Composition

Abstract

The present invention relates to compositions and methods for making such compositions.

Description

[Technical field]

[0001] The present invention relates to compositions, and methods of making such compositions, wherein the compositions comprise at least these components: i) at least one semiconductor light-emitting nanoparticle; and ii) at least one antioxidant; iii) liquid organic compounds; Includes. [Background technology]

[0002] Semiconductor light-emitting nanoparticles, also called quantum materials such as quantum dots, quantum rods, tetrapods, etc., are of great interest as color conversion materials in LEDs and displays due to their narrow emission. To use quantum materials in applications such as down-conversion layers in LCDs, color filters directly above LEDs, and color converters, the semiconductor nanoparticles must be incorporated into a thin layer that protects the nanoparticles. Polymer films containing quantum materials are one way to achieve these desired thin layers. For this purpose, various polymers such as acrylates, siloxanes, silazanes, epoxies, silicones, etc. have been used. Acrylates, among others, are used in large quantities for backlight film applications.

[0003] The incorporation of quantum materials such as quantum dots into this type of layer causes a decrease in their luminescence quantum yield (QY). This occurs due to the aggregation of the quantum materials in the solid polymer film and due to chemical processes that affect the organic molecules (known as ligands) attached to the surface of the quantum material, causing the delamination of the ligands from the surface of the quantum material. This can also occur during the shelf life of the dispersion containing the quantum material before preparing a layer from it. Furthermore, the conditions under which the dispersion is polymerized to form the polymer layer containing the quantum dots themselves can cause a decrease in the luminescence quantum yield of the resulting layer. Summary of the Invention

[0004] Therefore, despite all past efforts, it remains an object to provide a dispersion of semiconductor light-emitting nanoparticles, such as quantum materials, with improved properties and / or versatility. Generally speaking, it is an object of the present invention to at least partially overcome at least one disadvantage known from the prior art.

[0005] Another object is to provide a composition comprising semiconductor light-emitting nanoparticles such as said quantum material for application onto a substrate that can be used to manufacture a layer with said quantum material, wherein the quantum yield of the quantum material is preserved, increased or at least modestly reduced compared to that known in the art.

[0006] Another object of the present invention is to provide semiconductor luminescent nanoparticles, such as quantum materials, in compositions that are more efficient and / or exhibit higher power output than those known in the art.

[0007] It is another object of the present invention to provide semiconductor luminescent nanoparticles in a dispersion that can be stored for extended periods of time. Another object of the present invention is to provide a dispersion having semiconductor light-emitting nanoparticles that is unaffected or little affected during application and solidification to form a layer on a substrate. Another object is to provide a dispersion having semiconductor light-emitting nanoparticles that are protected from photo-oxidation.

[0008] A contribution to the solution of at least one of the above objects is provided by the subject matter of the aspects forming a category. Sub-aspects subordinate to the aspects forming a category represent preferred aspects of the invention, the subject matter of which also contributes to the solution of at least one of the above objects.

[0009] Preferred Aspects (1) Contains at least these ingredients: i) at least one semiconductor light-emitting nanoparticle; ii) at least one antioxidant; iii) a polymerizable component; and iv) Liquid organic compounds A composition comprising, consisting essentially of, or consisting of. Preferably, the composition comprises in the range of 50 to 400 parts of the polymerizable component based on 100 parts of said semiconductor light-emitting nanoparticles in the composition.

[0010] (2) The antioxidant is selected from the group consisting of: A) hydroxyphenol compounds, comprising at least one hydroxyphenol fragment and at least one hydroxy group, where the hydroxyphenol fragment has at least one tert-alkyl group alpha to the at least one hydroxy group, such as, for example, 2-tert-butylhydroquinone; 4-tert-butylcatechol; 6-tert-butyl-2,4-xylenol; 3,5-di-tert-butyl-4-hydroxytoluene; 2,6-di-tert-butylphenol; or a combination of two or more thereof; A) Hydroxyphenol compounds having two hydroxy groups, such as hydroquinone; B) 2,2-diphenyl-1-picrylhydrazyl; C) alkoxyphenol; D) heterocyclic thiazines; E) polyphenols; and F) hindered amine stabilizers such as 2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethylpiperidine; or a combination of two or more thereof, for example a combination of two or more antioxidants from one of groups A) to G), or a combination of two or more antioxidants selected from different groups A) to G); The composition of embodiment 1, selected from the group consisting of:

[0011] Preferably, the antioxidant is a hydroxyphenol compound, comprising at least one hydroxyphenol fragment and at least one hydroxy group, where the hydroxyphenol fragment has at least one tert-alkyl group in the alpha position relative to the at least one hydroxy group, such as 2-tert-butylhydroquinone; 4-tert-butylcatechol; 6-tert-butyl-2,4-xylenol; 3,5-di-tert-butyl-4-hydroxytoluene; 2,6-di-tert-butylphenol; or a combination of two or more thereof, and even more preferably, it is 3,5-di-tert-butyl-4-hydroxytoluene.

[0012] (3) The composition of any one of the preceding embodiments, wherein the polymerizable component is selected from the group consisting of UV curable monomers and thermally curable monomers. (4) The composition of any one of the preceding embodiments, wherein the composition comprises at least one antioxidant in the range of 20 to 1,000 parts based on 100 parts of semiconductor luminescent nanoparticles in the composition.

[0013] (5) The composition of any one of the preceding embodiments, wherein the composition further comprises a divalent metal ion and an organic additive composed of at least one functionalized hydrocarbon group. (6) The composition of any one of the preceding embodiments, wherein the quantum material comprises In and P.

