WO2022073948A1 - Particule et procédé de fabrication d'une particule - Google Patents

Particule et procédé de fabrication d'une particule Download PDF

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Publication number
WO2022073948A1
WO2022073948A1 PCT/EP2021/077327 EP2021077327W WO2022073948A1 WO 2022073948 A1 WO2022073948 A1 WO 2022073948A1 EP 2021077327 W EP2021077327 W EP 2021077327W WO 2022073948 A1 WO2022073948 A1 WO 2022073948A1
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WIPO (PCT)
Prior art keywords
phosphor
range
polymer
inorganic
light
Prior art date
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PCT/EP2021/077327
Other languages
English (en)
Inventor
Hiroki Yoshizaki
Hiroshi Okura
Ryota YAMANASHI
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Merck Patent Gmbh
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Publication of WO2022073948A1 publication Critical patent/WO2022073948A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
    • H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
    • H01L33/502—Wavelength conversion materials
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G9/00—Cultivation in receptacles, forcing-frames or greenhouses; Edging for beds, lawn or the like
    • A01G9/14—Greenhouses
    • A01G9/1407—Greenhouses of flexible synthetic material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/67—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals
    • C09K11/676—Aluminates; Silicates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/67—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals
    • C09K11/68—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals containing chromium, molybdenum or tungsten
    • C09K11/685—Aluminates; Silicates
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05C—INDEXING SCHEME RELATING TO MATERIALS, MATERIAL PROPERTIES OR MATERIAL CHARACTERISTICS FOR MACHINES, ENGINES OR PUMPS OTHER THAN NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES
    • F05C2203/00—Non-metallic inorganic materials
    • F05C2203/04—Phosphor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
    • H01L2933/0008—Processes
    • H01L2933/0033—Processes relating to semiconductor body packages
    • H01L2933/0041—Processes relating to semiconductor body packages relating to wavelength conversion elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
    • H01L33/505—Wavelength conversion elements characterised by the shape, e.g. plate or foil
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301—Details of OLEDs
    • H10K2102/331—Nanoparticles used in non-emissive layers, e.g. in packaging layer

Definitions

  • the present invention relates to a particle comprising a phosphorcontaining inner core, an outer core surrounding the inner core, and a polymer shell enclosing the outer core, a method for the preparation of said particle and to uses of said particle, especially in agriculture. Furthermore, the present invention relates to a composition, a formulation, an optical sheet, an optical device, and a greenhouse, a plant, a container and a method comprising said particle.
  • WO 2017/129351 A1 discloses utilizing an inorganic phosphor for agriculture.
  • a color conversion foil including a plurality of inorganic phosphor materials, a light emitting diode comprising an inorganic phosphor material and optical devices comprising a light conversion foil for agriculture are known in the prior art, for example as described in JP 2007-135583 A, WO 1993/009664 A1 , JP H09-249773 A, JP 2001 -28947 A, JP 2004-113160
  • a phosphor particle with a light conversion and light reflection function that produces optimal blue, red and infrared light
  • improved optical properties such as light scattering, absorbing, refraction and/or reflection ability of a phosphor particle
  • improved long term moisture durability, improved water resistance, and improved UV-stability good durability of a phosphor particle or of an optical sheet using a phosphor particle
  • an phosphor particle having a higher EQE improved dispersibility of phosphor particles in a formulation, composition and/or in a matrix material of a film or sheet
  • improved transparency of a film or sheet preferably improved transparency of an agricultural film; avoiding or reducing scratching of the kneading machine or of an inflation molding machine caused by a phosphor particle
  • the present invention in one aspect provides for a particle comprising: at least one inner core, which comprises a phosphor; an outer core, which at least partially surrounds the at least one inner core; and a shell, which encloses the outer core, wherein the shell comprises a polymer layer.
  • the present invention in another aspect provides also for a method for preparing a particle of the invention, which includes the steps: (a) preparing a suspension of a phosphor and adding to the suspension a mixture of one or more polymer precursor; and (b) polymerizing the resulting mixture by applying heat; or which includes the steps: (a’) preparing a solution of the one or more polymer precursor; and (b’) adding a phosphor to this solution.
  • the present invention relates to a use of the particle of the present invention in agriculture, in a light emitting diode (LED) or in a solar cell.
  • LED light emitting diode
  • the present invention furthermore relates to a composition comprising at least one particle of the present invention and a further material.
  • the present invention also relates to a formulation comprising at least one particle of the present invention or the composition of the present invention, and a solvent.
  • the present invention relates to a use of the particle of the present invention, the composition of the present invention, or the formulation of the present invention, in a method for preparing an optical sheet or in agriculture, preferably for preparing an agricultural sheet or for controlling a condition of a living organism.
  • the invention relates to an optical sheet comprising at least one particle of the present invention or the composition of the present invention, preferably said optical sheet is an agricultural sheet.
  • the present invention furthermore relates to a method for preparing said optical sheet, and to a use of said optical sheet in an optical device, and to a method for preparing said agriculture sheet.
  • the invention relates to an optical device comprising at least one optical sheet of the present invention, preferably said optical device is a lighting device, more preferably it is a Light Emitting Diode, and to a method for the preparation of the optical device.
  • the invention relates to a use of the optical sheet of the present invention or the optical device of the present invention for agriculture, preferably for greenhouse or for controlling a condition of a living organism in agriculture.
  • the invention in another aspect, relates to a greenhouse comprising an optical sheet of the present invention or an optical device of the invention.
  • the invention relates to a use of the particle of the present invention, the composition of the present invention, the formulation of the present invention, the optical sheet of the present invention, the optical device of the present invention, or the greenhouse of the present invention for the cultivation of algae, bacteria, and/or plankton, preferably it is photo planktons, preferably for improvement of controlling property of a phytoplankton condition, photosynthetic bacteria and/or alga, preferably acceleration of growth of phytoplankton, photosynthetic bacteria and/or alga; improvement of controlling property of plant condition, preferably controlling of a plant height; controlling of color of fruits; promotion and inhibition of germination; controlling of synthesis of chlorophyll and carotenoids, preferably by blue light; plant growth promotion; adjustment and I or acceleration of flowering time of plants; controlling of production of plant components, such as increasing production amount, controlling of polyphenols content, sugar content, vitamin content of plants; controlling of secondary metabolites, preferably controlling of polyphenols, and/or anthocyanin
  • the invention relates to a method of supplying the particle of the present invention, the composition of the present invention, or the formulation of the present invention to at least one portion of a plant.
  • the invention relates to a method of supplying the particle of the present invention, the composition of the present invention, or the formulation of the present invention to at least one portion of a plant.
  • the invention relates to a method for modulating a condition of a plant, plankton, and/or a bacterium.
  • the invention relates to a plant obtained or obtainable by the method of the present invention, or plankton obtained or obtainable by the method of the present invention, or a bacterium obtained or obtainable by the method of the present invention.
  • the invention in another aspect, relates to a container comprising at least one plant, plankton, and/or one bacterium of the present invention.
  • Figs. 1-1 and 1-2 are photographs of encapsulated particles according to the present invention obtained from working example 1 .
  • Fig. 2 is a photograph of encapsulated particles according to the present invention obtained from working example 2.
  • Figs. 3-1 and 3-2 are photographs of encapsulated particles according to the present invention obtained from working example 3.
  • Fig. 4 is a schematic drawing showing an embodiment of an encapsulated particle according to the present invention.
  • Fig. 5 is a schematic drawing showing another embodiment of an encapsulated particle according to the present invention.
  • the term ’’plant means a multicellular organism in the kingdom Plantae that use photosynthesis to make their own food.
  • the plant can be flowers, vegetables, fruits, grasses, trees and horticultural crops (preferably flowers and horticultural crops, more preferably flowers).
  • the plant can be foliage plants.
  • Exemplified embodiments of grasses are a poaceae, bambuseae (preferably sasa, phyllostachys), oryzeae (preferably oryza), pooideae (preferably poeae), triticeae (preferably elymus), elytrigia, hordeum, triticum, secale, arundineae, centotheceae, chloridoideae, hordeum vulgare, avena sativa, secale cereal, andropogoneae (preferably coix), cymbopogon, saccharum, sorghum, zea (preferably zea mays), sorghum bicolor, saccharum officinarum, coix lacryma-jobi van, paniceae (preferably panicum), setaria, echinochloa (preferably panicum miliaceum), echinochloa esculenta, and setaria italic.
  • Embodiments of vegetables are stem vegetables, leaves vegetables, flowers vegetables, stalk vegetables, bulb vegetables, seed vegetables (preferably beans), roots vegetables, tubers vegetables, and fruits vegetables.
  • One embodiment of the plant can be Gaillardia, Lettuce, Rucola, Komatsuna (Japanese mustard spinach) or Radish (preferably Gaillardia, Lettuce, or Rucola).
  • light modulating material is a material which can change at least one of physical properties of light. Preferably it is selected from pigments, dyes and luminescent materials.
  • pigments stands for materials that are insoluble in an aqueous solution and changes the color of reflected or transmitted light as the result of wavelength-selective absorption and/or reflection, e.g. Inorganic pigments, organic pigments and inorganic-organic hybrid pigments.
  • dye means colored substances that are soluble in an aqueous solution and changes the color as the result of wavelength-selective absorption of irradiation.
  • the term “luminescent” means spontaneous emission of light by a substance not resulting from heat. It is intended to include both, phosphorescent light emission as well as fluorescent light emission.
  • the term “light luminescent material” is a material which can emit either fluorescent light or phosphorescent light.
  • the term “phosphorescent light emission” is defined as being a spin prohibition light emission from a triplet state or higher spin state (e.g. quintet) of spin multiplicity (2S+1 ) > 3, wherein S is the total spin angular momentum (sum of all the electron spins).
  • photon down-conversion is a process which leads to the emission of light at longer wavelength than the excitation wavelength, e.g. by the absorption of one photon leads to the emission of light at longer wavelength.
  • photon up-conversion is a process that leads to the emission of light at shorter wavelength than the excitation wavelength, e.g. by the two- photon absorption (TPA) or Triplet-triplet annihilation (TTA), wherein the mechanisms for photon up-conversion are well known in the art.
  • TPA two- photon absorption
  • TTA Triplet-triplet annihilation
  • organometallic material means a material of organometallic compounds and organic compounds without any metals or metal ions.
  • organometallic compounds stands for chemical compounds containing at least one chemical bond between a carbon atom of an organic molecule and a metal, including alkaline, alkaline earth, and transition metals, e.g. Alq3, LiQ, lr(ppy)3.
  • the inorganic materials include phosphors as well as semiconductor nanoparticles.
  • a “Phosphor” within the meaning of the present application is a materials which absorbs electromagnetic radiation of a specific wavelength range, preferably blue and/or ultraviolet (UV) electromagnetic radiation and converts the absorbed electromagnetic radiation into electromagnetic radiation having a different wavelength range, preferably visible (VIS) light such as violet, blue, green, yellow, orange, or red light, or the near infrared light (NIR).
  • VIS visible
  • NIR near infrared light
  • UV electromagnetic radiation with a wavelength from 100 nm to 389nm, shorter than that of visible light but longer than X-rays.
  • VIS electromagnetic radiation with a wavelength from 390 nm to 700 nm.
  • NIR is electromagnetic radiation with a wavelength from 701 nm to 1 ,000 nm.
  • semiconductor nanoparticle in the present application denotes a crystalline nanoparticle which consists of a semiconductor material.
  • Semiconductor nanoparticles are also referred to as quantum materials in the present application. They represent a class of nanomaterials with physical properties that are widely tunable by controlling particle size, composition and shape. Among the most evident size dependent property of this class of materials is the tunable fluorescence emission. The tunability is afforded by the quantum confinement effect, where reducing particle size leads to a “particle in a box” behavior, resulting in a blue shift of the band gap energy and hence the light emission.
  • the emission of CdSe nanocrystals can be tuned from 660 nm for particles of diameter of ⁇ 6.5 nm, to 500 nm for particles of diameter of ⁇ 2 nm. Similar behavior can be achieved for other semiconductors when prepared as nanocrystals allowing for broad spectral coverage from the UV (using ZnSe, CdS for example) throughout the visible (using CdSe, InP for example) to the near-IR (using InAs for example).
  • Semiconductor nanoparticles may have an organic ligand on the outermost surface of the nanoparticles.
  • emission means the emission of electromagnetic waves by electron transitions in atoms and molecules.
  • the term “transparent” means at least around 60 % of incident light transmittal. Preferably, it is over 70 %, more preferably over 75%, and most preferably, it is over 80 %.
  • the present invention relates to a particle which comprises: at least one inner core comprising a phosphor; an outer core at least partially surrounding the at least one inner core; and a shell enclosing the outer core, wherein the shell comprises a polymer layer.
  • the particle comprises only one inner core comprising a phosphor, as illustrated in Fig. 4.
