WO2022013049A1 - Procédé de fabrication d'une particule - Google Patents

Procédé de fabrication d'une particule Download PDF

Info

Publication number
WO2022013049A1
WO2022013049A1 PCT/EP2021/068947 EP2021068947W WO2022013049A1 WO 2022013049 A1 WO2022013049 A1 WO 2022013049A1 EP 2021068947 W EP2021068947 W EP 2021068947W WO 2022013049 A1 WO2022013049 A1 WO 2022013049A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
acid
range
inorganic phosphor
phosphor
Prior art date
Application number
PCT/EP2021/068947
Other languages
English (en)
Inventor
Ryota YAMANASHI
Hiroki Yoshizaki
Hiroshi Okura
David Downey
Kenji Toda
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.)
Filing date
Publication date
Application filed by Merck Patent Gmbh filed Critical Merck Patent Gmbh
Publication of WO2022013049A1 publication Critical patent/WO2022013049A1/fr

Links

Classifications

    • 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
    • C09K11/64—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing aluminium
    • C09K11/641—Chalcogenides
    • C09K11/643—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
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7708—Vanadates; Chromates; Molybdates; Tungstates

Definitions

  • the present invention relates to a particle of a polymer coated inorganic phosphor, 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.
  • a novel method for fabricating a particle of polymer coated inorganic phosphor comprising at least the following steps: a) Preparing a 1 st reaction mixture by mixing at least 1 st polymer precursor, an inorganic phosphor and optionally a polymerization initiator, together with at least a 1 st solvent; b) Reacting the 1 st polymer precursor in the 1 st reaction mixture without using water as a solvent to form a 1 st polymer coating layer on the surface of the inorganic phosphor, preferably said reaction is triggered by applying irradiation of rays to the 1 st reaction mixture and/or by Appling a heat treatment, preferably said polymerization initiator is selected from one or more members of the group consisting of photo acid-generators, photo radical – generators, photo base – generators, heat acid-generators, heat base – generators and heat radical – generators, preferably said ray is visible light, UV
  • the invention relates to a particle of polymer coated inorganic phosphor obtained or obtainable by the method of the present invention.
  • the present invention also relates to a particle comprising an inorganic phosphor and a transparent polymer, wherein said inorganic phosphor is at least partially coated by said transparent polymer, 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 polyethylene terephthalate, polyurethane, polyacrylonitrile, epoxy resin derived from glycidyl function on (meth)acrylate monomer, biodegradable polymer such as polylactide, polyglycolide, polyhydroxyalkanoate, polycaprolactone.
  • the present invention also relates to a use of the particle of the present invention in agriculture. In another aspect, the present invention also relates to a use of the particle of the present invention in a Light Emitting Diode or in a solar cell. 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.
  • 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 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), (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.
  • the invention 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).
  • 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;
  • the invention relates to a method of supplying the particle of the present invention, or the composition of any one of the present inventions, 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 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).
  • 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.
  • 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.
  • 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.
  • organic 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. Alq 3 , LiQ, Ir(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.
  • rare earth metal elements for example La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu
  • transition metal elements for example Cr, Mn, Fe, Co, Ni, Cu, Ag, Au and Zn
  • main group metal elements for example Na, Tl, Sn, Pb, Sb and Bi.
  • Suitable phosphors include phosphors based on garnet, silicate, orthosilicate, thiogallate, sulfide, nitride, silicon-based oxynitride, nitridosilicate, nitridoaluminumsilicate, oxonitridosilicate, oxonitridoaluminumsilicate and rare earth doped sialon.
  • 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 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. Preferably, it is over 70 %, more preferably, over 75%, the most preferably, it is over 80 %.
  • Fig.1 shows a cross sectional view of a schematic of one embodiment of an optical sheet (100) of the invention.
  • Fig.2 shows a cross sectional view of a schematic of one embodiment of an optical device (200) of the invention.
  • Fig.3 shows a cross sectional view of a schematic of another embodiment of an optical device of the invention.
  • Fig.4 shows a schematic of another embodiment of an optical device of the invention.
  • Fig.5 shows a SEM image from working example 1.
  • Fig.6 shows a SEM image from working example 1.
  • Fig.7 shows a synthesis process of working example 10
  • Fig.8 shows emission and absorption spectrum of the phosphor obtained in working example 10.
  • List of reference signs in figure 1 100.
  • 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 List of reference signs in figure 4 400.
  • an optical device 100 an optical sheet 100a. a first layer of the optical sheet 100b. a second layer of the optical sheet (optional) 100c. a third layer of the optical sheet (optional) 410.
