Materials with fluorescent properties, their preparation methods and demonstration devices

Abstract

This invention relates to a material with fluorescent properties, a method for preparing the same, and a display device. The material comprises a first microsphere, a second microsphere, and a dispersion system. The first microsphere comprises a polymer matrix and quantum dot material A dispersed therein and bonded to its molecular chains. The polymer matrix is ​​derived from a monomer containing a (meth)acrylate monomer, and the quantum dot material A is derived from a first fluorescent quantum dot containing ligand A (including a carboxyl group or its salt, a carboxylic acid ester group, and a polymerizable group having unsaturated bonds). The second microsphere comprises a core particle containing an inorganic non-metallic material and quantum dot material B bonded to its surface (having modified groups including aliphatic groups having 10 or more carbon atoms). The quantum dot material B is a second fluorescent quantum dot containing ligand B (including aliphatic groups having 10 or more carbon atoms). The density of both microspheres is greater than the density of the dispersion system. The two microspheres satisfy at least one of the following: (1) they have different densities, and (2) they have different particle sizes.

Description

Technical Field This invention relates to a material with fluorescent properties, its preparation method, and a display device. Background Technology Flowing sand decorations are creative products that combine art and entertainment, typically consisting of a sealed glass container, colored sand, and a frame. The colored sand inside flows and forms patterns, providing a delightful experience. However, existing quicksand paintings have a monotonous effect and limited color vibrancy. Moreover, the light transmittance of quicksand materials on the market is very poor. Therefore, the visual appeal of these quicksand paintings needs to be improved. Quantum dots (QDs) generally refer to nanocrystals with radii smaller than or close to the exciton Bohr radius, especially semiconductor nanocrystals. The particle size of quantum dots typically ranges from 1 nanometer to tens of nanometers, and they are usually spherical or near-spherical. Due to the quantum confinement of electrons and holes, the continuous band structure transforms into a discrete energy level structure with molecular properties. The band gap increases as the size decreases. Therefore, they can exhibit fluorescence upon stimulation and possess various unique physical effects (e.g., quantum size effect, surface effect, dielectric confinement effect, quantum tunneling effect, and Coulomb blocking effect). Thus, the use of quantum dots has the potential to improve the visual appeal of display devices such as quicksand paintings. Summary of the Invention <<The Problem the Invention Aims to Solve>> In view of the above, the technical problem to be solved by the present invention is to provide an easily obtainable fluorescent material and a method thereof that improves visual appeal, especially providing clear visibility in darker environments. In addition, the technical problem to be solved by the present invention is to provide a display device with improved visual appeal. <<Solutions for Problem Solving>> The inventors have discovered that the above-mentioned problems that the invention aims to solve can be solved by the following technical solutions.

[0001] A fluorescent material comprising a first microsphere, a second microsphere, and a dispersion system. The first microsphere comprises: a polymer matrix and quantum dot material A dispersed in the polymer matrix and bonded to the molecular chains of the polymer matrix. The polymer matrix is ​​derived from monomers containing (meth)acrylate monomers. The quantum dot material A is derived from a first fluorescent quantum dot containing ligand A, wherein ligand A comprises a carboxyl group or its salt, a carboxylic acid ester group, and a polymeric group having an unsaturated bond. The second microsphere comprises: a core particle containing an inorganic non-metallic material and quantum dot material B bonded to the surface of the core particle containing the inorganic non-metallic material. The surface of the core particles containing inorganic non-metallic materials has modifying groups, including aliphatic groups having more than 10 carbon atoms. The quantum dot material B is a second fluorescent quantum dot containing ligand B, wherein ligand B comprises an aliphatic group having more than 10 carbon atoms. The density of both the first microsphere and the second microsphere is greater than the density of the dispersion system. The first microsphere and the second microsphere satisfy at least one of the following conditions (1) and (2): (1) The density of the first microsphere is different from that of the second microsphere. (2) The particle size of the first microsphere is different from that of the second microsphere.

[0002] According to the fluorescent material described in [1], the content of the first microsphere is more than 10% by volume and less than 50% by volume relative to the total volume of the first microsphere and the second microsphere is more than 50% by volume and less than 90% by volume.

[0003] According to the fluorescent material described in [1] or [2], wherein the particle size of the first microsphere is 10–200 μm; and / or The second microsphere has a particle size of 10–200 μm; and / or The density difference between the first microsphere and the second microsphere is 0.26–1.65 g / cm³. 3 .

[0004] The material with fluorescent properties according to any one of [1] to [3], wherein the dispersion system comprises a dispersion medium and an optional surfactant.

[0005] The material with fluorescent properties according to any one of [1] to [4], wherein, The ligand A is selected from at least one of aliphatic dicarboxylic acid mono(meth)acryloyloxyalkyl esters, compounds in which the carboxyl group of the aliphatic dicarboxylic acid mono(meth)acryloyloxyalkyl ester forms a salt, and ((meth)acryloyloxy)alkyl acids. The ligand B is selected from at least one of oleic acid, oleylamine, stearic acid, and 1-dodecyl mercaptan; The monomer is a (meth)acrylate monomer, or a combination of a (meth)acrylate monomer and at least one monomer selected from vinyl ether monomers and vinyl carboxylic acid ester monomers; The inorganic non-metallic material is a silicon-containing inorganic non-metallic material.

[0006] The fluorescent material according to any one of [1] to [5] has 3 to 7 colors.

[0007] A method for preparing a material with fluorescent properties according to any one of [1] to [6], comprising: (1) The step of preparing the first microspheres includes: (A1) Prepare quantum dot material A. (A2) Disperse the quantum dot material A in a monomer to form mixture a. (A3) The first microspheres are obtained by adding at least the mixture a to an aqueous phase containing water and a surfactant to form an oil phase as a dispersed phase and polymerizing the mixture. The oil phase contains an initiator. (2) The step of preparing the second microsphere includes: (B1) The modified groups are bonded to the surface of the core particles containing inorganic non-metallic materials to form the modified groups. (B2) The core particles containing inorganic non-metallic materials bonded with the modified groups are dispersed in a solution containing the quantum dot material B to obtain a dispersion. (B3) By adjusting the compatibility of the dispersion liquid, the quantum dot material B is precipitated and bonded to the surface of the core particles containing inorganic non-metallic materials bonded with the modified groups; (3) Mix the first microsphere, the second microsphere and the dispersion system together.

[0008] According to the preparation method described in [7], wherein, In (A3), the mass concentration of the quantum dot material in the oil phase is 0.0001–50%; and / or In (A3), the amount of the initiator is 0.1 to 5% by mass relative to 100% of the total mass of all monomers in the oil phase; and / or In (A3), the amount of surfactant is 0.1 to 7% by mass relative to 100% of the total mass of water in the aqueous phase; and / or In (A3), the aqueous phase further comprises a monomer solubility modifier, wherein optionally, the amount of the monomer solubility modifier is 1 to 10% by mass relative to 100% by mass of the total mass of water in the aqueous phase; and / or In (A3), the volume ratio of the oil phase to the water in the aqueous phase is 1:1 to 1:10; and / or In (A3), the polymerization temperature is 50-85°C, the polymerization time is greater than 1 hour, and the stirring speed is 200-1200 rpm.

[0009] According to the preparation method described in [8], wherein, In (B1), before bonding the modified groups, the core particles containing inorganic non-metallic materials are subjected to hydrophilic treatment; In (B3), the adjustment of the compatibility of the dispersion includes at least one adjustment selected from temperature adjustment and polarity adjustment.

