WO2022112459A1 - Light emitting polymer material particle - Google Patents

Light emitting polymer material particle Download PDF

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Publication number
WO2022112459A1
WO2022112459A1 PCT/EP2021/083076 EP2021083076W WO2022112459A1 WO 2022112459 A1 WO2022112459 A1 WO 2022112459A1 EP 2021083076 W EP2021083076 W EP 2021083076W WO 2022112459 A1 WO2022112459 A1 WO 2022112459A1
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Prior art keywords
polymer material
light
material particle
organic light
present
Prior art date
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PCT/EP2021/083076
Other languages
French (fr)
Inventor
Hiroki Yoshizaki
Hiroshi Okura
Ryota YAMANASHI
Marco Greb
Original Assignee
Merck Patent Gmbh
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Publication of WO2022112459A1 publication Critical patent/WO2022112459A1/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
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G13/00—Protecting plants
    • A01G13/02—Protective coverings for plants; Coverings for the ground; Devices for laying-out or removing coverings
    • A01G13/0231—Tunnels, i.e. protective full coverings for rows of plants
    • 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
    • A01G13/00—Protecting plants
    • A01G13/02—Protective coverings for plants; Coverings for the ground; Devices for laying-out or removing coverings
    • A01G13/0256—Ground coverings
    • A01G13/0268—Mats or sheets, e.g. nets or fabrics
    • A01G13/0275—Films
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G9/00—Cultivation in receptacles, forcing-frames or greenhouses; Edging for beds, lawn or the like
    • A01G9/14—Greenhouses
    • A01G9/1407—Greenhouses of flexible synthetic material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02—Homopolymers or copolymers of hydrocarbons
    • C09D125/04—Homopolymers or copolymers of styrene
    • C09D125/08—Copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/132—Phenols containing keto groups, e.g. benzophenones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3437—Six-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes

Definitions

  • the present invention relates to a polymer material particle comprising at least one organic light luminescent material and at least one UV absorbing agent, to a method for preparing said polymer material particle and to uses of said polymer material particle, especially in agriculture. Furthermore, the present invention relates to a composition, a formulation, an optical sheet, an agricultural film, an optical device, a greenhouse, a plant, a container and methods comprising said polymer material particle.
  • WO 2019/020602 A1 and WO 2019/020653 A1 discloses utilizing an inorganic phosphor in agriculture.
  • a polymer material particle with a light conversion and light reflection function that produces optimal blue, red and infrared light a polymer material particle with good light-extraction efficiency in an external/internal environment through controlling the refractive index and light dispersion of an organic light luminescent material or by using an organic light luminescent material; a polymer material particle with improved optical properties such as light scattering, absorbing, refraction and/or reflection ability of an organic light luminescent material; a polymer material particle with superior emission characteristics and high quantum efficiency (EQE) of an organic light luminescent material or by using an organic light luminescent material a polymer material particle which efficiently achieves a uniform and bright outgoing light by effectively absorbing the whole lights from a light source by using an organic light luminescent material a polymer material particle with improved long-term moisture durability, improved water resistance, and improved UV-stability and good light durability of an organic light luminescent material; improved
  • the present invention in one aspect provides for a polymer material particle comprising at least one organic light luminescent material and at least one UV absorbing agent.
  • the present invention in another aspect provides for a method for preparing a polymer material particle of the invention, which includes the steps: (a) preparing a suspension by mixing at least one organic light luminescent material, at least one UV absorbing agent and one or more polymer precursors in a liquid phase; and (b) polymerizing the resulting mixture by applying heat.
  • the present invention relates to a use of the polymer material particle of the present invention in agriculture, in an optical sheet, optical film, optical net, optical fiber, optical nonwoven fabric or optical plate, in a spraying, coating or painting agent, in a Light Emitting Diode, in a solar cell or in a plant cultivation pot.
  • the invention relates to a use of the optical sheet of the present invention, the agricultural film of the present invention, or the optical device of the present invention for agriculture, preferably for greenhouse or for controlling a condition of a living organism in agriculture.
  • the invention relates to a use of the polymer material particle of the present invention, the composition of the present invention, the formulation of the present invention, the optical sheet of the present invention, the agricultural film of the present invention, the optical device of the present invention, or the greenhouse of the present invention for the cultivation of algae, bacteria, and/or plankton, preferably it is photo planktons, preferably for improvement of controlling property of a phytoplankton condition, photosynthetic bacteria and/or alga, preferably acceleration of growth of phytoplankton, photosynthetic bacteria and/or alga; improvement of controlling property of plant condition, preferably controlling of a plant height; controlling of color of fruits; promotion and inhibition of germination; controlling of synthesis of chlorophyll and carotenoids, preferably by blue light; plant growth promotion; adjustment and / 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
  • the invention relates to a plant obtained or obtainable by the method of the present invention, or plankton obtained or obtainable by the method of the present invention, or a bacterium obtained or obtainable by the method of the present invention.
  • the 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
  • Embodiments of vegetables are stem vegetables, leaves vegetables, flowers vegetables, stalk vegetables, bulb vegetables, seed vegetables (preferably beans), roots vegetables, tubers vegetables, and fruits vegetables.
  • One embodiment of the plant can be Gaillardia, Lettuce, Rucola, Komatsuna (Japanese mustard spinach) or Radish (preferably Gaillardia, Lettuce, or Rucola).
  • light modulating material is a material which can change at least one of physical properties of light.
  • it is selected from pigments, dyes and light luminescent materials including organic and inorganic light luminescent materials.
  • pigments stands for materials that are insoluble in an aqueous solution and changes the color of reflected or transmitted light as the result of wavelength-selective absorption and/or reflection, e.g. Inorganic pigments, organic pigments and inorganic-organic hybrid pigments.
  • dye means colored substances that are soluble in an aqueous solution and changes the color as the result of wavelength-selective absorption of irradiation.
  • luminescent means spontaneous emission of light by a substance not resulting from heat. It is intended to include both, phosphorescent light emission as well as fluorescent light emission.
  • the term “light luminescent material” is a material which can emit either fluorescent light or phosphorescent light.
  • phosphorescent light emission or “phosphorescence” is defined as being a spin prohibition light emission from a triplet state or higher spin state (e.g. quintet) of spin multiplicity (2S+1) > 3, wherein S is the total spin angular momentum (sum of all the electron spins).
  • photon down-conversion is a process which leads to the emission of light at longer wavelength than the excitation wavelength, e.g. by the absorption of one photon leads to the emission of light at longer wavelength.
  • photon up-conversion is a process that leads to the emission of light at shorter wavelength than the excitation wavelength, e.g. by the two- photon absorption (TPA) or Triplet-triplet annihilation (TTA), wherein the mechanisms for photon up-conversion are well known in the art.
  • TPA two- photon absorption
  • TTA Triplet-triplet annihilation
  • organometallic 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, transition metals, lanthanides, actinides, and semimetals.
  • the inorganic light luminescent materials include phosphors as well as semiconductor nanoparticles.
  • a “Phosphor” within the meaning of the present application is a materials which absorbs electromagnetic radiation of a specific wavelength range, preferably blue and/or ultraviolet (UV) electromagnetic radiation and converts the absorbed electromagnetic radiation into electromagnetic radiation having a different wavelength range, preferably visible (VIS) light such as violet, blue, green, yellow, orange, or red light, or the near infrared light (NIR).
  • VIS visible
  • NIR near infrared light
  • UV electromagnetic radiation with a wavelength from 100 nm to 389nm, shorter than that of visible light but longer than X-rays.
  • VIS electromagnetic radiation with a wavelength from 390 nm to 700 nm.
  • NIR electromagnetic radiation with a wavelength from 701 nm to 1,000 nm.
  • the emission of CdSe nanocrystals can be tuned from 660 nm for particles of diameter of around 6.5 nm, to 500 nm for particles of diameter of around 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 present invention relates to a polymer material particle which comprises at least one organic light luminescent material and at least one UV absorbing agent.
  • the particle comprises or is comprised of polymerized units of one or more appropriate polymerizable monomeric molecules which form a polymer sphere containing the at least one organic light luminescent material and the at least one UV absorbing agent.
  • Suitable polymerizable monomers for forming a polymer material of the polymer material particle can be selected from various kinds of generally known and/or commercially available polymerizable substances. Especially suitable are polymerizable monomeric molecules which form a transparent polymer.
  • Suitable commercially available organic light luminescent material are Lumogen® F Orange 240; Lumogen® Red 300; Lumogen® Red 305; Lumogen® Violet 570; “MK-2” (2-Cyano-3-[5’”-(9-ethyl-9H-carbazol-3-yl)- 3’,3”,3”’,4-tetra-n-hexyl-[2,2’,5’,2”,5”,2”’]-quarterthiophen-5-yl]acrylic acid); “D102” (5-[[4-[4-(2,2-diphenylethenyl)phenyl]-1 , 2, 3, 3a, 4,8b- hexahydrocyclopent[b]indol-7-yl]methylene]-4-oxo-2-thioxo-3- thiazolidineacetic acid); “D205” (5-[[4-[4-(2,2-diphenylethenyl)phenyl]-
  • said polymer material of the particle is selected from one or more member of the group consisting of polyurethanes, poly(meth)acrylates, poly(butylmethacrylate), ethylene-acrylate copolymer, acrylonitrile- butadiene-styrene copolymer, polyesters, polyacrylonitriles, polyacrylurethanes, polyacrylurethanesilicones, polyfluoroacrylurethanes, polyfluoroacrylates, polyvinylchloride, polystyreneacrylates, polybutyrals, polychlorovinylidenes, melamine resins, phenol resins, epoxy resins, urea resins, unsaturated polyester resins, polycarbonates, polysulfones, polyethers, polyamides, polystyrenes including poly(styrene-co- divinylbenzenes, polyisobutylenes, polyethylene, polyethylene terephthalate, polypropylenes, poly(sty
  • the polymerizable monomer for forming the polymer material has intramoleculary integrated at least one chromophore moiety and at least one polymerizable group or moiety.
  • the particle comprises or is comprised of polymerized units of a polymerizable monomeric organic light luminescent material, which can be derived from the organic light luminescent material described herein and contains at least one polymerizable group or moiety and at least one chromophore moiety.
  • the polymer material of the particle comprises or is comprised of polymerized units of a polymerizable monomeric organic light luminescent material having intramoleculary integrated at least one chromophore moiety and at least one polymerizable group or moiety.
  • This embodiment allows for extending the variety of emitting polymer range.
  • Suitable benzophenones are commercially available and include, but are not limited to: Uvinul ® 3049 (commercially available also under the trading names Benzophenone 6, Cyasorb ® UV 12, NSC 40149, Seesorb 107, UV 49, Uvinul ® 3049, Uvinul ® D 49); Uvinul ® 3050 (commercially available also under the trading names BP 2, Benzophenone 2, Dainsorb P 6, Eversorb ® 51, NSC 38556, SUV 1 , Seesorb 106, Sumisorb 150, T 0118, Uvinul ® D 50); ADEKASTAB 1413 (commercially available also under the trading names ARO 8, Aduvex 248, Advastab ® 46, Anti-UV P, Asahi 1413, BP 12, Benzon OO, Benzophenone 12, C 81, Carstab ® 700, Chemisorb 81, Chimassorb ® 81 , Cyasorb ® 531 , Cyasorb ® UV 531 , Cyasorb
  • the amount of the UV absorbing agent is preferably in the range from 0.1- 10.0 wt.%, related to the total weight of the particle.
  • the polymer material particle further comprises at least one stabilizing agent.
  • the stabilizing agent further improves the photoprotection effect described above.
  • ADKSTAB LA-57 (commercially available also under the trading names ADKSTAB LA-57MP, DN 44, LA 57, Mark LA 57); ADKSTAB LA-63P; ADKSTAB LA-68; ADKSTAB LA-72 (commercially available also under the trading names Antioxidant 292, BASF 292, Chiguard ® 353, Chisorb ® 292, HALPS 292, HALS 4, HS 508, JCK-W-US, LA 72, LA 77ME, LS 292, LS 508, LS 765, Light Stabilizer 292, Light, Stabilizer 765, Lowilite 76, Sanol 292, Sanol LS 292, Sanol LS 508, Sanol LS 765, Songlight 2920LQ, TIN 292, TN 765, Tinuvin ® 292, Tinuvin ® 765, Tinuvin ® 766, UV 55-07051 , UV 765); 770DF (commercially available also under the trading names ADK
  • the polymer material particle of the invention has an average particle size in the range of 1 to 1000 pm, more preferably in the range of 10 to 800 pm, as measureing the longest length of 100 particles each independently by scanning electron microscopy.
  • the particle has an external quantum efficiency (EQE) of 10% or more, preferably it is from 10% to 90%, more preferably from 20% to 80%, further more preferably from 30% to 80%, the most preferably it is from 40% to 80%.
  • EQE external quantum efficiency
  • said suspension in step (a) and (a’) further comprises at least one stabilizing agent, which is more preferably selected from hindered amine light stabilizers.
  • the heat acid-generator is, for example, a salt or ester capable of generating an organic acid.
  • examples thereof include: various aliphatic sulfonic acids and salts thereof; various aliphatic carboxylic acids, such as, citric acid, acetic acid and maleic acid, and salts thereof; various aromatic carboxylic acids, such as, benzoic acid and phthalic acid, and salts thereof; aromatic sulfonic acids and ammonium salts thereof; various amine salts; aromatic diazonium salts; and phosphonic acid and salts thereof.
  • Examples of the preferred heat acid-generators containing sulfonate ions include p-toluenesulfonates, benzenesulfonates, p- dodecylbenzenesulfonates, 1 ,4-naphthalenedisulfonates, and methanesulf
  • Examples of the above heat base-generator include: imidazole derivatives, such as, N-(2-nitrobenzyloxycarbonyl)imidazole, N-(3-nitrobenzyloxy- carbonyl)imidazole, N-(4-nitrobenzyloxycarbonyl)imidazole, N-(5-methyl-2- nitrobenzyloxycarbonyl)imidazole, and N-(4-chloro-2-nitro- benzyloxycarbonyl)imidazole; 1 ,8-diazabicyclo(5,4,0)undecene-7, tertiary amines, quaternary ammonium
  • 2,2' azobis(2- methylvaleronitrile), 2,2‘-azobis(dimethylvaleronitrile), azobisisobutyronitrile or a combination of any of these can be used preferably.
  • X- is preferably a counter ion represented by any of the following formulas:
  • Y is a halogen atom
  • the counter ion examples include: BF 4 _ , (C6Fs) 4 B ⁇ , ((CF 3 ) 2 C 6 H 3 ) 4 B-, PFe-, (CF 3 CF 2 ) 3 PF 3 -, SbFe , (C 6 F 5 ) 4 Ga-, ((CF 3 ) 2 C 6 H 3 ) 4 Ga-, SCN , (CF 3 S02)3C-, (CF 3 S02)2N-, formate ion, acetate ion, trifluoromethanesulfonate ion, nonafluorobutanesulfonate ion, methane- sulfonate ion, butanesulfonate ion, benzenesulfonate ion, p- toluenesulfonate ion, and sulfonate ion.
  • those generating sulfonic acids or boric acids are particularly preferred.
  • examples thereof include tricumyliodonium teterakis(pentafluorophenyl)- borate (PFIOTOINITIATOR2074 [trademark], manufactured by Rhodorsil), diphenyliodonium tetra(perfluorophenyl)borate, and a compound having sulfonium ion and pentafluoroborate ion as the cation and anion moieties, respectively.
  • examples of the photo acid-generators also include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphor- sulfonate, triphenylsulfonium tetra(perfluorophenyl)borate, 4- acetoxyphenyldimethylsulfonium hexafluoroarsenate, 1-(4-n- butoxynaphthalene-1-yl)tetrahydrothiophenium trifluoromethanesulfonate,
  • each A is independently a substituent group selected from the group consisting of an alkyl group of 1 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkylcarbonyl group of 1 to 20 carbon atoms, an arylcarbonyl group of 6 to 20 carbon atoms, hydroxyl group, and amino group; each p 2 is independently an integer of 0 to 5; and B is a fluorinated alkylsulfonate group, a fluorinated arylsulfonate group, a fluorinated alkylborate group, an alkylsulfonate group or an arylsulfonate group.
  • photo acid-generators in which the cations and anions in the above formulas have exchanged each other or combined with various other cations and anions described above.
  • any one of the sulfonium ions represented by the above formulas can be combined with tetra(perfluorophenyl)borate ion, and also any one of the iodonium ions represented by the above formulas can be combined with tetra(perfluorophenyl)borate ion.
