WO2022090444A1 - Phosphor - Google Patents

Phosphor Download PDF

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Publication number
WO2022090444A1
WO2022090444A1 PCT/EP2021/080084 EP2021080084W WO2022090444A1 WO 2022090444 A1 WO2022090444 A1 WO 2022090444A1 EP 2021080084 W EP2021080084 W EP 2021080084W WO 2022090444 A1 WO2022090444 A1 WO 2022090444A1
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WIPO (PCT)
Prior art keywords
phosphor
composition
light
present
combination
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Application number
PCT/EP2021/080084
Other languages
French (fr)
Inventor
Ryota YAMANASHI
Hiroki Yoshizaki
Hiroshi Okura
David Downey
Kenji Toda
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Merck Patent Gmbh
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Publication of WO2022090444A1 publication Critical patent/WO2022090444A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/67—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G9/00—Cultivation in receptacles, forcing-frames or greenhouses; Edging for beds, lawn or the like
    • A01G9/24—Devices or systems for heating, ventilating, regulating temperature, illuminating, or watering, in greenhouses, forcing-frames, or the like

Definitions

  • the present invention relates to a phosphor, a composition, a formulation, an optical sheet, an optical device, a greenhouse, use and a method.
  • red phosphors examples include 3.5MgO-0.5MgF 2 - GeO 2 :Mn 4+ (Ref. 4) and (k-x)MgO-xAF 2 -GeO 2 :yMn 4+ (Ref. 1 ).
  • k is a real number from 2.8 to 5
  • x is a real number from 0.1 to 0.7
  • y is a real number from 0.005 to 0.015
  • A is Ca, Sr, Ba, Zn or a mixture thereof.
  • These phosphors contain fluorine. Therefore, it is believed that they are chemically unstable.
  • a 2 [MF 6 ]:Mn 4+ (Ref. 2) and CaAISiN 3 :Eu 2+ (Ref. 3) are practical red phosphors for white LEDs.
  • A is Li, Na, K, Rb, Cs or NF
  • M is Ge, Si, Sn, Ti or Zr.
  • improved light emission ability such as deep red light emission ability, near infrared light emission ability and/or blue light emission ability preferably suitable for controlling a condition of a plant, phytoplankton, bacteria and/or alga, optimized peak light emission wavelength, optimized peak maximum light emission wavelength, improved Full Width at Half Maximum
  • improved light absorption optimized peak light absorption wavelength
  • preferable light emission / light absorption spectrum preferable light emission / light absorption ratio
  • improved chemical stability such as better long term moisture durability and/or water resistance, UV resistivity; higher EQE; stronger light emission intensity; improved and/or well controlled average particle size
  • improved optical properties such as light scattering, absorbing, refraction and/or reflection ability of 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; simpler and/
  • A is a cation selected from one or more members of the group consisting of Li + , Na + , K + , Rb + and Cs + ; preferably A is Li + , Na + , K + or a combination of these, more preferably A 2 is Li + 2 , Na + 2 , K + 2 or a combination of Li + i and Na + i, Li + i and K + i, Na + i and K + i or a combination of Na + 2 /3, Li + 2 /3 and K + 2 /3;
  • B is a cation selected from one or more members of the group consisting of Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ and Zn 2+ , preferably B is Mg 2+ , Zn 2+ or a combination of Mg 2+ and Zn 2+ ;
  • C is a cation selected from one or more members of the group consisting of Ti 4+ , Zr 4+ , Hf 4+ , Si 4+ , Ge 4+ , and Sn 4+ , preferably C is Ti 4+ , Zr 4+ or Ge 4+ or a combination of these;
  • M is Mn 4+ , Mn 2+ , Fe 3+ Ti 3+ or Cr 3+ , preferably Mn 4+ or Cr 3+ , more preferably Mn 4+ .
  • the present invention relates to a composition , preferably an agricultural composition, containing at least the phosphor of the present invention, and another material, preferably 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.
  • the present invention relates to a formulation containing at least one phosphor of the present invention or the composition of the present invention, and a solvent.
  • the invention relates to an optical sheet (100) comprising at least one layer containing at least one phosphor of the present invention or the composition of the present invention, preferably said optical sheet is an agricultural sheet.
  • the present invention relates to a method for preparing the optical sheet, preferably for preparing the agriculture sheet, wherein the method comprises the following steps (A) and (B),
  • composition of the present invention or the formulation of the present invention in a first shaping, preferably onto a substrate or into an inflation molding machine, and
  • the invention relates to an optical device (200) comprising at least one phosphor of the present invention or 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.
  • 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 a greenhouse comprising the phosphor of the present invention, composition of the present invention, formulation of the present invention, the optical sheet (100) of the present invention or the optical device (200) of the present invention.
  • the invention relates to a use of the phosphor of the present invention, composition of the present invention, formulation of the present invention, the optical sheet (100) of the present invention or the optical device (200) of the present invention or the greenhouse of the present invention for controlling a condition of a plant or cultivation of algae, bacteria, preferably said bacteria are photosynthetic bacteria, and/or plankton, preferably photo plankton.
  • the invention relates to a method for preparing the optical device (200) of the present invention, comprising following step (A);
  • the invention in another aspect, relates to a method of supplying the particle of the present invention, the composition of any one of the present invention or the formulation of the present invention to at least one portion of a plant.
  • 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 Gai I lard ia, Lettuce, Rucola, Komatsuna (Japanese mustard spinach) or Radish (preferably Gaillardia, Lettuce, or Rucola).
  • light modulating material is a material which can change at least one of physical properties of light. Preferably it is selected from pigments, dyes and luminescent materials.
  • pigments stands for materials that are insoluble in an aqueous solution and changes the color of reflected or transmitted light as the result of wavelength-selective absorption and/or reflection, e.g. Inorganic pigments, organic pigments and inorganic-organic hybrid pigments.
  • dye means colored substances that are soluble in an aqueous solution and changes the color as the result of wavelength-selective absorption of irradiation.
  • luminescent means spontaneous emission of light by a substance not resulting from heat. It is intended to include both, phosphorescent light emission as well as fluorescent light emission.
  • light luminescent material is a material which can emit either fluorescent light or phosphorescent light.
  • phosphorescent light emission is defined as being a spin prohibition light emission from a triplet state or higher spin state (e.g. quintet) of spin multiplicity (2S+1 ) > 3, wherein S is the total spin angular momentum (sum of all the electron spins).
  • Wavelength converting material or briefly referred to as a “converter” means a material that converts light of a first wavelength to light of a second wavelength, wherein the second wavelength is different from the first wavelength.
  • Wavelength converting materials include organic materials and inorganic materials that can achieve photon up-conversion, and organic materials and inorganic materials that can achieve photon down-conversion.
  • photon down-conversion is a process which leads to the emission of light at longer wavelength than the excitation wavelength, e.g. by the absorption of one photon leads to the emission of light at longer wavelength.
  • photon up-conversion is a process that leads to the emission of light at shorter wavelength than the excitation wavelength, e.g. by the two- photon absorption (TPA) or Triplet-triplet annihilation (TTA), wherein the mechanisms for photon up-conversion are well known in the art.
  • TPA two- photon absorption
  • TTA Triplet-triplet annihilation
  • organometallic material means a material of organometallic compounds and organic compounds without any metals or metal ions.
  • organometallic compounds stands for chemical compounds containing at least one chemical bond between a carbon atom of an organic molecule and a metal, including alkaline, alkaline earth, and transition metals, e.g. Alqs, LiQ, lr(ppy)s.
  • the inorganic materials include phosphors and semiconductor nanoparticles.
  • a “phosphor” is a fluorescent or a phosphorescent inorganic material which contains one or more light emitting centers.
  • the light emitting centers are formed by activator elements such as e.g. atoms or ions of rare earth metal elements, for example La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, and/or atoms or ions of transition metal elements, for example Or, Mn, Fe, Co, Ni, Cu, Ag, Au and Zn, and/or atoms or ions of main group metal elements, for example Na, Tl, Sn, Pb, Sb and Bi.
  • activator elements such as e.g. atoms or ions of rare earth metal elements, for example La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu
  • transition metal elements for example Or, Mn, Fe, Co, Ni, Cu,
  • Suitable phosphors include phosphors based on garnet, silicate, orthosilicate, thiogallate, sulfide, nitride, silicon-based oxynitride, nitridosilicate, nitridoaluminumsilicate, oxonitridosilicate, oxonitridoaluminumsilicate and rare earth doped sialon.
  • Phosphors within the meaning of the present application are materials which absorb electromagnetic radiation of a specific wavelength range, preferably blue and/or ultraviolet (UV) electromagnetic radiation and convert the absorbed electromagnetic radiation into electromagnetic radiation having a different wavelength range, preferably visible (VIS) light such as violet, blue, green, yellow, orange, or red light, or the near infrared light (NIR).
  • UV ultraviolet
  • VIS visible
  • NIR near infrared light
  • UV is electromagnetic radiation with a wavelength from 100 nm to 389nm, shorter than that of visible light but longer than X-rays.
  • VIS is electromagnetic radiation with a wavelength from 390 nm to 700 nm.
  • NIR is electromagnetic radiation with a wavelength from 701 nm to 1 ,000 nm.
  • semiconductor nanoparticle in the present application denotes a crystalline nanoparticle which consists of a semiconductor material.
  • Semiconductor nanoparticles are also referred to as quantum materials in the present application. They represent a class of nanomaterials with physical properties that are widely tunable by controlling particle size, composition and shape. Among the most evident size dependent property of this class of materials is the tunable fluorescence emission. The tunability is afforded by the quantum confinement effect, where reducing particle size leads to a “particle in a box” behavior, resulting in a blue shift of the band gap energy and hence the light emission.
  • the emission of CdSe nanocrystals can be tuned from 660 nm for particles of diameter of ⁇ 6.5 nm, to 500 nm for particles of diameter of ⁇ 2 nm. Similar behavior can be achieved for other semiconductors when prepared as nanocrystals allowing for broad spectral coverage from the UV (using ZnSe, CdS for example) throughout the visible (using CdSe, InP for example) to the near-IR (using InAs for example).
  • Semiconductor nanoparticles may have an organic ligand on the outermost surface of the nanoparticles.
  • emission means the emission of electromagnetic waves by electron transitions in atoms and molecules.
  • the term “transparent” means at least around 60 % of incident light transmittal.
  • 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 schematic of fabrication process of the phosphor of the working example 1 .
  • Fig. 6 shows the emission spectra of the phosphor obtained in the working example 1 .
  • an optical sheet (a color conversion sheet, an agricultural sheet)
  • an optical device (a light emitting diode device)
  • an optical device (a light emitting diode device)
  • B is a cation selected from one or more members of the group consisting of Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ and Zn 2+ , preferably B is Mg 2+ , Zn 2+ or a combination of Mg 2+ and Zn 2+ ;
  • C is a cation selected from one or more members of the group consisting of Ti 4+ , Zr 4+ , Hf 4+ , Si 4+ , Ge 4+ , and Sn 4+ , preferably C is Ti 4+ , Zr 4+ or Ge 4+ or a combination of these;
  • M is Mn 4+ , Mn 2+ , Fe 3+ Ti 3+ or Cr 3+ , preferably Mn 4+ or Cr 3+ , more preferably Mn 4+ .
  • transition metal ions of M 1 defined above is doped into “C” site of the formula (I) above.
  • the total amount of M is 0.01 wt.% to 10wt.% based on the total amount of the phosphor, preferably it is from 0.1 wt.% to 5wt%, more preferably from 0.5wt.% to 2wt%, more preferably from 0.7 to 1.5wt.%.
  • the phosphor is represented by following chemical formula (III),
  • a 1 A 2 BCO 6 M -(III) wherein A 1 and A 2 are each independently of each other, a cation selected from the group consisting of Li + , Na + , K + , Rb + and Cs + , preferably A 1 A 2 is l_i + 2, Na + 2, K + 2 or a combination of Li + i and Na + i, Li + i and K + i, Na + i and K + i or a combination of Na + 2/3, Li + 2/3 and K + 2/3.
  • B is Mg 2+ , Zn 2+ or a combination of Mg 2+ and Zn 2+ such as a combination of Mg 2+ o.5 and Zn 2+ o.5.
  • C is Ti 4+ , Zr 4+ or Ge 4+ or a combination of Ti 4+ o.s and Zr 4+ o.s, Ti 4+ o.s and Ge 4+ o.s or a combination of Zr 4+ o.s and Ge 4+ o.5.
  • the phosphor is (Li,K)2MgTiO4: M.
  • the M is Mn 4+ .
  • the phosphor is (Li,K)2MgTiO4:Mn 4+ .
  • the peak maximum light wavelength of light emitted from the inorganic phosphor in the range from 660 nm to 710 nm is very suitable for plant condition control, especially for plant growth promotion.
  • the inorganic phosphor having at least one light absorption peak wavelength in UV and / or purple light wavelength region from 300 nm to 430 nm may keep harmful insects off plants.