[0010] A display device that uses or includes a fluorescent material according to any one of [1] to [6] or a fluorescent material obtained by any one of [7] to [9]. <<The Effects of the Invention>> In this invention, by employing two types of materials—a first microsphere and a second microsphere—with different densities and / or particle sizes, the flow rates of the two types of microspheres differ, thereby creating a layered effect in the artwork. Furthermore, under excitation light (e.g., visible or ultraviolet light), the quantum dots loaded on the microspheres emit fluorescence, making the overall color of the display device using this fluorescent material richer and brighter, thus improving the visual appeal of the display device. In this invention, the display device uses the fluorescent materials described above, resulting in richer and brighter colors, thereby improving visual appeal. Attached Figure Description Figure 1 An example of the demonstration device of the present invention is shown. Figure 2 , 3 Examples of the microspheres of the present invention under natural light and ultraviolet light are shown respectively. Detailed Implementation Various exemplary embodiments, features, and aspects of the present invention will be described in detail below. The term "exemplary" as used herein means "serving as an example, embodiment, or illustration." Any embodiment described herein as "exemplary" is not necessarily to be construed as superior to or better than other embodiments. Furthermore, to better illustrate the present invention, numerous specific details are set forth in the following detailed embodiments. Those skilled in the art should understand that the present invention can be practiced without certain specific details. In other instances, methods, means, apparatus, and steps well known to those skilled in the art have not been described in detail in order to highlight the spirit of the present invention. Unless otherwise stated, all units used in this specification are international standard units, and all numerical values ​​and ranges appearing in this invention should be understood to include systematic errors that are unavoidable in industrial production. In this specification, the word "may" has two meanings: to perform a certain process and not to perform a certain process. In this specification, references to "some specific / preferred embodiments," "other specific / preferred embodiments," "implementation," etc., refer to specific elements (e.g., features, structures, properties, and / or characteristics) related to that embodiment, which are included in at least one of the embodiments described herein and may or may not be present in other embodiments. Furthermore, it should be understood that these elements may be combined in any suitable manner in various embodiments. In this specification, the numerical range referred to as "value A to value B" refers to the range including endpoint values ​​A and B. The numerical range referred to as "above" and "below" refers to the range including endpoint values. The numerical range referred to as "greater than" and "less than" refers to the range excluding endpoint values. In this specification, "optional" or "optionally" means that the event or situation described below may or may not occur, and the description includes both the scenario in which the event occurs and the scenario in which the event does not occur. Unless otherwise stated, the term "particle size" used in this specification refers to "average particle size," which can be measured using a commercial particle size analyzer or scanning electron microscope. <<Materials with Fluorescent Properties>> The fluorescent material of the present invention includes a first microsphere, a second microsphere, and a dispersion system. The first microsphere comprises: a polymer matrix and a quantum dot material A dispersed in the polymer matrix and bonded to the molecular chains of the polymer matrix. The polymer matrix is ​​derived from monomers containing (meth)acrylate monomers. The quantum dot material A is derived from a first fluorescent quantum dot containing ligand A, which includes a carboxyl group or its salt, a carboxylic acid ester group, and a polymeric group having an unsaturated bond. The second microsphere comprises: a core particle containing an inorganic non-metallic material and a quantum dot material B bonded to the surface of the core particle containing the inorganic non-metallic material. The surface of the core particles containing inorganic non-metallic materials has modified groups, including aliphatic groups having more than 10 carbon atoms. The quantum dot material B is a second fluorescent quantum dot containing ligand B, wherein ligand B comprises an aliphatic group having 10 or more carbon atoms. The density of the first microsphere and the density of the second microsphere are both greater than the density of the dispersion system. The first microsphere and the second microsphere satisfy at least one of the following conditions (1) and (2): (1) the density of the first microsphere is different from the density of the second microsphere; (2) the particle size of the first microsphere is different from the particle size of the second microsphere. When this condition is met, the two types of microspheres can be separated or distinguished from each other to a certain extent during flow, thereby resulting in a strong sense of layering and a good visual effect. In some preferred embodiments, from the viewpoint of achieving better technical effects, the density difference between the first microsphere and the second microsphere is preferably 0.26–1.65 g / cm³. 3 More preferably, it is 0.30–1.52 g / cm³. 3 . In some specific implementations, the first microspheres may have substantially uniform density, or may include various first microspheres with different densities (having more than two densities, such as 2, 3, 5, or 8 densities). In some specific implementations, the second microspheres may have substantially uniform density, or may include various second microspheres with different densities (having more than two densities, such as 2, 3, 5, or 8 densities). Here, "substantially" refers to the situation within ±5% of the average density of the microspheres. In some specific implementations, the first microspheres may have substantially uniform particle size, or may include various first microspheres with different particle sizes (having more than two particle sizes, such as 2, 3, 5, or 8 particle sizes). In some specific implementations, the second microspheres may have substantially uniform particle size, or may include various second microspheres with different particle sizes (having more than two particle sizes, such as 2, 3, 5, or 8 particle sizes). Here, "substantially" refers to the situation within ±5% of the average particle size of the microspheres. In some preferred embodiments, from the viewpoint of achieving better technical effects, the content of the first microsphere is preferably more than 10% by volume and less than 50% by volume relative to the total volume of the first microsphere and the second microsphere (100% by volume), more preferably 15% to 40% by volume, for example, 25% by volume. In some preferred embodiments, from the viewpoint of achieving better technical effects, the content of the second microsphere is greater than 50% and less than 90% by volume relative to the total volume of the first microsphere and the second microsphere (100% by volume), more preferably 60-85% by volume, for example, 75% by volume. In some preferred embodiments, the fluorescent material preferably has multiple colors, more preferably 3 to 7 colors. In this invention, there are no particular limitations on the colors displayed by the first and second microspheres. A single first microsphere, under ultraviolet light irradiation, can display the emission color of the first fluorescent quantum dot, such as red, yellow, or blue, or it can display the composite emission color of the first fluorescent quantum dot after color recombination, such as pink or white. The color recombination technique can employ existing methods, such as combining various first fluorescent quantum dots of multiple colors (at least two colors) to form a first fluorescent quantum dot displaying a composite color. The color after monomer polymerization is transparent, and a single first microsphere can exhibit the color of the quantum dot under natural light, such as colors within the range of white-yellow-orange-red-brown-black. A single second microsphere can display the same color as the emission color of the second fluorescent quantum dot under ultraviolet light. A single second microsphere can exhibit the color of the sand itself under natural light; for example, if the second microsphere is blue under natural light, which is the color of the sand itself, then the second fluorescent quantum dot would be white under natural light. In some specific implementations, the first microsphere has multiple colors. The term "first microsphere has multiple colors" means that while a single first microsphere exhibits one color, multiple first microspheres can exhibit multiple colors. In some specific implementations, the second microspheres have multiple colors. The term "second microspheres have multiple colors" means that while a single second microsphere may exhibit one color, multiple second microspheres can exhibit multiple colors. In addition, different types of components (e.g., first microspheres, second microspheres, and other components) contained in a material with fluorescent properties can be of the same size, and components of the same type can have different colors and / or different sizes, so that they can be better separated from each other during flow, thereby making the layering effect stronger. The composition of the fluorescent material of the present invention will be described in more detail below. <The First Microsphere> In this invention, the first microsphere comprises: a polymer matrix and a quantum dot material A dispersed in the polymer matrix and bonded to the molecular chains of the polymer matrix. In other words, the first microsphere is obtained by polymerizing monomers and also involving the quantum dot material A in the polymerization. In this invention, the polymer matrix is ​​derived from monomers containing (meth)acrylate monomers (i.e., the polymer matrix is ​​a polymer formed by polymerizing monomers containing (meth)acrylate monomers). There are no particular limitations on the specific composition of the monomers, including (meth)acrylate monomers. In some preferred embodiments, the polymers obtained by polymerizing the monomers of the present invention have high transparency, for example, a light transmittance of over 90% over a 1 mm optical path. In some preferred embodiments, from the viewpoint of easily increasing the transparency of the resulting first microspheres, the monomer is a (meth)acrylate monomer, or a combination of a (meth)acrylate monomer