  • Those can be still also employed as the photo acid-generators.
  • photo radical-generator examples include azo compounds, peroxides, acyl phosphine oxides, alkyl phenons, oxime esters, and titanocenes.
  • Examples of the photo base-generator include multi-substituted amide compounds having amide groups, lactams, imide compounds, and compounds having those structures.
  • the present invention also relates to a use of the polymer material particle of the present invention in agriculture.
  • the present invention also relates to a use of the polymer material particle of the present invention in an optical sheet, an optical film, an optical net, an optical fiber, an optical nonwoven fabric or an optical plate.
  • the present invention also relates to a use of the polymer material particle of the present invention in a spraying agent, a coating agent or a painting agent.
  • the present invention relates to a use of the polymer material particle of the present invention in a Light Emitting Diode, in a solar cell or in a plant cultivation pot.
  • the present invention also relates to a composition
  • a composition comprising, essentially consisting of, or consisting of, at least one polymer material particle of the present invention and a further material.
  • the further material is a matrix material and said composition can optionally comprises one or more additives selected from one or more members of the group consisting of light modulating materials such as dyes, for example blue or red dyes, pigments, light luminescent materials including organic and inorganic light luminescent materials, for example another organic light luminescent material or inorganic phosphors; photo initiators; co-polymerizable monomers; cross linkable monomers; bromine-containing monomers; sulfur-containing monomers; adjuvants; adhesives; insecticides; insect attractants; metal oxides; Al, Ag, Au nanoparticles; dispersants; surfactants; fungicides and antimicrobial agents.
  • light modulating materials such as dyes, for example blue or red dyes, pigments, light luminescent materials including organic and inorganic light luminescent materials, for example another organic light luminescent material or inorganic phosphors
  • photo initiators co-polymerizable monomers; cross linkable monomers; bromine-containing monomers; sulfur-
  • the matrix material has a weight average molecular weight in the range from 5,000 to 50,000 preferably, more preferably from 10,000 to 30,000.
  • thermosetting polymer publicly known transparent thermosetting polymer can be used preferably.
  • OE6550 (trade mark) series Dow Corning
  • thermoplastic polymers may be copolymerized if necessary.
  • the phosphor is a fluorescent or a phosphorescent inorganic material which contains one or more light emitting centers (i.e. , a so called “inorganic phosphor”).
  • the light emitting centers are formed by activator elements such as e.g. atoms or ions of rare earth metal elements, for example La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er,
  • Tm, Yb and Lu and/or atoms or ions of transition metal elements, for example Cr, Mn, Fe, Co, Ni, Cu, Ag, Au and Zn, and/or atoms or ions of main group metal elements, for example Na, Tl, Sn, Pb, Sb and Bi.
  • suitable phosphors include phosphors based on garnet, silicate, orthosilicate, thiogallate, sulfide, nitride, silicon-based oxynitride, nitridosilicate, nitridoaluminumsilicate, oxonitridosilicate, oxonitridoaluminumsilicate and rare earth doped SiAION.
  • the inorganic phosphor is selected from the group consisting of AI 2 0 3 :Cr 3+ , Y 3 AI 5 0i2:Cr 3+ , MgO:Cr 3+ , ZnGa 2 0 4 :Cr 3+ , MgAI 2 0 4 :Cr 3+ , Gd 3 Ga 5 0i 2 :Cr 3+ , LiAI 5 0 8 :Cr 3+ , MgSr 3 Si 2 0 8 :Eu 2+ ,Mn 2+ , Sr 3 MgSi 2 0s:Mn 4+ , Sr 2 MgSi 2 07:Mn 4+ , SrMgSi 2 06:Mn 4+ , BaMg6Ti60i9:Mn 4+ , Cai 4 AhoZn60 35 :Mn 4+ , Mg 8 Ge 2 0nF 2 :Mn 4+ , Mg 2 Ti0 4 :Mn 4+ ,
  • 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 to better plant growth, if it is combined with emission light from the organic light luminescent material having the peak wavelength of light emitted from the organic light luminescent material in the range from 600 nm to 820 nm, especially the combination of the blue light around 450 nm wavelength and emission light from the organic light luminescent material having the peak wavelength of light emitted from the organic light luminescent material in the range from 690 nm to 790 nm is preferable for better plant growth.
  • 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 invention relates to use of the polymer material particle of the present invention, or the composition of the present invention, or the formulation of the present invention, in a method for preparing an optical sheet or in agriculture, preferably for preparing an agricultural sheet or for controlling a condition of a living organism.
  • Fabrication method for coating of optical sheet by the light reflecting material is not particularly limited. Publicly known methods such as vacuum deposition, sputtering, chemical vapor deposition, printing can be used.
  • the concentration of the polymer material particle of the present invention in the sheet varies from a high concentration on one side of the sheet to a low concentration of the opposite side of the sheet, preferably it is varying from a high concentration on one side of the sheet to a low concentration of the opposite side of the sheet in-plane direction.
  • step (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 composition under ray of light to thereby form the agricultural film on the surface of the agricultural material
  • the composition or the formulation in step (A’) is provided by immersion coating, gravure coating, roll coating, bar coating, brush coating, spray coating, doctor coating, flow coating, spin coating, slit coating, or by painting.
  • composition comprising at least one polymer material particle according to any one of embodiments 1 to 17 and a further material, preferably selected from one or more members of the group consisting of matrix materials; light modulating materials such as dyes, for example blue or red dyes, pigments, light luminescent materials including organic and inorganic light luminescent materials, for example another organic light luminescent material or an inorganic phosphor; photo initiators; co- polymerizable monomers; cross linkable monomers; bromine-containing monomers; sulfur-containing monomers; adjuvants; adhesives; insecticides; insect attractants; metal oxides; Al, Ag, Au nanoparticles; dispersants; surfactants; fungicides and antimicrobial agents. 21.
  • light modulating materials such as dyes, for example blue or red dyes, pigments, light luminescent materials including organic and inorganic light luminescent materials, for example another organic light luminescent material or an inorganic phosphor
  • photo initiators co- polymerizable monomers; cross linkable mono
  • composition according to embodiment 20, wherein the total amount of the polymer material particle of the composition is in the range from 0.01 wt.% to 10 wt.% based on the total amount of the composition, preferably it is from 0.05 wt.% to 5 wt.%, more preferably from 0.05 wt.% to 3 wt.%, furthermore preferably it is from 0.1 wt.% to 1 wt.%. 22.
  • Optical device comprising at least one optical sheet according to embodiment 25, preferably said optical device is a lighting device, more preferably it is a Light Emitting Diode.
  • optical sheet according to embodiment 25 Use of the optical sheet according to embodiment 25, the agricultural film according to embodiment 28, or the optical device of embodiment 30 for agriculture, preferably for greenhouse or for controlling a condition of a living organism in agriculture.
  • a greenhouse comprising the optical sheet according to embodiment 25, the agricultural film according to embodiment 28, or the optical device of embodiment 30.
  • Method for modulating a condition of a plant, plankton, and/or a bacterium comprising at least following step of providing the optical sheet according to embodiment 25 or the agricultural film according to embodiment 28 between a light source and a plant, between a light source and plankton, preferably said plankton is phytoplankton, between a light source and a bacterium, preferably said bacterium is a photosynthetic bacterium, and/or providing the optical sheet according to embodiment 25 or the agricultural film according to embodiment 28 over a ridge in a field or over a surface of planter, preferably said planter is a nutrient film technique hydroponics system or a deep flow technique hydroponics system to control plant growth.
  • a container comprising at least one plant, plankton, and/or a bacterium according to embodiment 38
  • Technical effects
  • a polymer material particle with a light conversion and light reflection function that produces optimal blue, red and infrared light a polymer material particle with good light-extraction efficiency in an external/internal environment through controlling the refractive index and light dispersion of an organic light luminescent material or by using an organic light luminescent material; a polymer material particle with improved optical properties such as light scattering, absorbing, refraction and/or reflection ability of an organic light luminescent material; a polymer material particle with superior emission characteristics and high quantum efficiency (EQE) of an organic light luminescent material or by using an organic light luminescent material a polymer material particle which efficiently achieves a uniform and bright outgoing light by effectively absorbing the whole lights from a light source by using an organic light luminescent material a polymer material particle with improved long-term moisture durability, improved water resistance, and improved UV-stability and good light durability of an organic light luminescent material; improved dispersibility of polymer material particles and organic light luminescent material in a formulation, composition and/or in
  • microparticles are formed, which are collected from the suspension by aspirator filtration, then are washed with 500 mL of distilled water, 500 mL of ethanol (Sigma-Aldrich) and diethylether (Sigma-Aldrich) in this order. Then, the washed particles are dried in an oven at 50 °C under vacuum for 2 h. 9.46 g of polymer material particles are obtained as illustrated in Figs. 1a and 1b (average diameter: 40 pm; determined by scanning electron microscopy (SEM; Hitachi S- 5200)). Workinq Example 2: Preparation of particle dispersed film
  • 1 g of polymer material particles obtained from working example 1 are dispersed in 10 g of silicone agents mixture (5g of KE-109E-A and 5g of KE-109E-B; Shin-Etsu Chemical) with revolving/rotating mixer (stirring at 2000 rpm for 1 min. and deforming at 2200 rpm for 30 sec.).
  • silicone agents mixture 5g of KE-109E-A and 5g of KE-109E-B; Shin-Etsu Chemical
  • the resulting mixture is applied on a glass plate, and the silicone mixture is cured at room temperature overnight. After curing, the cured silicone film is peeled off.
  • Working Example 3 Film durability check (1) The silicone film prepared as described in working example 2 is irradiated with sunlight for 1 week. After irradiation of sunlight, the film is checked for the change of transmitted light by a solar simulator.

Abstract

The present invention relates to a polymer material particle comprising at least one organic light luminescent material and at least one UV absorbing agent.

Description

Light Emitting Polymer Material Particle
Field of the Invention
The present invention relates to a polymer material particle comprising at least one organic light luminescent material and at least one UV absorbing agent, to a method for preparing said polymer material particle and to uses of said polymer material particle, especially in agriculture. Furthermore, the present invention relates to a composition, a formulation, an optical sheet, an agricultural film, an optical device, a greenhouse, a plant, a container and methods comprising said polymer material particle.
Background Art
WO 2019/020602 A1 and WO 2019/020653 A1 discloses utilizing an inorganic phosphor in agriculture.
JP H01 -103658 A describes a polycarbonate resin with a core-shell polymer having a core comprising a rubbery crosslinked polymer of a (2- 8C) alkyl acrylate and a shell comprising, e.g., methyl methacrylate polymer, and the use of this resin to produce molded products.
Patent Literature
1. WO 2019/020602 A1
2. WO 2019/020653 A1
3. JP H01 -103658 A
Summary of the Invention
The inventors surprisingly have found that there are still one or more considerable problems for which improvements are desired, as listed below: A polymer material particle with a light conversion and light reflection function that produces optimal blue, red and infrared light; a polymer material particle with good light-extraction efficiency in an external/internal environment through controlling the refractive index and light dispersion of an organic light luminescent material or by using an organic light luminescent material; a polymer material particle with improved optical properties such as light scattering, absorbing, refraction and/or reflection ability of an organic light luminescent material; a polymer material particle with superior emission characteristics and high quantum efficiency (EQE) of an organic light luminescent material or by using an organic light luminescent material a polymer material particle which efficiently achieves a uniform and bright outgoing light by effectively absorbing the whole lights from a light source by using an organic light luminescent material a polymer material particle with improved long-term moisture durability, improved water resistance, and improved UV-stability and good light durability of an organic light luminescent material; improved dispersibility of polymer material particles and organic light luminescent material in a formulation, composition and/or in a matrix material of a film or sheet; improved transparency of a film or sheet, preferably improved transparency of an agricultural film; an optical sheet or agricultural film with good light-extraction efficiency in an external/internal environment by using a polymer material particle; an optical sheet or agricultural film with improved long-term moisture durability, improved water resistance, and improved UV-stability and good light durability by using a polymer material particle; an optical sheet or agricultural film which shows improved color fastness and color stability on colorless materials, and less back scattering of a fluorescent/reflection material; an optical sheet or agricultural film with reduced accumulated stress in a resin body; an optical sheet or agricultural film, which shows better light-extraction; an optical sheet or agricultural film having a lower refractive index so that visible light is easily transmitted; an optical sheet or agricultural film comprising an organic light luminescent material and matrix material, which shows better plant growth ability; improvement of controlling property of a phytoplankton condition, photosynthetic bacteria and/or alga, preferably acceleration of growth of phytoplankton, photosynthetic bacteria and/or alga; improvement of controlling property of plant condition, preferably controlling of a plant height; controlling of color of fruits; promotion and inhibition of germination; controlling of synthesis of chlorophyll and carotenoids, preferably by blue light; plant growth promotion; adjustment and/or acceleration of flowering time of plants; controlling of production of plant components, such as increasing production amount, controlling of polyphenols content, sugar content, vitamin content of plants; controlling of secondary metabolites, preferably controlling of polyphenols, and/or anthocyanins; controlling of a disease resistance of plants; controlling of ripening of fruits, or controlling of weight of plant. The present inventors have found that one or more of the above described problems can be addressed by the features as defined in the independent claims.
Specifically, to solve one or more of the above described problems, the present invention in one aspect provides for a polymer material particle comprising at least one organic light luminescent material and at least one UV absorbing agent.
Moreover, to solve one or more of the above-described problems, the present invention in another aspect provides for a method for preparing a polymer material particle of the invention, which includes the steps: (a) preparing a suspension by mixing at least one organic light luminescent material, at least one UV absorbing agent and one or more polymer precursors in a liquid phase; and (b) polymerizing the resulting mixture by applying heat.
In another aspect, the present invention relates to a use of the polymer material particle of the present invention in agriculture, in an optical sheet, optical film, optical net, optical fiber, optical nonwoven fabric or optical plate, in a spraying, coating or painting agent, in a Light Emitting Diode, in a solar cell or in a plant cultivation pot.
In another aspect, the present invention furthermore relates to a composition comprising at least one polymer material particle of the present invention and a further material.
In another aspect, the present invention also relates to a formulation comprising at least one polymer material particle of the present invention or the composition of the present invention, and a solvent.
In another aspect, the present invention relates to a use of the polymer material particle of the present invention, the composition of the present invention, or the formulation of the present invention, in a method for preparing an optical sheet or in agriculture, preferably for preparing an agricultural sheet or for controlling a condition of a living organism. In another aspect, the invention relates to an optical sheet comprising at least one polymer material particle 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 furthermore relates to a method for preparing said optical sheet, and to a use of said optical sheet in an optical device.
In another aspect, the present invention furthermore relates to a method for preparing an agricultural film, wherein the method comprises the following steps (A’) and (B’): (A’) providing a composition comprising at least one polymer material particle comprising at least one organic light luminescent material and at least one UV absorbing agent, and a matrix material, or a formulation comprising said composition and a solvent, onto a surface of an agricultural material; 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 composition under ray of light to form the agricultural film on the surface of the agricultural material, preferably the composition or the formulation in step (A’) is provided by immersion coating, gravure coating, roll coating, bar coating, brush coating, spray coating, doctor coating, flow coating, spin coating, slit coating, or by painting: and to an agricultural sheet obtained or obtainable by this method. In another aspect, the invention provides for an agricultural film obtained or obtainable by said method.
In another aspect, the invention relates to an optical device comprising at least one optical sheet of the present invention, preferably said optical device is a lighting device, more preferably it is a Light Emitting Diode, and to a method for the preparation of the optical device.
In another aspect, the invention relates to a use of the optical sheet of the present invention, the agricultural film of the present invention, or the optical device of the present invention for agriculture, preferably for greenhouse or for controlling a condition of a living organism in agriculture.
In another aspect, the invention relates to a greenhouse comprising an optical sheet of the present invention, an agricultural film of the present invention or an optical device of the invention.
