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WO2019020661A1 - Composition - Google Patents

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Publication number
WO2019020661A1
WO2019020661A1 PCT/EP2018/070101 EP2018070101W WO2019020661A1 WO 2019020661 A1 WO2019020661 A1 WO 2019020661A1 EP 2018070101 W EP2018070101 W EP 2018070101W WO 2019020661 A1 WO2019020661 A1 WO 2019020661A1
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WO
WIPO (PCT)
Prior art keywords
phosphor
group
agriculture
mass
plant
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2018/070101
Other languages
English (en)
Inventor
Hiroshi Okura
Stephan Dertinger
Ryuta Suzuki
Kazuhisa AZUMA
Eiji Nishihara
Tadashi Ishigaki
Koutoku Ohmi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Merck Patent GmbH
Original Assignee
Merck Patent GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Merck Patent GmbH filed Critical Merck Patent GmbH
Publication of WO2019020661A1 publication Critical patent/WO2019020661A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/64—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing aluminium
    • C09K11/641—Chalcogenides
    • C09K11/642—Chalcogenides with zinc or cadmium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/67—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals
    • C09K11/671—Chalcogenides
    • C09K11/673—Chalcogenides with alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/67—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals
    • C09K11/68—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals containing chromium, molybdenum or tungsten
    • C09K11/685—Aluminates; Silicates

Definitions

  • the present invention relates to an agriculture composition, a method manufacturing thereof, a method applying thereof to the surface of a plant leaves, a method producing a plant, and a method enhancing a
  • JP 2007-135583 A mentions an organic dye having a peak wavelength at 613 nm and suggestion to use it with a thermoplastic resin as an agriculture film.
  • a polypropylene film containing an organic dye with peak light emission wavelength at 592 nm is disclosed in WO 1993/009664 A1 .
  • JP H09-249773 A mentions an organic dye having peak light wavelength ⁇ at 592 nm and a suggestion to use it with a polyolefin resin as an
  • JP 2001 -28947 A A combination of an ultraviolet light emitting diode, blue, red, yellow light 5 emitting diodes for green house light source is disclosed in JP 2001 -28947 A.
  • JP 2004-1 13160 A discloses a plant growth kit with a light emitting diode Q light source containing blue and red light emitting diodes.
  • Non Patent Literature 1 (Ba,Ca,Sr)3MgSi2O8:Eu 2+ ,Mn 2+ phosphor and a suggestion to use it as an agricultural lamp are described on Non Patent Literature 1 .
  • Patent Literature 1 A method applying composition including specific particulate materials to the surface of crop is described on EP 101 1309B1 .
  • the inventors thought the wavelength by the natural light and an artificial light (e.g., a fluorescent lamp) is not optimal for growing plants, and an agriculture composition is useful which convert light and emit light with peak wavelength in the range of 430 - 500 nm or 600 - 730 nm.
  • an artificial light e.g., a fluorescent lamp
  • a phosphor(s) which is useful for plant photosynthesis.
  • a phosphor(s) is desirable which exhibits good UV stability, good color fastness, good color stability, and less concentration quenching.
  • One aspect of this invention provides applying method of an agriculture composition to the surface of a plant leaves. So, an embodiment of this
  • compositions which adhere to the surface are useful.
  • a composition comprising a phosphor(s) and a spreading agent(s) is useful. Applying measure of the composition is not limited to liquid state. In the case the composition is in the liquid state when applying, a phosphor(s) 10 which exhibits good solubility and/or good suspensibility is desirable.
  • an agriculture composition comprising at least one phosphor which has a peak emission light wavelength in the range of 430 ⁇ 5 - 500 nm and/or 600 - 730 nm.
  • the agriculture composition comprising at least one phosphor which has a peak emission light wavelength in the range of 430 ⁇ 5 - 500 nm and/or 600 - 730 nm.
  • the phosphor in the agriculture composition is at
  • the phosphor is at least one metal oxide 25 phosphor represented by following formula (I).