  • said method comprises, essentially consisting of, or consisting of, at least the following steps: a) Preparing a 1 st reaction mixture by mixing at least 1 st polymer precursor, an inorganic phosphor and optionally a polymerization initiator, together with at least a 1 st solvent; b) Reacting the 1 st polymer precursor in the 1 st reaction mixture without using water as a solvent to form a 1 st polymer coating layer on the surface of the inorganic phosphor, preferably said reaction is triggered by applying irradiation of rays to the 1 st reaction mixture and/or by applying a heat treatment, preferably said polymerization initiator is selected from one or more members of the group consisting of photo acid-generators, photo radical – generators, photo base – generators, heat acid-generators, heat base – generator
  • polymer coated inorganic phosphor(s) can be removed from the reaction mixture by publicly known method. It is believed that water damage during the reaction step b) to the phosphor is prevented since said reaction step b) is carried out without using water as a solvent.
  • no water is used at least in step b), preferably no water is used in step a) and step b), more preferably no water is used in the whole fabrication process to avoid any water damage to the inorganic phosphor.
  • a plurality of inorganic phosphors is used in all the steps of the method.
  • said heat treatment is applied in step b) and at least one polymerization initiators selected from heat acid-generators, heat base – generators, heat radical – generators or a combination of any of these is added in the first reaction mixture in step a).
  • said irradiation of rays to the 1 st reaction mixture is applied in step b) and at least one polymerization initiators selected from photo acid-generators, photo radical – generators, photo base – generators or a combination of any of these is added in the first reaction mixture in step a).
  • heat acid- generators heat base – generators and/or heat radical – generators can be added as the second polymerization initiators.
  • heating treatment process to complete polymerization process can be applied after step b) when said irradiation is applied in step b).
  • said 1 st polymer precursor is an acidic monomer or an acidic oligomer, 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]eth
  • said 1 st polymer precursor is a (meth)acrylate monomer represented by chemical formula (I), X is a non-substituted or substituted alkyl group, aryl group or an alkoxy group; R 1 is a hydrogen atom, halogen atom of Cl, Br, or F, methyl group, alkyl group, aryl group, alkoxy group, ester group, or a carboxylic acid group; m is 1, 2 or 3 when Y is a phosphonic acid, m is 1 when Y is not a phosphonic acid; Y is an anchoring group selected from one or more members of the group consisting of phosphine groups, phosphine oxide groups, phosphate
  • the reaction in step (b) is carried out at the temperature in the range from 35°C to 120°C, preferably from 50°C to 100°C, more preferably from 50°C to 85 °C, even more preferably from 55°C to 80°C, further more preferably from 60°C to 76 °C. more preferably said reaction is triggered by applying a heat treatment at the temperature mentioned above.
  • irradiation of rays to the 1 st reaction mixture can be applied in step b) together with said heat treatment.
  • the total amount of the 1 st polymer precursor used in step (b) is in the range from 0.5 to 20 (parts) pts.wt based on the total amount of the inorganic phosphor used in step (b), more preferably it is in the range from 1 to 10 pts.wt, even more preferably it is in the range from 2 to 7.5 pts.wt, further more preferably it is in the range from 3 to 5 pts.wt. It is believed that if the amount of the 1 st polymer precursor is 0,5 pts.wt.
  • the inorganic phosphor can realize a good polymer coating and can reduce or preferably prevent an incomplete polymer coating. And if the amount of the 1 st polymer precursor is 20 pts.wt. or less based on the total amount of the inorganic phosphor, it can reduce or preferably prevent the situation that the redundant too much 1 st polymer is attached onto the inorganic phosphor.
  • said inorganic phosphor contains one or more of elements selected from the group consisting of alkali metal elements, alkaline metal elements, phosphorous atom, boron atom and sulfur atom, preferably said alkali metal element is Li, Na, Ka or a combination of any of these, and said alkaline metal element is Be, Mg, Ca, Sr, Ba or a combination of any of these.
  • the polymer coating by the method of the present invention is especially preferable to the inorganic phosphors containing one or more of elements selected from the group consisting of alkali metal elements, alkaline metal elements, and phosphorous atom, preferably said alkali metal element is Li, Na, Ka or a combination of any of these, and said alkaline metal element is Be, Mg, Ca, Sr, Ba or a combination of any of these to avoid any water damage to the phosphors.
  • the inorganic phosphor has a peak wavelength of light emitted from the inorganic phosphor in the range of 600 nm or more, preferably in the range from 600 to 1500 nm, more preferably in the range from 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
  • 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.
  • the term peak wavelength is related to a side peak.
  • the term peak wavelength is related to the main peak having maximum intensity/absorption.
  • the phosphor is a nontoxic phosphor, preferably it is an edible phosphor.
  • 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 SiAlON phosphors, preferably, it is a metal oxide phosphor, more preferably it is a Mn activated metal oxide phosphor or a Mn activated phosphate based phosphor, even more preferably it is a Mn activated metal oxide phosphor.
