WO2021099351A1 - Method for fabricating a particle - Google Patents

Method for fabricating a particle Download PDF

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Publication number
WO2021099351A1
WO2021099351A1 PCT/EP2020/082477 EP2020082477W WO2021099351A1 WO 2021099351 A1 WO2021099351 A1 WO 2021099351A1 EP 2020082477 W EP2020082477 W EP 2020082477W WO 2021099351 A1 WO2021099351 A1 WO 2021099351A1
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WO
WIPO (PCT)
Prior art keywords
group
combination
members
range
inorganic phosphor
Prior art date
Application number
PCT/EP2020/082477
Other languages
French (fr)
Inventor
Hiroshi Okura
Hiroki Yoshizaki
Ryota YAMANASHI
David Downey
Werner Stockum
Prashanth GARAPATI
Michael SCHABERGER
Yoshio Kobayashi
Noriko Yamauchi
Original Assignee
Merck Patent Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
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Publication of WO2021099351A1 publication Critical patent/WO2021099351A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • 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
    • A01G7/00—Botany in general
    • A01G7/04—Electric or magnetic or acoustic treatment of plants for promoting growth
    • A01G7/045—Electric or magnetic or acoustic treatment of plants for promoting growth with electric lighting
    • 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
    • C09K11/671—Chalcogenides
    • C09K11/673—Chalcogenides with alkaline earth metals
    • 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
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier 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 with at least one potential-jump barrier or surface barrier 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier 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 with at least one potential-jump barrier or surface barrier 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier 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 with at least one potential-jump barrier or surface barrier 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
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier 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 with at least one potential-jump barrier or surface barrier 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
    • H01L33/507—Wavelength conversion elements the elements being in intimate contact with parts other than the semiconductor body or integrated with parts other than the semiconductor body
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
    • Y02P60/14—Measures for saving energy, e.g. in green houses

Definitions

  • the present invention relates to a particle comprising an inorganic phosphor and a coating layer, a composition, a formulation, an optical sheet, an optical device, a greenhouse, use, a plant, a container and a method.
  • WO 2019/020602 A1 and WO 2019/020653 A1 disclose a use of an inorganic phosphor for agriculture. And it also discloses that the inorganic phosphor materials can be phosphor particles with or without silicon dioxide coating.
  • improved transparency of a film preferably improved transparency of an agricultural film, avoiding or reducing a scratch of an inflation molding machine caused by an inorganic phosphor, avoiding or reducing a situation that an optical sheet comprising an inorganic phosphor is contaminated with a dust from an inflation molding machine, improved long term moisture durability, improved water resistance, a water free coating process to avoid any damage to a phosphor during the coating process, an inorganic phosphor having a coating layer with higher EQE, improved and well controlled average particle size, improved optical properties such as light scattering, absorbing, refraction and/or reflection ability of inorganic phosphors, improved dispersibility of inorganic phosphors in a formulation, composition and/or in a matrix material of a film, better compatibility of an inorganic phosphor with a matrix material, improvement of controlling property of a phytoplankton condition, photosynthetic bacteria and/
  • a novel particle comprising an inorganic phosphor and a transparent polymer layer placed onto the outermost surface of said inorganic phosphor, preferably 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, polyethylene polyethyleneterephthalate, polyurethane, polyacrylonitrile, epoxy resin derived from glycidyl function on (meth)acrylate monomer, biodegradable polymer such as polylactide, polyglycolide, polyhydroxyalkanoate, polycaproractone.
  • the present invention also relates to a use of the particle of the present invention for agriculture.
  • the present invention furthermore relates to a composition comprising at least one particle of the present invention and another material.
  • the present invention 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 an optical sheet fabrication process or in agriculture, preferably for fabricating an agricultural sheet or for controlling a condition of a living organism.
  • the invention relates to an optical sheet (100) 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 invention relates to an optical device (200) comprising at least one optical sheet (100) of the present invention, preferably said optical device is a lighting device, more preferably it is a light emitting diode device.
  • the invention in another aspect, relates to a greenhouse comprising an optical sheet (100) of the present invention.
  • the invention relates to a use of the optical sheet (100) of the present invention or the optical device (200) of the present invention for agriculture, preferably for greenhouse or for controlling a condition of a living organism in agriculture.
  • the invention relates to a method for preparing the optical sheet (100), preferably for preparing the agriculture sheet, wherein the method comprises following steps (a) and (b),
  • the invention relates to a method for preparing the optical device (200) of the present invention, comprising following step (A);
  • the invention relates to a method for preparing the agriculture sheet, wherein the method comprises following steps (a ' ) and
  • composition comprising a particle comprising an inorganic phosphor and a coating layer onto the outermost surface of the inorganic phosphor, and another material, or the formulation comprising said composition and a solvent in a first shaping, preferably providing the composition into an inflation moulding machine, and
  • said coating layer is a transparent polymer layer or a metal oxide coating layer
  • said particle is the particle of the present invention or a particle comprising an inorganic phosphor coated by a metal oxide coating layer selected from one or more members of the group consisting of S1O2, T1O2, ZnOa, ZrOa and AI2O3, more preferably it is selected from S1O2, T1O2, ⁇ ⁇ a combination of any of these, preferably said inorganic phosphor is the inorganic phosphor as described in the section of “Inorganic phosphor”.
  • the present invention relates to use of a particle of metal oxide coated inorganic phosphor comprising an inorganic phosphor and at least one metal oxide coating layer onto the outermost surface of said phosphor, for agriculture, preferably said metal oxide coating layer is selected from one or more members of the group consisting of Si02, T1O2, Zn02, ZrO ⁇ and AI2O3, more preferably it is selected from Ti02, ⁇ ⁇ a combination of Si02, T1O2 and Zn02, preferably for greenhouse or for controlling a condition of a living organism in agriculture, preferably said inorganic phosphor is the inorganic phosphor as described in the section of “Inorganic phosphor”.
  • the present invention also relates to a method for preparing the optical device (200) of the present invention, comprising following step (A);
  • the invention relates to a use of the particle of the present invention, or the composition of the present invention, the formulation of the present invention, the optical sheet (100) of the present invention, the optical device (200) of the present invention or the green house of the present invention for cultivation of algae, bacteria, preferably said bacteria are photosynthetic bacteria, and/or planktons, 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 / 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,
  • the invention relates to a method of supplying the particle of the present invention, or the composition of any one of the present invention, 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, comprising at least following step (C),
  • (C) providing the optical sheet (100) of the present invention, between a light source and a plant, between a light source and a plankton, preferably said plankton is a phytoplankton, between a light source and a bacterium, preferably said bacterium is a photosynthetic bacterium, or providing the optical sheet (100) of the present invention 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 invention relates to a plant obtained or obtainable by the method of the present invention, or a 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, one plankton, and/or a bacterium of 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 var., 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.
  • 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.
  • 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).
  • Wavelength converting material or briefly referred to as a “converter” means a material that converts light of a first wavelength to light of a second wavelength, wherein the second wavelength is different from the first wavelength.
  • Wavelength converting materials include organic materials and inorganic materials that can achieve photon up-conversion, and organic materials and inorganic materials that can achieve photon down-conversion.
  • 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. Alqs, LiQ, lr(ppy>3.
  • the inorganic materials include phosphors and semiconductor nanoparticles.
  • a “phosphor” is a fluorescent or a phosphorescent inorganic material which contains one or more light emitting centers.
  • the light emitting centers are formed by activator elements such as e.g. 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 Cr, 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 e.g. 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,
  • Suitable phosphors include phosphors based on garnet, silicate, orthosilicate, thiogallate, sulfide, nitride, silicon-based oxynitride, nitridosilicate, nitridoaluminumsilicate, oxonitridosilicate, oxonitridoaluminumsilicate and rare earth doped sialon.
  • Phosphors within the meaning of the present application are materials which absorb electromagnetic radiation of a specific wavelength range, preferably blue and/or ultraviolet (UV) electromagnetic radiation and convert 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).
  • UV ultraviolet
  • VIS visible
  • NIR near infrared light
  • UV is electromagnetic radiation with a wavelength from 100 nm to 389nm, shorter than that of visible light but longer than X-rays.
  • VIS is 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.
  • it is over 70 %, more preferably, over 75%, the most preferably, it is over 80 %.
  • Fia. 1 shows a cross sectional view of a schematic of one embodiment of an optical sheet (100) of the invention.
  • Fia. 2 shows a cross sectional view of a schematic of one embodiment of an optical device (200) of the invention.
  • Fia. 3 shows a cross sectional view of a schematic of another embodiment of an optical device of the invention.
  • an optical sheet (a color conversion sheet) 110.
  • a particle of the invention 120.
  • an optical device (a light emitting diode device)
  • an optical device (a light emitting diode device)
  • a color conversion sheet 310 a particle of the invention 320. a matrix material
  • said particle comprises, essentially consisting of, or consisting of an inorganic phosphor and a transparent polymer layer placed onto the outermost surface of said inorganic phosphor, preferably 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, polyethylene polyethyleneterephthalate, polyurethane, polyacrylonitrile, epoxy resin derived from glycidyl function on (meth)acrylate monomer, biodegradable polymer such as polylactide, polyglycolide, polyhydroxyalkanoate, polycaproractone.
  • 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, polyethylene polyethyleneterephthalate, polyurethane, polyacrylonitrile, epoxy resin derived from glycidyl function on (meth)acrylate monomer, biodegradable poly
  • the polymer 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.
  • the polymer is derived or derivable from an acidic monomer or acidic oligomer having 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, preferably said acidic monomer is a (meth)acrylate monomer, more preferably said polymer is derived from an acidic monomer and another monomer having no anchoring group, even more preferably said polymer is derived from an acidic (meth)acrylate monomer and (meth)acrylate monomer having no anchoring group.
  • the polymer is derived or derivable from an acidic monomer having at least one anchoring group listed above.
  • said acidic monomer 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, 1-[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-cyclohexanedicar
  • the acidic monomer disclosed above is suitable to form a polymer to form a polymer coating layer directly onto an inorganic phosphor since said acidic monomer has a group which can attach onto the surface of the inorganic phosphor.
  • 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 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, and / or at least one inorganic phosphor 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 nm, even more preferably in the range from 350 nm to 500 nm, furthermore preferably in the range from 400 nm
  • 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.
  • peak wavelength is related to a side peak.
  • peak wavelength is related to the main peak having maximum intensity/absorption.
  • the phosphor is a nontoxic phosphor, preferably it is an edible phosphor.
  • said 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 Fe, Eu, Ce and/or Mn activated metal oxide phosphor or a Fe, Eu, Ce and/or Mn activated phosphate based phosphor, even more preferably it is a Fe, Eu, Ce and/or Mn activated metal oxide phosphor. More preferably, the inorganic phosphor
  • a 1 xB 1 yO z :X - (I) wherein A 1 is a trivalent cation and is selected from the group consisting of Y, Gd, Lu, Ce, La, Tb, Sc, and Sm, B 1 is a trivalent cation and is selected from the group consisting of Al, Ga, Lu, Sc, In; x ⁇ 0; y ⁇ 1 ; 1.5(x+y) z, X is a luminescent ion and is selected from one or more members of the group consisting of Ce 3+ , Pr 3+ , Nd 3+ , Nd 4+ , Pm 3+ , Sm 3+ , Eu 3+ , Eu 2+ , Gd 3+ , Tb 3+ , Dy 2+ , Dy 3+ , Dy 4+ , Ho 2+ , Ho 3+ , Er 3+ , Tm 3+ , Yb 3+ , Yb 2+ , Cr 3+ , Mn 2+ , Mn
  • a 2 aZbO c :X - (II) wherein A 2 is a divalent cation and is selected from the group consisting of Mg, Zn, Cu, Co, Ni, Fe, Ca, Sr, Ba, Mn, Ce and Sn; Z is a trivalent cation and is selected from the group consisting of Al, Ga, Lu, Sc and In; b ⁇ 0; a ⁇ 1 ; (a+1 ,5b) c, X is a luminescent ion and is selected from one or more members of the group consisting of Ce 3+ , Pr 3+ , Nd 3+ , Nd 4+ , Pm 3+ , Sm 3+ , Eu 3+ , Eu 2+ , Gd 3+ , Tb 3+ , Dy 2+ , Dy 3+ , Dy 4+ , Ho 2+ , Ho 3+ , Er 3+ , Tm 3+ , Yb 3+ , Yb 2+ , Cr 3+ ,
  • X is a luminescent ion and is selected from one or more members of the group consisting of Ce 3+ , Pr 3+ , Nd 3+ , Nd 4+ , Pm 3+ , Sm 3+ , Eu 3+ , Eu 2+ , Gd 3+ , Tb 3+ , Dy 2+ , Dy 3+ , Dy 4+ , Ho 2+ , Ho 3+ , Er 3+ , Tm 3+ , Yb 3+ , Yb 2+ , Cr 3+ , Mn 2+ , Mn 4+ and Fe 3+ , preferably X is selected from Ce 3+ , Eu 3+ , Eu 2+ , Tb 3+ , Cr 3
  • Mn 4+ Mn 4+ , Fe 3+ or a combination of any of these, more preferably X is Mn 4+ , even more preferably formula (III) is CaAl12O19:Mn 4+ ;
  • D 2 is a trivalent cation and is selected from one or more members of the group consisting of Al 3+ , Ga 3+ , Lu 3+ , Sc 3+ , La 3+ and In 3+ ;
  • E 2 is a trivalent cation and is selected from the group consisting of Al 3+ , Ga 3+ ,
  • Lu 3+ , Sc 3+ , La 3+ and In 3+ ; h ⁇ 0; a ⁇ g; (1.5g+1 ,5h) I, preferably D 2 is La 3+ , E 2 is Al 3+ , Gd 3+ or a combination of these, g is 1 , h is 12, i is 19, X is a luminescent ion and is selected from one or more members of the group consisting of Ce 3+ , Pr 3+ , Nd 3+ , Nd 4+ , Pm 3+ , Sm 3+ , Eu 3+ , Eu 2+ , Gd 3+ , Tb 3+ , Dy 2+ , Dy 3+ , Dy 4+ , Ho 2+ , Ho 3+ , Er 3+ , Tm 3+ , Yb 3+ , Yb 2+ , Cr 3+ , Mn 2+ , Mn 4+ and Fe 3+ , preferably X is selected from Ce 3+ , Eu 3+ , Eu 2
  • 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 In 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 In 3+ ;
  • a 3 is a trivalent cation and is selected from one or more members of the group consisting of Ce 3+ , Pr 3+ , Nd 3+ , Tb 3+ , Dy 3+ , Ti 3+ , V 3+ , Cr 3+ , Mn 3+ , Fe 3+ , Co 3+ , Ni 3+ , Zr 3+ , Nb 3+ , Mo 3+ , Tc 3+ , Ru 3+ , Rh 3+ , Pd 3+ , Hf 3+ , Ta 3+ , W 3+ , Re 3+ , Os 3+ , Ir 3+ , Pt 3+ , Si 3+ , Ge 3+ , Sn 3+ , Pb 3+ , S 3+ , Se 3+ , Te 3+ and Po 3+ ;
  • X is selected from Ce 3+ , Eu 3+ , Eu 2+ , Tb 3+ , Cr 3+ , Mn 2+ , Mn 4+ , Fe 3+ or a combination of any of these, more preferably X is Ce 3+ ; a is 1 , z is 2; more preferably the formula is ZrO2:Ce 3+ ;
  • a 4 is a monovalent cation and is selected from one or more members of the group consisting of Li + , Na + , K + , Rb + , Cs + , V + , Cr + , Mn + , Co + , Ni + , Cu + , Pd + . Ag + .
  • B 2 is a tetravalent cation and is selected from one or more members of the group consisting of Ce 3+ , Pr 3+ , Nd 3+ , Tb 3+ , Dy 3+ , Ti 3+ , V 3+ , Cr 3+ , Mn 3+ , Fe 3+ , Co 3+ , Ni 3+ , Zr 3+ , Nb 3+ , Mo 3+ , Tc 3+ , Ru 3+ , Rh 3+ , Pd 3+ , Hf 3+ , Ta 3+ , W 3+ , Re 3+ , Os 3+ , Ir 3+ , Pt 3+ , Si 3+ , Ge 3+ , Sn 3+ , Pb 3+ , S 3+ , Se 3+ , Te 3+ and Po 3+ ;
  • C 1 is a tetravalent cation and is selected from one or more members of the group consisting of Ce 3+ , Pr 3+ , Nd 3+ , Tb 3+ , Dy 3+ , Ti 3+ , V 3+ , Cr 3+ , Mn 3+ , Fe 3+ , Co 3+ , Ni 3+ , Zr 3+ , Nb 3+ , Mo 3+ , Tc 3+ , Ru 3+ , Rh 3+ , Pd 3+ , Hf 3+ , Ta 3+ , W 3+ , Re 3+ , Os 3+ , Ir 3+ , Pt 3+ , Si 3+ , Ge 3+ , Sn 3+ , Pb 3+ , S 3+ , Se 3+ , Te 3+ and Po 3+ ;
  • B 2 is Ce 3+ , Ti 3+ , Zr 3+ , Hf 3+ , Si 3+ , Ge 3+ , Sn 3+ , or a combination of any of these,
  • C 1 is Ce 3+ , Ti 3+ , Zr 3+ , Hf 3+ , Si 3+ , Ge 3+ , Sn 3+ , or a combination of any of these;
  • X is Ce 3+ , Eu 3+ , Eu 2+ , Tb 3+ , Cr 3+ , Mn 2+ , Mn 4+ and Fe 3+ , or a combination of any of these, more preferably X is Eu 2+ ; a is 2, b is 1 , c is 2, z is 7; more preferably, formula is K2ZrSi20?:Eu 2+ ;
  • a 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+ ;
  • B 3 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+ , Ir 3+ , Au 3+ , B 3+ , Al 3+ , Ga 3+ , ln 3+ , Tl 3+ , P 3+ , As 3+ , Sb 3+
  • C 2 is a tetravalent cation and is selected from one or more members of the group consisting of Ce 3+ , Pr 3+ , Nd 3+ , Tb 3+ , Dy 3+ , Ti 3+ , V 3+ , Cr 3+ , Mn 3+ , Fe 3+ , Co 3+ , Ni 3+ , Zr 3+ , Nb 3+ , Mo 3+ , Tc 3+ , Ru 3+ , Rh 3+ , Pd 3+ , Hf 3+ , Ta 3+ , W 3+ , Re 3+ , Os 3+ , Ir 3+ , Pt 3+ , Si 3+ , Ge 3+ , Sn 3+ , Pb 3+ , S 3+ , Se 3+ , Te 3+ and Po 3+ ;
  • D 3 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+ , Ir 3+ , Au 3+ , B 3+ , Al 3+ , Ga 3+ , In 3+ , TI 3+ , P 3+ , As 3+ , Sb 3+ and Bi
  • B 3 is Sc 3+ , Y 3+ , La 3+ , Lu 3+ , B 3+ , Al 3+ , Ga 3+ , In 3+ , P 3+ , Bi 3+ , or a combination of any of these;
  • C 2 is Ce 3+ , Ti 3+ , Zr 3+ , Hf 3+ , Si 3+ , Ge 3+ , Sn 3+ , or a combination of any of these;
  • D 3 is Sc 3+ , Y 3+ , La 3+ , Lu 3+ , B 3+ , Al 3+ , Ga 3+ , In 3+ , P 3+ , Bi 3+ , or a combination of any of these;
  • X is Ce 3+ , Eu 3+ , Eu 2+ , Tb 3+ , Cr 3+ , Mn 2+ , Mn 4+ and Fe 3+ , or a combination of any of these; a is 2, b is 1 , c is 2, d is 3, z is 12; more preferably the formula is Ca2YZr2Al3O12:Ce 3+ ; A 6 aB 4 bO z :X -(IX) wherein A6 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+
  • B 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+ , Ir 3+ , Au 3+ , B 3+ , Al 3+ , Ga 3+ , In 3+ , TI 3+ , P 3+ , As 3+ , Sb 3+ and Bi
  • B 4 is Sc 3+ , Y 3+ , La 3+ , Lu 3+ , B 3+ , Al 3+ , Ga 3+ , In 3+ , P 3+ , Bi 3+ , or a combination of any of these;
  • X is Ce 3+ , Eu 3+ , Eu 2+ , Tb 3+ , Cr 3+ , Mn 2+ , Mn 4+ and Fe 3+ , or a combination of any of these, more preferably X is Ce 3+ ; a is 3, b is 5, z is 12; more preferably the formula is Y3Al5O12: Ce 3+ ;
  • a 7 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+ , Ir 3+ , Au 3+ , B 3+ , Al 3+ , Ga 3+ , In 3+ , TI 3+ , P 3+ , As 3+ , Sb 3+ and Bi
  • B 5 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+ , Ir 3+ , Au 3+ , B 3+ , Al 3+ , Ga 3+ , In 3+ , Tl 3+ , P 3+ , As 3+ , Sb 3+ and Bi 3
  • C 3 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+ ;
  • B 5 is Sc 3+ , Y 3+ , La 3+ , Lu 3+ , B 3+ , Al 3+ , Ga 3+ , In 3+ , P 3+ , Bi 3+ , or a combination of any of these;
  • C 3 is Sc 3+ , Y 3+ , La 3+ , Lu 3+ , B 3+ , Al 3+ , Ga 3+ , In 3+ , P 3+ , Bi 3+ , or a combination of any of these;
  • X is Ce 3+ , Eu 3+ , Eu 2+ , Tb 3+ , Cr 3+ , Mn 2+ , Mn 4+ and Fe 3+ , or a combination of any of these, more preferably X is Ce 3+ ; a is 3, b is 2, c is 3, z is 12; more preferably, formula is Y3Ga2Al3O12: Ce 3+ ;
  • a 8 is a monovalent cation and is selected from one or more members of the group consisting of Li + , Na + , K + , Rb + , Cs + , V + , Cr + , Mn + , Co + , Ni + , Cu + , Pd + , Ag + . Au + and TI + ;
  • B 8 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+ , Ir 3+ , Au 3+ , B 3+ , Al 3+ , Ga 3+ , In 3+ , TI 3+ , P 3+ , As 3+ , Sb 3+ and Bi
  • B® is Sc 3+ , Y 3+ , La 3+ , Lu 3+ , B 3+ , Al 3+ , Ga 3+ , In 3+ , P 3+ , Bi 3+ , or a combination of any of these;
  • X is Ce 3+ , Eu 3+ , Eu 2+ , Tb 3+ , Cr 3+ , Mn 2+ , Mn 4+ and Fe 3+ , or a combination of any of these, more preferably X is Mn 4+ ; a is 1 , b is 5, z is 8; more preferably the formula is LiAlsOsiMn 4+ ;
  • 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+ , Hg 2+ , Ge 2+ , Sn 2+ and Pb 2+ ;
  • B 7 is a tetravalent cation and is selected from one or more members of the group consisting of Ce 3+ , Pr 3+ , Nd 3+ , Tb 3+ , Dy 3+ , Ti 3+ , V 3+ , Cr 3+ , Mn 3+ , Fe 3+ , Co 3+ , Ni 3+ , Zr 3+ , Nb 3+ , Mo 3+ , Tc 3+ , Ru 3+ , Rh 3+ , Pd 3+ , Hf 3+ , Ta 3+ , W 3+ , Re 3+ , Os 3+ , Ir 3+ , Pt 3+ , Si 3+ , Ge 3+ , Sn 3+ , Pb 3+ , S 3+ , Se 3+ , Te 3+ and Po 3+ ;
  • B 7 is Ce 3+ , Ti 3+ , Zr 3+ , Hf 3+ , Si 3+ , Ge 3+ , Sn 3+ , or a combination of any of these;
  • a 11 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 + , Pt 2+ , Zn 2+ , Cd 2+ , Hg 2+ , Ge 2+ , Sn 2+ and Pb 2+ ;
  • B 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+ , Hg 2+ , Ge 2+ , Sn 2+ and Pb 2+ ;
  • C 5 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
  • B 9 is Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ and Zn 2+ , or a combination of any of these;
  • C 5 is Sc 3+ , Y 3+ , La 3+ , Lu 3+ , B 3+ , Al 3+ , Ga 3+ , ln 3+ , P 3+ , Bi 3+ , or a combination of any of these;
  • X is Ce 3+ , Eu 3+ , Eu 2+ , Tb 3+ , Cr 3+ , Mn 2+ , Mn 4+ and Fe 3+ , or a combination of any of these, more preferably X is Mn 4+ ; even more preferably the formula is CaMgAli6027:Mn 4+ , Ca2Mg2Al28046:Mn 4+ , Sr2MgAl22036:Mn 4+ or BaMgAhoOi7:Mn 4+ .
  • the inorganic phosphor is selected from one or more of members of the group consisting of Al203:Cr 3+ , Y 3 AI 5 0i2:Cr 3+ , MgAI 2 0 4 : Cr 3+ , CaAh 2 0i 9 :Mn 4+ , LaAI0 3 :Mn 4+ , CaYA10 4 :Mn 4+ , Zr0 2 :Ce 3+ , K 2 ZrSi 2 0 7 :Eu 2+ , Ca 2 YZr 2 A1 3 0i 2 :Ce 3+ , Y 3 AI 5 01 2 :Ce 3+ , Y 3 Ga 2 AI 3 01 2 :Ce 3+ , LiAI 5 0 8 :Mn 4+ , Li 2 MgZr0 4 :Mn 4+ , CaZr0 3 :Mn 4+ , CaMgAli 6 0 27 :Mn 4+ , Ca 2
  • the particle comprising one or more of above mentioned phosphors are particularly suitable to avoid or reduce a scratch of an inflation molding machine caused by an inorganic phosphor, to avoid or reduce a situation that an optical sheet comprising an inorganic phosphor is contaminated with a dust from an inflation molding machine and to make an optical sheet with improved transparency.
  • the inorganic phosphors can emit a light having the peak wavelength of light emitted from the inorganic phosphor in the range from 660 nm to 710 nm.
  • 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. Therefore, in some embodiments of the present invention, 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 650 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 at least one inorganic phosphor is a plurality of inorganic phosphor having the first and second peak wavelength of light emitted from the inorganic phosphor, or a plurality of inorganic phosphor having the first and second peak wavelength of light emitted from the inorganic phosphor, or a combination of these.