  • the particle comprises more than one inner core, preferably 2, 3 or 4 inner cores, each comprising a phosphor as illustrated in Fig. 5.
  • the particle comprises only one inner core.
  • the term “shell” or “shell layer”, which terms are used interchangeably herein, means the structure which forms an outer layer that partially or completely encloses the outer core. It should be understood that the shell, which encloses the outer core, at least indirectly also encloses the at least one inner core. Preferably, said shell completely encloses the outer core, such that the outer core and the at least one inner core comprising a phosphor are encapsulated within said shell, thereby forming an encapsulated phosphor particle.
  • core and “shell” are well known in the art and typically used in the field of quantum materials, such as US 8221651 B2.
  • the polymer layer comprises, essentially consists of, or consists of a polymer.
  • the polymer is an organic polymer, and preferably is selected from one or more member of the group consisting of polyurethanes, polyureas, poly(meth)acrylates, polyesters, polyacrylurethanes, polyacrylurethanesilicones, polyfluoroacrylurethanes, polyfluoroacrylates, polysilicones, polystyreneacrylates, polybutyrals, polychlorovinylidenes, meramine resins, phenol resins, polycarbonates, polysulfones, polyethers, polyamides, polystyrenes including poly(styrene-co-divinylbenzenes, polyisobutylenes, ethyl cellulose and poly(lactic acid); or an inorganic polymer, and preferably is selected from one or more member of the group consisting of polysilanes, polysilox
  • the polymer is an organic polymer, and even more preferably it is selected from one or more member of the group consisting of polystyrenes including P oly(styrene-co-divinylbenzenes, poly(meth)acrylates, polyisobutylenes and ethyl cellulose.
  • the polymer layer is a transparent polymer layer.
  • the polymer layer has an incident light transmittal of at least around 60 %. More preferably, it is over 70 %, more preferably, over 75%, most preferably, it is over 80 % incident light transmittal.
  • said transparent polymer is an organic polymer, more preferably it is selected from one or more member of the group consisting of (meth)acrylate polymers, polystyrenes including poly(styrene-co-divinylbenzenes, polyisobutylene, ethyl cellulose.
  • the shell comprises the polymer layer and one or more further layers, at least one of which is of a material different than the polymer layer, and preferably being one or more further polymer layers. More preferably, at least one of the one or more further polymer layers, preferably all of the further polymer layers, are independently selected from the above defined organic polymers and inorganic polymers, or combinations of one or more of each.
  • the location of the polymer layer is not particularly limited, that is, it may be the innermost layer, i.e. , the layer being in direct physical contact with the outer core, or the outermost layer of the shell, or an intermediate layer in case the shell comprises more than one further layers.
  • the shell comprises or consists of three layers, one of which is the polymer layer as defined above (layer A) and two further polymer layers, which are of a material different form each other and different to the polymer layer (layers B and C). Accordingly, the following layer sequences are possible according to exemplary embodiments of the present invention (from the innermost to the outermost shell layer): ABC; ACB, BAC, CAB, BCA, CBA.
  • the shell comprises or consists of three layers, one of which is the polymer layer as defined above (layer A) and two further polymer layers, which are of the same material but different to the polymer layer (layers B and B’). Accordingly, the following layer sequences are possible according to exemplary embodiments of the present invention (from the innermost to the outermost shell layer): ABB’; AB’B, BAB’, B’AB, BB’A, B’BA.
  • the shell comprises or consists of three layers, one of which is the polymer layer as defined above (layer A) and two further polymer layers, one of which is of the same material as the polymer layer (layer A’) and one of which is of a different material (layer B).
  • layer A the polymer layer as defined above
  • layer B two further polymer layers, one of which is of the same material as the polymer layer (layer A’) and one of which is of a different material
  • layer B the following layer sequences are possible according to exemplary embodiments of the present invention (from the innermost to the outermost shell layer): ABA’; AA’B, BAA’, A’AB, BA’A, A’BA.
  • the shell comprises a first polymer layer and a second polymer layer, which are independently selected from an organic polymer, an inorganic polymer and a combination of an organic polymer and an inorganic polymer, preferably from an organic polymer and an inorganic polymer, more preferably said first polymer layer is the polymer layer described above and said second polymer layer is a further layer, that is, a further polymer layer being of a material different than the polymer layer.
  • the material of the further polymer layer is selected from the above defined organic polymers and inorganic polymers, or combinations of one or more of each.
  • the location of the first polymer layer is not particularly limited, too, that is, it may be the innermost layer, i.e. , the layer being in direct physical contact with the outer core, or the outermost layer of the shell.
  • the shell according to the present invention consists of the first polymer layer and the second polymer layer.
  • the shell is a single layer, that is, the shell only comprises, essentially consist of, or consist of the polymer layer described above.
  • the outer core according to the present invention may comprise any one or more materials selected from organic liquids and organic solids, which include, for example, refractive index modifiers such as oc- bromonaphthalene, oc-iodonaphthalene, 1 ,2-dibromobenzene, 1 ,3- dibromobenzene, iodobenzene or 1 ,3-diiodobenzene, dye solutions, fragrance or perfuming agents such as limonene, rosemary oil, and the like, drugs, pesticides, or nutrients, without being limited thereto; inorganic liquids and inorganic solids, which include, for example, silicon-based liquids or resins, such as silicones, polycarbosilanes and polysilazines, which give high transmittance and high barrier ability against water degradation, without being limited thereto; and gases, for example, CO2, CO, SO2, NO, or N2, without being limited thereto, and including air.
  • the at least one inner core comprising a phosphor is at least partially surrounded by the outer core.
  • the one or more inner cores not necessarily have to be located in the center of the particle and the outer core, respectively.
  • the one or more inner cores may freely “float” or “drift” within the outer core, such that one inner core or more inner cores may at least temporarily be in contact with the inner surface of the shell, or some inner cores may agglomerate, and consequently may only be partially surrounded by the outer core.
  • the one or more inner cores not necessarily have to be located in the center of the particle and of the outer core, respectively. In each case it is however preferable that the one or more inner cores are not in direct physical contact with the shell.
  • a type of shape of the particle of the present invention is not particularly limited.
  • the particles may be spherical shaped, as illustrated in Figs. 1-1 , 1-2 and Fig. 2, or elongated shaped, as illustrated in Figs. 3-1 , 3-2 provided herein.
  • the phosphor may at least partially, preferably completely be coated with at least one polymer material and/or at least one inorganic material.
  • the at least one inner core comprises, essentially consists of, or consists of the phosphor and a layer of at least one polymer material and/or of at least one inorganic material coated onto the outermost surface of said phosphor, such that the layer at least partially, but preferably completely covers said phosphor.
  • the phosphor including the coating layer is at least partially surrounded by the outer core.
  • said at least one polymer material for coating the phosphor is an organic polymer, more preferably a transparent organic polymer, and particularly preferably it is selected from one or more member of the group consisting of (meth)acrylate polymers, polystyrenes, polyethylene polyethyleneterephthalate, polyurethane, polyacrylonitrile, epoxy resin derived from glycidyl function on (meth)acrylate monomer, biodegradable polymer such as polylactide, polyglycolide, polyhydroxyalkanoate, polycaproractone, without being limited thereto.
  • the polymer material for coating the inner core has at least one anchoring group selected from one or more members of the group consisting of phosphine groups, phosphine oxide groups, phosphate groups, phosphonate groups, thiol groups, tertiary amine, carboxyl groups, hetero cyclic groups, silane groups, sulfonic acids, hydroxyl groups, succinates and phosphonic acids.
  • anchoring group selected from one or more members of the group consisting of phosphine groups, phosphine oxide groups, phosphate groups, phosphonate groups, thiol groups, tertiary amine, carboxyl groups, hetero cyclic groups, silane groups, sulfonic acids, hydroxyl groups, succinates and phosphonic acids.
  • Said at least one inorganic material for coating the phosphor is preferably a metal oxide selected from one or more members of the group consisting of SiC>2, TiO2, ZnO2, ZrO2 and AI2O3, without being limited thereto, and more preferably it is selected from SiC>2, TiO2, ZnChor a combination of any of these.
  • Fig. 4 is a schematic drawing illustrating an encapsulated particle according to the present invention containing one inner core.
  • encapsulated particle 10 has one inner core 5 which consists of phosphor 4 and coating layer 3, which is made of a polymer material and/or an inorganic material and is coated onto the outermost surface of phosphor 4.
  • the inner core 5 is completely surrounded by outer core 2.
  • Outer core 2 in turn is completely enclosed by shell 1 .
  • Fig. 5 is a schematic drawing illustrating an encapsulated particle according to the present invention containing four inner cores. Referring to Fig. 5, in encapsulated particle 20 some of the four inner cores 25 are completely, some only partly surrounded by outer core 22. Shell 21 completely encloses the outer core 22 and each of four inner cores 25.
  • the particle has an external quantum efficiency (EQE) of 10% or more, preferably it is from 10% to 90%, more preferably from 20% to 80%, further more preferably from 30% to 80%, the most preferably it is from 40% to 80%.
  • EQE external quantum efficiency
  • the EQE is calculated by the below Equation (1 ):
  • EQE total number of photons emitted from the phosphor sample/ total number of photons irradiated to the phosphor sample
  • the data for calculating the EQE i.e. , the total number of photons emitted from the phosphor sample (i.e., emission light) and the total number of photons irradiated to the phosphor sample (i.e., excitation light) are obtained using a spectrophotofluorometer FP6500 (from JASCO) equipped with a xenon lamp.
  • the following measurement setup is applied:
  • the peak maximum wavelength of excitation light 320 nm
  • the measurement range of Excitation light 300-400 nm
  • the measurement range of Emission light 650-800 nm Slit distance: 3 mm
  • Luminescent (emission) band width 3 nm
  • a target powder phosphor sample for EQE measurement is set to a glass cell.
  • the glass cell is set to behind the integrating sphere with respect to the excitation light.
  • EQE measurement and calculation is performed by the following procedure of steps A) to D) in this sequence, using a sample prepared as described above:
  • Peak wavelength of this emission spectrum of the measured phosphor is referred to as A nm
  • the EQE value is calculated by sample and reference spectra. Excitation range: 300 ⁇ (B+50) nm Emission range: (B+50) ⁇ 800 nm
  • the phosphor comprised in the at least one inner core is not particularly limited.
  • An inorganic phosphor or an organic phosphor can be used as desired.
  • the phosphor is a fluorescent or a phosphorescent inorganic material which contains one or more light emitting centers (i.e. , a so called “inorganic phosphor”).
  • the light emitting centers are formed by activator elements such as e.g.
  • rare earth metal elements for example La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu
  • transition metal elements for example Cr, Mn, Fe, Co, Ni, Cu, Ag, Au and Zn
  • main group metal elements for example Na, Tl, Sn, Pb, Sb and Bi.
  • Suitable phosphors include phosphors based on garnet, silicate, orthosilicate, thiogallate, sulfide, nitride, silicon-based oxynitride, nitridosilicate, nitridoaluminumsilicate, oxonitridosilicate, oxonitridoaluminumsilicate and rare earth doped sialon.
  • said inorganic phosphor contains one or more of elements selected from the group consisting of alkali metal elements, alkaline metal elements, phosphorous atom, boron atom and sulfur atom, preferably said alkali metal element is Li, Na, Ka or a combination of any of these, and said alkaline metal element is Be, Mg, Ca, Sr, Ba or a combination of any of these.
  • the coating obtained by the method of the present invention is especially preferable to inorganic phosphors containing one or more of elements selected from the group consisting of alkali metal elements, alkaline metal elements, and phosphorous atom, preferably said alkali metal element is Li, Na, Ka or a combination of any of these, and said alkaline metal element is Be, Mg, Ca, Sr, Ba or a combination of any of these to avoid any water damage to the phosphors.
  • the inorganic phosphor has a peak wavelength of light emitted from the inorganic phosphor in the range of 600 nm or more, preferably in the range from 600 to 1500 nm, more preferably in the range from 600 to 800 nm, even more preferably in the range from 620 to 780 nm, furthermore preferably in the range from 650 to 750 nm, much more preferably it is from 650 nm to 740 nm, the most preferably from 660 nm to 720 nm; or the phosphor has a peak wavelength of light emitted from the phosphor in the range of 500 nm or less, preferably in the range from 300 nm to 500 nm, more preferably in the range from 350 nm to 495 nm, even more preferably in the range from 400 nm to 490 nm, furthermore preferably in the range from 405 nm to 490 nm, much more preferably in the range from 405 nm to
  • peak wavelength comprises both the main peak of an emission/absorption spectrum having maximum intensity/absorption and side peaks having smaller intensity/absorption than the main peak.
  • the term peak wavelength is related to a side peak.
  • the term peak wavelength is related to the main peak having maximum intensity/absorption.
  • the phosphor is a nontoxic phosphor and/or an edible phosphor.