  • Mn 4+ activated metal oxide phosphors Mn, Eu activated metal oxide phosphors, Mn 2+ activated metal oxide phosphors, Fe 3+ activated metal oxide phosphors can be used preferably from the viewpoint of environmentally friendly since these phosphors do not create Cr 6+ during synthesis procedure.
  • the Mn 4+ activated metal oxide phosphors are very useful for plant growth, since it shows narrow full width at half maximum (hereafter “FWHM”) of the light emission, and have the peak absorption wavelength in UV and green wavelength region such as 350 nm and 520 nm, and the emission peak wavelength is in near infrared ray region in the range of 600 nm or more, preferably in the range from 600 to 1500 nm, more preferably in the range from 650 to 1000 nm, even more preferably in the range from 650 to 800 nm, furthermore preferably in the range from 650 to 750 nm, much more preferably it is from 660 nm to 730 nm, the most preferably from 670 nm to 710nm.
  • FWHM narrow full width at half maximum
  • the Mn 4+ activated metal oxide phosphors can absorb the specific UV light which attracts insects, and green light which does not give any advantage for plant growth, and can convert the absorbed light to longer wavelength in the range of 600 nm or more, preferably in the range from 600 to 1500 nm, more preferably in the range from 650 to 1000 nm, even more preferably in the range from 650 to 800 nm, furthermore preferably in the range from 650 to 750 nm, much more preferably it is from 660 nm to 730 nm, the most preferably from 670 nm to 710nm, which can effectively accelerate plant growth.
  • a metal oxide phosphor As a metal oxide phosphor, another new light emitting phosphor represented by following general formula (VI), (VI ⁇ ), (VII), (VII ⁇ ) (VIII), (IX), (X), (XI), (XII), (XIII) which can exhibit deep red-light emission, preferably with a sharp emission around 700 nm under excitation light of 300 to 400 nm, which are suitable to promote plant growth, can be used preferably.
  • said inorganic phosphor is an inorganic phosphor represented by formula (III), (VI), (VI ⁇ ), (VII), (VII ⁇ ) or (XII); preferably said inorganic phosphor is selected from one or more members of the group consisting of (Mg,Zn)Ga 2 O 4 :Cr 3+ , Ca 2 (Ga,Al)NbO 6 :Cr 3+ , LiInSi 2 O 6 :Cr 3+ , Na 3 AlF 6 :Cr 3+ , Mg 3 Ga 2 GeO 8 :Cr 3+ , SrMgAl 10 O 17 :Cr 3+ , Na 2 TiSiO 5 :Cr 3+ , MgAl 2 O 4 :Cr 3+ , Mg 3 Ga 2 GeO 8 :Cr 3+ , Zn3Ga 2 Ge 2 O 10 :Cr 3+ , Sr 2 MgWO 6 :Cr 3+ , Li 2 ZnG
  • the method of the present invention is especially suitable for the following phosphors to improve water stability and prevent EQE drop: (Ca,Sr,Ba)(Mg,Zn)Si 2 O 6 :Eu 2+ ,Mn 2+ , (Ca,Sr,Ba) 2 (Mg,Zn)Si 2 O 7 :Eu 2+ ,Mn 2+ , (Ca,Sr,Ba) 3 (Mg,Zn)Si 2 O 8 :Eu 2+ ,Mn 2+ ,(Sr,Ba) 4 Al 2 S 7 :Eu 2+ ,(Ca,Sr)S:Eu 2+ ,(Ca,S r,Ba) 5 (PO 4 ) 3 Cl:Eu 2+ , NaMgPO 4 :Eu 2+ (olivine), Ca 3 (PO 4 ) 2 :Eu 2+ , Ba 2 Mg(PO 4 ) 2 :Eu 2+ , (Li,
  • an inorganic phosphor or its substances denaturated (e.g., degraded) from an inorganic phosphor, which less harms animals, plants and/or environment (e.g., soil, water) is desirable.
  • the phosphor is nontoxic phosphors, preferably it is edible phosphors, more preferably as edible phosphors, MgSiO 3 :Mn 2+ , MgO:Fe 3+ and/or CaMgSi 2 O 6 :Eu 2+ , Mn 2+ are useful.
  • the term “edible” means safe to eat, fit to eat, fit to be eaten, fit for human consumption.
  • Said inorganic phosphors represented by chemical formula (VI), (VI ⁇ ), (VII), (VII ⁇ ) and (VIII) can be fabricated as described in WO 2019/020602 A1.
  • 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.
  • 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 1 st 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 ( o 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-nona
  • the 1 st 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 ⁇ -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
  • 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
  • Those base- generators as well as the acid-generators and / or radical – generators can be used singly or in mixture.
  • 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.
  • the above photo acid-generator include diazomethane compounds, diphenyliodonium salts, triphenylsulfonium salts, sulfonium salts, ammonium salts, phosphonium salts and sulfonamide compounds.
  • 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: SbY 6 -, AsY6-, R a p PY 6-p -, R a q BY 4-q -, R a q GaY 4-q -, R a SO 3 -, (R a SO 2 ) 3 C-, (R a SO 2 ) 2 N-, R a COO-, and SCN- in which 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: BF 4 -, (C 6 F 5 ) 4 B-, ((CF 3 ) 2 C 6 H 3 ) 4 B-, PF 6 -, (CF 3 CF 2 ) 3 PF 3 -, SbF 6 -, (C 6 F 5 ) 4 Ga-, ((CF 3 ) 2 C 6 H 3 ) 4 Ga-, SCN-, (CF 3 SO 2 ) 3 C-, (CF 3 SO 2 ) 2 N-, 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, 1-(4,7-dibutoxy-1-naphthalenyl)tetrahydrothiophenium tri- fluoromethanesulfonate, diphenyliodonium trifluoromethanesulfonate, and diphenyliodonium hexafluoroarsenate.
  • each A is independently a substituent group selected from the group consisting of an alkyl group of 1 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkyl carbonyl group of 1 to 20 carbon atoms, an aryl carbonyl 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 alkyl sulfonate group, a fluorinated aryl sulfonate group, a fluorinated alkyl borate group, an alkyl sulfonate group or an aryl sulfonate 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(perfluoro- phenyl)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.
  • the method further comprises following step (c), (d) and (e), preferably in this sequence, (c) mixing a 2 nd polymer precursor in a 2 nd solvent to form a 2 nd reaction mixture; (d) adding the 2 nd reaction mixture into the 1 st reaction mixture to form a 3 rd reaction mixture; (e) reacting the 2 nd polymer precursor in the 3 rd reaction mixture to form the 1 st polymer coating layer on the surface of the inorganic phosphor or to form a 2 nd polymer coating layer on the 1 st polymer coating layer.