  • the inorganic phosphor can have at least one light absorption peak wavelength in UV and / or purple light wavelength reason from 300 nm to 430 nm.
  • an inorganic phosphor having a first peak wavelength of light emitted from the inorganic phosphor in the range from 400nm to 500nm and a second peak wavelength of light emitted from the inorganic phosphor from 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.
  • the phosphor of the present invention is very useful for agriculture use, especially a controlling a condition of a living organism, especially for controlling a condition of a plant or cultivation of algae, bacteria, preferably said bacteria are photosynthetic bacteria, and/or plankton, preferably photo plankton. The most preferably for controlling a condition of a plant.
  • said phosphor is an 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.
  • a publicly known synthesis method can be used like described in “Narita, K., 2006, Methods of Phosphor Synthesis and Related Technology, In: Yen, W.M., Shionoya, S., Yamamoto, H.
  • conventional solid state reaction method can be used like described in working example 1 .
  • the raw materials publicly known materials, such as oxides, carbonates, hydroxides, nitrates, chlorides, fluorides, ammonium salts, citrates, phosphates, sulfates and/or borates can be used.
  • the present invention also relates to a composition
  • a composition comprising, essentially consisting of, or consisting of, at least one phosphor of the present invention and another material.
  • said composition is an agricultural composition.
  • the phosphor of the present invention is very useful for agriculture use, especially a controlling a condition of a living organism, especially for controlling a condition of a plant or cultivation of algae, bacteria, preferably said bacteria are photosynthetic bacteria, and/or plankton, preferably photo plankton.
  • the most preferably the phosphor is useful for controlling a condition of a plant.
  • composition preferably an agricultural composition, contains at least the phosphor of the present invention and another material, preferably 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; brominecontaining monomers; sulfur-containing monomers; polymers; adjuvants; adhesives; insecticides; insect attractants; metal oxides; Al, Ag, Au nanoparticles; dispersants; surfactants; fungicides and antimicrobial agents.
  • said another material is a matrix material and said composition can optionally comprises one or more additional additives selected from one or more members of the group consisting of light modulating materials such as dyes e.g. yellow dyes, pigments, light luminescent materials incl. organic and inorganic light luminescent materials, e.g. another inorganic phosphors; photo initiators; co-polymerizable monomers; cross linkable monomers; brominecontaining monomers; sulfur-containing monomers; adjuvants; adhesives; insecticides; insect attractants; metal oxides; Al, Ag, Au nanoparticles; dispersants; surfactants; fungicides and antimicrobial agents.
  • light modulating materials such as dyes e.g. yellow dyes, pigments, light luminescent materials incl. organic and inorganic light luminescent materials, e.g. another inorganic phosphors; photo initiators; co-polymerizable monomers; cross linkable monomers; brominecontaining monomers; sulfur-containing monomers
  • said composition comprises a plurality of the phosphors.
  • the total amount of the 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.
  • said matrix material is an organic material, and/or an inorganic material.
  • Publicly known organic and/or inorganic materials can be used.
  • the matrix material is an organic material.
  • the matrix material is an organic oligomer or an organic polymer material, more preferably an organic polymer selected from the group consisting of a transparent photosetting polymer, a thermosetting polymer, a thermoplastic polymer, or a combination of any of these, can be used preferably.
  • the matrix material is an organic material, and/or an inorganic material, preferably the matrix material is an organic material, more preferably it is an organic oligomer or an organic polymer material, even more preferably an organic polymer selected from the group consisting of a transparent photosetting polymer, a thermosetting polymer, a thermoplastic polymer, or a combination of any of these.
  • organic polymer materials polysaccharides, polyethylene, polypropylene, polystyrene, polymethyl pentene, polybutene, butadiene styrene, polyvinyl chloride, polystyrene, polymethacrylic styrene, styreneacrylonitrile, acrylonitrile-butadiene-styrene, polyethylene terephthalate, polymethyl methacrylate, polyphenylene ether, polyacrylonitrile, polyvinyl alcohol, acrylonitrile polycarbonate, polyvinylidene chloride, polycarbonate, polyamide, polyacetal, polybutylene terephthalate, polytetrafluoroethylene, ethyl vinyl acetate copolymer, ethylene tetrafluorethylen copolymer, polyamide, phenol, melamine, urea, urethane, epoxy, unsaturated polyester, polyallyl sulfone, polyacrylate
  • (meth)acrylates can be used preferably.
  • unsubstituted alkyl-(meth) acrylates for examples, methyl-acrylate, methyl-methacrylate, ethyl-acrylate, ethyl-methacrylate, butyl-acrylate, butyl-methacrylate, 2-ethylhexyl-acrylate, 2-ethylhexyl- methacrylate; substituted alkyl-(meth)acrylates, for examples, hydroxylgroup, epoxy group, or halogen substituted alkyl-(meth)acrylates; cyclopentenyl(meth)acrylate, tetra-hydro furfuryl-(meth)acrylate, benzyl (meth)acrylate, polyethylene-glycol di-(meth)acrylates.
  • the matrix material has a weight average molecular weight in the range from 5,000 to 50,000 preferably, more preferably from 10,000 to 30,000.
  • thermosetting polymer publicly known transparent thermosetting polymer can be used preferably.
  • OE6550 (trademark) series Dow Corning.
  • thermoplastic polymer the type of thermoplastic polymer is not particularly limited.
  • thermoplastic polymers can be copolymerized if necessary.
  • thermoplastic polymer or thermosetting polymer based on their physical properties.
  • the matrix materials and the inorganic phosphors of the present invention 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 light luminescent materials, which emits preferably blue, red light and/or near infrared light.
  • light luminescent materials publicly available light luminescent organic materials such as organic dyes, and/or light luminescent inorganic materials such as phosphors can be used singly or in combination.
  • any type of publicly known inorganic phosphors preferably inorganic phosphors having a peak wavelength of light emitted from the inorganic phosphor in the range of 600 nm or more, preferably in the range from 650 to 1500 nm, more preferably in the range from 650 to 1000 nm, even more preferably in the range from 650 to 800 nm, furthermore preferably in the range from 650 to 750 nm, much more preferably it is from 660 nm to 730 nm, furthermore preferably it is from 660 nm to 710 nm, the most preferably from 670 nm to 710nm, and / or at least one inorganic phosphor having a peak wavelength of light emitted from the inorganic phosphor in the range of 500 nm or less, preferably in the range from 250 nm to 500 nm, more preferably in the range from 300 nm
  • the peak light wavelength of the light emitted from the phosphor in the rage 660 nm to 710 nm is specifically useful for plant growth.
  • inorganic phosphors come into consideration for the present invention as 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 SiAION 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 SiAION phosphors, preferably, it is a metal oxide phosphor, more preferably it is a Mn activated metal oxide phosphor or a Mn activated phosphate based phosphor, even more preferably it is a Mn activated metal oxide phosphor.
  • Preferred metal-oxide phosphors are arsenates, germanates, halogermanates, indates, lanthanates, niobates, scandates, stannates, tantalates, titanates, vanadates, halovanadates, phosphovanadates, yttrates, zirconates, molybdate and tungstate. 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 Al2O3:Cr 3+ , Y3Al5O12:Cr 3+ , MgO:Cr 3+ , ZnGa2O4:Cr 3+ , MgAl2O4:Cr 3+ , Gd 3 Ga 5 O 12 :Cr 3+ , LiAl 5 O 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 Ti 6 O 19 :Mn 4+ , Ca 14 Al 10 Zn6O35:Mn 4+ , Mg8Ge2O 11 F 2 :Mn 4+ , Mg 2 TiO 4 :Mn 4+ , Y 2 M
  • Mn 4+ activated metal oxide phosphors Mn, Eu activated metal oxide phosphors, Mn 2+ activated metal oxide phosphors, Fe 3+ activated metal oxide phosphors can be used preferably from the viewpoint of environmentally friendly since these phosphors do not create Cr 6+ during synthesis procedure.
  • any type of publicly known materials for example as described in the second chapter of Phosphor handbook (Yen, Shinoya, Yamamoto), can be used if desired.
  • the blue light especially around 450 nm wavelength light may lead better plant growth, if it is combined with emission light from the inorganic phosphor having the peak wavelength of light emitted from the inorganic phosphor in the range from 660 nm to 740 nm, especially the combination of the blue light around 450 nm wavelength and emission light from the inorganic phosphor having the peak wavelength of light emitted from the inorganic phosphor in the range from 670 nm to 710 nm is preferable for better plant growth.
  • the composition can further comprise at least one blue light emitting inorganic phosphor having peak wavelength of light emitted from the inorganic phosphor around 450 nm, like described in the second chapter of Phosphor handbook (Yen, Shinoya, Yamamoto).
  • said additional inorganic phosphor is a different type of inorganic phosphor from the inorganic phosphor of the present invention
  • the composition can embrace one or more of publicly available vinyl monomers that are co- polymerizable.
  • vinyl monomers such as acrylamide, acetonitrile, diacetone-acrylamide, styrene, and vinyl-toluene or a combination of any of these.
  • the composition can further include one or more of publicly available crosslinkable monomers.
  • cyclopentenyl(meth)acrylates tetra-hydro furfuryl- (meth)acrylate; benzyl (meth)acrylate; the compounds obtained by reacting a polyhydric alcohol with and a,[3-unsaturated carboxylic acid, such as polyethylene-glycol di-(meth)acrylates (ethylene numbers are 2- 14), tri-methylol propane di(meth)acrylate, tri-methylol propane di (meth)acrylate, tri-methylol propane tri-(meth)acrylate, tri-methylol propane ethoxy tri-(meth) acrylate, tri-methylol propane propoxy tri-(meth) acrylate, tetra-methylol methan tri-(meth) acrylate), tetra-methylol methane tetra(meth) acrylate, polypropylene glycol di(meth)acrylates (propylene number therein are 2-14), Di-penta-erythr
  • the crosslinkable monomer is selected from the group consisting of tri-methylol-propane tri (meth)acrylate, di-pentaerythritol tetra-(meth)acrylate, di-pentaerythritol hexa-(meth)acrylate, bisphenol-A polyoxyethylene dimethacrylate and a combination thereof.
  • the vinyl monomers and the crosslinkable monomers described above can be used alone or in combination.
  • the composition can further comprise publicly known one or more of bromine-containing monomers, sulfur-containing monomers.
  • the type of bromine and sulfur atom-containing monomers (and polymers containing the same) are not particularly limited and can be used preferably as desired.
  • new frontier® BR-31 new Frontier® BR-30, new Frontier® BR-42M (available from DAI-ICHI KOGYO SEIYAKU CO., LTD) or a combination of any of these
  • sulfur-containing monomer composition IU-L2000, IU-L3000, IU-MS1010 (available from MITSUBISHI GAS CHEMICAL COMPANY, INC.) or a combination of any of these, can be used preferably.
  • the photo initiator can be a photo initiator that can generates a free radical when it is exposed to an ultraviolet light or a visible light.
  • a photo initiator that can generates a free radical when it is exposed to an ultraviolet light or a visible light.
  • benzoin-methyl-ether benzoin-ethyl-ether, benzoin-propyl-ether, benzoin-isobutyl-ether, benzoin-phenyl-ether, benzoin-ethers, benzophenone, N,N’-tetramethyl- 4,4’-diaminobenzophenone (Michler’s-ketone), N,N’-tetraethyl- 4,4’diaminobenzophenone, benzophenones, benzil-dimethyl-ketal (Ciba specialty chemicals, IRGACURE® 651 ), benzil-diethyl-ketal, dibenzil ketals, 2,2-dimethoxy-2-phenylacetophenone, p
  • An adjuvant can enhance permeability of effective component (e.g. insecticide), inhibit precipitation of solute in the composition, or decrease a phytotoxicity.
  • a surfactant means it does not comprise or is not comprised by other additives, for example a spreading agent, a surface treatment and an adjuvant.
  • said adjuvant can be selected from the group consisting of a mineral oil, an oil of vegetable or animal origin, alkyl esters of such oils or mixtures of such oils and oil derivatives, and combination thereof.
  • the weight ratio of each 1 additive of dispersant, surfactant, fungicide, antimicrobial agent and antifungal agent, to the weight of the invention phosphor in the total amount of the composition is in the range from 50 wt.% to 200 wt.%, more preferably it is from 75 wt.% to 150 wt.%.
  • Exemplified embodiment of an adjuvant is Approach Bl (Trademark, Kao Corp.).
  • the invention in another aspect, relates to a formulation comprising, essentially consisting of, or a consisting of at least one particle of the present invention or the composition of the present invention, and a solvent.
  • said formulation comprises a plurality of the inorganic phosphors or the composition of the present invention.
  • solvent wide variety of publicly known solvents can be used preferably. There are no particular restrictions on the solvent as long as it can dissolve or disperse the matrix material, and the particle of the composition. Preferably a plurality of particles of the present invention are in the formulation.