and at least one monomer selected from vinyl ether monomers and vinyl carboxylate monomers. Examples of (meth)acrylate monomers include, but are not limited to: alkyl (meth)acrylates (e.g., C1-C8 alkyl esters of (meth)acrylate), such as methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, etc.; hydroxyalkyl (meth)acrylates (e.g., C1-C8 hydroxyalkyl esters of (meth)acrylate), such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc.; glycidyl (meth)acrylate, etc. Methyl (meth)acrylate and glycidyl (meth)acrylate are preferred, and methyl (meth)acrylate is more preferred. Examples of vinyl ether monomers include, but are not limited to: methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether, diethylene glycol vinyl ether, dipropylene glycol vinyl ether, vinyl phenyl glycidyl ether, vinyl glycidyl ether, etc. Examples of vinyl carboxylate monomers include, but are not limited to, C2-C12 vinyl carboxylate esters, such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl octanoate, vinyl heptanoate, etc. Vinyl acetate is preferred among these. In this invention, quantum dot material A is derived from a first fluorescent quantum dot containing ligand A (hereinafter sometimes referred to as quantum dot material A'), wherein ligand A includes a carboxyl group or its salt, a carboxylic acid ester group, and a polymeric group having an unsaturated bond. There are no particular restrictions on the specific structure of ligand A, as long as it contains a carboxyl group or its salt, a carboxylic acid ester group, and a polymerizable group with an unsaturated bond. Specifically, in this invention, ligand A includes three types of groups: 1. a carboxyl group or a salt of the corresponding carboxyl group; 2. a carboxylic acid ester group; and 3. a polymerizable group with an unsaturated bond. In some preferred embodiments, the first fluorescent quantum dot is bonded via the carboxyl group or a salt thereof. The presence of the carboxyl group or a salt thereof serves to bond ligand A to the first fluorescent quantum dot. In some preferred embodiments, the carboxylic acid ester group is located at a site in ligand A that is away from the carboxyl group or its salt. The presence of the carboxylic acid ester group can improve the dispersibility of the first fluorescent quantum dot in the monomer. It should be noted that the carboxylic acid involved in the carboxylic acid ester group is structurally independent of the carboxyl group or its salt mentioned above; they may be the same as or different from each other. In addition, the term "away from" means that the carboxylic acid ester group and the carboxyl group (or its salt) are not attached to the same carbon atom. In some preferred embodiments, at least one of the polymerizable groups with unsaturated bonds is located at the end of the main chain of ligand A. In this invention, the polymerizable groups with unsaturated bonds participate in the polymerization of monomers, thereby forming a "polymer macromolecular ligand" network structure for the quantum dot material, which effectively prevents the migration and aggregation of quantum dots. Furthermore, while there are no particular restrictions on the types of polymerizable groups with unsaturated bonds, the polymerizable groups with unsaturated bonds are preferably polymerizable groups with olefinic unsaturated bonds. Additionally, there are no particular restrictions on the number of polymerizable groups with unsaturated bonds; at least one is acceptable, for example, one or two. In addition, ligand A may also have other affinity groups that are the same as those contained in the monomer described later (i.e., ligand A and the monomer have locally similar molecular structures), thereby improving the affinity between the first fluorescent quantum dot and the monomer and making it more conducive to the dispersion of the first fluorescent quantum dot. Examples of such affinity groups include, but are not limited to, alkoxy groups, epoxy groups, arylita-al ... In some more preferred embodiments, ligand A is at least one selected from aliphatic dicarboxylic acid mono(meth)acryloyloxyalkyl esters, compounds in which the carboxyl group of the aliphatic dicarboxylic acid mono(meth)acryloyloxyalkyl ester forms a salt, and ((meth)acryloyloxy)alkyl acids. In some specific embodiments, the carboxyl salt in the compound formed by the carboxyl group of the aliphatic dicarboxylic acid mono(meth)acryloyloxyalkyl ester is preferably an alkali metal carboxyl salt. In some specific embodiments, the aliphatic dicarboxylic acid mono(meth)acryloyloxyalkyl ester is preferably a C2-C12 dicarboxylic acid, more preferably a C4-C12 dicarboxylic acid. In some specific embodiments, the alkyl group in the aliphatic dicarboxylic acid mono(meth)acryloyloxyalkyl ester is preferably a C1 to C6 alkyl group, more preferably a C1 to C4 alkyl group. In some specific embodiments, the alkyl acid in ((meth)acryloyloxy)alkyl acid is preferably a C1 to C12 alkyl acid, and more preferably a C3 to C6 alkyl acid. Examples of ligand A include, but are not limited to: succinic acid mono{(meth)acryloyloxyethyl} ester, succinic acid mono{(meth)acryloyloxyethyl} ester sodium salt, succinic acid mono{(meth)acryloyloxyethyl} ester potassium salt, maleic acid mono{(meth)acryloyloxyethyl} ester, maleic acid mono{(meth)acryloyloxyethyl} ester sodium salt, maleic acid mono{(meth)acryloyloxyethyl} ester potassium salt, itaconic acid mono{(meth)acryloyloxyethyl} ester, itaconic acid mono{(meth)acryloyloxyethyl} ester sodium salt, itaconic acid mono{(meth)acryloyloxyethyl} ester potassium salt, glutaric acid 1-[2-(acryloyloxy)ethyl] ester; glutaric acid 1-[2-(methacryloyloxy)ethyl] ester [2-(methacryloyloxy)ethyl] ester, sodium salt of 1-[2-(methacryloyloxy)ethyl] ester; potassium salt of 1-[2-(methacryloyloxy)ethyl] ester, succinic acid mono{(meth)acryloyloxypropyl} ester, sodium salt of succinic acid mono{(meth)acryloyloxypropyl} ester, potassium salt of succinic acid mono{(meth)acryloyloxypropyl} ester, maleic acid mono{(meth)acryloyloxypropyl} ester, sodium salt of maleic acid mono{(meth)acryloyloxypropyl} ester, potassium salt of maleic acid mono{(meth)acryloyloxypropyl} ester, itaconic acid mono{(meth)acryloyloxypropyl} ester, sodium salt of itaconic ... Potassium salt of 1-[2-(acryloyloxy)propyl] glutarate; sodium salt of 1-[2-(methacryloyloxy)propyl] glutarate; potassium salt of 1-[2-(methacryloyloxy)propyl] glutarate; succinic acid mono{(meth)acryloyloxybutyl} ester; sodium salt of succinic acid mono{(meth)acryloyloxybutyl} ester; potassium salt of succinic acid mono{(meth)acryloyloxybutyl} ester; maleic acid mono{(meth)acryloyloxybutyl} ester; sodium salt of maleic acid mono{(meth)acryloyloxybutyl} ester; potassium salt of itaconic acid mono{(meth)acryloyloxybutyl} ester; Acryloyloxybutyl ester, itaconic acid mono-(meth)acryloyloxybutyl ester sodium salt, itaconic acid mono-(meth)acryloyloxybutyl ester potassium salt, glutaric acid 1-[2-(acryloyloxy)butyl] ester; glutaric acid 1-[2-(methacryloyloxy)butyl] ester, glutaric acid 1-[2-(acryloyloxy)butyl] ester sodium salt; glutaric acid 1-[2-(methacryloyloxy)butyl] ester potassium salt, ((meth)acryloyloxy)acetic acid, ((meth)acryloyloxy)butyric acid, β-(acryloyloxy)propionic acid, 4-(acryloyloxy)butyric acid, 5-(acryloyloxy)valerate, 6-(acryloyloxyhexanoic acid), etc. These ligands can be used alone or in combination of two or more. In some more preferred embodiments, ligand A is more preferably at least one selected from aliphatic dicarboxylic acid mono(meth)acryloyloxyalkyl esters and compounds in which the carboxyl group of the aliphatic dicarboxylic acid mono(meth)acryloyloxyalkyl esters forms a salt. In this invention, there is no particular limitation on the first fluorescent quantum dot constituting quantum dot material A (or quantum dot material A'), and it can be appropriately selected according to actual needs. In some specific embodiments, examples of the first fluorescent quantum dot may include: quantum dots of group II-VI compounds selected from CdS, CdSe, CdTe, ZnS, ZnSe, PbS, and PbSe; quantum dots of group IV-VI compounds selected from SnTe, PbSe, GeS, GeSe, GeTe, SnS, SnSe, PbS, PbSe, and PbTe; quantum dots of group III-V compounds selected from InP, GaP, GaN, and AlN; quantum dots of core-shell structured materials selected from CdS / ZnS, CdSe / CdS, CdSe / ZnS, CdSe / CdS / ZnS, CdTe / CdS, CdTe / CdS / ZnS, ZnSe / ZnS, InP / ZnSe, InP / ZnS, InP / ZnSe / ZnS, and InP / GaP / ZnS; perovskite quantum dots; and carbon quantum dots. These quantum dots can be used alone or in combination of two or more. In some preferred embodiments, the first fluorescent quantum dot is preferably at least one selected from perovskite quantum dots, carbon quantum dots, and group II-VI compounds. In addition to the polymer matrix and quantum dot material A, the first microsphere may optionally include other components, such as pigments, dyes, antibacterial agents, surfactants, and other polymers that are not chemically bonded to quantum dot material A. There are no particular limitations on the size of the first microsphere, which can be appropriately adjusted according to the application scenario. In some preferred embodiments, the size of the first microsphere can be 10–200 μm, preferably 20–200 μm, for example preferably 35–180 μm, for example preferably 30–150 μm, such as 40 μm, 60 μm, 80 μm, 100 μm, 120 μm, 140 μm, 160 μm, 180 μm, etc. There are no particular limitations on the density of the first microspheres; it can be adjusted appropriately according to the application scenario. In some preferred embodiments, the density of the first microspheres can be 1.1–1.9 g / cm³. 3 Preferably, the concentration is 1.15–1.5 g / cm³. 3 For example, 1.15–1.19 g / cm³ 3 . <Second Microsphere> In this invention, the second microsphere comprises: a core particle containing an inorganic non-metallic material and a quantum dot material B bonded to the surface of the core particle containing the inorganic non-metallic material. The surface of the core particle containing the inorganic non-metallic material has modifying groups, the modifying groups including aliphatic groups having 10 or more carbon atoms, and the quantum dot material B is a second fluorescent quantum dot containing ligand B, the ligand B including aliphatic groups having 10 or more carbon atoms. Based on the principle of compatibility, this invention modifies the surface of the core particles containing inorganic non-metallic materials to have a medium- to long-chain aliphatic structure that is highly compatible with quantum dot material B. Through this configuration, the core particles containing inorganic non-metallic materials and quantum dot material B can be tightly bonded together to form a second microsphere with a core-shell structure. There are no particular restrictions on the specific types of inorganic non-metallic materials. Inorganic non-metallic materials can be carbon-based, nitrogen-based, silicon-based inorganic materials, or inorganic