[0014] (7) The composition of any one of the preceding embodiments, wherein the liquid organic compound is selected from the group consisting of monoalkyl ethers, diethylene glycol dialkyl ethers, alkylene glycol ether acetates such as ethylene or propylene glycol alkyl ether acetates, aromatic hydrocarbons, ketones, alcohol esters, and ethylene carbonate, or a combination of two or more thereof.

[0015] (8) The composition according to any one of the preceding embodiments, wherein the quantum yield of the composition 16 hours after preparation is at least 90% relative to the composition upon preparation and under the conditions described herein.

[0016] (9) Follow these steps at least: (i) providing quantum materials; (ii) providing at least one antioxidant; (iii) providing a liquid organic component; (iv) mixing the components of steps (i)-(iii); A method of making the composition of any one of aspects (1)-(8), comprising, consisting essentially of, or consisting of.

[0017] (10) The composition has a resistance of 0.025 to 1 W / cm 2 The method of embodiment (9), wherein the photosensitive layer is irradiated with light having a wavelength selected from the range of 300 to 600 nm and having an intensity in the range of 300 to 600 nm. (11) Follow these steps at least: (a) providing a substrate; (b) providing a composition according to any one of aspects (1) to (8), or a composition obtainable by a method according to any one of aspects (9) or (10); (c) applying the composition to a substrate to form a layer; (d) polymerizing the composition; A method of producing a polymer layer comprising, consisting essentially of, or consisting of.

[0018] (12) At least the following: (aa) At least (A) Semiconductor light-emitting nanoparticles; (B) a matrix polymer; and (C) at least one antioxidant; A layer comprising: Preferably, the at least one oxidizing agent is one of the following: A) hydroxyphenol compounds, comprising at least one hydroxyphenol fragment and at least one hydroxy group, where the hydroxyphenol fragment has at least one tert-alkyl group alpha to the at least one hydroxy group, such as, for example, 2-tert-butylhydroquinone; 4-tert-butylcatechol; 6-tert-butyl-2,4-xylenol; 3,5-di-tert-butyl-4-hydroxytoluene; 2,6-di-tert-butylphenol; or a combination of two or more thereof; B) Hydroxyphenol compounds having two hydroxy groups, such as hydroquinone; C) 2,2-diphenyl-1-picrylhydrazyl; D) alkoxyphenols; E) heterocyclic thiazines; F) polyphenols; and hindered amine stabilizers such as 2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethylpiperidine; or a combination of two or more thereof, for example a combination of two or more antioxidants from one of groups A) to G), or a combination of two or more antioxidants selected from different groups A) to G); (bb) substrate; (cc) optionally one or more further layers; A layered composite comprising, consisting essentially of, or consisting of.

[0019] (13) An optical device comprising the layered composite of embodiment (12) or obtainable by the method of embodiment (11).

[0020] (14) The following: A) hydroxyphenol compounds, comprising at least one hydroxyphenol fragment and at least one hydroxy group, where the hydroxyphenol fragment has at least one tert-alkyl group alpha to the at least one hydroxy group, such as, for example, 2-tert-butylhydroquinone; 4-tert-butylcatechol; 6-tert-butyl-2,4-xylenol; 3,5-di-tert-butyl-4-hydroxytoluene; 2,6-di-tert-butylphenol; or a combination of two or more thereof; B) Hydroxyphenol compounds having two hydroxy groups, such as hydroquinone; C) 2,2-diphenyl-1-picrylhydrazyl; D) alkoxyphenols; E) heterocyclic thiazines; F) polyphenols; and G) hindered amine stabilizers such as 2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethylpiperidine; or a combination of two or more thereof, for example a combination of two or more antioxidants from one of groups A) to G), or a combination of two or more antioxidants selected from different groups A) to G); Use of an antioxidant selected from the group consisting of: (I) the storage time of the dispersion containing the quantum material; (II) the quantum yield of a dispersion containing the quantum material; (III) the quantum yield of the layer containing the quantum material; (IV) thermal stability of the layer containing the quantum material; (V) the photostability of the layer containing the quantum material; or Selected from the group consisting of combinations of two or more thereof; The above uses.

[0021] definition The term "ranging from x to y" is understood in this context to include all values ​​between the numbers x and y, and also the limits forming the numbers x and y. For example, the term "ranging from 2 to 13" includes 2, 13 and all numbers in between. A liquid is a compound or a mixture of two or more compounds that is liquid at room temperature (20° C.). This means that a maximum of 1% by weight of such a liquid will not pass through a filter with 1 μm pores.

[0022] A liquid organic compound is a compound composed of one or more carbon-carbon and / or carbon-hydrogen bonds. It may further contain heteroatoms, such as one or more selected from the group consisting of N, O, P, and S.

[0023] A "polymer" is a material constructed from one or more repeating units. A "polymerizable component" describes a compound that can form a polymer during polymerization or that can be incorporated into a polymer. The compound may be followed by a phrase in parentheses, in which case the parentheses describe, for illustrative purposes, the trade name under which the compound may be purchased. Parts relate to amounts by weight. For example, providing 100 g of A, 6 g of B and 12 g of C means 100 parts of A, 6 parts of B and 12 parts of C.

[0024] Detailed Description of the Invention The first aspect of the present invention is a method for producing a composition comprising at least these ingredients: i) at least one semiconductor light-emitting nanoparticle; and ii) at least one antioxidant; iii) liquid organic compounds; A composition comprising, consisting essentially of, or consisting of.

[0025] Preferably, the composition comprises in the range of 20 to 1,000 parts of the polymerizable component based on 100 parts of said semiconductor light-emitting nanoparticles. More preferably, the composition contains a polymerizable component in the range of 20 to 1,000% by weight based on the total amount of the semiconductor light-emitting nanoparticles.