  • C1 is a monovalent cation which is at least one selected from the group consisting of Li, Na, K, Rb and Cs,
  • C2 is a divalent cation which is at least one selected from the group consisting of Mg, Zn, Cu, Co, Ni, Fe, Ca, Sr, Ba, Mn, Ce and Sn,
  • C3 is a trivalent cation which is at least one selected from the group consisting of Y, Gd, Lu, Ce, La, Tb, Sc, Sm, Al, Ga, and In,
  • C4 is a tetravalent cation which is at least one selected from the group consisting of Si, Ti, and Ge
  • MC is a metal cation which is at least one selected from the group consisting of Cr 3+ , Eu 2+ , Mn 2+ , Mn 4+ , Fe 3+ , and Ce 3+
  • Cr 3+ , Eu 2+ , Mn 2+ , Mn 4+ , Fe 3+ , and Ce 3+ and
  • p, q, r, s and t are integers on or more than 0, satisfying that
  • inventors found a method for manufacturing the agriculture composition comprising adding at least one phosphor into a base composition.
  • a preferable embodiment of a base composition is a pesticide formulation and a fertilizer formulation.
  • the agriculture composition is good for implementation by applying to the surface of a plant leaves. With this agriculture composition, plant can be produced and/or enhanced its photosynthesis.
  • inventors provided a use at least one phosphor for agriculture with applying the phosphor(s) to the surface of a plant leaves.
  • the above agriculture purpose is preferably producing a plant, and/or enhancing a photosynthesis of a plant. Later described phosphors can be used for this use. Agriculture compositions described below are other preferable embodiments when the phosphors applied onto the plant leaves in said use.
  • Fig. 1 shows black sheets covering a hydroponics system to cut natural light reaching to the system.
  • Fig. 2 shows a photo of Gaillardia plants of working example 5.
  • Fig. 3 shows the excitation and emission spectra of a phosphor synthesized as synthesis example 4.
  • Fig. 4 shows the excitation and emission spectra of a phosphor synthesized as synthesis example 5.
  • Fig. 5 shows the excitation and emission spectra of a phosphor synthesized as synthesis example 6.
  • Fig. 9 shows leaves numbers of Arabidopsis thaliana.
  • Fig. 10 shows weights of Arabidopsis thaliana.
  • Ci-6 alkyl chain refers to an alkyl chain having a chain of between 1 and 6 carbons (e.g., methyl, ethyl, propyl, butyl, pentyl and hexyl).
  • fluorescent is defined as the physical process of light emission by a substance that has absorbed light or other electromagnetic radiation. It is a form of luminescence. In most cases, the emitted light has a longer wavelength, and therefore lower energy, than the absorbed radiation.
  • inorganic means any material not containing carbon atoms or any compound that containing carbon atoms ionically bound to other atoms such as carbon monoxide, carbon dioxide, carbonates, cyanides, cyanates, carbides, and thiocyanates.
  • emission means the emission of electromagnetic waves by electron transitions in atoms and molecules.
  • the term peak wavelength is related to a side peak.
  • peak wavelength is related to the main peak having maximum
  • an agriculture composition comprising at least one phosphor which has a peak emission light wavelength in the range of 430 - 500 nm or 600 - 730 nm, is provided.
  • Phosphor handbook (Yen, Shinoya, Yamamoto), can be used as desired.
  • Those phosphors can be inorganic phosphors and/or organic phosphors.
  • Inorganic phosphors of this invention can be selected from the group consisting of sulfides, thiogallates, nitrides, oxy-nitrides, silicates, metal oxides, apatites, phosphates, selenides, borates, carbon materials, and a combination thereof.
  • silicate is a fluorescent mica and/or a fluorescent pearl pigment.
  • the inorganic phosphors can be at least one metal oxide phosphor represented by following formula (I).
  • C3 selected from Y, Gd, Al, and/or Ga is preferable, selected from Al is more preferable.
  • C4 is a tetravalent cation which is at least one selected from the group consisting of Si, Ti, and Ge.
  • phosphor represented by formula (I) is one phosphor represented by formula (I).
  • Mn 2+ and/or Mn 4+ is preferable.
  • MC selected from Cr 3+ , "Eu 2+ , Mn 2+ ", Mn 2+ , and Mn 4+ is more preferable. In the case plural MC selected, selecting same valent number cations is one preferable embodiment.
  • p, q, r, s and t are integers on or more than 0, satisfying that
  • (1 p+2q+3r+4s) 2t. At least one of p, q, r and s is on or more than 1 . It is one preferable embodiment that p, q, r, and s are each independently 0 - 6, more preferably 0 - 5, further preferably 0 - 3, furthermore preferably 0 - 2. It is preferable embodiment that t is 1 - 20, more preferably 1 - 9, further preferably 2 - 8, furthermore preferably 2 - 5.