materials formed by any two elements among carbon, nitrogen, and silicon. In addition, inorganic non-metallic materials can be oxides formed from various metals. In some preferred embodiments, the inorganic nonmetallic material is preferably a silicon-containing inorganic nonmetallic material. The silicon-containing inorganic nonmetallic material may be, for example, an oxide of silicon, or an inorganic compound formed from silicon with carbon or nitrogen. In some more preferred embodiments, the inorganic nonmetallic material more preferably comprises at least one selected from silicates and silicon dioxide, and more preferably comprises silicates. Furthermore, the aforementioned inorganic non-metallic materials can be formed from a single material or through a composite of multiple materials. This composite process can include both physical and chemical processes. In some specific embodiments, the core particles of the present invention are substantially formed from the inorganic non-metallic material. There are no particular limitations on the size of the core particles in this invention, and it can be adjusted according to the needs of the final product. In some specific embodiments, the size of the core particles can be 10–200 μm, preferably 15–200 μm, preferably 18–180 μm, preferably 25–150 μm, such as 20 μm, 40 μm, 60 μm, 80 μm, 100 μm, 120 μm, 140 μm, 160 μm, 180 μm, etc. Since the modified groups and quantum dot material B do not substantially occupy a size in the micrometer sense, the size of the core particles in this invention can also be regarded as the size of the second microsphere. There is no particular limitation on the density of the nuclear particles in this invention, and it can be adjusted according to the needs of the final product. In some specific embodiments, the density of the nuclear particles can be 2.0–3.2 g / cm³. 3 Preferably, it is 2.2–2.8 g / cm³. 3For example, 2.5–2.65 g / cm³ 3 . Furthermore, there are no particular restrictions on the shape of the aforementioned nuclear particles, but they are preferably (approximately) spherical. The surface modification groups of the core particles include aliphatic groups with more than 10 carbon atoms. These medium- and long-chain aliphatic groups can improve the hydrophobicity of the core particles and increase their compatibility with the ligands of quantum dot material B, thus facilitating their bonding. While there is no upper limit, the maximum number of carbon atoms in the modifying group can be 30. In some preferred embodiments, the modifying group preferably comprises an aliphatic group with 14 to 25 carbon atoms, especially a linear aliphatic group. Specific examples include (linear) aliphatic groups with 16, 18, 20, and 22 carbon atoms. In some other preferred embodiments, the aliphatic group can be a saturated aliphatic group or an unsaturated aliphatic group. Preferably, in the unsaturated aliphatic group, from the perspective of stability, the degree of unsaturation does not exceed 2, and more preferably 1. Furthermore, there are no particular restrictions on the method of introducing the modifying group, but in some preferred embodiments, it can be introduced by reacting the surface of the core particle with a silane having the above-mentioned aliphatic group, for example as described later in this invention. In this invention, quantum dot material B is a second fluorescent quantum dot containing ligand B, wherein ligand B comprises an aliphatic group having 10 or more carbon atoms. There are no particular restrictions on the specific structure of ligand B, as long as it contains an aliphatic group with 10 or more carbon atoms. In some preferred embodiments, the aliphatic group in ligand B is located away from the site that bonds to the second fluorescent quantum dot. Furthermore, the term "away" means that the aliphatic group is not bonded to the second fluorescent quantum dot. When ligand B possesses medium- to long-chain aliphatic groups with the aforementioned number of carbon atoms, it can increase the compatibility with the ligands of quantum dot material B, thereby facilitating their bonding. While there is no upper limit, the maximum number of carbon atoms in the aliphatic groups contained in ligand B can be 30. In some preferred embodiments, ligand B preferably contains aliphatic groups with 14 to 25 carbon atoms, especially linear aliphatic groups. Specific examples include (linear) aliphatic groups with 16, 18, 20, or 22 carbon atoms. In some other preferred embodiments, the aliphatic group contained in ligand B can be a saturated aliphatic group or an unsaturated aliphatic group. Preferably, in the unsaturated aliphatic group, from the perspective of stability, the degree of unsaturation does not exceed 2, and more preferably 1. Examples of ligand B include, but are not limited to, carboxylic acid compounds such as oleic acid, dodecanoic acid, tetradecanoic acid, and stearic acid; amine compounds such as oleylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, and tetracosamine; and thiol compounds such as 1-dodecylthiol and 1-hexadecylthiol. In some preferred embodiments, ligand B is preferably selected from at least one of oleic acid, oleylamine, stearic acid, and 1-dodecyl mercaptan. In this invention, there is no particular limitation on the second fluorescent quantum dot constituting quantum dot material B, and it can be appropriately selected according to actual needs. Specific examples of the second fluorescent quantum dots constituting quantum dot material B can be listed as those listed regarding quantum dot material A. In addition to the core particles and quantum dot material B, the second microsphere optionally includes a protective layer formed on the layer of said quantum dot material B. In some preferred embodiments, the protective layer may be made of an organosilicon material (e.g., an organosilicon polymer). There are no particular limitations on the size of the second microsphere, which can be appropriately adjusted according to the application scenario. In some preferred embodiments, the size of the second microsphere is preferably 10–200 μm, more preferably 10–180 μm, and even more preferably 15–150 μm, such as 20 μm, 40 μm, 60 μm, 80 μm, 100 μm, 120 μm, 140 μm, 160 μm, 180 μm, etc. There are no particular limitations on the density of the second microspheres; it can be adjusted appropriately according to the application scenario. In some preferred embodiments, the density of the second microspheres can be 2.0–3.2 g / cm³. 3 Preferably, it is 2.2–2.8 g / cm³. 3 For example, 2.5–2.65 g / cm³ 3 . <Distributed Systems> In this invention, there are no particular limitations on the composition of the dispersion system. In some preferred embodiments, the dispersion system comprises a dispersion medium and optionally a surfactant. There are no particular restrictions on the dispersion medium, as long as the second microsphere and the first microsphere can flow freely. Examples of dispersion media include water, alcohol compounds such as ethanol and isopropanol. In some specific embodiments, the dispersion system comprises water and a surfactant. In other specific embodiments, the dispersion system comprises an alcohol compound. Ethanol is preferably used as the alcohol compound. When the dispersion medium is an alcohol compound, surfactants are preferably not used. In this invention, the term "surfactant" refers to a substance that can dissolve in water to reduce the surface tension of the water, and various substances known in the art can generally be used. <Other Ingredients> Materials with fluorescent properties can also contain other components as needed, such as other conventional colored microspheres that do not contain quantum dots, dyes, or other solid decorative particles such as black gold stone, gold powder (glitter) and silver powder. <<Preparation Methods of Materials with Fluorescent Properties>> The method for preparing the above-mentioned fluorescent material of the present invention includes: (1) The step of preparing the first microspheres includes: (A1) Prepare quantum dot material A, (A2) Disperse said quantum dot material A in a monomer to form mixture a, (A3) Form an oil phase as a dispersed phase by adding at least said mixture a to an aqueous phase containing water and a surfactant, and polymerize to obtain the first microspheres, said oil phase containing an initiator. (2) The step of preparing the second microsphere includes: (B1) The modified group is bonded to the surface of the core particles containing inorganic non-metallic material to form the modified group. (B2) The core particles containing inorganic non-metallic material with the modified group bonded are dispersed in a solution containing the quantum dot material B to obtain a dispersion. (B3) By adjusting the compatibility of the dispersion, the quantum dot material B is precipitated and bonded to the surface of the core particles containing inorganic non-metallic material with the modified group bonded. (3) Mix the first microsphere, the second microsphere and the dispersion system together. The steps will be described in more detail below. <Step (1): Preparation of the first microsphere> In this invention, step (1) includes the following steps: (A1) preparing quantum dot material A, (A2) dispersing the quantum dot material A in a monomer to form a mixture a, (A3) forming an oil phase as a dispersed phase by adding at least the mixture a to an aqueous phase containing water and a surfactant and making the oil phase contain an initiator, and performing polymerization to obtain the first microsphere. (Process (A1)) In process (A1), quantum dot material A is prepared. In this invention, there are no particular limitations on the preparation method of quantum dot material A. Various methods known in the art can be used. For example, quantum dot material A of this invention can be obtained by ligand exchange of quantum dot material with original ligands (e.g., oleylamine, oleic acid, etc.). In some preferred embodiments, the quantum dot material A is obtained by stirring a dispersion containing quantum dots with original ligands to a solution containing said ligand A and then performing ligand exchange. In some specific embodiments, ligand exchange is performed as follows: fluorescent quantum dots having original ligands (e.g., oleic acid, oleylamine, etc.) are dispersed in organic solvent A (e.g., chloroform, dichloromethane, hexane, toluene, etc.), with a dispersion concentration of 1–300 mg / mL; ligand A of the present invention is dissolved in organic solvent B (e.g., chloroform, dichloromethane, etc.); the quantum dot material dispersion and the ligand A solution of the present invention are mixed at a volume ratio of 1:1 to 4:1 and stirred until homogeneous to perform ligand exchange. (Process (A2)) In step (A2), the quantum dot material A is dispersed in a monomer to form mixture a. The details of the individual components have been described above and will not be repeated here. There are no particular