In still another aspect, the invention relates to a use of the polymer material particle of the present invention, the composition of the present invention, the formulation of the present invention, the optical sheet of the present invention, the agricultural film of the present invention, the optical device of the present invention, or the greenhouse of the present invention for the cultivation of algae, bacteria, and/or plankton, preferably it is photo planktons, preferably for improvement of controlling property of a phytoplankton condition, photosynthetic bacteria and/or alga, preferably acceleration of growth of phytoplankton, photosynthetic bacteria and/or alga; improvement of controlling property of plant condition, preferably controlling of a plant height; controlling of color of fruits; promotion and inhibition of germination; controlling of synthesis of chlorophyll and carotenoids, preferably by blue light; plant growth promotion; adjustment and / or acceleration of flowering time of plants; controlling of production of plant components, such as increasing production amount, controlling of polyphenols content, sugar content, vitamin content of plants; controlling of secondary metabolites, preferably controlling of polyphenols, and/or anthocyanins; controlling of a disease resistance of plants; controlling of ripening of fruits, or controlling of weight of plant. In another aspect, the invention relates to a method of supplying the polymer material particle of the present invention, the composition of the present invention, or the formulation of the present invention to at least one portion of a plant. In another aspect, the invention relates to a method for modulating a condition of a plant, plankton, and/or a bacterium.
In another aspect, the invention relates to a plant obtained or obtainable by the method of the present invention, or plankton obtained or obtainable by the method of the present invention, or a bacterium obtained or obtainable by the method of the present invention.
In another aspect, the invention relates to a container comprising at least one plant, plankton, and/or one bacterium of the present invention.
Further advantages of the present invention will become evident from the following detailed description.
Brief Description of the Drawings Figs. 1a and 1b are photographs of polymer material particles according to the present invention obtained from working example 1.
Detailed Description of the Invention hereinafter, the best mode for carrying out the present invention is described in detail. - Definition of terms
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 terms “including”, “comprising”, “containing”, as well as other forms such as “includes”, “included”, “comprises”, “comprised”, “contains” and “contained” 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
Figure imgf000009_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 van, paniceae (preferably panicum), setaria, echinochloa (preferably panicum miliaceum), echinochloa esculenta, and setaria italic. Embodiments of vegetables are stem vegetables, leaves vegetables, flowers vegetables, stalk vegetables, bulb vegetables, seed vegetables (preferably beans), roots vegetables, tubers vegetables, and fruits vegetables. One embodiment of the plant can be Gaillardia, Lettuce, Rucola, Komatsuna (Japanese mustard spinach) or Radish (preferably Gaillardia, Lettuce, or Rucola).
The 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 light luminescent materials including organic and inorganic light 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" or “phosphorescence” 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” or “fluorescence” is a spin allowed light emission from a singlet state of spin multiplicity (2S+1 ) =1.
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, transition metals, lanthanides, actinides, and semimetals.
Within the meaning of the present application, the inorganic light luminescent materials include phosphors as well as semiconductor nanoparticles. A “Phosphor” within the meaning of the present application is a materials which absorbs electromagnetic radiation of a specific wavelength range, preferably blue and/or ultraviolet (UV) electromagnetic radiation and converts the absorbed electromagnetic radiation into electromagnetic radiation having a different wavelength range, preferably visible (VIS) light such as violet, blue, green, yellow, orange, or red light, or the near infrared light (NIR).
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 around 6.5 nm, to 500 nm for particles of diameter of around 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%, and most preferably, it is over 80 %. - Polymer material particle
In one aspect, the present invention relates to a polymer material particle which comprises at least one organic light luminescent material and at least one UV absorbing agent. Preferably, the particle comprises or is comprised of polymerized units of one or more appropriate polymerizable monomeric molecules which form a polymer sphere containing the at least one organic light luminescent material and the at least one UV absorbing agent. Suitable polymerizable monomers for forming a polymer material of the polymer material particle can be selected from various kinds of generally known and/or commercially available polymerizable substances. Especially suitable are polymerizable monomeric molecules which form a transparent polymer.
The at least one organic light luminescent material can emit either fluorescent light.
Preferably, the at least one organic light luminescent material has a peak wavelength of light emitted from the organic light luminescent material in the range of 600 nm or more, preferably in the range from 600 to 1000 nm, more preferably in the range from 600 to 820 nm, even more preferably in the range from 620 to 800 nm, furthermore preferably in the range from 650 to 800 nm, much more preferably it is from 650 nm to 790 nm, the most preferably from 690 nm to 790 nm; or the at least one organic light luminescent material has a peak wavelength of light emitted from the organic light luminescent material 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 500 nm, much more preferably in the range from 420 nm to 480 nm, the most preferably in the rage from 430 nm to 460 nm; or the at least one organic light luminescent material has a first peak wavelength of light emitted from the organic light luminescent material in the range of 500 nm or less, and a second peak wavelength of light emitted from the phosphor in the range of 600 nm or more, preferably the first peak wavelength of light emitted from the phosphor is in the range from 250 nm to 500 nm, and the second peak light emission wavelength is in the range from 600 nm to 1000 nm, more preferably the first peak wavelength of light emitted from the phosphor is in the range from 300 nm to 500 nm, and the second peak light emission wavelength is in the range from 600 nm to 820 nm, even more preferably the first peak wavelength of light emitted from the phosphor is in the range from 350 nm to 500 nm, and the second peak light emission wavelength is in the range from 620 nm to 800 nm, furthermore preferably the first peak wavelength of light emitted from the phosphor is in the range from 400 nm to 500 nm, and the second peak light emission wavelength is in the range from 650 nm to 800 nm, much more preferably the first peak wavelength of light emitted from the phosphor is in the range from 420 nm to 480 nm, and the second peak light emission wavelength is in the range from 650 nm to 790 nm, the most preferably the first peak wavelength of light emitted from the phosphor is in the rage from 430 nm to 460 nm and the second peak wavelength of light emitted from the phosphor is in the range from 690 nm to 790 nm. According to the present invention the term peak wavelength comprises both the main peak of an emission/absorption spectrum having maximum intensity/absorption and side peaks having smaller intensity/absorption than the main peak. Preferably, the term peak wavelength is related to a side peak. Preferably, the term peak wavelength is related to the main peak having maximum intensity/absorption.
The at least one organic light luminescent material is preferably a fluorescent organic material or fluorophore, which terms are used interchangeably herein. Further preferably, the at least one organic light luminescent material is a fluorescent organic material selected from fluorescent proteins or peptides, fluorescent small organic compounds, fluorescent oligomers and polymers, fluorescent multi-component systems and fluorescent organometallic compounds, and combinations of any of these, more preferably from fluorescent small organic compounds and fluorescent organometallic compounds, and combinations thereof.
Exemplary fluorescent small organic compounds which can be employed as organic light luminescent material in the polymer material particle of the present invention include, but are not limited to, the following dyes:
Xanthenes, such as fluorescein, rhodamines, Oregon green, eosins, and Texas red; perylenes, such as perylene, 2,5,8, 11-Tetra-tert-butylperylene; cyanines, such as cyanine, indocarbocyanine, oxacarbocyanine, thiacarbocyanine, phycocyanine, allophycocyanine, and merocyanines; chrysenes, such as 3-(Diphenylamino)dibenzo[g,p]chrysene; squaraines and ring-substituted squaraines, including Seta and Square dyes; naphthalenes, including dansyl and prodan derivatives; coumarins, such as Coumarin 153, 337, or 478; oxadiazoles, such as pyridyloxazole, nitrobenzoxadiazole and benzoxadiazole; anthracenes, such as anthraquinones, including DRAQ5, DRAQ7 and CyTRAK Orange; pyrenes, such as cascade blue, 1 ,3,6,8-Tetraphenylpyrene; dicyanomethylenepyranes, such as DCJTB, 4-(Dicyanomethylene)-2- methyl-6-[2-(2,3,6,7-tetrahydro-1 H,5H-benzo[ij]quinolizin-9-yl)vinyl]-4H- pyran, 4-(Dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H- pyran; oxazines, such as nile red, nile blue, cresyl violet, oxazine 170; acridines, such as proflavin, acridine orange, 10-[4-[4,6-Di(adamantan-1- yl)-1 ,3,5-triazin-2-yl]phenyl]-9,9-dimethyl-9, 10-dihydroacridine, 10-[4-[4,6- Di(1 -adamantyl)-1 ,3,5-triazin-2-yl]phenyl]-10H-spiro[acridine-9,9'-fluorene]; quinacridones, such as Quinacridone, N,N'-Dimethylquinacridone, 5,12- Dibutyl-1 ,3,8,10-tetramethylquinacridone, N,N'-Dibutylquinacridone; arylmethines, such as auramine, crystal violet, malachite green; tetrapyrroles, such as porphins, phthalocyanine, bilirubin, and dipyrromethenes, such as BODIPY, aza-BODIPY. Exemplary fluorescent organometallic compounds which can be employed as organic light luminescent material in the polymer material particle of the present invention include organometallic compounds containing alkaline, alkaline earth, transition metals, lanthanides, actinides, and semimetals, without being limited thereto. Preferably, the metal/semimetal is selected from aluminium (Al), terbium (Tb) (III), europium (Eu) (III), ruthenium (Ru) (II), zinc (Zn) (II) and beryllium (Be) (II). Preferred examples of fluorescent organometallic compounds are bis[2-(2-pyridinyl)phenolato]beryllium(ll), Tris(1 ,3-diphenyl-1 ,3-propanedionato)(1 , 10-phenanthroline)europium(lll),
(1 , 10-Phenanthroline)tris[4,4,4-trifluoro-1 -(2-thienyl)-1 ,3- butanedionato]europium(lll), Tris(acetylacetonato)(1 ,10- phenanthroline)europium(lll), Tris(1 ,10-phenanthroline)ruthenium(ll) Bis(hexafluorophosphate), without being limited thereto.
Suitable commercially available organic light luminescent material are Lumogen® F Orange 240; Lumogen® Red 300; Lumogen® Red 305; Lumogen® Violet 570; “MK-2” (2-Cyano-3-[5’”-(9-ethyl-9H-carbazol-3-yl)- 3’,3”,3”’,4-tetra-n-hexyl-[2,2’,5’,2”,5”,2”’]-quarterthiophen-5-yl]acrylic acid); “D102” (5-[[4-[4-(2,2-diphenylethenyl)phenyl]-1 , 2, 3, 3a, 4,8b- hexahydrocyclopent[b]indol-7-yl]methylene]-4-oxo-2-thioxo-3- thiazolidineacetic acid); “D205” (5-[[4-[4-(2,2-diphenylethenyl)phenyl]-
1,2,3,3a,4,8b-hexahydrocyclopent[b]indol-7-yl]methylene]-2-(3-octyl-4-oxo- 2-thioxo-5-thiazolidinylidene)-4-oxo-3-thiazolidineacetic acid); “D358” (5- [3-(carboxymethyl)-5-[[4-[4-(2,2-diphenylethenyl)phenyl]-1 , 2, 3, 3a, 4,8b- hexahydrocyclopent[b]indol-7-yl]methylene]-4-oxo-2-thiazolidinylidene]-4- oxo-2-thioxo-3-thiazolidinedodecanoic acid); “D131” (2-cyano-3-[4-[4-(2,2- diphenylethenyl)phenyl]-1,2,3,3a,4,8b-hexahydrocyclopent[b]indol-7-yl]-2- propenoic acid), “N3” (cis-bis(isothiocyanato)bis(2,2'-bipyridyl-4,4'- dicarboxylato)ruthenium(ll)); “N719” (di-tetrabutylammonium cis- bis(isothiocyanato)bis(2,2'-bipyridyl-4,4'-dicarboxylato) ruthenium(ll)); “Z907” (cis-Bis(isothiocyanato)(2,2'-bipyridyl-4,4'-dicarboxylato)(4,4'-di- nonyl-2'-bipyridyl)ruthenium(ll)); “K19” ([[2,2'-bipyridine]-4,4'- dicarboxylato(2-)-KN1 ,KN1 '][4,4'-bis[(1 E)-2-[4-(hexyloxy)phenyl]ethenyl]- 2,2'-bipyridine-KN1,KN1']bis (thiocyanato-KN)ruthenate(ll)); “C101” (cis- bis(isothiocyanato)(2,2'-bipyridyl-4,4'-dicarboxylato)(4,4'-bis(5- hexylthiophen-2-yl)-2,2'-bipyridyl)ruthenium(ll)); “C106” (cis- bis(isothiocyanato)(2,2'-bipyridyl-4,4'-dicarboxylato)(4,4'-bis(5- (hexylthio)thiophen-2-yl)-2,2'-bipyridyl)ruthenium(ll)), without being limited thereto. Particularly preferable according to the present invention are the following materials: As blue materials; Lumogen F 570, DyLight 405, DY-405, Alexa Fluor 405, AMCA, AMCA-X, Pacific Blue, DY-415, Royal Blue, ATTO 425. Lumogen F 570 is most preferred. As red materials, Lumogen F Red 305, Cy5.5, DY-677, DY-678, HiLyte Fluor 680, DY-675, DY-676, IRDye700DX, DY-681 , DY-680, DY-682, DyLight 680, Alexa Fluor 700, DY-700, DY-701 , PREX710, DY-730, DY-732, DY-734, DY-731, DY-752, DY-750, DyLight 750, HiLyte Fluor 750, DY-749, HiLyte Plus 750, DY-751, DyLight 800, IRDye800CW, DY-780, DY-781, DY-782, DY-776, DY-777. Lumogen F Red 305 is most preferred.
According to one preferred embodiment of the present invention, said polymer material of the particle is selected from one or more member of the group consisting of polyurethanes, poly(meth)acrylates, poly(butylmethacrylate), ethylene-acrylate copolymer, acrylonitrile- butadiene-styrene copolymer, polyesters, polyacrylonitriles, polyacrylurethanes, polyacrylurethanesilicones, polyfluoroacrylurethanes, polyfluoroacrylates, polyvinylchloride, polystyreneacrylates, polybutyrals, polychlorovinylidenes, melamine resins, phenol resins, epoxy resins, urea resins, unsaturated polyester resins, polycarbonates, polysulfones, polyethers, polyamides, polystyrenes including poly(styrene-co- divinylbenzenes, polyisobutylenes, polyethylene, polyethylene terephthalate, polypropylene, ethyl cellulose and poly(lactic acid) polysilanes, polysiloxanes, polysilicones, polyphosphazenes, polygermanes, polystannanes, polyborazines, polycarbosilanes and polysilazines; and more preferably is a transparent polymer.
According to another preferred embodiment, which is also understood to fall under the present invention, the polymerizable monomer for forming the polymer material has intramoleculary integrated at least one chromophore moiety and at least one polymerizable group or moiety. Such compounds are disclosed for example in JP 2017-195825 A, which compounds are hereby incorporated in its entity by reference. Consequently, according to this preferred embodiment the particle comprises or is comprised of polymerized units of a polymerizable monomeric organic light luminescent material, which can be derived from the organic light luminescent material described herein and contains at least one polymerizable group or moiety and at least one chromophore moiety. In other words, the polymer material of the particle comprises or is comprised of polymerized units of a polymerizable monomeric organic light luminescent material having intramoleculary integrated at least one chromophore moiety and at least one polymerizable group or moiety. This embodiment allows for extending the variety of emitting polymer range.
Preferably according to this embodiment, the particle comprises or is comprised of polymerized units of the polymerizable monomeric organic light luminescent material and polymerized units of one or more further polymerizable monomer. In other words, it is further preferable according to this embodiment that the polymer material of the particle is, or is formed by, a copolymer-kind of structure including structural units of the at least one polymerizable group or moiety of the polymerizable monomeric organic light luminescent material and structural units of one or more further polymerizable monomers, in particular one or more monomers for forming a polymer as described above, and. The at least one polymerizable moiety or group of the polymerizable monomeric organic light luminescent material according to this embodiment is preferably selected from a vinyl moiety, a C1-5 alkylacrylate moiety and an acrylate moiety. As mentioned above, the polymerizable monomeric organic light luminescent material according to this embodiment can be derived from the organic light luminescent material described herein and is preferably derived from the fluorescent organic material described herein. The at least one chromophore moiety of the polymerizable monomeric organic light luminescent material therefore is more preferably derived from xanthene dyes, perylene dyes, cyanine dyes, chrysene dyes, squaraine dyes and ring-substituted squaraine dyes, naphthalene dyes, coumarin dyes, oxadiazole dyes, anthracene dyes, pyrene dyes, dicyanomethylenepyrane dyes, oxazine dyes, acridine dyes, quinacridone dyes, arylmethine dyes, tetrapyrrole dyes, and dipyrromethene dyes, and combinations thereof, as described above. Exemplary suitable polymerizable organic light luminescent materials include decyloxy-1 ,4-phenylene, 9,9-dioctylfluorene, 3-methyl-4- cyclohexylthiophene, 3-cyclohexylthiophene, (1,4-phenylene-1,2- diphenylvinylene), 2-dimethyloctylsilyl-1 ,4-phenylenevinylene, 3- octylthiophene, 2,5-pyridinevinylene, phenylenevinylene, and 2,5-dialkoxy- 1,4-phenyleneethynylene, without being limited thereto.