  • the solvent can be selected from the group consisting of water, ethylene glycol monoalkyl ethers, such as, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers, such as, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates, such as, methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol alkyl ether acetates, such as, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate; aromatic hydrocarbons, such as,
  • propylene glycol alkyl ether acetates such as, propylene glycol monomethyl ether acetate (hereafter “PGMEA”), propylene glycol monoethyl ether acetate, or propylene glycol monopropyl ether acetate and / or aromatic hydrocarbons, such as, benzene, toluene and xylene, can be used for
  • PGMEA propylene glycol monomethyl ether acetate
  • aromatic hydrocarbons such as, benzene, toluene and xylene
  • 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 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”.
  • 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 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).
  • it is over 70 %, more preferably, over 75%, the most preferably, it is over 80 %.
  • the term “transparent” means at least around 60 % of incident light transmittal at the thickness used in a the optical medium (100) and at a wavelength or a range of wavelength used during operation of the optical medium (100).
  • it is over 70 %, more preferably, over 75%, the most preferably, it is over 80 %.
  • said reflector is a metal substrate, preferably Al substrate, Cu substrate, metal alloy substrate is useful from the view point of high light reflection at deep red-light wavelength and lower cost.
  • a material for the selective light reflection reflector is not particularly limited. Well known materials for a selective light reflector can be used preferably as desired.
  • the selective light reflector can be a single layer or multiple layers. ln a preferred embodiment, the selective light reflector comprises at least a selective light reflecting layer selected from the group consisting of Al layer, Al + MgF2 stacked layers, Al + SiO stacked layers, Al + dielectric multiple layer, Au layer, dielectric multiple layer, Cr + Au stacked layers; with the selective light reflection layer more preferably being Al layer, Al + MgF2 stacked layers, Al + SiO stacked layers.
  • said selective light reflecting layer is stacked onto a transparent substrate.
  • the methods of preparing the selective light reflection layer can vary as desired and selected from well-known techniques.
  • the selective light reflection layer expect for cholesteric liquid crystal layers can be prepared by a gas phase-based coating process (such as Sputtering, Chemical Vapor Deposition, vapor deposition, flash evaporation), or a liquid-based coating process.
  • a gas phase-based coating process such as Sputtering, Chemical Vapor Deposition, vapor deposition, flash evaporation
  • the optical sheet is an agricultural sheet, a color conversion sheet for optical device, a remote phosphor tape for LED, or another sheet such as an optical filter.
  • the layer thickness of the optical sheet is in the range from 5 pm to 1 mm, preferably it is in the range from 10 pm to 500 pm, more preferably it is from 30 pm to 200 pm, even more preferably from 50 pm to 100 pm from the view point of better light conversion property and lower production cost.
  • the total amount of the particle in the optical sheet is in the range from 0.01wt.% 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 optical sheet (100) is useful for agriculture.
  • the optical medium (100) is useful for a mulch cultivation sheet to cover at least a part of a ridge in a field or to cover at least a part of a surface of planter, such as a surface of nutrient film technique hydroponics system or a deep flow technique hydroponics system.
  • the optical sheet as a mulch cultivation sheet can control plant condition such as plant growth and to protect a plant and/or a ridge or a surface of planter as a mulch cultivation sheet at the same time preferably.
  • the invention relates to use of the optical sheet (100) as a mulch cultivation sheet to cover a ridge in a field or to cover a surface of planter, preferably said planter is a nutrient film technique hydroponics system or a deep flow technique hydroponics system.
  • one side of the optical sheet (100) is coated by a light reflecting material which can reflect at least blue, red, and/or infrared light.
  • a light reflecting material any kinds of less toxic known light reflecting materials such as Al, metal oxides can be used preferably, more preferably Al, or AIO2 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 invention relates to use of the composition, or formulation in an optical sheet fabrication process.
  • the present invention furthermore relates to method for preparing the optical sheet (100), preferably for preparing the agriculture sheet, wherein the method comprises the following steps (A) and (B),
  • composition of the present invention or the formulation of the present invention in a first shaping, preferably onto a substrate or into an inflation moulding machine, and
  • steps (A) and (B) of the method are in this sequence.
  • the composition in step (A) is provided by spin coating, spray coating, bar coating, or a slit coating method.
  • the composition or the formulation in step (B) is provided into an inflation-molding machine and the matrix material is fixed by heat treatment of the machine.
  • the details of the composition and the formulation are described in the section of “composition” and the section of “formulation”.
  • the present invention relates to an optical device (200) comprising at least one phosphor of the present invention, composition of the present invention or at least one optical sheet (100) of the present invention, preferably said optical device (200) is a lighting device, such as a Light Emitting Diode.
  • the optical device (200) may further comprises a light source, a light re-directing device, and/or a reflector.
  • said light source is a light emitting diode, or an organic light emitting diode.
  • the optical device (200) comprises at least one optical sheet (100) 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 (200) is a lighting device, a light emitting diode device for agriculture, or building materials of greenhouse.
  • the present invention furthermore relates to method for preparing the optical device (200), wherein the method comprises following step (C),
  • the present invention relates to a use of the phosphor of the present invention, composition of the present invention, formulation of the present invention, 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 present invention relates to a greenhouse comprising the phosphor of the present invention, composition of the present invention, formulation of the present invention, the optical sheet (100) of the present invention or the optical device (200) of the present invention.
  • the present invention relates to use of the phosphor of the present invention, 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 greenhouse of the present invention for controlling a condition of a plant or cultivation of algae, bacteria, preferably said bacteria are photosynthetic bacteria, and/or plankton, preferably photo plankton.
  • present invention relates to a method of supplying the phosphor of the present invention, the composition of the present invention or the formulation of the present invention, to at least one portion of a plant.
  • any kinds of publicly known supplying method can be used. Such as spray, painting, coating.
  • the present invention further relates to a plant, alga, a plankton, or a bacterium obtained or obtainable by the method.
  • a plankton is a phytoplankton
  • said bacterium is a photosynthetic bacterium.
  • said living organism is not particularly limited.
  • a biological cell a plant, plankton, bacterium, alga, insects, animals.
  • the plant can be flowers, vegetables, fruits, grasses, trees and horticultural crops (preferably flowers and horticultural crops, more preferably flowers).
  • the plant can be foliage plants.
  • grasses are a poaceae, bambuseae (preferably sasa, phyllostachys), oryzeae (preferably oryza), pooideae (preferably poeae), triticeae (preferably elymus), elytrigia, hordeum, triticum, secale, arundineae, centotheceae, chloridoideae, hordeum vulgare, avena sativa, secale cereal, andropogoneae (preferably coix), cymbopogon, saccharum, sorghum, zea (preferably zea mays), sorghum bicolor, saccharum officinarum, coix lacryma
  • Embodiments of vegetables are stem vegetables, leaves vegetables, flowers vegetables, stalk vegetables, bulb vegetables, seed vegetables (preferably beans), roots vegetables, tubers vegetables, and fruits vegetables.
  • One embodiment of the plant can be Gai llardia, Lettuce, Rucola, Komatsuna (Japanese mustard spinach) or Radish (preferably Gai Hard ia, Lettuce, or Rucola).
  • the environment of growing plant can be natural environment, a greenhouse, a plant factory and indoor cultivation, preferably natural environment and a green house.
  • One embodiment of the natural environment is an outside farm.
  • a light emitting phosphor represented by following chemical formula (I), preferably for agriculture use,
  • B is a cation selected from one or more members of the group consisting of Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ and Zn 2+ , preferably B is Mg 2+ , Zn 2+ or a combination of Mg 2+ and Zn 2+ ;
  • C is a cation selected from one or more members of the group consisting of Ti 4+ , Zr 4+ , Hf 4+ , Si 4+ , Ge 4+ , and Sn 4+ , preferably C is Ti 4+ , Zr 4+ or Ge 4+ or a combination of these;
  • M is Mn 4+ , Mn 2+ , Fe 3+ Ti 3+ or Cr 3+ , preferably Mn 4+ or Cr 3+ , more preferably Mn 4+ .
  • the phosphor of embodiment 1 or 2 is represented by following chemical formula (III), A 1 A 2 BCO 6 : M -(III) wherein A 1 and A 2 are each independently of each other, a cation selected from the group consisting of Li + , Na + , K + , Rb + and Cs + , preferably A 1 A 2 is Li + 2, Na + 2, K + 2 or a combination of Li + i and Na + i, Li + i and K + i, Na + i and K + i or a combination of Na + 2/3, Li + 2/3 and K + 2/3.
  • the phosphor of any one of embodiments 1 to 5, is (Li,K)2MgTiO4: M.
  • a composition preferably an agricultural composition, containing at least the phosphor of any one of embodiments 1 to 7, and another material, preferably 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.
  • a formulation containing at least one phosphor of any one of embodiments 1 to 7 or a composition of embodiment 8, and a solvent.
  • Optical sheet (100) comprising at least one layer containing at least one phosphor of any one of embodiments 1 to 7, or the composition of embodiment 8, preferably said optical sheet is an agricultural sheet.
  • composition according to embodiment 8 or the formulation according to embodiment 9 in a first shaping, preferably onto a substrate or into an inflation moulding machine, and
  • An optical device (200) comprising at least one phosphor of any one of embodiments 1 to 7, a composition of embodiment 8 or at least one optical sheet (100) of embodiment 10, preferably said optical device (200) is a lighting device, more preferably it is a Light Emitting Diode.
  • a greenhouse comprising the phosphor of embodiments 1 to 7, composition of embodiment 8, formulation of embodiment 9, the optical sheet (100) of embodiment 10 or the optical device (200) of embodiment 12. 15. Use of the phosphor of any one of embodiments 1 to 7, the composition of embodiment 8, the formulation of embodiment 9, the optical sheet (100) of embodiment 10, the optical device (200) of embodiment 12 or the greenhouse of embodiment 14 for controlling a condition of a plant or cultivation of algae, bacteria, preferably said bacteria are photosynthetic bacteria, and/or plankton, preferably photo plankton.
  • improved light emission ability such as deep red light emission ability, near infrared light emission ability and/or blue light emission ability preferably suitable for controlling a condition of a plant, phytoplankton, bacteria and/or alga, optimized peak light emission wavelength, optimized peak maximum light emission wavelength, improved Full Width at Half Maximum; improved light absorption, optimized peak light absorption wavelength; preferable light emission / light absorption spectrum; preferable light emission / light absorption ratio; improved chemical stability such as better long term moisture durability and/or water resistance, UV resistivity; higher EQE; stronger light emission intensity; improved and/or well controlled average particle size; improved optical properties such as light scattering, absorbing, refraction and/or reflection ability of 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; simpler and/or easier synthesis method; improvement of controlling property of a phytoplank
  • 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 (Li,K)2MgTiO4:Mn 4+ is successfully synthesized as main phase.
  • the photoluminescence excitation spectrum shows ultraviolet region from 300 nm to 550 nm and emission spectrum showed the deep red region from 650 nm to 800 nm peaked at 675 nm.
  • an agricultural solution is prepared using 1 wt.% (Li,K) 2 MgTiO4:Mn 4+ phosphors in aqueous solution.
  • the light source of the systems is both same white LED set on top of the box of the system.
  • the same number of young lettuce and rucola as the test plants are set into both hydroponics systems A and B and enough water is set under the plants in the systems.
  • the aqueous solution is sprayed 10 times on the plants of the hydroponics system A on the first day and the 8th day.

Abstract

The present invention relates to a phosphor.

Description

Phosphor
Field of the Invention
The present invention relates to a phosphor, a composition, a formulation, an optical sheet, an optical device, a greenhouse, use and a method.
Background Art
Examples of currently known red phosphors include 3.5MgO-0.5MgF2- GeO2:Mn4+ (Ref. 4) and (k-x)MgO-xAF2-GeO2:yMn4+ (Ref. 1 ). (k is a real number from 2.8 to 5, x is a real number from 0.1 to 0.7, y is a real number from 0.005 to 0.015, and A is Ca, Sr, Ba, Zn or a mixture thereof.) These phosphors contain fluorine. Therefore, it is believed that they are chemically unstable.
A2[MF6]:Mn4+ (Ref. 2) and CaAISiN3:Eu2+ (Ref. 3) are practical red phosphors for white LEDs. (A is Li, Na, K, Rb, Cs or NF , M is Ge, Si, Sn, Ti or Zr.) It is seen that the emission wavelength of these phosphors is in a shorter wavelength side and the synthesis method is complicated and difficult.