restrictions on the mass concentration of quantum dot material in mixture a. In some specific embodiments, the mass concentration of quantum dot material in mixture a (relative to the total mass of all mixture a) is preferably 0.0001–50%, more preferably 0.001–20%, further preferably 0.005–10%, and particularly preferably 0.01–50%. In this invention, there are no particular limitations on the method of dissolving quantum dot materials in monomers. Any method known in the art can be used, such as immersing quantum dot materials in monomers, dissolving quantum dot materials in monomers under mechanical force (e.g., vortexing, stirring, etc.), etc. There are no particular restrictions on whether mixture a contains an initiator. In some specific implementations, to prevent prepolymerization of mixture a before formal polymerization, mixture a does not contain an initiator. In other specific embodiments, particularly where no other oily mixtures (such as liquid b described later) are added to the aqueous phase, mixture a includes an initiator. Specific examples of initiators include, but are not limited to: azo initiators, such as azobisisobutyronitrile, azobisisovalerate, and azobisisoheptanenitrile; and organic peroxide initiators, such as tert-butyl peroxynivalenate, tert-butyl peroxynivalenate, disec-butyl peroxydicarbonate, bis(hexadecyl)dicarbonate peroxide, tert-pentyl peroxynivalenate, tert-butyl peroxynivalenate, di-(4-tert-butylcyclohexyl peroxydicarbonate), dicyclohexyl peroxydicarbonate, and diisopropyl peroxydicarbonate. Esters, such as dibutyl peroxide dicarbonate, di(2-ethylhexyl) peroxide dicarbonate, tert-butyl peroxide 2-ethylhexanoate, ditetradecyl peroxide dicarbonate, tert-butyl peroxide acetate, cumyl peroxide neodecanoate, ditert-butyl peroxide, cyclohexylsulfonyl peroxide, benzoyl peroxide, diisobutyryl peroxide, 1,1,3,3-tetramethylbutyl peroxide neodecanoate, di-3-methoxybutyl peroxide dicarbonate, and 1,1,3,3-tetramethylbutyl peroxide pentyl peroxide, etc. These initiators can be used alone or in combination of two or more. When an initiator is included, the amount of initiator is preferably 0.1 to 5% by mass, more preferably 0.2 to 4% by mass, relative to 100% by mass of all monomers in mixture a. In this invention, there is no particular restriction on the timing of adding the initiator to mixture a. For example, the initiator can be added to the aforementioned mixture a containing quantum dot material and monomer, or the initiator can be added to the monomer to form a mixture first, and then the quantum dot material can be added to the mixture to form mixture a. In addition, in some specific embodiments, mixture a may optionally contain a crosslinking agent. (Process (A3)) The first microspheres are obtained by adding at least the mixture a to an aqueous phase containing water and a surfactant to form an oil phase as a dispersed phase and including an initiator in the oil phase, and by polymerization. In this invention, there are no particular restrictions on the polymerization method; preferably, suspension polymerization can be used. In this invention, the mixture a can be dispersed into an oil phase, or a liquid b containing monomers but not quantum dot materials can be added to the aqueous phase in addition to the mixture a to form an oil phase together with the mixture a. The liquid b may include monomers, and, as needed, initiators and other reagents such as chain transfer agents; the monomers can be of various types. There are no particular restrictions on whether liquid b contains an initiator. In some preferred embodiments, particularly where mixture a does not contain an initiator, liquid b may also contain an initiator. Examples of initiators are the same as those listed with respect to mixture a. In addition, in some specific embodiments, liquid b may optionally contain a crosslinking agent. In this invention, the oil phase, which is the dispersed phase, also contains an initiator. In this case, there are no particular limitations on the method of introducing the initiator into the oil phase; as described above, it can be introduced from mixture a, liquid b, or both mixture a and liquid b, as needed. In some preferred embodiments, from the viewpoint of more easily achieving the effects of the invention, the amount of initiator is preferably 0.1 to 5% by mass, more preferably 0.2 to 4% by mass, relative to 100% by mass of all monomers in the oil phase. In some preferred embodiments, the mass concentration of quantum dot material in the oil phase (relative to the total mass of all oil phases) is preferably 0.0001–50%, more preferably 0.001–20%, and even more preferably 0.005–10%. In some preferred embodiments, from the viewpoint of more easily achieving the effects of the present invention, the amount of surfactant used is 0.1 to 7% by mass relative to 100% of the total mass of water in the aqueous phase. Generally, the amount of surfactant affects the morphology of the microspheres; too little surfactant results in larger microspheres and poorer size uniformity, while too much surfactant leads to difficulties in subsequent removal and higher impurity levels in the microspheres. In this invention, the term "surfactant" refers to a substance that can reduce the surface tension of water. There are no particular restrictions on the type of surfactant, as long as it does not involve secondary ligand exchange with the quantum dot material (e.g., it cannot be an acid surfactant or an amine surfactant). In the case of suspension polymerization, the surfactant can be a dispersant known in the art. Examples include, but are not limited to: water-soluble organic substances, such as alcohol surfactants, nitrile surfactants, ether surfactants (e.g., polyvinyl alcohol, methylcellulose, hydroxymethylcellulose, hydroxypropylcellulose, etc.); and water-insoluble inorganic powders (e.g., magnesium carbonate, basic magnesium carbonate, calcium carbonate, barium sulfate, calcium sulfate, calcium phosphate, talc, kaolin, etc.). These surfactants can be used alone or in combination of two or more. In some preferred embodiments, from the viewpoint of more easily achieving the effects of the invention, the surfactant is preferably a combination of a water-soluble organic compound and a water-insoluble inorganic powder, more preferably a combination of polyvinyl alcohol and basic magnesium carbonate. In this case, relative to 100% of the total mass of water in the aqueous phase, the amount of water-soluble organic matter is preferably 0.1 to 5% by mass, for example, 0.5% by mass, 0.8% by mass, 1% by mass, 2% by mass, 2.5% by mass, 3% by mass, 4% by mass, etc., and the amount of water-insoluble inorganic powder is preferably 0.1 to 2% by mass, for example, 0.2% by mass, 0.5% by mass, 0.8% by mass, 1% by mass, 1.5% by mass, 1.8% by mass, etc. As long as the polymerization reaction can achieve polymerization, there are no particular restrictions on whether the aqueous phase contains monomer solubility modifiers. In some specific implementations, the aqueous phase also includes a monomer solubility modifier. The role of the monomer solubility modifier is to reduce the solubility of the monomer in water, thereby making suspension polymerization more favorable. The monomer solubility modifier is preferably a water-soluble metal salt, such as an alkali metal halide, an alkaline earth metal halide, or an alkali metal sulfate. In some particularly preferred embodiments, the monomer solubility modifier is particularly preferably sodium chloride. In some preferred embodiments, from the viewpoint of more easily achieving the effects of the invention, the amount of monomeric solubility modifier is 1 to 10% by mass relative to 100% by mass of the total mass of water in the aqueous phase. In this invention, there are no particular limitations on the method for preparing the aqueous phase, and any method known in the art can be used. For example, components such as water, surfactants, and optional monomer solubility modifiers can be mixed under heating (e.g., heating to a temperature of 60–85°C, such as 80°C) and stirring. In this invention, there are no particular restrictions on the ratio of the oil phase to the water phase, which can be adjusted as needed. In some preferred embodiments, the volume ratio of the oil phase to the water phase is 1:1 to 1:10. In this invention, there are no particular limitations on the implementation method of step (A3), and any method known in the art can be used. In some specific embodiments, an oily mixture containing an initiator is added to a solution containing water, a dispersant, and sodium chloride, and then heated and continuously stirred. In this invention, there are no particular restrictions on the polymerization conditions, which can be adjusted as needed. In some specific implementations, the stirring speed is preferably 200–1200 rpm, more preferably 300–900 rpm. Generally, the stirring speed affects the size of the microspheres; typically, the higher the stirring speed, the smaller the microsphere size. In some specific implementations, the polymerization temperature can be 50–85°C. In some specific implementations, the aggregation time can be greater than 1 hour, preferably greater than 1.5 hours. (Other processes) The method for preparing the first microspheres may optionally include other steps known in the art, such as filtering the product, washing the resulting product, drying the resulting product, and, after obtaining the first microspheres, adding monomers (e.g., mixture a, liquid b, etc.) to the polymerization system again as needed to perform polymerization again (this step can be performed multiple times as needed), etc. <Step (2): Preparation of the second microsphere> In this invention, step (2) includes the following steps: (B1) bonding the modified group to the surface of the core particles containing inorganic non-metallic material; (B2) dispersing the core particles containing inorganic non-metallic material with the modified group bonded in a solution containing the quantum dot material B to obtain a dispersion; (B3) adjusting the compatibility of the dispersion to allow the quantum dot material B to precipitate and bind to the surface of the core particles containing inorganic non-metallic material with the modified group bonded. (Process (B1)) In step (B1), the modified groups are bonded to the surface of the core particles containing inorganic non-metallic materials to form the modified groups. There are no particular restrictions on the way these modified groups are bonded; modified groups can be bonded to the surface of the nuclear particles using various chemical methods known in the art. In some preferred embodiments, when using silicon-containing inorganic non-metallic materials, the modifying groups are preferably introduced by grafting silanes containing the aliphatic and alkoxy groups onto the surface of the core particles. For example, more specifically, the core particles are mixed with silanes containing the aliphatic and alkoxy groups, and