[0026] The composition can be of any type known to those skilled in the art. The composition can be a suspension, so it may contain liquid and solid components. An example of a liquid component is a liquid organic compound. A quantum material is an example of a solid component. Each of the additional components of the composition can be in a solid or liquid state at room temperature (20°C). Each of the additional components that are solid at room temperature can be present as a solid in the composition, or can be at least partially dissolved or form a gel through the liquid component of the composition.

[0027] Said semiconductor light-emitting nanoparticles can be any kind of publicly known semiconductor light-emitting nanoparticles. For example, publicly known nano-sized inorganic phosphor materials and quantum materials. The quantum material as a component of the composition can be any kind of quantum material known to those skilled in the art and considered to be potentially useful. The quantum material in the context of the present invention can be any shape of known shapes of quantum materials, but is preferably selected from rods, dots, platelets, flowers and wires. Furthermore, the quantum material can include a combination of two or more of the aforementioned shapes.

[0028] The semiconductor luminescent nanoparticles may include one or more organic ligands. The quantum material can emit light. Even more preferably, the quantum material includes one or more semiconductor luminescent particles or semiconductor luminescent nanoparticles. The semiconductor luminescent nanoparticles usually further include one or more organic ligands. The quantum material can emit light that is tunable, sharp, and in the VIS and IR ranges. VIS refers to light with wavelengths of 400-700 nm; IR refers to light with wavelengths of more than 700 nm up to about 1 mm.

[0029] The term "semiconductor" in the present context describes a material whose electronic structure comprises a conduction band, a valence band, and a band gap between the two. The band gap of a semiconductor material is usually greater than zero and less than 4 eV at a temperature of 300 K. That is, a "semiconductor" material has an electrical conductivity at room temperature that is between that of a conductor (such as copper) and an insulator (such as glass). Preferably, a semiconductor material has an electrical conductivity that increases with temperature.

[0030] The term "nanoparticles" refers to particles having a size between 0.1 nm and 999 nm, preferably between 0.5 nm and 150 nm, more preferably between 1 nm and 50 nm. The term "size" in this context refers to the average diameter of the longest axis that can be established through the particle referred to. The size of these nanoparticles refers to the dimensions of the inorganic semiconductor nanoparticles and does not take into account the dimensions of the ligands that may be present on the surface of the inorganic semiconductor nanoparticles, or other surface modifications applied thereto. The average diameter of a given particle is calculated based on statistics measured by transmission electron microscopy (TEM).

[0031] The term "luminescence" refers to the property of a material or object to emit light of a wavelength of at least 350 nm to 1000 nm upon external optical excitation, such as an incident beam of light of a particular wavelength or range of wavelengths. The term "semiconductor luminescent nanoparticles" in the present context refers to luminescent materials according to the definition of "semiconductor" and with a nanoparticle size between 0.1 nm and 999 nm, preferably 1 nm and 150 nm, more preferably 1 nm and 50 nm.

[0032] In one embodiment, the quantum material is selected from the group consisting of II-VI, III-V, and IV-VI semiconductors, and combinations of two or more thereof. In another embodiment, the quantum material comprises at least one semiconductor nanoparticle selected from the group consisting of Cds, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, GaAs, GaP, GaAs, GaSb, HgS, HgSe, HgSe, HgTe, InAs, InP, InPZn, InPZnS, InSb, AlAs, AlP, AlSb, CuS, CuSe, CuInS2, CuInSe2, Cu(ZnSn)S4, Cu(InGa)S4, TiO2, InGaP, ZnSeS, alloys, and combinations of two or more thereof.

[0033] For example, for red emitting uses, CdSe / CdS, CdSeS / CdZnS, CdSeS / CdS / ZnS, ZnSe / CdS, CdSe / ZnS, InP / ZnS, InP / ZnSe, InP / ZnSe / ZnS, InPZn / ZnS, InPZn / ZnSe / ZnS dots or rods, ZnSe / CdS, ZnSe / ZnS and combinations of two or more thereof. For example, for green emitting uses, CdSe / CdS, CdSeS / CdZnS, CdSeS / CdS / ZnS, ZnSe / CdS, CdSe / ZnS, InP / ZnS, InP / ZnSe, InP / ZnSe / ZnS, InPZn / ZnS, InPZn / ZnSe / ZnS, ZnSe / CdS, ZnSe / ZnS and combinations of two or more thereof. For example, for blue emitting applications, examples include ZnSe, ZnS, ZnSe / ZnS and combinations of two or more thereof.

[0034] As quantum materials, publicly available materials, such as CdSeS / ZnS alloyed quantum materials product numbers 753793, 753777, 753785, 753807, 753750, 753742, 753769, 753866, InP / ZnS quantum materials product numbers 776769, 776750, 776793, 776777, 776785, PbS core type quantum materials product numbers 747017, 747025, 747076, 747084, or CdSe / ZnS alloyed quantum materials product numbers 754226, 748021, 694592, 694657, 694649, 694630, 694622 from Sigma-Aldrich, can preferably be used as desired.

[0035] In some embodiments, the semiconductor nanoparticles can be selected from anisotropic shaped structures, such as quantum rod materials, to achieve better outcoupling effects (e.g., ACS Nano, 2016, 10 (6), pp 5769-5781). Examples of quantum rod materials are described, for example, in International Publication No. WO2010 / 095140A.