  • said 2 nd polymer precursor is a monomer or an oligomer having at least one reaction group, more preferably it is a monomer having at least one reaction group, even more preferably, it is selected from one or more members of the group consisting of (meth)acrylate monomers, such as 1-[2-[(2-methyl-1-oxo-2- propen-1-yl)oxy]ethyl] ester butanedioic acid (Kyoeisha Chemical “LIGHT ESTER HO-MS(N)”), 1-[2-[(2-methyl-1-oxo-2-propen-1-yl)oxy]ethyl] ester 1, 2-cyclohexanedicarboxylic acid (Kyoeisha Chemical “LIGHT ESTER HO- HH(N)”), 2-methacryloyloxyethyl acid phosphate (Kyoeisha Chemical “LIGHT ESTER P-1M(N)”), bis(2-methacrylate monomers, such as 1-[2-[(2-methyl
  • the 2 nd 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 ( o 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
  • alcohols including primary alcohol having 1 to 40 carbon
  • 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,
  • said step (a) further comprise following step (a1) and (a2), preferably in this sequence, (a1) mixing a 1 st polymer precursor with a 2 nd solvent to form a reaction mixture a1, preferably said 1 st polymer precursor is a styreme monomer; (a2) mixing an inorganic phosphor with a surfactant in a 1 st solvent to form a reaction mixture a2, 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; preferably said anchoring group is a carboxyl group or a phosphonate group, more
  • step (a2) is carried out at the temperature in the rage from 10°C to 35°C (at room temperature), more preferably in the rage from 15°C to 30°C.
  • the surfactant having an anchoring group is very preferable to form a polymer layer onto the inorganic phosphor efficiently, since the surfactant can bound onto the outermost surface of the inorganic phosphor.
  • surfactant having an anchoring group is used together with a monomer or oligomer which does not have any anchoring group to form a polymer layer onto the surface of the inorganic phosphor efficiently.
  • a publicly known surfactant having an anchoring 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 JP 2 014-196466 A1, or dispersants such as BYK (TM) -100 series e.g. BYK (TM) -103, 110, 111, 118 (from BYK) can be used preferably.
  • BYK (TM) -100 series e.g. BYK (TM) -103, 110, 111, 118 (from BYK)
  • TM BYK
  • TM BYK
  • TM TM-103
  • 110, 111, 118 from BYK
  • -Ultrasound irradiation preferably ultrasound irradiation is applied to said reaction mixture, preferably it is applied to the 3 rd reaction mixture, preferably the frequency of the ultrasound is in the rage from 1 to 1,000 kHz, more preferably from 5 to 500 kHz, even more preferably from 10 to 400 kHz.
  • the ultrasound irradiation it is especially useful applying the ultrasound irradiation to the reaction mixture to emulsify it when the 1 st solvent and the 2 nd solvent are different of each other and they are not miscible with each other. It is believed that applying the ultrasound irradiation at 1,000 kHz or less is preferable to avoid a dimple of the polymer coating. And to accelerate polymerization and to make a smaller emulsion in the reaction mixture, applying ultrasound irradiation at 5 kHz or more is preferable.
  • the present invention relates to a particle of polymer coated inorganic phosphor comprising an inorganic phosphor and a polymer layer placed onto the outer most surface of the inorganic phosphor obtained or obtainable by the method of the present invention.
  • the present invention relates to a particle comprising, essentially consisting of, or consisting of, an inorganic phosphor and a transparent polymer, wherein said inorganic phosphor is at least partially coated by a transparent polymer, preferably said inorganic phosphor is completely coated by said transparent polymer as a polymer layer, preferably said polymer is an organic polymer, more preferably said polymer 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 polymer forms a polymer coating layer directly onto the inorganic phosphor, more preferably the polymer coated inorganic phosphor itself is not in the form of film or sheet.
  • the inorganic part of the inorganic phosphor contains one or more of elements selected from the group consisting of alkali metal elements, alkaline metal elements, and phosphorous atom, preferably said alkali metal element is Li, Na, Ka or a combination of any of these, and said alkaline metal element is Be, Mg, Ca, Sr, Ba or a combination of any of these.
  • the inorganic phosphors as described in the section of “Inorganic phosphor” above can be used preferably.
  • said transparent polymer is derived or derivable from the 1 st polymer precursor, or derived or derivable from the 1 st and 2 nd polymer precursors of the present invention.
  • said transparent polymer comprises at least one of 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 Y is carboxyl group, phosphonate group or a phosphonic acid, preferably said transparent polymer comprises a plurality of anchoring groups from the view point of stronger anchoring ability to the phosphor surface.
  • the present invention also relates to use of the particle of the present invention in agriculture.
  • the present invention also relates to use of the inorganic phosphor of the present invention in a Light Emitting Diode or in a solar cell.
  • -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.
  • 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.
  • 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.
  • 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 0.1wt.% to 10wt.%, more preferably from 0.5wt.% to 5wt.%, furthermore preferably it is from 1wt.% to 3wt.% from the view point of better light conversion property, lower production cost and less production damage of a production machine.