  • the term “edible” means safe to eat, fit to eat, fit to be eaten, fit for human consumption.
  • said inorganic phosphor is selected from the group consisting of metal-oxide phosphors, silicate and halide phosphors, phosphate phosphors, borate and borosilicate phosphors, aluminate, gallate and alumosilicate phosphors, sulfate, sulfide, selenide and telluride phosphors, nitride and oxynitride phosphors and SiAION phosphors, preferably, it is a metal oxide phosphor, more preferably it is a Mn activated metal oxide phosphor or a Mn activated phosphate based phosphor, even more preferably it is a Mn activated metal oxide phosphor.
  • Mn 4+ activated metal oxide phosphors Mn, Eu activated metal oxide phosphors, Mn 2+ activated metal oxide phosphors, Fe 3+ activated metal oxide phosphors can be used preferably from the viewpoint of environmentally friendliness, since these phosphors do not create Cr 6+ during synthesis procedure.
  • the Mn 4+ activated metal oxide phosphors are very useful for plant growth, since it shows narrow full width at half maximum (hereafter “FWHM”) of the light emission, and have the peak absorption wavelength in UV and green wavelength region such as 350 nm and 520 nm, and the emission peak wavelength is in near infrared ray region in the range of 600 nm or more, preferably in the range from 600 to 1500 nm, more preferably in the range from 650 to 1000 nm, even more preferably in the range from 650 to 800 nm, furthermore preferably in the range from 650 to 750 nm, much more preferably it is from 660 nm to 730 nm, the most preferably from 670 nm to 710 nm.
  • FWHM narrow full width at half maximum
  • the Mn 4+ activated metal oxide phosphors can absorb the specific UV light which attracts insects, and green light which does not give any advantage for plant growth, and can convert the absorbed light to longer wavelength in the range of 600 nm or more, preferably in the range from 600 to 1500 nm, more preferably in the range from 650 to 1000 nm, even more preferably in the range from 650 to 800 nm, furthermore preferably in the range from 650 to 750 nm, much more preferably it is from 660 nm to 730 nm, the most preferably from 670 nm to 710nm, which can effectively accelerate plant growth.
  • the inorganic phosphor is selected from one or more of Mn activated metal oxide phosphors or Mn activated phosphate based phosphors represented by one of the following formulae (I) to (XII),
  • X a ZbOc:Mn 4+
  • X is a monovalent cation and is selected from one or more members of the group consisting of Li + , Na + , K + , Ag + and Cu +
  • a 2 is a divalent cation and is selected from one or more members of the group consisting of Mg 2+ , Zn 2+ , Cu 2+ , Co 2+ , Ni 2+ , Fe 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Mn 2+ , Ce 2+ and Sn 2+
  • B 2 is a tetravalent cation and is Al 3+ , Ga 3+ or a combination of these; preferably A 2 is Mg 2+ , Zn 2+ or a combination of Mg 2+ and Zn 2+ , B 1 is Ti 3+ , Zr 3+ or a combination of Ti 3+ and Zr 3 , more preferably formula (III) is (Ca, Sr, Ba)i4(AI,
  • M 2 is a divalent cation selected from Ca 2+ , Sr 2+ , Ba 2+ or a combination of any of these
  • Q is a divalent cation selected from one or more members of the group consisting of Mg 2+ , Sr 2+ , Ba 2+ , Zn 2+ , Cu 2+ , Co 2+ , Ni 2+ , Fe 2+ , Ca 2+ , Mn 2+ , Ce 2+ ;
  • Mn is Mn4 + ;
  • a 4 is at least one cation selected from the group consisting of Mg 2+ , Ca 2+ , Sr 2+ and Ba 2+ Zn 2+ , preferably A 4 is Ba 2+ ;
  • B 3 is at least one cation selected from the group consisting of Sc 3+ , Y 3+ , La 3+ , Ce 3+ , B 3+ , Al 3+ and Ga 3+ , preferably B 3 is Y 3+ ;
  • C 1 is at least one cation selected from the group consisting of V 5+ , Nb 5+ and Ta 5+ , preferably C 1 is Ta 5+ ; preferably Mn is Mn 4+ , more preferably said phosphor is Ba 2 YTaOe:Mn 4+ ;
  • a 5 is at least one cation selected from the group consisting of Li + , Na + , K + Rb + and Cs + , preferably A 5 is Na + ;
  • B 4 is at least one cation selected from the group consisting of Sc 3+ , La 3+ , Ce 3+ B 3+ , Al 3+ and Ga 3+ , preferably B 4 is La 3+ ;
  • C 2 is at least one cation selected from the group consisting of Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ and Zn 2+ , preferably C 2 is Mg 2+ ;
  • D 1 is at least one cation selected from the group consisting of Mo 6+ and W 3 *, preferably D 1 is W 6 *, preferably Mn is Mn 4+ , more preferably said phosphor is more preferably the phosphor is NaLaMgWOe:Mn 4+ ;
  • a 6 is at least one cation selected from the group consisting of is a trivalent cation and is selected from one or more members of the group consisting of Sc 3+ , Y 3+ , La 3+ , Ce 3+ , Pr 3+ , Nd 3+ , Pm 3+ , Sm 3+ , Eu 3+ , Gd 3+ , Tb 3+ , Dy 3+ , Ho 3+ , Er 3+ , Tm 3+ , Yb 3+ , Lu 3+ , Ti 3+ , V 3+ , Cr 3+ , Mn 3+ , Fe 3+ , Co 3+ , Ni 3+ , Cu 3+ ,
  • B 5 is a divalent cation and is selected from one or more members of the group consisting of Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Nd 2+ , Sm 2+ , Eu 2+ , Dy 2+ , Ho 2+ , Tm 2+ , Yb 2+ , Ti 2+ , V 2+ , Cr 2+ , Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ , Cu 2+ , Mo 2+ , Pd 2+ , Ag 2+ , W 2 *, Pt 2+ , Zn 2+ , Cd 2+ , Hg 2+ , Ge 2+ , Sn 2+ and Pb 2+ ,
  • C 3 is a tetravalent cation and is selected from one or more members of the group consisting of Ce 4+ , Pr 4+ , Nd 4+ , Tb 4+ , Dy 4+ , Ti 4+ , V 4+ , Cr 4+ , Mn 4+ , Fe 4+ , Co 4+ , Ni 4+ , Zr 4+ , Nb 4+ , Mo 4+ , Tc 4+ , Ru 4+ , Rh 4+ , Pd 4+ , Hf 4+ , Ta 4+ , W 4+ , Re 4+ , Os 4+ , lr 4+ , Pt 4+ , Si 4+ , Ge 4+ , Sn 4+ , Pb 4+ , S 4+ , Se 4+ , Te 4+ and Po 4+ , preferably A 6 is Sc 3+ , Y 3+ , La 3+ , Lu 3+ , B 3+ , Al 3+ , Ga 3+ , ln
  • a 7 is a divalent cation and is selected from one or more members of the group consisting of Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Nd 2+ , Sm 2+ , Eu 2+ , Dy 2+ , Ho 2+ , Tm 2+ , Yb 2+ , Ti 2+ , V 2+ , Cr 2+ , Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ , Cu 2+ , Mo 2+ , Pd 2+ , Ag 2+ , W 2 *, Pt 2+ , Zn 2+ , Cd 2+ , Hg 2+ , Ge 2+ , Sn 2+ and Pb 2+ ,
  • B 6 is a trivalent cation and is selected from one or more members of the group consisting of Sc 3+ , Y 3+ , La 3+ , Ce 3+ , Pr 3+ , Nd 3+ , Pm 3+ , Sm 3+ , Eu 3+ , Gd 3+ , Tb 3+ , Dy 3+ , Ho 3+ , Er 3+ , Tm 3+ , Yb 3+ , Lu 3+ , Ti 3+ , V 3+ , Cr 3+ , Mn 3+ , Fe 3+ , Co 3+ , Ni 3+ , Cu 3+ , Nb 3+ , Mo 3+ , Ru 3+ , Rh 3+ , Pd 3+ , Ag 3+ , Ta 3+ , W 3 *, lr 3+ , Au 3+ , B 3+ , Al 3+ , Ga 3+ , ln 3+ , Tl 3+ , P 3+ , As 3+ , Sb 3+
  • a 8 is a divalent cation and is selected from one or more members of the group consisting of Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Nd 2+ , Sm 2+ , Eu 2+ , Dy 2+ , Ho 2+ , Tm 2+ , Yb 2+ , Ti 2+ , V 2+ , Cr 2+ , Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ , Cu 2+ , Mo 2+ , Pd 2+ , Ag 2+ , W 2 *, Pt 2+ , Zn 2+ , Cd 2+ , Hg 2+ , Ge 2+ , Sn 2+ and Pb 2+ ,
  • B 7 is a divalent cation and is selected from one or more members of the group consisting of Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Nd 2+ , Sm 2+ , Eu 2+ , Dy 2+ , Ho 2+ , Tm 2+ , Yb 2+ , Ti 2+ , V 2+ , Cr 2+ , Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ , Cu 2+ , Mo 2+ , Pd 2+ , Ag 2+ , W 2 *, Pt 2+ , Zn 2+ , Cd 2+ , Hg 2+ , Ge 2+ , Sn 2+ and Pb 2+ ,
  • C 4 is a trivalent cation and is selected from one or more members of the group consisting of Sc 3+ , Y 3+ , La 3+ , Ce 3+ , Pr 3+ , Nd 3+ , Pm 3+ , Sm 3+ , Eu 3+ , Gd 3+ , Tb 3+ , Dy 3+ , Ho 3+ , Er 3+ , Tm 3+ , Yb 3+ , Lu 3+ , Ti 3+ , V 3+ , Cr 3+ , Mn 3+ , Fe 3+ , Co 3+ , Ni 3+ , Cu 3+ , Nb 3+ , Mo 3+ , Ru 3+ , Rh 3+ , Pd 3+ , Ag 3+ , Ta 3+ , W 3 *, lr 3+ , Au 3+ , B 3+ , Al 3+ , Ga 3+ , ln 3+ , Tl 3+ , P 3+ , As 3+ , Sb 3+
  • a 9 is a divalent cation and is selected from one or more members of the group consisting of Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Nd 2+ , Sm 2+ , Eu 2+ , Dy 2+ , Ho 2+ , Tm 2+ , Yb 2+ , Ti 2+ , V 2+ , Cr 2+ , Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ , Cu 2+ , Mo 2+ , Pd 2+ , Ag 2+ , W 2 *, Pt, 2+ Zn 2+ , Cd 2+ , H 2+ g, Ge 2+ , Sn 2+ and Pb 2+ ;
  • B 8 is a pentavalent cation and is selected from one or more members of the group consisting of V 5+ , Cr 5+ , Mn 5+ , Co 5+ , Nb 5+ , Mo 5+ , Tc 5+ , Ru 5+ , Rh 5+ , Ta 5+ , W 5+ , Re 5+ , Os 5+ , lr 5+ , Pt 5+ , Au 5+ , P 5+ , As 5+ , Sb 5+ and Bi 5+ ;
  • C 5 is at monovalent anion and is selected from one or more members of the group consisting of F; Cl; Br and I;
  • C 5 is F; Cl; or a combination of any of these; a is 5, b is 1 , c is 1 , n is 3 z is 4; more preferably the formula is (Ca,Sr,Ba)5(PO4)3CI:Eu 2+ .
  • a new light emitting phosphor represented by general formula (VI), (VI'), (VII), (VII') (VIII) which can exhibit deep red-light emission, preferably with a sharp emission around 700 nm under excitation light of 300 to 400 nm, which are suitable to promote plant growth, can be used preferably.
  • said inorganic phosphor is an inorganic phosphor represented by formula (III), (VI), (VI'), (VII), (VII') or (XII);
  • said inorganic phosphor is selected from one or more members of the group consisting of (Mg,Zn)Ga2O4:Cr 3+ , Ca 2 (Ga,AI)NbO 6 :Cr 3+ , LilnSi 2 O 6 :Cr 3+ , Na 3 AIF 6 :Cr 3+ , Mg 3 Ga 2 GeO 8 :Cr 3+ , SrMgAlioOi?:Cr 3+ , Na 2 TiSiO 5 :Cr 3+ , MgAI 2 O 4 :Cr 3+ , Mg 3 Ga 2 GeO 8 :Cr 3+ , Zn 3 Ga 2 Ge 2 Oio:Cr 3+ , Sr 2 MgWO 6 :Cr 3+ , Li 2 ZnGe 3 O 8 :Cr 3+ , Mg 4 Ga 4 Ge 3 0i6:Cr 3+ , La 2 MgGeO 6 :Cr 3+ ,
  • the method of the present invention is especially suitable for the following phosphors to improve water stability and prevent EQE drop: (Ca,Sr,Ba)(Mg,Zn)Si 2 O 6 :Eu 2+ ,Mn 2+ , (Ca,Sr,Ba) 2 (Mg,Zn)Si 2 O 7 :Eu 2+ ,Mn 2+ , (Ca,Sr,Ba) 3 (Mg,Zn)Si 2 O 8 :Eu 2+ ,Mn 2+ , (Sr,Ba)4AI 2 S 7 :Eu 2+ , (Ca,Sr)S:Eu 2+ , (Ca,Sr,Ba)5(PO 4 ) 3 CI:Eu 2+ , NaMgPO 4 :Eu 2+ (olivine), Ca 3 (PO 4 ) 2 :Eu 2+ , Ba 2 Mg(PO 4 ) 2 :Eu 2+ , (Li,
  • an inorganic phosphor or its substances denaturated (e.g., degraded) from an inorganic phosphor, which less harms animals, plants and/or environment (e.g., soil, water) is desirable.