  • the particle can be fabricated by using a publicly known method like described in working examples with using water, solvent, polymer precursor, polymerization initiator and optionally a surfactant.
  • the solvent is an organic solvent, preferably 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 alcohol, 1-nonadecanol (
  • ethers such as tetrahydrofuran, 1 ,3-dimethoxyethane, 1 ,2-dimethoxypropane, 1 ,3- dimethoxypropane, 2,2-dimethoxypropane, 2,2-diethoxypropane, diethylene glycol ethyl ether, diethylene glycol diethyl ether, diethylene glycol propyl ether, diethylene glycol dipropyl ether, diethylene glycol butyl ether, diethylene glycol dibutyl ether, di(propylene glycol) methyl ether, di(propylene glycol) dimethyl ether, di(propylene glycol) dimethyl ether, di(propylene glycol) dimethyl ether, di(propylene glycol) dimethyl ether, di(propylene glycol) dimethyl ether, di(propylene glycol) dimethyl ether, di(propylene glycol) dimethyl ether, di(propylene glycol) dimethyl ether, di
  • said polymer precursor is an acidic monomer or an acidic origomer, preferably it is an 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, 1-[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-cyclohexan
  • the acidic monomer disclosed above is suitable to form a polymer to form a polymer coating layer directly onto an inorganic phosphor since said acidic monomer has a group which can attach onto the surface of the inorganic phosphor.
  • the reaction mixture can further contain a polymerization initiator.
  • a polymerization initiator there are two kinds of polymerization initiators which can be used in the present invention: one is a polymerization initiator generating an acid, base, or radical when exposed to radiation, and the other is a polymerization initiator generating an acid, base or radical when exposed to heat.
  • the polymerization initiator can lead better polymer coating onto the inorganic phosphor and results in improved passivation of polymer coated inorganic phosphor.
  • the polymerization initiator adoptable in the present is, for example, a photo acid-generator, which decomposes when exposed to radiation and releases an acid serving as an active substance for photo-curing the composition; a photo radical - generator, which releases a radical; a photo base-generator, which releases a base; a heat acid-generator, 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, ⁇ -rays and y-rays.
  • the amount of the polymerization initiator is in the range from 0.001 to 10 weight parts, more preferably 0.01 to 5 weight parts, based on 100 weight parts of the 1 st polymer precursor.
  • 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
  • heat base-generator examples 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 salts, and mixture thereof.
  • Those base- generators as well as the acid-generators and / or radical - generators can be used singly or in mixture.
  • 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 + 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.
  • the counter ion examples include: ⁇ , formate ion, acetate ion, trifluoromethanesulfonate ion, nonafluorobutanesulfonate ion, methane- sulfonate ion, butanesulfonate ion, benzenesulfonate ion, p- toluenesulfonate ion, and sulfonate ion.
  • those generating sulfonic acids or boric acids are particularly preferred.
  • examples thereof include tricumyliodonium teterakis(pentafluorophenyl)- 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 triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphor- sulfonate, triphenylsulfonium tetra(perfluorophenyl)borate, 4- acetoxyphenyldimethylsulfonium hexafluoroarsenate, 1-(4-n- butoxynaphthalene-1-yl)tetrahydrothiophenium trifluoromethanesulfonate,
  • 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.
  • the photo radical-generator 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.
  • a publicly known surfactant having an ancoring group selected so that the surfactant can attach onto the outer most surface of the inorganic phosphor can be used preferably for the present invention.
  • said surfactant contains at least one anchoring group selected from the 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; even more preferably said anchoring group is a carboxyl group or a phosphonate group, further more preferably it is a phosphonate group from the view point of stronger bonding ability.
  • PW-36 from Kusumoto Chemicals Ltd. surfactants disclosed in JP2014-196466 A1 , or dispersants such as BYK ( TM ) -100 series e.g. BYK ( TM ) 103, 110, 111 , 118 (from BYK) can be used preferably.
  • the present invention also relates to use of the particle of the present invention in agriculture.
  • 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 another material.
  • said another material can preferably be 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 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; adjuvants; adhesive
  • said another 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;
  • said composition comprises a plurality of the particles of the present invention.
  • the total amount of the particle of the polymer coated inorganic phosphor of the present invention in the composition can be in the range from 0.01wt.% to 99.9wt.%, preferably it is in the range from 0,01wt% to 30wt.% based on the total amount of the composition, preferably it is from 0.1 wt.% 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 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, styrene- acrylonitrile, 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, polyvin
  • (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, hydroxyl- group, 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 the type of thermoplastic polymer is not particularly limited.
  • thermoplastic polymers can be copolymerized if necessary.
  • thermoplastic polymer or thermosetting polymer based on their physical properties.
  • the matrix materials and the inorganic phosphors mentioned above in - Matrix materials, and in - Inorganic phosphors, can be preferably used for a fabrication of the color conversion sheet (100) and the light emitting diode device (200) of the present invention.
  • the composition can optionally further comprise one or more of additional inorganic phosphors, which emits blue or red light.
  • any type of publicly known inorganic phosphors preferably 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, and / or at least one inorganic phosphor 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
  • Preferred metal-oxide phosphors are arsenates, germanates, halogerman- ates, indates, lanthanates, niobates, scandates, stannates, tantalates, titanates, vanadates, halovanadates, phosphovanadates, yttrates, zirconates, molybdate and tungstate.
  • said 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 Fe, Eu, Ce and/or Mn activated metal oxide phosphor or a Fe, Eu, Ce and/or Mn activated phosphate based phosphor, even more preferably it is a Fe, Eu, Ce and/or Mn activated metal oxide phosphor.
  • the inorganic phosphor is selected from the group consisting of Al2O3:Cr 3+ , Y3Al5O12:Cr 3+ , MgO:Cr 3+ , ZnGa 2 O4 :Cr 3+ , MgAl2O4:Cr 3+ ,
  • 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 further 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 inorganic phosphor is a different type of inorganic phosphor from 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.
  • crosslinkable monomers for example, cyclopentenyl(meth)acrylates; tetra-hydro furfuryl- (meth)acrylate; benzyl (meth)acrylate; the compounds obtained by reacting a polyhydric alcohol with and ⁇ , ⁇ -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-(metha) acrylate, tetra-methylol methan tri-(meth) acrylate), tetra-methylol methane tetra(metha) acrylate, polyprop
  • 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 permeability of effective component (e.g. insecticide), inhibit precipitation of solute in the composition, or decrease a phytotoxicity.
  • 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.
  • 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.
  • the weight ratio of each 1 additive of dispersant, surfactant, fungicide, antimicrobial agent and antifungal agent, to the weight of the invention phosphor 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 a 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 inorganic phosphors or the composition of the present invention.
  • solvent 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. Preferably a plurality of particles of the present invention are in the formulation.
  • 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 for
  • benzene, toluene, or xylene can be used.
  • the amount of the solvent in the formulation can be freely controlled.
  • the formulation if it is to be spray-coated, it 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 an optical sheet fabrication process or in agriculture, preferably for fabricating an agricultural sheet or for controlling a condition of a living organism.
  • the invention relates to an optical sheet (100) 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 (100) comprises a plurality of particles of the present invention or the composition.
  • the optical sheet (100) can be a film, or a fiber mat. According to the present invention, in some embodiments, the optical sheet (100) can be rigid or flexible.
  • the optical sheet (100) can be any structure. Such as plane, curved, wave formed structures to increase a growth of plant.
  • the optical sheet (100) comprises at least a first layer (100a) comprising at least the composition or the first layer (100a) 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 (100b), preferably the second layer (100b) 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.
  • 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
  • the second layer (100b) comprises at least the inorganic phosphor of the present invention, and a second material selected from adhesives, and/or insecticides.
  • the second layer (100b) can further comprises a matrix material described in the section of “matrix material”.
  • the second layer (100b) 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 (100b) 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 (100b) of the optical medium (100) is a light reflecting layer, preferably the second layer (100b) 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 (100b) 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 (100a) one side of the optical medium (100) is fully covered by the second layer.
  • the optical medium (100) optionally may comprise a third layer (100c) or more layers.
  • said first layer (100a), optionally the second layer (100b), the third layer (100c) 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 (100) 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 (100) comprises a first layer(100a), wherein the first layer (100a) 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 described in the section of “Additive”.
  • the concentration of the particle of the present invention (110) in the sheet is 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 (100) may 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 medium (100). 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 medium (100) and at a wavelength or a range of wavelength used during operation of the optical medium (100).
  • it is over 70 %, more preferably, over 75%, the most preferably, it is over 80 %.
  • said reflector is a metal substrate, 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 + MgFa 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 + MgFa 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 can be 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 medium is an optical sheet, for example, a color conversion sheet, a remote phosphor tape, or another sheet or a filter for agriculture.
  • the layer thickness of the optical sheet is 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 is in the range from 0.01 wt.% to 30wt.% based on the total amount of the matrix material, preferably it is from 0.1 wt.% 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 invention relates to an optical device (200) comprising the optical sheet (100), or the composition and further comprising a light source, a light re-directing device, and/or a reflector.
  • a light source is a light emitting diode, or an organic light emitting diode.
  • the optical device (200) comprises at least one optical sheet and a supporting part, preferably the supporting part comprises at least one attaching part to attach the optical medium, and optionally a base part to support optical medium and supporting part itself, more preferably the supporting part comprises one or more of attaching part to attach one or more of optical medium.
  • the optical device is a lighting device, a light emitting diode device for agriculture, or building materials of greenhouse. -Use of composition or formulation
  • the invention relates to use of the composition, or formulation in an optical sheet fabrication process.
  • the invention relates to use of the optical sheet (100) or the optical device (200) 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 (100).
  • the present invention furthermore relates to method for preparing the optical sheet (100), preferably for preparing the agriculture sheet, wherein the method comprises following steps (N) and (P), (N) providing the composition or the formulation of the present invention in a first shaping, preferably providing the composition onto a substrate or into an inflation moulding machine, and
  • the method comprises following steps (N) and (P) in this sequence.
  • the composition in step (N) is provided by spin coating, spray coating, bar coating, or a slit coating method.
  • the composition or the formulation in step (N) 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 method for preparing the optical device (200), wherein the method comprises following step (A),
  • the optical sheet (100) is useful for agriculture.
  • the optical medium (100) 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 use of the optical sheet (100) 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 (100) 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 AlOa is used as the light reflecting material.
  • said one side of the optical medium (100) is fully covered by the light reflecting material.
  • Fabrication method for coating of optical medium (100) 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 (100) may be used to control growth of plankton, preferably said plankton is a phytoplankton.
  • the present invention relates to use of the particle, the composition, the formulation, the optical medium (100), the optical device (200), or the green house, for cultivation of algae, bacteria, preferably said bacteria are photosynthetic bacteria, and/or planktons, 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 / 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
  • the present invention furthermore relates to method of supplying the inorganic phosphor, the composition or the formulation of the present invention to at least one portion of a plant.
  • the present invention furthermore relates to modulating a condition of a plant, a plankton, or a bacterium, comprising at least following step (C), (C) providing the optical sheet (100), between a light source and a plant, between a light source and a plankton, preferably said plankton is a phytoplankton, between a light source and a bacterium, preferably said bacterium is a photosynthetic bacterium, and/or providing the optical sheet (100), 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.
  • step (C) providing the optical sheet (100), between a light source and a plant, between a light source and a plankton, preferably said plankton is a phytoplankton, between a light source and a bacterium, preferably said bacterium is a
  • the optical sheet (100) 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, a plankton, or a bacterium obtained or obtainable by the method.
  • a plankton is a phytoplankton
  • said bacterium is a photosynthetic bacterium.
  • the present invention furthermore relates to a container comprising at least one plant, a plankton, or a bacterium obtained or obtainable by the method of the present invention.
  • a container comprising at least one plant, a plankton, or a bacterium obtained or obtainable by the method of the present invention.
  • said plankton is a 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.
  • 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
  • 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 an inorganic phosphor and a transparent polymer layer placed onto the outermost surface of said inorganic phosphor, preferably 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, polyethylene polyethyleneterephthalate, polyurethane, polyacrylonitrile, epoxy resin derived from glycidyl function on (meth)acrylate monomer, biodegradable polymer such as polylactide, polyglycolide, polyhydroxyalkanoate, polycaproractone.
  • the polymer 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.
  • the inorganic phosphor has a peak wavelength of light emitted from the inorganic phosphor in the range of 650 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, and / or at least one inorganic phosphor 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 nm, even more preferably in the range from 350 nm to 500 nm, furthermore preferably in the range from 400 nm to 500n
  • any one of embodiments 1 to 4 wherein 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.
  • 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 SiA
  • a 2 aZbO c :X - (II) wherein A 2 is a divalent cation and is selected from the group consisting of Mg, Zn, Cu, Co, Ni, Fe, Ca, Sr, Ba, Mn, Ce and Sn; Z is a trivalent cation and is selected from the group consisting of Al, Ga, Lu, Sc and In; b ⁇ 0; a ⁇ 1 ; (a+1 ,5b) c, X is a luminescent ion and is selected from one or more members of the group consisting of Ce 3+ , Pr 3+ , Nd 3+ , Nd 4+ , Pm 3+ , Sm 3+ , Eu 3+ , Eu 2+ , Gd 3+ , Tb 3+ , Dy 2+ , Dy 3+ , Dy 4+ , Ho 2+ , Ho 3+ , Er 3+ , Tm 3+ , Yb 3+ , Yb 2+ , Cr 3+ ,
  • X is a luminescent ion and is selected from one or more members of the group consisting of Ce 3+ , Pr 3+ , Nd 3+ , Nd 4+ , Pm 3+ , Sm 3+ , Eu 3+ , Eu 2+ , Gd 3+ , Tb 3+ , Dy 2+ , Dy 3+ , Dy 4+ , Ho 2+ , Ho 3+ , Er 3+ , Tm 3+ , Yb 3+ , Yb 2+ , Cr 3+ , Mn 2+ , Mn 4+ and Fe 3+ , preferably X is selected from Ce 3+ , Eu 3+ , Eu 2+ , Tb 3+ , Cr 3
  • Mn 4+ Mn 4+ , Fe 3+ or a combination of any of these, more preferably X is Mn 4+ , even more preferably formula (III) is CaAl12O19:Mn 4+ ;
  • Lu 3+ , Sc 3+ , La 3+ and In 3+ ; h ⁇ 0; a ⁇ g; (1 ,5g+1 ,5h) I, preferably D 2 is La 3+ , E 2 is Al 3+ , Gd 3+ or a combination of these, g is 1 , h is 12, i is 19, X is a luminescent ion and is selected from one or more members of the group consisting of Ce 3+ , Pr 3+ , Nd 3+ , Nd 4+ , Pm 3+ , Sm 3+ , Eu 3+ , Eu 2+ , Gd 3+ , Tb 3+ , Dy 2+ , Dy 3+ , Dy 4+ , Ho 2+ , Ho 3+ , Er 3+ , Tm 3+ , Yb 3+ , Yb 2+ , Cr 3+ , Mn 2+ , Mn 4+ and Fe 3+ , preferably X is selected from Ce 3+ , Eu 3+ ,
  • Mn 4+ Mn 4+ , Fe 3+ or a combination of any of these, more preferably X is Mn 4+ , even more preferably formula (IV) is LaAIO3:Mn 4+ ;
  • GjJkLiOm:X - (V) 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 In 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 In 3+ ; l ⁇ 0; k ⁇ 0; j ⁇ 0; (j+1.5k+1.5l) m, preferably G is selected from Ca 2+ , Sr 2+ , Ba 2+ or a
  • X is selected from Ce 3+ , Eu 3+ , Eu 2+ , Tb 3+ , Cr 3+ , Mn 2+ , Mn 4+ , Fe 3+ or a combination of any of these, more preferably X is Ce 3+ ; a is 1 , z is 2; more preferably the formula is ZrO2:Ce 3+
  • a 4 is a monovalent cation and is selected from one or more members of the group consisting of Li+, Na+, K+, Rb+, Cs+, V+, Cr+, Mn+, Co+, Ni+, Cu+, Pd + . Ag + . Au + and TI + ;
  • B 2 is a tetravalent cation and is selected from one or more members of the group consisting of Ce 3+ , Pr 3+ , Nd 3+ , Tb 3+ , Dy 3+ , Ti 3+ , V 3+ , Cr 3+ , Mn 3+ , Fe 3+ , Co 3+ , Ni 3+ , Zr 3+ , Nb 3+ , Mo 3+ , Tc 3+ , Ru 3+ , Rh 3+ , Pd 3+ , Hf 3+ , Ta 3+ , W 3+ , Re 3+ , Os 3+ , Ir 3+ , Pt 3+ , Si 3+ , Ge 3+ , Sn 3+ , Pb 3+ , S 3+ , Se 3+ , Te 3+ and Po 3+ ;
  • C 1 is a tetravalent cation and is selected from one or more members of the group consisting of Ce 3+ , Pr 3+ , Nd 3+ , Tb 3+ , Dy 3+ , Ti 3+ , V 3+ , Cr 3+ , Mn 3+ , Fe 3+ , Co 3+ , Ni 3+ , Zr 3+ , Nb 3+ , Mo 3+ , Tc 3+ , Ru 3+ , Rh 3+ , Pd 3+ , Hf 3+ , Ta 3+ , W 3+ , Re 3+ , Os 3+ , Ir 3+ , Pt 3+ , Si 3+ , Ge 3+ , Sn 3+ , Pb 3+ , S 3+ , Se 3+ , Te 3+ and Po 3+ ;
  • B 2 is Ce 3+ , Ti 3+ , Zr 3+ , Hf 3+ , Si 3+ , Ge 3+ , Sn 3+ , or a combination of any of these,
  • C 1 is Ce 3+ , Ti 3+ , Zr 3+ , Hf 3+ , Si 3+ , Ge 3+ , Sn 3+ , or a combination of any of these;
  • X is Ce 3+ , Eu 3+ , Eu 2+ , Tb 3+ , Cr 3+ , Mn 2+ , Mn 4+ and Fe 3+ , or a combination of any of these, more preferably X is Eu 2+ ; a is 2, b is 1 , c is 2, z is 7; more preferably, formula isK2ZrSi20?:Eu 2+ ;
  • a 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+ ;
  • B 3 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+ , Ir 3+ , Au 3+ , B 3+ , Al 3+ , Ga 3+ , In 3+ , TI 3+ , P 3+ , As 3+ , Sb 3+ and Bi
  • D 3 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+ , Ir 3+ , Au 3+ , B 3+ , Al 3+ , Ga 3+ , In 3+ , TI 3+ , P 3+ , As 3+ , Sb 3+ and Bi
  • B 3 is Sc 3+ , Y 3+ , La 3+ , Lu 3+ , B 3+ , Al 3+ , Ga 3+ , In 3+ , P 3+ , Bi 3+ , or a combination of any of these;
  • C 2 is Ce 3+ , Ti 3+ , Zr 3+ , Hf 3+ , Si 3+ , Ge 3+ , Sn 3+ , or a combination of any of these;
  • D 3 is Sc 3+ , Y 3+ , La 3+ , Lu 3+ , B 3+ , Al 3+ , Ga 3+ , In 3+ , P 3+ , Bi 3+ , or a combination of any of these;
  • X is Ce 3+ , Eu 3+ , Eu 2+ , Tb 3+ , Cr 3+ , Mn 2+ , Mn 4+ and Fe 3+ , or a combination of any of these; a is 2, b is 1 , c is 2, d is 3, z is 12; more preferably the formula is Ca2YZr2Al3O12:Ce 3+
  • A® 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+ , Ir 3+ , Au 3+ , B 3+ , Al 3+ , Ga 3+ , ln 3+ , Tl 3+ , P 3+ , As 3+ , Sb 3+
  • B 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+ , Ir 3+ , Au 3+ , B 3+ , Al 3+ , Ga 3+ , In 3+ , TI 3+ , P 3+ , As 3+ , Sb 3+ and Bi
  • B 4 is Sc 3+ , Y 3+ , La 3+ , Lu 3+ , B 3+ , Al 3+ , Ga 3+ , In 3+ , P 3+ , Bi 3+ , or a combination of any of these;
  • X is Ce 3+ , Eu 3+ , Eu 2+ , Tb 3+ , Cr 3+ , Mn 2+ , Mn 4+ and Fe 3+ , or a combination of any of these, more preferably X is Ce 3+ ; a is 3, b is 5, z is 12; more preferably the formula is YsAlsO-iaiCe 3+ ;
  • a 7 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+ , Ir 3+ , Au 3+ , B 3+ , Al 3+ , Ga 3+ , In 3+ , TI 3+ , P 3+ , As 3+ , Sb 3+ and Bi
  • B 5 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+ , Ir 3+ , Au 3+ , B 3+ , Al 3+ , Ga 3+ , In 3+ , TI 3+ , P 3+ , As 3+ , Sb 3+ and Bi
  • B 5 is Sc 3+ , Y 3+ , La 3+ , Lu 3+ , B 3+ , Al 3+ , Ga 3+ , In 3+ , P 3+ , Bi 3+ , or a combination of any of these;
  • C 3 is Sc 3+ , Y 3+ , La 3+ , Lu 3+ , B 3+ , Al 3+ , Ga 3+ , In 3+ , P 3+ , Bi 3+ , or a combination of any of these;
  • X is Ce 3+ , Eu 3+ , Eu 2+ , Tb 3+ , Cr 3+ , Mn 2+ , Mn 4+ and Fe 3+ , or a combination of any of these, more preferably X is Ce 3+ ; a is 3, b is 2, c is 3, z is 12; more preferably, formula is YsGazAlsO-iaiCe 3+ ;
  • a 8 is a monovalent cation and is selected from one or more members of the group consisting of Li + , Na + , K + , Rb + , Cs + , V + , Cr + , Mn + , Co + , Ni + , Cu + , Pd + , Ag + . Au + and TI + ;
  • B 8 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+ , Ir 3+ , Au 3+ , B 3+ , Al 3+ , Ga 3+ , In 3+ , TI 3+ , P 3+ , As 3+ , Sb 3+ and Bi
  • B6 is Sc 3+ , Y 3+ , La 3+ , Lu 3+ , B 3+ , Al 3+ , Ga 3+ , In 3+ , P 3+ , Bi 3+ , or a combination of any of these;
  • X is Ce 3+ , Eu 3+ , Eu 2+ , Tb 3+ , Cr 3+ , Mn 2+ , Mn 4+ and Fe 3+ , or a combination of any of these, more preferably X is Mn 4+ ; a is 1 , b is 5, z is 8; more preferably the formula is LiAlsOsiMn 4+ ;
  • 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+ , Hg 2+ , Ge 2+ , Sn 2+ and Pb 2+ ;
  • B 7 is a tetravalent cation and is selected from one or more members of the group consisting of Ce 3+ , Pr 3+ , Nd 3+ , Tb 3+ , Dy 3+ , Ti 3+ , V 3+ , Cr 3+ , Mn 3+ , Fe 3+ , Co 3+ , Ni 3+ , Zr 3+ , Nb 3+ , Mo 3+ , Tc 3+ , Ru 3+ , Rh 3+ , Pd 3+ , Hf 3+ , Ta 3+ , W 3+ , Re 3+ , Os 3+ , Ir 3+ , Pt 3+ , Si 3+ , Ge 3+ , Sn 3+ , Pb 3+ , S 3+ , Se 3+ , Te 3+ and Po 3+ ;
  • B 7 is Ce 3+ , Ti 3+ , Zr 3+ , Hf 3+ , Si 3+ , Ge 3+ , Sn 3+ , or a combination of any of these;
  • X is Ce 3+ , Eu 3+ , Eu 2+ , Tb 3+ , Cr 3+ , Mn 2+ , Mn 4+ and Fe 3+ , or a combination of any of these, more preferably X is Mn 4+ , a is 1 , b is 1 , z is 3, more preferably the formula is CaZrOsiMn 4+ A 10 aB 8 bC 4 cO z :X -(Xlll) wherein
  • a 10 is a monovalent cation and is selected from one or more members of the group consisting of Li + , Na + , K + , Rb + , Cs + , V + , Cr + , Mn + , Co + , Ni + , Cu + , Pd + . Ag + . Au + and Tl + ;
  • B 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+ ;
  • C 4 is a tetravalent cation and is selected from one or more members of the group consisting of Ce 3+ , Pr 3+ , Nd 3+ , Tb 3+ , Dy 3+ , Ti 3+ , V 3+ , Cr 3+ , Mn 3+ , Fe 3+ , Co 3+ , Ni 3+ , Zr 3+ , Nb 3+ , Mo 3+ , Tc 3+ , Ru 3+ , Rh 3+ , Pd 3+ , Hf 3+ , Ta 3+ , W 3+ , Re 3+ , Os 3+ , Ir 3+ , Pt 3+ , Si 3+ , Ge 3+ , Sn 3+ , Pb 3+ , S 3+ , Se 3+ , Te 3+ and Po 3+ ;
  • B 9 is Sc 2+ , Y 2+ , La 2+ , Lu 2+ , B 2+ , Al 2+ , Ga 2+ , In 2+ , P 2+ , Bi 2+ , or a combination of any of these;
  • C 5 is Ce 3+ , Ti 3+ , Zr 3+ , Hf 3+ , Si 3+ , Ge 3+ , Sn 3+ , or a combination of any of these;
  • X is Ce 3+ , Eu 3+ , Eu 2+ , Tb 3+ , Cr 3+ , Mn 2+ , Mn 4+ and Fe 3+ , or a combination of any of these, more preferably X is Mn 4+ ; a is 2, b is 1 , c is 1 , z is 4; more preferably, formula is LhMgZrO ⁇ Mn 4+ ;
  • a 11 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+ , Ft 2+ , Zn 2+ , Cd 2+ , Hg 2+ , Ge 2+ , Sn 2+ and Pb 2+ ;
  • B 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+ , Hg 2+ , Ge 2+ , Sn 2+ and Pb 2+ ;
  • C 5 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+ , Ir 3+ , Au 3+ , B 3+ , Al 3+ , Ga 3+ , In 3+ , TI 3+ , P 3+ , As 3+ , Sb 3+ and Bi
  • B 9 is Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ and Zn 2+ , or a combination of any of these;
  • C 5 is Sc 3+ , Y 3+ , La 3+ , Lu 3+ , B 3+ , Al 3+ , Ga 3+ , In 3+ , P 3+ , Bi 3+ , or a combination of any of these;
  • X is Ce 3+ , Eu 3+ , Eu 2+ , Tb 3+ , Cr 3+ , Mn 2+ , Mn 4+ and Fe 3+ , or a combination of any of these, more preferably X is Mn 4+ ; even more preferably the formula is CaMgAl16O 2 7:Mn 4+ , Ca2Mg2Al28O36:Mn 4+ , Sr2MgAl22O36:Mn 4+ or BaMgAl10-iyiMn 4+ , preferably the inorganic phosphor is selected from one or more of members of the group consisting of
  • composition comprising at least one particle of any one of embodiments 1 to 6, and another material.