Patent Literature
1. J P 2008-202044 A1
2. WO 2007/100824 A1
3. WO 2005/052087 A1
Non- Patent Literature
4. Phosphor Research Society of The Electrochemical Society of Japan, Phosphor handbook, Ohm Inc., 1987, 231.
Summary of the invention
The inventors surprisingly have found that there are still one or more of considerable problems for which improvement are desired, as listed below; improved light emission ability, such as deep red light emission ability, near infrared light emission ability and/or blue light emission ability preferably suitable for controlling a condition of a plant, phytoplankton, bacteria and/or alga, optimized peak light emission wavelength, optimized peak maximum light emission wavelength, improved Full Width at Half Maximum; improved light absorption, optimized peak light absorption wavelength; preferable light emission / light absorption spectrum; preferable light emission / light absorption ratio; improved chemical stability such as better long term moisture durability and/or water resistance, UV resistivity; higher EQE; stronger light emission intensity; improved and/or well controlled average particle size; improved optical properties such as light scattering, absorbing, refraction and/or reflection ability of 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; simpler and/or easier synthesis method; improvement of controlling property of a phytoplankton condition, photosynthetic bacteria and/or alga, preferably acceleration of growth of phytoplankton, photosynthetic bacteria and/or alga; improvement of controlling property of plant condition, preferably controlling of a plant height; controlling of color of fruits; promotion and inhibition of germination; controlling of synthesis of chlorophyll and carotenoids, preferably by blue light; plant growth promotion; adjustment and I or acceleration of flowering time of plants; controlling of production of plant components, such as increasing production amount, controlling of polyphenols content, sugar content, vitamin content of plants; controlling of secondary metabolites, preferably controlling of polyphenols, and/or anthocyanins; controlling of a disease resistance of plants; controlling of ripening of fruits, or controlling of weight of plant.
Then, it is found that a novel light emitting phosphor epresented by following chemical formula (I), preferably for agricultural use, A2BCO4:M -(I) wherein A is a cation selected from one or more members of the group consisting of Li+, Na+, K+, Rb+ and Cs+; preferably A is Li+, Na+, K+ or a combination of these, more preferably A2 is Li+ 2, Na+ 2, K+ 2 or a combination of Li+i and Na+i, Li+i and K+i, Na+i and K+i or a combination of Na+ 2/3, Li+ 2/3 and K+ 2/3;
B is a cation selected from one or more members of the group consisting of Mg2+, Ca2+, Sr2+, Ba2+ and Zn2+, preferably B is Mg2+, Zn2+ or a combination of Mg2+ and Zn2+;
C is a cation selected from one or more members of the group consisting of Ti4+, Zr4+, Hf4+, Si4+, Ge4+, and Sn4+, preferably C is Ti4+, Zr4+ or Ge4+ or a combination of these;
M is Mn4+, Mn2+, Fe3+ Ti3+or Cr3+, preferably Mn4+ or Cr3+, more preferably Mn4+.
In another aspect, the present invention relates to a composition , preferably an agricultural composition, containing at least the phosphor of the present invention, and another material, preferably 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.
In another aspect, the present invention relates to a formulation containing at least one phosphor of the present invention or the composition of the present invention, and a solvent. In another aspect, the invention relates to an optical sheet (100) comprising at least one layer containing at least one phosphor of the present invention or the composition of the present invention, preferably said optical sheet is an agricultural sheet.
In another aspect, the present invention relates to a method for preparing the optical sheet, preferably for preparing the agriculture sheet, wherein the method comprises the 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 onto a substrate or into an inflation molding machine, and
B) fixing the matrix material by evaporating a solvent of the formulation and/or by polymerizing the composition by applying heat or by exposing the photosensitive composition under ray of light.
In another aspect, the invention relates to an optical device (200) comprising at least one phosphor of the present invention or 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.
In another aspect, the present invention relates to a use of the particle of the present invention, the composition of the present invention, or the formulation of the present invention, in an optical sheet fabrication process or in agriculture, preferably for fabricating an agricultural sheet or for controlling a condition of a living organism.
In another aspect, the invention relates to a greenhouse comprising the phosphor of the present invention, composition of the present invention, formulation of the present invention, the optical sheet (100) of the present invention or the optical device (200) of the present invention. In another aspect, the invention relates to a use of the phosphor of the present invention, composition of the present invention, formulation of the present invention, the optical sheet (100) of the present invention or the optical device (200) of the present invention or the greenhouse of the present invention for controlling a condition of a plant or cultivation of algae, bacteria, preferably said bacteria are photosynthetic bacteria, and/or plankton, preferably photo plankton.
In another aspect, 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 (100) of the present invention, in an optical device (200).
In another aspect, the invention relates to a method of supplying the particle of the present invention, the composition of any one of the present invention or the formulation of the present invention to at least one portion of a plant.
Further advantages of the present invention will become evident from the following detailed description.
Definition of the terms
The above outlines and the following details are for describing the present invention and are not for limiting the claimed invention. Unless otherwise stated, the following terms used in the specification and claims shall have the following meanings for this application.
In this application, the use of the singular includes the plural, and the words “a”, “an” and “the” mean “at least one”, unless specifically stated otherwise. In this specification, when one concept component can be exhibited by plural species, and when its amount (e.g. weight %, mol %) is described, the amount means the total amount of them, unless specifically stated otherwise.
Furthermore, the use of the term “including”, as well as other forms such as “includes” and “included”, is not limiting. Also, terms such as “element” or “component” encompass both elements or components comprising one unit and elements or components that comprise more than one unit, unless specifically stated otherwise. As used herein, the term “and/or” refers to any combination of the elements including using a single element. In the present specification, when the numerical range is shown using “to”, the numerical range includes both numbers before and after the “to”,
Figure imgf000007_0001
and the unit is common for the both numbers, unless otherwise specified. For example, 5 to 25 mol% means 5 mol% or more and 25 mol% or less.
The section headings used herein are for organizational purposes and are not to be construed as limiting the subject matter described. All documents, or portions of documents, cited in this application, including, but not limited to, patents, patent applications, articles, books, and treatises, are hereby expressly incorporated herein by reference in their entirety for any purpose. If one or more of the incorporated literatures and similar materials defines a term in a manner that contradicts the definition of that term in this application, this application controls.
According to the present invention, the term ’’plant” means a multicellular organism in the kingdom Plantae that use photosynthesis to make their own food. Then according to the present invention, the plant can be flowers, vegetables, fruits, grasses, trees and horticultural crops (preferably flowers and horticultural crops, more preferably flowers). As one embodiment of the invention, the plant can be foliage plants. Exemplified embodiments of grasses are a poaceae, bambuseae (preferably sasa, phyllostachys), oryzeae (preferably oryza), pooideae (preferably poeae), triticeae (preferably elymus), elytrigia, hordeum, triticum, secale, arundineae, centotheceae, chloridoideae, hordeum vulgare, avena sativa, secale cereal, andropogoneae (preferably coix), cymbopogon, saccharum, sorghum, zea (preferably zea mays), sorghum bicolor, saccharum officinarum, coix lacryma-jobi var., paniceae (preferably panicum), setaria, echinochloa (preferably panicum miliaceum), echinochloa esculenta, and setaria italic. Embodiments of vegetables are stem vegetables, leaves vegetables, flowers vegetables, stalk vegetables, bulb vegetables, seed vegetables (preferably beans), roots vegetables, tubers vegetables, and fruits vegetables. One embodiment of the plant can be Gai I lard ia, Lettuce, Rucola, Komatsuna (Japanese mustard spinach) or Radish (preferably Gaillardia, Lettuce, or Rucola).
The term “light modulating material” is a material which can change at least one of physical properties of light. Preferably it is selected from pigments, dyes and luminescent materials.
The term “pigments” stands for materials that are insoluble in an aqueous solution and changes the color of reflected or transmitted light as the result of wavelength-selective absorption and/or reflection, e.g. Inorganic pigments, organic pigments and inorganic-organic hybrid pigments.
The term “dyes" means colored substances that are soluble in an aqueous solution and changes the color as the result of wavelength-selective absorption of irradiation.
The term “luminescent” means spontaneous emission of light by a substance not resulting from heat. It is intended to include both, phosphorescent light emission as well as fluorescent light emission. Thus, the term “light luminescent material" is a material which can emit either fluorescent light or phosphorescent light.
The term “phosphorescent light emission" is defined as being a spin prohibition light emission from a triplet state or higher spin state (e.g. quintet) of spin multiplicity (2S+1 ) > 3, wherein S is the total spin angular momentum (sum of all the electron spins).
The term “fluorescent light emission” is a spin allowed light emission from a singlet state of spin multiplicity (2S+1 ) =1 .
The term “wavelength converting material” or briefly referred to as a “converter” means a material that converts light of a first wavelength to light of a second wavelength, wherein the second wavelength is different from the first wavelength. Wavelength converting materials include organic materials and inorganic materials that can achieve photon up-conversion, and organic materials and inorganic materials that can achieve photon down-conversion.
The term “photon down-conversion” is a process which leads to the emission of light at longer wavelength than the excitation wavelength, e.g. by the absorption of one photon leads to the emission of light at longer wavelength.
The term “photon up-conversion” is a process that leads to the emission of light at shorter wavelength than the excitation wavelength, e.g. by the two- photon absorption (TPA) or Triplet-triplet annihilation (TTA), wherein the mechanisms for photon up-conversion are well known in the art.
The term “organic material" means a material of organometallic compounds and organic compounds without any metals or metal ions. The term “organometallic compounds” stands for chemical compounds containing at least one chemical bond between a carbon atom of an organic molecule and a metal, including alkaline, alkaline earth, and transition metals, e.g. Alqs, LiQ, lr(ppy)s.
The inorganic materials include phosphors and semiconductor nanoparticles.
A “phosphor” is a fluorescent or a phosphorescent inorganic material which contains one or more light emitting centers. The light emitting centers are formed by activator elements such as e.g. atoms or ions of rare earth metal elements, for example La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, and/or atoms or ions of transition metal elements, for example Or, Mn, Fe, Co, Ni, Cu, Ag, Au and Zn, and/or atoms or ions of main group metal elements, for example Na, Tl, Sn, Pb, Sb and Bi. Examples of suitable phosphors include phosphors based on garnet, silicate, orthosilicate, thiogallate, sulfide, nitride, silicon-based oxynitride, nitridosilicate, nitridoaluminumsilicate, oxonitridosilicate, oxonitridoaluminumsilicate and rare earth doped sialon. Phosphors within the meaning of the present application are materials which absorb electromagnetic radiation of a specific wavelength range, preferably blue and/or ultraviolet (UV) electromagnetic radiation and convert the absorbed electromagnetic radiation into electromagnetic radiation having a different wavelength range, preferably visible (VIS) light such as violet, blue, green, yellow, orange, or red light, or the near infrared light (NIR).
Here, the term “UV” is electromagnetic radiation with a wavelength from 100 nm to 389nm, shorter than that of visible light but longer than X-rays.
The term “VIS” is electromagnetic radiation with a wavelength from 390 nm to 700 nm. The term “NIR” is electromagnetic radiation with a wavelength from 701 nm to 1 ,000 nm.
The term "semiconductor nanoparticle" in the present application denotes a crystalline nanoparticle which consists of a semiconductor material. Semiconductor nanoparticles are also referred to as quantum materials in the present application. They represent a class of nanomaterials with physical properties that are widely tunable by controlling particle size, composition and shape. Among the most evident size dependent property of this class of materials is the tunable fluorescence emission. The tunability is afforded by the quantum confinement effect, where reducing particle size leads to a “particle in a box” behavior, resulting in a blue shift of the band gap energy and hence the light emission. For example, in this manner, the emission of CdSe nanocrystals can be tuned from 660 nm for particles of diameter of ~6.5 nm, to 500 nm for particles of diameter of ~2 nm. Similar behavior can be achieved for other semiconductors when prepared as nanocrystals allowing for broad spectral coverage from the UV (using ZnSe, CdS for example) throughout the visible (using CdSe, InP for example) to the near-IR (using InAs for example).
Semiconductor nanoparticles may have an organic ligand on the outermost surface of the nanoparticles.
The term “emission” means the emission of electromagnetic waves by electron transitions in atoms and molecules.
According to the present invention, the term “transparent” means at least around 60 % of incident light transmittal.
Preferably, it is over 70 %, more preferably, over 75%, the most preferably, it is over 80 %. Brief Description of drawings
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 schematic of fabrication process of the phosphor of the working example 1 .
Fig. 6: shows the emission spectra of the phosphor obtained in the working example 1 .
List of reference signs in figure 1
100. an optical sheet (a color conversion sheet, an agricultural sheet)
110. a particle of the invention
120. a matrix material
130. an additive (optional)
List of reference signs in figure 2
200. an optical device (a light emitting diode device)
210. a particle of the invention
220. a matrix material
230. a light emitting diode element
240. conductive wires
250. a molding Material 260a. a cup
260b. a mount lead
270. an inner lead
List of reference signs in figure 3
300. an optical device (a light emitting diode device)
301. a color conversion sheet
310. a particle of the invention
320. a matrix material
330. a light emitting diode element
340. an additive (optional)
350. a casing
360. converted light
370. emitted light
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. a supporting part
Detailed Description of the invention
According to the present invention, light emitting phosphor represented by following chemical formula (I),
A2BCO4:M -(I) wherein A is a cation selected from one or more members of the group consisting of Li+, Na+, K+, Rb+ and Cs+; preferably A is Li+, Na+, K+ or a combination of these, more preferably A2 is Li+ 2, Na+ 2, K+ 2 or a combination of Li+i and Na+i, Li+i and K+i, Na+i and K+i or a combination of Na+2/3, Li+2/3 and K+2/3;
B is a cation selected from one or more members of the group consisting of Mg2+, Ca2+, Sr2+, Ba2+ and Zn2+, preferably B is Mg2+, Zn2+ or a combination of Mg2+ and Zn2+;
C is a cation selected from one or more members of the group consisting of Ti4+, Zr4+, Hf4+, Si4+, Ge4+, and Sn4+, preferably C is Ti4+, Zr4+ or Ge4+ or a combination of these;
M is Mn4+, Mn2+, Fe3+ Ti3+or Cr3+, preferably Mn4+ or Cr3+, more preferably Mn4+.