  • the 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.
  • the thermosetting polymer publicly known transparent thermosetting polymer can be used preferably. Such as OE6550 (trademark) series (Dow Corning).
  • the thermoplastic polymer the type of thermoplastic polymer is not particularly limited.
  • thermoplastic polymers can be copolymerized if necessary.
  • 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.
  • 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
  • inorganic phosphors come into consideration for the present invention as an additional inorganic phosphor, such as, for example, metal-oxide phosphors, silicate and halide phosphors, phosphate and halophosphate phosphors, borate and borosilicate phosphors, aluminate, gallate and alumosilicate phosphors, phosphors, sulfate, sulfide, selenide and telluride phosphors, nitride and oxynitride phosphors and SiAlON phosphors.
  • the additional 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 SiAlON phosphors, preferably, it is a metal oxide phosphor, more preferably it is a Mn activated metal oxide phosphor or a Mn activated phosphate based phosphor, even more preferably it is a Mn activated metal oxide phosphor.
  • Preferred metal-oxide phosphors are arsenates, germanates, halogermanates, indates, lanthanates, niobates, scandates, stannates, tantalates, titanates, vanadates, halovanadates, phosphovanadates, yttrates, zirconates, molybdate and tungstate. Even more preferably, it is a metal oxide phosphor, more preferably it is a Mn activated metal oxide phosphor or a Mn activated phosphate based phosphor, even more preferably it is a Mn activated metal oxide phosphor.
  • 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, SiAlONs, halogen compounds and oxy compounds, such as preferably oxysulfides or oxychlorides phosphors, preferably, it is a metal oxide phosphor, more preferably it is a Mn activated metal oxide phosphor or a Mn activated phosphate based phosphor, even more preferably it is a Mn activated metal oxide phosphor.
  • the inorganic phosphor is selected from the group consisting of Al 2 O 3 :Cr 3+ , Y 3 Al 5 O 12 :Cr 3+ , MgO:Cr 3+ , ZnGa 2 O 4 :Cr 3+ , MgAl 2 O 4 :Cr 3+ , Gd3Ga5O 12 :Cr 3+ , LiAl5O 8 :Cr 3+ , MgSr 3 Si 2 O 8 :Eu 2+ ,Mn 2+ , Sr 3 MgSi 2 O 8 :Mn 4+ , Sr 2 MgSi 2 O 7 :Mn 4+ , SrMgSi 2 O 6 :Mn 4+ , BaMg 6 Ti6O19:Mn 4+ , Ca 14 Al 10 Zn 6 O 35 :Mn 4+ , Mg 8 Ge 2 O 11 F 2 :Mn 4+ , Mg 2 TiO 4 :Mn 4+ , Ca 14 Al
  • 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 -Vinzl monomers
  • 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.
  • 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-(meth) acrylate, tetra- methylol methan tri-(meth) acrylate), tetra-methylol methane tetra(meth) acrylate,
  • 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.
  • bromine and sulfur atom-containing monomers 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
  • 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 BI (Trademark, Kao Corp.).
  • 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.
  • 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.
  • 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,
  • 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.
  • the formulation can contain the solvent in an amount of 90 wt.% or more based on total amount of the formulation.
  • the content of the solvent is normally 60 wt.% or more, preferably in the range from 70 wt.% to 95 wt.% based on the total amount of the formulation.
  • the invention relates to use of the particle of the present invention, or the composition of the present invention, or the formulation of the present invention, in 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.
  • 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.
  • 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”. According to the present invention, said inorganic phosphor is described in the section of “inorganic phosphors” above.
  • 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).
  • said reflector is a metal substrate, preferably Al substrate, Cu substrate, metal alloy substrate is useful from the viewpoint 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.
  • the selective light reflector comprises at least a selective light reflecting layer selected from the group consisting of Al layer, Al + MgF 2 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 + MgF 2 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.
  • 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 ⁇ m to 1 mm, preferably it is in the range from 10 ⁇ m to 500 ⁇ m, more preferably it is from 30 ⁇ m to 200 ⁇ m, even more preferably from 50 ⁇ m to 100 ⁇ m 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 0.01wt.% to 30wt.% based on the total amount of the matrix material, preferably it is from 0.1wt.% to 10wt.%, more preferably from 0.5wt.% to 5wt.%, furthermore preferably it is from 1wt.% to 3wt.%, from the view point of better light conversion property, lower production cost and less production damage of a production machine.
  • the 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.
  • 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. -Green House In another aspect, 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 (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.
  • 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), (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”.
  • 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. 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.
  • 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.
  • 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 AlO 2 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.