  • composition of embodiment 8, wherein said another material is 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 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; adjuvant
  • the total amount of the particle of the composition is in the range from 0.01 wt.% to 30wt.% based on the total amount of the composition, preferably it is from 0.1 wt.% to 10wt.%, more preferably from 0.5wt.% to 5wt.%, furthermore preferably it is from 1wt.% to 3wt.%.
  • a formulation comprising at least one particle of any one of embodiments 18 to 20, or the composition of any one of embodiments 23 to 26, and a solvent.
  • An optical sheet (100) comprising at least one particle of any one of embodiments 1 to 6, or the composition of any one of embodiments 8 to 11 , preferably said optical sheet is an agricultural sheet.
  • An optical device (200) comprising at least one optical sheet (100) of embodiment 14, preferably said optical device is a lighting device, more preferably it is a light emitting diode device.
  • a greenhouse comprising the optical sheet (100) of embodiment 14.
  • optical sheet (100) of embodiment 14 or the optical device (200) of embodiment 15 for agriculture, preferably for greenhouse or for controlling a condition of a living organism in agriculture.
  • Method for preparing the agriculture sheet wherein the method comprises following steps (a ' ) and (b ' ),
  • composition comprising a particle comprising an inorganic phosphor and a coating layer onto the outermost surface of the inorganic phosphor, and another material, or the formulation comprising said composition and a solvent in a first shaping, preferably providing the composition into an inflation moulding machine, and
  • said coating layer is a transparent polymer layer or a metal oxide coating layer
  • said particle is the one according to any one of embodiments 1 to 6 or a particle comprising an inorganic phosphor coated by a metal oxide coating layer selected from one or more members of the group consisting of SiOa, TiOa, ZnOa, ZrOa and AI2O3, more preferably it is selected from SiOa, TiOa, ZnOaor a combination of any of these, preferably said inorganic phosphor is the inorganic phosphor as described in the section of “Inorganic phosphor” above.
  • a particle of metal oxide coated inorganic phosphor comprising an inorganic phosphor and at least one metal oxide coating layer onto the outermost surface of said phosphor, for agriculture, preferably said metal oxide coating layer is selected from one or more members of the group consisting of S1O2, T1O2, ZnOa, ZrOa and AI2O3, more preferably it is selected from T1O2, ZnOaor a combination of S1O2, T1O2 and Zn02, preferably for greenhouse or for controlling a condition of a living organism in agriculture, preferably said inorganic phosphor is the inorganic phosphor as described in the section of “Inorganic phosphor” above.
  • Method for preparing the optical device (200) of embodiment 15, comprising following step (A); (A) providing the optical sheet (100) of embodiment 14, in an optical device (200).
  • Method for modulating a condition of a plant, plankton, and/or a bacterium comprising at least following step (C),
  • (C) providing the optical sheet (100) of embodiment 14, between a light source and a plant, between a light source and a plankton, preferably said plankton is a phytoplankton, between a light source and a bacterium, preferably said bacterium is a photosynthetic bacterium, or providing the optical sheet (100) of embodiment 14 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.
  • a container comprising at least one plant, one plankton, and/or a bacterium of embodiment 26.
  • the present invention provides one or more of following effects; improved transparency of a film, preferably improved transparency of an agricultural film, avoiding or reducing a scratch of an inflation molding machine caused by an inorganic phosphor, avoiding or reducing a situation that an optical sheet comprising an inorganic phosphor is contaminated with a dust from an inflation molding machine, improved long term moisture durability, improved water resistance, a water free coating process to avoid any damage to a phosphor during the coating process, an inorganic phosphor having a coating layer with higher EQE, improved and well controlled average particle size, improved optical properties such as light scattering, absorbing, refraction and/or reflection ability of inorganic phosphors, improved dispersibility of inorganic phosphors in a formulation, composition and/or in a matrix material of a film, better compatibility of an inorganic phosphor with a matrix material, improvement of controlling property of a phytoplankton condition, photosynthetic bacteria and/or alga, preferably acceleration of growth of phytoplankt
  • the phosphor precursors of Al2O3:Cr 3+ phosphors are synthesized by a conventional co-precipitation method.
  • the raw materials of Aluminium Nitrate Nonahydrate and Chromium(lll) nitrate nonahydrate are dissolved in deionized water with a stoichiometric molar ratio of 0.99:0.01.
  • NH4HCO3 is added to the mixed chloride solution as a precipitant, and the mixture is stirred at 60 °C for 2h.
  • the resultant solution is dried at 95 °C for 12 h, then the preparation of the precursors is completed.
  • the obtained precursors are oxidized by calcination at 1300 °C for 3 h in air.
  • XRD measurements are performed using an X-ray diffractometer (RIGAKU RAD-RC).
  • Photoluminescence (PL) spectra are measured using a spectrofluorometer (JASCO FP-6500) at room temperature.
  • the absorption peak wavelength of Al2O3:Cr 3+ is 420 nm and 560 nm, the emission peak wavelength is in the range from 690 nm to 698 nm, the full width at half maximum (hereafter “FWHM”) of the light emission from Al2O3:Cr 3+ is in the range from 90 nm to 120 nm.
  • FWHM full width at half maximum
  • the formation of the polymer layer on the phosphor surface is carried out in a reactor.
  • Al2O3:Cr 3+ dispersed in water and 3- Methacryloxypropyltrimethoxysilane (MPTMS) dispersed in ethanol are charged into the reactor; the resulting mixed solution is stirred for 2 hours at 35°C.
  • methyl methacrylate, Monomer (MMA) is charged into the reactor. Afterwards, it is deoxygenated by bubbling with nitrogen by stirring for 15 minutes.
  • the polymerization is initiated by injection of Potassium peroxydisulfate (KPS) dissolved in water; it continued for 3 hours.
  • KPS Potassium peroxydisulfate
  • the mixed solution is filtered and vacuum dried to obtain the Al2O3:Cr 3+ PMMA powder.
  • KPS Potassium peroxydisulfate
  • the phosphor master batch is prepared by mixing polymer-coated Al2O3:Cr 3+ at high concentration with resin (NIPOLON® 180).
  • resin 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 went through bulges like a balloon by enclosed air. Then it is cooled by cooling air, which flowed 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 shows the materials used in the foil fabrication.
  • a foil is fabricated in the same manner as described in working example 2 except for Al2O3:Cr 3+ without polymer coating layer is used instead of the polymer coated Al2O3:Cr 3+ of working example 1.
  • the foils produced are measured by the UV-2550 spectrometer created by Shimazu.
  • the transmittance of the foil with the polymer-coated Al2O3:Cr 3+ is confirmed to have an improvement of approximately 25% as compared to the foil with the non-polymer-coated Al2O3:Cr 3+ .
  • This result may be attributed to the fact that when the phosphors are mixed in the inflation molding machine, the polymer-coated Al2O3:Cr 3+ does not leave scratches that generate contamination in the machine. Accordingly, it is seen that the transmittance of the foil produced by this method for the present invention are effectively applicable in the agricultural field.
  • the formation of the polymer layer on the phosphor surface is carried out in a reactor.
  • Mg 2 Ti0 4 :Mn 4+ dispersed in water and 3- Methacryloxypropyltrimethoxysilane (MPTMS) dispersed in ethanol are charged into the reactor; the resulting mixed solution is stirred for 2 hours at 35°C.
  • Mg 2 Ti0 4 :Mn 4+ dispersed in water and 3- Methacryloxypropyltrimethoxysilane (MPTMS) dispersed in ethanol are charged into the reactor; the resulting mixed solution is stirred for 2 hours at 35°C.
  • methyl methacrylate Monomer (MMA) is charged into the reactor. Afterwards, it is deoxygenated by bubbling with nitrogen by stirring for 15 minutes.
  • the polymerization is initiated by injection of Potassium peroxydisulfate (KPS) dissolved in water; it continued for 3 hours.
  • KPS Potassium peroxydisulfate
  • the mixed solution is
  • the produced phosphors are stirred in 50°C water for 24 hours.
  • the emission intensity of the polymer-coated Mg2Ti04:Mn 4+ is confirmed to have an improvement of approximately 30% as compared to the non-polymer-coated Mg2Ti04:Mn 4+ .
  • This approach is applicable on the technique of placing a phosphor on leaves and promoting plant growth. Accordingly, it is observed that the high durable phosphor produced by the method according to the present invention is effectively applicable to the agricultural field.

Abstract

The present invention relates to a method for fabricating a particle.

Description

Method for fabricating a particle
Field of the Invention
The present invention relates to a particle comprising an inorganic phosphor and a coating layer, a composition, a formulation, an optical sheet, an optical device, a greenhouse, use, a plant, a container and a method.
Background Art WO 2017/129351 A1 discloses a use of an inorganic phosphor for agriculture.
WO 2019/020602 A1 and WO 2019/020653 A1 disclose a use of an inorganic phosphor for agriculture. And it also discloses that the inorganic phosphor materials can be phosphor particles with or without silicon dioxide coating.
Patent Literature
1. WO 2017/129351 A1 2. WO 2019/020602 A1
3. WO 2019/020653 A1
Non- Patent Literature
Summary of the invention
The inventors surprisingly have found that there are still one or more of considerable problems for which improvement are desired, as listed below; improved transparency of a film, preferably improved transparency of an agricultural film, avoiding or reducing a scratch of an inflation molding machine caused by an inorganic phosphor, avoiding or reducing a situation that an optical sheet comprising an inorganic phosphor is contaminated with a dust from an inflation molding machine, improved long term moisture durability, improved water resistance, a water free coating process to avoid any damage to a phosphor during the coating process, an inorganic phosphor having a coating layer with higher EQE, improved and well controlled average particle size, improved optical properties such as light scattering, absorbing, refraction and/or reflection ability of inorganic phosphors, improved dispersibility of inorganic phosphors in a formulation, composition and/or in a matrix material of a film, better compatibility of an inorganic phosphor with a matrix material, 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 / 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 ripening of fruits, or controlling of weight of plant.
Then, it is found that a novel particle comprising an inorganic phosphor and a transparent polymer layer placed onto the outermost surface of said inorganic phosphor, preferably 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, polyethylene polyethyleneterephthalate, polyurethane, polyacrylonitrile, epoxy resin derived from glycidyl function on (meth)acrylate monomer, biodegradable polymer such as polylactide, polyglycolide, polyhydroxyalkanoate, polycaproractone. In another aspect, the present invention also relates to a use of the particle of the present invention for agriculture.
In another aspect, the present invention furthermore relates to a composition comprising at least one particle of the present invention and another material.
In another aspect, the present invention relates to a formulation comprising at least one particle of the present invention or the composition of the present invention, and a solvent.
In another aspect, 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 an optical sheet fabrication process or in agriculture, preferably for fabricating an agricultural sheet or for controlling a condition of a living organism.
In another aspect, the invention relates to an optical sheet (100) comprising at least one particle of the present invention or the composition of the present invention, preferably said optical sheet is an agricultural sheet.
In another aspect, the invention relates to an optical device (200) comprising at least one optical sheet (100) of the present invention, preferably said optical device is a lighting device, more preferably it is a light emitting diode device.
In another aspect, the invention relates to a greenhouse comprising an optical sheet (100) of the present invention.
In another aspect, the invention relates to a use of the optical sheet (100) of the present invention or the optical device (200) of the present invention for agriculture, preferably for greenhouse or for controlling a condition of a living organism in agriculture.
In another aspect, the invention relates to a method for preparing the optical sheet (100), preferably for preparing the agriculture sheet, wherein the method comprises following steps (a) and (b),
(a) providing the composition of the present invention, or the formulation of the present invention in a first shaping, preferably providing the composition onto a substrate or into an inflation moulding machine, and
(b) fixing the matrix material by evaporating a solvent and / or polymerizing the composition by heat treatment, or exposing the photosensitive composition under ray of light or a combination of any of these.
In another aspect, the invention relates to a method for preparing the optical device (200) of the present invention, comprising following step (A);
In another aspect, the invention relates to a method for preparing the agriculture sheet, wherein the method comprises following steps (a') and
(b'),
(a') providing the composition comprising a particle comprising an inorganic phosphor and a coating layer onto the outermost surface of the inorganic phosphor, and another material, or the formulation comprising said composition and a solvent in a first shaping, preferably providing the composition into an inflation moulding machine, and
(b') fixing the matrix material by evaporating a solvent and / or polymerizing the composition by heat treatment, or exposing the photosensitive composition under ray of light or a combination of any of these, preferably said coating layer is a transparent polymer layer or a metal oxide coating layer, more preferably said particle is the particle of the present invention or a particle comprising an inorganic phosphor coated by a metal oxide coating layer selected from one or more members of the group consisting of S1O2, T1O2, ZnOa, ZrOa and AI2O3, more preferably it is selected from S1O2, T1O2, ΖΠΟΣ ΟΓ a combination of any of these, preferably said inorganic phosphor is the inorganic phosphor as described in the section of “Inorganic phosphor”.
In another aspect, the present invention relates to use of a particle of metal oxide coated inorganic phosphor comprising an inorganic phosphor and at least one metal oxide coating layer onto the outermost surface of said phosphor, for agriculture, preferably said metal oxide coating layer is selected from one or more members of the group consisting of Si02, T1O2, Zn02, ZrO∑ and AI2O3, more preferably it is selected from Ti02, ΖΠΟΣ ΟΓ a combination of Si02, T1O2 and Zn02, preferably for greenhouse or for controlling a condition of a living organism in agriculture, preferably said inorganic phosphor is the inorganic phosphor as described in the section of “Inorganic phosphor”.
In another aspect, the present invention also relates to a method for preparing the optical device (200) of the present invention, comprising following step (A);
(A) providing the optical sheet of the present invention, in an optical device (200).
In another aspect, the invention relates to a use of the particle of the present invention, or the composition of the present invention, the formulation of the present invention, the optical sheet (100) of the present invention, the optical device (200) of the present invention or the green house of the present invention for cultivation of algae, bacteria, preferably said bacteria are photosynthetic bacteria, and/or planktons, 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 / 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 ripening of fruits, or controlling of weight of plant.
In another aspect, the invention relates to a method of supplying the particle of the present invention, or the composition of any one of the present invention, the formulation of the present invention to at least one portion of a plant.
In another aspect, the invention relates to a method for modulating a condition of a plant, plankton, and/or a bacterium, comprising at least following step (C),
(C) providing the optical sheet (100) of the present invention, between a light source and a plant, between a light source and a plankton, preferably said plankton is a phytoplankton, between a light source and a bacterium, preferably said bacterium is a photosynthetic bacterium, or providing the optical sheet (100) of the present invention 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.
In another aspect, the invention relates to a plant obtained or obtainable by the method of the present invention, or a plankton obtained or obtainable by the method of the present invention, or a bacterium obtained or obtainable by the method of the present invention.
In another aspect, the invention relates to a container comprising at least one plant, one plankton, and/or a bacterium of the present invention.
Further advantages of the present invention will become evident from the following detailed description.
Definition of the terms
The above outlines and the following details are for describing the present invention and are not for limiting the claimed invention. Unless otherwise stated, the following terms used in the specification and claims shall have the following meanings for this application.
In this application, the use of the singular includes the plural, and the words “a”, “an” and “the” mean “at least one”, unless specifically stated otherwise. In this specification, when one concept component can be exhibited by plural species, and when its amount (e.g. weight %, mol %) is described, the amount means the total amount of them, unless specifically stated otherwise.
Furthermore, the use of the term “including”, as well as other forms such as “includes” and “included”, is not limiting. Also, terms such as “element” or “component” encompass both elements or components comprising one unit and elements or components that comprise more than one unit, unless specifically stated otherwise. As used herein, the term “and/or” refers to any combination of the elements including using a single element. In the present specification, when the numerical range is shown using “to”, or the numerical range includes both numbers before and after the “to”, “-” or and the unit is common for the both numbers, unless otherwise specified. For example, 5 to 25 mol% means 5 mol% or more and 25 mol% or less.
The section headings used herein are for organizational purposes and are not to be construed as limiting the subject matter described. All documents, or portions of documents, cited in this application, including, but not limited to, patents, patent applications, articles, books, and treatises, are hereby expressly incorporated herein by reference in their entirety for any purpose. If one or more of the incorporated literatures and similar materials defines a term in a manner that contradicts the definition of that term in this application, this application controls.
According to the present invention, the term "plant” means a multicellular organism in the kingdom Plantae that use photosynthesis to make their own food. Then according to the present invention, the plant can be flowers, vegetables, fruits, grasses, trees and horticultural crops (preferably flowers and horticultural crops, more preferably flowers). As one embodiment of the invention, 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 var., 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 term “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.
The term “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.
The term “dyes" 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.
Thus, 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). The term “fluorescent light emission” is a spin allowed light emission from a singlet state of spin multiplicity (2S+1 ) =1.
The term “wavelength converting material” or briefly referred to as a “converter” means a material that converts light of a first wavelength to light of a second wavelength, wherein the second wavelength is different from the first wavelength. Wavelength converting materials include organic materials and inorganic materials that can achieve photon up-conversion, and organic materials and inorganic materials that can achieve photon down-conversion.
The term “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.
The term “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.
The term “organic material" means a material of organometallic compounds and organic compounds without any metals or metal ions.
The term “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. Alqs, LiQ, lr(ppy>3.
The inorganic materials include phosphors and semiconductor nanoparticles. A “phosphor” is a fluorescent or a phosphorescent inorganic material which contains one or more light emitting centers. The light emitting centers are formed by activator elements such as e.g. 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 Cr, 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. Examples of suitable phosphors include phosphors based on garnet, silicate, orthosilicate, thiogallate, sulfide, nitride, silicon-based oxynitride, nitridosilicate, nitridoaluminumsilicate, oxonitridosilicate, oxonitridoaluminumsilicate and rare earth doped sialon. Phosphors within the meaning of the present application are materials which absorb electromagnetic radiation of a specific wavelength range, preferably blue and/or ultraviolet (UV) electromagnetic radiation and convert 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).
Here, the term “UV” is electromagnetic radiation with a wavelength from 100 nm to 389nm, shorter than that of visible light but longer than X-rays.
The term “VIS” is electromagnetic radiation with a wavelength from 390 nm to 700 nm.
The term “NIR” is electromagnetic radiation with a wavelength from 701 nm to 1 ,000 nm.
The term "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. For example, in this manner, 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.
The term “emission” means the emission of electromagnetic waves by electron transitions in atoms and molecules.
According to the present invention, the term “transparent” means at least around 60 % of incident light transmittal.
Preferably, it is over 70 %, more preferably, over 75%, the most preferably, it is over 80 %.
Brief Description of drawings
Fia. 1 : shows a cross sectional view of a schematic of one embodiment of an optical sheet (100) of the invention.
Fia. 2: shows a cross sectional view of a schematic of one embodiment of an optical device (200) of the invention. Fia. 3: shows a cross sectional view of a schematic of another embodiment of an optical device of the invention.
List of reference signs in figure 1
100. an optical sheet (a color conversion sheet) 110. a particle of the invention 120. a matrix material 130. an additive (optional)
List of reference signs in figure 2
200. an optical device (a light emitting diode device)
210. a particle of the invention
220. a matrix material
230. a light emitting diode element
240. conductive wires
250. a molding Material
260a. a cup
260b. a mount lead
270. an inner lead
List of reference signs in figure 3
300. an optical device (a light emitting diode device)
301. a color conversion sheet 310. a particle of the invention 320. a matrix material
330. a light emitting diode element 340. an additive (optional)
350. a casing 360. converted light 370. emitted light
Detailed Description of the invention - Particle
According to the present invention, said particle comprises, essentially consisting of, or consisting of an inorganic phosphor and a transparent polymer layer placed onto the outermost surface of said inorganic phosphor, preferably 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, polyethylene polyethyleneterephthalate, polyurethane, polyacrylonitrile, epoxy resin derived from glycidyl function on (meth)acrylate monomer, biodegradable polymer such as polylactide, polyglycolide, polyhydroxyalkanoate, polycaproractone.
In a preferred embodiment of the present invention, the polymer 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.
More preferably, the polymer is derived or derivable from an acidic monomer or acidic oligomer having 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, preferably said acidic monomer is a (meth)acrylate monomer, more preferably said polymer is derived from an acidic monomer and another monomer having no anchoring group, even more preferably said polymer is derived from an acidic (meth)acrylate monomer and (meth)acrylate monomer having no anchoring group. Even more preferably, the polymer is derived or derivable from an acidic monomer having at least one anchoring group listed above. Furthermore preferably, said acidic monomer 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, 1-[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-cyclohexanedicarboxylic acid (for example, Kyoeisha Chemical “LIGHT ESTER HO-HH(N)”), 2- methacryloyloxyethyl acid phosphate (for example, Kyoeisha Chemical “LIGHT ESTER P-1 M(N)”), bis(2-methacryloyloxyethyl acid) phosphate (for example, Kyoeisha Chemical “LIGHT ESTER P-2M(N)”), 1 -[2-[(1 -oxo- 2-propen-1-yl)oxy]ethyl] ester butanedioic acid (for example, Kyoeisha Chemical “LIGHT ACRYLATE HOA-MS(N)”), 1-[2-[(1-oxo-2-propen-1-yl) oxyjethyl] ester 1 ,2-cyclohexanedicarboxylic acid (for example, Kyoeisha Chemical “LIGHT ACRYLATE HOA-HH(N)”), 1-[2-[(1-oxo-2-propen-1-yl) oxyjethyl] ester 1 ,2-Benzenedicarboxylic acid (for example, Kyoeisha Chemical “LIGHT ACRYLATE HOA-MPL(N)”), 2-(phosphonooxy)ethyl ester 2-propenoic acid (for example, Kyoeisha Chemical “LIGHT ACRYLATE P-1 M(N)”), 1 -[1 -[[4-[1 -[4-[2-hydroxy-3-[(1 -oxo-2-propen-1 -yl) oxy]propoxy]phenyl]-1 -methylethyl]phenoxy]methyl]-2-[(1 -oxo-2-propen-1 - yl)oxy]ethyl] ester 4-cyclohexene-1 ,2-dicarboxylic acid; and styrene delivative monomer such as 4-vinylbenzoic acid, 4-(1-methylethenyl) benzoic acid.
It is believed that the acidic monomer disclosed above is suitable to form a polymer to form a polymer coating layer directly onto an inorganic phosphor since said acidic monomer has a group which can attach onto the surface of the inorganic phosphor.
-Inorganic phosphor In a preferred embodiment of the present invention, 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 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, and / or at least one inorganic phosphor 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 nm, even more preferably in the range from 350 nm to 500 nm, furthermore preferably in the range from 400 nm to 500nm, much more preferably in the range from 420 nm to 480 nm, the most preferably in the rage from 430 nm to 460 nm, and / or at least one inorganic phosphor having a first peak wavelength of light emitted from the inorganic phosphor in the range of 500nm or less, and a second peak wavelength of light emitted from the inorganic phosphor in the range of 600 nm or more, preferably the first peak wavelength of light emitted from the inorganic phosphor is in the range from 250nm to 500nm, and the second peak light emission wavelength is in the range from 600 nm to 1500 nm, more preferably the first peak wavelength of light emitted from the inorganic phosphor is in the range from 300nm to 500nm, and the second peak light emission wavelength is in the range from 600 nm to 1000 nm, even more preferably the first peak wavelength of light emitted from the inorganic phosphor is in the range from 350nm to 500nm, and the second peak light emission wavelength is in the range from 650 nm to 800 nm, furthermore preferably the first peak wavelength of light emitted from the inorganic phosphor is in the range from 400nm to 500nm, and the second peak light emission wavelength is in the range from 650 nm to 750 nm, much more preferably the first peak wavelength of light emitted from the inorganic phosphor is in the range from 420 nm to 480 nm, and the second peak light emission wavelength is in the range from 660 nm to 740 nm, the most preferably the first peak wavelength of light emitted from the inorganic phosphor is in the rage from 430 nm to 460 nm and the second peak wavelength of light emitted from the inorganic phosphor is in the range from 660 nm to 710 nm.
According to the present invention the term 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.
Preferably, the term “peak wavelength” is related to a side peak.
Preferably, the term “peak wavelength” is related to the main peak having maximum intensity/absorption.
In some embodiments of the present invention, the phosphor is a nontoxic phosphor, preferably it is an edible phosphor.