It is believed that the transition metal ions of M1 defined above is doped into “C” site of the formula (I) above.
In a preferred embodiment of the present invention, the total amount of M is 0.01 wt.% to 10wt.% based on the total amount of the phosphor, preferably it is from 0.1 wt.% to 5wt%, more preferably from 0.5wt.% to 2wt%, more preferably from 0.7 to 1.5wt.%.
In a preferred embodiment of the present invention, the phosphor is represented by following chemical formula (III),
A1A2BCO6: M -(III) wherein A1 and A2 are each independently of each other, a cation selected from the group consisting of Li+, Na+, K+, Rb+ and Cs+, preferably A1 A2 is l_i+2, Na+2, K+2 or a combination of Li+i and Na+i, Li+i and K+i, Na+i and K+i or a combination of Na+2/3, Li+2/3 and K+2/3.
In a more preferred embodiment of the present invention, B is Mg2+, Zn2+ or a combination of Mg2+ and Zn2+ such as a combination of Mg2+o.5 and Zn2+o.5. In a more preferred embodiment of the present invention, C is Ti4+, Zr4+ or Ge4+ or a combination of Ti4+o.s and Zr4+o.s, Ti4+o.s and Ge4+o.s or a combination of Zr4+o.s and Ge4+o.5.
Furthermore preferably, the phosphor is (Li,K)2MgTiO4: M.
In a preferred embodiment of the present invention, the M is Mn4+. The most preferably, the phosphor is (Li,K)2MgTiO4:Mn4+.
It is believed that the peak maximum light wavelength of light emitted from the inorganic phosphor in the range from 660 nm to 710 nm is very suitable for plant condition control, especially for plant growth promotion. Without wishing to be bound by theory, it is believed that the inorganic phosphor having at least one light absorption peak wavelength in UV and / or purple light wavelength region from 300 nm to 430 nm may keep harmful insects off plants.
Therefore, in some embodiments of the present invention, the inorganic phosphor can have at least one light absorption peak wavelength in UV and / or purple light wavelength reason from 300 nm to 430 nm.
In some embodiments of the present invention, from the viewpoint of improved plant growth and improved homogeneous of blue and red (or infrared) light emission from the composition or from the light converting sheet, an inorganic phosphor having a first peak wavelength of light emitted from the inorganic phosphor in the range from 400nm to 500nm and a second peak wavelength of light emitted from the inorganic phosphor from 650 nm to 750 nm can be used preferably.
More preferably, the inorganic phosphor having the first peak wavelength of light emitted from the inorganic phosphor is in the range from 430 nm to 490 nm, and the second peak light emission wavelength is in the range from 660 nm to 740 nm, more preferably the first peak wavelength of light emitted from the inorganic phosphor is 450 nm and the second peak wavelength of light emitted from the inorganic phosphor is in the range from 660 nm to 710 nm, is used.
It is believed that the phosphor of the present invention is very useful for agriculture use, especially a controlling a condition of a living organism, especially for controlling a condition of a plant or cultivation of algae, bacteria, preferably said bacteria are photosynthetic bacteria, and/or plankton, preferably photo plankton. The most preferably for controlling a condition of a plant.
Preferably, said phosphor is an 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.
To fabricate the phosphor, a publicly known synthesis method can be used like described in “Narita, K., 2006, Methods of Phosphor Synthesis and Related Technology, In: Yen, W.M., Shionoya, S., Yamamoto, H.
(Eds.), Phosphor Handbook, second ed., CRC Press, New York, pp. 341- 354 (Chapter 4, Section 1)“,
“Lehmann, W. 2004. Phosphor Preparation. In: Yen, W.M. and Weber, M.J. (Eds.), Inorganic phosphors, CRC Press, New York, pp.19-24 (Section 2)“.
Preferably, conventional solid state reaction method can be used like described in working example 1 . As the raw materials, publicly known materials, such as oxides, carbonates, hydroxides, nitrates, chlorides, fluorides, ammonium salts, citrates, phosphates, sulfates and/or borates can be used.
-Composition
In another aspect, the present invention also relates to a composition comprising, essentially consisting of, or consisting of, at least one phosphor of the present invention and another material. Preferably, said composition is an agricultural composition. As discussed above, it is believed that the phosphor of the present invention is very useful for agriculture use, especially a controlling a condition of a living organism, especially for controlling a condition of a plant or cultivation of algae, bacteria, preferably said bacteria are photosynthetic bacteria, and/or plankton, preferably photo plankton. The most preferably the phosphor is useful for controlling a condition of a plant.
Thus, according to the present invention, composition, preferably an agricultural composition, contains at least the phosphor of the present invention and another material, preferably 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; brominecontaining monomers; sulfur-containing monomers; polymers; adjuvants; adhesives; insecticides; insect attractants; metal oxides; Al, Ag, Au nanoparticles; dispersants; surfactants; fungicides and antimicrobial agents.
In some embodiments of the invention, said another material is a matrix material and said composition can optionally comprises one or more additional additives selected from one or more members of the group consisting of light modulating materials such as dyes e.g. yellow dyes, pigments, light luminescent materials incl. organic and inorganic light luminescent materials, e.g. another inorganic phosphors; photo initiators; co-polymerizable monomers; cross linkable monomers; brominecontaining monomers; sulfur-containing monomers; adjuvants; adhesives; insecticides; insect attractants; metal oxides; Al, Ag, Au nanoparticles; dispersants; surfactants; fungicides and antimicrobial agents.
In some embodiments, said composition comprises a plurality of the phosphors.
Thus, in some embodiments of the present invention, the total amount of the 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.
- Matrix materials as another material
According to the present invention, in some embodiments, said matrix material is an organic material, and/or an inorganic material. Publicly known organic and/or inorganic materials can be used. Preferably the matrix material is an organic material.
Preferably, the matrix material is an organic oligomer or an organic polymer material, more preferably an organic polymer selected from the group consisting of a transparent photosetting polymer, a thermosetting polymer, a thermoplastic polymer, or a combination of any of these, can be used preferably.
Thus, in some embodiments of the present invention, the matrix material is an organic material, and/or an inorganic material, preferably the matrix material is an organic material, more preferably it is an organic oligomer or an organic polymer material, even more preferably an organic polymer selected from the group consisting of a transparent photosetting polymer, a thermosetting polymer, a thermoplastic polymer, or a combination of any of these.
As organic polymer materials, polysaccharides, polyethylene, polypropylene, polystyrene, polymethyl pentene, polybutene, butadiene styrene, polyvinyl chloride, polystyrene, polymethacrylic styrene, styreneacrylonitrile, acrylonitrile-butadiene-styrene, polyethylene terephthalate, polymethyl methacrylate, polyphenylene ether, polyacrylonitrile, polyvinyl alcohol, acrylonitrile polycarbonate, polyvinylidene chloride, polycarbonate, polyamide, polyacetal, polybutylene terephthalate, polytetrafluoroethylene, ethyl vinyl acetate copolymer, ethylene tetrafluorethylen copolymer, polyamide, phenol, melamine, urea, urethane, epoxy, unsaturated polyester, polyallyl sulfone, polyacrylate, hydroxybenzoic acid polyester, polyetherimide, polycyclohexylenedimethylene terephthalate, polyethylene naphthalate, polyester carbonate, polylactic acid, phenolic resin, silicone or a combination of any of these can be used preferably.
As the photosetting polymer, several kinds of (meth)acrylates can be used preferably. Such as unsubstituted alkyl-(meth) acrylates, for examples, methyl-acrylate, methyl-methacrylate, ethyl-acrylate, ethyl-methacrylate, butyl-acrylate, butyl-methacrylate, 2-ethylhexyl-acrylate, 2-ethylhexyl- methacrylate; substituted alkyl-(meth)acrylates, for examples, hydroxylgroup, epoxy group, or halogen substituted alkyl-(meth)acrylates; cyclopentenyl(meth)acrylate, tetra-hydro furfuryl-(meth)acrylate, benzyl (meth)acrylate, polyethylene-glycol di-(meth)acrylates.
In view of better coating performance of the composition, sheet strength, and good handling, the matrix material has a weight average molecular weight in the range from 5,000 to 50,000 preferably, more preferably from 10,000 to 30,000.
According to the present invention, the molecular weight Mw is determined by means of GPC (= gel permeation chromatography) against an internal polystyrene standard.
As the thermosetting polymer, publicly known transparent thermosetting polymer can be used preferably. Such as OE6550 (trademark) series (Dow Corning).
As the thermoplastic polymer, the type of thermoplastic polymer is not particularly limited. For example, natural rubber(refractive index(n)=1.52), poly-isoprene(n=1.52), poly 1 ,2-butadine(n=1 .50), polyisobutene(n=1.51 ), polybutene(n=1.51 ), poly-2-heptyl 1 ,3-butadine(n=1 .50), poly-2 -t-butyl-1 , 3- butadine(n=1 .51 ), poly-1 ,3-butadine(n=1 .52), polyoxyethylene(n=1 .46), polyoxypropylene(n=1 .45), polyvinylethyl ether(n=1 .45), polyvinylhexylether(n=1.46), polyvinylbutylether(n=1 .46), polyethers, poly vinyl acetate(n=1.47), poly esters, such as poly vinyl propionate(n=1.47), poly urethane(n=1 .5 to 1 .6), ethyl celullose(n=1.48), poly vinyl chloride(n=1.54 to 1.55), poly acrylo nitrile(n=1 .52), poly methacrylonitrile(n=1 .52), poly-sulfone(n=1 .63), poly sulfide(n=1 .60), phenoxy resin(n=1.5 to 1.6), polyethylacrylate(n=1 .47), poly butyl acrylate(n=1 .47), poly-2-ethylhexyl acrylate(n=1 .46), poly-t-butyl acrylate(n=1 .46), poly-3-ethoxypropylacrylate(n=1 .47), polyoxycarbonyl tetra-methacrylate(n=1 .47), polymethylacrylate(n=1 .47 to 1.48), polyisopropylmethacrylate(n=1.47), polydodecyl methacrylate(n=1 .47), polytetradecyl methacrylate(n=1 .47), poly-n-propyl methacrylate(n=1 .48), poly-3, 3, 5-trimethylcyclohexyl methacrylate(n=1 .48), polyethylmethacrylate(n=1 .49), poly-2-nitro-2- methylpropylmethacrylate(n=1 .49), poly-1 ,1 -diethylpropylmethacrylate (n=1 .49), poly(meth)acrylates, such as polymethylmethacrylate(n=1.49), or a combination of any of these, can be used preferably as desired.
In some embodiment of the present invention, such thermoplastic polymers can be copolymerized if necessary.
A polymer, which can be copolymerized with the thermoplastic polymer described above is for example, urethane acrylate, epoxy acrylate, polyether acrylate, or, polyester acrylate (n= 1 .48 to 1 .54) can also be employed. From the viewpoint of adhesiveness of the color conversion sheet, urethane acrylate, epoxy acrylate, and polyether acrylate are preferable.
According to the present invention, elastomers are incorporated into either thermoplastic polymer or thermosetting polymer based on their physical properties.
The matrix materials and the inorganic phosphors of the present invention can be preferably used for a fabrication of the color conversion sheet (100) and the light emitting diode device (200) of the present invention.
In some embodiments of the present invention, the composition can optionally further comprise one or more of light luminescent materials, which emits preferably blue, red light and/or near infrared light.
As the light luminescent materials, publicly available light luminescent organic materials such as organic dyes, and/or light luminescent inorganic materials such as phosphors can be used singly or in combination.