[0036] In further embodiments, the length of the overall structure of the quantum material, such as the quantum rod material / or quantum material, is between 1 nm and 500 nm, preferably between 1 nm and 160 nm, or between 1 nm and 20 nm, or between 5 nm and 15 nm. The surface of the semiconductor nanoparticles can be overcoated with one or more surface ligands. Without wishing to be bound by theory, it is believed that such surface ligands can allow the nano-sized fluorescent material to be more easily dispersed in a solvent.

[0037] Examples of suitable commonly used surface ligands include phosphines and phosphine oxides such as trioctylphosphine oxide (TOPO), trioctylphosphine (TOP), and tributylphosphine (TBP); phosphonic acids such as dodecylphosphonic acid (DDPA), tridecylphosphonic acid (TDPA); amines such as oleylamine, dedecylamine (DDA), tetradecylamine (TDA), hexadecylamine (HDA), and octadecylamine (ODA); thiols such as oleylamine (OLA), 1-octadecene (ODE), hexadecanethiol, and hexanethiol; mercaptocarboxylic acids such as mercaptopropionic acid and mercaptoundecanoic acid; carboxylic acids such as oleic acid, stearic acid, myristic acid, and acetic acid; and any combination thereof. Furthermore, the ligands may include Zn-oleate, Zn-acetate, Zn-myristate, Zn-stearate, Zn-laurate, and Zn-carboxylate. Moreover, preferably, polyethyleneimine (PEI) can be used.

[0038] In a preferred embodiment, the composition comprises at least one liquid organic compound. The composition often comprises at least one liquid organic compound in an amount of 2,000 to 50,000 parts, for example 5,000 to 25,000 parts, or 6,000 to 10,000 parts, based on 100 parts of the semiconductor light-emitting nanoparticles in the composition. In one embodiment, the liquid organic compound comprises at least one organic solvent.

[0039] More preferably, the composition comprises at least one liquid organic compound. The composition often comprises 2,000 to 50,000 wt%, for example 5,000 to 25,000 wt%, or 6,000 to 10,000 wt%, of at least one liquid organic compound, based on the total amount of the semiconductor light-emitting nanoparticles in the composition.

[0040] The solvents include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ... The solvent may be selected from the group consisting of propylene glycol alkyl ether acetates such as propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, aromatic hydrocarbons such as benzene, toluene and xylene, ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin, esters such as ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and ethyl lactate, and cyclic asterates such as γ-butyrolactone. The preferred solvent is propylene glycol monomethyl ether acetate (hereinafter "PGMEA"), propylene glycol monoethyl ether acetate, or propylene glycol alkyl ether acetate such as propylene glycol monopropyl ether acetate.

[0041] In further embodiments, the liquid organic compound comprises a combination of two or more of the above organic solvents, which includes two or more solvents from one group, or two or more solvents from different groups above.

[0042] The composition comprises at least one antioxidant. The at least one antioxidant is selected from the group consisting of: A) hydroxyphenol compounds, comprising at least one hydroxyphenol fragment and at least one hydroxy group, where the hydroxyphenol fragment has at least one tert-alkyl group alpha to the at least one hydroxy group, such as, for example, 2-tert-butylhydroquinone; 4-tert-butylcatechol; 6-tert-butyl-2,4-xylenol; 3,5-di-tert-butyl-4-hydroxytoluene; 2,6-di-tert-butylphenol; or a combination of two or more thereof; B) Hydroxyphenolic compounds having two hydroxy groups, such as hydroquinone; C) 2,2-diphenyl-1-picrylhydrazyl; D) Alkoxyphenols, such as 3,5-di-t-butyl-4-hydroxyanisole; E) Heterocyclic thiazines, such as 10-methylphenothiazine; F) Polyphenols, such as carnosol; G) hindered amine stabilizers such as 2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethylpiperidine; or a combination of the two thereof.

[0043] In one embodiment, the composition may include a combination of two or more antioxidants from groups A) to G), e.g., a combination of two or more antioxidants from one of groups A) through G), or a combination of two or more antioxidants selected from different groups A) to G). In further embodiments, the composition comprises one or more antioxidants, wherein one of the antioxidants is 3,5-di-tert-butyl-4-hydroxytoluene (CAS: 128-37-0).

[0044] In a preferred embodiment of the present invention, the antioxidant is a hydroxyphenol compound, comprising at least one hydroxyphenol fragment and at least one hydroxy group, the hydroxyphenol fragment having at least one tert-alkyl group in alpha position to the at least one hydroxy group, such as 2-tert-butylhydroquinone; 4-tert-butylcatechol; 6-tert-butyl-2,4-xylenol; 3,5-di-tert-butyl-4-hydroxytoluene; 2,6-di-tert-butylphenol; or a combination of two or more thereof, and even more preferably it is 3,5-di-tert-butyl-4-hydroxytoluene.

[0045] The polymerizable compound can be any such compound known to those of skill in the art and believed to be potentially useful in compositions that include semiconductor light-emitting nanoparticles. In one embodiment, the polymerizable component may be selected from the group consisting of UV curable monomers and thermosetting monomers. Examples of UV curable monomers include, but are not limited to, acrylic monomers, methacrylic monomers, alkenes, alkynes, and thiols. Examples of thermosetting monomers include, but are not limited to, epoxy-amines and thiol-enes.

[0046] In another embodiment, the amount of the at least one antioxidant is in the range of 20 to 1,000 parts, such as 50 to 500 parts, or 100 to 200 parts, based on 100 parts of the semiconductor luminescent nanoparticles. In a preferred embodiment of the present invention, the amount of the at least one antioxidant is in the range of 20 to 1,000% by weight, based on the total amount of inorganic portions of the semiconductor luminescent nanoparticles in the composition, for example, in the range of 50 to 500% by weight, or 100 to 200% by weight, based on the total amount of inorganic portions of the semiconductor luminescent nanoparticles in the composition.