  • the phosphor is nontoxic phosphors, preferably it is edible phosphors, more preferably as edible phosphors, MgSiO3:Mn 2+ , MgO:Fe 3+ and/or CaMgSi 2 0e:Eu 2+ , Mn 2+ are useful.
  • Said inorganic phosphors represented by chemical formula (VI), (VI'), (VII), (VI I') and (VIII) can be fabricated as described in WO 2019/020602 A1.
  • inorganic phosphors are preferred having a peak wavelength of light emitted from the inorganic phosphor in the range from 660 nm to 710 nm. It is believed that the peak maximum light wavelength of light emitted from the inorganic phosphor in the range from 660 nm to 710 nm is very suitable for plant condition control, especially for plant growth promotion.
  • the inorganic phosphor having at least one light absorption peak wavelength in UV and/or purple light wavelength region from 300 nm to 430 nm may keep harmful insects off plants.
  • the inorganic phosphor can have at least one light absorption peak wavelength in UV and/or purple light wavelength reason from 300 nm to 430 nm.
  • an inorganic phosphor having a first peak wavelength of light emitted from the inorganic phosphor in the range from 400nm to 500nm and a second peak wavelength of light emitted from the inorganic phosphor from 600 nm to 750 nm can be used preferably.
  • the inorganic phosphor having the first peak wavelength of light emitted from the inorganic phosphor is in the range from 430 nm to 490 nm, and the second peak light emission wavelength is in the range from 660 nm to 740 nm, more preferably the first peak wavelength of light emitted from the inorganic phosphor is 450 nm and the second peak wavelength of light emitted from the inorganic phosphor is in the range from 660 nm to 710 nm, is used.
  • said inorganic phosphor is a plurality of inorganic phosphors having the first and second peak wavelength of light emitted from the inorganic phosphor, or a plurality of inorganic phosphors having the first and second peak wavelength of light emitted from the inorganic phosphor, or a combination of these.
  • the encapsulated particle can be prepared by using publicly known methods for constructing a capsule shell structure for core substances.
  • Such publicly known methods include, without being limited thereto, chemical methods based, for example, on the suspension polymerization method, the mini-emulsion polymerization method, the soap-free emulsion polymerization method and the dispersion polymerization method, or physiochemical methods based, for example, on the coacervation method or the dry ing-in-liqu id method, or mechanical methods based, for example, on the spray-drying method or the dryblending method.
  • Preferred methods according to the present invention are the ones described in the working examples below, which are based on the suspension polymerization method, which includes according to a preferred embodiment the steps of preparing a suspension of a phosphor as a core material; adding to the suspension a mixture of one or more polymerizable monomer/polymer precursor; and polymerizing the resulting mixture by applying heat or irradiating light; or are based on the coacervation method, which includes according to a preferred embodiment the steps of preparing a solution of the one or more polymerizable monomer/polymer precursor, optionally at an elevated temperature, and adding a phosphor as a core material to this solution, optionally at an elevated temperature.
  • said phosphor used as core material is preferably an inorganic phosphor as described in the section “Phosphor” above.
  • the suspension polymerization method includes in-situ polymerization comprising one or more of the following steps of: preparing a suspension of a phosphor core material, for example in ethanol; adding to the suspension an appropriate dispersant agent; adding to the dispersion a mixture of one or more polymerizable monomer/polymer precursor, for example styrene, divinylbenzene, methylmethacrylate (MMA), ethyl cellulose, and an appropriate polymerization initiator, for example Luperox A75® (benzoyl peroxide; Sigma-Aldrich), Luperox® LP (lauroyl peroxide; Sigma-Aldirch), azobisisobutyronitrile (AIBN), V-65 [2,2’-azobis(2,4- dimethylvaleronitrile)], V-70 [2,2’-azobis(4-methoxy-2,4- dimethylvaleronitrile)] (Fujifilm Wa
  • the suspension polymerization method includes in-situ polymerization comprising one or more of the following steps of: preparing an oil/water emulsion including the phosphor core material, optionally by adding a homogenizer (for example, AHG-160A) and a dispersant stabilizer (for example, gum arabic from acacia tree; Sigma-Aldrich); adding to the oil/water emulsion a mixture of one or more polymerizable monomer/polymer precursor, for example styrene, divinylbenzene, methylmethacrylate (MMA), ethyl cellulose, and an appropriate polymerization initiator, for example Luperox A75® (benzoyl peroxide; Sigma-Aldrich), Luperox® LP (lauroyl peroxide; Sigma-Aldirch), azobisisobutyronitrile (AIBN), V-65 [2,2’-azobis(2,4-dimethylvaleronitrile
  • a homogenizer for example
  • the coacervation method includes one or more of the following steps of: dissolving an polymer material (for example polystyrene, poly(styrene-co- divinylbenzene, poly(meth)acrylate, polyisobutylene, ethyl cellulose) in an appropriate solvent, such as cyclohexane, optionally at an elevated temperature; adding a phosphor core material to this solution; stirring the resulting mixture, optionally at the elevated temperature; cooling the mixture to room temperature or slightly below; collecting, washing and drying the resulted material.
  • an polymer material for example polystyrene, poly(styrene-co- divinylbenzene, poly(meth)acrylate, polyisobutylene, ethyl cellulose
  • an appropriate solvent such as cyclohexane
  • the coacervation method includes one or more of the following steps of: dissolving two parts by weight (based on the amount of the phosphor particle) a phase separation inducer in an appropriate solvent, optionally at an elevated temperature, for example polyisobutylene in cyclohexane at 80°C; adding to this solution a phosphor core material and two parts by weight of a polymer material, for example polystyrene, poly(styrene-co- divinylbenzene, poly(meth)acrylate, ethyl cellulose; stirring the resulting mixture, optionally at the elevated temperature; cooling the mixture to room temperature; removing excess solvent, phase separation inducer and polymer material, for example by decantation; collecting, washing and drying the resulted material.
  • a phase separation inducer in an appropriate solvent, optionally at an elevated temperature, for example polyisobutylene in cyclohexane at 80°C
  • a polymer material for example polystyrene, poly(styren
  • the solvent is preferably an organic solvent.
  • said organic solvent is selected from one or more members of the group consisting of alcohols including primary alcohol having 1 to 40 carbon atoms, preferably 1 to 25 carbon atoms, more preferably 2 to 20 carbon atoms, such as methanol, ethanol, isopropyl alcohol, butyl alcohol, 1 -pentanol, tetrahydrofurfuryl alcohol, 1 -hexanol, 1 -heptanol, 1 -octanol, 1 -nonanol, 1- decanol (boiling point (°C): 9.6), 1 -undecanol (14), 1 -dodecanol (26), 1- tridecanol (32), 1 -tetradecanol (40), 1 -pentadecanol (46), 1 -hexadecanol (55), 1 -heptadecanol (55), 1 -octadecyl
  • said polymer precursor is an organic polymer precursor, preferably selected from acidic monomer, more preferably it is selected from one or more members of the group consisting of acrylic acid, 2-chloroacrylic acid, 2-bromoacrylic acid, methacrylic acid, 2-phenylacrylic acid, 2-(methoxymethyl)-2-propenoic acid, 2-methylenesuccinic acid, methyl itaconate, ethyl itaconate, 2- methylene-4-oxo-pentanoic acid, propylacrylic acid, 6-methacryloxy1-[2- [(2-methyl-1 -oxo-2-propen-1 -yl)oxy]ethyl] ester butanedioic acid (for example, Kyoeisha Chemical “LIGHT ESTER HO-MS(N)”), 1-[2-[(2- methyl-1 -oxo-2-propen-1 -yl)oxy]ethyl] ester 1 ,2-cyclo
  • the dispersant agent/stabilizer preferably is selected from one or more members of sodium dodecylbenzene sulfonate (Sigma-Aldrich), Span® 80 (Sigma-Aldrich), lecithin (soybean, Sigma-Aldrich), PW-36 (Kusumoto Chemicals), DISPERBYK-103, DISPERBYK-110, DISPERBYK-111 , DISPERBYK-118, DISPERBYK-142 (BYK Chemie) and gum arabic (from acacia tree; Sigma-Aldrich).
  • the homogenizer preferably is selected from AHG-160A, SONICATOR 85, HK- 1 , Power homogenizer S-303, ULTRA-TURRAX T-25, and ULTRA- TURRAX T-50.
  • the phase separation inducers preferably is selected from polyisobutylene, triscalcium phosphate (Fujifilm Wako), gum Arabic, gelatin, casein, collagen, albumin, cellulose, agar, dextrin (Sigma-Aldrich).
  • a polymerization initiator generating an acid, base, or radical when exposed to radiation in general can be used, or a polymerization initiator generating an acid, base or radical when exposed to heat can be used, as desired.
  • the polymerization initiator adoptable in the present invention is, for example, a photo acid-generator, which decomposes when exposed to radiation and releases an acid serving as an active substance for photocuring the composition; a photo radical - generator, which releases a radical; a photo base-generator, which releases a base; a heat acidgenerator, which decomposes when exposed to heat and releases an acid serving as an active substance for heat-curing the composition; a heat radical - generator, which releases a radical; and a heat base-generator, which releases a base.
  • the radiation include visible light, UV rays, IR rays, X-rays, electron beams, a-rays and y-rays.
  • the heat acid-generator is, for example, a salt or ester capable of generating an organic acid.
  • examples thereof include: various aliphatic sulfonic acids and salts thereof; various aliphatic carboxylic acids, such as, citric acid, acetic acid and maleic acid, and salts thereof; various aromatic carboxylic acids, such as, benzoic acid and phthalic acid, and salts thereof; aromatic sulfonic acids and ammonium salts thereof; various amine salts; aromatic diazonium salts; and phosphonic acid and salts thereof.
  • salts of organic acids and organic bases are preferred, and further preferred are salts of sulfonic acids and organic bases.
  • Examples of the preferred heat acid-generators containing sulfonate ions include p-toluenesulfonates, benzenesulfonates, p- dodecylbenzenesulfonates, 1 ,4-naphthalenedisulfonates, and methanesulf
  • Examples of the above heat base-generator include: imidazole derivatives, such as, N-(2-nitrobenzyloxycarbonyl)imidazole, N-(3-nitrobenzyloxy- carbonyl)imidazole, N-(4-nitrobenzyloxycarbonyl)imidazole, N-(5-methyl-2- nitrobenzyloxycarbonyl)imidazole, and N-(4-chloro-2-nitro- benzyloxycarbonyl)imidazole; 1 ,8-diazabicyclo(5,4,0)undecene-7, tertiary amines, quaternary ammonium
  • 2,2' azobis(2- methylvaleronitrile), 2,2‘-azobis(dimethylvaleronitrile), azobisisobutyronitrile or a combination of any of these can be used preferably.
  • photo acid-generator examples include diazomethane compounds, diphenyliodonium salts, triphenylsulfonium salts, sulfonium salts, ammonium salts, phosphonium salts and sulfonamide compounds.
  • the structures of those photo acid-generators can be represented by the formula (A):
  • R + X- (A) wherein in formula (A), R + is hydrogen or an organic ion modified by carbon atoms or other hetero atoms provided that the organic ion is selected from the group consisting of alkyl groups, aryl groups, alkenyl groups, acyl groups and alkoxy groups.
  • R + is diphenyliodonium ion or triphenylsulfonium ion.
  • X’ is preferably a counter ion represented by any of the following formulas:
  • Y is a halogen atom
  • R a is an alkyl group of 1 to 20 carbon atoms or an aryl group of 6 to 20 carbon atoms provided that each group is substituted with a substituent group selected from the group consisting of fluorine, nitro group and cyano group, p is a number of 0 to 6, and q is a number of 0 to 4.
  • counter ion examples include: BF ⁇ , (CeFs ⁇ B;
  • those generating sulfonic acids or boric acids are particularly preferred.
  • examples thereof include tricumyliodonium teterakis(pentafluoro phenyl) borate (PHOTOINITIATOR2074 [trademark], manufactured by Rhodorsil), diphenyliodonium tetra(perfluorophenyl)borate, and a compound having sulfonium ion and pentafluoroborate ion as the cation and anion moieties, respectively.