- Other phosphors as another material in the composition According to the present invention, any type of publicly known inorganic phosphors, preferably inorganic phosphors having a peak wavelength of light emitted from the inorganic phosphor in the range of 600 nm or more, preferably in the range from 650 to 1500 nm, more preferably in the range from 650 to 1000 nm, even more preferably in the range from 650 to 800 nm, furthermore preferably in the range from 650 to 750 nm, much more preferably it is from 660 nm to 730 nm, furthermore preferably it is from 660 nm to 710 nm, the most preferably from 670 nm to 710nm, and / or at least one inorganic phosphor having a peak wavelength of light emitted from the inorganic phosphor in the range of 500 nm or less, preferably in the range from 250 nm to 500 nm, more preferably in the range from 300 nm to 500 nm, even more preferably in the range from 350 nm to 500 nm, furthermore preferably in the range from 400 nm to 500nm, much more preferably in the range from 420 nm to 480 nm, the most preferably in the rage from 430 nm to 460 nm, and / or at least one inorganic phosphor having a first peak wavelength of light emitted from the inorganic phosphor in the range of 500nm or less, and a second peak wavelength of light emitted from the inorganic phosphor in the range of 600 nm or more, preferably the first peak wavelength of light emitted from the inorganic phosphor is in the range from 250nm to 500nm, and the second peak light emission wavelength is in the range from 600 nm to 1500 nm, more preferably the first peak wavelength of light emitted from the inorganic phosphor is in the range from 300nm to 500nm, and the second peak light emission wavelength is in the range from 650 nm to 1000 nm, even more preferably the first peak wavelength of light emitted from the inorganic phosphor is in the range from 350nm to 500nm, and the second peak light emission wavelength is in the range from 650 nm to 800 nm, furthermore preferably the first peak wavelength of light emitted from the inorganic phosphor is in the range from 400nm to 500nm, and the second peak light emission wavelength is in the range from 650 nm to 750 nm, much more preferably the first peak wavelength of light emitted from the inorganic phosphor is in the range from 420 nm to 480 nm, and the second peak light emission wavelength is in the range from 660 nm to 740 nm, the most preferably the first peak wavelength of light emitted from the inorganic phosphor is in the rage from 430 nm to 460 nm and the second peak wavelength of light emitted from the inorganic phosphor is in the range from 660 nm to 710 nm, can be used preferably.
It is believed that the peak light wavelength of the light emitted from the phosphor in the rage 660 nm to 710 nm is specifically useful for plant growth.
A wide variety of 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 SiAION phosphors.
In some embodiments of the present invention, 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 SiAION phosphors, preferably, it is a metal oxide phosphor, more preferably it is a Mn activated metal oxide phosphor or a Mn activated phosphate based phosphor, even more preferably it is a Mn activated metal oxide phosphor.
Preferred metal-oxide phosphors are arsenates, germanates, halogermanates, indates, lanthanates, niobates, scandates, stannates, tantalates, titanates, vanadates, halovanadates, phosphovanadates, yttrates, zirconates, molybdate and tungstate. 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. Thus, in some embodiments of the present invention, said inorganic phosphor is selected from the group consisting of metal oxides, silicates and halosilicates, phosphates and halophosphates, borates and borosilicates, aluminates, gallates and alumosilicates, molybdates and tungstates, sulfates, sulfides, selenides and tellurides, nitrides and oxynitrides, 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. For example, the inorganic phosphor is selected from the group consisting of Al2O3:Cr3+, Y3Al5O12:Cr3+, MgO:Cr3+, ZnGa2O4:Cr3+, MgAl2O4:Cr3+, Gd3Ga5O12:Cr3+, LiAl5O8:Cr3+, MgSr3Si2O8:Eu2+,Mn2+, Sr3MgSi2O8:Mn4+, Sr2MgSi2O7:Mn4+, SrMgSi2O6:Mn4+, BaMg6Ti6O19:Mn4+, Ca14Al10Zn6O35:Mn4+, Mg8Ge2O11F2:Mn4+, Mg2TiO4:Mn4+, Y2MgTiO6:Mn4+, Li2TiO3:Mn4+, K2SiF6:Mn4+, K3SiF7:Mn4+, K2TiF6:Mn4+, K2NaAlF6:Mn4+, BaSiF6:Mn4+, CaAl12O19:Mn4+, MgSiO3:Mn2+, Si5P6O25:Mn4+, NaLaMgWO6:Mn4+, Ba2YTaO6:Mn4+, ZnAl2O4:Mn2+, CaGa2S4:Mn2+, CaAlSiN3:Eu2+, SrAlSiN3:Eu2+, Sr2Si5N8:Eu2+, SrLiAlN4:Eu2+, CaMgSi2O6:Eu2+, Sr2MgSi2O7:Eu2+, SrBaMgSi2O7:Eu2+, Ba3MgSi2O8:Eu2+, LiSrPO4:Eu2+, LiCaPO4:Eu2+, NaSrPO4:Eu2+, KBaPO4:Eu2+, KSrPO4:Eu2+, KMgPO4:Eu2+, ^-Sr2P2O7:Eu2+, ^-Ca2P2O7:Eu2+, Mg3(PO4)2:Eu2+, Mg3Ca3(PO4)4:Eu2+, BaMgAl10O17:Eu2+, SrMgAl10O17:Eu2+, AlN:Eu2+, Sr5(PO4)3Cl:Eu2+, NaMgPO4 (glaserite):Eu2+, Na3Sc2(PO4)3:Eu2+, LiBaBO3:Eu2+, SrAISi4N7:Eu2+, Ca2SiO4:Eu2+, NaMgPO4:Eu2+, CaS:Eu2+, Y2O3:Eu3+, YVO4:EU3+, LiAIO2:Fe3+, LiAI5O8: Fe3+, NaAISiO4:Fe3+, MgO:Fe3+, Gd3Ga5O12:Cr3+,Ce3+, (Ca, Ba, Sr)2MgSi2O7:Eu,Mn, CaMgSi2O6:Eu2+,Mn2+, NaSrBO3:Ce3+, NaCaBO3:Ce3+, Ca3(BO3)2:Ce3+, Sr3(BO3)2:Ce3+, Ca3Y(GaO)3(BO3)4:Ce3+, Ba3Y(BO3)3:Ce3+, CaYAIO4:Ce3+, Y2SiO5:Ce3+, YSiO2N:Ce3+, Y5(SiO4)3N:Ce3+, Ca2AI3O6FGd3Ga5Oi2:Cr3+,Ce3+, ZnS, InP/ZnS, CulnS2, CulnSe2, CulnS2/ZnS, carbon/graphen quantum dots and a combination of any of these as described in the second chapter of Phosphor handbook (Yen, Shinoya, Yamamoto).
It is believed that the Mn4+ activated metal oxide phosphors, Mn, Eu activated metal oxide phosphors, Mn2+ activated metal oxide phosphors, Fe3+ activated metal oxide phosphors can be used preferably from the viewpoint of environmentally friendly since these phosphors do not create Cr6+ during synthesis procedure.
As an additional inorganic phosphor which emits blue or red light, any type of publicly known materials, for example as described in the second chapter of Phosphor handbook (Yen, Shinoya, Yamamoto), can be used if desired.
Without wishing to be bound by theory, it is believed that the blue light especially around 450 nm wavelength light may lead better plant growth, if it is combined with emission light from the inorganic phosphor having the peak wavelength of light emitted from the inorganic phosphor in the range from 660 nm to 740 nm, especially the combination of the blue light around 450 nm wavelength and emission light from the inorganic phosphor having the peak wavelength of light emitted from the inorganic phosphor in the range from 670 nm to 710 nm is preferable for better plant growth. Thus, more preferably, the composition can further comprise at least one blue light emitting inorganic phosphor having peak wavelength of light emitted from the inorganic phosphor around 450 nm, like described in the second chapter of Phosphor handbook (Yen, Shinoya, Yamamoto).
In some embodiments, said additional inorganic phosphor is a different type of inorganic phosphor from the inorganic phosphor of the present invention
-Co-polymerizable monomers
In some embodiments of the present invention, the composition can embrace one or more of publicly available vinyl monomers that are co- polymerizable. Such as acrylamide, acetonitrile, diacetone-acrylamide, styrene, and vinyl-toluene or a combination of any of these.
-Crosslinkable monomers
According to the present invention, the composition can further include one or more of publicly available crosslinkable monomers.
For example, cyclopentenyl(meth)acrylates; tetra-hydro furfuryl- (meth)acrylate; benzyl (meth)acrylate; the compounds obtained by reacting a polyhydric alcohol with and a,[3-unsaturated carboxylic acid, such as polyethylene-glycol di-(meth)acrylates (ethylene numbers are 2- 14), tri-methylol propane di(meth)acrylate, tri-methylol propane di (meth)acrylate, tri-methylol propane tri-(meth)acrylate, tri-methylol propane ethoxy tri-(meth) acrylate, tri-methylol propane propoxy tri-(meth) acrylate, tetra-methylol methan tri-(meth) acrylate), tetra-methylol methane tetra(meth) acrylate, polypropylene glycol di(meth)acrylates (propylene number therein are 2-14), Di-penta-erythritol penta(meth)acrylate, di- penta-erythritol hexa(meth)acrylate, bis-phenol-A Polyoxyethylene di- (meth)acrylate, bis-phenol-A dioxyethylene di-(meth)acrylate, bis-phenol-A trioxyethylene di-(meth)acrylate, bis-phenol-A decaoxyethylene di- (meth)acrylate; the compounds obtained from an addition of an a, [3- unsaturated carboxylic acid to a compound having glycidyl, such as trimethylol propane trig lycidy lether triacrylate, bis-phenol A diglycidy lether diacrylates; chemicals having poly-carboxylic acids, such as a phtalic anhydride; or chemicals having hydroxy and ethylenic unsaturated group, such as the esters with hydroxyethyl (meth)acrylate; alkyl-ester of acrylic acid or methacylic acid, such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethyl hexyl (meth)acrylate; urethane (meth)acrylate, such as the reactants of Tolylene diisocyanate and 2- hydroxyethyl (meth)acrylate, the reactants of tri-methyl hexamethylene diisocyanate and cyclohexane dimethanol, and 2-hydroxyethyl (meth)acrylate; and a combination of any of these.
In a preferred embodiment of the present invention, the crosslinkable monomer is selected from the group consisting of tri-methylol-propane tri (meth)acrylate, di-pentaerythritol tetra-(meth)acrylate, di-pentaerythritol hexa-(meth)acrylate, bisphenol-A polyoxyethylene dimethacrylate and a combination thereof.
The vinyl monomers and the crosslinkable monomers described above can be used alone or in combination.
From the viewpoint of controlling the refractive index of the composition and I or the refractive index of the color conversion sheet according to the present invention, the composition can further comprise publicly known one or more of bromine-containing monomers, sulfur-containing monomers. The type of bromine and sulfur atom-containing monomers (and polymers containing the same) are not particularly limited and can be used preferably as desired.
For example, as bromine-containing monomers, new frontier® BR-31 , new Frontier® BR-30, new Frontier® BR-42M (available from DAI-ICHI KOGYO SEIYAKU CO., LTD) or a combination of any of these, as the sulfur-containing monomer composition, IU-L2000, IU-L3000, IU-MS1010 (available from MITSUBISHI GAS CHEMICAL COMPANY, INC.) or a combination of any of these, can be used preferably.
-Photo initiator for the composition
In a preferred embodiment of the present invention, the photo initiator can be a photo initiator that can generates a free radical when it is exposed to an ultraviolet light or a visible light. For example, benzoin-methyl-ether, benzoin-ethyl-ether, benzoin-propyl-ether, benzoin-isobutyl-ether, benzoin-phenyl-ether, benzoin-ethers, benzophenone, N,N’-tetramethyl- 4,4’-diaminobenzophenone (Michler’s-ketone), N,N’-tetraethyl- 4,4’diaminobenzophenone, benzophenones, benzil-dimethyl-ketal (Ciba specialty chemicals, IRGACURE® 651 ), benzil-diethyl-ketal, dibenzil ketals, 2,2-dimethoxy-2-phenylacetophenone, p-tert-butyldichloro acetophenone, p-dimethylamino acetophenone, acetophenones, 2,4- dimetyl thioxanthone, 2,4-diisopropyl thioxanthone, thioxanthones, hydroxy cyclohexyl phenyl ketone (Ciba specialty chemicals, IRGACURE® 184), 1 -(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1 -on (Merck, Darocure® 1116), 2-hydroxy-2-methyl-1-phenylpropane-1-on (Merck, Darocure® 1173).
-Adjuvant
An adjuvant can enhance permeability of effective component (e.g. insecticide), inhibit precipitation of solute in the composition, or decrease a phytotoxicity. Here, a surfactant means it does not comprise or is not comprised by other additives, for example a spreading agent, a surface treatment and an adjuvant.
Preferably said adjuvant can be selected from the group consisting of a mineral oil, an oil of vegetable or animal origin, alkyl esters of such oils or mixtures of such oils and oil derivatives, and combination thereof. As one embodiment, the weight ratio of each 1 additive of dispersant, surfactant, fungicide, antimicrobial agent and antifungal agent, to the weight of the invention phosphor in the total amount of the composition is in the range from 50 wt.% to 200 wt.%, more preferably it is from 75 wt.% to 150 wt.%. Exemplified embodiment of an adjuvant is Approach Bl (Trademark, Kao Corp.).
- Formulation
In another aspect, the invention relates to a formulation comprising, essentially consisting of, or a consisting of at least one particle of the present invention or the composition of the present invention, and a solvent. Preferably said formulation comprises a plurality of the inorganic phosphors or the composition of the present invention.
- Solvent for the formulation
As a solvent, wide variety of publicly known solvents can be used preferably. There are no particular restrictions on the solvent as long as it can dissolve or disperse the matrix material, and the particle of the composition. Preferably a plurality of particles of the present invention are in the formulation.