  • MC can be replaced with same valent number cation. In the case MC is Eu 2+ and/or Mn 2+ , q is on or more than 1 is preferable. In the case MC is Cr 3+ Fe 3+ and/or Ce 3+ , r is on or more than 1 is preferable. In the case MC is Mn 4+ , s is on or more than 1 is preferable.
  • the inorganic phosphor can be a Cr activated metal oxide phosphor, and/or a Mn activated metal oxide phosphor.
  • A is a trivalent cation and is selected from the group consisting of Y, Gd, Lu, Ce, La, Tb, Sc, and Sm. Preferably A is selected from Y and Gd.
  • B is a trivalent cation and is selected from the group consisting of Al, Ga, Lu, Sc, and In. Preferably B is selected from Al and Ga.
  • x is 0 - 5, and y is 1 - 8. More preferably x is 0 - 3, and y is 1 - 5.
  • Another embodiment of the Cr activated metal oxide phosphor is represented by following formula (III).
  • X is a divalent cation and is selected from the group consisting of Mg, Zn, Cu, Co, Ni, Fe, Ca, Sr, Ba, Mn, Ce and Sn.
  • X is selected from Mg, Co, and Mn.
  • a is 1 - 3, and b is 0 - 6. More preferably a is 1 - 2, and b is 0 - 4.
  • Mn activated metal oxide phosphor is represented by following formula (IV).
  • MC 2+ is a divalent metal cation selected from “Eu 2+ “, “Mn 2+ “, or “Eu 2+ , Mn 2+ “.
  • MC 2+ is selected from “Mn 2+ “, or “Eu 2+ ,Mn 2+ “.
  • C2, C3, C4, q, r, s and t are each independently same to above describing about formula (I).
  • Embodiments of C2, C3, C4, q, r, s and t are each independently same to above describing about formula (I).
  • Mn activated metal oxide phosphor is represented by following formula (V).
  • C2, C3, C4, q, r, s and t are each independently same to above describing about formula (I).
  • Embodiments of C2, C3, C4, q, r, s and t are each independently same to above describing about formula (I).
  • the inorganic compound As a preferred embodiment of the present invention, the inorganic
  • phosphor can be selected from the group consisting of Al2O3:Cr 3+ , Y 3 AI 5 Oi 2 :Cr 3+ , MgO:Cr 3+ , ZnGa 2 O 4 :Cr 3+ , MgAI 2 O 4 :Cr 3+ , Sr 3 MgSi 2 O8:Mn 4+ , Sr 2 MgSi 2 O 7 :Mn 4+ , SrMgSi 2 O 6 :Mn 4+ , Mg 2 SiO :Mn 2+ , BaMg 6 Ti 6 Oi9:Mn 4+ , Mg 2 TiO 4 :Mn 4+ , Li 2 TiO 3 :Mn 4+ , CaAli 2 Oi 9 :Mn 4+ , ZnAI 2 O 4 :Mn 2+ , LiAIO 2 :Fe 3+ ,
  • MgSr 3 Si 2 O8:Eu 2+ , Mn 2+ means both Eu 2+ and Mn 2+ works as co-activations of a metal oxide phosphor of the invention.
  • (Ca, Ba, Sr) in one embodiment "(Ca, Ba, Sr)
  • MgSi2O6:Eu2 + , Mn 2+ means that Ca, Ba and Sr can be replaced each other to work as this phosphor.
  • a quantum dot material can be used as an inorganic phosphor.
  • Preferable 25 embodiments of it is ZnS, InP/ZnS, CulnS 2 , CulnSe 2 , CulnS 2 /ZnS and/or carbon quantum dot.
  • One preferred embodiment of this carbon quantum dot is a graphene quantum dot.
  • micronutrients and/or fertilizer are examples of micronutrients and/or fertilizer.
  • Organic phosphors of this invention can be selected from the group consisting of fluorescein derivative, rhodamine derivative, coumarin derivative, pyrene derivative, cyanine derivative, perylene derivative, and di-cyano-methylene derivative, and combination thereof.
  • Organic compounds which exhibit photo-luminesce can be used for this the purpose of the invention.
  • such compound is known as an emitter or a dopant.
  • a fluorescent emitter in OLED can be more preferable for the invention.
  • our invention provides an agriculture composition comprising the phosphor.
  • an intermediate and an intermediate state e.g. an intermediate of a polymer sheet, the polymer sheet is a final product
  • the agriculture composition comprises less solidifying component (e.g. polymer, resin and/or crosslinking agent).