It is further preferable according to the present invention that the polymer material of the polymer material particle is transparent. The at least one UV absorbing agent is preferably selected from triazines, benzotriazoles, benzophenones, ethanediamides and cyanoacrylates, and combinations of any of these. The UV absorbing agent ensures a photoprotection effect by preventing the degradation of the organic light luminescent material molecules in the particle by excess UV rays and oxygen.
Suitable cyanoacrylates are commercially available and include, but are not limited to: Uvinul® 3035 (commercially available also under the trading names Etocrilene, Etocrylene, N 35, NSC 52678, Seesorb 501 , UV 3035, UV 335, UV Absorber 2, Uvinul® N 35, Viosorb 910); Uvinul®3039 (commercially available also under the trading names Agent AT 539, CA 1 , CA 1 (light stabilizer), Escalol™ 597, Eusolex OCR, N 539, Neo Heliopan 303, Octocrilene, Octocrylene, Parsol 340, Sanduvor 3039, Seesorb 502, UV 3039, Uvinul® 3039, Uvinul® N 539, Uvinul® N 539SG, Uvinul® N 539T, Viosorb 930); and Uvinul® 3030 (commercially available also under the trading names UV 3030, Uvinul® 3030-12).
Suitable ethanediamides are commercially available and include, but are not limited to: CHIGUARD® 1033 (commercially available also under the trading names Tinuvin® 312, Hostavin VSU, Sanduvol VSU, Revonox 420, Sabostab UV 312, Songsorb 3120).
Suitable benzophenones are commercially available and include, but are not limited to: Uvinul®3049 (commercially available also under the trading names Benzophenone 6, Cyasorb® UV 12, NSC 40149, Seesorb 107, UV 49, Uvinul® 3049, Uvinul® D 49); Uvinul® 3050 (commercially available also under the trading names BP 2, Benzophenone 2, Dainsorb P 6, Eversorb® 51, NSC 38556, SUV 1 , Seesorb 106, Sumisorb 150, T 0118, Uvinul® D 50); ADEKASTAB 1413 (commercially available also under the trading names ARO 8, Aduvex 248, Advastab® 46, Anti-UV P, Asahi 1413, BP 12, Benzon OO, Benzophenone 12, C 81, Carstab® 700, Chemisorb 81, Chimassorb® 81 , Cyasorb® 531 , Cyasorb® UV 531 , Cyasorb® UV 532, Cytec UV 531 , GW 531 , Hostavin ARO 8, LA 1413, Lowilite 22, Mark 1413, NSC 163400, Octabenzone, Ongrostab HOB, Rhodialux P, Riasorb UV 531 , Sanduvor 3035, Seesorb 102, Seikalizer E, Specta-Sorb UV 531 , Spectra-Sorb UV 531 , Sumisorb 130, Tinuvin® UV 531 , UF 4, UV 1 , V 1 (ultraviolet absorber), UV 53, V 531 , Uvinul® 3008, Uvinul® M 408, V 130, Viosorb 130, Zislizer E). Suitable benzotriazoles are commercially available and include, but are not limited to: CHIGUARD® 5228 (commercially available also under the trading names BASF 928, Chisorb® 5228, Tinuvin® 928, UV 928); CHIGUARD® 5330; CHIGUARD® 5405 (commercially available also under the trading names Tinuvin® 405, UV 405); ADKSTAB LA-36 (commercially available also under the trading names ADKSTAB LA-36RG, Benazol PBKh, Bumetrizole, CBT, Cibatex LF, Eversorb® 73, Hostavin 3326, J 395, J 395 (light stabilizer), JC 30S, JF 79, Kemisorb® 73, LA 36, Light Stabilizer 326, Lowilite 26, Mark LA 36, Riasorb UV 326, Seesorb 703, Songsorb 3260, Sumisorb 300, T 326, TNV 326, Tin 326, Tinogard AS,
Tinuvin® 326, Tomisorb 600, UV 326, Uvinul® 3026, VS 550, Viosorb 550); ADKSTAB LA-32 (commercially available also under the trading names ADK-ARKLS DN 13, BT 1, BT 1 (light stabilizer), Benazol II, Benazol P, Chisorb® P, Dainsorb T 1 , Drometrizole, Eversorb® 71 , JCK-W-UA, JF 77, JF 77P, JF 77T, Kemisorb® 71, LA 32, Lowilite 55, Mark LA 32, NSC 91885, Seesorb 701, Seikalizer AZ, Solartex UVP, Songsorb 1000, Sumisorb 200, Tinuvin® P, Tinuvin® PED, Tinuvin® UV-P, UV 71 , UV Absorber 1, UV-P, UV-P (UV stabilizer), UVA-P, Uvasorb SV, Uvinul® 3033P, Viosorb 520); ADKSTAB LA-31 R (commercially available also under the trading names ADKSTAB LA-31 RG, ADK-ARKLS LA-31 , Adeka Nol UC 3125, Bisoctrizole, Bisoctyltriazole, CHIGUARD® 5431, Chisorb® 5431, Eversorb® 78, FAT 75'634, JF 832, Kemisorb® 279, LA 31, LA 31 RG, MBBT, Mark LA 31 , Mixxim ADK LA 31 , Mixxim BB 100, T 360, Tinosorb M, Tinuvin® 360, Tinuvin® 360ED, Tinuvin® 5431 , UC 3125, UV 360, UV 5431 , ZINC 11677911 ); ADKSTAB LA-29 (commercially available also under the trading names BLS 5411 , Biosoap 583, Chisorb® 5411 , Cyasorb® 5411 , Eversorb® 72, Fisorb 329, JF 83, Kemisorb® 79, LA 29, Octrizole, Seesorb 709, Seesorb 709G, Songsorb 3290, Spectra-Sorb UV 5411 , Sumisorb 340, Tinuvin® 329, UV 329, UV 5411 , UVA 235, UVA 5411 , Uvinul® 3029, Viosorb 583); ADKSTAB LA-24 (commercially available also under the trading names BLS 234, Benzotriazole BT, Chiguard® 234, Chisorb® 234, Eversorb® 234, Eversorb® 76, Jinwei 234, Light Stabilizer 234, Lowilite 234, Milestab 234PD, Songsorb 2340, T 234, Tinuvin® 234, Tinuvin® 234D, Tinuvin® 900, UV 234, UV 234 (antioxidant), UV Absorber 234, UVA 234, Uvinul® 3034).
Suitable triazines are commercially available and include, but are not limited to: ADKSTAB LA-46; ADKSTAB LA-70F (commercially available also under the trading names LA-F 70, T 712).
ADKSTAB LA-36 (Tinuvin 326) and ADEKASTAB 1413 (Chimassorb 81) are preferred as UV absorbing agent, ADEKASTAB 1413 (Chimassorb 81) is most preferred. The amount of the organic light luminescent material is preferably in the range from 0.1 -2.0 wt.%, related to the total weight of the particle.
The amount of the UV absorbing agent is preferably in the range from 0.1- 10.0 wt.%, related to the total weight of the particle.
In a further preferred embodiment of the present invention, the polymer material particle further comprises at least one stabilizing agent. The stabilizing agent further improves the photoprotection effect described above.
Preferably, the at least one stabilizing agent is selected from hindered amine light stabilizers (HALS).
Suitable HALS materials are commercially available and include, but are not limited to: ADKSTAB LA-52 (commercially available also under the trading names ADKSTAB LA 52MP, ADK-ARKLS DN 44M, ADK-LA 52,
DN 44M, LA 52, Mark LA 52); ADKSTAB LA-57 (commercially available also under the trading names ADKSTAB LA-57MP, DN 44, LA 57, Mark LA 57); ADKSTAB LA-63P; ADKSTAB LA-68; ADKSTAB LA-72 (commercially available also under the trading names Antioxidant 292, BASF 292, Chiguard® 353, Chisorb® 292, HALPS 292, HALS 4, HS 508, JCK-W-US, LA 72, LA 77ME, LS 292, LS 508, LS 765, Light Stabilizer 292, Light, Stabilizer 765, Lowilite 76, Sanol 292, Sanol LS 292, Sanol LS 508, Sanol LS 765, Songlight 2920LQ, TIN 292, TN 765, Tinuvin® 292, Tinuvin® 765, Tinuvin® 766, UV 55-07051 , UV 765); 770DF (commercially available also under the trading names ADKSTAB LA-77, ADKSTAB LA- 77Y, Adeka LA 77, Antioxidant 770, BLS 1770, Chisorb® 770, Eversorb® 90, GW 480, HA 10, HA 70G, HALS 770, HS 770, Hillite 77, Hisorb 770, JF 90, Kemistab 77, LA 77, LA 77G, LA 77Y, LS 770, Light Stabilizer 770, Lowilite 77, MA 90, Mark LA 77, NF 90, Riasorb UV 770, SB-UVA 677, Sanol, Sanol 770, Sanol LS 107, Sanol LS 700, Sanol LS 770, Sanol LS 770P, Songlight 7700, Sumisorb 577, T 770, TIN 770, TN 770, Tinuvin® 770, Tinuvin® 770DF, Tinuvin® 770DF1 , Tinuvin® 770LS, Tinuvin® DF 770, UV 770, UV 770DF, Uvinul® 4077, Uvinul® 4077H, Viosorb 04, ZX 70); ADKSTAB LA-81 (LA 81 ); ADKSTAB LA-82, (commercially available also under the trading names C 10-3410, Chisorb® 582L, FA 711 MM, FA 712MM, Fancryl FA 711 HM, Fancryl FA 711 MM, Fancryl FA 77, LA 82, LS 3410, Mark LA 82, Newcol 3410, Newcol LS 3410, P 1513, Sanol LS 3410); ADKSTAB LA-87 (commercially available also under the trading names FA 711 H, FA 711 HA, FA 712HM, Fancryl, FA 712HM, LA 87, Mark LA 87, TAA-ol methacrylate); ADKSTAB LA-402AF; ADKSTAB LA- 40MP/LA- 40Si.
A type of shape of the polymer material particle of the present invention is not particularly limited. For examples, the polymer material particles may have a spherical shape, an elliptic shape or an elongated shaped, wherein the spherical shape is preferred. That is, according to preferred embodiments of the invention the polymer material particle may be in the form of a sphere, a spheroid or ellipsoid, or a rod, but is preferably in the form of a sphere.
Further preferably, the polymer material particle of the invention has an average particle size in the range of 1 to 1000 pm, more preferably in the range of 10 to 800 pm, as measureing the longest length of 100 particles each independently by scanning electron microscopy.
In a further preferred embodiment of the present invention, the particle has an external quantum efficiency (EQE) of 10% or more, preferably it is from 10% to 90%, more preferably from 20% to 80%, further more preferably from 30% to 80%, the most preferably it is from 40% to 80%.
The EQE is calculated by the below Equation (1):
Equation (1): EQE = total number of photons emitted from the phosphor sample/ total number of photons irradiated to the phosphor sample
The data for calculating the EQE (i.e. , the total number of photons emitted from the phosphor sample (i.e., emission light) and the total number of photons irradiated to the phosphor sample (i.e., excitation light) are obtained using a spectrophotofluorometer FP6500 (from JASCO) equipped with a xenon lamp. The following measurement setup is applied:
Measurement conditions: 25 °C in air The peak maximum wavelength of excitation light: 320 nm The measurement range of Excitation light: 300-400 nm The measurement range of Emission light: 650-800 nm Slit distance: 3 mm Excitation band width: 3 nm Luminescent (emission) band width: 3 nm Measurement response speed: 0.5 sec
For sample preparation, a target powder phosphor sample for EQE measurement is set to a glass cell. The glass cell is set to behind the integrating sphere with respect to the excitation light. The EQE measurement and calculation is performed by the following procedure of steps A) to D) in this sequence, using a sample prepared as described above:
Step A) Emission spectrum measurement of the phosphor sample: Excitation wavelength (light source): 365 nm Measurement range: 400~800 nm
Peak wavelength of this emission spectrum of the measured phosphor is referred to as A nm Step B) Excitation spectrum measurement of the phosphor sample: Emission wavelength (light source): A nm Measurement range: 300~(A-20) nm
Peak wavelength of this excitation spectrum of the measured phosphor is referred to as B nm
Step C) Emission spectrum measurement for QE calculation of the phosphor sample:
Emission wavelength (light source): B nm Measurement range: 300~800 nm Standard white board made by Ba2SQ4 is also measured as reference. Step D) EQE calculation of the phosphor sample:
The EQE value is calculated by sample and reference spectra.
Excitation range: 300~(B+50) nm Emission range: (B+50)~800 nm
- Method for polymer material particle preparation According to the present invention, the polymer material particle can be prepared by using publicly known polymerization method for preparing polymer material particles including, but not limited to, suspension polymerization, emulsion polymerization, inverse emulsion polymerization, soap-free emulsion polymerization, seed emulsion polymerization, dispersion polymerization, non-aqueous phase dispersion polymerization, interfacial condensation encapsulation, multi-phase emulsion encapsulation, and concentric double orifice encapsulation.
A preferred method according to the present invention is the one described in the working example below, which is based on the suspension polymerization method, which includes according to a preferred embodiment the steps of
(a) preparing a suspension by mixing at least one organic light luminescent material, at least one UV absorbing agent and one or more polymerizable monomers/polymer precursors in a liquid phase, preferably water; and (b) polymerizing the resulting mixture by applying heat.
A preferred method according to another embodiment of the present invention includes the steps of
(a’) preparing a suspension by mixing at least one polymerizable organic light luminescent material and at least one UV absorbing agent, and optionally one or more polymerizable monomers/polymer precursors, in a liquid phase, preferably water; and
(b’) polymerizing the resulting mixture by applying heat. Further preferably, said suspension in step (a) and (a’) further comprises at least one stabilizing agent, which is more preferably selected from hindered amine light stabilizers.
That is, according to a further preferred embodiment the method for polymer material particle preparation of the present invention includes the steps of (a) preparing a suspension by mixing at least one organic light luminescent material, at least one UV absorbing agent, at least one stabilizing agent and one or more polymerizable monomers/polymer precursors in a liquid phase, preferably water; and (b) polymerizing the resulting mixture by applying heat.
According to another further preferred embodiment the method for polymer material particle preparation of the present invention includes the steps of (a’) preparing a suspension by mixing at least one polymerizable organic light luminescent material, at least one UV absorbing agent and at least one stabilizing agent, and optionally one or more polymerizable monomers/polymer precursors, in a liquid phase, preferably water; and (b’) polymerizing the resulting mixture by applying heat. According to the method of the present invention, said at least one
(polymerizable) organic light luminescent material, said at least one UV absorbing agent and said at least one stabilizing agent are preferably as described in the section “Polymer material particle” above. According to a more preferred embodiment of the present invention, the suspension polymerization method comprises one or more of the following steps: preparing a solution by dissolving in an appropriate solvent, such as toluene, at least one organic light luminescent material, at least one UV absorbing agent, a polymerization initiator, for example benzoyl peroxide, one or more polymerizable monomers/polymer precursors, for example styrene, divinylbenzene and/or methylmethacrylate (MMA), and optionally at least one stabilizing agent; emulsifying this solution in an aqueous solution optionally containing a dispersant agent and/or a dispersant stabilizer; heating the resulting mixture under stirring, for example at 400 rpm at over 70 °C for about 6 hours; cooling to room temperature; collecting, washing and drying the resulting microsphere material.
Appropriate solvents, polymer precursors, polymerization initiators, phase separation inducers, homogenizers and dispersant agents/stabilizers can be selected by those skilled in the art as desired in accordance with the selected fabrication method.