In a preferred embodiment of the present invention, the solvent can be selected from the group consisting of water, ethylene glycol monoalkyl ethers, such as, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers, such as, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates, such as, methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol alkyl ether acetates, such as, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate; aromatic hydrocarbons, such as, benzene, toluene and xylene; ketones, such as, methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols, such as, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin; esters, such as, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and ethyl lactate; and cyclic asters, such as, y-butyrolactone. Those solvents are used singly or in combination of two or more, and the amount thereof depends on the coating method and the thickness of the coating.
More preferably, propylene glycol alkyl ether acetates, such as, propylene glycol monomethyl ether acetate (hereafter “PGMEA”), propylene glycol monoethyl ether acetate, or propylene glycol monopropyl ether acetate and / or aromatic hydrocarbons, such as, benzene, toluene and xylene, can be used for
Even more preferably, benzene, toluene, or xylene can be used.
The amount of the solvent in the formulation can be freely controlled.
For example, if the formulation is to be spray-coated, it can contain the solvent in an amount of 90 wt.% or more based on total amount of the formulation. Further, if a slit-coating method, which is often adopted in coating a large substrate, is to be carried out, the content of the solvent is normally 60 wt.% or more, preferably in the range from 70 wt.% to 95 wt.% based on the total amount of the formulation.
- An optical sheet (100)
In another aspect, the invention relates to an optical sheet (100) comprising at least one particle of the present invention, or the composition of the present invention, preferably said optical sheet is an agricultural sheet. Preferably said optical sheet (100) comprises a plurality of particles of the present invention or the composition. In some embodiments of the invention, the optical sheet (100) can be a film, or a fiber mat.
According to the present invention, in some embodiments, the optical sheet (100) can be rigid or flexible.
In some embodiments of the present invention, the optical sheet (100) can be any structure. Such as plane, curved, wave formed structures to increase a growth of plant.
In some embodiments of the invention, the optical sheet (100) comprises at least a first layer (100a) comprising at least the composition or the first layer (100a) made from the composition.
According to the present invention, said fiber mat can be fabricated by using publicly known spinning method. And said cover layer can be fabricated by using a known method such as a spinning, dip coating, bar coating, printing, and/or spin coating.
In some embodiments of the invention, the sheet further comprises a second layer (100b), preferably the second layer (100b) comprises at least a material selected from one or more members of the group consisting of adhesives, insecticides, insect attractants, yellow dye, pigments, phosphors, metal oxides, Al, Ag, Au, and antimicrobials, more preferably said pigments are yellow pigments, blue pigments or a combination of these, and said phosphors are phosphors of the present invention or phosphors that can emit a light with a peak maximum light wavelength in the range from 350nm to 500nm, and/or 550nm to 600nm, more preferably in the range from 380nm to 490nm, and/or 570nm to 590nm.
In some embodiments of the present invention, the second layer (100b) comprises at least the inorganic phosphor of the present invention, and a second material selected from adhesives, and/or insecticides.
In some embodiments of the present invention, the second layer (100b) can further comprises a matrix material described in the section of “matrix material”.
According to the present invention, said inorganic phosphor is described in the section of “inorganic phosphors” above.
In some embodiments of the present invention, the second layer (100b) comprises at least a first material selected from one or more of the members of the group consisting of yellow pigments, yellow phosphors, yellow dyes, and insect attractants, and a second material selected from adhesives, and/or insecticides.
Such second layer (100b) can be fabricated by a publicly known method. For example, spray coating, bar coating, slit coating, dip coating, spin coating, inkjet printing can be used.
In some embodiments of the present invention, the second layer (100b) of the optical medium (100) is a light reflecting layer, preferably the second layer (100b) as the reflecting layer comprises at least a light reflecting material which can reflect at least blue, red, and/or infrared light, even more preferably the second layer (100b) essentially consists of or consists of one or more of light reflecting materials.
As a light reflecting material any kinds of less toxic known light reflecting materials such as Al, Cu, Ag, Au, and metal oxides can be used preferably, more preferably Al, or Cu is used as the light reflecting material from the view point of high light reflection at deep red-light wavelength and lower cost. In some embodiments, said first layer is at least partially covered by said second layer, preferably at least one side of said first layer (100a) one side of the optical medium (100) is fully covered by the second layer.
In some embodiments, the optical medium (100) optionally may comprise a third layer (100c) or more layers.
In some embodiments, said first layer (100a), optionally the second layer (100b), the third layer (100c) or more layers can be sandwiched by, or fully or partially covered by one or more of optically transparent protection layers.
According to the present invention, said protection layer can be made from any publicly known transparent materials suitable for optical films.
Fabrication method for coating of optical sheet (100) by the light reflecting material is not particularly limited. Publicly known methods such as vacuum deposition, sputtering, chemical vapor deposition, printing can be used.
In some embodiments of the invention, the optical sheet (100) comprises a first layer(100a), wherein the first layer (100a) comprises, in the first layer, at least a first area comprising the composition according to the present invention and a second area, preferably said second area comprising at least one additive described in the section of “Additive”.
In some embodiments of the invention, the concentration of the particle of the present invention (110) in the sheet is varies from a high concentration on one side of the sheet to a low concentration of the opposite side of the sheet, preferably it is varying from a high concentration on one side of the sheet to a low concentration of the opposite side of the sheet in-plane direction. In some embodiments of the invention, the optical sheet (100), may further comprises a substrate, preferably said substrate is an optically transparent substrate, colored substrate, selective light reflector, or a light reflector.
According to the present invention, the term “light reflect” means reflecting at least around 60 % of incident light at a wavelength or a range of wavelength used during operation of the optical medium (100).
Preferably, it is over 70 %, more preferably, over 75%, the most preferably, it is over 80 %.
According to the present invention, the term “transparent” means at least around 60 % of incident light transmittal at the thickness used in a the optical medium (100) and at a wavelength or a range of wavelength used during operation of the optical medium (100).
Preferably, it is over 70 %, more preferably, over 75%, the most preferably, it is over 80 %.
In some embodiments of the present invention, said reflector is a metal substrate, preferably Al substrate, Cu substrate, metal alloy substrate is useful from the view point of high light reflection at deep red-light wavelength and lower cost.
A material for the selective light reflection reflector is not particularly limited. Well known materials for a selective light reflector can be used preferably as desired.
According to the present invention, the selective light reflector can be a single layer or multiple layers. ln a preferred embodiment, the selective light reflector comprises at least a selective light reflecting layer selected from the group consisting of Al layer, Al + MgF2 stacked layers, Al + SiO stacked layers, Al + dielectric multiple layer, Au layer, dielectric multiple layer, Cr + Au stacked layers; with the selective light reflection layer more preferably being Al layer, Al + MgF2 stacked layers, Al + SiO stacked layers.
Preferably, said selective light reflecting layer is stacked onto a transparent substrate.
In general, the methods of preparing the selective light reflection layer can vary as desired and selected from well-known techniques.
In some embodiments, the selective light reflection layer expect for cholesteric liquid crystal layers can be prepared by a gas phase-based coating process (such as Sputtering, Chemical Vapor Deposition, vapor deposition, flash evaporation), or a liquid-based coating process.
In some embodiments of the present invention, the optical sheet is an agricultural sheet, a color conversion sheet for optical device, a remote phosphor tape for LED, or another sheet such as an optical filter.
In some embodiments of the present invention, the layer thickness of the optical sheet is in the range from 5 pm to 1 mm, preferably it is in the range from 10 pm to 500 pm, more preferably it is from 30 pm to 200 pm, even more preferably from 50 pm to 100 pm from the view point of better light conversion property and lower production cost.
In some embodiments of the present invention, the total amount of the particle in the optical sheet is in the range from 0.01wt.% 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.
According to the present invention, the optical sheet (100) is useful for agriculture.
Particularly, the optical medium (100) is useful for a mulch cultivation sheet to cover at least a part of a ridge in a field or to cover at least a part of a surface of planter, such as a surface of nutrient film technique hydroponics system or a deep flow technique hydroponics system.
It is believed that the optical sheet as a mulch cultivation sheet can control plant condition such as plant growth and to protect a plant and/or a ridge or a surface of planter as a mulch cultivation sheet at the same time preferably.
Therefore, more preferably, the invention relates to use of the optical sheet (100) as a mulch cultivation sheet to cover a ridge in a field or to cover a surface of planter, preferably said planter is a nutrient film technique hydroponics system or a deep flow technique hydroponics system.
Even more preferably, one side of the optical sheet (100) is coated by a light reflecting material which can reflect at least blue, red, and/or infrared light. As a light reflecting material any kinds of less toxic known light reflecting materials such as Al, metal oxides can be used preferably, more preferably Al, or AIO2 is used as the light reflecting material.
Preferably, said one side of the optical medium (100) is fully covered by the light reflecting material. Fabrication method for coating of optical medium (100) by the light reflecting material is not particularly limited. Publicly known methods such as vacuum deposition, sputtering, chemical vapor deposition, printing can be used.
-Use of composition or formulation
In another aspect, the invention relates to use of the composition, or formulation in an optical sheet fabrication process.
-Method for preparing the optical sheet (100)
In another aspect, the present invention furthermore relates to method for preparing the optical sheet (100), preferably for preparing the agriculture sheet, wherein the method comprises the 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 onto a substrate or into an inflation moulding machine, and
B) fixing the matrix material by evaporating a solvent of the formulation and/or by polymerizing the composition by applying heat or by exposing the photosensitive composition under ray of light.
In a preferred embodiment, steps (A) and (B) of the method are in this sequence.
In some embodiments of the present invention, the composition in step (A) is provided by spin coating, spray coating, bar coating, or a slit coating method.
In a preferred embodiment of the present invention, the composition or the formulation in step (B) is provided into an inflation-molding machine and the matrix material is fixed by heat treatment of the machine. The details of the composition and the formulation are described in the section of “composition” and the section of “formulation”.
-Optical device (200)
In another aspect, the present invention relates to an optical device (200) comprising at least one phosphor of the present invention, composition of the present invention or at least one optical sheet (100) of the present invention, preferably said optical device (200) is a lighting device, such as a Light Emitting Diode.
In some embodiments of the present invention, the optical device (200) may further comprises a light source, a light re-directing device, and/or a reflector.
Preferably said light source is a light emitting diode, or an organic light emitting diode.
In some embodiments of the present invention, the optical device (200) comprises at least one optical sheet (100) and a supporting part, preferably the supporting part comprises at least one attaching part to attach the optical medium, and optionally a base part to support optical medium and supporting part itself, more preferably the supporting part comprises one or more of attaching part to attach one or more of optical medium.
In a preferred embodiment of the present invention, the optical device (200) is a lighting device, a light emitting diode device for agriculture, or building materials of greenhouse.
-Method for preparing the optical device (200) In another aspect, the present invention furthermore relates to method for preparing the optical device (200), wherein the method comprises following step (C),
(C) providing the optical sheet (100) in an optical device.
-Use for agriculture
In another aspect, the present invention relates to a use of the phosphor of the present invention, composition of the present invention, formulation of the present invention, 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.
-Greenhouse
In another aspect, the present invention relates to a greenhouse comprising the phosphor of the present invention, composition of the present invention, formulation of the present invention, the optical sheet (100) of the present invention or the optical device (200) of the present invention.
-Use for plant, algae, bacteria
In another aspect, the present invention relates to use of the phosphor of the present invention, 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 greenhouse of the present invention for controlling a condition of a plant or cultivation of algae, bacteria, preferably said bacteria are photosynthetic bacteria, and/or plankton, preferably photo plankton.
-Method of supply
In another aspect, present invention relates to a method of supplying the phosphor of the present invention, the composition of the present invention or the formulation of the present invention, to at least one portion of a plant. According to the present invention, any kinds of publicly known supplying method can be used. Such as spray, painting, coating.
-Plant, plankton or bacterium
In another aspect, the present invention further relates to a plant, alga, a plankton, or a bacterium obtained or obtainable by the method. Preferably said plankton is a phytoplankton, and said bacterium is a photosynthetic bacterium.
According to the present invention, said living organism is not particularly limited. Such as a biological cell, a plant, plankton, bacterium, alga, insects, animals.
According to the present invention, the plant can be flowers, vegetables, fruits, grasses, trees and horticultural crops (preferably flowers and horticultural crops, more preferably flowers). As one embodiment of the invention, the plant can be foliage plants. Exemplified embodiments of grasses are a poaceae, bambuseae (preferably sasa, phyllostachys), oryzeae (preferably oryza), pooideae (preferably poeae), triticeae (preferably elymus), elytrigia, hordeum, triticum, secale, arundineae, centotheceae, chloridoideae, hordeum vulgare, avena sativa, secale cereal, andropogoneae (preferably coix), cymbopogon, saccharum, sorghum, zea (preferably zea mays), sorghum bicolor, saccharum officinarum, coix lacryma-jobi van, paniceae (preferably panicum), setaria, echinochloa (preferably panicum miliaceum), echinochloa esculenta, and setaria italic. Embodiments of vegetables are stem vegetables, leaves vegetables, flowers vegetables, stalk vegetables, bulb vegetables, seed vegetables (preferably beans), roots vegetables, tubers vegetables, and fruits vegetables. One embodiment of the plant can be Gai llardia, Lettuce, Rucola, Komatsuna (Japanese mustard spinach) or Radish (preferably Gai Hard ia, Lettuce, or Rucola). The environment of growing plant can be natural environment, a greenhouse, a plant factory and indoor cultivation, preferably natural environment and a green house. One embodiment of the natural environment is an outside farm.