  • 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.
  • said 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.
  • 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).
  • 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.
  • Method for fabricating a particle of a polymer coated inorganic phosphor comprising at least the following steps: a) Preparing a 1 st reaction mixture by mixing at least 1 st polymer precursor, an inorganic phosphor and optionally a polymerization initiator together with at least a 1 st solvent; b) Reacting the 1 st polymer precursor in the 1 st reaction mixture without using water as a solvent to form a 1 st polymer coating layer on the surface of the inorganic phosphor, preferably said reaction is triggered by applying irradiation of rays to the 1 st reaction mixture and/or by applying a heat treatment, preferably said polymerization initiator is selected from one or more members of the group consisting of photo acid-generators, photo radical – generators, photo base – generators, heat acid-generators, heat base – generators and heat radical – generators, preferably said ray is visible light, UV rays, IR rays,
  • the 1 st solvent is an organic solvent
  • said organic solvent is selected from one or more members of the group consisting of alcohols including primary alcohol having 1 to 40 carbon atoms, preferably 1 to 25 carbon atoms, more preferably 2 to 20 carbon atoms, such as methanol, ethanol, isopropyl alcohol, butyl alcohol, 1-pentanol, tetrahydrofurfuryl alcohol, 1-hexanol, 1- heptanol, 1-octanol, 1-nonanol, 1-decanol (boiling point ( o 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-
  • alcohols including primary alcohol having
  • Z 1 is symbol A, hydrogen atom, D, F, Cl, Br, I, a branched or straight alkyl chain having 1-15 carbon atoms, a branched or straight alkylene chain or alkoxylene chain having1 to 15 carbon atoms or an aryl group having 3 to 15 carbon atoms
  • Z 2 is symbol A, hydrogen atom, D, F, Cl, Br, I, a branched or straight alkyl chain having 1-15 carbon atoms, a branched or straight alkylene chain or alkoxylene chain having1 to 15 carbon atoms or an aryl group having 3 to 15 carbon atoms. 6.
  • step (b) is carried out at the temperature in the range from 35°C to 120°C, preferably from 50°C to 100°C, more preferably from 50°C to 85 °C, even more preferably from 55°C to 80°C, further more preferably from 60°C to 76 °C. 7.
  • the total amount of the 1 st polymer precursor used in step (b) is in the range from 0.5 to 20 (parts) pts.wt based on the total amount of the inorganic phosphor used in step (b), preferably it is in the range from 1 to 10 pts.wt, more preferably it is in the range from 2 to 7.5 pts.wt, even more preferably it is in the range from 3 to 5 pts.wt. 8.
  • the method of any one of embodiments 1 to 7, further comprises following step (c), (d) and (e), (c) mixing a 2 nd polymer precursor in a 2 nd solvent to form a 2 nd reaction mixture; (d) adding the 2 nd reaction mixture into the 1 st reaction mixture to form a 3 rd reaction mixture; (e) reacting the 2 nd polymer precursor in the 3 rd reaction mixture to form the 1 st polymer coating layer on the surface of the inorganic phosphor or to form a 2 nd polymer coating layer on the 1 st polymer coating layer.
  • step (a) further comprise following step (a1) and (a2), (a1) mixing a 1 st polymer precursor with a 2 nd solvent to form a reaction mixture a1, preferably said 1 st polymer precursor is a styreme monomer; (a2) mixing an inorganic phosphor with a surfactant in a 1 st solvent to form a reaction mixture a2, 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; preferably said anchoring group is a carboxyl group or a phosphonate group, more preferably it is a phosphonate group, preferably
  • said 2 nd polymer precursor is selected from one or more members of the group consisting of (meth)acrylate monomers, such as 1-[2-[(2-methyl-1-oxo-2- propen-1-yl)oxy]ethyl] ester butanedioic acid, 1-[2-[(2-methyl-1-oxo-2- propen-1-yl)oxy]ethyl] ester 1,2-cyclohexanedicarboxylic acid, 2- methacryloyloxyethyl acid phosphate (Kyoeisha Chemical “LIGHT ESTER P-1M(N)”), bis(2-methacryloyloxyethyl acid) phosphate, 1-[2-[(1-oxo-2- propen-1-yl)oxy]ethyl] ester butanedioic acid, 1-[2-[(1-oxo-2-propen-1-yl) oxy]ethyl] ester 1,2-cyclo
  • the 2 nd solvent is an organic solvent
  • said organic solvent is selected from one or more members of the group consisting of alcohols including primary alcohol having 1 to 40 carbon atoms, preferably 1 to 25 carbon atoms, more preferably 2 to 20 carbon atoms such as methanol, ethanol, isopropyl alcohol, butyl alcohol, 1-pentanol, tetrahydrofurfuryl alcohol, 1-hexanol, 1- heptanol, 1-octanol, 1-nonanol, 1-decanol (boiling point ( o 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
  • 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,
  • the inorganic phosphor contains one or more of elements selected from the group consisting of alkali metal elements, alkaline metal elements, phosphorous atom, boron atom and sulfur atom, preferably said alkali metal element is Li, Na, Ka or a combination of any of these, and said alkaline metal element is Be, Mg, Ca, Sr, Ba or a combination of any of these. 14.
  • 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
  • the phosphor is a nontoxic phosphor, preferably it is an edible phosphor.
  • 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 SiAlON phosphors, preferably, it is a metal oxide phosphor, more preferably it is a Mn activated metal oxide phosphor or a Mn activated phosphate based phosphor, even more preferably it is a Mn activated metal oxide phosphor.