  • examples of the photo acid-generators also include triphenyl sulfonium trifluoromethanesulfonate, triphenylsulfonium camphor sulfonate, triphenylsulfonium tetra(perfluorophenyl)borate, 4- acetoxyphenyldimethylsulfonium hexafluoroarsenate, 1-(4-n- butoxynaphthalene-1-yl)tetrahydrothiophenium trifluoromethanesulfonate, 1 -(4,7-dibutoxy-1 -naphthalenyl)tetrahydrothiophenium trifluoromethanesulfonate, diphenyliodonium trifluoromethanesulfonate, and diphenyliodonium hexafluoroarsenate.
  • each A is independently a substituent group selected from the group consisting of an alkyl group of 1 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkylcarbonyl group of 1 to 20 carbon atoms, an arylcarbonyl group of 6 to 20 carbon atoms, hydroxyl group, and amino group; each p 2 is independently an integer of 0 to 5; and
  • B’ is a fluorinated alkylsulfonate group, a fluorinated arylsulfonate group, a fluorinated alkylborate group, an alkylsulfonate group or an arylsulfonate group.
  • photo acid-generators in which the cations and anions in the above formulas have exchanged each other or combined with various other cations and anions described above.
  • any one of the sulfonium ions represented by the above formulas can be combined with tetra(perfluorophenyl)borate ion, and also any one of the iodonium ions represented by the above formulas can be combined with tetra(perfluorophenyl)borate ion.
  • Those can be still also employed as the photo acid-generators.
  • photo radical-generator examples include azo compounds, peroxides, acyl phosphine oxides, alkyl phenons, oxime esters, and titanocenes.
  • acyl phosphine oxides As the photo radical-generator, acyl phosphine oxides, alkyl phenons, oxime esters, or a combination of any of these are more preferable.
  • Examples of the photo base-generator include multi-substituted amide compounds having amide groups, lactams, imide compounds, and compounds having those structures.
  • the present invention also relates to use of the particle of the present invention in agriculture.
  • the present invention also relates to use of the particle of the present invention in a Light Emitting Diode or in a solar cell.
  • the present invention also relates to a composition
  • a composition comprising, essentially consisting of, or consisting of, at least one particle of the present invention and a further material.
  • said composition comprises a plurality of the particles of the present invention.
  • the total amount of the at least one particle of the present invention in the composition may be in the range from 0.01wt.% to 99.9wt.%, preferably in the range from 0,01 wt% to 30wt.%, based on the total amount of the composition, and more preferably it is from 0.1wt.% to 10wt.%, even more preferably from 0.5wt.% to 5wt.%, and furthermore preferably from 1wt.% to 3wt.% from the view point of better light conversion property, lower production cost and less production damage of a production machine.
  • the further material is preferably selected from one or more members of the group consisting of matrix materials; light modulating materials such as dyes e.g. yellow dyes, pigments, light luminescent materials incl. organic and inorganic light luminescent materials, e.g. another inorganic phosphor; photo initiators; co-polymerizable monomers; cross linkable monomers; bromine-containing monomers; sulfur-containing monomers; adjuvants; adhesives; insecticides; insect attractants; metal oxides; Al, Ag, Au nanoparticles; dispersants; surfactants; fungicides and antimicrobial agents.
  • light modulating materials such as dyes e.g. yellow dyes, pigments, light luminescent materials incl. organic and inorganic light luminescent materials, e.g. another inorganic phosphor
  • photo initiators co-polymerizable monomers; cross linkable monomers; bromine-containing monomers; sulfur-containing monomers; adjuvants; adhesives; insecticides
  • the further material is a matrix material and said composition can optionally comprises one or more additives selected from one or more members of the group consisting of light modulating materials such as dyes e.g. yellow dyes, pigments, light luminescent materials incl. organic and inorganic light luminescent materials, e.g. another inorganic phosphors; photo initiators; co- polymerizable monomers; cross linkable monomers; bromine-containing monomers; sulfur-containing monomers; adjuvants; adhesives; insecticides; insect attractants; metal oxides; Al, Ag, Au nanoparticles; dispersants; surfactants; fungicides and antimicrobial agents.
  • light modulating materials such as dyes e.g. yellow dyes, pigments, light luminescent materials incl. organic and inorganic light luminescent materials, e.g. another inorganic phosphors; photo initiators; co- polymerizable monomers; cross linkable monomers; bromine-containing monomers; sulfur-containing monomers;
  • the matrix material is an organic material.
  • the matrix material is an organic oligomer or an organic polymer material, more preferably an organic polymer selected from the group consisting of a transparent photosetting polymer, a thermosetting polymer, a thermoplastic polymer, or a combination of any of these, can be used preferably.
  • the matrix material is an organic material, and/or an inorganic material, preferably the matrix material is an organic material, more preferably it is an organic oligomer or an organic polymer material, even more preferably an organic polymer selected from the group consisting of a transparent photosetting polymer, a thermosetting polymer, a thermoplastic polymer, or a combination of any of these.
  • organic polymer materials polysaccharides, polyethylene, polypropylene, polystyrene, polymethyl pentene, polybutene, butadiene styrene, polyvinyl chloride, polystyrene, polymethacrylic styrene, styreneacrylonitrile, acrylonitrile-butadiene-styrene, polyethylene terephthalate, polymethyl methacrylate, polyphenylene ether, polyacrylonitrile, polyvinyl alcohol, acrylonitrile polycarbonate, polyvinylidene chloride, polycarbonate, polyamide, polyacetal, polybutylene terephthalate, polytetrafluoroethylene, ethyl vinyl acetate copolymer, ethylene tetrafluorethylen copolymer, polyamide, phenol, melamine, urea, urethane, epoxy, unsaturated polyester, polyallyl sulfone, polyacrylate
  • (meth)acrylates can be used preferably.
  • unsubstituted alkyl-(meth) acrylates for examples, methyl-acrylate, methyl-methacrylate, ethyl-acrylate, ethyl-methacrylate, butyl-acrylate, butyl-methacrylate, 2-ethylhexyl-acrylate, 2-ethylhexyl- methacrylate; substituted alkyl-(meth)acrylates, for examples, hydroxylgroup, epoxy group, or halogen substituted alkyl-(meth)acrylates; cyclopentenyl(meth)acrylate, tetra-hydro furfuryl-(meth)acrylate, benzyl (meth)acrylate, polyethylene-glycol di-(meth)acrylates.
  • the matrix material has a weight average molecular weight in the range from 5,000 to 50,000 preferably, more preferably from 10,000 to 30,000.
  • thermosetting polymer publicly known transparent thermosetting polymer can be used preferably.
  • OE6550 trade mark
  • Dow Coming OE6550 series
  • thermoplastic polymer is not particularly limited.
  • thermoplastic polymers may be copolymerized if necessary.
  • thermoplastic polymer or thermosetting polymer based on their physical properties.
  • the matrix materials and the inorganic phosphors mentioned above in the sections “Matrix materials as said further material” and “Phosphor”, can be preferably used for a fabrication of the color conversion sheet and the light emitting diode device of the present invention.
  • the composition can optionally further comprise one or more additional inorganic phosphor, which emits blue or red light.
  • inorganic phosphors having a peak wavelength of light emitted from the inorganic phosphor in the range of 600 nm or more, preferably in the range from 650 to 1500 nm, more preferably in the range from 650 to 1000 nm, even more preferably in the range from 650 to 800 nm, furthermore preferably in the range from 650 to 750 nm, much more preferably it is from 660 nm to 730 nm, furthermore preferably it is from 660 nm to 710 nm, the most preferably from 670 nm to 710nm; or having a peak wavelength of light emitted from the inorganic phosphor in the range of 500 nm or less, preferably in the range from 250 nm to 500 nm, more preferably in the range from 300 nm to 500
  • the peak light wavelength of the light emitted from the phosphor in the rage 660 nm to 710 nm is specifically useful for plant growth.
  • inorganic phosphors come into consideration for the present invention as the additional another inorganic phosphor, such as, for example, metal-oxide phosphors, silicate and halide phosphors, phosphate and halophosphate phosphors, borate and borosilicate phosphors, aluminate, gallate and alumosilicate phosphors, phosphors, sulfate, sulfide, selenide and telluride phosphors, nitride and oxynitride phosphors and SiAION phosphors.
  • metal-oxide phosphors silicate and halide phosphors
  • phosphate and halophosphate phosphors phosphate and halophosphate phosphors
  • borate and borosilicate phosphors aluminate
  • gallate and alumosilicate phosphors phosphors
  • phosphors sulfate, sulfide,
  • the additional another inorganic phosphor is selected from the group consisting of metal-oxide phosphors, silicate and halide phosphors, phosphate phosphors, borate and borosilicate phosphors, aluminate, gallate and alumosilicate phosphors, sulfate, sulfide, selenide and telluride phosphors, nitride and oxynitride phosphors and SiAION phosphors, preferably, it is a metal oxide phosphor, more preferably it is a Mn activated metal oxide phosphor or a Mn activated phosphate based phosphor, even more preferably it is a Mn activated metal oxide phosphor.
  • Preferred metal-oxide phosphors are arsenates, germanates, halogermanates, indates, lanthanates, niobates, scandates, stannates, tantalates, titanates, vanadates, halovanadates, phosphovanadates, yttrates, zirconates, molybdate and tungstate.
  • it is a metal oxide phosphor, more preferably it is a Mn activated metal oxide phosphor or a Mn activated phosphate based phosphor, even more preferably it is a Mn activated metal oxide phosphor.
  • said another inorganic phosphor is selected from the group consisting of metal oxides, silicates and halosilicates, phosphates and halophosphates, borates and borosilicates, aluminates, gallates and alumosilicates, molybdates and tungstates, sulfates, sulfides, selenides and tellurides, nitrides and oxynitrides, SiAIONs, halogen compounds and oxy compounds, such as preferably oxysulfides or oxychlorides phosphors, preferably, it is a metal oxide phosphor, more preferably it is a Mn activated metal oxide phosphor or a Mn activated phosphate based phosphor, even more preferably it is a Mn activated metal oxide phosphor.
  • the another inorganic phosphor is selected from the group consisting of Al2O3:Cr 3+ , Y3AlsOi2:Cr 3+ , MgO:Cr 3+ , ZnGa2O4:Cr 3+ , MgAI 2 O 4 :Cr 3+ , Gd 3 Ga 5 0i2:Cr 3+ , LiAI 5 O 8 :Cr 3+ , MgSr 3 Si2O8:Eu 2+ ,Mn 2+ , Sr3MgSi2O8:Mn 4+ , Sr2MgSi2O 7 :Mn 4+ , SrMgSi2O6:Mn 4+ , BaMg6TieOi9:Mn 4+ , Cai4AlioZne035:Mn 4+ , Mg8Ge20nF2:Mn 4+ , Mg2TiO 4 :Mn 4+ , Y
  • Mn 4+ activated metal oxide phosphors Mn, Eu activated metal oxide phosphors, Mn 2+ activated metal oxide phosphors, Fe 3+ activated metal oxide phosphors can be used preferably from the viewpoint of environmentally friendly since these phosphors do not create Cr 6+ during synthesis procedure.
  • any type of publicly known materials for example as described in the second chapter of Phosphor handbook (Yen, Shinoya, Yamamoto), can be used if desired.
  • the blue light especially around 450 nm wavelength light may lead better plant growth, if it is combined with emission light from the inorganic phosphor having the peak wavelength of light emitted from the inorganic phosphor in the range from 660 nm to 740 nm, especially the combination of the blue light around 450 nm wavelength and emission light from the inorganic phosphor having the peak wavelength of light emitted from the inorganic phosphor in the range from 670 nm to 710 nm is preferable for better plant growth.
  • the composition can additionally comprise at least one blue light emitting inorganic phosphor having peak wavelength of light emitted from the inorganic phosphor around 450 nm, like described in the second chapter of Phosphor handbook (Yen, Shinoya, Yamamoto).
  • said additional another inorganic phosphor is a different type of inorganic phosphor than the inorganic phosphor of the present invention.
  • the composition can embrace one or more of publicly available vinyl monomers that are co- polymerizable.
  • vinyl monomers such as acrylamide, acetonitrile, diacetone-acrylamide, styrene, and vinyl-toluene or a combination of any of these.
  • the composition can further include one or more of publicly available crosslinkable monomers.