Thus, in some embodiments of the present invention, said 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 Fe, Eu, Ce and/or Mn activated metal oxide phosphor or a Fe, Eu, Ce and/or Mn activated phosphate based phosphor, even more preferably it is a Fe, Eu, Ce and/or Mn activated metal oxide phosphor. More preferably, the inorganic phosphor is represented by any one of the following formulae (I) to (XIV);
A1xB1yOz:X - (I) wherein A1 is a trivalent cation and is selected from the group consisting of Y, Gd, Lu, Ce, La, Tb, Sc, and Sm, B1 is a trivalent cation and is selected from the group consisting of Al, Ga, Lu, Sc, In; x≥0; y≥1 ; 1.5(x+y) = z, X is a luminescent ion and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Nd4+, Pm3+, Sm3+, Eu3+, Eu2+, Gd3+, Tb3+, Dy2+, Dy3+, Dy4+, Ho2+, Ho3+, Er3+, Tm3+, Yb3+, Yb2+, Cr3+, Mn2+, Mn4+ and Fe3+, preferably X is selected from Ce3+, Eu3+, Eu2+, Tb3+, Cr3+, Mn2+,
Mn4+, Fe3+ or a combination of any of these, more preferably X is Ce3+, more preferably the formula is Al2O3:Cr3+ or YsAlsOiaiCr3+, even more preferably it is Al2O3:Cr3+;
A2aZbOc:X - (II) wherein A2 is a divalent cation and is selected from the group consisting of Mg, Zn, Cu, Co, Ni, Fe, Ca, Sr, Ba, Mn, Ce and Sn; Z is a trivalent cation and is selected from the group consisting of Al, Ga, Lu, Sc and In; b≥0; a≥1 ; (a+1 ,5b) = c, X is a luminescent ion and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Nd4+, Pm3+, Sm3+, Eu3+, Eu2+, Gd3+, Tb3+, Dy2+, Dy3+, Dy4+, Ho2+, Ho3+, Er3+, Tm3+, Yb3+, Yb2+, Cr3+, Mn2+, Mn4+ and Fe3+, preferably X is selected from Ce3+, Eu3+, Eu2+, Tb3+, Cr3+, Mn2+, Mn4+, Fe3+ or a combination of any of these, more preferably X is Ce3+, more preferably the formula is ZnGa2O4: Cr3+ or MgAbO4: Cr3+, even more preferably it is MgAl2O4: Cr3+;
D1 dE1eOf:X - (III) wherein D1 is a divalent cation and is selected from one or more members of the group consisting of Mg2+, Zn2+, Cu2+, Co2+, Ni2+, Fe2+, Ca2+, Sr2+, Ba2+, Mn2+, Ce2+ and Sn2+; E1 is a trivalent cation and is selected from the group consisting of Al3+, Ga3+, Lu3+, Sc3+, La3+ and In3+; e≥10; d≥0;
(d+1 ,5e) = f, preferably D1 is Ca2+, Sr2+, Ba2+ or a combination of any of these, E1 is Al3+, Gd3+ or a combination of these, d is 1 , e is 12, f is 19, X is a luminescent ion and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Nd4+, Pm3+, Sm3+, Eu3+, Eu2+, Gd3+, Tb3+, Dy2+, Dy3+, Dy4+, Ho2+, Ho3+, Er3+, Tm3+, Yb3+, Yb2+, Cr3+, Mn2+, Mn4+ and Fe3+, preferably X is selected from Ce3+, Eu3+, Eu2+, Tb3+, Cr3+, Mn2+,
Mn4+, Fe3+ or a combination of any of these, more preferably X is Mn4+, even more preferably formula (III) is CaAl12O19:Mn4+;
D2 0E2 hOi:X - (IV) wherein D2 is a trivalent cation and is selected from one or more members of the group consisting of Al3+, Ga3+, Lu3+, Sc3+, La3+ and In3+; E2 is a trivalent cation and is selected from the group consisting of Al3+, Ga3+,
Lu3+, Sc3+, La3+ and In3+; h≥0; a≥g; (1.5g+1 ,5h) = I, preferably D2 is La3+, E2 is Al3+, Gd3+ or a combination of these, g is 1 , h is 12, i is 19, X is a luminescent ion and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Nd4+, Pm3+, Sm3+, Eu3+, Eu2+, Gd3+, Tb3+, Dy2+, Dy3+, Dy4+, Ho2+, Ho3+, Er3+, Tm3+, Yb3+, Yb2+, Cr3+, Mn2+, Mn4+ and Fe3+, preferably X is selected from Ce3+, Eu3+, Eu2+, Tb3+, Cr3+, Mn2+,
Mn4+, Fe3+ or a combination of any of these, more preferably X is Mn4+, even more preferably formula (IV) is LaAIOsiMn4+; GjJkLiOm:X - (V) wherein G is a divalent cation and is selected from one or more members of the group consisting of Mg2+, Zn2+, Cu2+, Co2+, Ni2+, Fe2+, Ca2+, Sr2+, Ba2+, Mn2+, Ce2+ and Sn2+; J is a trivalent cation and is selected from the group consisting of Y3+, Al3+, Ga3+, Lu3+, Sc3+, La3+ and In3+; L is a trivalent cation and is selected from the group consisting of Al3+, Ga3+, Lu3+, Sc3+, La3+ and In3+; l≥0; k≥0; j≥0; (j+1.5k+1.5l) = m, preferably G is selected from Ca2+, Sr2+, Ba2+ or a combination of any of these; J is Y3+, Lu3+ or a combination of these; L is Al3+, Gd3+ or a combination of these; j is 1 , k is 1 , 1 is 1 , m is 4; X is a luminescent ion and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Nd4+, Pm3+, Sm3+, Eu3+, Eu2+, Gd3+, Tb3+, Dy2+, Dy3+, Dy4+, Ho2+, Ho3+, Er3+, Tm3+, Yb3+, Yb2+, Cr3+, Mn2+, Mn4+ and Fe3+, preferably X is selected from Ce3+, Eu3+, Eu2+, Tb3+, Cr3+, Mn2+, Mn4+, Fe3+ or a combination of any of these, more preferably X is Mn4+; even more preferably it is CaYAlO4:Mn4+; and A3aOz:X - (VI) wherein
A3 is a trivalent cation and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Tb3+, Dy3+, Ti3+, V3+, Cr3+, Mn3+, Fe3+, Co3+, Ni3+, Zr3+, Nb3+, Mo3+, Tc3+, Ru3+, Rh3+, Pd3+, Hf3+, Ta3+, W3+, Re3+, Os3+, Ir3+, Pt3+, Si3+, Ge3+, Sn3+, Pb3+, S3+, Se3+, Te3+ and Po3+;
X is a luminescent ion and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Nd4+, Pm3+, Sm3+, Eu3+, Eu2+, Gd3+, Tb3+, Dy2+, Dy3+, Dy4+, Ho2+, Ho3+, Er3+, Tm3+, Yb3+, Yb2+, Cr3+, Mn2+, Mn4+ and Fe3+; a≥0; z≥0; 2a = z; preferably, A3 is Ce3+, Ti3+, Zr3+, Hf3+, Si3+, Ge3+, Sn3+, or a combination of any of these;
X is selected from Ce3+, Eu3+, Eu2+, Tb3+, Cr3+, Mn2+, Mn4+, Fe3+ or a combination of any of these, more preferably X is Ce3+; a is 1 , z is 2; more preferably the formula is ZrO2:Ce3+;
A4aB2bC1cOz:X - (VII) wherein
A4 is a monovalent cation and is selected from one or more members of the group consisting of Li+, Na+, K+, Rb+, Cs+, V+, Cr+, Mn+, Co+, Ni+, Cu+, Pd+. Ag+. Au+ and TI+; B2 is a tetravalent cation and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Tb3+, Dy3+, Ti3+, V3+, Cr3+, Mn3+, Fe3+, Co3+, Ni3+, Zr3+, Nb3+, Mo3+, Tc3+, Ru3+, Rh3+, Pd3+, Hf3+, Ta3+, W3+, Re3+, Os3+, Ir3+, Pt3+, Si3+, Ge3+, Sn3+, Pb3+, S3+, Se3+, Te3+ and Po3+;
C1 is a tetravalent cation and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Tb3+, Dy3+, Ti3+, V3+, Cr3+, Mn3+, Fe3+, Co3+, Ni3+, Zr3+, Nb3+, Mo3+, Tc3+, Ru3+, Rh3+, Pd3+, Hf3+, Ta3+, W3+, Re3+, Os3+, Ir3+, Pt3+, Si3+, Ge3+, Sn3+, Pb3+, S3+, Se3+, Te3+ and Po3+;
X is a luminescent ion and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Nd4+, Pm3+, Sm3+, Eu3+, Eu2+, Gd3+, Tb3+, Dy2+, Dy3+, Dy4+, Ho2+, Ho3+, Er3+, Tm3+, Yb3+, Yb2+, Cr3+, Mn2+, Mn4+ and Fe3+; a≥0; b≥0; c≥0; z≥0; (0.5a+2b+2c) = z; preferably A4 is Li+, Na+, K+, Rb+, Cs+ or a combination of any of these,
B2 is Ce3+, Ti3+, Zr3+, Hf3+, Si3+, Ge3+, Sn3+, or a combination of any of these,
C1 is Ce3+, Ti3+, Zr3+, Hf3+, Si3+, Ge3+, Sn3+, or a combination of any of these;
X is Ce3+, Eu3+, Eu2+, Tb3+, Cr3+, Mn2+, Mn4+ and Fe3+, or a combination of any of these, more preferably X is Eu2+; a is 2, b is 1 , c is 2, z is 7; more preferably, formula is K2ZrSi20?:Eu2+;
A5aB3bC2cD3dOz:X - (VIII) wherein
A5 is a divalent cation and is selected from one or more members of the group consisting of Mg2+, Ca2+, Sr2+, Ba2+, Nd2+, Sm2+, Eu2+, Dy2+, Ho2+, Tm2+, Yb2+, Ti2+, V2+, Cr2+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Mo2+, Pd2+, Ag2+, W2+, Pt2+, Zn2+, Cd2+, Hg2+, Ge2+, Sn2+ and Pb2+;
B3 is a trivalent cation and is selected from one or more members of the group consisting of Sc3+, Y3+, La3+, Ce3+, Pr3+, Nd3+, Pm3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+, Ti3+, V3+, Cr3+, Mn3+, Fe3+, Co3+, Ni3+, Cu3+, Nb3+, Mo3+, Ru3+, Rh3+, Pd3+, Ag3+, Ta3+, W3+, Ir3+, Au3+, B3+, Al3+, Ga3+, ln3+, Tl3+, P3+, As3+, Sb3+ and Bi3+;
C2 is a tetravalent cation and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Tb3+, Dy3+, Ti3+, V3+, Cr3+, Mn3+, Fe3+, Co3+, Ni3+, Zr3+, Nb3+, Mo3+, Tc3+, Ru3+, Rh3+, Pd3+, Hf3+, Ta3+, W3+, Re3+, Os3+, Ir3+, Pt3+, Si3+, Ge3+, Sn3+, Pb3+, S3+, Se3+, Te3+ and Po3+;
D3 is a trivalent cation and is selected from one or more members of the group consisting of Sc3+, Y3+, La3+, Ce3+, Pr3+, Nd3+, Pm3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+, Ti3+, V3+, Cr3+, Mn3+, Fe3+, Co3+, Ni3+, Cu3+, Nb3+, Mo3+, Ru3+, Rh3+, Pd3+, Ag3+, Ta3+, W3+, Ir3+, Au3+, B3+, Al3+, Ga3+, In3+, TI3+, P3+, As3+, Sb3+ and Bi3+;
X is a luminescent ion and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Nd4+, Pm3+, Sm3+, Eu3+, Eu2+, Gd3+, Tb3+, Dy2+, Dy3+, Dy4+, Ho2+, Ho3+, Er3+, Tm3+, Yb3+, Yb2+, Cr3+, Mn2+, Mn4+ and Fe3+; a≥0; b≥0; c≥0; d≥0; z≥0; (a+1 ,5b+2c+1 ,5d) = z; preferably A5 is Mg2+, Ca2+, Sr2+, Ba2+ and Zn2+, or a combination of any of these;
B3 is Sc3+, Y3+, La3+, Lu3+, B3+, Al3+, Ga3+, In3+, P3+, Bi3+, or a combination of any of these;
C2 is Ce3+, Ti3+, Zr3+, Hf3+, Si3+, Ge3+, Sn3+, or a combination of any of these;
D3 is Sc3+, Y3+, La3+, Lu3+, B3+, Al3+, Ga3+, In3+, P3+, Bi3+, or a combination of any of these;
X is Ce3+, Eu3+, Eu2+, Tb3+, Cr3+, Mn2+, Mn4+ and Fe3+, or a combination of any of these; a is 2, b is 1 , c is 2, d is 3, z is 12; more preferably the formula is Ca2YZr2Al3O12:Ce3+; A6aB4bOz:X -(IX) wherein A6 is a trivalent cation and is selected from one or more members of the group consisting of Sc3+, Y3+, La3+, Ce3+, Pr3+, Nd3+, Pm3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+, Ti3+, V3+, Cr3+, Mn3+, Fe3+, Co3+, Ni3+, Cu3+, Nb3+, Mo3+, Ru3+, Rh3+, Pd3+, Ag3+, Ta3+, W3+, Ir3+, Au3+, B3+, Al3+, Ga3+, In3+, TI3+, P3+, As3+, Sb3+ and Bi3+;
B4 is a trivalent cation and is selected from one or more members of the group consisting of Sc3+, Y3+, La3+, Ce3+, Pr3+, Nd3+, Pm3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+, Ti3+, V3+, Cr3+, Mn3+, Fe3+, Co3+, Ni3+, Cu3+, Nb3+, Mo3+, Ru3+, Rh3+, Pd3+, Ag3+, Ta3+, W3+, Ir3+, Au3+, B3+, Al3+, Ga3+, In3+, TI3+, P3+, As3+, Sb3+ and Bi3+;
X is a luminescent ion and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Nd4+, Pm3+, Sm3+, Eu3+, Eu2+, Gd3+, Tb3+, Dy2+, Dy3+, Dy4+, Ho2+, Ho3+, Er3+, Tm3+, Yb3+, Yb2+, Cr3+, Mn2+, Mn4+ and Fe3+; a≥0; b≥0; z≥0; (1.5a+1.5b) = z; preferably A® is Sc3+, Y3+, La3+, Lu3+, B3+, Al3+, Ga3+, In3+, P3+, Bi3+, or a combination of any of these;
B4 is Sc3+, Y3+, La3+, Lu3+, B3+, Al3+, Ga3+, In3+, P3+, Bi3+, or a combination of any of these;
X is Ce3+, Eu3+, Eu2+, Tb3+, Cr3+, Mn2+, Mn4+ and Fe3+, or a combination of any of these, more preferably X is Ce3+; a is 3, b is 5, z is 12; more preferably the formula is Y3Al5O12: Ce3+;
A7aB5bC3cOz:X -(X) wherein
A7 is a trivalent cation and is selected from one or more members of the group consisting of Sc3+, Y3+, La3+, Ce3+, Pr3+, Nd3+, Pm3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+, Ti3+, V3+, Cr3+, Mn3+, Fe3+, Co3+, Ni3+, Cu3+, Nb3+, Mo3+, Ru3+, Rh3+, Pd3+, Ag3+, Ta3+, W3+, Ir3+, Au3+, B3+, Al3+, Ga3+, In3+, TI3+, P3+, As3+, Sb3+ and Bi3+;
B5 is a trivalent cation and is selected from one or more members of the group consisting of Sc3+, Y3+, La3+, Ce3+, Pr3+, Nd3+, Pm3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+, Ti3+, V3+, Cr3+, Mn3+, Fe3+, Co3+, Ni3+, Cu3+, Nb3+, Mo3*, Ru3+, Rh3+, Pd3+, Ag3+, Ta3+, W3+, Ir3+, Au3+, B3+, Al3+, Ga3+, In3+, Tl3+, P3+, As3+, Sb3+ and Bi3+;
C3 is a trivalent cation and is selected from one or more members of the group consisting of Sc3+, Y3+, La3+, Ce3+, Pr3+, Nd3+, Pm3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+, Ti3+, V3+, Cr3+, Mn3+, Fe3+, Co3+, Ni3+;
X is a luminescent ion and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Nd4+, Pm3+, Sm3+, Eu3+, Eu2+, Gd3+, Tb3+, Dy2+, Dy3+, Dy4+, Ho2+, Ho3+, Er3+, Tm3+, Yb3+, Yb2+, Cr3+, Mn2+, Mn4+ and Fe3+; a≥0; b≥0; c≥0; z≥0 (1.5a+1.5b+1.5c) = z; preferably A7 is Sc3+, Y3+, La3+, Lu3+, B3+, Al3+, Ga3+, In3+, P3+, Bi3+, or a combination of any of these;
B5 is Sc3+, Y3+, La3+, Lu3+, B3+, Al3+, Ga3+, In3+, P3+, Bi3+, or a combination of any of these;
C3 is Sc3+, Y3+, La3+, Lu3+, B3+, Al3+, Ga3+, In3+, P3+, Bi3+, or a combination of any of these;
X is Ce3+, Eu3+, Eu2+, Tb3+, Cr3+, Mn2+, Mn4+ and Fe3+, or a combination of any of these, more preferably X is Ce3+; a is 3, b is 2, c is 3, z is 12; more preferably, formula is Y3Ga2Al3O12: Ce3+;
A8aB6bOz:X -(XI) wherein
A8 is a monovalent cation and is selected from one or more members of the group consisting of Li+, Na+, K+, Rb+, Cs+, V+, Cr+, Mn+, Co+, Ni+, Cu+, Pd+, Ag+. Au+ and TI+;
B8 is a trivalent cation and is selected from one or more members of the group consisting of Sc3+, Y3+, La3+, Ce3+, Pr3+, Nd3+, Pm3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+, Ti3+, V3+, Cr3+, Mn3+, Fe3+, Co3+, Ni3+, Cu3+, Nb3+, Mo3+, Ru3+, Rh3+, Pd3+, Ag3+, Ta3+, W3+, Ir3+, Au3+, B3+, Al3+, Ga3+, In3+, TI3+, P3+, As3+, Sb3+ and Bi3+; X is a luminescent ion and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Nd4+, Pm3+, Sm3+, Eu3+, Eu2+, Gd3+, Tb3+, Dy2+, Dy3+, Dy4+, Ho2+, Ho3+, Er3+, Tm3+, Yb3+, Yb2+, Cr3+, Mn2+, Mn4+ and Fe3+; a≥0; b≥0; z≥0 (0.5a+1.5b) = z; preferably A8 is Li+, Na+, K+, Rb+, Cs+ or a combination of any of these,
B® is Sc3+, Y3+, La3+, Lu3+, B3+, Al3+, Ga3+, In3+, P3+, Bi3+, or a combination of any of these;
X is Ce3+, Eu3+, Eu2+, Tb3+, Cr3+, Mn2+, Mn4+ and Fe3+, or a combination of any of these, more preferably X is Mn4+; a is 1 , b is 5, z is 8; more preferably the formula is LiAlsOsiMn4+;
A9aB7bOz:X -(XII) wherein
A9 is a divalent cation and is selected from one or more members of the group consisting of Mg2+, Ca2+, Sr2+, Ba2+, Nd2+, Sm2+, Eu2+, Dy2+, Ho2+, Tm2+, Yb2+, Ti2+, V2+, Cr2+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Mo2+, Pd2+, Ag2+, W2+, Pt2+, Zn2+, Cd2+, Hg2+, Ge2+, Sn2+ and Pb2+;
B7 is a tetravalent cation and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Tb3+, Dy3+, Ti3+, V3+, Cr3+, Mn3+, Fe3+, Co3+, Ni3+, Zr3+, Nb3+, Mo3+, Tc3+, Ru3+, Rh3+, Pd3+, Hf3+, Ta3+, W3+, Re3+, Os3+, Ir3+, Pt3+, Si3+, Ge3+, Sn3+, Pb3+, S3+, Se3+, Te3+ and Po3+;
X is a luminescent ion and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Nd4+, Pm3+, Sm3+, Eu3+, Eu2+, Gd3+, Tb3+, Dy2+, Dy3+, Dy4+, Ho2+, Ho3+, Er3+, Tm3+, Yb3+, Yb2+, Cr3+, Mn2+, Mn4+ and Fe3+; a≥0; b≥0; z≥0 (a+2b) = z; preferably, A9 is Mg2+, Ca2+, Sr2+, Ba2+ and Zn2+, or a combination of any of these;
B7 is Ce3+, Ti3+, Zr3+, Hf3+, Si3+, Ge3+, Sn3+, or a combination of any of these;
Figure imgf000027_0001
A11 is a divalent cation and is selected from one or more members of the group consisting of Mg2+, Ca2+, Sr2+, Ba2+, Nd2+, Sm2+, Eu2+, Dy2+, Ho2+, Tm2+, Yb2+, Ti2+, V2+, Cr2+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Mo2+, Pd2+, Ag2+, W+, Pt2+, Zn2+, Cd2+, Hg2+, Ge2+, Sn2+ and Pb2+;
B9 is a divalent cation and is selected from one or more members of the group consisting of Mg2+, Ca2+, Sr2+, Ba2+, Nd2+, Sm2+, Eu2+, Dy2+, Ho2+, Tm2+, Yb2+, Ti2+, V2+, Cr2+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Mo2+, Pd2+, Ag2+,W2+, Pt2+, Zn2+, Cd2+, Hg2+, Ge2+, Sn2+ and Pb2+;
C5 is a trivalent cation and is selected from one or more members of the group consisting of Sc3+, Y3+, La3+, Ce3+, Pr3+, Nd3+, Pm3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+, Ti3+, V3+, Cr3+, Mn3+, Fe3+, Co3+, Ni3+, Cu3+, Nb3+, Mo3+, Ru3+, Rh3+, Pd3+, Ag3+, Ta3+, W3+, lr3+, Au3+, B3+, Al3+, Ga3+, ln3+, Tl3+, P3+, As3+, Sb3+ and Bi3+;
X is a luminescent ion and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Nd4+, Pm3+, Sm3+, Eu3+, Eu2+, Gd3+, Tb3+, Dy2+, Dy3+, Dy4+, Ho2+, Ho3+, Er3+, Tm3+, Yb3+, Yb2+, Cr3+, Mn2+, Mn4+ and Fe3+; a³0; b³0; c³0; z³0 (0.5a+b+2c) = z; preferably A11 is Mg2+, Ca2+, Sr2+, Ba2+ and Zn2+, or a combination of any of these;
B9 is Mg2+, Ca2+, Sr2+, Ba2+ and Zn2+, or a combination of any of these;
C5 is Sc3+, Y3+, La3+, Lu3+, B3+, Al3+, Ga3+, ln3+, P3+, Bi3+, or a combination of any of these;
X is Ce3+, Eu3+, Eu2+, Tb3+, Cr3+, Mn2+, Mn4+ and Fe3+, or a combination of any of these, more preferably X is Mn4+; even more preferably the formula is CaMgAli6027:Mn4+, Ca2Mg2Al28046:Mn4+, Sr2MgAl22036:Mn4+ or BaMgAhoOi7:Mn4+.
In a further preferable embodiment, the inorganic phosphor is selected from one or more of members of the group consisting of Al203:Cr3+, Y3AI50i2:Cr3+, MgAI204: Cr3+, CaAh20i9:Mn4+, LaAI03:Mn4+, CaYA104:Mn4+, Zr02:Ce3+, K2ZrSi207:Eu2+, Ca2YZr2A130i2:Ce3+, Y3AI5012:Ce3+, Y3Ga2AI3012:Ce3+, LiAI508:Mn4+, Li2MgZr04:Mn4+, CaZr03:Mn4+, CaMgAli6027:Mn4+, Ca2Mg2AI28046:Mn4+, Sr2MgAI22036:Mn4+ and BaMgAl10O17:Mn4+.
Since above mentioned inorganic phosphors are believed to have higher hardness, it is believed that the particle comprising one or more of above mentioned phosphors are particularly suitable to avoid or reduce a scratch of an inflation molding machine caused by an inorganic phosphor, to avoid or reduce a situation that an optical sheet comprising an inorganic phosphor is contaminated with a dust from an inflation molding machine and to make an optical sheet with improved transparency.
There phosphors are publicly available like described in the second chapter of Phosphor handbook (Yen, Shinoya, Yamamoto), WO 2017/129351 A1 , WO 2019/020602 A1 and WO 2019/020653 A1.
In some embodiments of the present invention, the inorganic phosphors can emit a light having the 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. Without wishing to be bound by theory, it is believed that 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. Therefore, in some embodiments of the present invention, 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. In some embodiments of the present invention, from the viewpoint of improved plant growth and improved homogeneous of blue and red (or infrared) light emission from the composition or from the light converting sheet, 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 650 nm to 750 nm can be used preferably.
More 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.
Preferably, said at least one inorganic phosphor is a plurality of inorganic phosphor having the first and second peak wavelength of light emitted from the inorganic phosphor, or a plurality of inorganic phosphor having the first and second peak wavelength of light emitted from the inorganic phosphor, or a combination of these.
According to the present invention, the particle can be fabricated by using a publicly known method like described in working examples with using water, solvent, polymer precursor, polymerization initiator and optionally a surfactant.
-Solvent
In a preferred embodiment of the present invention, the solvent is an organic solvent, preferably 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 alcohol, 1-nonadecanol (64), 1-eicosanol (67); secondary alcohol having 3 to 40, preferably 3 to 25, more preferably 3 to 20 carbon atoms such as 2-propanol, 1-methoxy-2-propanol, 2-butanol, 2-pentanol, 2-hexanol, 2-heptanol, cyclohexanol and tertiary alcohol having 4 to 40 carbon atoms, preferably 4 to 25 carbon atoms, more preferably 4 to 20 carbon atoms such as tert-butyl alcohol, 2-methyl-2-pentanol, 3-methyl-3- pentanol; diol having 2 to 10 carbon atoms such as ethylene glycol, 1 ,3- propanediol, propylene glycol, 1 ,4-butanediol, 1 ,5-pentanediol, 1 ,6- hexanediol, 1 ,7-heptanediol, 1 ,8-octanediol, 1 ,9-nonanediol, 1 ,10- decanediol, 1 ,4-cyclohexanedimethanol; heteroaromatic alcohol such as furfuryl alcohol, (5-methyl-2-furyl)methanol, 1-(2-furyl)ethan-1-ol, 2,5- furandimethanol, 2-thiophemethanol, 2-thiopheethanol; ketones such as (acetone), ethyl methyl ketone, diethyl ketone, methyl propyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone, acetophenone; cycloalkane having carbon atoms 6 to 12 such as cyclohexane, methylcyclohexane, 1 ,1-dimethylcyclohexane, 1 ,2-dimethylcyclohexane,
1 ,3-dimethylcyclohecxane, 1 ,4-dimethylcyclohexane, 1,3,5- trimethylcyclohexane, 1-ethyl-4-methylcyclohexane, cycloheptane, cyclooctane, cyclononane, and cyclodecane; ethers such as tetrahydrofuran, 1 ,3-dimethoxyethane, 1 ,2-dimethoxypropane, 1 ,3- dimethoxypropane, 2,2-dimethoxypropane, 2,2-diethoxypropane, diethylene glycol ethyl ether, diethylene glycol diethyl ether, diethylene glycol propyl ether, diethylene glycol dipropyl ether, diethylene glycol butyl ether, diethylene glycol dibutyl ether, di(propylene glycol) methyl ether, di(propylene glycol) dimethyl ether, di(propylene glycol) propyl ether, 1 ,2- dimethoxycyclohexane, 1-methoxy-4-methylcyclohexane, 1 ,3-dioxane, 1 ,4-dioxane, poly(ethylene glycol) tetrahydrofurfuryl ether, tetrahydrofurfuryl alcohol polyethylerene glycol ether, tetraglycol, ethyl tetrahydrofurfuryl ether; esters such as methyl acetate, ethyl acetate, isoamyl acetate, butyl acetae, n-butyl acetate, sec-buyl acetate, isobutyl acetate, propyl acetate, isopropyl acetate, amyl acetate, pentyl acetate, isopentyl acetate, 2-ethoxyethyl acetate, hexyl acetate, cyclohexyl acetate, heptyl acetate, lauryl acetate, dodecyl acetate, ethyl 2-(benzyloxy)acetate, benzyl acetate, phenyl acetate, 4-tert-pentylcyclohexyl acetate, 1 ,2- diacetoxycyclohexane, 1 ,3-diacetoxycyclohexane, 1,3,5- triacetoxycyclohexane, tetrahydrofurfuryl acetate, tetrahydrofurfuryl butyrate, dimethyl carbonate, diethyl carbonate, dethylene carbonate, propylene carbonate, ethylene carbonate, diallyl carbonate, dipropyl carbonate, dibenzyl carbonate; and amide such as N,N- dimethylacetamide, N,N-dimethylformamide.