  • the mass ratio of the solidifying component to the total mass of the agriculture composition is 0 - 0.5 mass %, preferably 0 - 0.1 mass %, and more preferably 0 - 0.01 mass %.
  • An agriculture composition comprises no solidifying component (0 mass %) is one preferable embodiment.
  • polymer and resin can has a weight average molecular weight in the range 5,000 - 50,000, more specifically 10,000 - 30,000.
  • Additive The agriculture composition can further comprise additives.
  • Comprising a spreading agent and/or a surface treatment agent is one preferable embodiment.
  • a spreading agent functions improving spreading performances, wettability, and/or adhesion of the agriculture composition.
  • a surface treatment agent can change the polarity of the phosphor or leave surface (preferably the phosphor) to decrease repulsive force between them.
  • a spreading agent can be selected from the group consisting of isopropyl myristate, isopropyl palmitate, caprylic/capric acid esters of saturated C12- 18 fatty alcohols, oleic acid, oleyl ester, ethyl oleate, triglycerides, silicone oils, dipropylene glycol methyl ether, and combination thereof.
  • Approach Bl Trade mark, Kao Corp.
  • the mass ratio of the spreading agent to the mass of the phosphor in the agriculture composition is 5 - 200 mass %, preferably 5 - 100 mass %, more preferably 5 - 20 mass %, and furthermore preferably 7.5 - 15 mass %.
  • the mass ratio of the surface treatment agent to the mass of the phosphor in the agriculture composition is 5 - 200 mass %, preferably 5 - 100 mass %, more preferably 5 - 20 mass %, and furthermore preferably 7.5 - 15 mass %.
  • an 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.
  • polyoxyethylene fatty acid monoethers polyoxyethylene-polyoxypropylene block polymer
  • acetylene alcohol acetylene glycol derivatives (e.g., acetylene glycol, polyethoxyate of acetylene alcohol, and polyethoxyate of acetylene glycol); silicon-containing surfactants (e.g., Fluorad (Trademark, Sumitomo 3M Ltd), MEGAFAC (Trademark, DIC Corp.), and Surufuron (Trademark, Asahi Glass Co., Ltd.)); and organic siloxane surfactants, such as, KP341 (Trademark, Shin-Etsu Chemical Co., Ltd.).
  • silicon-containing surfactants e.g., Fluorad (Trademark, Sumitomo 3M Ltd), MEGAFAC (Trademark, DIC Corp.), and Surufuron (Trademark, Asahi Glass Co., Ltd.)
  • acetylene glycols examples include: 3-methyl-1 -butyne-3-ol, 3-methyl-1 -pentyne-3-ol, 3,6-dimethyl-4-octyne-3,6-diol, 2,4,7,9- tetramethyl- 5-decyne-4,7-diol, 3,5-dimethyl-1 -hexyne-3-ol, 2,5-dimethyl-3- hexyne-2,5-diol, and 2,5-dimethyl-2,5- hexanediol.
  • anionic surfactants include: ammonium salts and organic amine salts of alkyldiphenylether disulfonic acids, ammonium salts and organic amine salts of alkyldiphenylether sulfonic acids, ammonium salts and organic amine salts of alkylbenzenesulfonic acids, ammonium salts and organic amine salts of polyoxyethylenealkylether sulfuric acids, and ammonium salts and organic amine salts of alkyl-sulfuric acids.
  • amphoteric surfactants include 2-alkyl-N- carboxymethyl-N-hydroxyethyl imidazolium betaine, and laurylic acid amidopropyl hydroxy sulfone betaine.
  • an active ingredient of pesticide formulation is a pesticide ingredient.
  • an active ingredient of fertilizer formulation is a fertilizer ingredient.
  • composition is 5 - 200 mass %, preferably 5 - 200 mass %, more preferably 5 - 150 mass %, further preferably 5 - 20 mass %, and furthermore preferably 7.5 - 15 mass %.
  • mass ratio of each 1 additive of dispersant, surfactant, fungicide, antimicrobial agent and antifungal agent, to the mass of the phosphor in the agriculture composition is 5 - 200 mass %, preferably 5 - 200 mass %, more preferably 5 - 150 mass %, further preferably 5 - 20 mass %, and furthermore preferably 7.5 - 15 mass %.
  • the agriculture composition can further comprise at least one solvent which comprises at least one selected from the group of water and organic solvent.