The solvent is preferably an organic solvent. Preferably said organic solvent is selected from one or more members of the group consisting of alcohols including primary alcohol having 1 to 40 carbon atoms, preferably 1 to 25 carbon atoms, more preferably 2 to 20 carbon atoms, such as methanol, ethanol, isopropyl alcohol, butyl alcohol, 1-pentanol, tetrahydrofurfuryl alcohol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1- decanol (boiling point (°C): 9.6), 1-undecanol (14), 1-dodecanol (26), 1- tridecanol (32), 1 -tetradecanol (40), 1-pentadecanol (46), 1 -hexadecanol (55), 1-heptadecanol (55), 1-octadecyl alcohol, 1-nonadecanol (64), 1- eicosanol (67); secondary alcohol having 3 to 40, preferably 3 to 25, more preferably 3 to 20 carbon atoms such as 2-propanol, 1-methoxy-2- propanol, 2-butanol, 2-pentanol, 2-hexanol, 2-heptanol, cyclohexanol and tertiary alcohol having 4 to 40 carbon atoms, preferably 4 to 25 carbon atoms, more preferably 4 to 20 carbon atoms such as tert-butyl alcohol, 2- methyl-2-pentanol, 3-methyl-3-pentanol; diol having 2 to 10 carbon atoms such as ethylene glycol, 1,3-propanediol, propylene glycol, 1 ,4-butanediol, 1,5-pentanediol, 1 ,6-hexanediol, 1,7-heptanediol, 1 ,8-octanediol, 1,9- nonanediol, 1 ,10-decanediol, 1 ,4-cyclohexanedimethanol; heteroaromatic alcohol such as furfuryl alcohol, (5-methyl-2-furyl)methanol, 1-(2- furyl)ethan-1-ol, 2,5-furandimethanol, 2-thiophemethanol, 2- thiopheethanol; ketones such as (acetone), ethyl methyl ketone, diethyl ketone, methyl propyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone, acetophenone; cycloalkane having carbon atoms 6 to 12 such as cyclohexane, methylcyclohexane, 1 ,1-dimethylcyclohexane, 1,2- dimethylcyclohexane, 1,3-dimethylcyclohecxane, 1,4- dimethylcyclohexane, 1 ,3,5-trimethylcyclohexane, 1 -ethyl-4- methylcyclohexane, cycloheptane, cyclooctane, cyclononane, and cyclodecane; ethers such as tetrahydrofuran, 1 ,3-dimethoxyethane, 1,2- dimethoxypropane, 1,3-dimethoxypropane, 2,2-dimethoxypropane, 2,2- diethoxypropane, diethylene glycol ethyl ether, diethylene glycol diethyl ether, diethylene glycol propyl ether, diethylene glycol dipropyl ether, diethylene glycol butyl ether, diethylene glycol dibutyl ether, di(propylene glycol) methyl ether, di(propylene glycol) dimethyl ether, di(propylene glycol) propyl ether, 1,2-dimethoxycyclohexane, 1-methoxy-4- methylcyclohexane, 1,3-dioxane, 1,4-dioxane, poly(ethylene glycol) tetrahydrofurfuryl ether, tetrahydrofurfuryl alcohol polyethylerene glycol ether, tetraglycol, ethyl tetrahydrofurfuryl ether; esters such as methyl acetate, ethyl acetate, isoamyl acetate, butyl acetae, n-butyl acetate, sec- buyl acetate, isobutyl acetate, propyl acetate, isopropyl acetate, amyl acetate, pentyl acetate, isopentyl acetate, 2-ethoxyethyl acetate, hexyl acetate, cyclohexyl acetate, heptyl acetate, lauryl acetate, dodecyl acetate, ethyl 2-(benzyloxy)acetate, benzyl acetate, phenyl acetate, 4-tert- pentylcyclohexyl acetate, 1 ,2-diacetoxycyclohexane, 1,3- diacetoxycyclohexane, 1 ,3,5-triacetoxycyclohexane, tetrahydrofurfuryl acetate, tetrahydrofurfuryl butyrate, dimethyl carbonate, diethyl carbonate, dethylene carbonate, propylene carbonate, ethylene carbonate, diallyl carbonate, dipropyl carbonate, dibenzyl carbonate; amide such as N,N- dimethylacetamide, N,N-dimethylformamide, and toluene.
In a preferable embodiment of the present invention, said polymerizable monomer or polymer precursor is an organic polymer precursor, preferably selected from acidic monomer, more preferably it is selected from one or more members of the group consisting of acrylic acid, 2-chloroacrylic acid, 2-bromoacrylic acid, methacrylic acid, 2-phenylacrylic acid, 2- (methoxymethyl)-2-propenoic acid, 2-methylenesuccinic acid, methyl itaconate, ethyl itaconate, 2-methylene-4-oxo-pentanoic acid, propylacrylic acid, 6-methacryloxy1-[2-[(2-methyl-1-oxo-2-propen-1-yl)oxy]ethyl] ester butanedioic acid (for example, Kyoeisha Chemical “LIGHT ESTER HO- MS(N)”), 1-[2-[(2-methyl-1-oxo-2-propen-1-yl)oxy]ethyl] ester 1,2- cyclohexanedicarboxylic acid (for example, Kyoeisha Chemical “LIGHT ESTER HO-HH(N)”), 2-methacryloyloxyethyl acid phosphate (for example, Kyoeisha Chemical “LIGHT ESTER P-1M(N)”), bis(2-methacryloyloxyethyl acid) phosphate (for example, Kyoeisha Chemical “LIGHT ESTER P- 2M(N)”), 1-[2-[(1-oxo-2-propen-1-yl)oxy]ethyl] ester butanedioic acid (for example, Kyoeisha Chemical “LIGHT ACRYLATE HOA-MS(N)”), 1-[2-[(1- oxo-2-propen-1 -yl)oxy]ethyl] ester 1 ,2-cyclohexanedicarboxylic acid (for example, Kyoeisha Chemical “LIGHT ACRYLATE HOA-HH(N)”), 1-[2-[(1- oxo-2-propen-1 -yl)oxy]ethyl] ester 1 ,2-Benzenedicarboxylic acid (for example, Kyoeisha Chemical “LIGHT ACRYLATE HOA-MPL(N)”), 2- (phosphonooxy)ethyl ester 2-propenoic acid (for example, Kyoeisha Chemical “LIGHT ACRYLATE P-1M(N)”), 1-[1-[[4-[1-[4-[2-hydroxy-3-[(1- oxo-2-propen-1 -yl)oxy]propoxy]phenyl]-1 -methylethyl]phenoxy]methyl]-2- [(1-oxo-2-propen-1-yl)oxy]ethyl] ester 4-cyclohexene-1 ,2-dicarboxylic acid; and styrene derivative monomer such as 4-vinylbenzoic acid, 4-(1- methylethenyl)benzoic acid. In some embodiments of the method of the present invention, the dispersant agent/dispersant stabilizer preferably is selected from one or more members of sodium dodecylbenzene sulfonate (Sigma-Aldrich), Span® 80 (Sigma-Aldrich), lecithin (soybean, Sigma-Aldrich), PW-36 (Kusumoto Chemicals), DISPERBYK-103, DISPERBYK-110, DISPERBYK-111, DISPERBYK-118, DISPERBYK-142 (BYK Chemie) and gum arabic (from acacia tree; Sigma-Aldrich).
In some embodiments of the method of the present invention, which require the presence of a polymerization initiator, in general a polymerization initiator generating an acid, base, or radical when exposed to radiation, can be used, or a polymerization initiator generating an acid, base or radical when exposed to heat can be used, as desired.
The polymerization initiator adoptable in the present invention is, for example, a photo acid-generator, which decomposes when exposed to radiation and releases an acid serving as an active substance for photo curing the composition; a photo radical - generator, which releases a radical; a photo base-generator, which releases a base; a heat acid- generator, which decomposes when exposed to heat and releases an acid serving as an active substance for heat-curing the composition; a heat radical - generator, which releases a radical; and a heat base-generator, which releases a base. Examples of the radiation include visible light, UV rays, IR rays, X-rays, electron beams, a-rays and y-rays.
The heat acid-generator is, for example, a salt or ester capable of generating an organic acid. Examples thereof include: various aliphatic sulfonic acids and salts thereof; various aliphatic carboxylic acids, such as, citric acid, acetic acid and maleic acid, and salts thereof; various aromatic carboxylic acids, such as, benzoic acid and phthalic acid, and salts thereof; aromatic sulfonic acids and ammonium salts thereof; various amine salts; aromatic diazonium salts; and phosphonic acid and salts thereof.
Among the heat acid-generators usable in the present invention, salts of organic acids and organic bases are preferred, and further preferred are salts of sulfonic acids and organic bases.
Examples of the preferred heat acid-generators containing sulfonate ions include p-toluenesulfonates, benzenesulfonates, p- dodecylbenzenesulfonates, 1 ,4-naphthalenedisulfonates, and methanesulf Examples of the above heat base-generator include: imidazole derivatives, such as, N-(2-nitrobenzyloxycarbonyl)imidazole, N-(3-nitrobenzyloxy- carbonyl)imidazole, N-(4-nitrobenzyloxycarbonyl)imidazole, N-(5-methyl-2- nitrobenzyloxycarbonyl)imidazole, and N-(4-chloro-2-nitro- benzyloxycarbonyl)imidazole; 1 ,8-diazabicyclo(5,4,0)undecene-7, tertiary amines, quaternary ammonium salts, and mixture thereof. Those base- generators as well as the acid-generators and / or radical - generators can be used singly or in mixture.
As the examples of the heat radical-generator, 2,2' azobis(2- methylvaleronitrile), 2,2‘-azobis(dimethylvaleronitrile), azobisisobutyronitrile or a combination of any of these can be used preferably.
Examples of the above photo acid-generator include diazomethane compounds, diphenyliodonium salts, triphenylsulfonium salts, sulfonium salts, ammonium salts, phosphonium salts and sulfonamide compounds. The structures of those photo acid-generators can be represented by the formula (A):
R+X- (A), wherein in formula (A), R+ is hydrogen or an organic ion modified by carbon atoms or other hetero atoms provided that the organic ion is selected from the group consisting of alkyl groups, aryl groups, alkenyl groups, acyl groups and alkoxy groups. For example, R+ is diphenyliodonium ion or triphenylsulfonium ion.
Further, X- is preferably a counter ion represented by any of the following formulas:
SbY6 ,
AsYe ,
RapPY6-p-,
RaqBY4-q , RaqGaY -q-,
RaS03-,
(RaS02)3C-,
(RaS02)2N-,
RaCOO , and SCN- in which
Y is a halogen atom,
Ra is an alkyl group of 1 to 20 carbon atoms or an aryl group of 6 to 20 carbon atoms provided that each group is substituted with a substituent group selected from the group consisting of fluorine, nitro group and cyano group, p is a number of 0 to 6, and q is a number of 0 to 4.
Specific examples of the counter ion include: BF4 _, (C6Fs)4B·, ((CF3)2C6H3)4B-, PFe-, (CF3CF2)3PF3-, SbFe , (C6F5)4Ga-, ((CF3)2C6H3)4Ga-, SCN , (CF3S02)3C-, (CF3S02)2N-, formate ion, acetate ion, trifluoromethanesulfonate ion, nonafluorobutanesulfonate ion, methane- sulfonate ion, butanesulfonate ion, benzenesulfonate ion, p- toluenesulfonate ion, and sulfonate ion.
Among the photo acid-generators usable in the present invention, those generating sulfonic acids or boric acids are particularly preferred. Examples thereof include tricumyliodonium teterakis(pentafluorophenyl)- borate (PFIOTOINITIATOR2074 [trademark], manufactured by Rhodorsil), diphenyliodonium tetra(perfluorophenyl)borate, and a compound having sulfonium ion and pentafluoroborate ion as the cation and anion moieties, respectively. Further, examples of the photo acid-generators also include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphor- sulfonate, triphenylsulfonium tetra(perfluorophenyl)borate, 4- acetoxyphenyldimethylsulfonium hexafluoroarsenate, 1-(4-n- butoxynaphthalene-1-yl)tetrahydrothiophenium trifluoromethanesulfonate,
1 -(4,7-dibutoxy-1 -naphthalenyl)tetrahydrothiophenium tri fluoromethanesulfonate, diphenyliodonium trifluoromethanesulfonate, and diphenyliodonium hexafluoroarsenate. Furthermore, it is still also possible to adopt photo acid-generators represented by the following formulas:
Figure imgf000036_0001
in which each A is independently a substituent group selected from the group consisting of an alkyl group of 1 to 20 carbon atoms, an alkoxy group of 1 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkylcarbonyl group of 1 to 20 carbon atoms, an arylcarbonyl group of 6 to 20 carbon atoms, hydroxyl group, and amino group; each p2 is independently an integer of 0 to 5; and B is a fluorinated alkylsulfonate group, a fluorinated arylsulfonate group, a fluorinated alkylborate group, an alkylsulfonate group or an arylsulfonate group. It is also possible to use photo acid-generators in which the cations and anions in the above formulas have exchanged each other or combined with various other cations and anions described above. For example, any one of the sulfonium ions represented by the above formulas can be combined with tetra(perfluorophenyl)borate ion, and also any one of the iodonium ions represented by the above formulas can be combined with tetra(perfluorophenyl)borate ion. Those can be still also employed as the photo acid-generators.
Examples of the photo radical-generator include azo compounds, peroxides, acyl phosphine oxides, alkyl phenons, oxime esters, and titanocenes.
According to the present invention, as the photo radical-generator, acyl phosphine oxides, alkyl phenons, oxime esters, or a combination of any of these are more preferable. For examples, 2,2-dimethxye-1 ,2- diphenylethane-1 -on, 1 -hydroxy-cyclohexylphenylketone, 2-hydroxy-2- methyl-1 -phenylpropan-1 -on, 1 -[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2- methyl-1 -propane-1 -on, 2-hydroxy-1 -{4-[4-(2-hydroxy-2- methylpropionyl)benzyl]phenyl}-2-methylpropane-1 -on, 2-methyl-1 -(4- methylthiophenyl)-2-morpholinopropane-1 -on, 2-benzyl-2-dimethylamino-
1-(4-morpholinophenyl)-1-butanone, 2-(dimethylamino) -2-[(4- methylphenon)methyl]-1 -[4-(4-morpholinyl)phenyl]-1 -butanone, 2,4,6- trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6- trimethylbenzoyl)phenylphosphine oxide, 1 ,2-octanedione 1-[4- (phenylthio)-2-(o-benzoyl oxime)], ethanone 1 -[9-ethyl-6-(2- methylbenzoyl)-9H-carbazole-3-yl]-1-(o-acetyl oxime) or a combination of any of these can be used preferably.
Examples of the photo base-generator include multi-substituted amide compounds having amide groups, lactams, imide compounds, and compounds having those structures.
- Use of the polymer material particle
In another aspect, the present invention also relates to a use of the polymer material particle of the present invention in agriculture. In a further aspect, the present invention also relates to a use of the polymer material particle of the present invention in an optical sheet, an optical film, an optical net, an optical fiber, an optical nonwoven fabric or an optical plate. In a further aspect, the present invention also relates to a use of the polymer material particle of the present invention in a spraying agent, a coating agent or a painting agent.
In a still further aspect, the present invention relates to a use of the polymer material particle of the present invention in a Light Emitting Diode, in a solar cell or in a plant cultivation pot.
- Composition
In another aspect, the present invention also relates to a composition comprising, essentially consisting of, or consisting of, at least one polymer material particle of the present invention and a further material.
Preferably, said composition comprises a plurality of the polymer material particle of the present invention. Thus, in a more preferably embodiment of the present invention, the total amount of the at least one polymer material particle of the present invention in the composition may be in the range from 0.01 wt.% to 99.9 wt.%, preferably in the range from 0.01 wt.% to 10 wt.%, based on the total amount of the composition, and more preferably it is from 0.05 wt.% to 5 wt.%, even more preferably from 0.05 wt.% to 3 wt.%, and furthermore preferably from 0.1 wt.% to 1 wt.% from the view point of better light conversion property, lower production cost and less production damage of a production machine.
The further material is preferably selected from one or more members of the group consisting of matrix materials; light modulating materials such as dyes, for example blue or red dyes, pigments, light luminescent materials including organic and inorganic light luminescent materials, for example another organic light luminescent material or an inorganic phosphor; photo initiators; co-polymerizable monomers; cross linkable monomers; bromine- containing monomers; sulfur-containing monomers; adjuvants; adhesives; insecticides; insect attractants; metal oxides; Al, Ag, Au nanoparticles; dispersants; surfactants; fungicides and antimicrobial agents.
In a preferred embodiment of the invention, the further material is a matrix material and said composition can optionally comprises one or more additives selected from one or more members of the group consisting of light modulating materials such as dyes, for example blue or red dyes, pigments, light luminescent materials including organic and inorganic light luminescent materials, for example another organic light luminescent material or inorganic phosphors; photo initiators; co-polymerizable monomers; cross linkable monomers; bromine-containing monomers; sulfur-containing monomers; adjuvants; adhesives; insecticides; insect attractants; metal oxides; Al, Ag, Au nanoparticles; dispersants; surfactants; fungicides and antimicrobial agents.
- Matrix materials as said further material According to the present invention, said matrix material may be an organic material, and/or an inorganic material, preferably AI2O3, fused composition of TeCte: Na2Co3 : ZnO : BaCo3 = 7:1:1 :1, and fused mixture of TeC : Na2Co3 : ZnO : BaCo3 = 7:1:1 :1 and AI2O3 are excluded. Preferably, the matrix material is an organic material.