-Polymer precursor
In a preferable embodiment of the present invention, said polymer precursor is an acidic monomer or an acidic origomer, preferably it is an 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, 1-[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-cyclohexanedicarboxylic acid (for example, Kyoeisha Chemical “LIGHT ESTER HO-HH(N)”), 2- methacryloyloxyethyl acid phosphate (for example, Kyoeisha Chemical “LIGHT ESTER P-1 M(N)”), bis(2-methacryloyloxyethyl acid) phosphate (for example, Kyoeisha Chemical “LIGHT ESTER P-2M(N)”), 1 -[2-[(1 -oxo- 2-propen-1-yl)oxy]ethyl] ester butanedioic acid (for example, Kyoeisha Chemical “LIGHT ACRYLATE HOA-MS(N)”), 1-[2-[(1-oxo-2-propen-1-yl) oxy]ethyl] ester 1 ,2-cyclohexanedicarboxylic acid (for example, Kyoeisha Chemical “LIGHT ACRYLATE HOA-HH(N)”), 1-[2-[(1-oxo-2-propen-1-yl) oxy]ethyl] ester 1 ,2-Benzenedicarboxylic acid (for example, Kyoeisha Chemical “LIGHT ACRYLATE HOA-MPL(N)”), 2-(phosphonooxy)ethyl ester 2-propenoic acid (for example, Kyoeisha Chemical “LIGHT ACRYLATE P-1 M(N)”), 1 -[1 -[[4-[1 -[4-[2-hydroxy-3-[(1 -oxo-2-propen-1 -yl) oxy]propoxy]phenyl]-1 -methylethyl]phenoxy]methyl]-2-[(1 -oxo-2-propen-1 - yl)oxy]ethyl] ester 4-cyclohexene-1 ,2-dicarboxylic acid; and styrene delivative monomer such as 4-vinylbenzoic acid, 4-(1-methylethenyl) benzoic acid.
It is beleaved that the acidic monomer disclosed above is suitable to form a polymer to form a polymer coating layer directly onto an inorganic phosphor since said acidic monomer has a group which can attach onto the surface of the inorganic phosphor.
-Polymerization initiator
In a preferred embodiment of the present invention, the reaction mixture can further contain a polymerization initiator. Generally, there are two kinds of polymerization initiators which can be used in the present invention: one is a polymerization initiator generating an acid, base, or radical when exposed to radiation, and the other is a polymerization initiator generating an acid, base or radical when exposed to heat. Without wishing to be bound by theory, it is believed that the polymerization initiator can lead better polymer coating onto the inorganic phosphor and results in improved passivation of polymer coated inorganic phosphor.
The polymerization initiator adoptable in the present is, for example, a photo acid-generator, which decomposes when exposed to radiation and releases an acid serving as an active substance for photo-curing the composition; a photo radical - generator, which releases a radical; a photo base-generator, which releases a base; a heat acid-generator, 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. Examples of the radiation include visible light, UV rays, IR rays, X-rays, electron beams, α-rays and y-rays.
In a preferred embodiment of the present invention, the amount of the polymerization initiator is in the range from 0.001 to 10 weight parts, more preferably 0.01 to 5 weight parts, based on 100 weight parts of the 1st polymer precursor.
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. Among the heat acid-generators usable in the present invention, 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 salts, and mixture thereof. Those base- generators as well as the acid-generators and / or radical - generators can be used singly or in mixture.
As the examples of the heat radical-generator, 2,2‘ azobis(2- methylvaleronitrile), 2,2‘-azobis(dimethylvaleronitrile), azobisisobutyronitrile or a combination of any of these can be used preferably.
Examples of the above photo acid-generator 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 the 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. For example, R+ is diphenyliodonium ion or triphenylsulfonium ion.
Further, X" is preferably a counter ion represented by any of the following formulas:
SbYe-,
AsY6 ,
Ra PPY6-p-,
RaqBY4-q-,
Ra qGaY4-q, RaS03-,
(RaS02)3C-,
(RaS02)2N-,
RaCOO', and SCN- in which
Y is a halogen atom,
Ra 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.
Concrete examples of the counter ion include:
Figure imgf000036_0001
Figure imgf000036_0002
Figure imgf000036_0003
·, formate ion, acetate ion, trifluoromethanesulfonate ion, nonafluorobutanesulfonate ion, methane- sulfonate ion, butanesulfonate ion, benzenesulfonate ion, p- toluenesulfonate ion, and sulfonate ion.
Among the photo acid-generators usable in the present invention, those generating sulfonic acids or boric acids are particularly preferred. Examples thereof include tricumyliodonium teterakis(pentafluorophenyl)- 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. Further, examples of the photo acid-generators also include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphor- sulfonate, triphenylsulfonium tetra(perfluorophenyl)borate, 4- acetoxyphenyldimethylsulfonium hexafluoroarsenate, 1-(4-n- butoxynaphthalene-1-yl)tetrahydrothiophenium trifluoromethanesulfonate,
1 -(4,7-dibutoxy-l -naphthalenyl)tetrahydrothiophenium tri- fluoromethanesulfonate, diphenyliodonium trifluoromethanesulfonate, and diphenyliodonium hexafluoroarsenate. Furthermore, it is still also possible to adopt photo acid-generators represented by the following formulas:
Figure imgf000037_0001
Figure imgf000037_0002
Figure imgf000038_0001
in which 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.
It is also possible to use 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. For example, 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. Examples of the photo radical-generator include azo compounds, peroxides, acyl phosphine oxides, alkyl phenons, oxime esters, and titanocenes.
According to the present invention, as the photo radical-generator, acyl phosphine oxides, alkyl phenons, oxime esters, or a combination of any of these are more preferable. For examples, 2,2-dimethxye-1 ,2- diphenylethane-1 -on, 1 -hydroxy-cyclohexylphenylketone, 2-hydroxy-2- methyl-1 -phenylpropan-1 -on, 1 -[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2- methyl-1 -propane-1 -on, 2-hydroxy-1 -{4-[4-(2-hydroxy-2- methylpropionyl)benzyl]phenyl}-2-methylpropane-1 -on, 2-methyl-1 -(4- methylthiophenyl)-2-morpholinopropane-1-on, 2-benzyl-2-dimethylamino- 1-(4-morpholinophenyl)-1-butanone, 2-(dimethylamino) -2-[(4- methylphenon)methyl]-1 -[4-(4-morpholinyl)phenyl]-1 -butanone, 2,4,6- trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6- trimethylbenzoyl)phenylphosphine oxide, 1 ,2-octanedione 1-[4- (phenylthio)-2-(o-benzoyl oxime)], ethanone 1-[9-ethyl-6-(2- methylbenzoyl)-9H-carbazole-3-yl]-1-(o-acetyl oxime) or a combination of any of these can be used preferably.
Examples of the photo base-generator include multi-substituted amide compounds having amide groups, lactams, imide compounds, and compounds having those structures.
-Surfactant
According to the present invention, a publicly known surfactant having an ancoring group selected so that the surfactant can attach onto the outer most surface of the inorganic phosphor, can be used preferably for the present invention. More preferably said surfactant contains at least one anchoring group selected from the 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; even more preferably said anchoring group is a carboxyl group or a phosphonate group, further more preferably it is a phosphonate group from the view point of stronger bonding ability.
For example, PW-36 from Kusumoto Chemicals Ltd., surfactants disclosed in JP2014-196466 A1 , or dispersants such as BYK(™)-100 series e.g. BYK(™) 103, 110, 111 , 118 (from BYK) can be used preferably.
-Use of the particle
In another aspect, the present invention also relates to use of the particle of the present invention in agriculture.
-Composition
In another aspect, the present invention also relates to a composition comprising, essentially consisting of, or consisting of, at least one particle of the present invention and another material.
In some embodiments of the present invention, said another material can preferably be 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 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.
In some embodiments of the invention, said another 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.
Preferably, said composition comprises a plurality of the particles of the present invention.
Thus, in some embodiments of the present invention, the total amount of the particle of the polymer coated inorganic phosphor of the present invention in the composition can be in the range from 0.01wt.% to 99.9wt.%, preferably it is in the range from 0,01wt% to 30wt.% based on the total amount of the composition, preferably it is from 0.1 wt.% 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.
- Matrix materials as said another material
According to the present invention, in some embodiments, said matrix material is an organic material, and/or an inorganic material, preferably AI2O3, fused composition of TeO2 : Na2Co3 : ZnO : BaCo3 = 7:1 :1 :1, and fused mixture of TeO2 : Na2Co3 : ZnO : BaCo3 = 7:1 :1 :1 and Al2O3 are excluded. Preferably the matrix material is an organic material.
Preferably, 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.
Thus, in some embodiments of the present invention, 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.
As organic polymer materials, polysaccharides, polyethylene, polypropylene, polystyrene, polymethyl pentene, polybutene, butadiene styrene, polyvinyl chloride, polystyrene, polymethacrylic styrene, styrene- acrylonitrile, 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, hydroxybenzoic acid polyester, polyetherimide, polycyclohexylenedimethylene terephthalate, polyethylene naphthalate, polyester carbonate, polylactic acid, phenolic resin, silicone or a combination of any of these can be used preferably.
As the photosetting polymer, several kinds of (meth)acrylates can be used preferably. Such as 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, hydroxyl- group, epoxy group, or halogen substituted alkyl-(meth)acrylates; cyclopentenyl(meth)acrylate, tetra-hydro furfuryl-(meth)acrylate, benzyl (meth)acrylate, polyethylene-glycol di-(meth)acrylates.
In view of better coating performance of the composition, sheet strength, and good handling, 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.
According to the present invention, the molecular weight Mw is determined by means of GPC (= gel permeation chromatography) against an internal polystyrene standard.
As the thermosetting polymer, publicly known transparent thermosetting polymer can be used preferably. Such as OE6550 (trade mark) series (Dow Coming).
As the thermoplastic polymer, the type of thermoplastic polymer is not particularly limited. For example, natural rubber(refractive index(n)=1.52), poly-isoprene(n=1.52), poly 1 ,2-butadine(n=1.50), polyisobutene(n=1.51 ), polybutene(n=1.51), poly-2-heptyl 1 ,3-butadine(n=1.50), poly-2-t-buty 1-1,3- butadine(n=1.51 ), poly-1 ,3-butadine(n=1.52), polyoxyethy lene(n= 1.46), polyoxypropylene(n=1.45), polyvinylethyl ether(n=1.45), polyvinylhexylether(n=1.46), polyvinylbutylether(n=1.46), polyethers, poly vinyl acetate(n=1.47), poly esters, such as poly vinyl propionate(n=1.47), poly urethane(n=1.5 to 1.6), ethyl celullose(n=1.48), poly vinyl chloride(n=1.54 to 1.55), poly acrylo nitrile(n=1.52), poly methacrylonitrile(n=1.52), poly-sulfone(n=1.63), poly sulfide(n=1.60), phenoxy resin(n=1.5 to 1.6), polyethylacrylate(n=1.47), poly butyl acrylate(n=1.47), poly-2-ethylhexyl acrylate(n=1.46), poly-t-butyl acrylate(n=1.46), poly-3-ethoxypropy lacry late(n= 1.47), polyoxycarbonyl tetra-methacrylate(n=1.47), polymethylacrylate(n=1.47 to 1.48), polyisopropylmethacrylate(n=1.47), polydodecyl methacrylate(n=1.47), polytetradecyl methacrylate(n=1.47), poly-n-propyl methacrylate(n=1.48), poly-3,3,5-trimethylcyclohexyl methacrylate(n=1.48), polyethylmethacrylate(n=1.49), poly-2-nitro-2- methylpropylmethacrylate(n=1.49), poly-1 ,1-diethylpropylmethacrylate (n=1.49), poly(meth)acrylates, such as polymethylmethacrylate(n=1.49), or a combination of any of these, can be used preferably as desired.
In some embodiment of the present invention, such thermoplastic polymers can be copolymerized if necessary.
A polymer, which can be copolymerized with the thermoplastic polymer described above is for example, urethane acrylate, epoxy acrylate, polyether acrylate, or, polyester acrylate (n=1.48 to 1.54) can also be employed. From the viewpoint of adhesiveness of the color conversion sheet, urethane acrylate, epoxy acrylate, and polyether acrylate are preferable.
According to the present invention, elastomers are incorporated into either thermoplastic polymer or thermosetting polymer based on their physical properties.
The matrix materials and the inorganic phosphors mentioned above in - Matrix materials, and in - Inorganic phosphors, can be preferably used for a fabrication of the color conversion sheet (100) and the light emitting diode device (200) of the present invention.
In some embodiments of the present invention, the composition can optionally further comprise one or more of additional inorganic phosphors, which emits blue or red light.
- Another Inorganic phosphors as an another material in the composition According to the present invention, any type of publicly known inorganic phosphors, preferably 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, and / or at least one inorganic phosphor 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 nm, even more preferably in the range from 350 nm to 500 nm, furthermore preferably in the range from 400 nm to 500nm, much more preferably in the range from 420 nm to 480 nm, the most preferably in the rage from 430 nm to 460 nm, and / or at least one inorganic phosphor having a first peak wavelength of light emitted from the inorganic phosphor in the range of 500nm or less, and a second peak wavelength of light emitted from the inorganic phosphor in the range of 600 nm or more, preferably the first peak wavelength of light emitted from the inorganic phosphor is in the range from 250nm to 500nm, and the second peak light emission wavelength is in the range from 600 nm to 1500 nm, more preferably the first peak wavelength of light emitted from the inorganic phosphor is in the range from 300nm to 500nm, and the second peak light emission wavelength is in the range from 650 nm to 1000 nm, even more preferably the first peak wavelength of light emitted from the inorganic phosphor is in the range from 350nm to 500nm, and the second peak light emission wavelength is in the range from 650 nm to 800 nm, furthermore preferably the first peak wavelength of light emitted from the inorganic phosphor is in the range from 400nm to 500nm, and the second peak light emission wavelength is in the range from 650 nm to 750 nm, much more preferably the first peak wavelength of light emitted from the inorganic phosphor is in the range from 420 nm to 480 nm, and the second peak light emission wavelength is in the range from 660 nm to 740 nm, the most preferably the first peak wavelength of light emitted from the inorganic phosphor is in the rage from 430 nm to 460 nm and the second peak wavelength of light emitted from the inorganic phosphor is in the range from 660 nm to 710 nm, can be used preferably. it is believed that 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.
Preferred metal-oxide phosphors are arsenates, germanates, halogerman- ates, indates, lanthanates, niobates, scandates, stannates, tantalates, titanates, vanadates, halovanadates, phosphovanadates, yttrates, zirconates, molybdate and tungstate.
Thus, in some embodiments of the present invention, said 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 Fe, Eu, Ce and/or Mn activated metal oxide phosphor or a Fe, Eu, Ce and/or Mn activated phosphate based phosphor, even more preferably it is a Fe, Eu, Ce and/or Mn activated metal oxide phosphor.
For example, the inorganic phosphor is selected from the group consisting of Al2O3:Cr3+, Y3Al5O12:Cr3+, MgO:Cr3+, ZnGa2O4 :Cr3+, MgAl2O4:Cr3+,
Figure imgf000047_0001
Figure imgf000047_0002
carbon/graphen quantum dots and a combination of any of these as described in the second chapter of Phosphor handbook (Yen, Shinoya, Yamamoto).
It is believed that the Mn4+ activated metal oxide phosphors, Mn, Eu activated metal oxide phosphors, Mn2+ activated metal oxide phosphors, Fe3+ activated metal oxide phosphors can be used preferably from the viewpoint of environmentally friendly since these phosphors do not create Cr6+ during synthesis procedure. As an additional inorganic phosphor which emits blue or red light, 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.
Without wishing to be bound by theory, it is believed that 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.
Thus, more preferably, the composition can further 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).
In some embodiments, said additional inorganic phosphor is a different type of inorganic phosphor from the inorganic phosphor of the present invention
-Vinzl monomers
In some embodiments of the present invention, the composition can embrace one or more of publicly available vinyl monomers that are co- polymerizable. Such as acrylamide, acetonitrile, diacetone-acrylamide, styrene, and vinyl-toluene or a combination of any of these.
-Crosslinkable monomers According to the present invention, the composition can further include one or more of publicly available crosslinkable monomers. For example, cyclopentenyl(meth)acrylates; tetra-hydro furfuryl- (meth)acrylate; benzyl (meth)acrylate; the compounds obtained by reacting a polyhydric alcohol with and α,β-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-(metha) acrylate, tetra-methylol methan tri-(meth) acrylate), tetra-methylol methane tetra(metha) acrylate, polypropylene glycol di(metha)acrylates (propylene number therein are 2-14), Di-penta-erythritol penta(meth)acrylate, di- penta-erythritol hexa(meth)acrylate, bis-phenol-A Polyoxyethylene di- (meth)acrylate, bis-phenol-A dioxyethylene di-(meth)acrylate, bis-phenol-A trioxyethylene di-(meth)acrylate, bis-phenol-A decaoxyethylene di- (meth)acrylate; the compounds obtained from an addition of an α,β- unsaturated carboxylic acid to a compound having glycidyl, such as tri- methylol propane trig lycidy lether triacrylate, bis-phenol A diglycidylether diacrylates; chemicals having poly-carboxylic acids, such as a phtalic anhydride; or chemicals having hydroxy and ethylenic unsaturated group, such as the esters with hydroxyethyl (meth)acrylate; alkyl-ester of acrylic acid or methacylic acid, such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethyl hexyl (meth)acrylate; urethane (meth)acrylate, such as the reactants of Tolylene diisocyanate and 2- hydroxyethyl (meth)acrylate, the reactants of tri-methyl hexamethylene diisocyanate and cyclohexane dimethanol, and 2-hydroxyethyl (meth)acrylate; and a combination of any of these.
In a preferred embodiment of the present invention, 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.
From the viewpoint of controlling the refractive index of the composition and / or the refractive index of the color conversion sheet according to the present invention, 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.
For example, as bromine-containing monomers, 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, as the 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.
-Photo initiator for the composition
In a preferred embodiment of the present invention, 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. For example, 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-tert-butyldichloro acetophenone, p-dimethylamino acetophenone, acetophenones, 2,4- dimetyl thioxanthone, 2,4-diisopropyl thioxanthone, thioxanthones, hydroxy cyclohexyl phenyl ketone (Ciba specialty chemicals, IRGACURE® 184), 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-on (Merck, Darocure® 1116), 2-hydroxy-2-methyl-1 -phenylpropane-1 -on (Merck, Darocure® 1173).
-Adjuvant
An adjuvant can enhance permeability of effective component (e.g. insecticide), inhibit precipitation of solute in the composition, or decrease a phytotoxicity. Here, 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.
Preferably 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.
As one embodiment, the weight ratio of each 1 additive of dispersant, surfactant, fungicide, antimicrobial agent and antifungal agent, to the weight of the invention phosphor 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.).
- Formulation
In another aspect, the invention relates to a formulation comprising, essentially consisting of, or a consisting of at least one particle of the present invention or the composition of the present invention, and a solvent. Preferably said formulation comprises a plurality of the inorganic phosphors or the composition of the present invention.
- Solvent for the formulation
As a solvent, 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. Preferably a plurality of particles of the present invention are in the formulation.
In a preferred embodiment of the present invention, 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, benzene, toluene and xylene; ketones, such as, methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols, such as, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin; esters, such as, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and ethyl lactate; and cyclic asters, such as, γ-butyrolactone. Those solvents are used singly or in combination of two or more, and the amount thereof depends on the coating method and the thickness of the coating.
More preferably, 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 for
Even more preferably, benzene, toluene, or xylene can be used.
The amount of the solvent in the formulation can be freely controlled. For example, if the formulation is to be spray-coated, it can contain the solvent in an amount of 90 wt.% or more based on total amount of the formulation. Further, if a slit-coating method, which is often adopted in coating a large substrate, is to be carried out, 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.
-Use of the particle, the composition or the formulation In another aspect, 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 an optical sheet fabrication process or in agriculture, preferably for fabricating an agricultural sheet or for controlling a condition of a living organism. - An optical sheet (100)
In another aspect, the invention relates to an optical sheet (100) comprising at least one particle of the present invention, or the composition of the present invention, preferably said optical sheet is an agricultural sheet. Preferably said optical sheet (100) comprises a plurality of particles of the present invention or the composition.
In some embodiments of the invention, the optical sheet (100) can be a film, or a fiber mat. According to the present invention, in some embodiments, the optical sheet (100) can be rigid or flexible.
In some embodiments of the present invention, the optical sheet (100) can be any structure. Such as plane, curved, wave formed structures to increase a growth of plant. In some embodiments of the invention, the optical sheet (100) comprises at least a first layer (100a) comprising at least the composition or the first layer (100a) made from the composition.
According to the present invention, said fiber mat can be fabricated by using publicly known spinning method. And said cover layer can be fabricated by using a known method such as a spinning, dip coating, bar coating, printing, and/or spin coating.
In some embodiments of the invention, the sheet further comprises a second layer (100b), preferably the second layer (100b) 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.
In some embodiments of the present invention, the second layer (100b) comprises at least the inorganic phosphor of the present invention, and a second material selected from adhesives, and/or insecticides.
In some embodiments of the present invention, the second layer (100b) can further comprises a matrix material described in the section of “matrix material”.
According to the present invention, said inorganic phosphor is described in the section of “inorganic phosphors” above. In some embodiments of the present invention, the second layer (100b) 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 (100b) 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.
In some embodiments of the present invention, the second layer (100b) of the optical medium (100) is a light reflecting layer, preferably the second layer (100b) 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 (100b) essentially consists of, or consists of one or more of light reflecting materials.
As a light reflecting material 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.
In some embodiments, said first layer is at least partially covered by said second layer, preferably at least one side of said first layer (100a) one side of the optical medium (100) is fully covered by the second layer.
In some embodiments, the optical medium (100) optionally may comprise a third layer (100c) or more layers.
In some embodiments, said first layer (100a), optionally the second layer (100b), the third layer (100c) or more layers can be sandwiched by, or fully or partially covered by one or more of optically transparent protection layers.
According to the present invention, said protection layer can be made from any publicly known transparent materials suitable for optical films.
Fabrication method for coating of optical sheet (100) by the light reflecting material is not particularly limited. Publicly known methods such as vacuum deposition, sputtering, chemical vapor deposition, printing can be used.
In some embodiments of the invention, the optical the sheet (100) comprises a first layer(100a), wherein the first layer (100a) 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 described in the section of “Additive”.
In some embodiments of the invention, the concentration of the particle of the present invention (110) in the sheet is 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.
In some embodiments of the invention, the optical sheet (100), may further comprises a substrate, preferably said substrate is an optically transparent substrate, colored substrate, selective light reflector, or a light reflector.
According to the present invention, 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 medium (100). Preferably, it is over 70 %, more preferably, over 75%, the most preferably, it is over 80 %.
According to the present invention, the term “transparent” means at least around 60 % of incident light transmittal at the thickness used in a the optical medium (100) and at a wavelength or a range of wavelength used during operation of the optical medium (100).
Preferably, it is over 70 %, more preferably, over 75%, the most preferably, it is over 80 %.
In some embodiments of the present invention, said reflector is a metal substrate, 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.
According to the present invention, the selective light reflector can be a single layer or multiple layers.
In a preferred embodiment, the selective light reflector comprises at least a selective light reflecting layer selected from the group consisting of Al layer, Al + MgFa 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 + MgFa stacked layers, Al + SiO stacked layers.
Preferably, said selective light reflecting layer is stacked onto a transparent substrate. In general, the methods of preparing the selective light reflection layer can vary as desired and selected from well-known techniques.
In some embodiments, the selective light reflection layer expect for cholesteric liquid crystal layers can be prepared by a gas phase based coating process (such as Sputtering, Chemical Vapor Deposition, vapor deposition, flash evaporation), or a liquid-based coating process.
In some embodiments of the present invention, the optical medium is an optical sheet, for example, a color conversion sheet, a remote phosphor tape, or another sheet or a filter for agriculture.
In some embodiments of the present invention, the layer thickness of the optical sheet is 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.
In some embodiments of the present invention, the total amount of the particle in the optical sheet is in the range from 0.01 wt.% to 30wt.% based on the total amount of the matrix material, preferably it is from 0.1 wt.% 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.
- Optical device
In another aspect, the invention relates to an optical device (200) comprising the optical sheet (100), or the composition and further comprising a light source, a light re-directing device, and/or a reflector. Preferably said light source is a light emitting diode, or an organic light emitting diode.
