross-linked siloxane polymers;- wherein the graft binders comprise siloxane graft binders having x1 Si structural elements, wherein at least one Si structural element of each Si binder siloxane graft comprises a side group having a graft functionality selected from the group consisting of a side group comprising amine or a side group comprising carboxylic acid; wherein the side group is a side group of non-terminal Si structural elements;- wherein the curable siloxane polymers have y1 Si structural elements;- wherein x1 is at least 20, wherein y1 is at least 2, and where x1/y1 >1.
[0010]
A LIGHT CONVERTER according to claim 9, characterized in that x1 is at least 40, wherein y1 is at least 7, and wherein at least 90% of the Si structural elements of the siloxane graft binders have side groups of methyl, wherein at least 90% of the Si structural elements of the siloxane polymers have methyl side groups, and wherein the light converter nanoparticles (120) are selected from the group consisting of core shell nanoparticles, wherein cores and shells comprise one or more of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSe, CdZn , CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSe, GaN, In, Al, In, , GaNAs, GaPAs, AlNP, AlNAs, AlPAs, InNP, InNAs, InPAs, GaAlNP, GaAlNAs, GaAlPAs, GaInNP, GaInNAs, GaInPAs, InAlNP, InAlNAs, and InAlPAs.
[0011]
A LIGHT CONVERTER according to any one of claims 9 or 10, characterized in that the light converter is obtainable by the process as defined in any one of claims 1 to 8, and wherein x1/y1>1,2.
[0012]
12. LIGHTING DEVICE (1), characterized in that it comprises: - a light source (10) configured to generate light from the light source (11), - a light converter (100) obtainable by the process, as defined in any of claims 1 to 8, configured to convert at least part of the light from the light source (11) into visible light from the converter (121).
[0013]
13. LIGHTING DEVICE (1) according to claim 12, characterized in that the light converter (100) is configured at a non-zero distance from the light source (10).
[0014]
14. LIGHTING DEVICE (1), according to claim 12, characterized in that the light converter (100) is configured in physical contact with the light source (10).
[0015]
15. LIQUID CRYSTAL DISPLAY DEVICE (2), characterized in that it comprises a backlighting unit (200), wherein the backlighting unit (200) comprises one or more lighting devices (1), as defined in any one of claims 12 to 14.

类似技术:

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