More 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 a preferred embodiment 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, styrene- butadiene, polyvinyl chloride, polymethacrylic styrene, styrene-acrylonitrile, acrylonitrile-butadiene-styrene, polyethylene terephthalate, polymethyl methacrylate, polyphenylene ether, polyacrylonitrile, polyvinyl alcohol, acrylonitrile polycarbonate, polyvinylidene chloride, polycarbonate, polyamide, polyacetal, polybutylene terephthalate, polytetrafluoroethylene, ethylene-vinyl acetate copolymer, ethylene-tetrafluorethylen copolymer, polyamide, melamine resin, urea resin, polyurethane, epoxy resin, unsaturated polyester resin, polyallyl sulfone, polyacrylate, hydroxybenzoic acid polyester, polyetherimide, polycyclohexylenedimethylene terephthalate, polyethylene naphthalate, polyester carbonate, polylactic acid, phenolic resin, silicone resin or a combination of any of these can be used preferably. As the photosetting polymer, several kinds of (meth)acrylates can be used preferably. Such as unsubstituted alkyl-(meth) acrylates, for examples, methyl-acrylate, methyl-methacrylate, ethyl-acrylate, ethyl-methacrylate, butyl-acrylate, butyl-methacrylate, 2-ethylhexyl-acrylate, 2-ethylhexyl- methacrylate; substituted alkyl-(meth)acrylates, for examples, hydroxyl- group, epoxy group, or halogen substituted alkyl-(meth)acrylates; cyclopentenyl(meth)acrylate, tetra-hydro furfuryl-(meth)acrylate, benzyl (meth)acrylate, polyethylene-glycol di-(meth)acrylates.
In view of better coating performance of the composition, sheet strength, and good handling, the matrix material has a weight average molecular weight in the range from 5,000 to 50,000 preferably, more preferably from 10,000 to 30,000.
According to the present invention, the molecular weight Mw is determined by means of GPC (= gel permeation chromatography) against an internal polystyrene standard.
As the thermosetting polymer, publicly known transparent thermosetting polymer can be used preferably. Such as OE6550 (trade mark) series (Dow Corning). 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.
According to the present invention, such thermoplastic polymers may 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 mentioned in this section and the inorganic phosphors mentioned below in the section “Inorganic phosphor as a further material in the composition” can be preferably used for a fabrication of the color conversion sheet and the light emitting diode device of the present invention.
According to the present invention, the composition can optionally further comprise one or more inorganic phosphor, which emits blue or red light.
- Inorganic phosphors as said further material in the composition According to the present invention, any type of publicly known inorganic phosphors may be used.
Preferably, the phosphor is a fluorescent or a phosphorescent inorganic material which contains one or more light emitting centers (i.e. , a so called “inorganic phosphor”). Preferably, the light emitting centers are formed by activator elements such as e.g. atoms or ions of rare earth metal elements, for example La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er,
Tm, Yb and Lu, and/or atoms or ions of transition metal elements, for example Cr, Mn, Fe, Co, Ni, Cu, Ag, Au and Zn, and/or atoms or ions of main group metal elements, for example Na, Tl, Sn, Pb, Sb and Bi. Examples of suitable phosphors include phosphors based on garnet, silicate, orthosilicate, thiogallate, sulfide, nitride, silicon-based oxynitride, nitridosilicate, nitridoaluminumsilicate, oxonitridosilicate, oxonitridoaluminumsilicate and rare earth doped SiAION.
According to a preferred embodiment of the present invention, inorganic phosphors having a peak wavelength of light emitted from the inorganic phosphor in the range of 600 nm or more, preferably in the range from 650 to 1500 nm, more preferably in the range from 650 to 1000 nm, even more preferably in the range from 650 to 800 nm, furthermore preferably in the range from 650 to 750 nm, much more preferably it is from 660 nm to 730 nm, furthermore preferably it is from 660 nm to 710 nm, the most preferably from 670 nm to 710nm; or having a peak wavelength of light emitted from the inorganic phosphor in the range of 500 nm or less, preferably in the range from 250 nm to 500 nm, more preferably in the range from 300 nm to 500 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; or 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 the inorganic phosphor of the composition, 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 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, halogerman- ates, 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 a further preferred embodiment of the present invention, said inorganic phosphor is selected from the group consisting of metal oxides, silicates and halosilicates, phosphates and halophosphates, borates and borosilicates, aluminates, gallates and alumosilicates, molybdates and tungstates, sulfates, sulfides, selenides and tellurides, nitrides and oxynitrides, SiAIONs, halogen compounds and oxy compounds, such as preferably oxysulfides or oxychlorides phosphors, preferably, it is a metal oxide phosphor, more preferably it is a 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 AI203:Cr3+, Y3AI50i2:Cr3+, MgO:Cr3+, ZnGa204:Cr3+, MgAI204:Cr3+, Gd3Ga50i2:Cr3+, LiAI508:Cr3+, MgSr3Si208:Eu2+,Mn2+, Sr3MgSi20s:Mn4+, Sr2MgSi207:Mn4+, SrMgSi206:Mn4+, BaMg6Ti60i9:Mn4+, Cai4AhoZn6035:Mn4+, Mg8Ge20nF2:Mn4+, Mg2Ti04:Mn4+, Y2MgTi06:Mn4+, Li2Ti03:Mn4+, K2SiF6:Mn4+, K3SiF7:Mn4+, K2TiF6:Mn4+, K2NaAIF6:Mn4+, BaSiF6:Mn4+, CaAh20i9:Mn4+, MgSiOs:Mn2+, Si5P6025:Mn4+, NaLaMgW06:Mn4+, Ba2YTa06:Mn4+, ZnAI204:Mn2+, CaGa2S4:Mn2+, CaAISiN3:Eu2+, SrAISiN3:Eu2+, Sr2Si5N8:Eu2+, SrLiAIN :Eu2+, CaMgSi206:Eu2+, Sr2MgSi207:Eu2+, SrBaMgSi207:Eu2+, Ba3MgSi208:Eu2+,
LiSrP04:Eu2+, LiCaP04:Eu2+, NaSrP04:Eu2+, KBaP04:Eu2+, KSrP04:Eu2+, KMgP04:Eu2+, a-Sr2P207:Eu2+, a-Ca2P207:Eu2+, Mg3(P04)2:Eu2+, Mg3Ca3(P04)4: Eu2+, BaMgAhoOi7:Eu2+, SrMgAlioOi7:Eu2+, AIN:Eu2+, Sr5(P04)3CI:Eu2+, NaMgP04 (glaserite):Eu2+, Na3Sc2(P04)3:Eu2+, LiBaB03:Eu2+, SrAISUN7:Eu2+, Ca2Si04:Eu2+, NaMgP04:Eu2+, CaS:Eu2+,
Y203:EU3+, YV04:EU3+, LiAI02:Fe3+, LiAlsOe: Fe3+, NaAISi04:Fe3+,
MgO:Fe3+, Gd3Ga5012:Cr3+,Ce3+, (Ca, Ba, Sr)2MgSi207:Eu,Mn, CaMgSi206:Eu2+,Mn2+, NaSrB03:Ce3+, NaCaB03:Ce3+, Ca3(B03)2:Ce3+, Sr3(B03)2:Ce3+, Ca3Y(Ga0)3(B03)4:Ce3+, Ba3Y(B03)3:Ce3+, CaYAI04:Ce3+, Y2Si05:Ce3+, YSi02N:Ce3+, Y5(Si0 )3N:Ce3+,
Ca2AI306FGd3Ga50i2: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 friendliness, since these phosphors do not create Cr6+ during synthesis procedure.
As an 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 to better plant growth, if it is combined with emission light from the organic light luminescent material having the peak wavelength of light emitted from the organic light luminescent material in the range from 600 nm to 820 nm, especially the combination of the blue light around 450 nm wavelength and emission light from the organic light luminescent material having the peak wavelength of light emitted from the organic light luminescent material in the range from 690 nm to 790 nm is preferable for better plant growth.
Thus, more preferably, the composition of the invention can additionally comprise at least one blue light emitting inorganic phosphor having peak wavelength of light emitted from the inorganic phosphor around 450 nm, like described in the second chapter of Phosphor handbook (Yen, Shinoya, Yamamoto).
- Vinyl 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,b-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,b- unsaturated carboxylic acid to a compound having glycidyl, such as tri- methylol propane triglycidylether triacrylate, bis-phenol A diglycidylether diacrylates; chemicals having poly-carboxylic acids, such as a phtalic anhydride; or chemicals having hydroxy and ethylenic unsaturated group, such as the esters with hydroxyethyl (meth)acrylate; alkyl-ester of acrylic acid or methacylic acid, such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethyl hexyl (meth)acrylate; urethane (meth)acrylate, such as the reactants of Tolylene diisocyanate and 2- hydroxyethyl (meth)acrylate, the reactants of tri-methyl hexamethylene di isocyanate and cyclohexane dimethanol, and 2-hydroxyethyl (meth)acrylate; and a combination of any of these.
In a preferred embodiment of the present invention, the crosslinkable monomer is selected from the group consisting of tri-methylol-propane tri (meth)acrylate, di-pentaerythritol tetra-(meth)acrylate, di-pentaerythritol hexa-(meth)acrylate, bisphenol-A polyoxyethylene dimethacrylate and a combination thereof. The vinyl monomers and the crosslinkable monomers described above can be used alone or in combination.
From the viewpoint of controlling the refractive index of the composition and/or the refractive index of the color conversion sheet according to the present invention, the composition can further comprise publicly known one or more of bromine-containing monomers, sulfur-containing monomers. The type of bromine and sulfur atom-containing monomers (and polymers containing the same) are not particularly limited and can be used preferably as desired.
For example, as bromine-containing monomers, new frontier® BR-31, new Frontier® BR-30, new Frontier® BR-42M (available from DAI-ICHI KOGYO SEIYAKU CO., LTD) or a combination of any of these, as the sulfur-containing monomer composition, IU-L2000, IU-L3000, IU-MS1010 (available from MITSUBISHI GAS CHEMICAL COMPANY, INC.) or a combination of any of these, can be used preferably.
-Photo initiator for the composition In a preferred embodiment of the present invention, the photo initiator can be a photo initiator that can generates a free radical when it is exposed to an ultraviolet light or a visible light. For example, benzoin-methyl-ether, benzoin-ethyl-ether, benzoin-propyl-ether, benzoin-isobutyl-ether, benzoin- phenyl-ether, benzoin-ethers, benzophenone, N,N’-tetramethyl-4,4’- diaminobenzophenone (Michler’s-ketone), N,N’-tetraethyl-
4,4’diaminobenzophenone, benzophenones, benzil-dimethyl-ketal (Ciba specialty chemicals, IRGACURE® 651), benzil-diethyl-ketal, dibenzil ketals, 2,2-dimethoxy-2-phenylacetophenone, p-tert-butyldichloro acetophenone, p-dimethylamino acetophenone, acetophenones, 2,4- dimetyl thioxanthone, 2,4-diisopropyl thioxanthone, thioxanthones, hydroxy cyclohexyl phenyl ketone (Ciba specialty chemicals, IRGACURE® 184), 1 -(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1 -on (Merck, Darocure® 1116), 2-hydroxy-2-methyl-1-phenylpropane-1-on (Merck, Darocure® 1173).
-Adjuvant, dispersant, surfactant, fungicide and antimicrobial agent An adjuvant can enhance the permeability of the effective component (e.g. an insecticide), inhibit precipitation of solute in the composition, or decrease phytotoxicity. 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.
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.
According to a further preferred embodiment, the weight ratio of each one additive, to the weight of the coated phosphor of the invention in the total amount of the composition is in the range from 50 wt.% to 200 wt.%, more preferably it is from 75 wt.% to 150 wt.%. Exemplified embodiment of an adjuvant is Approach Bl (Trademark, Kao Corp.).
- Formulation In another aspect, the invention relates to a formulation comprising, essentially consisting of, or consisting of at least one polymer material particle of the present invention or the composition of the present invention, and a solvent. Preferably, said formulation comprises a plurality of the polymer material particles or the composition of the present invention. As a solvent for the formulation, a wide variety of publicly known solvents can be used preferably. There are no particular restrictions on the solvent as long as it can dissolve or disperse the matrix material, and the polymer material particle of the composition.
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. 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. Even more preferably, benzene, toluene, or xylene can be used. The solvent is used singly or in combination of two or more, and the amount thereof can be freely controlled depending on the coating method and the thickness of the coating. For example, if the formulation is to be spray-coated, it can contain the solvent in an amount of 90 wt.% or more based on total amount of the formulation. Further, if a slit-coating method, which is often adopted in coating a large substrate, is to be carried out, the content of the solvent is normally 60 wt.% or more, preferably in the range from 70 wt.% to 95 wt.% based on the total amount of the formulation.
- Use of the polymer material particle, the composition, or the formulation In another aspect, the invention relates to use of the polymer material particle of the present invention, or the composition of the present invention, or the formulation of the present invention, in a method for preparing an optical sheet or in agriculture, preferably for preparing an agricultural sheet or for controlling a condition of a living organism.
- An optical sheet In another aspect, the invention relates to an optical sheet comprising at least one polymer material particle of the present invention, or the composition of the present invention, preferably said optical sheet is an agricultural sheet. Preferably said optical sheet comprises a plurality of polymer material particles of the present invention or the composition.
According to the present invention, the optical sheet can be a film, or a fiber mat.
Further, the optical sheet according to the present invention can be rigid or flexible. Further, the optical sheet according to the present invention can be any structure, such as plane, curved, wave formed structures to increase a growth of plant. In a preferred embodiment of the invention, the optical sheet comprises at least a first layer comprising at least the composition or the first layer 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 a further preferred embodiment of the invention, the sheet further comprises a second layer, preferably the second layer comprises at least a material selected from one or more members of the group consisting of adhesives, insecticides, insect attractants, yellow dye, pigments, phosphors, metal oxides, Al, Ag, Au, and antimicrobials, more preferably said pigments are yellow pigments, blue pigments or a combination of these, and said phosphors are phosphors of the present invention or phosphors that can emit a light with a peak maximum light wavelength in the range from 350nm to 500nm, and/or 550nm to 600nm, more preferably in the range from 380nm to 490nm, and/or 570nm to 590nm. In a further preferred embodiment of the present invention, the second layer comprises at least one inorganic phosphor, and a second material selected from adhesives, and/or insecticides. In a further preferred embodiment of the present invention, the second layer further comprises a matrix material as described in the section of “Matrix material as said further material”. According to the present invention, said inorganic phosphor is described in the section of “Inorganic phosphors as said further material in the composition” above.
In a further preferred embodiment of the present invention, the second layer comprises at least a first material selected from one or more of the members of the group consisting of yellow pigments, yellow phosphors, yellow dyes, and insect attractants, and a second material selected from adhesives, and/or insecticides. Such second layer can be fabricated by a publicly known method. For example, spray coating, bar coating, slit coating, dip coating, spin coating, inkjet printing can be used.
In another preferred embodiment of the present invention, the second layer of the optical sheet is a light reflecting layer, preferably the second layer as the reflecting layer comprises at least a light reflecting material which can reflect at least blue, red, and/or infrared light, even more preferably the second layer essentially consists of or consists of one or more of light reflecting materials.
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 a further preferred embodiment, said first layer is at least partially covered by said second layer, preferably at least one side of said first layer of the optical sheet is fully covered by the second layer.
According to the invention, the optical sheet optionally comprises a third layer or more layers.
In a further preferred embodiment, said first layer, the second layer, and the optional third layer or more layers can be sandwiched by, or fully or partially covered by one or more of optically transparent protection layers.
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 by the light reflecting material is not particularly limited. Publicly known methods such as vacuum deposition, sputtering, chemical vapor deposition, printing can be used.
According to another preferred embodiment of the invention, the optical the sheet comprises a first layer, wherein the first layer comprises, in the first layer, at least a first area comprising the composition according to the present invention and a second area, preferably said second area comprising at least one additive as described above.
According to another preferred embodiment of the invention, the concentration of the polymer material particle of the present invention in the sheet varies from a high concentration on one side of the sheet to a low concentration of the opposite side of the sheet, preferably it is varying from a high concentration on one side of the sheet to a low concentration of the opposite side of the sheet in-plane direction.