In some embodiments of the present invention, the optical device (200) comprises at least one optical sheet and a supporting part, preferably the supporting part comprises at least one attaching part to attach the optical medium, and optionally a base part to support optical medium and supporting part itself, more preferably the supporting part comprises one or more of attaching part to attach one or more of optical medium.
In a preferred embodiment of the present invention, the optical device is a lighting device, a light emitting diode device for agriculture, or building materials of greenhouse. -Use of composition or formulation
In another aspect, the invention relates to use of the composition, or formulation in an optical sheet fabrication process.
-Use of the optical sheet (100) or the optical device (200)
In another aspect, the invention relates to use of the optical sheet (100) or the optical device (200) of the present invention for agriculture, preferably for greenhouse or for controlling a condition of a living organism in agriculture.
-Green House
In another aspect, the present invention furthermore relates to a greenhouse comprising the optical sheet (100).
-Method for preparing the optical sheet (100)
In another aspect, the present invention furthermore relates to method for preparing the optical sheet (100), preferably for preparing the agriculture sheet, wherein the method comprises following steps (N) and (P), (N) providing the composition or the formulation of the present invention in a first shaping, preferably providing the composition onto a substrate or into an inflation moulding machine, and
(P) fixing the matrix material by evaporating a solvent and / or polymerizing the composition by heat treatment, or exposing the photosensitive composition under ray of light or a combination of any of these.
In a preferred embodiment, the method comprises following steps (N) and (P) in this sequence.
In some embodiments of the present invention, the composition in step (N) is provided by spin coating, spray coating, bar coating, or a slit coating method.
In a preferred embodiment of the present invention, the composition or the formulation in step (N) is provided into an inflation-molding machine and the matrix material is fixed by heat treatment of the machine.
-Method for preparing the optical device (200)
In another aspect, the present invention furthermore relates to method for preparing the optical device (200), wherein the method comprises following step (A),
(A) providing the optical sheet (100) in an optical device.
The details of the composition and the formulation are described in the section of “composition” and the section of “formulation”. Especially, according to the present invention, the optical sheet (100) is useful for agriculture.
Particularly, the optical medium (100) 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.
It is believed that 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.
Therefore, more preferably, the invention relates to use of the optical sheet (100) 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.
Even more preferably, one side of the optical sheet (100) is coated by a light reflecting material which can reflect at least blue, red, and/or infrared light. As 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 AlOa is used as the light reflecting material.
Preferably, said one side of the optical medium (100) is fully covered by the light reflecting material.
Fabrication method for coating of optical medium (100) by the light reflecting material is not particularly limited. Publicly known methods such as vacuum deposition, sputtering, chemical vapor deposition, printing can be used. In some embodiment, the optical sheet (100) may be used to control growth of plankton, preferably said plankton is a phytoplankton.
In another aspect, the present invention relates to use of the particle, the composition, the formulation, the optical medium (100), the optical device (200), or the green house, for cultivation of algae, bacteria, preferably said bacteria are photosynthetic bacteria, and/or planktons, 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 / 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 ripening of fruits, or controlling of weight of plant.
In another aspect, the present invention furthermore relates to method of supplying the inorganic phosphor, the composition or the formulation of the present invention to at least one portion of a plant.
In another aspect, the present invention furthermore relates to modulating a condition of a plant, a plankton, or a bacterium, comprising at least following step (C), (C) providing the optical sheet (100), between a light source and a plant, between a light source and a plankton, preferably said plankton is a phytoplankton, between a light source and a bacterium, preferably said bacterium is a photosynthetic bacterium, and/or providing the optical sheet (100), 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.
In a preferred embodiment of the present invention, the optical sheet (100) is provided directly onto a ridge in a field or onto a surface of planter.
According to the present invention, the light source is the sun or an artificial light source, preferably said artificial light source is a light emitting diode.
In another aspect, the present invention further relates to a plant, a plankton, or a bacterium obtained or obtainable by the method. Preferably said plankton is a phytoplankton, and said bacterium is a photosynthetic bacterium.
In another aspect, the present invention furthermore relates to a container comprising at least one plant, a plankton, or a bacterium obtained or obtainable by the method of the present invention. Preferably said plankton is a phytoplankton, and said bacterium is a photosynthetic bacterium.
According to the present invention, the plant can be flowers, vegetables, fruits, grasses, trees and horticultural crops (preferably flowers and horticultural crops, more preferably flowers). As one embodiment of the invention, 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 var., 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.
Preferable embodiments
1. A particle comprising an inorganic phosphor and a transparent polymer layer placed onto the outermost surface of said inorganic phosphor, preferably 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, polyethylene polyethyleneterephthalate, polyurethane, polyacrylonitrile, epoxy resin derived from glycidyl function on (meth)acrylate monomer, biodegradable polymer such as polylactide, polyglycolide, polyhydroxyalkanoate, polycaproractone.
2. The particle of embodiment 1 , wherein the polymer 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.
3. The particle of embodiment 1 or 2, wherein the polymer is derived or derivable from an acidic monomer having 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, preferably said acidic monomer is a (meth)acrylate monomer, more preferably said polymer is derived from an acidic monomer and another monomer having no anchoring group, even more preferably said polymer is derived from an acidic (meth)acrylate monomer and (meth)acrylate monomer having no ancoring group.
4. The particle of any one of embodiments 1 to 3, wherein the inorganic phosphor has a peak wavelength of light emitted from the inorganic phosphor in the range of 650 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, and / or at least one inorganic phosphor 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 nm, even more preferably in the range from 350 nm to 500 nm, furthermore preferably in the range from 400 nm to 500nm, much more preferably in the range from 420 nm to 480 nm, the most preferably in the rage from 430 nm to 460 nm, and / or at least one inorganic phosphor having a first peak wavelength of light emitted from the inorganic phosphor in the range of 500nm or less, and a second peak wavelength of light emitted from the inorganic phosphor in the range of 600 nm or more, preferably the first peak wavelength of light emitted from the inorganic phosphor is in the range from 250nm to 500nm, and the second peak light emission wavelength is in the range from 600 nm to 1500 nm, more preferably the first peak wavelength of light emitted from the inorganic phosphor is in the range from 300nm to 500nm, and the second peak light emission wavelength is in the range from 600 nm to 1000 nm, even more preferably the first peak wavelength of light emitted from the inorganic phosphor is in the range from 350nm to 500nm, and the second peak light emission wavelength is in the range from 650 nm to 800 nm, furthermore preferably the first peak wavelength of light emitted from the inorganic phosphor is in the range from 400nm to 500nm, and the second peak light emission wavelength is in the range from 650 nm to 750 nm, much more preferably the first peak wavelength of light emitted from the inorganic phosphor is in the range from 420 nm to 480 nm, and the second peak light emission wavelength is in the range from 660 nm to 740 nm, the most preferably the first peak wavelength of light emitted from the inorganic phosphor is in the rage from 430 nm to 460 nm and the second peak wavelength of light emitted from the inorganic phosphor is in the range from 660 nm to 710 nm.
5. The particle of any one of embodiments 1 to 4, wherein 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.
6. The particle of any one of embodiments 1 to 5, wherein the inorganic phosphor is represented by any one of the following formulae (I) to (XIV); A1xB1yOz:X - (I) wherein A1 is a trivalent cation and is selected from the group consisting of Y, Gd, Lu, Ce, La, Tb, Sc, and Sm, B1 is a trivalent cation and is selected from the group consisting of Al, Ga, Lu, Sc, In; x≥0; y≥1 ; 1.5(x+y) = z, X is a luminescent ion and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Nd4+, Pm3+, Sm3+, Eu3+, Eu2+, Gd3+, Tb3+, Dy2+, Dy3+, Dy4+, Ho2+, Ho3+, Er3+, Tm3+, Yb3+, Yb2+, Cr3+, Mn2+, Mn4+ and Fe3+, preferably X is selected from Ce3+, Eu3+, Eu2+, Tb3+, Cr3+, Mn2+,
Mn4+, Fe3+ or a combination of any of these, more preferably X is Ce3+, more preferably the formula is Al2O3:Cr3+ or YsAlsOiaiCr3+, even more preferably it is Al2O3:Cr3+;
A2aZbOc:X - (II) wherein A2 is a divalent cation and is selected from the group consisting of Mg, Zn, Cu, Co, Ni, Fe, Ca, Sr, Ba, Mn, Ce and Sn; Z is a trivalent cation and is selected from the group consisting of Al, Ga, Lu, Sc and In; b≥0; a≥1 ; (a+1 ,5b) = c, X is a luminescent ion and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Nd4+, Pm3+, Sm3+, Eu3+, Eu2+, Gd3+, Tb3+, Dy2+, Dy3+, Dy4+, Ho2+, Ho3+, Er3+, Tm3+, Yb3+, Yb2+, Cr3+, Mn2+, Mn4+ and Fe3+, preferably X is selected from Ce3+, Eu3+, Eu2+, Tb3+, Cr3+, Mn2+, Mn4+, Fe3+ or a combination of any of these, more preferably X is Ce3+, more preferably the formula is ZnGa2O4: Cr3+ or MgAl2O4: Cr3+, even more preferably it is MgAl2O4: Cr3+;
D1 dE1eOf:X - (III) wherein D1 is a divalent cation and is selected from one or more members of the group consisting of Mg2+, Zn2+, Cu2+, Co2+, Ni2+, Fe2+, Ca2+, Sr2+, Ba2+, Mn2+, Ce2+ and Sn2+; E1 is a trivalent cation and is selected from the group consisting of Al3+, Ga3+, Lu3+, Sc3+, La3+ and In3+; e≥10; d≥0;
(d+1 ,5e) = f, preferably D1 is Ca2+, Sr2+, Ba2+ or a combination of any of these, E1 is Al3+, Gd3+ or a combination of these, d is 1 , e is 12, f is 19, X is a luminescent ion and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Nd4+, Pm3+, Sm3+, Eu3+, Eu2+, Gd3+, Tb3+, Dy2+, Dy3+, Dy4+, Ho2+, Ho3+, Er3+, Tm3+, Yb3+, Yb2+, Cr3+, Mn2+, Mn4+ and Fe3+, preferably X is selected from Ce3+, Eu3+, Eu2+, Tb3+, Cr3+, Mn2+,
Mn4+, Fe3+ or a combination of any of these, more preferably X is Mn4+, even more preferably formula (III) is CaAl12O19:Mn4+;
D2 gE2 hOi:X - (IV) wherein D2 is a trivalent cation and is selected from one or more members of the group consisting of Al3+, Ga3+, Lu3+, Sc3+, La3+ and In3+; E2 is a trivalent cation and is selected from the group consisting of Al3+, Ga3+,
Lu3+, Sc3+, La3+ and In3+; h≥0; a≥g; (1 ,5g+1 ,5h) = I, preferably D2 is La3+, E2 is Al3+, Gd3+ or a combination of these, g is 1 , h is 12, i is 19, X is a luminescent ion and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Nd4+, Pm3+, Sm3+, Eu3+, Eu2+, Gd3+, Tb3+, Dy2+, Dy3+, Dy4+, Ho2+, Ho3+, Er3+, Tm3+, Yb3+, Yb2+, Cr3+, Mn2+, Mn4+ and Fe3+, preferably X is selected from Ce3+, Eu3+, Eu2+, Tb3+, Cr3+, Mn2+,
Mn4+, Fe3+ or a combination of any of these, more preferably X is Mn4+, even more preferably formula (IV) is LaAIO3:Mn4+;
GjJkLiOm:X - (V) wherein G is a divalent cation and is selected from one or more members of the group consisting of Mg2+, Zn2+, Cu2+, Co2+, Ni2+, Fe2+, Ca2+, Sr2+, Ba2+, Mn2+, Ce2+ and Sn2+; J is a trivalent cation and is selected from the group consisting of Y3+, Al3+, Ga3+, Lu3+, Sc3+, La3+ and In3+; L is a trivalent cation and is selected from the group consisting of Al3+, Ga3+, Lu3+, Sc3+, La3+ and In3+; l≥0; k≥0; j≥0; (j+1.5k+1.5l) = m, preferably G is selected from Ca2+, Sr2+, Ba2+ or a combination of any of these; J is Y3+, Lu3+ or a combination of these; L is Al3+, Gd3+ or a combination of these; j is 1 , k is 1 , 1 is 1 , m is 4; X is a luminescent ion and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Nd4+, Pm3+, Sm3+, Eu3+, Eu2+, Gd3+, Tb3+, Dy2+, Dy3+, Dy4+, Ho2+, Ho3+, Er3+, Tm3+, Yb3+, Yb2+, Cr3+, Mn2+, Mn4+ and Fe3+, preferably X is selected from Ce3+, Eu3+, Eu2+, Tb3+, Cr3+, Mn2+, Mn4+, Fe3+ or a combination of any of these, more preferably X is Mn4+; even more preferably it is CaYAlO:Mn4+; and
A3aOz:X - (VI) wherein A3 is a trivalent cation and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Tb3+, Dy3+, Ti3+, V3+, Cr3+, Mn3+, Fe3+, Co3+, Ni3+, Zr3+, Nb3+, Mo3+, Tc3+, Ru3+, Rh3+, Pd3+, Hf3+, Ta3+, W3+, Re3+, Os3+, Ir3+, Pt3+, Si3+, Ge3+, Sn3+, Pb3+, S3+, Se3+, Te3+ and Po3+;
X is a luminescent ion and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Nd4+, Pm3+, Sm3+, Eu3+, Eu2+, Gd3+, Tb3+, Dy2+, Dy3+, Dy4+, Ho2+, Ho3+, Er3+, Tm3+, Yb3+, Yb2+, Cr3+, Mn2+, Mn4+ and Fe3+; a≥0; z≥0; 2a = z; preferably, A3 is Ce3+, Ti3+, Zr3+, Hf3+, Si3+, Ge3+, Sn3+, or a combination of any of these;
X is selected from Ce3+, Eu3+, Eu2+, Tb3+, Cr3+, Mn2+, Mn4+, Fe3+ or a combination of any of these, more preferably X is Ce3+; a is 1 , z is 2; more preferably the formula is ZrO2:Ce3+
A4aB2bC1cOz:X - (VII) wherein
A4 is a monovalent cation and is selected from one or more members of the group consisting of Li+, Na+, K+, Rb+, Cs+, V+, Cr+, Mn+, Co+, Ni+, Cu+, Pd+. Ag+. Au+ and TI+;
B2 is a tetravalent cation and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Tb3+, Dy3+, Ti3+, V3+, Cr3+, Mn3+, Fe3+, Co3+, Ni3+, Zr3+, Nb3+, Mo3+, Tc3+, Ru3+, Rh3+, Pd3+, Hf3+, Ta3+, W3+, Re3+, Os3+, Ir3+, Pt3+, Si3+, Ge3+, Sn3+, Pb3+, S3+, Se3+, Te3+ and Po3+;
C1 is a tetravalent cation and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Tb3+, Dy3+, Ti3+, V3+, Cr3+, Mn3+, Fe3+, Co3+, Ni3+, Zr3+, Nb3+, Mo3+, Tc3+, Ru3+, Rh3+, Pd3+, Hf3+, Ta3+, W3+, Re3+, Os3+, Ir3+, Pt3+, Si3+, Ge3+, Sn3+, Pb3+, S3+, Se3+, Te3+ and Po3+;
X is a luminescent ion and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Nd4+, Pm3+, Sm3+, Eu3+, Eu2+, Gd3+, Tb3+, Dy2+, Dy3+, Dy4+, Ho2+, Ho3+, Er3+, Tm3+, Yb3+, Yb2+, Cr3+, Mn2+, Mn4+ and Fe3+; a≥0; b≥0; c≥0; z≥0; (0.5a+2b+2c) = z; preferably A4 is Li+, Na+, K+, Rb+, Cs+ or a combination of any of these,
B2 is Ce3+, Ti3+, Zr3+, Hf3+, Si3+, Ge3+, Sn3+, or a combination of any of these,
C1 is Ce3+, Ti3+, Zr3+, Hf3+, Si3+, Ge3+, Sn3+, or a combination of any of these;
X is Ce3+, Eu3+, Eu2+, Tb3+, Cr3+, Mn2+, Mn4+ and Fe3+, or a combination of any of these, more preferably X is Eu2+; a is 2, b is 1 , c is 2, z is 7; more preferably, formula isK2ZrSi20?:Eu2+;
A5aB3bC2cD3dOz:X - (VIII) wherein
A5 is a divalent cation and is selected from one or more members of the group consisting of Mg2+, Ca2+, Sr2+, Ba2+, Nd2+, Sm2+, Eu2+, Dy2+, Ho2+, Tm2+, Yb2+, Ti2+, V2+, Cr2+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Mo2+, Pd2+, Ag2+, W2+, Pt2+, Zn2+, Cd2+, Hg2+, Ge2+, Sn2+ and Pb2+;
B3 is a trivalent cation and is selected from one or more members of the group consisting of Sc3+, Y3+, La3+, Ce3+, Pr3+, Nd3+, Pm3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+, Ti3+, V3+, Cr3+, Mn3+, Fe3+, Co3+, Ni3+, Cu3+, Nb3+, Mo3+, Ru3+, Rh3+, Pd3+, Ag3+, Ta3+, W3+, Ir3+, Au3+, B3+, Al3+, Ga3+, In3+, TI3+, P3+, As3+, Sb3+ and Bi3+; C2 is a tetravalent cation and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Tb3+, Dy3+, Ti3+, V3+, Cr3+, Mn3+, Fe3+, Co3+, Ni3+, Zr3+, Nb3+, Mo3+, Tc3+, Ru3+, Rh3+, Pd3+, Hf3+, Ta3+, W3+, Re3+, Os3+, Ir3+, Pt3+, Si3+, Ge3+, Sn3+, Pb3+, S3+, Se3+, Te3+ and Po3+;
D3 is a trivalent cation and is selected from one or more members of the group consisting of Sc3+, Y3+, La3+, Ce3+, Pr3+, Nd3+, Pm3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+, Ti3+, V3+, Cr3+, Mn3+, Fe3+, Co3+, Ni3+, Cu3+, Nb3+, Mo3+, Ru3+, Rh3+, Pd3+, Ag3+, Ta3+, W3+, Ir3+, Au3+, B3+, Al3+, Ga3+, In3+, TI3+, P3+, As3+, Sb3+ and Bi3+;
X is a luminescent ion and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Nd4+, Pm3+, Sm3+, Eu3+, Eu2+, Gd3+, Tb3+, Dy2+, Dy3+, Dy4+, Ho2+, Ho3+, Er3+, Tm3+, Yb3+, Yb2+, Cr3+, Mn2+, Mn4+ and Fe3+; a≥0; b≥0; c≥0; d≥0; z≥0; (a+1 ,5b+2c+1 ,5d) = z; preferably A5 is Mg2+, Ca2+, Sr2+, Ba2+ and Zn2+, or a combination of any of these;
B3 is Sc3+, Y3+, La3+, Lu3+, B3+, Al3+, Ga3+, In3+, P3+, Bi3+, or a combination of any of these;
C2 is Ce3+, Ti3+, Zr3+, Hf3+, Si3+, Ge3+, Sn3+, or a combination of any of these;
D3 is Sc3+, Y3+, La3+, Lu3+, B3+, Al3+, Ga3+, In3+, P3+, Bi3+, or a combination of any of these;
X is Ce3+, Eu3+, Eu2+, Tb3+, Cr3+, Mn2+, Mn4+ and Fe3+, or a combination of any of these; a is 2, b is 1 , c is 2, d is 3, z is 12; more preferably the formula is Ca2YZr2Al3O12:Ce3+
A6aB4bOz:X -(IX) wherein
A® is a trivalent cation and is selected from one or more members of the group consisting of Sc3+, Y3+, La3+, Ce3+, Pr3+, Nd3+, Pm3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+, Ti3+, V3+, Cr3+, Mn3+, Fe3+, Co3+, Ni3+, Cu3+, Nb3+, Mo3+, Ru3+, Rh3+, Pd3+, Ag3+, Ta3+, W3+, Ir3+, Au3+, B3+, Al3+, Ga3+, ln3+, Tl3+, P3+, As3+, Sb3+ and Bi3+;
B4 is a trivalent cation and is selected from one or more members of the group consisting of Sc3+, Y3+, La3+, Ce3+, Pr3+, Nd3+, Pm3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+, Ti3+, V3+, Cr3+, Mn3+, Fe3+, Co3+, Ni3+, Cu3+, Nb3+, Mo3+, Ru3+, Rh3+, Pd3+, Ag3+, Ta3+, W3+, Ir3+, Au3+, B3+, Al3+, Ga3+, In3+, TI3+, P3+, As3+, Sb3+ and Bi3+;
X is a luminescent ion and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Nd4+, Pm3+, Sm3+, Eu3+, Eu2+, Gd3+, Tb3+, Dy2+, Dy3+, Dy4+, Ho2+, Ho3+, Er3+, Tm3+, Yb3+, Yb2+, Cr3+, Mn2+, Mn4+ and Fe3+; a≥0; b≥0; z≥0; (1.5a+1.5b) = z; preferably A® is Sc3+, Y3+, La3+, Lu3+, B3+, Al3+, Ga3+, In3+, P3+, Bi3+, or a combination of any of these;
B4 is Sc3+, Y3+, La3+, Lu3+, B3+, Al3+, Ga3+, In3+, P3+, Bi3+, or a combination of any of these;
X is Ce3+, Eu3+, Eu2+, Tb3+, Cr3+, Mn2+, Mn4+ and Fe3+, or a combination of any of these, more preferably X is Ce3+; a is 3, b is 5, z is 12; more preferably the formula is YsAlsO-iaiCe3+;
A7aB5bC3cOz:X -(X) wherein
A7 is a trivalent cation and is selected from one or more members of the group consisting of Sc3+, Y3+, La3+, Ce3+, Pr3+, Nd3+, Pm3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+, Ti3+, V3+, Cr3+, Mn3+, Fe3+, Co3+, Ni3+, Cu3+, Nb3+, Mo3+, Ru3+, Rh3+, Pd3+, Ag3+, Ta3+, W3+, Ir3+, Au3+, B3+, Al3+, Ga3+, In3+, TI3+, P3+, As3+, Sb3+ and Bi3+;
B5 is a trivalent cation and is selected from one or more members of the group consisting of Sc3+, Y3+, La3+, Ce3+, Pr3+, Nd3+, Pm3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+, Ti3+, V3+, Cr3+, Mn3+, Fe3+, Co3+, Ni3+, Cu3+, Nb3+, Mo3+, Ru3+, Rh3+, Pd3+, Ag3+, Ta3+, W3+, Ir3+, Au3+, B3+, Al3+, Ga3+, In3+, TI3+, P3+, As3+, Sb3+ and Bi3+; C3 is a trivalent cation and is selected from one or more members of the group consisting of Sc3+, Y3+, La3+, Ce3+, Pr3+, Nd3+, Pm3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+, Ti3+, V3+, Cr3+, Mn3+, Fe3+, Co3+, Ni3+;
X is a luminescent ion and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Nd4+, Pm3+, Sm3+, Eu3+, Eu2+, Gd3+, Tb3+, Dy2+, Dy3+, Dy4+, Ho2+, Ho3+, Er3+, Tm3+, Yb3+, Yb2+, Cr3+, Mn2+, Mn4+ and Fe3+; a≥0; b≥0; c≥0; z≥0 (1.5a+1.5b+1.5c) = z; preferably A7 is Sc3+, Y3+, La3+, Lu3+, B3+, Al3+, Ga3+, In3+, P3+, Bi3+, or a combination of any of these;
B5 is Sc3+, Y3+, La3+, Lu3+, B3+, Al3+, Ga3+, In3+, P3+, Bi3+, or a combination of any of these;
C3 is Sc3+, Y3+, La3+, Lu3+, B3+, Al3+, Ga3+, In3+, P3+, Bi3+, or a combination of any of these;
X is Ce3+, Eu3+, Eu2+, Tb3+, Cr3+, Mn2+, Mn4+ and Fe3+, or a combination of any of these, more preferably X is Ce3+; a is 3, b is 2, c is 3, z is 12; more preferably, formula is YsGazAlsO-iaiCe3+;
A8aBebOz:X -(XI) wherein
A8 is a monovalent cation and is selected from one or more members of the group consisting of Li+, Na+, K+, Rb+, Cs+, V+, Cr+, Mn+, Co+, Ni+, Cu+, Pd+, Ag+. Au+ and TI+;
B8 is a trivalent cation and is selected from one or more members of the group consisting of Sc3+, Y3+, La3+, Ce3+, Pr3+, Nd3+, Pm3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+, Ti3+, V3+, Cr3+, Mn3+, Fe3+, Co3+, Ni3+, Cu3+, Nb3+, Mo3+, Ru3+, Rh3+, Pd3+, Ag3+, Ta3+, W3+, Ir3+, Au3+, B3+, Al3+, Ga3+, In3+, TI3+, P3+, As3+, Sb3+ and Bi3+;
X is a luminescent ion and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Nd4+, Pm3+, Sm3+, Eu3+, Eu2+, Gd3+, Tb3+, Dy2+, Dy3+, Dy4+, Ho2+, Ho3+, Er3+, Tm3+, Yb3+, Yb2+, Cr3+, Mn2+, Mn4+ and Fe3+; a≥0; b≥0; z≥0 (0.5a+1.5b) = z; preferably A8 is Li+, Na+, K+, Rb+, Cs+ or a combination of any of these,
B6 is Sc3+, Y3+, La3+, Lu3+, B3+, Al3+, Ga3+, In3+, P3+, Bi3+, or a combination of any of these;
X is Ce3+, Eu3+, Eu2+, Tb3+, Cr3+, Mn2+, Mn4+ and Fe3+, or a combination of any of these, more preferably X is Mn4+; a is 1 , b is 5, z is 8; more preferably the formula is LiAlsOsiMn4+;
A9aB7bOz:X -(XII) wherein
A9 is a divalent cation and is selected from one or more members of the group consisting of Mg2+, Ca2+, Sr2+, Ba2+, Nd2+, Sm2+, Eu2+, Dy2+, Ho2+, Tm2+, Yb2+, Ti2+, V2+, Cr2+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Mo2+, Pd2+, Ag2+, W2+, Pt2+, Zn2+, Cd2+, Hg2+, Ge2+, Sn2+ and Pb2+;
B7 is a tetravalent cation and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Tb3+, Dy3+, Ti3+, V3+, Cr3+, Mn3+, Fe3+, Co3+, Ni3+, Zr3+, Nb3+, Mo3+, Tc3+, Ru3+, Rh3+, Pd3+, Hf3+, Ta3+, W3+, Re3+, Os3+, Ir3+, Pt3+, Si3+, Ge3+, Sn3+, Pb3+, S3+, Se3+, Te3+ and Po3+;
X is a luminescent ion and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Nd4+, Pm3+, Sm3+, Eu3+, Eu2+, Gd3+, Tb3+, Dy2+, Dy3+, Dy4+, Ho2+, Ho3+, Er3+, Tm3+, Yb3+, Yb2+, Cr3+, Mn2+, Mn4+ and Fe3+; a≥0; b≥0; z≥0 (a+2b) = z; preferably, A9 is Mg2+, Ca2+, Sr2+, Ba2+ and Zn2+, or a combination of any of these;
B7 is Ce3+, Ti3+, Zr3+, Hf3+, Si3+, Ge3+, Sn3+, or a combination of any of these;
X is Ce3+, Eu3+, Eu2+, Tb3+, Cr3+, Mn2+, Mn4+ and Fe3+, or a combination of any of these, more preferably X is Mn4+, a is 1 , b is 1 , z is 3, more preferably the formula is CaZrOsiMn4+ A10aB8bC4cOz:X -(Xlll) wherein
A10 is a monovalent cation and is selected from one or more members of the group consisting of Li+, Na+, K+, Rb+, Cs+, V+, Cr+, Mn+, Co+, Ni+, Cu+, Pd+. Ag+. Au+ and Tl+;
B8 is a divalent cation and is selected from one or more members of the group consisting of Mg2+, Ca2+, Sr2+, Ba2+, Nd2+, Sm2+, Eu2+, Dy2+, Ho2+, Tm2+, Yb2+, Ti2+, V2+, Cr2+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Mo2+, Pd2+, Ag2+, W2+, Pt2+, Zn2+, Cd2+, Hg2+, Ge2+, Sn2+ and Pb2+;
C4 is a tetravalent cation and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Tb3+, Dy3+, Ti3+, V3+, Cr3+, Mn3+, Fe3+, Co3+, Ni3+, Zr3+, Nb3+, Mo3+, Tc3+, Ru3+, Rh3+, Pd3+, Hf3+, Ta3+, W3+, Re3+, Os3+, Ir3+, Pt3+, Si3+, Ge3+, Sn3+, Pb3+, S3+, Se3+, Te3+ and Po3+;
X is a luminescent ion and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Nd4+, Pm3+, Sm3+, Eu3+, Eu2+, Gd3+, Tb3+, Dy2+, Dy3+, Dy4+, Ho2+, Ho3+, Er3+, Tm3+, Yb3+, Yb2+, Cr3+, Mn2+, Mn4+ and Fe3+; a≥0; b≥0; c≥0; z≥0 (0.5a+b+2c) = z; preferably A10 is Li+, Na+, K+, Rb+, Cs+ or a combination of any of these,
B9 is Sc2+, Y2+, La2+, Lu2+, B2+, Al2+, Ga2+, In2+, P2+, Bi2+, or a combination of any of these;
C5 is Ce3+, Ti3+, Zr3+, Hf3+, Si3+, Ge3+, Sn3+, or a combination of any of these;
X is Ce3+, Eu3+, Eu2+, Tb3+, Cr3+, Mn2+, Mn4+ and Fe3+, or a combination of any of these, more preferably X is Mn4+; a is 2, b is 1 , c is 1 , z is 4; more preferably, formula is LhMgZrO^Mn4+;
A11aB9bC5cOz:X -(XIV) wherein
A11 is a divalent cation and is selected from one or more members of the group consisting of Mg2+, Ca2+, Sr2+, Ba2+, Nd2+, Sm2+, Eu2+, Dy2+, Ho2+, Tm2+, Yb2+, Ti2+, V2+, Cr2+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Mo2+, Pd2+, Ag2+, W2+, Ft2+, Zn2+, Cd2+, Hg2+, Ge2+, Sn2+ and Pb2+;
B9 is a divalent cation and is selected from one or more members of the group consisting of Mg2+, Ca2+, Sr2+, Ba2+, Nd2+, Sm2+, Eu2+, Dy2+, Ho2+, Tm2+, Yb2+, Ti2+, V2+, Cr2+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Mo2+, Pd2+, Ag2+, W2+, Pt2+, Zn2+, Cd2+, Hg2+, Ge2+, Sn2+ and Pb2+;
C5 is a trivalent cation and is selected from one or more members of the group consisting of Sc3+, Y3+, La3+, Ce3+, Pr3+, Nd3+, Pm3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+, Ti3+, V3+, Cr3+, Mn3+, Fe3+, Co3+, Ni3+, Cu3+, Nb3+, Mo3+, Ru3+, Rh3+, Pd3+, Ag3+, Ta3+, W3+, Ir3+, Au3+, B3+, Al3+, Ga3+, In3+, TI3+, P3+, As3+, Sb3+ and Bi3+;
X is a luminescent ion and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Nd4+, Pm3+, Sm3+, Eu3+, Eu2+, Gd3+, Tb3+, Dy2+, Dy3+, Dy4+, Ho2+, Ho3+, Er3+, Tm3+, Yb3+, Yb2+, Cr3+, Mn2+, Mn4+ and Fe3+; a≥0; b≥0; c≥0; z≥0 (0.5a+b+2c) = z; preferably A11 is Mg2+, Ca2+, Sr2+, Ba2+ and Zn2+, or a combination of any of these;
B9 is Mg2+, Ca2+, Sr2+, Ba2+ and Zn2+, or a combination of any of these;
C5 is Sc3+, Y3+, La3+, Lu3+, B3+, Al3+, Ga3+, In3+, P3+, Bi3+, or a combination of any of these;
X is Ce3+, Eu3+, Eu2+, Tb3+, Cr3+, Mn2+, Mn4+ and Fe3+, or a combination of any of these, more preferably X is Mn4+; even more preferably the formula is CaMgAl16O27:Mn4+, Ca2Mg2Al28O36:Mn4+, Sr2MgAl22O36:Mn4+ or BaMgAl10-iyiMn4+, preferably the inorganic phosphor is selected from one or more of members of the group consisting of