optionally, a hydrolysis coupling reaction can be carried out in the presence of water, organic solvents, and / or catalysts. In some preferred embodiments, the silane containing the aliphatic group and alkoxy group is preferably an alkyltrialkoxysilane. The alkyl group, as the aliphatic group, is preferably an alkyl group with 8 to 30 carbon atoms, more preferably an alkyl group with 10 to 25 carbon atoms. Furthermore, in some preferred embodiments, from the viewpoint of better achieving the desired technical effects of the present invention, the alkoxy groups contained in the silane preferably each have 1 to 8 carbon atoms, more preferably 1 to 5. Particularly preferably, the alkoxy groups are methoxy and / or ethoxy groups. In some particularly preferred embodiments, the silane containing the aliphatic group and alkoxy group is particularly preferably at least one selected from hexadecyltrimethoxysilane, heptadecanyltrimethoxysilane, octadecyltrimethoxysilane, and nonadecanyltrimethoxysilane. In this invention, there are no particular restrictions on the form in which silane is used; preferably, a silane solution is used. Examples of solvents used to dissolve silane include, but are not limited to, alkane solvents, such as n-pentane, n-hexane, cyclohexane, n-heptane, etc.; and aromatic solvents, such as benzene, toluene, xylene, etc. Furthermore, there are no particular restrictions on the concentration of silane in the silane solution, which can be appropriately adjusted according to actual needs. For example, the concentration of silane in the silane solution is preferably 0.005–0.2 g / mL, more preferably 0.01–0.1 g / mL. There are no particular restrictions on the reaction conditions for grafting silane onto the surface of the nucleus particle. In some specific embodiments, the reaction temperature for the grafting reaction can be room temperature to 69°C, for example, 15 to 45°C. In other specific embodiments, the reaction time for the grafting reaction can be 1 hour to 7 days, for example, 6 hours to 5 days, or 12 hours to 3 days. Furthermore, in some preferred embodiments, to impart sufficient hydrophilic groups, the core particles containing the inorganic non-metallic material are subjected to a hydrophilic treatment before the modified groups are bonded. Such hydrophilic groups may include hydroxyl, amino, carboxyl, sulfonic acid, mercapto groups, or groups that can be generated by hydrolysis. There are no particular limitations on such hydrophilic treatment. For example, it can be carried out by etching, acid solution treatment, etc. Optionally, heating treatment can be performed during the process as needed. In some preferred embodiments, when using silicon-containing inorganic non-metallic materials, the hydrophilic treatment of the core particles is preferably carried out by: etching the core particles with an acid solution, and then reacting them with water under heating to generate a high-silicon film on the surface of the core particles; and then treating the surface of the core particles with the high-silicon film generated with an oxidant. In this invention, the so-called "high-silicon film" refers to a silicon film with high silicon content obtained by reacting silicon-containing inorganic non-metallic materials in the core particles with water (i.e., high-temperature hydrolysis). Compared with the original surface, its silicon content ratio is greatly increased. For example, within a thickness range of 2nm on the surface, the mass ratio of Si element can reach about 70%. Its main constituent elements are Si, O and H. Since silanes are linked through hydroxyl groups on the surface of the core particles, and after the above-mentioned reaction with water and oxidation treatment, a large number of hydroxyl groups (Si-OH) will be grafted onto Si in the high-silicon film, thus ensuring that more silanes can be linked, improving the bonding ability with quantum dot material B. There are no particular restrictions on the etching conditions (temperature and time, etc.) using acid solutions; commonly used etching conditions for glass products in the art can be used. Furthermore, examples of acid solutions used as etching solutions include, but are not limited to, dilute hydrochloric acid solutions, dilute nitric acid solutions, and dilute sulfuric acid solutions. There is no particular limitation on the temperature for the above reaction with water. However, in some preferred embodiments, from the viewpoint of more easily obtaining sufficient hydroxyl groups on the surface of the base microspheres, the temperature for the above reaction with water is 150–300°C, for example 180–250°C. There is no particular limitation on the reaction time with water described above. However, in some preferred embodiments, from the viewpoint of more easily obtaining sufficient hydroxyl groups on the surface of the base microspheres, for example, it can be 12 hours or more, preferably 24 hours or more, and even more preferably 2 to 10 days, for example, 5 days. Examples of oxidizing agents include, but are not limited to, hydrogen peroxide, and mixed solutions of hydrogen peroxide and concentrated sulfuric acid (e.g., piranha etching solution (a mixed solution of 30% hydrogen peroxide and 70% concentrated sulfuric acid)). In some specific embodiments, the core particles are immersed in an oxidant to allow the high-silica layer to bond a large number of hydroxyl groups. In this case, the immersion temperature can be, for example, room temperature to 200°C, preferably 50 to 120°C; the immersion time can be, for example, 5 hours to 2 days, preferably 8 hours to 24 hours. (Process (B2)) In step (B2), the core particles containing inorganic non-metallic materials bonded with the modified groups are dispersed in a solution containing the quantum dot material B to obtain a dispersion. The solvent used in the solution containing the quantum dot material B can, in principle, be any nonpolar or weakly polar solvent that has good solubility for the quantum dot material B. That is, such a solvent is sufficient to make the solution containing the quantum dot material B exhibit a substantially homogeneous state. For such solvents, preferred solvents can be octadecene, diphenyl ether, paraffin oil, etc., and more preferably octadecene. In the dispersion step, since the core particles with modified groups are generally hydrophobic, they can be more easily and uniformly dispersed in the above solvent / solution. There are no particular restrictions on the temperature at which the dispersion step is performed, as long as it does not lead to the precipitation of the second fluorescent quantum dot. Furthermore, in some preferred embodiments, the solid content of the solution containing the quantum dot material B can be 0.05 to 1 mg / ml before the addition of the core particles. (Process (B3)) In step (B3), by adjusting the compatibility of the dispersion liquid, the quantum dot material B is precipitated and bonded to the surface of the core particles containing inorganic non-metallic material bonded with the modified groups. During this process, the solubility of quantum dot material B in the solvent system decreases sharply due to the change in compatibility in the dispersion, and it moves towards the component or phase with high compatibility. As a result, quantum dot material B can be precipitated on the surface of the core particle with the help of its ligand B and form a strong bond. There are no particular limitations on the possible driving forces for the phase separation mentioned above; for example, it could be a change in temperature or a change in the polarity of the system. From the viewpoint of the intensity of phase separation, in some preferred embodiments, such phase separation is preferably achieved by adjusting the polarity of the dispersion. This can typically be achieved by providing a polar solvent to the dispersion obtained in step (B2). For such a polar solvent, various polar organic solvents known in the art can be used. Preferably, polar organic solvents with a polarity parameter of 4 or higher, such as alcohol solvents, ketone solvents, nitrile solvents, etc. Preferably, alcohol solvents such as methanol and ethanol can be used. Such solvents, in addition to phase separation, can also remove the original solvent contained in the quantum dot material B solution, so that the second microspheres obtained in step (B3) do not contain the aforementioned original solvent. There are no particular restrictions on the method of adding the above-mentioned polar solvents; they can be added in several batches. In some preferred embodiments, a polar solvent can be added to the dispersion in an amount sufficient to cause all quantum dot material B to precipitate from the surface of the core particles. This portion of the solvent forms a homogeneous mixture with the original nonpolar or weakly polar solvent in the dispersion. The liquid can then be drained, thereby removing most or all of the original nonpolar or weakly polar solvent. Furthermore, a polar solvent can be added to the system to promote complete phase separation. The second microsphere, as a solid product, can then be obtained through filtration or other methods. (Process (B4)) Step (2) in preparing the second microsphere may optionally include (B4) forming a protective layer on the surface of the core particle containing the inorganic non-metallic material incorporating the quantum dot material B. In this case, the stability of the second microsphere can be further improved. In some preferred embodiments, when the protective layer is made of an organosilicon material, the protective layer can be prepared as follows: core particles incorporating the quantum dot material B are added to a solution of alkyl orthosilicate (e.g., methyl orthosilicate TMOS or ethyl orthosilicate TEOS) to obtain a mixed solution, and an acid solution (e.g., 0.5–2 M, or 1 M hydrochloric acid solution) as a catalyst is added to the mixed solution (preferably, the amount of acid catalyst is typically 1%–5% of the volume of the alkyl orthosilicate), and water (e.g., deionized water, distilled water, etc.) is added under stirring to initiate the reaction. The mixture is stirred continuously until it begins to form a gel, and then dried and aged at room temperature. The resulting gel is then frozen to a low temperature, and then heated under vacuum conditions to remove the solvent directly from the solid state by sublimation. Finally, the prepared quantum dot composite material is crushed to obtain the desired microspheres with a core-shell-protective layer structure. (Other processes) The method for preparing the second microsphere may optionally include other steps known in the art, such as filtering the raw materials or the products obtained in each step, washing the raw materials or the products obtained in each step, drying the raw materials or the products obtained in each step, removing solvents, crushing materials, etc. <Step (3): Mixing Step> In step (3), the first microsphere, the second microsphere, and the dispersion system are mixed together. There are no particular restrictions on the mixing method; any method known in the art can be used. <<Exhibition Installation>> The display device of the present invention comprises the fluorescent material described above. Therefore, the visual appeal of the display device of the present invention is improved. In this invention, there are no particular restrictions on the types of display devices, and examples include sand paintings, mobile phone cases, three-dimensional decorations, pendants, etc. Example The embodiments of the present invention will be described in detail below with reference to examples. However, those skilled in the art will understand that the following examples are for illustrative purposes only and should not be considered as limiting the scope of the invention. Unless otherwise specified in the examples, conventional conditions or conditions recommended by the manufacturer are followed. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products. <<Example 1>> <Preparation of the First Microsphere> (1) Preparation of the oil phase CdSe / ZnS fluorescent quantum dots containing a ligand (mono-2-(methacryloyloxy)ethyl maleate) were dispersed in methyl methacrylate monomer to form an oily mixture. Benzoyl peroxide was then added to the oily mixture to obtain an oil phase. The mass ratio of benzoyl peroxide to CdSe / ZnS fluorescent quantum dots containing the ligand (mono-2-(methacryloyloxy)ethyl maleate) to methyl methacrylate was 3:3:200. The CdSe / ZnS fluorescent quantum dots emitted a bright green light under ultraviolet irradiation. The mass concentration of the fluorescent quantum dots in the oil phase was 1.5%, and the density of the methyl methacrylate monomer was 0.94 g / cm³. 3 . (2) Preparation of the aqueous phase The aqueous phase was obtained by mixing 120 mL of water, 2.5 g of polyvinyl alcohol, 2 g of basic magnesium carbonate, and 4 g of sodium chloride under heating and stirring conditions. (3) Obtaining the first microsphere The oil phase obtained in step (1) was added to the aqueous phase obtained in step (2), and the mixture was heated to 80°C with stirring at 800 r / min to carry out polymerization. Finally, the mixture was filtered, washed, and dried to obtain the first microsphere A, wherein the density of the first microsphere A was 1.19 g / cm³. 3 It is light yellow under natural light and emerald green under ultraviolet light, with a particle size of 10μm. <Preparation of the Second Microsphere> (1) Formation of nuclei with modified groups (a) Take 100g of sand, wash and dry it, and the density of the sand is 2.55g / cm³. 3 The particle size is 200μm and the color is blue. (b) The sand obtained in step (a) was treated with a 1 mol / L hydrochloric acid solution, etched at 120°C, and then cleaned and dried. (c) Place the etched sand obtained in step (b) into deionized water, soak it at 200°C and then dry it. (d) The sand obtained in step (c) was treated with a mixed solution of concentrated sulfuric acid and hydrogen peroxide, then rinsed with excess deionized water and dried. (e) The sand obtained in step (d) was redispersed with 300 ml of n-hexane, followed by the addition of 9 g of octadecyltrimethoxysilane and stirring to obtain core particle material with modified groups. (2) Obtaining the second microsphere Take 20g of the modified core particle material obtained in step (1) above, add 3ml of CdS fluorescent quantum dot solution (dissolved in octadecene, solid content 0.05mg / ml, CdS fluorescent quantum dots emit blue light under ultraviolet light), then add methanol solution, shake and let stand, remove methanol, repeat the above process of adding methanol, washing and removing several times to obtain the second microsphere A, wherein the density of the second microsphere A is 2.65g / cm³. 3 The particle size is 200μm, and the color is blue under natural light and under ultraviolet light. <<Example 2>> <Preparation of the First Microsphere> In Example 1, the green-emitting CdSe / ZnS fluorescent quantum dots were replaced with blue-emitting CdSe / ZnS quantum dots. Otherwise, the method was the same as in Example 1 for the preparation of the first microsphere, yielding first microsphere B (density 1.19 g / cm³). 3 The particle size is 10μm, and the color is white under natural light and blue under ultraviolet light. <Preparation of the Second Microsphere> In Example 1, the color of the sand was replaced with dark blue, and the blue-emitting CdS fluorescent quantum dots were replaced with dark blue-emitting CdS fluorescent quantum dots. Otherwise, the method was the same as in Example 1, yielding second microsphere B (density 2.65 g / cm³). 3 The first microsphere has a particle size of 200 μm, and the second microsphere has a density of 2.65 g / cm³. 3 The particle size is 200μm, and the color is dark blue under natural light and dark blue under ultraviolet light. <<Example 3>> <Preparation of the First Microsphere> The rotation speed in step (3) of <Preparation of the First Microsphere> in Example 2 was adjusted to 500 r / min. Otherwise, the method was the same as that in <Preparation of the First Microsphere> in Example 2, and the first microsphere D (density 1.19 g / cm³) was obtained. 3 The microspheres have a particle size of 125 μm, are white under natural light, and are blue under ultraviolet light. In Example 2, the blue-emitting CdSe / ZnS quantum dots were replaced with light-blue-emitting CdSe / ZnS quantum dots. The rotation speed in step (3) was adjusted to 550 r / min, and step (2) was adjusted as follows. Otherwise, the method was the same as in Example 2 for the preparation of the first microsphere, and the first microsphere F (density 1.19 g / cm³) was obtained. 3The microspheres have a particle size of 75 μm, are white under natural light, and light blue under ultraviolet light. (2) Preparation of the aqueous phase The aqueous phase was obtained by mixing 120 mL of water, 2 g of polyvinyl alcohol, 1.8 g of basic magnesium carbonate, and 4 g of sodium chloride under heating and stirring conditions. The rotation speed in step (3) of <Preparation of the First Microsphere> in Example 1 was adjusted to 500 r / min. Otherwise, the method was the same as that in <Preparation of the First Microsphere> in Example 1, and the first microsphere E (density 1.19 g / cm³) was obtained. 3 The microspheres have a particle size of 125 μm, appear light yellow under natural light, and emerald green under ultraviolet light. <Preparation of the Second Microsphere> In Example 1, the color of the sand was replaced with light blue, and the blue-emitting CdS fluorescent quantum dots were replaced with light blue-emitting CdS fluorescent quantum dots. Otherwise, the method was the same as in Example 1 for the preparation of the second microspheres, resulting in the second microsphere C (density 2.65 g / cm³). 3 The particle size is 200μm, and the color is light blue under natural light and light blue under ultraviolet light. In Example 1, the sand particle size was replaced with 125 μm. Otherwise, the method was the same as in Example 1 for the preparation of the second microspheres, yielding second microsphere D (density 2.65 g / cm³). 3 The microspheres have a particle size of 125 μm and are blue under natural light and also under ultraviolet light. In Example 1, the sand particle size was replaced with 125 μm, the color was changed to white, and the blue-emitting CdS fluorescent quantum dots were replaced with blue-green emitting CdS fluorescent quantum dots. Otherwise, the method was the same as in Example 1, yielding second microsphere E (density 2.65 g / cm³). 3 The microspheres have a particle size of 125 μm, are white under natural light, and are blue-green under ultraviolet light. Preparation of materials with fluorescent properties The first microspheres A, B, and F, and the second microspheres A, B, C, and D from Examples 1-3 were mixed with water and a surfactant to form a material with fluorescent properties. The volume ratio of the first microspheres to the second microspheres was 1:9. The fluorescent material was then placed in a display device, shaken, and after stabilization, irradiated with ultraviolet light to obtain… Figure 1After being irradiated with ultraviolet light, the first microsphere A appears emerald green, the first microsphere B appears blue, the first microsphere F appears blue, the second microsphere A appears blue, the second microsphere B appears dark blue, the second microsphere C appears light blue, and the second microsphere D appears blue. In addition, to easily demonstrate the visual effects of the fluorescent materials, each microsphere was mixed with water and a surfactant and added to the sample vials. Photographs of the resulting samples under natural light are shown below. Figure 2 The photographs of each sample obtained under ultraviolet light are shown in the figure. Figure 3 middle. Figure 2 and 3 In the experiment, bottle 1 contains the second microsphere D, bottle 2 contains the second microsphere D and the second microsphere E, bottle 3 contains the second microsphere D and the first microsphere F, bottle 4 contains the second microsphere D and the first microsphere E, and bottle 5 contains the first microsphere D and the first microsphere E. from Figure 2 and 3 As can be seen, the first microsphere D appears white under natural light and blue under ultraviolet light. The first microsphere E appears light yellow under natural light and emerald green under ultraviolet light. The first microsphere F appears white under natural light and light blue under ultraviolet light. The second microsphere D appears blue under both natural and ultraviolet light. The second microsphere E appears white under natural light and blue-green under ultraviolet light. like Figure 1 and Figure 2 As shown in bottles 3 and 4, the microsphere assembly of the present invention presents a beautiful, fluid, and varied visual effect. like Figure 2 As shown in bottle number 1, it is difficult to achieve the desired visual effect when using a certain type of microsphere. For example... Figure 2 As shown in bottles 2 and 5, when microspheres of the same density and particle size (the first microsphere or the second microsphere) are used, it is difficult to display the desired visual effect even when multiple colors are present. It should be noted that although the technical solution of the present invention has been described with specific examples, those skilled in the art will understand that the present invention should not be limited thereto. The various embodiments of the present invention have been described above. These descriptions are exemplary and not exhaustive, nor are they limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments. The terminology used herein is chosen to best explain the principles, practical application, or technical improvements to the embodiments in the market, or to enable others skilled in the art to understand the embodiments disclosed herein.