[0047] For the sake of clarity, according to the present invention, the term "inorganic portion of the semiconductor light-emitting nanoparticles" refers to all inorganic inclusions of the semiconductor light-emitting nanoparticles, and does not include organic ligands attached to the semiconductor light-emitting nanoparticles.

[0048] In another embodiment, the composition further comprises an organic additive that is composed of a divalent metal ion and at least one functionalized hydrocarbon group. The organic additive can be any that is known to those skilled in the art and considered suitable for the present invention. The metal ion in this context is a metal cation. Preferably, the organic additive is not polymeric / macromolecular.

[0049] The organic additive is represented by formula (Ia) or (Ib): M-(XY)2(Ia); XY(Ib) During the ceremony, M is a divalent metal ion; X is a hydrocarbon chain, and Y is a functional group. It can be defined as follows:

[0050] In a further preferred embodiment, the organic additive can be defined by formula (Ia) or (Ib), wherein at least one of the following applies: a) M is selected from the group consisting of Zn, Mg and Cd; b) Y is selected from the group consisting of carboxylate, carbamate, xanthate, phosphonate, phosphate, and thiolate.

[0051] Further preferred embodiments are combinations of two or more organic additives, where one of these features applies: a) with b), or two or more a) with one b), or two or more b) with one a), or two or more a) with two or more b).

[0052] In a further preferred embodiment of the present invention, the organic additive is a compound represented by the formula (II) [ka] During the ceremony, M is defined as above; R1 and R2 can be the same or different, linear or branched, each R1, R2 being selected from the group consisting of alkyl groups having a chain length of 1 to 16 carbon atoms or alkenyl groups having a chain length of 1 to 15 carbon atoms, preferably 1 to 11, or 1 to 6 carbon atoms; is defined as follows:

[0053] In a further preferred embodiment of the invention, the organic additive comprises a member selected from the group consisting of zinc carboxylates, cadmium carboxylates and magnesium carboxylates, or a combination of two or more members thereof. In a further preferred embodiment of the invention, the organic additive comprises a zinc carboxylate. In a further embodiment, the quantum material comprises In and P.

[0054] In a further embodiment, the quantum yield of the composition 16 hours after preparation is at least 90%, e.g., 94% or 96%, relative to the composition at the time of preparation and under the conditions described herein. The time of preparation is 0 hours after preparation.

[0055] In further embodiments, the composition generally comprises the following ranges of these components: at least one semiconductor light-emitting nanoparticle, such as a quantum dot material; and 20 to 1,000 parts of at least one antioxidant based on 100 parts of the semiconductor light-emitting nanoparticles; Optionally, 50 to 400 parts, or 100 to 200 parts, of further components, such as divalent metal ions and organic additives consisting of at least one functionalized hydrocarbon group; 6,000 to 10,000 parts of at least one liquid organic compound based on 100 parts of semiconductor light-emitting nanoparticles; Includes.

[0056] Preferably, the composition comprises the following ranges of these components: at least one semiconductor light-emitting nanoparticle, such as a quantum dot material; and 20 to 1,000 weight percent of at least one antioxidant, based on the total amount of inorganic portions of the semiconductor light-emitting nanoparticles in the composition; More preferably, it is in the range of 50-400% by weight, or 100-200% by weight, of further constituents, such as divalent metal ions and an organic additive consisting of at least one functionalized hydrocarbon group; 6,000 to 10,000 weight percent of at least one liquid organic compound, based on the total amount of semiconductor light-emitting nanoparticles in the composition; Includes.

[0057] The second aspect involves at least these steps: (i) providing semiconductor light-emitting nanoparticles; (ii) providing at least one antioxidant; (iii) providing a liquid organic component; (iv) mixing the components of steps (i)-(iii); A method of making a composition as described in the first aspect and embodiments thereof, comprising:

[0058] Steps (i)-(iv) can be performed in separate acts, or by simply combining some or all of the ingredients in a single container and forming the composition by agitating the contents of the container. The providing steps (i)-(iii) can be performed by any technique or means known in the art and deemed applicable by the skilled artisan, such as dropwise administration, injection into a mixing vessel, pouring, etc.

[0059] The composition of the second aspect can be obtained by stirring the components of steps (i) to (iii). The stirring can be performed in each of the preceding steps (i) to iv) individually or only in step (iv). In one embodiment, a liquid phase is provided in step (i) under stirring, comprising organic compounds and semiconductor light-emitting nanoparticles such as quantum materials, and stirring is maintained throughout each of the further steps (ii) and (iii). Moreover, stirring intervals can be incorporated between each of steps (i) to (iii). This allows the liquid phase, or a combination of the liquid phase from step (i) with one or more further components from steps (ii) or (iii), to settle and / or homogenize before adding another component.

[0060] The preparation of the composition can be operated under inert conditions, at room temperature as well as at elevated temperatures, and / or at normal, elevated or reduced pressure, all referring to the conditions in the mixing vessel. Preferably, step (i) is operated under inert conditions at temperatures ranging from 0 to 100°C and at ambient pressure, which was 1 bar (101.3 kPa) based on the absolute scale (0 kPa = absolute vacuum). Agitation can be achieved by rotating the mixing vessel or by inserting a rotating mixer into the static mixing vessel. A preferred mode of operation involves the use of a flask as a static mixing vessel and an agitator.