In a further preferred embodiment of the invention, the optical sheet, 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 sheet. 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 sheet and at a wavelength or a range of wavelength used during operation of the optical sheet. Preferably, it is over 70 %, more preferably, over 75%, the most preferably, it is over 80 %. Said reflector is preferably a metal substrate, more preferably Al substrate, Cu substrate, metal alloy substrate is useful from the view point of high light reflection at deep red-light wavelength and lower cost.
A material for the selective light reflection reflector is not particularly limited. Well known materials for a selective light reflector can be used preferably as desired.
According to the present invention, the selective light reflector can be a single layer or multiple layers. In a preferred embodiment, the selective light reflector comprises at least a selective light reflecting layer selected from the group consisting of Al layer, Al + 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 a preferred embodiment, the selective light reflection layer expect for cholesteric liquid crystal layers is prepared by a gas phase based coating process (such as Sputtering, Chemical Vapor Deposition, vapor deposition, flash evaporation), or a liquid-based coating process.
In a further preferred embodiment of the present invention, the optical sheet is, for example, a color conversion sheet, a light conversion foil, a remote phosphor tape, or another sheet or a filter for agriculture.
The layer thickness of the optical sheet may be in the range from 5 pm to 1 mm, preferably it is in the range from 10 pm to 500 pm, more preferably it is from 30 pm to 200 pm, even more preferably from 50 pm to 100 pm from the view point of better light conversion property and lower production cost.
The total amount of the polymer material particle in the optical sheet may be in the range from 0.01 wt.% to 10 wt.% based on the total amount of the composition, preferably it is from 0.05 wt.% to 5 wt.%, more preferably from 0.05 wt.% to 3 wt.%, furthermore preferably it is from 0,1 wt.% to 1 wt.%, from the view point of better light conversion property, lower production cost and less production damage of a production machine.
- Method for preparing the optical sheet
In another aspect, the present invention furthermore relates to a method for preparing an optical sheet, preferably for preparing an agriculture sheet, wherein the method comprises following steps (A) and (B), (A) providing the composition or the formulation of the present invention in a first shaping, preferably onto a substrate or into an inflation moulding machine, and
(B) fixing said composition or said formulation by evaporating a solvent of the formulation and/or by polymerizing the composition by heat treatment or exposing the photosensitive composition under ray of light.
In a preferred embodiment, the method comprises steps (A) and (B) in this sequence.
In a further preferred embodiment of the present invention, the composition or the formulation for preparing the optical sheet includes a matrix material, and in step (B) said matrix material is fixed by evaporating a solvent of the formulation and/or by polymerizing the composition by heat treatment or exposing the photosensitive composition under ray of light.
In a further preferred embodiment 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 more preferred embodiment of the present invention, the composition or the formulation in step (A) is provided into an inflation-molding machine and the matrix material is fixed by heat treatment of the machine.
- Method for preparing an agriculture film and agricultural film obtained therefrom
In another aspect, the present invention furthermore relates to a method for preparing an agriculture film, wherein the method comprises following steps (A’) and (B’),
(A’) providing a composition comprising at least one polymer material particle comprising at least one organic light luminescent material and at least one UV absorbing agent, and a matrix material, or a formulation comprising said composition and a solvent, onto a surface of an agricultural material, e.g., an existing optical or agricultural sheet, agricultural net or greenhouse; 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 composition under ray of light to thereby form the agricultural film on the surface of the agricultural material, preferably the composition or the formulation in step (A’) is provided by immersion coating, gravure coating, roll coating, bar coating, brush coating, spray coating, doctor coating, flow coating, spin coating, slit coating, or by painting.
According to this embodiment, the at least one organic light luminescent material and the at least one UV absorbing agent are the same as mentioned above in the section “Polymer material particle” with respect polymer material particle of the invention. Furthermore, according to this embodiment, the matrix material and the solvent in step (A’) are preferably the same as mentioned above in the sections “Composition” and “Formulation”, respectively.
In a preferred embodiment, the method comprises steps (A’) and (B’) in this sequence. In another aspect, the present invention furthermore relates to an agricultural film obtained or obtainable by said method for preparing an agriculture film.
The thickness of the agricultural film formed (i.e. without thickness of the existing agricultural material) may be in the range from 5 pm to 1 mm, preferably it is in the range from 10 pm to 500 pm, more preferably it is from 30 pm to 200 pm, even more preferably from 50 pm to 100 pm from the view point of better light conversion property and lower production cost. The total amount of the polymer material particle in the agricultural film (i.e. without the existing agricultural material) may be in the range from 0.01 wt.% to 10 wt.% based on the total amount of the composition, preferably it is from 0.05 wt.% to 5 wt.%, more preferably from 0.05 wt.% to 3 wt.%, furthermore preferably it is from 0,1 wt.% to 1 wt.%, from the view point of better light conversion property, lower production cost and less production damage of a production machine.
- Optical device The optical sheet according to present invention can suitably be used in an optical device, preferably in a lighting device, more preferably in a Light Emitting Diode. In another aspect, the invention therefore relates to an optical device comprising the optical sheet, or the composition and further comprising a light source, a light re-directing device, and/or a reflector.
Preferably said light source is a light emitting diode, or an organic light emitting diode.
In another embodiment of the present invention, the optical device comprises at least one optical sheet and a supporting part, preferably the supporting part comprises at least one attaching part to attach the optical sheet, and optionally a base part to support optical sheet and supporting part itself, more preferably the supporting part comprises one or more of attaching part to attach one or more of optical sheet.
In a preferred embodiment of the present invention, the optical device is a lighting device, a light emitting diode device for agriculture, or building materials of greenhouse.
- Method for preparing the optical device and use In another aspect, the present invention furthermore relates to a method for preparing the optical device, wherein the method comprises the step of providing the optical sheet in an optical device.
The details of the composition and the formulation are described above in the section “Composition” and the section “Formulation”. Especially, according to the present invention, the optical sheet or the agricultural film obtained or obtainable by the above-described method is useful for agriculture. Particularly, the optical sheet or the agricultural film 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 or the agricultural film 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 the use of the optical sheet or the agricultural film 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 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 sheet is fully covered by the light reflecting material. The fabrication method for coating of optical sheet by the light reflecting material is not particularly limited. Publicly known methods such as vacuum deposition, sputtering, chemical vapor deposition, printing can be used.
In another preferred embodiment, the optical sheet or the agricultural film may be used to control growth of plankton, preferably said plankton is a phytoplankton. In another aspect, the present invention relates to a use of the optical sheet, the agricultural film obtained or obtainable by the above-described method, or the optical device 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 furthermore relates to a greenhouse comprising the optical sheet of the present invention or the agricultural film obtained or obtainable by the method of the present invention as described above.
In another aspect, the present invention relates to a use of the polymer material particle, the composition, the formulation, the optical sheet, the agricultural film, the optical device, or the greenhouse of the present invention for cultivation of algae, bacteria, preferably said bacteria are photosynthetic bacteria, and/or plankton, preferably photo plankton, preferably for improvement of controlling property of a phytoplankton condition, photosynthetic bacteria and/or alga, preferably acceleration of growth of phytoplankton, photosynthetic bacteria and/or alga; improvement of controlling property of plant condition, preferably controlling of a plant height; controlling of color of fruits; promotion and inhibition of germination; controlling of synthesis of chlorophyll and carotenoids, preferably by blue light; plant growth promotion; adjustment and/or acceleration of flowering time of plants; controlling of production of plant components, such as increasing production amount, controlling of polyphenols content, sugar content, vitamin content of plants; controlling of secondary metabolites, preferably controlling of polyphenols, and/or anthocyanins; controlling of a disease resistance of plants; controlling of ripening of fruits, or controlling of weight of plant.
In another aspect, the present invention furthermore relates to a method of supplying the polymer material particle, the composition or the formulation of the present invention to at least one portion of a plant.
In another aspect, the present invention furthermore relates to a method for modulating a condition of a plant, plankton, and/or a bacterium, comprising at least the following step of providing the optical sheet or the agricultural film between a light source and a plant, between a light source and plankton, preferably said plankton is phytoplankton, between a light source and a bacterium, preferably said bacterium is a photosynthetic bacterium, and/or providing the optical sheet or the obtained agricultural film over a ridge in a field or over a surface of planter, preferably said planter is a nutrient film technique hydroponics system or a deep flow technique hydroponics system to control plant growth.
In a preferred embodiment of the present invention, the optical sheet is provided directly onto a ridge in a field or onto a surface of planter. According to the present invention, the light source is the sun or an artificial light source, preferably said artificial light source is a light emitting diode. In another aspect, the present invention further relates to a plant, plankton, or a bacterium obtained or obtainable by the method. Preferably said plankton is a phytoplankton, and said bacterium is a photosynthetic bacterium. - Container
In another aspect, the present invention furthermore relates to a container comprising at least one plant, plankton, or a bacterium obtained or obtainable by the method of the present invention. Preferably said plankton is phytoplankton, and said bacterium is a photosynthetic bacterium.
According to the present invention, the plant can be flowers, vegetables, fruits, grasses, trees and horticultural crops (preferably flowers and horticultural crops, more preferably flowers). As one embodiment of the invention, the plant can be foliage plants. Exemplified embodiments of grasses are a poaceae, bambuseae (preferably sasa, phyllostachys), oryzeae (preferably oryza), pooideae (preferably poeae), triticeae (preferably elymus), elytrigia, hordeum, triticum, secale, arundineae, centotheceae, chloridoideae, hordeum vulgare, avena sativa, secale cereal, andropogoneae (preferably coix), cymbopogon, saccharum, sorghum, zea (preferably zea mays), sorghum bicolor, saccharum officinarum, coix lacryma-jobi van, paniceae (preferably panicum), setaria, echinochloa (preferably panicum miliaceum), echinochloa esculenta, and setaria italic. Embodiments of vegetables are stem vegetables, leaves vegetables, flowers vegetables, stalk vegetables, bulb vegetables, seed vegetables (preferably beans), roots vegetables, tubers vegetables, and fruits vegetables. One embodiment of the plant can be Gaillardia, Lettuce, Rucola, Komatsuna (Japanese mustard spinach) or Radish (preferably Gaillardia, Lettuce, or Rucola). The environment of growing plant can be natural environment, a green house, a plant factory and indoor cultivation, preferably natural environment and a green house. One embodiment of the natural environment is an outside farm.
Preferred embodiments: 1. Polymer material particle comprising at least one organic light luminescent material and at least one UV absorbing agent.
2. Polymer material particle according to embodiment 1 , wherein the at least one organic light luminescent material emits fluorescent light.
3. Polymer material particle according to embodiment 1 or 2, wherein the at least one organic light luminescent material has a peak wavelength of light emitted from the organic light luminescent material in the range of 600 nm or more, preferably in the range from 600 to 1000 nm, more preferably in the range from 600 to 820 nm, even more preferably in the range from 620 to 800 nm, furthermore preferably in the range from 650 to 800 nm, much more preferably it is from 650 nm to 790 nm, the most preferably from 690 nm to 790 nm; or the at least one organic light luminescent material has a peak wavelength of light emitted from the organic light luminescent material 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 500 nm, much more preferably in the range from 420 nm to 480 nm, the most preferably in the rage from 430 nm to 460 nm; or the at least one organic light luminescent material has a first peak wavelength of light emitted from the organic light luminescent material in the range of 500 nm or less, and a second peak wavelength of light emitted from the phosphor in the range of 600 nm or more, preferably the first peak wavelength of light emitted from the phosphor is in the range from 250 nm to 500 nm, and the second peak light emission wavelength is in the range from 600 nm to 1000 nm, more preferably the first peak wavelength of light emitted from the phosphor is in the range from 300 nm to 500 nm, and the second peak light emission wavelength is in the range from 600 nm to 820 nm, even more preferably the first peak wavelength of light emitted from the phosphor is in the range from 350 nm to 500 nm, and the second peak light emission wavelength is in the range from 620 nm to 800 nm, furthermore preferably the first peak wavelength of light emitted from the phosphor is in the range from 400 nm to 500 nm, and the second peak light emission wavelength is in the range from 650 nm to 800 nm, much more preferably the first peak wavelength of light emitted from the phosphor is in the range from 420 nm to 480 nm, and the second peak light emission wavelength is in the range from 650 nm to 790 nm, the most preferably the first peak wavelength of light emitted from the phosphor is in the rage from 430 nm to 460 nm and the second peak wavelength of light emitted from the phosphor is in the range from 690 nm to 790 nm.
4. Polymer material particle according to any one of embodiments 1 to 3, wherein the at least one organic light luminescent material is a fluorescent organic material, preferably selected from fluorescent proteins or peptides, fluorescent small organic compounds, fluorescent oligomers and polymers, fluorescent multi-component systems and fluorescent organometallic compounds, and combinations of any of these.
5. Polymer material particle according to any one of embodiments 1 to 5, wherein the polymer material is selected from one or more member of the group consisting of polyurethanes, poly(meth)acrylates, poly(butylmethacrylate), ethylene-acrylate copolymer, acrylonitrile- butadiene-styrene copolymer, polyesters, polyacrylonitriles, polyacrylurethanes, polyacrylurethanesilicones, polyfluoroacrylurethanes, polyfluoroacrylates, polyvinylchloride, polystyreneacrylates, polybutyrals, polychlorovinylidenes, melamine resins, phenol resins, epoxy resins, urea resins, unsaturated polyester resins, polycarbonates, polysulfones, polyethers, polyamides, polystyrenes including poly(styrene-co- divinylbenzenes, polyisobutylenes, polyethylene, polyethylene terephthalate, polypropylene, ethyl cellulose and poly(lactic acid) polysilanes, polysiloxanes, polysilicones, polyphosphazenes, polygermanes, polystannanes, polyborazines, polycarbosilanes and polysilazines. 6. Polymer material particle according to any one of embodiments 1 to 3, wherein the polymer material comprises polymerized units of a polymerizable monomeric organic light luminescent material which is derived from the organic light luminescent material and contains intramoleculary integrated at least one chromophore moiety and at least one polymerizable moiety.
7. Polymer material particle according to embodiment 6, wherein the polymer material is a copolymer including structural units of the at least one polymerizable moiety of the polymerizable monomeric organic light luminescent material and structural units of one or more further polymerizable monomers, in particular one or more monomers for forming a polymer according to embodiment 5.
8. Polymer material particle according to embodiment 6 or 7, wherein the at least one polymerizable moiety is selected from a vinyl moiety, a C1-5 alkylacrylate moiety and an acrylate moiety, and/or wherein the at least one chromophore moiety of the polymerizable monomeric organic light luminescent material is derived from a fluorescent organic material, and preferably is derived from xanthene dyes, perylene dyes, cyanine dyes, chrysene dyes, squaraine dyes and ring-substituted squaraine dyes, naphthalene dyes, coumarin dyes, oxadiazole dyes, anthracene dyes, pyrene dyes, dicyanomethylenepyrane dyes, oxazine dyes, acridine dyes, quinacridone dyes, arylmethine dyes, tetrapyrrole dyes, and dipyrromethene dyes, and combinations thereof.
9. Polymer material particle according to any one of embodiments 1 to 8, wherein the polymer material is transparent.
10. Polymer material particle according to any one of embodiments 1 to 9, wherein the at least one UV absorbing agent is selected from triazines benzotriazoles, benzophenones, ethanediamides and cyanoacrylates, and combinations of any of these.
11. Polymer material particle according to any one of embodiments 1 to 10, wherein the amount of the organic light luminescent material is in the range from 0.1 -2.0 wt.%, related to the total weight of the particle.
12. Polymer material particle according to any one of embodiments 1 to 11 , wherein the amount of the UV absorbing agent is in the range from 0.1-10.0 wt.%, related to the total weight of the particle. 13. Polymer material particle according to any one of embodiments 1 to 12, wherein the polymer material particle further comprises at least one stabilizing agent.
14. Polymer material particle according to embodiment 13, wherein the stabilizing agent is selected from hindered amine light stabilizers.
15. Polymer material particle according to any one of embodiments 1 to 14, wherein the polymer material particle further comprises one or more scattering materials.
16. Polymer material particle according to any one of embodiments 1 to
15, wherein the polymer material particle has an average particle size in the range of 1 to 100 pm.
17. Polymer material particle according to any one of embodiments 1 to
16, wherein the polymer material particle has an EQE of 10% or more, preferably it is from 10% to 90%, more preferably from 20% to 80%, further more preferably from 30% to 80%, the most preferably it is from 40% to 80%, wherein the EQE is measured and calculated utilizing the procedure, conditions and equipment as described in the description.