Claims

1. A material having fluorescent properties, characterized in that, Includes the first microsphere, the second microsphere, and the dispersion system. The first microsphere comprises: a polymer matrix and quantum dot material A dispersed in the polymer matrix and bonded to the molecular chains of the polymer matrix. The polymer matrix is ​​derived from monomers containing (meth)acrylate monomers. The quantum dot material A is derived from a first fluorescent quantum dot containing ligand A, wherein ligand A comprises a carboxyl group or its salt, a carboxylic acid ester group, and a polymeric group having an unsaturated bond. The second microsphere comprises: a core particle containing an inorganic non-metallic material and quantum dot material B bonded to the surface of the core particle containing the inorganic non-metallic material. The surface of the core particles containing inorganic non-metallic materials has modifying groups, including aliphatic groups having more than 10 carbon atoms. The quantum dot material B is a second fluorescent quantum dot containing ligand B, wherein ligand B comprises an aliphatic group having more than 10 carbon atoms. The density of both the first microsphere and the second microsphere is greater than the density of the dispersion system. The first microsphere and the second microsphere satisfy at least one of the following conditions (1) and (2): (1) The density of the first microsphere is different from that of the second microsphere. (2) The particle size of the first microsphere is different from that of the second microsphere.

2. The material having fluorescent properties according to claim 1, wherein, Relative to the total volume of the first microsphere and the second microsphere (100% volume), the content of the first microsphere is 10% or more and less than 50% volume, and the content of the second microsphere is greater than 50% volume and less than 90% volume.

3. The material having fluorescent properties according to claim 1 or 2, characterized in that, The particle size of the first microsphere is 10–200 μm; and / or The second microsphere has a particle size of 10–200 μm; and / or The difference between the density of the first microspheres and the density of the second microspheres is 0.26 to 1.65 g / cm3 3 .

4. The material having fluorescent properties according to any one of claims 1 to 3, characterized in that, The dispersion system comprises a dispersion medium and an optional surfactant.

5. The material with fluorescent properties according to any one of claims 1 to 4, characterized in that, The ligand A is selected from at least one of aliphatic dicarboxylic acid mono(meth)acryloyloxyalkyl esters, compounds in which the carboxyl group of the aliphatic dicarboxylic acid mono(meth)acryloyloxyalkyl ester forms a salt, and ((meth)acryloyloxy)alkyl acids. The ligand B is selected from at least one of oleic acid, oleylamine, stearic acid, and 1-dodecyl mercaptan; The monomer is a (meth)acrylate monomer, or a combination of a (meth)acrylate monomer and at least one monomer selected from vinyl ether monomers and vinyl carboxylic acid ester monomers; The inorganic non-metallic material is a silicon-containing inorganic non-metallic material.

6. The material having fluorescent properties according to any one of claims 1 to 5, characterized in that, The fluorescent material has 3 to 7 colors.

7. A method for producing a material having fluorescent properties according to any one of claims 1 to 6, characterized by, include: (1) The step of preparing the first microspheres includes: (A1) Prepare quantum dot material A. (A2) Disperse the quantum dot material A in a monomer to form mixture a. (A3) The first microspheres are obtained by adding at least the mixture a to an aqueous phase containing water and a surfactant to form an oil phase as a dispersed phase and polymerizing the mixture. The oil phase contains an initiator. (2) The step of preparing the second microsphere includes: (B1) The modified groups are bonded to the surface of the core particles containing inorganic non-metallic materials to form the modified groups. (B2) The core particles containing inorganic non-metallic materials bonded with the modified groups are dispersed in a solution containing the quantum dot material B to obtain a dispersion. (B3) By adjusting the compatibility of the dispersion liquid, the quantum dot material B is precipitated and bonded to the surface of the core particles containing inorganic non-metallic materials bonded with the modified groups; (3) Mix the first microsphere, the second microsphere and the dispersion system together.

8. The preparation method according to claim 7, characterized in that, In (A3), the mass concentration of the quantum dot material in the oil phase is 0.0001–50%; and / or In (A3), the amount of the initiator is 0.1 to 5% by mass relative to 100% of the total mass of all monomers in the oil phase; and / or In (A3), the amount of surfactant is 0.1 to 7% by mass relative to 100% of the total mass of water in the aqueous phase; and / or In (A3), the aqueous phase further comprises a monomer solubility modifier, wherein optionally, the amount of the monomer solubility modifier is 1 to 10% by mass relative to 100% by mass of the total mass of water in the aqueous phase; and / or In (A3), the volume ratio of the oil phase to the water in the aqueous phase is 1:1 to 1:10; and / or In (A3), the polymerization temperature is 50-85°C, the polymerization time is greater than 1 hour, and the stirring speed is 200-1200 rpm.

9. The preparation method according to claim 8, characterized in that, In (B1), before bonding the modified groups, the core particles containing inorganic non-metallic materials are subjected to hydrophilic treatment; In (B3), the adjustment of the compatibility of the dispersion includes at least one adjustment selected from temperature adjustment and polarity adjustment.

10. A display device, characterized by It uses or includes materials with fluorescent properties according to any one of claims 1 to 6 or materials with fluorescent properties obtained by any one of claims 7 to 9.

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