  • a metal oxide phosphor As a metal oxide phosphor, another new light emitting phosphor represented by following general formula (VI), (VI ⁇ ), (VII), (VII ⁇ ) (VIII), (IX), (X), (XI), (XII), (XIII) which can exhibit deep red-light emission, preferably with a sharp emission around 700 nm under excitation light of 300 to 400 nm, which are suitable to promote plant growth, can be used preferably.
  • a particle of polymer coated inorganic phosphor obtained or obtainable by any one the method of embodiments 1 to 17.
  • composition of embodiment 23, wherein said another material is selected from one or more members of the group consisting of matrix materials; pigments; light luminescent materials; light scattering particles; photo initiators; co-polymerizable monomers; cross linkable monomers; bromine-containing monomers; sulfur-containing monomers; polymers; adjuvants; adhesives; insecticides; insect attractants; metal oxides; Al, Ag, Au nanoparticles; dispersants; surfactants; fungicides and antimicrobial agents. 25.
  • the total amount of the particle of the composition is in the range from 0.01wt.% to 30wt.% based on the total amount of the composition, preferably it is from 0.1wt.% to 10wt.%, more preferably from 0.5wt.% to 5wt.%, furthermore preferably it is from 1wt.% to 3wt.%. 26.
  • the matrix material is an organic material and/or an inorganic material
  • 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.
  • An optical sheet (100) comprising at least one particle of any one of embodiments 18 to 20, or the composition of any one of embodiments 23 to 26, preferably said optical sheet is an agricultural sheet.
  • An optical device (200) comprising at least one optical sheet (100) of embodiment 29, 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 29. 32.
  • 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 23 to 26, or the formulation according to embodiment 27 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. 34.
  • Method for preparing the optical device (200) of embodiment 30, comprising following step (A); (A) providing the optical sheet of embodiment 29, in an optical device (200). 35. Use of the particle of any one of embodiments 18 to 20, or the composition of any one of embodiments 23 to 26, the formulation of embodiment 27, the optical sheet (100) of embodiment 29, the optical device (200) of embodiment 30 or the green house of embodiment 31 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
  • 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 29, 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 29 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 present invention provides one or more of following effects; 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, reflaction 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
  • AIBN Azobisisobutyronitrile, Sigma-Aldrich
  • Working Example 2 measurements of optical properties
  • the absorbances, internal quantum efficiencies (IQE) and external quantum efficiencies (EQE) of the CZA phosphors before and after the polymer coating treatment of the working example 1 are measured with using spectrophotofluorometer FP 6 500 (from JASCO).
  • IQE internal quantum efficiencies
  • EQE external quantum efficiencies
  • Table.2 Absorbance, IQEs and EQEs change of before/after coating treatment of CZA (excitation at 320nm)
  • Table.3 Absorbance, IQEs and EQEs change of before/after coating treatment of CZA (excitation at 320nm)
  • Table.3 Absorbance, IQEs and EQEs change of before/after coating treatment of CZA (excitation at 320nm)
  • Table.2 Absorbance, IQEs and EQEs change of before/after coating treatment of CZA (excitation at 320nm)
  • Table.3 Absorbance, IQEs and EQEs change of before/after coating treatment of CZA (excitation at 320nm)
  • Table 2 and table 3 Polymer coated CZA phosphors kept very high level of absorbance, EQE and IQE at both excitation wavelengths (320 and 460 nm), compared to these of bare CZA phosphor.
  • Working Example 3 Water durability test The durability of the
  • the mixture is heated at 35 o C and is mechanically stirred at 200 rpm rotating speed for 2 hours. Then 200 mL of cyclohexane (Merck) solution of styrene monomer (Sigma-Aldrich; 20g) is added to the CZA dispersion. After addition of V-65 (Fujifilm Wako Pure Chemical Industry; 150 mg), ultrasound irradiation is started in Bransonic CPX2800H-J (40 kHz, 110W, Branson). Internal temperature is controlled at 60 o C and the mixture is stirred at 200 rpm rotating speed for 3 hours. Stirring and ultrasound irradiation are stopped, the mixture is cooled to room temperature.
  • Working Example 8 Water durability test The PS coated phosphors from working example 5 are used in the same manner as described in working example 3 instead of the polymer coated phosphors from working example 1.
  • Working Example 9 EQE measurement of inorganic phosphors EQE measurements are carried out in the same manner as described in working example 2 except for the following phosphors are used. Table 5 showed the results.
  • La 2 O 3 is pre- heated at 1200°C for 10 hours in air.
  • the starting materials are weighted according to the stoichiometric ratio and mixed with acetone in an agate mortar.
  • the mixture powder is pelletized at 10 MPa and put on an alumina container.
  • the mixture is heated at 900°C for 6 h in air.
  • the obtained materials are well grinded for the characterization.
  • XRD measurements are performed using an X-ray diffractometer (RIGAKU RAD-RC).
  • Photoluminescence (PL) spectra is measured using a spectrofluorometer (JASCO FP-6500) at room temperature.
  • the XRD patterns show that Na 3 La 3 W 2 O 12 is successfully synthesized as main phase.
  • the photoluminescence excitation spectrum shows ultraviolet region from 300 nm to 550 nm and emission spectrum shows the deep red region from 650 nm to 800 nm peaked at 700 nm.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Luminescent Compositions (AREA)