18. Method for preparing a polymer material particle of any one of embodiments 1 to 17, the method including the steps
(a) preparing a suspension by mixing at least one organic light luminescent material, at least one UV absorbing agent and one or more polymer precursors in a liquid phase; and
(b) polymerizing the resulting mixture by applying heat; or the method including the steps (a’) preparing a suspension by mixing at least one polymerizable organic light luminescent material and at least one UV absorbing agent, and optionally one or more polymerizable monomer/polymer precursor, in a liquid phase, preferably water; and (b’) polymerizing the resulting mixture by applying heat.
19. Use of a polymer material particle according to any one of embodiments 1 to 17 in agriculture, in an optical sheet, optical film, optical net, optical fiber, optical nonwoven fabric or optical plate, in a spraying, coating or painting agent, in a Light Emitting Diode, in a solar cell or in a plant cultivation pot.
20. Composition comprising at least one polymer material particle according to any one of embodiments 1 to 17 and a further material, preferably selected from one or more members of the group consisting of matrix materials; light modulating materials such as dyes, for example blue or red dyes, pigments, light luminescent materials including organic and inorganic light luminescent materials, for example another organic light luminescent material or an inorganic phosphor; photo initiators; co- polymerizable monomers; cross linkable monomers; bromine-containing monomers; sulfur-containing monomers; adjuvants; adhesives; insecticides; insect attractants; metal oxides; Al, Ag, Au nanoparticles; dispersants; surfactants; fungicides and antimicrobial agents. 21. The composition according to embodiment 20, wherein the total amount of the polymer material particle of the composition is in the range from 0.01 wt.% to 10 wt.% based on the total amount of the composition, preferably it is from 0.05 wt.% to 5 wt.%, more preferably from 0.05 wt.% to 3 wt.%, furthermore preferably it is from 0.1 wt.% to 1 wt.%. 22. The composition according to any one of embodiments 20 or 21 , wherein the matrix material is an organic material and/or an inorganic material, preferably the matrix material is an organic material, more preferably it is an organic oligomer or an organic polymer material, even more preferably an organic polymer selected from the group consisting of a transparent photosetting polymer, a thermosetting polymer, a thermoplastic polymer, or a combination of any of these.
23. Formulation comprising at least one polymer material particle according to any one of embodiments 1 to 17, or the composition according to any one of embodiments 20 to 22, and a solvent.
24. Use of the polymer material particle according to any one of embodiments 1 to 17, or the composition according to any one of embodiments 20 to 22, or the formulation according to embodiment 23, in a method for preparing an optical sheet or in agriculture, preferably for preparing an agricultural sheet or for controlling a condition of a living organism. 25. Optical sheet comprising at least one polymer material particle according to any one of embodiments 1 to 17, or the composition according to any one of embodiments 20 to 22, preferably said optical sheet is an agricultural sheet. 26. Method for preparing an optical sheet, preferably for preparing an agriculture sheet, wherein the method comprises the following steps (A) and (B),
(A) providing the composition according to any one of embodiments 20 to 22, or the formulation according to embodiment 23 in a first shaping, preferably onto a substrate or into an inflation moulding machine, and (B) fixing said composition or said formulation 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. 27. Method for preparing an agricultural film, wherein the method comprises the following steps (A’) and (B’),
(A’) providing a composition comprising at least one polymer material particle comprising at least one organic light luminescent material and at least one UV absorbing agent, and a matrix material, or a formulation comprising said composition and a solvent onto a surface of an agricultural material; 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 composition under ray of light to form the agricultural film on the surface of the agricultural material, preferably the composition or the formulation in step (A’) is provided by immersion coating, gravure coating, roll coating, bar coating, brush coating, spray coating, doctor coating, flow coating, spin coating, slit coating, or by painting.
28. Agricultural film obtained or obtainable by the method according to embodiment 27.
29. Use of the optical sheet according to embodiment 25 in an optical device, preferably in a lighting device, more preferably in a Light Emitting
Diode.
30. Optical device comprising at least one optical sheet according to embodiment 25, preferably said optical device is a lighting device, more preferably it is a Light Emitting Diode. 31. Method for preparing an optical device according to embodiment 29, the method comprising the step of providing the optical sheet of embodiment 25 in an optical device.
32. Use of the optical sheet according to embodiment 25, the agricultural film according to embodiment 28, or the optical device of embodiment 30 for agriculture, preferably for greenhouse or for controlling a condition of a living organism in agriculture.
33. A greenhouse comprising the optical sheet according to embodiment 25, the agricultural film according to embodiment 28, or the optical device of embodiment 30. 34. Use of the polymer material particle according to any one of embodiments 1 to 17, or the composition according to any one of embodiments 20 to 22, the formulation according to embodiment 23, the optical sheet according to embodiment 25, the agricultural film according to embodiment 28, the optical device according to embodiment 30 or the green house according to embodiment 33 for cultivation of algae, bacteria, preferably said bacteria are photosynthetic bacteria, and/or plankton, preferably it is photo planktons, preferably for improvement of controlling property of a phytoplankton condition, photosynthetic bacteria and/or alga, preferably acceleration of growth of phytoplankton, photosynthetic bacteria and/or alga; improvement of controlling property of plant condition, preferably controlling of a plant height; controlling of color of fruits; promotion and inhibition of germination; controlling of synthesis of chlorophyll and carotenoids, preferably by blue light; plant growth promotion; adjustment and / 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.
35. Method of supplying the polymer material particle according to any one of embodiments 1 to 17, or the composition according to any one of 20 to 22, or the formulation according to embodiment 23 to at least one portion of a plant.
36. Method for modulating a condition of a plant, plankton, and/or a bacterium, comprising at least following step of providing the optical sheet according to embodiment 25 or the agricultural film according to embodiment 28 between a light source and a plant, between a light source and plankton, preferably said plankton is phytoplankton, between a light source and a bacterium, preferably said bacterium is a photosynthetic bacterium, and/or providing the optical sheet according to embodiment 25 or the agricultural film according to embodiment 28 over a ridge in a field or over a surface of planter, preferably said planter is a nutrient film technique hydroponics system or a deep flow technique hydroponics system to control plant growth.
37. Method according to embodiment 36, wherein the light source is the sun or an artificial light source, preferably said artificial light source is a light emitting diode. 38. A plant obtained or obtainable by the method according to any one of embodiments 36 or 37, or plankton obtained or obtainable by the method according to embodiment 36 or 37, or a bacterium obtained or obtainable by the method according to embodiment 36 or 37.
39. A container comprising at least one plant, plankton, and/or a bacterium according to embodiment 38 Technical effects
The present invention provides one or more of following effects and advantages:
A polymer material particle with a light conversion and light reflection function that produces optimal blue, red and infrared light; a polymer material particle with good light-extraction efficiency in an external/internal environment through controlling the refractive index and light dispersion of an organic light luminescent material or by using an organic light luminescent material; a polymer material particle with improved optical properties such as light scattering, absorbing, refraction and/or reflection ability of an organic light luminescent material; a polymer material particle with superior emission characteristics and high quantum efficiency (EQE) of an organic light luminescent material or by using an organic light luminescent material a polymer material particle which efficiently achieves a uniform and bright outgoing light by effectively absorbing the whole lights from a light source by using an organic light luminescent material a polymer material particle with improved long-term moisture durability, improved water resistance, and improved UV-stability and good light durability of an organic light luminescent material; improved dispersibility of polymer material particles and organic light luminescent material in a formulation, composition and/or in a matrix material of a film or sheet; improved transparency of a film or sheet, preferably improved transparency of an agricultural film; an optical sheet or agricultural film with good light-extraction efficiency in an external/internal environment by using a polymer material particle; an optical sheet or agricultural film with improved long-term moisture durability, improved water resistance, and improved UV-stability and good light durability using a polymer material particle; an optical sheet or agricultural film which shows improved color fastness and color stability on colorless materials, and less back scattering of a fluorescent/reflection material; an optical sheet or agricultural film with reduced accumulated stress in a resin body; an optical sheet or agricultural film, which shows better light-extraction; an optical sheet or agricultural film having a lower refractive index so that visible light is easily transmitted; an optical sheet or agricultural film comprising an organic light luminescent material and matrix material, which shows better plant growth ability; improvement of controlling property of a phytoplankton condition, photosynthetic bacteria and/or alga, preferably acceleration of growth of phytoplankton, photosynthetic bacteria and/or alga; improvement of controlling property of plant condition, preferably controlling of a plant height; controlling of color of fruits; promotion and inhibition of germination; controlling of synthesis of chlorophyll and carotenoids, preferably by blue light; plant growth promotion; adjustment and/or acceleration of flowering time of plants; controlling of production of plant components, such as increasing production amount, controlling of polyphenols content, sugar content, vitamin content of plants; controlling of secondary metabolites, preferably controlling of polyphenols, and/or anthocyanins; controlling of a disease resistance of plants; controlling of ripening of fruits, or controlling of weight of plant.
The working examples below provide descriptions of the present invention but are not intended to limit scopes of the invention.
Working Examples
Working Example 1: Preparation of polymer material particle by suspension polymerization
200 mg of Lumogen® F Red 305 (BASF), 10 mg of [2-hydroxy-4- (octyloxy)phenyl]phenylmethanone (Sigma-Aldrich), 8.8 ml_ of styrene
(Sigma-Aldrich), 2.2 ml_ of divinylbenzene (Sigma-Aldrich), and 500 mg of benzoyl peroxide (Sigma-Aldrich) are dissolved in 5 ml_ of toluene. This toluene solution is added to a solution of 2.5 g of gum arabic from acacia tree (Sigma-Aldrich) and 2.5 g of sodium dodecylbenzene sulfonate (Sigma-Aldrich) in 195 mL water. The resulting two-phase system is emulsified by stirring with a rotating mixer at 400 rpm at 71-73°C for 6 h. After cooling to room temperature, the microparticles are formed, which are collected from the suspension by aspirator filtration, then are washed with 500 mL of distilled water, 500 mL of ethanol (Sigma-Aldrich) and diethylether (Sigma-Aldrich) in this order. Then, the washed particles are dried in an oven at 50 °C under vacuum for 2 h. 9.46 g of polymer material particles are obtained as illustrated in Figs. 1a and 1b (average diameter: 40 pm; determined by scanning electron microscopy (SEM; Hitachi S- 5200)). Workinq Example 2: Preparation of particle dispersed film
1 g of polymer material particles obtained from working example 1 are dispersed in 10 g of silicone agents mixture (5g of KE-109E-A and 5g of KE-109E-B; Shin-Etsu Chemical) with revolving/rotating mixer (stirring at 2000 rpm for 1 min. and deforming at 2200 rpm for 30 sec.). The resulting mixture is applied on a glass plate, and the silicone mixture is cured at room temperature overnight. After curing, the cured silicone film is peeled off.
Working Example 3: Film durability check (1) The silicone film prepared as described in working example 2 is irradiated with sunlight for 1 week. After irradiation of sunlight, the film is checked for the change of transmitted light by a solar simulator.
Working Example 4: Film durability check (2) The silicone film prepared as described in working example 2 is tested by weatherometer. After the machine treatment, the film is checked for the change of transmitted light by a solar simulator.

Claims

Claims
1. Polymer material particle comprising at least one organic light luminescent material and at least one UV absorbing agent.
2. Polymer material particle of claim 1 , wherein the at least one organic light luminescent material has a peak wavelength of light emitted from the organic light luminescent material in the range of 600 nm or more; or the at least one organic light luminescent material has a peak wavelength of light emitted from the organic light luminescent material in the range of 500 nm or less; or the at least one organic light luminescent material has a first peak wavelength of light emitted from the organic light luminescent material in the range of 500 nm or less, and a second peak wavelength of light emitted from the phosphor in the range of 600 nm or more.
3. Polymer material particle of claims 1 or 2, wherein the at least one organic light luminescent material is a fluorescent organic material.
4. Polymer material particle according to any one of claims 1 to 3, wherein the polymer material is selected from one or more member of the group consisting of polyurethanes, poly(meth)acrylates, poly(butylmethacrylate), ethylene-acrylate copolymer, acrylonitrile-butadiene-styrene copolymer, polyesters, polyacrylonitriles, polyacrylurethanes, polyacrylurethanesilicones, polyfluoroacrylurethanes, polyfluoroacrylates, polyvinylchloride, polystyreneacrylates, polybutyrals, polychlorovinylidenes, melamine resins, phenol resins, epoxy resins, urea resins, unsaturated polyester resins, polycarbonates, polysulfones, polyethers, polyamides, polystyrenes including poly(styrene-co- divinylbenzenes, polyisobutylenes, polyethylene, polyethylene terephthalate, polypropylene, ethyl cellulose and poly(lactic acid) polysilanes, polysiloxanes, polysilicones, polyphosphazenes, polygermanes, polystannanes, polyborazines, polycarbosilanes and polysilazines.
5. Polymer material particle according to any one of claims 1 to 4, wherein the at least one UV absorbing agent is selected from triazines benzotriazoles, benzophenones, ethanediamides and cyanoacrylates, and combinations of any of these.
6. Polymer material particle according to any one of claims 1 to 5, wherein the polymer material particle further comprises at least one stabilizing agent.
7. Polymer material particle according to claim 6, wherein the stabilizing agent is selected from hindered amine light stabilizers.
8. Polymer material particle according to any one of claims 1 to 7, wherein the polymer material particle further comprises one or more scattering materials.
9. Method for preparing a polymer material particle of any one of claims 1 to 8, the method including the steps
(a) preparing a suspension by mixing at least one organic light luminescent material, at least one UV absorbing agent and one or more polymer precursors in a liquid phase; and
(b) polymerizing the resulting mixture by applying heat.
10. Composition comprising at least one polymer material particle according to any one of claims 1 to 8 and a further material, preferably selected from one or more members of the group consisting of matrix materials; light modulating materials such as dyes, for example blue or red dyes, pigments, light luminescent materials including organic and inorganic light luminescent materials, for example another organic light luminescent material or an inorganic phosphor; photo initiators; co-polymerizable monomers; cross linkable monomers; bromine-containing monomers; sulfur-containing monomers; adjuvants; adhesives; insecticides; insect attractants; metal oxides; Al, Ag, Au nanoparticles; dispersants; surfactants; fungicides and antimicrobial agents.
11. Formulation comprising at least one polymer material particle according to any one of claims 1 to 8, or the composition of claim 10, and a solvent.
12. Use of the polymer material particle according to any one of claims 1 to 8, or the composition of claim 10, or the formulation of claim 11 , in a method for preparing an optical sheet or in agriculture, preferably for preparing an agricultural sheet or for controlling a condition of a living organism.
13. Optical sheet comprising at least one polymer material particle according to any one of claims 1 to 8, or the composition of claim 10, preferably said optical sheet is an agricultural sheet.
14. Optical device comprising at least one optical sheet of claim 13, preferably said optical device is a lighting device, more preferably it is a Light Emitting Diode.
15. A greenhouse comprising the optical sheet of claim 13, or the optical device of claim 14.
16. Method of supplying the polymer material particle according to any one of claims 1 to 8, or the composition of claim 10, or the formulation of claim 11 to at least one portion of a plant.
PCT/EP2021/083076 2020-11-30 2021-11-26 Light emitting polymer material particle WO2022112459A1 (en)

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JPH01103658A (en) 1987-07-16 1989-04-20 Takeda Chem Ind Ltd Polycarbonate resin composition
EP2135737A1 (en) * 2007-04-06 2009-12-23 Asahi Glass Company, Limited Wavelength conversion film, film for agricultural use, structure, and composition for forming coating film
WO2010023115A1 (en) * 2008-08-28 2010-03-04 Basf Se Stabilisers for inanimate organic materials
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JP2017195825A (en) 2016-04-27 2017-11-02 Jsr株式会社 Wavelength conversion film and cultivation methods of agricultural crops
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WO2019020602A2 (en) 2017-07-26 2019-01-31 Merck Patent Gmbh Phosphor and a composition

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01103658A (en) 1987-07-16 1989-04-20 Takeda Chem Ind Ltd Polycarbonate resin composition
EP2135737A1 (en) * 2007-04-06 2009-12-23 Asahi Glass Company, Limited Wavelength conversion film, film for agricultural use, structure, and composition for forming coating film
WO2010023115A1 (en) * 2008-08-28 2010-03-04 Basf Se Stabilisers for inanimate organic materials
WO2016112200A1 (en) * 2015-01-07 2016-07-14 Nitto Denko Corporation Thermal regulating wavelength conversion films incorporating phase change materials
DE102015014526A1 (en) * 2015-11-11 2017-05-11 Giesecke & Devrient Gmbh A security pigment, a luminescent polymer resin and a process for producing the same
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