  • cyclopentenyl(meth)acrylates tetra-hydro furfuryl- (meth)acrylate; benzyl (meth)acrylate; the compounds obtained by reacting a polyhydric alcohol with and a,[3-unsaturated carboxylic acid, such as polyethylene-glycol di-(meth)acrylates (ethylene numbers are 2- 14), tri-methylol propane di(meth)acrylate, tri-methylol propane di (meth)acrylate, tri-methylol propane tri-(meth)acrylate, tri-methylol propane ethoxy tri-(meth) acrylate, tri-methylol propane propoxy tri-(meth) acrylate, tetra-methylol methan tri-(meth) acrylate), tetra-methylol methane tetra(meth) acrylate, polypropylene glycol di(meth)acrylates (propylene number therein are 2-14), Di-penta-erythr
  • the crosslinkable monomer is selected from the group consisting of tri-methylol-propane tri (meth)acrylate, di-pentaerythritol tetra-(meth)acrylate, di-pentaerythritol hexa-(meth)acrylate, bisphenol-A polyoxyethylene dimethacrylate and a combination thereof.
  • the vinyl monomers and the crosslinkable monomers described above can be used alone or in combination.
  • the composition can further comprise publicly known one or more of bromine-containing monomers, sulfur-containing monomers.
  • the type of bromine and sulfur atom-containing monomers (and polymers containing the same) are not particularly limited and can be used preferably as desired.
  • new frontier® BR-31 new Frontier® BR-30, new Frontier® BR-42M (available from DAI-ICHI KOGYO SEIYAKU CO., LTD) or a combination of any of these
  • sulfur-containing monomer composition IU-L2000, IU-L3000, IU-MS1010 (available from MITSUBISHI GAS CHEMICAL COMPANY, INC.) or a combination of any of these, can be used preferably.
  • the photo initiator can be a photo initiator that can generates a free radical when it is exposed to an ultraviolet light or a visible light.
  • a photo initiator that can generates a free radical when it is exposed to an ultraviolet light or a visible light.
  • benzoin-methyl-ether benzoin-ethyl-ether, benzoin-propyl-ether, benzoin-isobutyl-ether, benzoin- phenyl-ether, benzoin-ethers, benzophenone, N,N’-tetramethyl-4,4’- diaminobenzophenone (Michler’s-ketone), N,N’-tetraethyl- 4,4’diaminobenzophenone, benzophenones, benzil-dimethyl-ketal (Ciba specialty chemicals, IRGACURE® 651 ), benzil-diethyl-ketal, dibenzil ketals, 2,2-dimethoxy-2-phenylacetophenone, p
  • An adjuvant can enhance the permeability of the effective component (e.g. an insecticide), inhibit precipitation of solute in the composition, or decrease phytotoxicity.
  • said adjuvant can be selected from the group consisting of a mineral oil, an oil of vegetable or animal origin, alkyl esters of such oils or mixtures of such oils and oil derivatives, and combination thereof.
  • a surfactant means it does not comprise or is not comprised by other additives, for example a spreading agent, a surface treatment and an adjuvant.
  • the weight ratio of each one additive, to the weight of the coated phosphor of the invention in the total amount of the composition is in the range from 50 wt.% to 200 wt.%, more preferably it is from 75 wt.% to 150 wt.%.
  • Exemplified embodiment of an adjuvant is Approach Bl (Trademark, Kao Corp.).
  • the invention in another aspect, relates to a formulation comprising, essentially consisting of, or consisting of at least one particle of the present invention or the composition of the present invention, and a solvent.
  • said formulation comprises a plurality of the particles or the composition of the present invention.
  • a solvent for the formulation a wide variety of publicly known solvents can be used preferably. There are no particular restrictions on the solvent as long as it can dissolve or disperse the matrix material, and the particle of the composition.
  • the solvent can be selected from the group consisting of water, 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 alkyl ether acetates, such as, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate; aromatic hydrocarbons, such as,
  • propylene glycol alkyl ether acetates such as, propylene glycol monomethyl ether acetate (hereafter “PGMEA”), propylene glycol monoethyl ether acetate, or propylene glycol monopropyl ether acetate and/or aromatic hydrocarbons, such as, benzene, toluene and xylene, can be used. Even more preferably, benzene, toluene, or xylene can be used.
  • PGMEA propylene glycol monomethyl ether acetate
  • aromatic hydrocarbons such as, benzene, toluene and xylene
  • benzene, toluene, or xylene can be used.
  • the solvent is used singly or in combination of two or more, and the amount thereof can be freely controlled depending on the coating method and the thickness of the coating.
  • the formulation can contain the solvent in an amount of 90 wt.% or more based on total amount of the formulation.
  • the content of the solvent is normally 60 wt.% or more, preferably in the range from 70 wt.% to 95 wt.% based on the total amount of the formulation.
  • the invention relates to use of the particle of the present invention, or the composition of the present invention, or the formulation of the present invention, in a method for preparing an optical sheet or in agriculture, preferably for preparing an agricultural sheet or for controlling a condition of a living organism.
  • the invention relates to an optical sheet comprising at least one particle of the present invention, or the composition of the present invention, preferably said optical sheet is an agricultural sheet.
  • said optical sheet comprises a plurality of particles of the present invention or the composition.
  • the optical sheet can be a film, or a fiber mat.
  • optical sheet according to the present invention can be rigid or flexible.
  • the optical sheet according to the present invention can be any structure, such as plane, curved, wave formed structures to increase a growth of plant.
  • the optical sheet comprises at least a first layer comprising at least the composition or the first layer made from the composition.
  • said fiber mat can be fabricated by using publicly known spinning method.
  • said cover layer can be fabricated by using a known method such as a spinning, dip coating, bar coating, printing, and/or spin coating.
  • the sheet further comprises a second layer, preferably the second layer comprises at least a material selected from one or more members of the group consisting of adhesives, insecticides, insect attractants, yellow dye, pigments, phosphors, metal oxides, Al, Ag, Au, and antimicrobials, more preferably said pigments are yellow pigments, blue pigments or a combination of these, and said phosphors are phosphors of the present invention or phosphors that can emit a light with a peak maximum light wavelength in the range from 350nm to 500nm, and/or 550nm to 600nm, more preferably in the range from 380nm to 490nm, and/or 570nm to 590nm.
  • the second layer comprises at least the inorganic phosphor of the present invention, and a second material selected from adhesives, and/or insecticides.
  • the second layer further comprises a matrix material as described in the section of “Matrix material as said further material”.
  • the second layer comprises at least a first material selected from one or more of the members of the group consisting of yellow pigments, yellow phosphors, yellow dyes, and insect attractants, and a second material selected from adhesives, and/or insecticides.
  • Such second layer can be fabricated by a publicly known method. For example, spray coating, bar coating, slit coating, dip coating, spin coating, inkjet printing can be used.
  • the second layer of the optical sheet is a light reflecting layer, preferably the second layer as the reflecting layer comprises at least a light reflecting material which can reflect at least blue, red, and/or infrared light, even more preferably the second layer essentially consists of or consists of one or more of light reflecting materials.
  • any kinds of less toxic known light reflecting materials such as Al, Cu, Ag, Au, and metal oxides can be used preferably, more preferably Al, or Cu is used as the light reflecting material from the view point of high light reflection at deep red-light wavelength and lower cost.
  • said first layer is at least partially covered by said second layer, preferably at least one side of said first layer one side of the optical sheet is fully covered by the second layer.
  • the optical sheet optionally comprises a third layer or more layers.
  • said first layer, the second layer, and the optional third layer or more layers can be sandwiched by, or fully or partially covered by one or more of optically transparent protection layers.
  • said protection layer can be made from any publicly known transparent materials suitable for optical films.
  • Fabrication method for coating of optical sheet by the light reflecting material is not particularly limited. Publicly known methods such as vacuum deposition, sputtering, chemical vapor deposition, printing can be used.
  • the optical the sheet comprises a first layer, wherein the first layer comprises, in the first layer, at least a first area comprising the composition according to the present invention and a second area, preferably said second area comprising at least one additive as described above.
  • the concentration of the particle of the present invention in the sheet varies from a high concentration on one side of the sheet to a low concentration of the opposite side of the sheet, preferably it is varying from a high concentration on one side of the sheet to a low concentration of the opposite side of the sheet in-plane direction.
  • the optical sheet further comprises a substrate, preferably said substrate is an optically transparent substrate, colored substrate, selective light reflector, or a light reflector.
  • the term “light reflect” means reflecting at least around 60 % of incident light at a wavelength or a range of wavelength used during operation of the optical sheet. Preferably, it is over 70 %, more preferably, over 75%, the most preferably, it is over 80 %.
  • the term “transparent” means at least around 60 % of incident light transmittal at the thickness used in a the optical sheet and at a wavelength or a range of wavelength used during operation of the optical sheet. Preferably, it is over 70 %, more preferably, over 75%, the most preferably, it is over 80 %.
  • Said reflector is preferably a metal substrate, more preferably Al substrate, Cu substrate, metal alloy substrate is useful from the view point of high light reflection at deep red-light wavelength and lower cost.
  • a material for the selective light reflection reflector is not particularly limited. Well known materials for a selective light reflector can be used preferably as desired.
  • the selective light reflector can be a single layer or multiple layers.
  • the selective light reflector comprises at least a selective light reflecting layer selected from the group consisting of Al layer, Al + MgF2 stacked layers, Al + SiO stacked layers, Al + dielectric multiple layer, Au layer, dielectric multiple layer, Cr + Au stacked layers; with the selective light reflection layer more preferably being Al layer, Al + MgF2 stacked layers, Al + SiO stacked layers.
  • said selective light reflecting layer is stacked onto a transparent substrate.
  • the methods of preparing the selective light reflection layer can vary as desired and selected from well-known techniques.
  • the selective light reflection layer expect for cholesteric liquid crystal layers is prepared by a gas phase based coating process (such as Sputtering, Chemical Vapor Deposition, vapor deposition, flash evaporation), or a liquid-based coating process.
  • a gas phase based coating process such as Sputtering, Chemical Vapor Deposition, vapor deposition, flash evaporation
  • the optical sheet is, for example, a color conversion sheet, a light conversion foil, a remote phosphor tape, or another sheet or a filter for agriculture.
  • the layer thickness of the optical sheet may be in the range from 5 pm to 1 mm, preferably it is in the range from 10 pm to 500 pm, more preferably it is from 30 pm to 200 pm, even more preferably from 50 pm to 100 pm from the view point of better light conversion property and lower production cost.
  • the total amount of the particle in the optical sheet may be in the range from 0.01wt.% to 30wt.% based on the total amount of the matrix material, preferably it is from 0.1wt.% to 10wt.%, more preferably from 0.5wt.% to 5wt.%, furthermore preferably it is from 1wt.% to 3wt.%, from the view point of better light conversion property, lower production cost and less production damage of a production machine.
  • the present invention furthermore relates to a method for preparing an optical sheet, preferably for preparing an agriculture sheet, wherein the method comprises following steps (A) and (B),
  • the method comprises steps (A) and (B) in this sequence.
  • the composition in step (A) is provided by spin coating, spray coating, bar coating, or a slit coating method.
  • the composition or the formulation in step (A) is provided into an inflation-molding machine and the matrix material is fixed by heat treatment of the machine.
  • the present invention furthermore relates to a method for preparing an agriculture sheet, wherein the method comprises following steps (A’) and (B’),
  • composition comprising at least one particle comprising a phosphor as an inner core, an outer core at least partially surrounding the inner core, and a transparent polymer layer as a shell enclosing the outer core; and a further material, or a formulation comprising said composition and a solvent in a first shaping;
  • said transparent polymer is an organic polymer, more preferably it is selected from one or more member of the group consisting of (meth)acrylate polymers, polystyrenes including poly(styrene-co- divinylbenzenes, polyisobutylene and ethyl cellulose.
  • the further material and the solvent in step (A’) are preferably the same as mentioned above in the sections “Composition” and “Formulation”, respectively.
  • the method comprises steps (A’) and (B’) in this sequence.
  • the optical sheet according to present invention can suitably be used in an optical device, preferably in a lighting device, more preferably in a Light Emitting Diode.
  • the invention therefore relates to an optical device comprising the optical sheet, or the composition and further comprising a light source, a light re-directing device, and/or a reflector.
  • the optical device comprises at least one optical sheet and a supporting part, preferably the supporting part comprises at least one attaching part to attach the optical sheet, and optionally a base part to support optical sheet and supporting part itself, more preferably the supporting part comprises one or more of attaching part to attach one or more of optical sheet.
  • the optical device is a lighting device, a light emitting diode device for agriculture, or building materials of greenhouse.
  • the present invention furthermore relates to method for preparing the optical device, wherein the method comprises the step of providing the optical sheet in an optical device.
  • composition The details of the composition and the formulation are described above in the section “Composition” and the section “Formulation”.
  • the optical sheet is useful for agriculture.
  • the optical sheet is useful for a mulch cultivation sheet to cover at least a part of a ridge in a field or to cover at least a part of a surface of planter, such as a surface of nutrient film technique hydroponics system or a deep flow technique hydroponics system.
  • the optical sheet as a mulch cultivation sheet can control plant condition such as plant growth and to protect a plant and/or a ridge or a surface of planter as a mulch cultivation sheet at the same time preferably.