  • Known usual water can be used as said water, which can be selected from agricultural water, tap-water, industrial water, pure water, distilled water and deionized water. Including said organic solvent in the agriculture composition is useful for dissolving the solute.
  • the organic solvent is preferably selected from alcohol solvent, ether solvent and mixture thereof.
  • One preferable embodiment of said alcohol solvent is selected from ethanol, isopropanol, cyclohexanol, phenoxyethanol, benzyl alcohol or mixture thereof. More preferable embodiment of said alcohol solvent is ethanol.
  • ether solvent is selected from dimethyl ether, propyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether or mixture thereof. More preferable embodiment of said ether solvent is dimethyl ether.
  • the mass ratio of said solvent(s) in the agriculture composition, to the total mass of the agriculture composition is preferably 70 - 99.95 mass %, more preferably 80 - 99.90 mass %, further preferably 90 - 99.90 mass %, furthermore preferably 95 - 99.50 mass %.
  • One embodiment of the mass ratio of said water to the sum of other solvents is preferably 80 - 100 mass %, more preferably 90 - 100 mass %, further preferably 95 - 100 mass %, furthermore preferably 99 - 100 mass %.
  • the said solvent is preferably water, ethanol, dimethyl ether or mixture thereof.
  • the solvent consisting of water is one preferred embodiment to avoid unnecessary effect for animals.
  • the mass ratio of the phosphor(s) to the total mass of the agriculture composition is preferably 0.05 - 30 mass %, more preferably 0.1 - 10 mass %, further preferably 0.5 - 5 mass %, furthermore preferably 0.8 - 3 mass %.
  • the applied amount of the phosphor(s) on leaves depends on the phosphor's concentration and the agriculture composition's dose to be applied. The skilled person can control them based on an applied measure, a purpose, plant species, and so on. Of course, the sum of the mass ratio of said solvent and the mass ratio of the phosphor(s) to the total mass of the agriculture composition doesn't exceed 100 mass %.
  • the mol/L of the phosphor(s) in the agriculture composition is preferably 10 "7 - 10 "2 mol/L, more preferably 10 "6 - 10 "3 mol/L, further preferably 10 "5 - 10 "4 mol/L.
  • known methods to get an average molecular weight preferably a weight average molecular weight
  • Inventors found a method for manufacturing an agriculture composition comprising adding at least one phosphor into a base composition.
  • the base composition comprises at least one solvent.
  • the definitions and embodiments of the phosphor and the solvent of this manufacturing method are independently same to described above.
  • the phosphor Before adding to the base composition, the phosphor can be solid state, and can be dissolved or dispensed in solvent. Some phosphors are good at dissolved by organic solvent. For avoiding evaporated or remained organic solvent affect the plant, soil or animals (including human), the skilled person can decrease the organic solvent concentration in the agriculture composition by diluting in the base composition.
  • One preferable embodiment of the mass ratio of water to the total mass of the base composition is preferably 80 - 100 mass %, more preferably 90 - 100 mass %, further preferably 95 - 100 mass %, furthermore preferably 99 - 100 mass %.
  • the base composition can be at least one selected from the group consisting of a pesticide formulation and a fertilizer formulation.
  • One embodiment of the manufacturing method is adding phosphor into the pesticide formulation to make an agriculture composition before applying it to plant.
  • Pesticide formulation can be at least one selected from the group consisting of an herbicide, insecticide, insect growth regulator, nematicide, termiticide, molluscicide, piscicide, avicide, rodenticide, predacide, bactericide, insect repellent, animal repellent, antimicrobial, fungicide, disinfectant, and sanitizer formulation.
  • Known fertilizer formulation can be used for this manufacturing method.
  • a fertilizer (fertiliser) ingredient can be natural or synthetic material. Components of the phosphor can function as fertilizer by themselves, and can be absorbed by plant root when swept away from the leave surface.
  • This invention provides a method comprising applying the agriculture composition to the surface of a plant leaves.
  • This applying method can set the phosphor on the leaves, which has a peak emission light wavelength 0 in the range of 430 - 500 nm or 600 - 730 nm. If the method applies
  • This invention provides a method producing a plant(s) with applying the agriculture composition to the surface of a plant leaves. And this invention provides a method enhancing a photosynthesis a plant(s) with applying the agriculture composition to the surface of a plant leaves.
  • the agriculture composition can be applied to the surface of the plant leaves by powdering, loading or combination thereof, preferably by powdering.