[0061] In a further embodiment, the composition obtained by the method of the second aspect can be irradiated with light. It has been found that exposing a composition comprising at least semiconductor light-emitting nanoparticles as described above to light can increase the quantum yield of the composition compared to a composition of quantum material that has not been so treated. In one embodiment, the wavelength of light is selected in the range of 350 to 500 nm.

[0062] The intensity of the light can be the same or can vary across wavelengths of the spectrum. In another embodiment of the invention, the intensity of the light is between 0.05 and 0.5 W / cm 2In a further embodiment, the composition has a luminance in the range of 0.025 to 1 W / cm 2 The optical fiber can be irradiated with light having a wavelength selected from the range of 300 to 600 nm and an intensity in the range.

[0063] A third aspect of the present invention provides a method for producing a method for a method for producing a liquid crystal display comprising at least these steps: (a) providing a substrate; (b) providing a composition according to the first aspect or one of its embodiments, or a composition obtainable by a method as described in the second aspect or one of its related embodiments; (c) applying the composition to a substrate to form a layer; and (d) polymerizing the composition; A method for producing a layered composite comprising:

[0064] A layered composite in this context refers to a product that includes at least a substrate and at least one layer. A layered composite may have more than one layer, for example 2, 3, 4, 5, 6, 7, 8, 9 or 10 layers. All of these layers may be disposed on one side of the substrate. In some substrates, one or more layers may be on a surface of the substrate that is different from the surface on which the layer of the present invention is formed. Moreover, a layered composite may have two or more layers formed from one or more equal or different compositions, as described above.

[0065] Providing the substrate in step (a) can be by any means known to those skilled in the art and deemed potentially useful for carrying out the present invention. Preferred methods of providing include mounting on a substrate holder, placing on a rotating dish, for example in a spin coater or inkjet printer. Suitable substrates can be of any type known to those skilled in the art and considered potentially useful for carrying out the present invention. Preferred substrates are pieces of glass, pieces of polymer, and layered structures.

[0066] Applying the composition in step (b) can be carried out by any means known to those skilled in the art and deemed potentially useful for carrying out the present invention. Preferred methods of applying include spin coating and dip coating.

[0067] After the composition is applied to the substrate in step (c) where the layer is formed, the composition is polymerized in step (d) to stabilize the layer on the substrate. The polymerization can be carried out by heat treatment. For further polymerization, any heat treatment means known to those skilled in the art and considered potentially useful can be used. The heat treatment can affect the evaporation of the solvent, as well as the polymerization and / or crosslinking reaction of one or more components of the composition. Such heat treatment can obtain a stable layer on the substrate that includes the quantum material described above.

[0068] In another embodiment, the polymerizing in step (d) can be carried out by UV treatment. In this case, the layer of the composition on the substrate is exposed to UV radiation, for example radiation with a wavelength in the range of 400-1,000 nm. Often, the UV radiation for polymerizing the composition has a wavelength in the range of 165-365 nm. In a further embodiment, the UV treatment is combined with a heat treatment, for example at a temperature in the range of 50-200°C or in the range of 80-150°C.

[0069] In one embodiment, at least one of the following features applies: a / Before carrying out step (b), the composition is irradiated with light. b / In step (c), the layer on the substrate is irradiated with light; Here, the light is 0.025 to 1 W / cm 2 The composition has an intensity in the range of 300 to 600 nm and a wavelength selected from the range of 300 to 600 nm.

[0070] It has been found that exposing a composition comprising a quantum material as described above to light can increase the quantum yield of the composition compared to a composition that has not been so treated. The light irradiation can be of any wavelength, spectrum and intensity that is considered potentially suitable by the skilled artisan. In one embodiment of the invention, the wavelength of light is selected in the range of 350-500 nm. The intensity of the light can be the same or vary over the entire spectrum of wavelengths. In another embodiment of the invention, light of a single wavelength can be selected. In this case, more than 90% of the applied light has the aforementioned wavelength ±2 nm. In another embodiment of the invention, the intensity of the light is 0.05-0.5 W / cm 2 In a further embodiment, the composition has a luminance in the range of 0.025 to 1 W / cm 2 The optical fiber can be irradiated with light having a wavelength selected from the range of 300 to 600 nm and having an intensity in the range of 100 to 600 nm.

[0071] A fourth aspect of the present invention is a layered composite obtainable by the method of the third aspect or one of its embodiments. As already mentioned, a preferred layered composite comprises a substrate and at least one layer, where at least one layer is a polymer film comprising a quantum material.

[0072] In one embodiment, the thickness of the layer ranges from 0.5 μm to 200 μm, for example, from 2 to 100 μm, or from 4 to 50 μm. The thickness of the layer is determined in a direction perpendicular to the plane generated by the surface of the substrate adjacent to the layer and each of the layers. The thickness of the layer can be determined by cutting a sample piece and analyzing the layer along a perpendicular cut through the substrate using a scanning electron microscope (SEM). Furthermore, if desired, two or more layers can be part of a layered composite material.

[0073] A fifth aspect of the invention is a layered composite comprising at least: aa) At least (A) Semiconductor light-emitting nanoparticles, (B) a matrix polymer; and (C) at least one antioxidant; A layer comprising: Preferably, the at least one antioxidant is one of the following: A) hydroxyphenol compounds, where the hydroxyphenol fragment has at least one tert-alkyl group alpha to at least one hydroxy group; B) hydroxyphenolic compounds having two hydroxy groups; C) 2,2-diphenyl-1-picrylhydrazyl; D) Alkoxyphenols, such as 3,5-di-t-butyl-4-hydroxyanisole; E) Heterocyclic thiazines, for example, 10-methylphenothiazine; F) polyphenols, such as carnosol; and G) hindered amine stabilizers such as 2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethylpiperidine; or a combination of two or more of them; Selected from the group consisting of: bb) substrate; cc) optionally one or more further layers.