  • the invention relates to the use of the optical sheet as a mulch cultivation sheet to cover a ridge in a field or to cover a surface of planter, preferably said planter is a nutrient film technique hydroponics system or a deep flow technique hydroponics system.
  • one side of the optical sheet is coated by a light reflecting material which can reflect at least blue, red, and/or infrared light.
  • a light reflecting material any kinds of less toxic known light reflecting materials such as Al, metal oxides can be used preferably, more preferably Al, or AIO2 is used as the light reflecting material.
  • said one side of the optical sheet is fully covered by the light reflecting material.
  • the fabrication method for coating of optical sheet by the light reflecting material is not particularly limited. Publicly known methods such as vacuum deposition, sputtering, chemical vapor deposition, printing can be used.
  • the optical sheet may be used to control growth of plankton, preferably said plankton is a phytoplankton.
  • the present invention relates to use of the optical sheet or the optical device of the present invention for agriculture, preferably for greenhouse or for controlling a condition of a living organism in agriculture.
  • the present invention furthermore relates to a greenhouse comprising the optical sheet of the present invention.
  • the present invention relates to use of the particle, the composition, the formulation, the optical sheet, the optical device, or the greenhouse of the present invention for cultivation of algae, bacteria, preferably said bacteria are photosynthetic bacteria, and/or plankton, preferably photo plankton, preferably for improvement of controlling property of a phytoplankton condition, photosynthetic bacteria and/or alga, preferably acceleration of growth of phytoplankton, photosynthetic bacteria and/or alga; improvement of controlling property of plant condition, preferably controlling of a plant height; controlling of color of fruits; promotion and inhibition of germination; controlling of synthesis of chlorophyll and carotenoids, preferably by blue light; plant growth promotion; adjustment and I or acceleration of flowering time of plants; controlling of production of plant components, such as increasing production amount, controlling of polyphenols content, sugar content, vitamin content of plants; controlling of secondary metabolites, preferably controlling of polyphenols, and/or anthocyanins; controlling of a disease resistance of plants; controlling of
  • the present invention furthermore relates to a method of supplying the particle, the composition or the formulation of the present invention to at least one portion of a plant.
  • the present invention furthermore relates to a method for modulating a condition of a plant, plankton, and/or a bacterium, comprising at least the following step of providing the optical sheet, between a light source and a plant, between a light source and plankton, preferably said plankton is phytoplankton, between a light source and a bacterium, preferably said bacterium is a photosynthetic bacterium, and/or providing the optical sheet, over a ridge in a field or over a surface of planter, preferably said planter is a nutrient film technique hydroponics system or a deep flow technique hydroponics system to control plant growth.
  • the optical sheet is provided directly onto a ridge in a field or onto a surface of planter.
  • the light source is the sun or an artificial light source, preferably said artificial light source is a light emitting diode.
  • the present invention further relates to a plant, plankton, or a bacterium obtained or obtainable by the method.
  • plankton is a phytoplankton
  • said bacterium is a photosynthetic bacterium.
  • the present invention furthermore relates to a container comprising at least one plant, plankton, or a bacterium obtained or obtainable by the method of the present invention.
  • a container comprising at least one plant, plankton, or a bacterium obtained or obtainable by the method of the present invention.
  • said plankton is phytoplankton
  • said bacterium is a photosynthetic bacterium.
  • the plant can be flowers, vegetables, fruits, grasses, trees and horticultural crops (preferably flowers and horticultural crops, more preferably flowers).
  • the plant can be foliage plants.
  • Exemplified embodiments of grasses are a poaceae, bambuseae (preferably sasa, phyllostachys), oryzeae (preferably oryza), pooideae (preferably poeae), triticeae (preferably elymus), elytrigia, hordeum, triticum, secale, arundineae, centotheceae, chloridoideae, hordeum vulgare, avena sativa, secale cereal, andropogoneae (preferably coix), cymbopogon, saccharum, sorghum, zea (preferably zea mays), sorghum bicolor, saccharum officinarum, coix lacryma-jobi van, paniceae (preferably panicum), setaria, echinochloa (preferably panicum miliaceum), echinochloa esculenta, and setaria italic.
  • Embodiments of vegetables are stem vegetables, leaves vegetables, flowers vegetables, stalk vegetables, bulb vegetables, seed vegetables (preferably beans), roots vegetables, tubers vegetables, and fruits vegetables.
  • One embodiment of the plant can be Gaillardia, Lettuce, Rucola, Komatsuna (Japanese mustard spinach) or Radish (preferably Gaillardia, Lettuce, or Rucola).
  • the environment of growing plant can be natural environment, a green house, a plant factory and indoor cultivation, preferably natural environment and a green house.
  • One embodiment of the natural environment is an outside farm.
  • a particle comprising: at least one inner core comprising a phosphor; an outer core at least partially surrounding the at least one inner core; and a shell enclosing the outer core, wherein the shell comprises a polymer layer.
  • polymer of the polymer layer is an organic polymer, and preferably is selected from one or more member of the group consisting of polyurethanes, polyureas, poly(meth)acrylates, polyesters, polyacrylurethanes, polyacrylurethanesilicones, polyfluoroacrylurethanes, polyfluoroacrylates, polysilicones, polystyreneacrylates, polybutyrals, polychlorovinylidenes, meramine resins, phenol resins, polycarbonates, polysulfones, polyethers, polyamides, polystyrenes including P oly(styrene-co-divinylbenzenes, polyisobutylenes, ethyl cellulose and poly(lactic acid); or an inorganic polymer, and preferably is selected from one or more member of the group consisting of polysilanes, polysiloxanes including inorganic silicones, polyphosphazen
  • polystyrenes including poly(styrene-co-divinylbenzenes, poly(meth)acrylates, polyisobutylenes and ethyl cellulose
  • the transparent polymer is an organic polymer, preferably an organic polymer selected from one or more member of the group consisting of polyurethanes, polyureas, poly(meth)acrylates, polyesters, polyacrylurethanes, polyacrylurethanesilicones, polyfluoroacrylurethanes, polyfluoroacrylates, polysilicones, polystyreneacrylates, polybutyrals, polychlorovinylidenes, meramine resins, phenol resins, polycarbonates, polysulfones, polyethers, polyamides, polystyrenes including poly(styrene-co-divinylbenzenes, polyisobutylenes, ethyl cellulose and poly(lactic acid), and more preferably is selected from one or more member of the group consisting of (meth)acrylate polymers, polystyrenes including P oly(styrene-co- divinylbenzenes, poly
  • the shell comprises the polymer layer and one or more further layers wherein at least one of the one or more further layers is of a material different than the polymer layer, and preferably being one or more further polymer layers.
  • the shell comprises a first polymer layer and a second polymer layer, which are independently selected from an organic polymer, an inorganic polymer and a combination of an organic polymer and an inorganic polymer, preferably from an organic polymer and an inorganic polymer, more preferably said first polymer layer is the polymer layer and said second polymer layer is a further layer.
  • outer core comprises one or more material selected from organic liquids and organic solids; inorganic liquids and inorganic solids; gases and air.
  • the inorganic phosphor has a fluorescent or a phosphorescent inorganic material which contains one or more light emitting centers formed by activator elements, such as atoms or ions of rare earth metal elements, for example La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, and/or atoms or ions of transition metal elements, for example Or, Mn, Fe, Co, Ni, Cu, Ag, Au and Zn, and/or atoms or ions of main group metal elements, for example Na, Tl, Sn, Pb, Sb and Bi.
  • activator elements such as atoms or ions of rare earth metal elements, for example La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu
  • transition metal elements for example Or, Mn, Fe, Co, Ni, Cu, Ag, Au and Zn
  • main group metal elements for example Na,
  • the inorganic phosphor contains one or more elements selected from the group consisting of alkali metal elements, alkaline metal elements, phosphorous atom, boron atom and sulfur atom, said alkali metal element preferably being Li, Na, Ka or a combination of any of these, and said alkaline metal element preferably being Be, Mg, Ca, Sr, Ba or a combination of any of these.
  • the inorganic phosphor is selected from the group consisting of metal-oxide phosphors, silicate and halide phosphors, phosphate phosphors, borate and borosilicate phosphors, aluminate, gallate and alumosilicate phosphors, sulfate, sulfide, selenide and telluride phosphors, nitride and oxynitride phosphors and SiAION phosphors, preferably, it is a metal oxide phosphor, more preferably it is a Mn activated metal oxide phosphor or a Mn activated phosphate based phosphor, even more preferably it is a Mn activated metal oxide phosphor.
  • a 2 is a divalent cation and is selected from one or more members of the group consisting of Mg 2+ , Zn 2+ , Cu 2+ , Co 2+ , Ni 2+ , Fe 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Mn 2+ , Ce 2+ and Sn 2+
  • B 2 is a tetravalent cation and is Al 3+ , Ga 3+ or a combination of these; preferably A 2 is Mg 2+ , Zn 2+ or a combination of Mg 2+ and Zn 2+ , B 1 is Ti 3+ , Zr 3+ or a combination of Ti 3+ and Zr 3 , more preferably formula (III) is (Ca, Sr, Ba)i4(AI,
  • GjJkLiOm:Mn 4+ (IV) wherein G is a divalent cation and is selected from one or more members of the group consisting of Mg 2+ , Zn 2+ , Cu 2+ , Co 2+ , Ni 2+ , Fe 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Mn 2+ , Ce 2+ and Sn 2+ ; J is a trivalent cation and is selected from the group consisting of Y 3+ , Al 3+ , Ga 3+ , Lu 3+ , Sc 3+ , La 3+ and ln 3+ ; L is a trivalent cation and is selected from the group consisting of Al 3+ , Ga 3+ , Lu 3+ , Sc 3+ , La 3+ and ln 3+ ; l ⁇ 0; k ⁇ O; j ⁇ O; (j+1.5k+1.5l) m, preferably G is selected from Ca 2+ , Sr 2+ , Ba
  • M 2 is a divalent cation selected from Ca 2+ , Sr 2+ , Ba 2+ or a combination of any of these
  • Q is a divalent cation selected from one or more members of the group consisting of Mg 2+ , Sr 2+ , Ba 2+ , Zn 2+ , Cu 2+ , Co 2+ , Ni 2+ , Fe 2+ , Ca 2+ , Mn 2+ , Ce 2+ ;
  • a 4 is at least one cation selected from the group consisting of Mg 2+ , Ca 2+ , Sr 2+ and Ba 2+ Zn 2+ , preferably A 4 is Ba 2+ ;
  • B 3 is at least one cation selected from the group consisting of Sc 3+ , Y 3+ , La 3+ , Ce 3+ , B 3+ , Al 3+ and Ga 3+ , preferably B 3 is Y 3+ ;
  • C 1 is at least one cation selected from the group consisting of V 5+ , Nb 5+ and Ta 5+ , preferably C 1 is Ta 5+ ; preferably Mn is Mn 4+ , more preferably said phosphor is Ba2YTaOe:Mn 4+ ;
  • a 5 is at least one cation selected from the group consisting of Li + , Na + , K + Rb + and Cs + , preferably A 5 is Na + ;
  • B 4 is at least one cation selected from the group consisting of Sc 3+ , La 3+ , Ce 3+ B 3+ , Al 3+ and Ga 3+ , preferably B 4 is La 3+ ;
  • C 2 is at least one cation selected from the group consisting of Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ and Zn 2+ , preferably C 2 is Mg 2+ ;
  • D 1 is at least one cation selected from the group consisting of Mo 6+ and W 3+ , preferably D 1 is W 6 *, preferably Mn is Mn 4+ , more preferably said phosphor is more preferably the phosphor is NaLaMgWOe:Mn 4+ ;