  • An applied amount of the agriculture composition as average can be
  • the leaves area of 1 plant can be measured by known method and Q device.
  • a leaf area meter can be used to measure it.
  • One embodiment is a LI3000C Area Meter (Li-COR Corp.).
  • the leaves area can be measured by separating all leaves from 1 plant body, getting a photo image or scan each 1 leaf, and processing these images.
  • the agriculture composition comprises a solvent(s)
  • the agriculture composition can be applied to the surface of the plant leaves by spraying, watering, dropping, dipping, coating or combination of thereof, preferably by spraying.
  • One embodiment of said coating is brush coating.
  • An average amount of the agriculture composition to be applied to the surface of the plant leaves can be 0.0005 - 0.1 mL/cm 2 of the surface,
  • the agriculture composition can be applied one or more times during the growing season of the plant. Growing season can be a period from the first
  • the plant can be flowers, vegetables, fruits, grasses, trees and
  • Chromium(lll) nitrate nonahydrate are dissolved in deionized water with a stoichiometric molar ratio of 0.99:0.01 .
  • NH 4 HCO3 is added to the mixed chloride solution as a precipitant, and the mixture is stirred at 60 °C for 2h.
  • the resultant solution is dried at 95 °C for 12 h, then the preparation of the precursors is completed.
  • the obtained precursors are oxidized by calcination at 1300 °C for 3 h in air.
  • XRD measurements are performed using an X-ray diffractometer (RIGAKU RAD-RC).
  • Photoluminescence (PL) spectra are measured using a Spectra fluorometer (JASCO FP-6500) at room temperature.
  • the absorption peak wavelengths of Al2O3:Cr 3+ are 410 - 430 nm and 550 - 570 nm, the emission peak wavelength is in the range from 680 - 700 nm, the full width at half maximum (hereafter "FWHM") of the light emission from Al2O3:Cr 3+ is on or less than 30 nm.
  • FWHM full width at half maximum
  • Hydroponics systems UH-CB01 G1 (UING Corp.) are prepared with a white LED light sources at the top of the systems. The systems are set inside of a room.
  • Photosynthetic Photon Flux Density are 200 mol-m _2 -s _1 . Puts the light on at 6:00am, puts the light off at 22:00 (light on 16 h/day). Black sheets are set to cover the system for cutting natural light reach plants as like shown in Fig 1 . The sheets are shut unless necessity e.g. watering, evaluation.
  • Composition 1 is sprayed on the working example group 1 approximately uniformly by 10 times spraying at 1 st day, 8 th day and 16 th day from planting date.
  • the 10 times spraying volume is approximately 8 mL.
  • Composition 2 and 3 are prepared same to the working example 1 with changing Al2O3:Cr 3+ phosphor concentration as 0.25 mass % and 0.50 mass %.
  • composition 1 (working example 1 , 1.0 mass %) is sprayed on 2 seedlings by 4 times spraying.
  • the 4 times spraying volume is approximately 4 mL.
  • composition 2 working example 3, 0.25 mass %) sprayed on 2 seedlings.
  • composition 3 working example 4, 0.50 mass %) sprayed on 2 seedlings.
  • Fig 2 shows those plants 57 days after planting. This test shows that the working example plants grow more than the comparative example ones. 1.0 mass % sprayed group bloomed at 57 days after planting. The growth is accelerated by a dense concentration composition. And a concentration dependency is observed in this test.
  • the precursors of Mg2TiO 4 :Mn 4+ phosphor is synthesized by a solid-state reaction.
  • the raw materials of Magnesium oxide, Titanium oxide and Manganese oxide are prepared with a stoichiometric molar ratio of
  • the absorption peak wavelengths of Mg2TiO 4 :Mn 4+ are 300 - 340 nm and 460 - 520 nm, the emission peak wavelength is in the range from 650 - 670 nm, the FWHM of the light emission from Mg2TiO 4 :Mn 4+ is on or less than 60 nm.
  • Composition 4 is prepared same to the working example 1 with changing from Al2O3:Cr 3+ (synthesis example 1 ) to Mg2TiO 4 :Mn 4+ (synthesis example 2).
  • Comparative example group 2 are grown in parallel.
  • Leaves weights at 23 rd days from planting date are evaluated as same procedures described in above working example 2. The results are shown in below Table 2.
  • comparative example group 3 (6 seedlings) by 10 times spraying.