Preferable embodiments
1. A light emitting phosphor represented by following chemical formula (I), preferably for agriculture use,
A2BCO4:M -(I) wherein A is a cation selected from one or more members of the group consisting of Li+, Na+, K+, Rb+ and Cs+; preferably A is Li+, Na+, K+ or a combination of these, more preferably A2 is Li+ 2, Na+ 2, K+ 2 or a combination of Li+i and Na+i, Li+i and K+i, Na+i and K+i or a combination of Na+ 2/3, Li+ 2/3 and K+ 2/3;
B is a cation selected from one or more members of the group consisting of Mg2+, Ca2+, Sr2+, Ba2+ and Zn2+, preferably B is Mg2+, Zn2+ or a combination of Mg2+ and Zn2+;
C is a cation selected from one or more members of the group consisting of Ti4+, Zr4+, Hf4+, Si4+, Ge4+, and Sn4+, preferably C is Ti4+, Zr4+ or Ge4+ or a combination of these;
M is Mn4+, Mn2+, Fe3+ Ti3+or Cr3+, preferably Mn4+ or Cr3+, more preferably Mn4+.
2. The phosphor of embodiment 1 , wherein the total amount of M is 0.01 wt.% to 10wt.% based on the total amount of the phosphor, preferably it is from 0.1 wt.% to 5wt%, more preferably from 0.5wt.% to 2wt%, more preferably from 0.7 to 1.5wt.%.
3. The phosphor of embodiment 1 or 2, is represented by following chemical formula (III), A1A2BCO6: M -(III) wherein A1 and A2 are each independently of each other, a cation selected from the group consisting of Li+, Na+, K+, Rb+ and Cs+, preferably A1 A2 is Li+2, Na+2, K+2 or a combination of Li+i and Na+i, Li+i and K+i, Na+i and K+i or a combination of Na+2/3, Li+2/3 and K+2/3.
4. The phosphor of any one of embodiments 1 to 3, wherein B is Mg2+, Zn2+ or a combination of Mg2+ and Zn2+ such as a combination of Mg2+o.5 and Zn2+o.5.
5. The phosphor of any one of embodiments 1 to 4, wherein C is Ti4+, Zr4+ or Ge4+ or a combination of Ti4+o.s and Zr4+o.s, Ti4+o.s and Ge4+o.s or a combination of Zr4+o.s and Ge4+o.5.
6. The phosphor of any one of embodiments 1 to 5, is (Li,K)2MgTiO4: M.
7. The phosphor of any one of embodiments 1 to 6, wherein the M is Mn4+, preferably the phosphor is (Li,K)2MgTiO4:Mn4+.
8. A composition, preferably an agricultural composition, containing at least the phosphor of any one of embodiments 1 to 7, and another material, preferably 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. 9. A formulation containing at least one phosphor of any one of embodiments 1 to 7 or a composition of embodiment 8, and a solvent.
10. Optical sheet (100) comprising at least one layer containing at least one phosphor of any one of embodiments 1 to 7, or the composition of embodiment 8, preferably said optical sheet is an agricultural sheet.
11. Method for preparing the optical sheet (100), preferably for preparing the agriculture sheet, wherein the method comprises the following steps (A) and (B),
C) providing the composition according to embodiment 8, or the formulation according to embodiment 9 in a first shaping, preferably onto a substrate or into an inflation moulding machine, and
D)fixing the matrix material by evaporating a solvent of the formulation and/or by polymerizing the composition by applying heat or by exposing the photosensitive composition under ray of light.
12. An optical device (200) comprising at least one phosphor of any one of embodiments 1 to 7, a composition of embodiment 8 or at least one optical sheet (100) of embodiment 10, preferably said optical device (200) is a lighting device, more preferably it is a Light Emitting Diode.
13. Use of the phosphor of embodiments 1 to 7, composition of embodiment 8, formulation of embodiment 9, optical sheet (100) of embodiment 10 or the optical device (200) of embodiment 12 for agriculture, preferably for greenhouse or for controlling a condition of a living organism in agriculture.
14. A greenhouse comprising the phosphor of embodiments 1 to 7, composition of embodiment 8, formulation of embodiment 9, the optical sheet (100) of embodiment 10 or the optical device (200) of embodiment 12. 15. Use of the phosphor of any one of embodiments 1 to 7, the composition of embodiment 8, the formulation of embodiment 9, the optical sheet (100) of embodiment 10, the optical device (200) of embodiment 12 or the greenhouse of embodiment 14 for controlling a condition of a plant or cultivation of algae, bacteria, preferably said bacteria are photosynthetic bacteria, and/or plankton, preferably photo plankton.
16. Method of supplying the phosphor of any one of embodiments 1 to 7, the composition of embodiment 8 or the formulation of embodiment 9, to at least one portion of a plant.
Technical effects
The present invention provides one or more of following effects; improved light emission ability, such as deep red light emission ability, near infrared light emission ability and/or blue light emission ability preferably suitable for controlling a condition of a plant, phytoplankton, bacteria and/or alga, optimized peak light emission wavelength, optimized peak maximum light emission wavelength, improved Full Width at Half Maximum; improved light absorption, optimized peak light absorption wavelength; preferable light emission / light absorption spectrum; preferable light emission / light absorption ratio; improved chemical stability such as better long term moisture durability and/or water resistance, UV resistivity; higher EQE; stronger light emission intensity; improved and/or well controlled average particle size; improved optical properties such as light scattering, absorbing, refraction and/or reflection ability of 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; simpler and/or easier synthesis method; improvement of controlling property of a phytoplankton condition, photosynthetic bacteria and/or alga, preferably acceleration of growth of phytoplankton, photosynthetic bacteria and/or alga; improvement of controlling property of plant condition, preferably controlling of a plant height; controlling of color of fruits; promotion and inhibition of germination; controlling of synthesis of chlorophyll and carotenoids, preferably by blue light; plant growth promotion; adjustment and I or acceleration of flowering time of plants; controlling of production of plant components, such as increasing production amount, controlling of polyphenols content, sugar content, vitamin content of plants; controlling of secondary metabolites, preferably controlling of polyphenols, and/or anthocyanins; controlling of a disease resistance of plants; controlling of ripening of fruits, or controlling of weight of plant.
The working examples below provide descriptions of the present inventions but not intended to limit scopes of the inventions.
Working Examples
Working Example 1 : Sr3LiTaO6:Mn4+(Mn concentration in the phosphor : 0.5mol%)
(Li,K)2MgTiO4:Mn4+ is prepared by conventional solid-state reaction method. Li2COs, K2CO3, MgO, TiC>2 and Mn02 are used as raw materials. The starting materials are weighted as Li: K: Mg: Ti: Mn = 2.5: 0.5: 1 : 0.995: 0.005. The total amount of Li and K charged as the raw material A of the chemical formula (I) is 50% more than the stoichiometric ratio. The weighted starting materials mixed with acetone in an agate mortar. The raw materials are 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 1000°C for 6 h in air. After cooling, the obtained materials are well grinded for the characterization.
To confirm the structure of the resultant materials, 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 (Li,K)2MgTiO4:Mn4+ is successfully synthesized as main phase. The photoluminescence excitation spectrum shows ultraviolet region from 300 nm to 550 nm and emission spectrum showed the deep red region from 650 nm to 800 nm peaked at 675 nm.
Working Example 2: Evaluation tests with 2MgTiO4:Mn4+
Figure imgf000046_0001
In order to evaluate the effect of the phosphor on plant growth, actual tests using two hydroponics systems (from IIING Corporation) are carried out. First, an agricultural solution is prepared using 1 wt.% (Li,K)2MgTiO4:Mn4+ phosphors in aqueous solution. The light source of the systems is both same white LED set on top of the box of the system. The same number of young lettuce and rucola as the test plants are set into both hydroponics systems A and B and enough water is set under the plants in the systems. Then, the aqueous solution is sprayed 10 times on the plants of the hydroponics system A on the first day and the 8th day. On the 16th day, the plants in the hydroponics system A, which is coated by (Li,K)2MgTiO4:Mn4+ by spray coating of the agricultural solution showed higher height on average compared to the plants of the hydroponics system B.

Claims

Patent Claims
1 . A light emitting phosphor represented by following chemical formula (I),
A2BCO4:M -(I) wherein A is a cation selected from one or more members of the group consisting of Li+, Na+, K+, Rb+ and Cs+; preferably A is Li+, Na+, K+ or a combination of these, more preferably A2 is Li+ 2, Na+ 2, K+ 2 or a combination of Li+i and Na+i, Li+i and K+i, Na+i and K+i or a combination of Na+ 2/3, Li+ 2/3 and K+ 2/3;
B is a cation selected from one or more members of the group consisting of Mg2+, Ca2+, Sr2+, Ba2+ and Zn2+, preferably B is Mg2+, Zn2+ or a combination of Mg2+ and Zn2+;
C is a cation selected from one or more members of the group consisting of Ti4+, Zr4+, Hf4+, Si4+, Ge4+, and Sn4+, preferably C is Ti4+, Zr4+ or Ge4+ or a combination of these;
M is Mn4+, Mn2+, Fe3+ Ti3+or Cr3+, preferably Mn4+ or Cr3+, more preferably Mn4+.
2. The phosphor of claim 1 , wherein the total amount of M is 0.01 wt.% to 10wt.% based on the total amount of the phosphor, preferably it is from 0.1 wt.% to 5wt%, more preferably from 0.5wt.% to 2wt%, more preferably from 0.7 to 1 ,5wt.%.
3. The phosphor of claim 1 or 2, is represented by following chemical formula (III),
A1A2BCO6: M -(III) wherein A1 and A2 are each independently of each other, a cation selected from the group consisting of Li+, Na+, K+, Rb+ and Cs+, preferably A1 A2 is l_i+2, Na+2, K+2 or a combination of Li+i and Na+i, Li+i and K+i, Na+i and K+i or a combination of Na+2/3, Li+2/3 and K+2/3.
4. The phosphor of any one of claims 1 to 3, wherein B is Mg2+, Zn2+ or a combination of Mg2+ and Zn2+ such as a combination of Mg2+o.5 and Zn2+o.5.
5. The phosphor of any one of claims 1 to 4, wherein C is Ti4+, Zr4+ or Ge4+ or a combination of Ti4+o.5 and Zr4+o.5, Ti4+o.s and Ge4+o.5 or a combination of Zr4+o.5 and Ge4+o.5.
6. The phosphor of any one of claims 1 to 5, is (Li,K)2MgTiO4: M.
7. The phosphor of any one of claims 1 to 6, wherein the M is Mn4+, preferably the phosphor is (Li,K)2MgTiO4:Mn4+.
8. A composition, preferably an agricultural composition, containing at least the phosphor of any one of claims 1 to 7, and another material, preferably 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.
9. A formulation containing at least one phosphor of any one of claims 1 to 7 or a composition of claim 8, and a solvent.
10. Optical sheet (100) comprising at least one layer containing at least one phosphor of any one of claims 1 to 7, or the composition of claim 8, preferably said optical sheet is an agricultural sheet.
11. Method for preparing the optical sheet (100), preferably for preparing the agriculture sheet, wherein the method comprises the following steps (A) and (B),
E) providing the composition according to claim 8, or the formulation according to claim 9 in a first shaping, preferably onto a substrate or into an inflation moulding machine, and
F) fixing the matrix material by evaporating a solvent of the formulation and/or by polymerizing the composition by applying heat or by exposing the photosensitive composition under ray of light.
12. An optical device (200) comprising at least one phosphor of any one of claims 1 to 7, a composition of claim 8 or at least one optical sheet (100) of claim 10, preferably said optical device is a lighting device, more preferably it is a Light Emitting Diode.
13. Use of the phosphor of claims 1 to 7, composition of claim 8, formulation of claim 9, optical sheet (100) of claim 10 or the optical device (200) of claim 12 for agriculture, preferably for greenhouse or for controlling a condition of a living organism in agriculture.
14. A greenhouse comprising the phosphor of claims 1 to 7, composition of claim 8, formulation of claim 9, the optical sheet (100) of claim 10 or the optical device (200) of claim 12.
15. Method of supplying the phosphor of any one of claims 1 to 7, the composition of claim 8 or the formulation of claim 9, to at least one portion of a plant.
PCT/EP2021/080084 2020-11-02 2021-10-29 Phosphor WO2022090444A1 (en)

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