[0074] Preferred embodiments of the components of the fifth aspect of the invention are the same as those described above, in particular as those described with respect to the first, second, third and fourth aspects. At least one layer in aa) is preferably obtained from a composition of the first aspect or one of its aspects and / or by one of the methods of the second and fourth aspects of the invention and their aspects. The matrix polymer is formed by polymerization of the polymerizable compound of the composition of the first aspect.

[0075] A sixth aspect of the present invention is an optical device comprising a layered composite as described above or obtainable by the method described above. The layered composite may be, for example, an optical sheet such as a color filter, a color conversion film, a remote phosphor tape, or another film or filter. The optical device comprising the layered composite can be any known to those skilled in the art, examples of which are liquid crystal display devices (LCDs), organic light emitting diodes (OLEDs), backlight units for optical displays, light emitting diode devices (LEDs), microelectromechanical systems (hereinafter "MEMS"), electrowetting displays, electrophoretic displays, lighting devices and solar cells.

[0076] The seventh aspect is: A) hydroxyphenol compounds, wherein the hydroxyphenol fragment has at least one tert-alkyl group alpha to at least one hydroxy group; B) hydroxyphenolic compounds having two hydroxy groups; C) 2,2-diphenyl-1-picrylhydrazyl; D) alkoxyphenols; E) heterocyclic thiazines; F) polyphenols; and G) hindered amine stabilizers; or a combination of two or more of them; Selected from the group consisting of: Antioxidants, Use of a quantum material or a quantum material layer for improving at least one characteristic, said characteristic being one of: (I) the storage time of the dispersion containing the quantum material; (II) the quantum yield of a dispersion containing the quantum material; (III) to increase the quantum yield of a layer containing a quantum material; (IV) to improve the thermal stability of layers containing quantum materials; (V) to improve the photostability of a layer that includes a quantum material; or Selected from the group consisting of combinations of two or more thereof; The above-mentioned uses.

[0077] Suitable antioxidants and further embodiments of this aspect are as described above in relation to the first aspect. This is especially applicable to the antioxidants of groups A) to G) and preferred combinations of two or more thereof.

[0078] According to the invention, the composition may contain two or more semiconductor luminescent nanoparticles. Preferably, the composition contains a plurality of the semiconductor luminescent nanoparticles.

[0079] Test Method Quantum yield Measurements of the quantum yield (QY), central wavelength (CWL, also referred to as peak wavelength), and full width at half maximum (FWHM, also referred to as peak band) in solution were performed using a Hamamatsu Quantaurus QY Absolute PL quantum yield spectrometer C11347-11 (hereinafter referred to as "Hamamatsu Quantaurus").

[0080] example The following examples illustrate some aspects of the present invention.The examples and embodiments described herein are for illustrative purposes only, and it is understood that various modifications or changes may be suggested by those skilled in the art in light of them without departing from the scope of the present invention.Therefore, the present invention is not limited by or to the examples.The amounts stated in the following tables are by weight % unless otherwise specified.

[0081] Example 1 - Synthesis of InP / ZnSe quantum materials 112 mg of InI3 and 150 mg of ZnCl2 are dissolved in 2.5 mL of oleylamine. The dispersion is heated to 180°C. 0.22 mL of hexaethylphosphoric triamide (CAS number 2283-11-6, also called DEA3P) is then added to the solution and kept at 180°C for more than 20 minutes. 0.55 mL of anionic selenium precursor (2MTOP:Se) is then slowly added to the dispersion. TOP:SE is prepared from Se (CAS number 7782-49-2, 99.99%) and trioctylphosphine (CAS:4731-53-7, 97%). The dispersion is then heated stepwise, followed by successive injections of 2.4 mL of 0.4 M Zn(oleate) in 1-octadecene (CAS number: 112-88-9, technical grade - 90%) and 0.38 mL of 2 MTOP:Se shell precursor at temperatures between 200 °C and 320 °C.

[0082] Example 2: Measurement of InP / ZnSe material in toluene with and without BHT. All the following examples (except Comparative Example 7 below) start with washing the mixed crude material with two washing cycles with toluene:ethanol (crude material:toluene:ethanol ratio is 1:1:2 v / v) and a third cycle by direct precipitation from hexane. According to TG analysis, this washing procedure reduces the initial organic content to 13-20% w / w.

[0083] Vials with dispersions of quantum material are adjusted to have 1 ml at a concentration of 20 mgr / ml (with respect to semiconductor nanoparticles, i.e. without counting the organic content). For samples with Zn-acetate and / or BHT, about 30% w / w of Zn-acetate (Zn(Ac)2) and / or about 5% w / w of BHT are added to the dispersion before the procedure and degassed for 1 h. Then 1 ml of QD (= quantum dots) solution in toluene is added and stirred for 1 h. The quantum yield is checked with 0.05 ml of solution for 4 ml of toluene in a Hamamatsu cuvette. After 0 and 16 h, the quantum yield of the samples is measured using a Hamamatsu absolute quantum yield spectrometer (model: Quantaurus C11347-11).

[0084] Comparative Example 1: In these examples, the performance of freshly cleaned samples (substrate + layer of quantum material) is investigated after cleaning and after 16 hours. The quantum yields are 65% and 55%, respectively (see Table 1). Comparative Example 2: In these examples, the performance of a freshly washed sample is investigated, similar to Comparative Example 1. However, the dispersion of the quantum material had an amount of BHT of about 5% w / w. The quantum yield is determined after washing and after 16 hours. The quantum yield is 65% and 64%, respectively.