  • the 10 times spraying volume is approximately 8 ml_.
  • the phosphors precursors are synthesized by a conventional polymerized complex method.
  • the raw materials of yttrium oxide, magnesium oxide, titanium oxide and manganese oxide are prepared with a stoichiometric molar ratio of 2.000:1 .000: 0.999:0.001 .
  • These chemicals are put in a mortar and mixed by a pestle for 30 minutes.
  • the resultant materials are oxidized by firing at 1500 °C for 6 h in air.
  • Photoluminescence (PL) spectra are measured using a Spectra
  • the absorption peak wavelengths of Y2MgTiO6:Mn 4+ are 300 - 340 nm and 320 - 490 nm, the emission peak wavelength is in the range from 700 nm.
  • Composition 5 is prepared same to the working example 1 with changing from Al2O3:Cr 3+ (synthesis example 1 ) to Y2MgTiO6:Mn 4+ (synthesis example 3).
  • composition 4 is sprayed on working example group 3 (6 seedlings) by 10 times spraying.
  • the 10 times spraying volume is approximately 8 ml_. 1 day after planting, water is sprayed on
  • comparative example group 3 (6 seedlings) by 10 times spraying.
  • the 10 times spraying volume is approximately 8 ml_.
  • Roots weights at 23 rd days from planting date are evaluated as same procedures described in above working example 2. In this example, not leaves but roots are treated and evaluated. The results are shown in below Table 4. Table 4
  • the present example refers to the synthesis of the phosphor Ba2YTaO6:Mn 4+ with a Mn concentration of 1 mol%.
  • the phosphor is
  • the photoluminescence excitation spectrum shows a UV region from 300 - 400 nm while the emission spectrum exhibits a deep red region from 630 - 710 nm.
  • Excitation and emission spectra are provided in Figure 3.
  • the absorption peak wavelengths of Ba2YTaO6:Mn 4+ is 310 - 340 nm, and the emission peak wavelength is in the range from 680 - 700 nm.
  • agate mortar The powder thus obtained is pelletized at 10 MPa, placed into an alumina container and heated at 1300 °C for 6 h in the presence of air. After cooling the residue is well grinded for characterization. For confirmation of the structure, XRD measurements are performed using an
  • the absorption peak wavelengths of NaLaMgWO6:Mn 4+ is 310 - 330 nm, and the emission peak wavelength is in the range from 690 - 720 nm.
  • the present example refers to the preparation of the phosphor Si5P6O25:Mn 4+ with an Mn concentration of 0.5 mol%.
  • the phosphor is prepared according to conventional solid-state reaction methods, using S1O2, NH 4 H2PO 4 and MnO2 as starting materials.
  • the chemicals are mixed according to their stoichiometric ratio and mixed with acetone in an agate mortar.
  • the powder thus obtained is pelletized at 10 MPa, placed into an alumina container, pre-heated 300 °C for 6 h.
  • the pre-heated powder is grinded, pelletized at 10 MPa, placed again in an alumina container and heated at 1000 °C for another 12 hours in the presence of air. After cooling the residue is well grinded for characterization.
  • XRD measurements are performed using an X-ray diffractometer.
  • Photoluminescence (PL) spectra are taken using a Spectra fluorometer at room temperature.
  • the XRD patterns proofs that the main phase of the product consisted of S15P6O25.
  • the photoluminescence excitation spectrum shows a UV region from 300 nm to 400 nm while the emission spectrum exhibited a deep red region in the range from 670 - 690 nm. Excitation and emission spectra are provided in Figure 5.
  • the phosphor precursors of CaMgSi2O6:Eu 2+ , Mn2 + are synthesized by a conventional co-precipitation method.
  • the two aqueous solutions are simultaneously stirred into deionized water.
  • the combined solution is heated to 90°C and evaporated to dryness.
  • the residue is annealed at 1000°C for 4 hours under an oxidative atmosphere, and the resulting oxide material is annealed at 1000°C for 4 hours under a reductive atmosphere.
  • XRD measurements are performed using an X-ray diffractometer (RIGAKU RAD-RC).
  • Photoluminescence (PL) spectra is measured using a Spectro fluorometer (JASCO FP-6500) at room temperature.
  • the emission peak wavelengths of CaMgSi 2 O 6 :Eu 2+ , Mn2 + is 570 - 600 nm and 670 - 710 nm.
  • Length and width of leaves are measured. Average of them are shown in below Figure 6.