Figure imgf000076_0001
Figure imgf000076_0002
Figure imgf000077_0001
7. Use of the particle of any one of embodiments 1 to 6 for agriculture.
8. A composition comprising at least one particle of any one of embodiments 1 to 6, and another material.
9. The composition of embodiment 8, wherein said another material is 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 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.
10. The composition of embodiment 8 or 9, the total amount of the particle of the composition is in the range from 0.01 wt.% to 30wt.% based on the total amount of the composition, preferably it is from 0.1 wt.% to 10wt.%, more preferably from 0.5wt.% to 5wt.%, furthermore preferably it is from 1wt.% to 3wt.%.
11. The composition according to any one of embodiments 8 to 10, wherein 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. 12. A formulation comprising at least one particle of any one of embodiments 18 to 20, or the composition of any one of embodiments 23 to 26, and a solvent.
13. Use of the particle of any one of embodiments 1 to 6, the composition of any one of embodiments 8 to 11 , or the formulation of embodiment 12, in an optical sheet fabrication process or in agriculture, preferably for fabricating an agricultural sheet or for controlling a condition of a living organism.
14. An optical sheet (100) comprising at least one particle of any one of embodiments 1 to 6, or the composition of any one of embodiments 8 to 11 , preferably said optical sheet is an agricultural sheet.
15. An optical device (200) comprising at least one optical sheet (100) of embodiment 14, preferably said optical device is a lighting device, more preferably it is a light emitting diode device.
16. A greenhouse comprising the optical sheet (100) of embodiment 14.
17. Use of the optical sheet (100) of embodiment 14 or the optical device (200) of embodiment 15 for agriculture, preferably for greenhouse or for controlling a condition of a living organism in agriculture.
18. Method for preparing the optical sheet (100), preferably for preparing the agriculture sheet, wherein the method comprises following steps (a) and (b),
(a) providing the composition according to any one of embodiments 8 to 11 , or the formulation according to embodiment 12 in a first shaping, preferably providing the composition onto a substrate or into an inflation moulding machine, and
(b) fixing the matrix material by evaporating a solvent and / or polymerizing the composition by heat treatment, or exposing the photosensitive composition under ray of light or a combination of any of these.
19. Method for preparing the agriculture sheet, wherein the method comprises following steps (a') and (b'),
(a') providing the composition comprising a particle comprising an inorganic phosphor and a coating layer onto the outermost surface of the inorganic phosphor, and another material, or the formulation comprising said composition and a solvent in a first shaping, preferably providing the composition into an inflation moulding machine, and
(b') fixing the matrix material by evaporating a solvent and / or polymerizing the composition by heat treatment, or exposing the photosensitive composition under ray of light or a combination of any of these, preferably said coating layer is a transparent polymer layer or a metal oxide coating layer, more preferably said particle is the one according to any one of embodiments 1 to 6 or a particle comprising an inorganic phosphor coated by a metal oxide coating layer selected from one or more members of the group consisting of SiOa, TiOa, ZnOa, ZrOa and AI2O3, more preferably it is selected from SiOa, TiOa, ZnOaor a combination of any of these, preferably said inorganic phosphor is the inorganic phosphor as described in the section of “Inorganic phosphor” above. 20. Use of a particle of metal oxide coated inorganic phosphor comprising an inorganic phosphor and at least one metal oxide coating layer onto the outermost surface of said phosphor, for agriculture, preferably said metal oxide coating layer is selected from one or more members of the group consisting of S1O2, T1O2, ZnOa, ZrOa and AI2O3, more preferably it is selected from T1O2, ZnOaor a combination of S1O2, T1O2 and Zn02, preferably for greenhouse or for controlling a condition of a living organism in agriculture, preferably said inorganic phosphor is the inorganic phosphor as described in the section of “Inorganic phosphor” above.
21. Method for preparing the optical device (200) of embodiment 15, comprising following step (A); (A) providing the optical sheet (100) of embodiment 14, in an optical device (200).
22. Use of the particle of any one of embodiments 1 to 6, the composition of any one of embodiments 8 to 11 , the formulation of embodiment 12, the optical sheet (100) of embodiment 14, the optical device (200) of embodiment 20 or the green house of embodiment 21 for cultivation of algae, bacteria, preferably said bacteria are photosynthetic bacteria, and/or planktons, 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 / 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 ripening of fruits, or controlling of weight of plant.
23. Method of supplying the particle of any one of embodiments 1 to 6, or composition of any one of claims 8 to 11 , or the formulation of embodiment 12 to at least one portion of a plant.
24. Method for modulating a condition of a plant, plankton, and/or a bacterium, comprising at least following step (C),
(C) providing the optical sheet (100) of embodiment 14, between a light source and a plant, between a light source and a plankton, preferably said plankton is a phytoplankton, between a light source and a bacterium, preferably said bacterium is a photosynthetic bacterium, or providing the optical sheet (100) of embodiment 14 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.
25. Method of embodiment 24, wherein the light source is the sun or an artificial light source, preferably said artificial light source is a light emitting diode.
26. A plant obtained or obtainable by the method of any one of embodiments 23 to 25, or a plankton obtained or obtainable by the method of embodiment 24 or 25, or a bacterium obtained or obtainable by the method of embodiment 24 or 25.
27. A container comprising at least one plant, one plankton, and/or a bacterium of embodiment 26.
Technical effects
The present invention provides one or more of following effects; improved transparency of a film, preferably improved transparency of an agricultural film, avoiding or reducing a scratch of an inflation molding machine caused by an inorganic phosphor, avoiding or reducing a situation that an optical sheet comprising an inorganic phosphor is contaminated with a dust from an inflation molding machine, improved long term moisture durability, improved water resistance, a water free coating process to avoid any damage to a phosphor during the coating process, an inorganic phosphor having a coating layer with higher EQE, improved and well controlled average particle size, improved optical properties such as light scattering, absorbing, refraction and/or reflection ability of inorganic phosphors, improved dispersibility of inorganic phosphors in a formulation, composition and/or in a matrix material of a film, better compatibility of an inorganic phosphor with a matrix material, 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 / 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 ripening of fruits, or controlling of weight of plant.
The working examples below provide descriptions of the present inventions but not intended to limit scopes of the inventions.
Workina Examples
Synthesis example: Synthesis of Al2O3:Cr3+ phosphors
The phosphor precursors of Al2O3:Cr3+ phosphors are synthesized by a conventional co-precipitation method. The raw materials of Aluminium Nitrate Nonahydrate and Chromium(lll) nitrate nonahydrate are dissolved in deionized water with a stoichiometric molar ratio of 0.99:0.01. NH4HCO3 is added to the mixed chloride solution as a precipitant, and the mixture is stirred at 60 °C for 2h. The resultant solution is dried at 95 °C for 12 h, then the preparation of the precursors is completed. The obtained precursors are oxidized by calcination at 1300 °C for 3 h in air. To confirm the structure of the resultant materials, XRD measurements are performed using an X-ray diffractometer (RIGAKU RAD-RC). Photoluminescence (PL) spectra are measured using a spectrofluorometer (JASCO FP-6500) at room temperature.
The absorption peak wavelength of Al2O3:Cr3+ is 420 nm and 560 nm, the emission peak wavelength is in the range from 690 nm to 698 nm, the full width at half maximum (hereafter “FWHM”) of the light emission from Al2O3:Cr3+ is in the range from 90 nm to 120 nm.
Working Example 1 : Polymer coating to Al^OaiCr3+ phosphor
The formation of the polymer layer on the phosphor surface is carried out in a reactor. Al2O3:Cr3+ dispersed in water and 3- Methacryloxypropyltrimethoxysilane (MPTMS) dispersed in ethanol are charged into the reactor; the resulting mixed solution is stirred for 2 hours at 35°C. After heating the reactor up to 70°C, methyl methacrylate, Monomer (MMA) is charged into the reactor. Afterwards, it is deoxygenated by bubbling with nitrogen by stirring for 15 minutes. The polymerization is initiated by injection of Potassium peroxydisulfate (KPS) dissolved in water; it continued for 3 hours. After polymerization, the mixed solution is filtered and vacuum dried to obtain the Al2O3:Cr3+ PMMA powder. The formation of the polymer layer on the phosphor surface is confirmed from the result of SEM imaging and elemental mapping of EDS.
Working Example 2: Foil fabrication
The creation of the foil containing Al2O3:Cr3+ is carried out by the extrusion inflation method. First, the phosphor master batch is prepared by mixing polymer-coated Al2O3:Cr3+ at high concentration with 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 went through bulges like a balloon by enclosed air. Then it is cooled by cooling air, which flowed 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 shows the materials used in the foil fabrication.
Table 1 - materials used in the foil fabrication
Figure imgf000084_0001
Comparative Example: Foil fabrication
A foil is fabricated in the same manner as described in working example 2 except for Al2O3:Cr3+ without polymer coating layer is used instead of the polymer coated Al2O3:Cr3+ of working example 1.
Workina Example 3: Transmittance test
The foils produced are measured by the UV-2550 spectrometer created by Shimazu. The transmittance of the foil with the polymer-coated Al2O3:Cr3+ is confirmed to have an improvement of approximately 25% as compared to the foil with the non-polymer-coated Al2O3:Cr3+. This result may be attributed to the fact that when the phosphors are mixed in the inflation molding machine, the polymer-coated Al2O3:Cr3+ does not leave scratches that generate contamination in the machine. Accordingly, it is seen that the transmittance of the foil produced by this method for the present invention are effectively applicable in the agricultural field.
Working Example 4: Polymer coating to Mg2TiO4:M n4+ phosphor
The formation of the polymer layer on the phosphor surface is carried out in a reactor. Mg2Ti04:Mn4+ dispersed in water and 3- Methacryloxypropyltrimethoxysilane (MPTMS) dispersed in ethanol are charged into the reactor; the resulting mixed solution is stirred for 2 hours at 35°C. After heating the reactor up to 70°C, methyl methacrylate, Monomer (MMA) is charged into the reactor. Afterwards, it is deoxygenated by bubbling with nitrogen by stirring for 15 minutes. The polymerization is initiated by injection of Potassium peroxydisulfate (KPS) dissolved in water; it continued for 3 hours. After polymerization, the mixed solution is filtered and vacuum dried to obtain the Mg2Ti04:Mn47PMMA powder. The formation of the polymer layer on the phosphor surface is confirmed from the result of SEM imaging and elemental mapping of EDS.
Workina Example 5: Water resistance test Mg2Ti04:Mn4+ phosphors are used as a comparative example.
-Test results-
To investigate their water resistance, the produced phosphors are stirred in 50°C water for 24 hours. The emission intensity of the polymer-coated Mg2Ti04:Mn4+ is confirmed to have an improvement of approximately 30% as compared to the non-polymer-coated Mg2Ti04:Mn4+.This approach is applicable on the technique of placing a phosphor on leaves and promoting plant growth. Accordingly, it is observed that the high durable phosphor produced by the method according to the present invention is effectively applicable to the agricultural field.

Claims

Patent Claims
1. A particle comprising an inorganic phosphor and a transparent polymer layer placed onto the outermost surface of said inorganic phosphor, preferably 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, polyethylene polyethyleneterephthalate, polyurethane, polyacrylonitrile, epoxy resin derived from glycidyl function on (meth)acrylate monomer, biodegradable polymer such as polylactide, polyglycolide, polyhydroxyalkanoate, polycaproractone.
2. The particle of claim 1 , wherein the polymer 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.
3. The particle of claim 1 or 2, wherein the polymer is derived or derivable from an acidic monomer having 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, preferably said acidic monomer is a (meth)acrylate monomer, more preferably said polymer is derived from an acidic monomer and another monomer having no anchoring group, even more preferably said polymer is derived from an acidic (meth)acrylate monomer and (meth)acrylate monomer having no anchoring group.
4. The particle of any one of claims 1 to 3, wherein the inorganic phosphor has a peak wavelength of light emitted from the inorganic phosphor in the range of 650 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, and / or at least one inorganic phosphor 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 nm, even more preferably in the range from 350 nm to 500 nm, furthermore preferably in the range from 400 nm to 500nm, much more preferably in the range from 420 nm to 480 nm, the most preferably in the rage from 430 nm to 460 nm, and / or at least one inorganic phosphor having a first peak wavelength of light emitted from the inorganic phosphor in the range of 500nm or less, and a second peak wavelength of light emitted from the inorganic phosphor in the range of 600 nm or more, preferably the first peak wavelength of light emitted from the inorganic phosphor is in the range from 250nm to 500nm, and the second peak light emission wavelength is in the range from 600 nm to 1500 nm, more preferably the first peak wavelength of light emitted from the inorganic phosphor is in the range from 300nm to 500nm, and the second peak light emission wavelength is in the range from 600 nm to 1000 nm, even more preferably the first peak wavelength of light emitted from the inorganic phosphor is in the range from 350nm to 500nm, and the second peak light emission wavelength is in the range from 650 nm to 800 nm, furthermore preferably the first peak wavelength of light emitted from the inorganic phosphor is in the range from 400nm to 500nm, and the second peak light emission wavelength is in the range from 650 nm to 750 nm, much more preferably the first peak wavelength of light emitted from the inorganic phosphor is in the range from 420 nm to 480 nm, and the second peak light emission wavelength is in the range from 660 nm to 740 nm, the most preferably the first peak wavelength of light emitted from the inorganic phosphor is in the rage from 430 nm to 460 nm and the second peak wavelength of light emitted from the inorganic phosphor is in the range from 660 nm to 710 nm.