[0085] [Table 1]

[0086] Example 3: Measurement of InP / ZnSe material in toluene with and without BHT and with and without zinc-carboxylate (e.g. zinc-acetate). The procedure for the following examples is generally the same as for Comparative Example No. 1. However, the change in quantum yield (QY) is - addition of 4 mg / ml of zinc carboxylate (Zn-acetate) to the dispersion, - addition of 5 parts of BHT to the dispersion (100 parts), -16 hours of exposure, Check accordingly.

[0087] The results are shown in Table 2. [Table 2]

[0088] According to the data in Table 2, samples show increased quantum yields when they contain the antioxidant BHT or are irradiated for 16 hours. Samples with 4 mg / ml zinc acetate generally show higher quantum yields (QY) than samples without it.

[0089] Example 4: Measurement of Nanoco red quantum dot material in PGMEA with and without BHT. No cleaning or irradiation was applied. The original dispersion of Nanoco red quantum dots in toluene (110 mg quantum dots / ml) is diluted with anhydrous toluene (Cas no. 108-88-3, 99.8%) to a concentration of 20 mg / ml in a total volume of 2 ml. Then, add the following to two empty vials: 1.20% w / w of 11-phosphonoundecyl acrylate 2. 20% w / w 11-phosphonoundecyl acrylate and ~5% w / w BHT; Add the following.

[0090] The vials are degassed for 1 hour prior to the addition of the quantum dot dispersion. 1 ml of the quantum dot solution is added to each vial and stirred for 1 hour. The toluene is then removed under a stream of argon. 1 ml of PGMEA is then added and stirred for >1 hour. The quantum yield of the reference sample in toluene is measured according to the procedure described in Example 2. According to the measurements in Table 3, the quantum yield loss is greater for the sample that does not contain BHT.

[0091] [Table 3]

[0092] Similar experiments with highly loaded (170mg / ml) Nanoco red quantum dots in PGMA are also performed, giving a QY of 81%. The same QY value is measured after 1-2 months of storage. The QY of a sample from the same series without BHT is not measured.

Claims

1. At least these ingredients: i) at least one semiconductor nanoparticle; ii) at least one antioxidant; iii) a polymerizable component; and iv) liquid organic compound A composition comprising: the composition further comprises a divalent metal ion and an organic additive comprising at least one functionalized hydrocarbon group; The liquid organic compound does not contain a polymerizable component. The composition.

2. The antioxidant is: A) a hydroxyphenol compound, comprising at least one hydroxyphenol fragment and at least one hydroxy group, wherein the hydroxyphenol fragment has at least one tert-alkyl group alpha to the at least one hydroxy group; B) a hydroxyphenol compound having two hydroxy groups; C) 2,2-diphenyl-1-picrylhydrazyl; D) alkoxyphenols; E) heterocyclic thiazines; F) polyphenols; and G) Hindered amine stabilizers such as 2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethylpiperidine; or a combination of two or more thereof; Selected from the group consisting of: The composition of claim 1.

3. The composition of claim 1 or 2, wherein the polymerizable component is selected from the group consisting of UV curable monomers and thermally curable monomers.

4. The composition of any one of claims 1 to 3, wherein the composition comprises at least one antioxidant in the range of 20 to 1,000 parts based on 100 parts of semiconductor nanoparticles in the composition.

5. The composition of any one of claims 1 to 4, wherein the semiconductor nanoparticles are quantum materials, the quantum materials comprising In and P.

6. 6. The composition of any one of claims 1 to 5, wherein the liquid organic compound is selected from the group consisting of monoalkyl ethers, diethylene glycol dialkyl ethers, alkylene glycol ether acetates, aromatic hydrocarbons, ketones, alcohol esters, and ethylene carbonate, or combinations of two or more thereof.

7. 7. The composition of any one of claims 1 to 6, wherein the quantum yield of the composition 16 hours after preparation is at least 90% relative to the composition as prepared and under the conditions described herein.

8. At least these steps: (i) providing a semiconductor nanoparticle, where the semiconductor nanoparticle is a quantum material; (ii) providing at least one antioxidant; (iii) providing a polymerizable component, a liquid organic compound, and an organic additive; (iv) mixing the ingredients of steps (i)-(iii); A method for producing the composition of any one of claims 1 to 7, comprising:

9. The composition has a resistivity of 0.025 to 1 W / cm ２ 9. The method of claim 8, wherein the light is irradiated with light of a wavelength selected from the range of 300 to 600 nm having an intensity in the range of

10. At least these steps: (a) providing a substrate; (b) providing a composition according to any one of claims 1 to 7, or a composition obtainable by the method according to any one of claims 8 or 9; (c) applying the composition to a substrate to form a layer; (d) polymerizing the composition; A method for producing a polymer layer comprising:

11. At least the following: (aa) at least (A) a quantum material comprising at least one type of semiconductor nanoparticle; (B) a matrix polymer; and (C) at least one antioxidant; a layer comprising a divalent metal ion and an organic additive comprising at least one functionalized hydrocarbon group; and (bb) substrate; A layered composite comprising:

12. An optical device comprising the layered composite of claim 11 or obtainable by the method of claim 10.

13. Use of the composition according to any one of claims 1 to 7 for improving at least one characteristic of a quantum material or a quantum material layer selected from the group consisting of: (I) storage time of the dispersion containing the quantum material; (II) the quantum yield of a dispersion containing the quantum material; (III) the quantum yield of the layer including the quantum material; (IV) the thermal stability of the layer including the quantum material; (V) the photostability of the layer containing the quantum material; or A combination of two or more of them.

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