  • a 6 is at least one cation selected from the group consisting of is a trivalent cation and is selected from one or more members of the group consisting of Sc 3+ , Y 3+ , La 3+ , Ce 3+ , Pr 3+ , Nd 3+ , Pm 3+ , Sm 3+ , Eu 3+ , Gd 3+ , Tb 3+ , Dy 3+ , Ho 3+ , Er 3+ , Tm 3+ , Yb 3+ , Lu 3+ , Ti 3+ , V 3+ , Cr 3+ , Mn 3+ , Fe 3+ , Co 3+ , Ni 3+ , Cu 3+ , Nb 3+ , Mo 3+ , Ru 3+ , Rh 3+ , Pd 3+ , Ag 3+ , Ta 3+ , W 3 *, lr 3+ , Au 3+ , B 3+ , Al 3+ , Ga 3+ , ln 3+ , Tl 3+ ,
  • B 5 is a divalent cation and is selected from one or more members of the group consisting of Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Nd 2+ , Sm 2+ , Eu 2+ , Dy 2+ , Ho 2+ , Tm 2+ , Yb 2+ , Ti 2+ , V 2+ , Cr 2+ , Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ , Cu 2+ , Mo 2+ , Pd 2+ , Ag 2+ , W 2 *, Pt 2+ , Zn 2+ , Cd 2+ , Hg 2+ , Ge 2+ , Sn 2+ and Pb 2+ ,
  • C 3 is a tetravalent cation and is selected from one or more members of the group consisting of Ce 4+ , Pr 4+ , Nd 4+ , Tb 4+ , Dy 4+ , Ti 4+ , V 4+ , Cr 4+ , Mn 4+ , Fe 4+ , Co 4+ , Ni 4+ , Zr 4+ , Nb 4+ , Mo 4+ , Tc 4+ , Ru 4+ , Rh 4+ , Pd 4+ , Hf 4+ , Ta 4+ , W 4+ , Re 4+ , Os 4+ , lr 4+ , Pt 4+ , Si 4+ , Ge 4+ , Sn 4+ , Pb 4+ , S 4+ , Se 4+ , Te 4+ and Po 4+ , preferably AMs Sc 3+ , Y 3+ , La 3+ , Lu 3+ , B 3+ , Al 3+ , Ga 3+ , ln 3
  • a 7 is a divalent cation and is selected from one or more members of the group consisting of Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Nd 2+ , Sm 2+ , Eu 2+ , Dy 2+ , Ho 2+ , Tm 2+ , Yb 2+ , Ti 2+ , V 2+ , Cr 2+ , Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ , Cu 2+ , Mo 2+ , Pd 2+ , Ag 2+ , W 2 *, Pt 2+ , Zn 2+ , Cd 2+ , Hg 2+ , Ge 2+ , Sn 2+ and Pb 2+ ,
  • B 6 is a trivalent cation and is selected from one or more members of the group consisting of Sc 3+ , Y 3+ , La 3+ , Ce 3+ , Pr 3+ , Nd 3+ , Pm 3+ , Sm 3+ , Eu 3+ , Gd 3+ , Tb 3+ , Dy 3+ , Ho 3+ , Er 3+ , Tm 3+ , Yb 3+ , Lu 3+ , Ti 3+ , V 3+ , Cr 3+ , Mn 3+ , Fe 3+ , B 3+ , Al 3+ , Ga 3+ , ln 3+ , Tl 3+ , P 3+ , As 3+ , Sb 3+ and Bi 3+ ;
  • a 8 is a divalent cation and is selected from one or more members of the group consisting of Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Nd 2+ , Sm 2+ , Eu 2+ , Dy 2+ , Ho 2+ , Tm 2+ , Yb 2+ , Ti 2+ , V 2+ , Cr 2+ , Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ , Cu 2+ , Mo 2+ , Pd 2+ , Ag 2+ , W 2 *, Pt 2+ , Zn 2+ , Cd 2+ , Hg 2+ , Ge 2+ , Sn 2+ and Pb 2+ ,
  • B 7 is a divalent cation and is selected from one or more members of the group consisting of Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Nd 2+ , Sm 2+ , Eu 2+ , Dy 2+ , Ho 2+ , Tm 2+ , Yb 2+ , Ti 2+ , V 2+ , Cr 2+ , Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ , Cu 2+ , Mo 2+ , Pd 2+ , Ag 2+ , W 2 *, Pt 2+ , Zn 2+ , Cd 2+ , Hg 2+ , Ge 2+ , Sn 2+ and Pb 2+ ,
  • C 4 is a trivalent cation and is selected from one or more members of the group consisting of Sc 3+ , Y 3+ , La 3+ , Ce 3+ , Pr 3+ , Nd 3+ , Pm 3+ , Sm 3+ , Eu 3+ , Gd 3+ , Tb 3+ , Dy 3+ , Ho 3+ , Er 3+ , Tm 3+ , Yb 3+ , Lu 3+ , Ti 3+ , V 3+ , Cr 3+ , Mn 3+ , Fe 3+ , Co 3+ , Ni 3+ , Cu 3+ , Nb 3+ , Mo 3+ , Ru 3+ , Rh 3+ , Pd 3+ , Ag 3+ , Ta 3+ , W 3 *, lr 3+ , Au 3+ , B 3+ , Al 3+ , Ga 3+ , ln 3+ , Tl 3+ , P 3+ , As 3+ , Sb 3+
  • a 9 is a divalent cation and is selected from one or more members of the group consisting of Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Nd 2+ , Sm 2+ , Eu 2+ , Dy 2+ , Ho 2+ , Tm 2+ , Yb 2+ , Ti 2+ , V 2+ , Cr 2+ , Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ , Cu 2+ , Mo 2+ , Pd 2+ , Ag 2+ , W 2 *, Pt, 2+ Zn 2+ , Cd 2+ , H 2+ g, Ge 2+ , Sn 2+ and Pb 2+ ;
  • B 8 is a pentavalent cation and is selected from one or more members of the group consisting of V 5+ , Cr 5+ , Mn 5+ , Co 5+ , Nb 5+ , Mo 5+ , Tc 5+ , Ru 5+ , Rh 5+ , Ta 5+ , W 5+ , Re 5+ , Os 5+ , lr 5+ , Pt 5+ , Au 5+ , P 5+ , As 5+ , Sb 5+ and Bi 5+ ;
  • C 5 is at monovalent anion and is selected from one or more members of the group consisting of F; Cl; Br and I;
  • a composition comprising at least one particle of any one of embodiments 1 to 18 and a further material, preferably selected from one or more members of the group consisting of matrix materials; light modulating materials such as dyes e.g. yellow dyes, pigments, light luminescent materials including organic and inorganic light luminescent materials, e.g. another inorganic phosphor; photo initiators; co- polymerizable monomers; crosslinkable monomers; bromine-containing monomers; sulfur-containing monomers; adjuvants; adhesives; insecticides; insect attractants; metal oxides; Al, Ag, Au nanoparticles; dispersants; surfactants; fungicides and antimicrobial agents.
  • matrix materials such as dyes e.g. yellow dyes, pigments, light luminescent materials including organic and inorganic light luminescent materials, e.g. another inorganic phosphor
  • photo initiators co- polymerizable monomers; crosslinkable monomers; bromine-containing monomers; sulfur-containing monomers; adju
  • composition according to embodiment 21 wherein the total amount of the particle of the composition is in the range from 0.01wt.% to 30wt.% based on the total amount of the composition, preferably it is from 0.1wt.% to 10wt.%, more preferably from 0.5wt.% to 5wt.%, furthermore preferably it is from 1wt.% to 3wt.%.
  • Formulation comprising at least one particle of any one of embodiments 1 to 18, or the composition of any one of embodiments 21 to 23, and a solvent.
  • An optical sheet comprising at least one particle of any one of embodiments 1 to 18, or the composition of any one of embodiments 21 to 23, preferably said optical sheet is an agricultural sheet.
  • a method for preparing an optical sheet preferably for preparing an agriculture sheet, wherein the method comprises the following steps (A) and (B),
  • composition comprising at least one particle comprising a phosphor as an inner core, an outer core at least partially surrounding the inner core, and a transparent polymer layer as a shell enclosing the outer core; and a further material, or a formulation comprising said composition and a solvent in a first shaping;
  • said transparent polymer is an organic polymer, more preferably it is selected from one or more member of the group consisting of (meth)acrylate polymers, polystyrenes including P oly(styrene-co- divinylbenzenes, polyisobutylene and ethyl cellulose.
  • An optical device comprising at least one optical sheet of embodiment 26, preferably said optical device is a lighting device, more preferably it is a Light Emitting Diode.
  • a greenhouse comprising the optical sheet of embodiment 26, or the optical device of embodiment 30.
  • a method for modulating a condition of a plant, plankton, and/or a bacterium comprising at least following step of providing the optical sheet of embodiment 26 between a light source and a plant, between a light source and plankton, preferably said plankton is phytoplankton, between a light source and a bacterium, preferably said bacterium is a photosynthetic bacterium, and/or providing the optical sheet of embodiment 26 over a ridge in a field or over a surface of planter, preferably said planter is a nutrient film technique hydroponics system or a deep flow technique hydroponics system to control plant growth.
  • the light source is the sun or an artificial light source, preferably said artificial light source is a light emitting diode.
  • a container comprising at least one plant, plankton, and/or a bacterium of embodiment 38.
  • a phosphor particle with a light conversion and light reflection function that produces optimal blue, red and infrared light
  • improved optical properties such as light scattering, absorbing, refraction and/or reflection ability of a phosphor particle
  • improved long term moisture durability, improved water resistance, and improved UV-stability good durability of a phosphor particle or of an optical sheet using a phosphor particle
  • an phosphor particle having a higher EQE improved dispersibility of phosphor particles in a formulation, composition and/or in a matrix material of a film or sheet
  • improved transparency of a film or sheet preferably improved transparency of an agricultural film
  • an incident light enters into the foil material having the refractive index n, then the light passes through a particle shell having the refractive index n’, finally the light acts to the phosphor after passing through an area between the particle shell and the phosphor (i.e. , the outer core) being made of a material that has the refractive index n”.
  • a converted light from the phosphor passes through the area between the particle shell and the phosphor (i.e., the outer core) being made of a material that has the refractive index n”, the particle shell having the refractive index n’ and the foil material having the refractive index n in this sequence, then it can reach a plant.
  • polystyrene (average M.W. 250,000, Acros Organics) is dissolved in 150 mL of cyclohexane (Merck) at 70 °C, and to this solution 619.2 mg of powdered “CZA” (Cai4AlioZne035:Mn 4+ ) is added as the inner core substance. The mixture is stirred for 1 hour at this temperature and then slowly cooled to 17 °C. 100 mL of n-hexane (Merck) is added, and the mixture is stirred at room temperature for 1 hour. After collecting the polystyrene encapsulated particles, they are washed with acetonitrile several times and dried at 50 °C.
  • PIB polyisobutylene
  • cyclohexane Merck
  • CZA Cai4AlioZne035:Mn 4+
  • EC ethyl cellulose
  • a phosphor master batch is prepared by mixing encapsulated Al20s:Cr 3+ particles at high concentration with low-density polyethylene resin (NIPOLON® 180).
  • This master batch, resin containing stabilizer and normal resin (NIPOLON® 180) are mixed at an arbitrary ratio and put into the inflation molding machine.
  • Raw materials are extruded by a screw, heated to about 170°C and melted.
  • the molten resin with phosphors is extruded and is drawn through bulges like a balloon by enclosed air. Then it is cooled by cooling air, which flows outside the balloon.
  • the balloon is pulled up and folded into two overlapping foils.
  • the film thickness is adjusted by controlling the nip roll speed.
  • the foil is pulled up by a rotary winding machine. Table 1 below shows the materials used in the foil fabrication.
  • a foil is fabricated in the same manner as described in working example 4, except for using Al20s:Cr 3+ particles not encapsulated by a polymer coating layer instead of the encapsulated Al20s:Cr 3+ particles of working example 1.
  • the foils produced are measured by the UV-2550 spectrometer created by Shimazu.
  • the transmittance of the foil with the encapsulated Al20s:Cr 3+ particles is confirmed to have an improvement of approximately 25% as compared to the foil with the Al20s:Cr 3+ particles not encapsulated. This result may be attributed to the fact that when the phosphors are mixed in the inflation molding machine, the encapsulated Al20s:Cr 3+ particles do not leave scratches that generate contamination in the machine. Accordingly, it is seen that the transmittance of the foil produced by this method in accordance with the present invention is improved, so that are they effectively applicable in the agricultural field.
  • Working Example 6 Foil fabrication The fabrication of a foil containing encapsulated CZA (Cai4AlioZne035:Mn 4+ ) particles obtained in working example 2 is carried out by the extrusion inflation method in the same manner as described in working example 4.
  • a foil is fabricated in the same manner as described in working examples 4 and 6, except for using CZA particles not encapsulated by a polymer coating layer instead of the encapsulated CZA particles of working example 2.
  • a custom-made plant chamber with LED lightings is prepared for the plant growth test. Seedlings of lettuce and ruccola are set in the plant chamber.

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Abstract

La présente invention concerne une particule, un procédé de préparation de ladite particule et des utilisations de ladite particule, en particulier dans l'agriculture.
PCT/EP2021/077327 2020-10-08 2021-10-05 Particule et procédé de fabrication d'une particule WO2022073948A1 (fr)

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CN116179200A (zh) * 2023-02-02 2023-05-30 浙江大学 一种稀土离子掺杂的多色可调铝锗酸盐荧光粉及其制备方法
CN116554876A (zh) * 2023-05-09 2023-08-08 中国科学院长春应用化学研究所 一种Fe3+掺杂的近红外发光材料、其制备方法及应用

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CN116179200A (zh) * 2023-02-02 2023-05-30 浙江大学 一种稀土离子掺杂的多色可调铝锗酸盐荧光粉及其制备方法
CN116554876A (zh) * 2023-05-09 2023-08-08 中国科学院长春应用化学研究所 一种Fe3+掺杂的近红外发光材料、其制备方法及应用

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