5. The particle of any one of claims 1 to 4, wherein 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.
6. The particle of any one of claims 1 to 5, wherein the inorganic phosphor is represented by any one of the following formulae (I) to (XIV);
A1xB1yOz:X - (I) wherein A1 is a trivalent cation and is selected from the group consisting of Y, Gd, Lu, Ce, La, Tb, Sc, and Sm, B1 is a trivalent cation and is selected from the group consisting of Al, Ga, Lu, Sc, In; x≥0; y≥1 ; 1.5(x+y) = z, X is a luminescent ion and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Nd4+, Pm3+, Sm3+, Eu3+, Eu2+, Gd3+, Tb3+, Dy2+, Dy3+, Dy4+, Ho2+, Ho3+, Er3+, Tm3+, Yb3+, Yb2+, Cr3+, Mn2+, Mn4+ and Fe3+, preferably X is selected from Ce3+, Eu3+, Eu2+, Tb3+, Cr3+, Mn2+,
Mn4+, Fe3+ or a combination of any of these, more preferably X is Ce3+, more preferably the formula is Al2O3:Cr3+ or Y3AlsO12:Cr3+, even more preferably it is Al2O3:Cr3+;
A2aZbOc:X - (II) wherein A2 is a divalent cation and is selected from the group consisting of Mg, Zn, Cu, Co, Ni, Fe, Ca, Sr, Ba, Mn, Ce and Sn; Z is a trivalent cation and is selected from the group consisting of Al, Ga, Lu, Sc and In; b≥0; a≥1 ; (a+1 ,5b) = c, X is a luminescent ion and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Nd4+, Pm3+, Sm3+, Eu3+, Eu2+, Gd3+, Tb3+, Dy2+, Dy3+, Dy4+, Ho2+, Ho3+, Er3+, Tm3+, Yb3+, Yb2+, Cr3+, Mn2+, Mn4+ and Fe3+, preferably X is selected from Ce3+, Eu3+, Eu2+, Tb3+, Cr3+, Mn2+, Mn4+, Fe3+ or a combination of any of these, more preferably X is Ce3+, more preferably the formula is ZnGa2O4: Cr3+ or MgAl2O4 Cr3+, even more preferably it is MgAl2O4 Cr3+; D1 dE1eOf:X - (III) wherein D1 is a divalent cation and is selected from one or more members of the group consisting of Mg2+, Zn2+, Cu2+, Co2+, Ni2+, Fe2+, Ca2+, Sr2+, Ba2+, Mn2+, Ce2+ and Sn2+; E1 is a trivalent cation and is selected from the group consisting of Al3+, Ga3+, Lu3+, Sc3+, La3+ and In3+; e≥10; d≥0;
(d+1 ,5e) = f, preferably D1 is Ca2+, Sr2+, Ba2+ or a combination of any of these, E1 is Al3+, Gd3+ or a combination of these, d is 1 , e is 12, f is 19, X is a luminescent ion and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Nd4+, Pm3+, Sm3+, Eu3+, Eu2+, Gd3+, Tb3+, Dy2+, Dy3+, Dy4+, Ho2+, Ho3+, Er3+, Tm3+, Yb3+, Yb2+, Cr3+, Mn2+, Mn4+ and Fe3+, preferably X is selected from Ce3+, Eu3+, Eu2+, Tb3+, Cr3+, Mn2+,
Mn4+, Fe3+ or a combination of any of these, more preferably X is Mn4+, even more preferably formula (III) is CaAl12O19:Mn4+; D2 gE2 hOi:X - (IV) wherein D2 is a trivalent cation and is selected from one or more members of the group consisting of Al3+, Ga3+, Lu3+, Sc3+, La3+ and In3+; E2 is a trivalent cation and is selected from the group consisting of Al3+, Ga3+,
Lu3+, Sc3+, La3+ and In3+; h≥0; a≥g; (1 ,5g+1 ,5h) = I, preferably D2 is La3+, E2 is Al3+, Gd3+ or a combination of these, g is 1 , h is 12, i is 19, X is a luminescent ion and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Nd4+, Pm3+, Sm3+, Eu3+, Eu2+, Gd3+, Tb3+, Dy2+, Dy3+, Dy4+, Ho2+, Ho3+, Er3+, Tm3+, Yb3+, Yb2+, Cr3+, Mn2+, Mn4+ and Fe3+, preferably X is selected from Ce3+, Eu3+, Eu2+, Tb3+, Cr3+, Mn2+, Mn4+, Fe3+ or a combination of any of these, more preferably X is Mn4+, even more preferably formula (IV) is LaAIO3:Mn4+;
Figure imgf000091_0001
wherein G is a divalent cation and is selected from one or more members of the group consisting of Mg2+, Zn2+, Cu2+, Co2+, Ni2+, Fe2+, Ca2+, Sr2+, Ba2+, Mn2+, Ce2+ and Sn2+; J is a trivalent cation and is selected from the group consisting of Y3+, Al3+, Ga3+, Lu3+, Sc3+, La3+ and In3+; L is a trivalent cation and is selected from the group consisting of Al3+, Ga3+, Lu3+, Sc3+, La3+ and In3+; l≥0; k≥0; j≥0; (j+1.5k+1.5l) = m, preferably G is selected from Ca2+, Sr2+, Ba2+ or a combination of any of these; J is Y3+, Lu3+ or a combination of these; L is Al3+, Gd3+ or a combination of these; j is 1 , k is 1 , 1 is 1 , m is 4; X is a luminescent ion and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Nd4+, Pm3+, Sm3+, Eu3+, Eu2+, Gd3+, Tb3+, Dy2+, Dy3+, Dy4+, Ho2+, Ho3+, Er3+, Tm3+, Yb3+, Yb2+, Cr3+, Mn2+, Mn4+ and Fe3+, preferably X is selected from Ce3+, Eu3+, Eu2+, Tb3+, Cr3+, Mn2+, Mn4+, Fe3+ or a combination of any of these, more preferably X is Mn4+; even more preferably it is CaYAlO4:Mn4+; and
A3aOz:X - (VI) wherein
A3 is a trivalent cation and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Tb3+, Dy3+, Ti3+, V3+, Cr3+, Mn3+, Fe3+, Co3+, Ni3+, Zr3+, Nb3+, Mo3+, Tc3+, Ru3+, Rh3+, Pd3+, Hf3+, Ta3+, W3+, Re3+, Os3+, Ir3+, Pt3+, Si3+, Ge3+, Sn3+, Pb3+, S3+, Se3+, Te3+ and Po3+; X is a luminescent ion and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Nd4+, Pm3+, Sm3+, Eu3+, Eu2+, Gd3+, Tb3+, Dy2+, Dy3+, Dy4+, Ho2+, Ho3+, Er3+, Tm3+, Yb3+, Yb2+, Cr3+, Mn2+, Mn4+ and Fe3+; a≥0; z≥0; 2a = z; preferably, A3 is Ce3+, Ti3+, Zr3+, Hf3+, Si3+, Ge3+, Sn3+, or a combination of any of these;
X is selected from Ce3+, Eu3+, Eu2+, Tb3+, Cr3+, Mn2+, Mn4+, Fe3+ or a combination of any of these, more preferably X is Ce3+; a is 1 , z is 2; more preferably the formula is ZrO2:Ce3+
A4aB2bC1cOz:X - (VII) wherein
A4 is a monovalent cation and is selected from one or more members of the group consisting of Li+, Na+, K+, Rb+, Cs+, V+, Cr+, Mn+, Co+, Ni+, Cu+, Pd+. Ag+. Au+ and TI+;
B2 is a tetravalent cation and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Tb3+, Dy3+, Ti3+, V3+, Cr3+, Mn3+, Fe3+, Co3+, Ni3+, Zr3+, Nb3+, Mo3+, Tc3+, Ru3+, Rh3+, Pd3+, Hf3+, Ta3+, W3+, Re3+, Os3+, Ir3+, Pt3+, Si3+, Ge3+, Sn3+, Pb3+, S3+, Se3+, Te3+ and Po3+;
C1 is a tetravalent cation and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Tb3+, Dy3+, Ti3+, V3+, Cr3+, Mn3+, Fe3+, Co3+, Ni3+, Zr3+, Nb3+, Mo3+, Tc3+, Ru3+, Rh3+, Pd3+, Hf3+, Ta3+, W3+, Re3+, Os3+, Ir3+, Pt3+, Si3+, Ge3+, Sn3+, Pb3+, S3+, Se3+, Te3+ and Po3+;
X is a luminescent ion and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Nd4+, Pm3+, Sm3+, Eu3+, Eu2+, Gd3+, Tb3+, Dy2+, Dy3+, Dy4+, Ho2+, Ho3+, Er3+, Tm3+, Yb3+, Yb2+, Cr3+, Mn2+, Mn4+ and Fe3+; a≥0; b≥0; c≥0; z≥0; (0.5a+2b+2c) = z; preferably A4 is Li+, Na+, K+, Rb+, Cs+ or a combination of any of these,
B2 is Ce3+, Ti3+, Zr3+, Hf3+, Si3+, Ge3+, Sn3+, or a combination of any of these,
C1 is Ce3+, Ti3+, Zr3+, Hf3+, Si3+, Ge3+, Sn3+, or a combination of any of these; X is Ce3+, Eu3+, Eu2+, Tb3+, Cr3+, Mn2+, Mn4+ and Fe3+, or a combination of any of these, more preferably X is Eu2+; a is 2, b is 1 , c is 2, z is 7; more preferably, formula isK^rShOyiEu2+;
A5aB3bC2cD3dOz:X - (VIII) wherein
A5 is a divalent cation and is selected from one or more members of the group consisting of Mg2+, Ca2+, Sr2+, Ba2+, Nd2+, Sm2+, Eu2+, Dy2+, Ho2+, Tm2+, Yb2+, Ti2+, V2+, Cr2+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Mo2+, Pd2+, Ag2+, W2+, Ft2+, Zn2+, Cd2+, Hg2+, Ge2+, Sn2+ and Pb2+;
B3 is a trivalent cation and is selected from one or more members of the group consisting of Sc3+, Y3+, La3+, Ce3+, Pr3+, Nd3+, Pm3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+, Ti3+, V3+, Cr3+, Mn3+, Fe3+, Co3+, Ni3+, Cu3+, Nb3+, Mo3+, Ru3+, Rh3+, Pd3+, Ag3+, Ta3+, W3+, Ir3+, Au3+, B3+, Al3+, Ga3+, In3+, TI3+, P3+, As3+, Sb3+ and Bi3+;
C2 is a tetravalent cation and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Tb3+, Dy3+, Ti3+, V3+, Cr3+, Mn3+, Fe3+, Co3+, Ni3+, Zr3+, Nb3+, Mo3+, Tc3+, Ru3+, Rh3+, Pd3+, Hf3+, Ta3+, W3+, Re3+, Os3+, Ir3+, Pt3+, Si3+, Ge3+, Sn3+, Pb3+, S3+, Se3+, Te3+ and Po3+;
D3 is a trivalent cation and is selected from one or more members of the group consisting of Sc3+, Y3+, La3+, Ce3+, Pr3+, Nd3+, Pm3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+, Ti3+, V3+, Cr3+, Mn3+, Fe3+, Co3+, Ni3+, Cu3+, Nb3+, Mo3+, Ru3+, Rh3+, Pd3+, Ag3+, Ta3+, W3+, Ir3+, Au3+, B3+, Al3+, Ga3+, In3+, TI3+, P3+, As3+, Sb3+ and Bi3+;
X is a luminescent ion and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Nd4+, Pm3+, Sm3+, Eu3+, Eu2+, Gd3+, Tb3+, Dy2+, Dy3+, Dy4+, Ho2+, Ho3+, Er3+, Tm3+, Yb3+, Yb2+, Cr3+, Mn2+, Mn4+ and Fe3+; a≥0; b≥0; c≥0; d≥0; z≥0; (a+1 ,5b+2c+1 ,5d) = z; preferably A5 is Mg2+, Ca2+, Sr2+, Ba2+ and Zn2+, or a combination of any of these; B3 is Sc3+, Y3+, La3+, Lu3+, B3+, Al3+, Ga3+, In3+, P3+, Bi3+, or a combination of any of these;
C2 is Ce3+, Ti3+, Zr3+, Hf3+, Si3+, Ge3+, Sn3+, or a combination of any of these;
D3 is Sc3+, Y3+, La3+, Lu3+, B3+, Al3+, Ga3+, In3+, P3+, Bi3+, or a combination of any of these;
X is Ce3+, Eu3+, Eu2+, Tb3+, Cr3+, Mn2+, Mn4+ and Fe3+, or a combination of any of these; a is 2, b is 1 , c is 2, d is 3, z is 12; more preferably the formula is Ca2YZr2Al3O12:Ce3+
A6aB4bOz:X -(IX) wherein
A® is a trivalent cation and is selected from one or more members of the group consisting of Sc3+, Y3+, La3+, Ce3+, Pr3+, Nd3+, Pm3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+, Ti3+, V3+, Cr3+, Mn3+, Fe3+, Co3+, Ni3+, Cu3+, Nb3+, Mo3+, Ru3+, Rh3+, Pd3+, Ag3+, Ta3+, W3+, Ir3+, Au3+, B3+, Al3+, Ga3+, In3+, TI3+, P3+, As3+, Sb3+ and Bi3+;
B4 is a trivalent cation and is selected from one or more members of the group consisting of Sc3+, Y3+, La3+, Ce3+, Pr3+, Nd3+, Pm3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+, Ti3+, V3+, Cr3+, Mn3+, Fe3+, Co3+, Ni3+, Cu3+, Nb3+, Mo3+, Ru3+, Rh3+, Pd3+, Ag3+, Ta3+, W3+, Ir3+, Au3+, B3+, Al3+, Ga3+, In3+, TI3+, P3+, As3+, Sb3+ and Bi3+;
X is a luminescent ion and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Nd4+, Pm3+, Sm3+, Eu3+, Eu2+, Gd3+, Tb3+, Dy2+, Dy3+, Dy4+, Ho2+, Ho3+, Er3+, Tm3+, Yb3+, Yb2+, Cr3+, Mn2+, Mn4+ and Fe3+; a≥0; b≥0; z≥0; (1.5a+1.5b) = z; preferably A6 is Sc3+, Y3+, La3+, Lu3+, B3+, Al3+, Ga3+, In3+, P3+, Bi3+, or a combination of any of these;
B4 is Sc3+, Y3+, La3+, Lu3+, B3+, Al3+, Ga3+, In3+, P3+, Bi3+, or a combination of any of these; X is Ce3+, Eu3+, Eu2+, Tb3+, Cr3+, Mn2+, Mn4+ and Fe3+, or a combination of any of these, more preferably X is Ce3+; a is 3, b is 5, z is 12; more preferably the formula is YsAlsO-iaiCe3+;
A7aB5bC3cOz:X -(X) wherein
A7 is a trivalent cation and is selected from one or more members of the group consisting of Sc3+, Y3+, La3+, Ce3+, Pr3+, Nd3+, Pm3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+, Ti3+, V3+, Cr3+, Mn3+, Fe3+, Co3+, Ni3+, Cu3+, Nb3+, Mo3+, Ru3+, Rh3+, Pd3+, Ag3+, Ta3+, W3+, Ir3+, Au3+, B3+, Al3+, Ga3+, In3+, TI3+, P3+, As3+, Sb3+ and Bi3+;
B5 is a trivalent cation and is selected from one or more members of the group consisting of Sc3+, Y3+, La3+, Ce3+, Pr3+, Nd3+, Pm3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+, Ti3+, V3+, Cr3+, Mn3+, Fe3+, Co3+, Ni3+, Cu3+, Nb3+, Mo3+, Ru3+, Rh3+, Pd3+, Ag3+, Ta3+, W3+, Ir3+, Au3+, B3+, Al3+, Ga3+, In3+, TI3+, P3+, As3+, Sb3+ and Bi3+;
C3 is a trivalent cation and is selected from one or more members of the group consisting of Sc3+, Y3+, La3+, Ce3+, Pr3+, Nd3+, Pm3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+, Ti3+, V3+, Cr3+, Mn3+, Fe3+, Co3+, Ni3+;
X is a luminescent ion and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Nd4+, Pm3+, Sm3+, Eu3+, Eu2+, Gd3+, Tb3+, Dy2+, Dy3+, Dy4+, Ho2+, Ho3+, Er3+, Tm3+, Yb3+, Yb2+, Cr3+, Mn2+, Mn4+ and Fe3+; a≥0; b≥0; c≥0; z≥0 (1.5a+1.5b+1.5c) = z; preferably A7 is Sc3+, Y3+, La3+, Lu3+, B3+, Al3+, Ga3+, In3+, P3+, Bi3+, or a combination of any of these;
B5 is Sc3+, Y3+, La3+, Lu3+, B3+, Al3+, Ga3+, In3+, P3+, Bi3+, or a combination of any of these;
C3 is Sc3+, Y3+, La3+, Lu3+, B3+, Al3+, Ga3+, In3+, P3+, Bi3+, or a combination of any of these; X is Ce3+, Eu3+, Eu2+, Tb3+, Cr3+, Mn2+, Mn4+ and Fe3+, or a combination of any of these, more preferably X is Ce3+; a is 3, b is 2, c is 3, z is 12; more preferably, formula is YsGazAlsO-iaiCe3+;
A8aBebOz:X -(XI) wherein
A8 is a monovalent cation and is selected from one or more members of the group consisting of Li+, Na+, K+, Rb+, Cs+, V+, Cr+, Mn+, Co+, Ni+, Cu+, Pd+, Ag+, Au+ and IT;
B8 is a trivalent cation and is selected from one or more members of the group consisting of Sc3+, Y3+, La3+, Ce3+, Pr3+, Nd3+, Pm3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+, Ti3+, V3+, Cr3+, Mn3+, Fe3+, Co3+, Ni3+, Cu3+, Nb3+, Mo3+, Ru3+, Rh3+, Pd3+, Ag3+, Ta3+, W3+, Ir3+, Au3+, B3+, Al3+, Ga3+, In3+, TI3+, P3+, As3+, Sb3+ and Bi3+;
X is a luminescent ion and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Nd4+, Pm3+, Sm3+, Eu3+, Eu2+, Gd3+, Tb3+, Dy2+, Dy3+, Dy4+, Ho2+, Ho3+, Er3+, Tm3+, Yb3+, Yb2+, Cr3+, Mn2+, Mn4+ and Fe3+; a≥0; b≥0; z≥0 (0.5a+1.5b) = z; preferably A8 is Li+, Na+, K+, Rb+, Cs+ or a combination of any of these,
B8 is Sc3+, Y3+, La3+, Lu3+, B3+, Al3+, Ga3+, In3+, P3+, Bi3+, or a combination of any of these;
X is Ce3+, Eu3+, Eu2+, Tb3+, Cr3+, Mn2+, Mn4+ and Fe3+, or a combination of any of these, more preferably X is Mn4+; a is 1 , b is 5, z is 8; more preferably the formula is LiAlsOsiMn4+;
A9aB7bOz:X -(XII) wherein
A9 is a divalent cation and is selected from one or more members of the group consisting of Mg2+, Ca2+, Sr2+, Ba2+, Nd2+, Sm2+, Eu2+, Dy2+, Ho2+, Tm2+, Yb2+, Ti2+, V2+, Cr2+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Mo2+, Pd2+, Ag2+, W2+, Pt2+, Zn2+, Cd2+, Hg2+, Ge2+, Sn2+ and Pb2+; B7 is a tetravalent cation and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Tb3+, Dy3+, Ti3+, V3+, Cr3+, Mn3+, Fe3+, Co3+, Ni3+, Zr3+, Nb3+, Mo3+, Tc3+, Ru3+, Rh3+, Pd3+, Hf3+, Ta3+, W3+, Re3+, Os3+, Ir3+, Pt3+, Si3+, Ge3+, Sn3+, Pb3+, S3+, Se3+, Te3+ and Po3+;
X is a luminescent ion and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Nd4+, Pm3+, Sm3+, Eu3+, Eu2+, Gd3+, Tb3+, Dy2+, Dy3+, Dy4+, Ho2+, Ho3+, Er3+, Tm3+, Yb3+, Yb2+, Cr3+, Mn2+, Mn4+ and Fe3+; a≥0; b≥0; z≥0 (a+2b) = z; preferably, A9 is Mg2+, Ca2+, Sr2+, Ba2+ and Zn2+, or a combination of any of these;
B7 is Ce3+, Ti3+, Zr3+, Hf3+, Si3+, Ge3+, Sn3+, or a combination of any of these;
X is Ce3+, Eu3+, Eu2+, Tb3+, Cr3+, Mn2+, Mn4+ and Fe3+, or a combination of any of these, more preferably X is Mn4+, a is 1 , b is 1 , z is 3, more preferably the formula is CaZrOsiMn4+
A10aB8bC4cOz:X -(XIII) wherein
A10 is a monovalent cation and is selected from one or more members of the group consisting of Li+, Na+, K+, Rb+, Cs+, V+, Cr+, Mn+, Co+, Ni+, Cu+, Pd+. Ag+. Au+ and TI+;
B8 is a divalent cation and is selected from one or more members of the group consisting of Mg2+, Ca2+, Sr2+, Ba2+, Nd2+, Sm2+, Eu2+, Dy2+, Ho2+, Tm2+, Yb2+, Ti2+, V2+, Cr2+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Mo2+, Pd2+, Ag2+, W2+, Pt2+, Zn2+, Cd2+, Hg2+, Ge2+, Sn2+ and Pb2+;
C4 is a tetravalent cation and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Tb3+, Dy3+, Ti3+, V3+, Cr3+, Mn3+, Fe3+, Co3+, Ni3+, Zr3+, Nb3+, Mo3+, Tc3+, Ru3+, Rh3+, Pd3+, Hf3+, Ta3+, W3+, Re3+, Os3+, Ir3+, Pt3+, Si3+, Ge3+, Sn3+, Pb3+, S3+, Se3+, Te3+ and Po3+;
X is a luminescent ion and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Nd4+, Pm3+, Sm3+, Eu3+, Eu2+, Gd3+, Tb3+, Dy2+, Dy3+, Dy4+, Ho2+, Ho3+, Er3+, Tm3+, Yb3+, Yb2+, Cr3+, Mn2+, Mn4+ and Fe3+; a≥0; b≥0; c≥0; z≥0 (0.5a+b+2c) = z; preferably A10 is Li+, Na+, K+, Rb+, Cs+ or a combination of any of these,
B9 is Sc2+, Y2+, La2+, Lu2+, B2+, Al2+, Ga2+, In2+, P2+, Bi2+, or a combination of any of these;
C5 is Ce3+, Ti3+, Zr3+, Hf3+, Si3+, Ge3+, Sn3+, or a combination of any of these;
X is Ce3+, Eu3+, Eu2+, Tb3+, Cr3+, Mn2+, Mn4+ and Fe3+, or a combination of any of these, more preferably X is Mn4+; a is 2, b is 1 , c is 1 , z is 4; more preferably, formula is LhMgZrO^Mn4+;
A11aB9bC5cOz:X -(XIV) wherein
A11 is a divalent cation and is selected from one or more members of the group consisting of Mg2+, Ca2+, Sr2+, Ba2+, Nd2+, Sm2+, Eu2+, Dy2+, Ho2+, Tm2+, Yb2+, Ti2+, V2+, Cr2+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Mo2+, Pd2+, Ag2+, W2+, Pt2+, Zn2+, Cd2+, Hg2+, Ge2+, Sn2+ and Pb2+;
B9 is a divalent cation and is selected from one or more members of the group consisting of Mg2+, Ca2+, Sr2+, Ba2+, Nd2+, Sm2+, Eu2+, Dy2+, Ho2+, Tm2+, Yb2+, Ti2+, V2+, Cr2+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Mo2+, Pd2+, Ag2+, W2+, Pt2+, Zn2+, Cd2+, Hg2+, Ge2+, Sn2+ and Pb2+;
C5 is a trivalent cation and is selected from one or more members of the group consisting of Sc3+, Y3+, La3+, Ce3+, Pr3+, Nd3+, Pm3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+, Ti3+, V3+, Cr3+, Mn3+, Fe3+, Co3+, Ni3+, Cu3+, Nb3+, Mo3+, Ru3+, Rh3+, Pd3+, Ag3+, Ta3+, W3+, Ir3+, Au3+, B3+, Al3+, Ga3+, In3+, TI3+, P3+, As3+, Sb3+ and Bi3+;
X is a luminescent ion and is selected from one or more members of the group consisting of Ce3+, Pr3+, Nd3+, Nd4+, Pm3+, Sm3+, Eu3+, Eu2+, Gd3+, Tb3+, Dy2+, Dy3+, Dy4+, Ho2+, Ho3+, Er3+, Tm3+, Yb3+, Yb2+, Cr3+, Mn2+, Mn4+ and Fe3+; a≥0; b≥0; c≥0; z≥0 (0.5a+b+2c) = z; preferably A11 is Mg2+, Ca2+, Sr2+, Ba2+ and Zn2+, or a combination of any of these;
B9 is Mg2+, Ca2+, Sr2+, Ba2+ and Zn2+, or a combination of any of these;
C5 is Sc3+, Y3+, La3+, Lu3+, B3+, Al3+, Ga3+, In3+, P3+, Bi3+, or a combination of any of these;
X is Ce3+, Eu3+, Eu2+, Tb3+, Cr3+, Mn2+, Mn4+ and Fe3+, or a combination of any of these, more preferably X is Mn4+; even more preferably the formula is CaMgAl1627: Mn4+, Ca2Mg2Al28O46:Mn4+, Sr2MgAl22O36:Mn4+ or BaMgAlioO17:Mn4+.
7. Use of the particle of any one of claims 1 to 6 for agriculture.
8. A composition comprising at least one particle of any one of claims 1 to 6, and another material.
9. The composition of claim 8, wherein said another material is 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 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.
10. The composition of claim 8 or 9, the total amount of the particle of the composition is in the range from 0.01 wt.% to 30wt.% based on the total amount of the composition, preferably it is from 0.1 wt.% to 10wt.%, more preferably from 0.5wt.% to 5wt.%, furthermore preferably it is from 1 wt.% to 3wt.%.
11. The composition according to any one of claims 8 to 10, wherein 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.
12. A formulation comprising at least one particle of any one of claims 18 to 20, or the composition of any one of claims 23 to 26, and a solvent.
13. Use of the particle of any one of claims 1 to 6, the composition of any one of claims 8 to 11 , or the formulation of claim 12, in an optical sheet fabrication process or in agriculture, preferably for fabricating an agricultural sheet or for controlling a condition of a living organism.
14. An optical sheet (100) comprising at least one particle of any one of claims 1 to 6, or the composition of any one of claims 8 to 11 , preferably said optical sheet is an agricultural sheet.
15. An optical device (200) comprising at least one optical sheet (100) of claim 14, preferably said optical device is a lighting device, more preferably it is a light emitting diode device.
16. A greenhouse comprising the optical sheet (100) of claim 14.
17. Use of the optical sheet (100) of claim 14 or the optical device (200) of claim 15 for agriculture, preferably for greenhouse or for controlling a condition of a living organism in agriculture.
18. Method for preparing the optical sheet (100), preferably for preparing the agriculture sheet, wherein the method comprises following steps (a) and (b),
(a) providing the composition according to any one of claims 8 to 11 , or the formulation according to claim 12 in a first shaping, preferably providing the composition onto a substrate or into an inflation moulding machine, and
(b) fixing the matrix material by evaporating a solvent and / or polymerizing the composition by heat treatment, or exposing the photosensitive composition under ray of light or a combination of any of these.
19. Method for preparing the agriculture sheet, wherein the method comprises following steps (a') and (b'),
(a') providing the composition comprising a particle comprising an inorganic phosphor and a coating layer onto the outermost surface of the inorganic phosphor, and another material, or the formulation comprising said composition and a solvent in a first shaping, preferably providing the composition into an inflation moulding machine, and
(b') fixing the matrix material by evaporating a solvent and / or polymerizing the composition by heat treatment, or exposing the photosensitive composition under ray of light or a combination of any of these, preferably said coating layer is a transparent polymer layer or a metal oxide coating layer, more preferably said particle is the one according to any one of claim 1 to 6 or a particle comprising an inorganic phosphor coated by a metal oxide coating layer selected from one or more members of the group consisting of SiO2, TiO2, ZnO2, ZrO2 and AI2O3, more preferably it is selected from SiO2, T1O2, ZnO2or a combination of any of these.
20. Use of a particle of metal oxide coated inorganic phosphor comprising an inorganic phosphor and at least one metal oxide coating layer onto the outermost surface of said phosphor, for agriculture, preferably said metal oxide coating layer is selected from one or more members of the group consisting of S1O2, T1O2, Zn02, ZrO∑ and AI2O3, more preferably it is selected from Ti02, ΖnΟ2 or a combination of Si02, T1O2 and Zn02, preferably for greenhouse or for controlling a condition of a living organism in agriculture.
21. Method for preparing the optical device (200) of claim 15, comprising following step (A);
(A) providing the optical sheet (100) of claim 14, in an optical device (200).
22. Use of the particle of any one of claimsl to 6, the composition of any one of claims 8 to 11 , the formulation of claim 12, the optical sheet (100) of claim 14, the optical device (200) of claim 20 or the green house of claim 21 for cultivation of algae, bacteria, preferably said bacteria are photosynthetic bacteria, and/or planktons, 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 / 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 ripening of fruits, or controlling of weight of plant.
23. Method of supplying the particle of any one of claims 1 to 6, or composition of any one of claims 8 to 11 , or the formulation of claim 12 to at least one portion of a plant.
24. Method for modulating a condition of a plant, plankton, and/or a bacterium, comprising at least following step (C),
(C) providing the optical sheet (100) of claim 14, between a light source and a plant, between a light source and a plankton, preferably said plankton is a phytoplankton, between a light source and a bacterium, preferably said bacterium is a photosynthetic bacterium, or providing the optical sheet (100) of claim 14 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.
25. Method of claim 24, wherein the light source is the sun or an artificial light source, preferably said artificial light source is a light emitting diode.
26. A plant obtained or obtainable by the method of any one of claims 23 to 25, or a plankton obtained or obtainable by the method of claim 24 or 25, or a bacterium obtained or obtainable by the method of claim 24 or 25.
27. A container comprising at least one plant, one plankton, and/or a bacterium of claim 26.
PCT/EP2020/082477 2019-11-21 2020-11-18 Method for fabricating a particle WO2021099351A1 (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007005645A1 (en) * 2007-01-31 2008-08-07 Henkel Ag & Co. Kgaa Polymer effect coated light effect pigments
US20100283076A1 (en) * 2007-11-12 2010-11-11 Merck Patent Gesellschaft Mit Berschrankter Haftun Coated phosphor particles with refractive index adaption
JP2014196466A (en) 2013-03-08 2014-10-16 楠本化成株式会社 Viscosity modifier for high concentration dispersion of inorganic fine particles and high concentration dispersion of inorganic fine particles blended with the same
CN106590622A (en) * 2016-12-01 2017-04-26 天津颐品农庄电子商务有限公司 Modified rare earth light conversion material high-molecular polymer agricultural film
WO2017129351A1 (en) 2016-01-26 2017-08-03 Merck Patent Gmbh A composition, color converting sheet and light emitting diode device
WO2019020653A1 (en) 2017-07-26 2019-01-31 Merck Patent Gmbh Composition
WO2019020602A2 (en) 2017-07-26 2019-01-31 Merck Patent Gmbh Phosphor and a composition

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007005645A1 (en) * 2007-01-31 2008-08-07 Henkel Ag & Co. Kgaa Polymer effect coated light effect pigments
US20100283076A1 (en) * 2007-11-12 2010-11-11 Merck Patent Gesellschaft Mit Berschrankter Haftun Coated phosphor particles with refractive index adaption
JP2014196466A (en) 2013-03-08 2014-10-16 楠本化成株式会社 Viscosity modifier for high concentration dispersion of inorganic fine particles and high concentration dispersion of inorganic fine particles blended with the same
WO2017129351A1 (en) 2016-01-26 2017-08-03 Merck Patent Gmbh A composition, color converting sheet and light emitting diode device
CN106590622A (en) * 2016-12-01 2017-04-26 天津颐品农庄电子商务有限公司 Modified rare earth light conversion material high-molecular polymer agricultural film
WO2019020653A1 (en) 2017-07-26 2019-01-31 Merck Patent Gmbh Composition
WO2019020602A2 (en) 2017-07-26 2019-01-31 Merck Patent Gmbh Phosphor and a composition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YENSHINOYAYAMAMOTO: "Phosphor handbook"

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