  • aqueous solutions are prepared, two each comprising 1 .00 mass% Al2O3:Cr 3+ phosphor (Synthesis Example 1 ) and Mg2 ⁇ nO 4 :Mn 4+ phosphor (Synthesis Example 2), and the other free of the phosphor (Control, 0 mass %).
  • seedlings of Arabidopsis thaliana are treated with phosphor solutions by spraying at the frequency of 1 time/ 1 week.
  • phosphor treating change the growing duration (days) from seeding until flowering begins. At the timing of flowering begins, leaves number of each seedlings are counted as show in below Figure 9, and each seedling is harvested and fresh weight is measured as shown in below Figure 10. Each number are average ones of each group. Phosphor treating slightly increases the growing duration of Arabidopsis thaliana until flowering. And phosphor treating increases leaves numbers and fresh weight of Arabidopsis thaliana.
  • the precursors of Cai 4 A oZn6O35:Mn 4+ are synthesized by a solid phase reaction.
  • the raw materials of calcium oxide, aluminium oxide, zinc oxide and manganese oxide are prepared with a stoichiometric molar ratio of 14.000:9.850:6.000:0.015.
  • the chemicals are put in a mortar and mixed by a pestle for 30 minutes.
  • the resultant materials are oxidized by firing at 1200 °C for 6 h in air.
  • XRD measurements are performed using an X-ray diffractometer (RIGAKU RAD-RC).
  • Photoluminescence (PL) spectra are measured using a Spectro fluorometer (JASCO FP-6500) at room temperature.
  • the absorption peak wavelengths are in the range of 280 - 340 nm, and 430 - 480 nm.
  • the emission peak wavelength is in the range from 690 - 740 nm.

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Abstract

La présente invention concerne une composition pour l'agriculture comprenant au moins un phosphore.
PCT/EP2018/070101 2017-07-26 2018-07-25 Composition Ceased WO2019020661A1 (fr)

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CN112322290A (zh) * 2020-11-24 2021-02-05 北京科技大学 Cr3+掺杂的锂镁基锗酸盐超宽带近红外发光材料及制备方法
WO2021122689A1 (fr) * 2019-12-19 2021-06-24 Rhodia Operations Procédé de traitement d'une plante
WO2021122691A1 (fr) * 2019-12-19 2021-06-24 Rhodia Operations Utilisation d'un luminophore inorganique pour augmenter le rendement de culture de maïs et de soja
WO2022013116A1 (fr) * 2020-07-13 2022-01-20 Merck Patent Gmbh Luminophore
US20220169923A1 (en) * 2020-11-30 2022-06-02 Nichia Corporation Oxide fluorescent material, light emitting device, and method for producing oxide fluorescent material

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MINA M. MEDIC ET AL: "Deep-Red Emitting Mn 4+ Doped Mg 2 TiO 4 Nanoparticles", JOURNAL OF PHYSICAL CHEMISTRY C, vol. 119, no. 1, 23 December 2014 (2014-12-23), pages 724 - 730, XP055505537, ISSN: 1932-7447, DOI: 10.1021/jp5095646 *
WEI LI ET AL: "Phytotoxicity, Uptake, and Translocation of Fluorescent Carbon Dots in Mung Bean Plants", ACS APPLIED MATERIALS & INTERFACES, vol. 8, no. 31, 26 July 2016 (2016-07-26), US, pages 19939 - 19945, XP055505409, ISSN: 1944-8244, DOI: 10.1021/acsami.6b07268 *
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021122689A1 (fr) * 2019-12-19 2021-06-24 Rhodia Operations Procédé de traitement d'une plante
WO2021122691A1 (fr) * 2019-12-19 2021-06-24 Rhodia Operations Utilisation d'un luminophore inorganique pour augmenter le rendement de culture de maïs et de soja
CN114829541A (zh) * 2019-12-19 2022-07-29 罗地亚经营管理公司 用于处理植物的方法
WO2022013116A1 (fr) * 2020-07-13 2022-01-20 Merck Patent Gmbh Luminophore
CN112322290A (zh) * 2020-11-24 2021-02-05 北京科技大学 Cr3+掺杂的锂镁基锗酸盐超宽带近红外发光材料及制备方法
US20220169923A1 (en) * 2020-11-30 2022-06-02 Nichia Corporation Oxide fluorescent material, light emitting device, and method for producing oxide fluorescent material

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