Abstract

La présente invention concerne un procédé de fabrication d'une particule de luminophore inorganique revêtu de polymère.
PCT/EP2021/068947 2020-07-13 2021-07-08 Procédé de fabrication d'une particule WO2022013049A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP20185540.0 2020-07-13
EP20185540 2020-07-13

Publications (1)

Publication Number Publication Date
WO2022013049A1 true WO2022013049A1 (fr) 2022-01-20

Family

ID=71607810

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2021/068947 WO2022013049A1 (fr) 2020-07-13 2021-07-08 Procédé de fabrication d'une particule

Country Status (2)

Country Link
AR (1) AR122955A1 (fr)
WO (1) WO2022013049A1 (fr)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030030067A1 (en) * 2001-06-06 2003-02-13 Wei Chen Upconversion luminescence materials and methods of making and using same
US20140155640A1 (en) * 2008-08-07 2014-06-05 Nanoco Technologies Ltd. Surface Functionalised Nanoparticles
JP2014196466A (ja) 2013-03-08 2014-10-16 楠本化成株式会社 無機微粒子高濃度分散体用粘性調整剤及びそれが配合された無機微粒子高濃度分散体
WO2017129351A1 (fr) 2016-01-26 2017-08-03 Merck Patent Gmbh Composition, feuille de conversion de couleur et dispositif de diode électroluminescente
US20170222097A1 (en) * 2014-07-22 2017-08-03 Koninklijke Philips N.V. Siloxane ligands to be used for dispersing quantum dots in silicone hosts to obtain color converters for led lighting
WO2019020653A1 (fr) 2017-07-26 2019-01-31 Merck Patent Gmbh Composition
WO2019020602A2 (fr) 2017-07-26 2019-01-31 Merck Patent Gmbh Luminophore et composition
WO2019211257A1 (fr) * 2018-05-03 2019-11-07 Merck Patent Gmbh Ligands réticulés

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030030067A1 (en) * 2001-06-06 2003-02-13 Wei Chen Upconversion luminescence materials and methods of making and using same
US20140155640A1 (en) * 2008-08-07 2014-06-05 Nanoco Technologies Ltd. Surface Functionalised Nanoparticles
JP2014196466A (ja) 2013-03-08 2014-10-16 楠本化成株式会社 無機微粒子高濃度分散体用粘性調整剤及びそれが配合された無機微粒子高濃度分散体
US20170222097A1 (en) * 2014-07-22 2017-08-03 Koninklijke Philips N.V. Siloxane ligands to be used for dispersing quantum dots in silicone hosts to obtain color converters for led lighting
WO2017129351A1 (fr) 2016-01-26 2017-08-03 Merck Patent Gmbh Composition, feuille de conversion de couleur et dispositif de diode électroluminescente
WO2019020653A1 (fr) 2017-07-26 2019-01-31 Merck Patent Gmbh Composition
WO2019020602A2 (fr) 2017-07-26 2019-01-31 Merck Patent Gmbh Luminophore et composition
WO2019211257A1 (fr) * 2018-05-03 2019-11-07 Merck Patent Gmbh Ligands réticulés

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
LEHMANN, W.: "Inorganic phosphors", 2004, CRC PRESS, article "Phosphor Preparation", pages: 19 - 24
NARITA, K.: "Phosphor Handbook", 2006, CRC PRESS, article "Methods of Phosphor Synthesis and Related Technology", pages: 341 - 354

Also Published As

Publication number Publication date
AR122955A1 (es) 2022-10-19

Similar Documents

Publication Publication Date Title
US20200231872A1 (en) Phosphor and a composition
WO2021099233A1 (fr) Procédé de fabrication d'une particule
WO2022073948A1 (fr) Particule et procédé de fabrication d'une particule
EP3408348B1 (fr) Utilisation de feuille de conversion de couleur
US20220095547A1 (en) Method for controlling a condition of a plant
US10808127B2 (en) Color conversion with solid matrix films and green rhodamines
US11275265B2 (en) Control of illumination spectra for LCD displays
CN107544178A (zh) 光转换元件及包含它的显示装置
US10227492B2 (en) Modifications of the sol-gel films and production processes thereof
JP2022502697A (ja) 量子ドットカラーフィルタインク組成物、および量子ドットカラーフィルタインク組成物を利用したデバイス
WO2022013049A1 (fr) Procédé de fabrication d'une particule
WO2021099351A1 (fr) Procédé de fabrication d'une particule
JP7077519B2 (ja) 色変換フィルム、これを含むバックライトユニット及びディスプレイ装置
WO2022112459A1 (fr) Particule de matériau polymère électroluminescent
WO2022090444A1 (fr) Luminophore
JP6937436B2 (ja) 色変換パネルおよび色変換パネルの製造方法
US20220095549A1 (en) Method for modulating a condition of a biological cell
WO2022013116A1 (fr) Luminophore
WO2022012810A1 (fr) Luminophore
CN1315981C (zh) 一种双波段荧光材料及制备方法
WO2019021756A1 (fr) Luminophore et son procédé de production, feuille de luminophore et dispositif d'éclairage
RU2579136C1 (ru) Светопреобразующий композиционный полимерный материал для парников и теплиц
WO2022189385A1 (fr) Composition comprenant des particules en forme de plaquettes
WO2016080857A1 (fr) Matériau composite polymérique transformant la lumière pour serres et orangeries
TW202412359A (zh) 量子點濾色器墨水組成物及使用其之裝置

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21737478

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21737478

Country of ref document: EP

Kind code of ref document: A1