EP3145314A1 - Potentialisation de cuivres insolubles et d'autres pesticides contenant du cuivre et supplémentation de la nutrition des végétaux - Google Patents

Potentialisation de cuivres insolubles et d'autres pesticides contenant du cuivre et supplémentation de la nutrition des végétaux

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Publication number
EP3145314A1
EP3145314A1 EP15796119.4A EP15796119A EP3145314A1 EP 3145314 A1 EP3145314 A1 EP 3145314A1 EP 15796119 A EP15796119 A EP 15796119A EP 3145314 A1 EP3145314 A1 EP 3145314A1
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EP
European Patent Office
Prior art keywords
copper
iron
compound
composition
zinc
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.)
Withdrawn
Application number
EP15796119.4A
Other languages
German (de)
English (en)
Other versions
EP3145314A4 (fr
Inventor
Robert Sabin
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Individual
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Individual
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Filing date
Publication date
Priority claimed from US14/625,405 external-priority patent/US9247734B2/en
Priority claimed from US14/674,607 external-priority patent/US9718739B2/en
Priority claimed from US14/689,675 external-priority patent/US9271502B2/en
Application filed by Individual filed Critical Individual
Publication of EP3145314A1 publication Critical patent/EP3145314A1/fr
Publication of EP3145314A4 publication Critical patent/EP3145314A4/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D9/00—Other inorganic fertilisers
    • C05D9/02—Other inorganic fertilisers containing trace elements
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C05G3/60—Biocides or preservatives, e.g. disinfectants, pesticides or herbicides; Pest repellants or attractants
    • 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
    • A01N59/16—Heavy metals; Compounds thereof
    • A01N59/20—Copper

Definitions

  • the present invention relates to potentiation of pesticides containing fixed copper in human, agricultural, fungicidal, bactericidal, anti-pathogen and biocidal applications, by increasing the activity of its biocidal effects, so that less polluting copper is used.
  • Xylellafastidosa infection is a bacterium, which inhabits the internal vascular compartment of the olive tree, the xylem, and causes like HLB, plants to diy out, die, leaving shriveled stumps, that are incapable of bearing fruit.
  • HLB disease of citrus is a devastating phloem limited incurable bacterial infection which is decimating/killing the citrus industry worldwide.
  • Novel Bactericides and Application Methods to Control Huanglongbing Disease of Citrus which discusses an overview of "inconsequential effect of nutritional treatments on Huanglongbing control, fruit quality, bacterial titer and disease progress" by T.R. Gottwald, J.H. Graham et al. See also,
  • Copper (II) hydroxide also known as cupric hydroxide and having the chemical formula Cu(OH) 2
  • Cu(OH) 2 Copper (II) hydroxide
  • cupric hydroxide also known as cupric hydroxide and having the chemical formula Cu(OH) 2
  • Cu(OH) 2 Copper (II) hydroxide
  • U.S. Patent Numbers 2,525,242 and 2,536,096 involve oxidation of copper metal in the presence of ammonia and U.S. Patent Number 4,944,935 discloses a similar process substituting ammonium ion for all or part of the ammonia.
  • the other processes start with a soluble copper salt, typically copper (II) sulfate.
  • U.S. Patent Number 4,404,169, European Patent Number EP 80226 BI and PCT Patent Publication WO 02/083566 A2 describe processes starting with copper (II) oxychloride. J. Komorowski-Kulik, Zeszyty, Naukowe Politecniki Sitaskiej, Series:
  • Nufarm discloses the history of copper fungicides, the history of copper hydroxide, how copper hydroxide works, how copper works, particle size of copper hydroxide fungicide and more infonnation, including about their products Champ® Dry Prill, Champ® Fomiula 2 Flowable and Champion® WP (See Nufarm Americas Inc., Nufarm Agriculture Division, "The Copper Champs! " ⁇ 2002.)
  • DuPont discloses a similar product, DuPont Kocide Blue Xtra with similar information. (DuPont (Australia) Ltd., DuPontTM Kocide Blue Xtra with BioActive Copper®
  • DuPont discloses a bewildering array of dozens of plant diseases, treated with
  • Copper pesticides, fungicides, and bactericides are extremely toxic to fish and aquatic organisms. (Nufarm Americas Inc., Agt Division, Champ® WG Specimen Label). Runoff from the use of copper fungicides, bactericides and algaecides into waterways, ground water and the ground is a very serious contamination problem well known to those in the art. For example, Scientific American, March 18,2013, "Fish Cannot Smell In Polluted Waters" by Brian Bienkowski, discloses: “copper is a poster child for water pollution” said Nathaniel Scholz, an excitology program manager at the National Oceanic and Atmospheric
  • Patent Number 5,385,934 of Schroth Methods for Preventing Precipitation of Copper Based Bactericidal Compositions Containing Iron, 1995, discloses the addition of an aggregation inhibiting salt to the copper plus iron compositions to prevent aggregate/or sediment formation upon the addition of Fe+3 to the composition.
  • Both of Schroth's patents taken together require five components - a copper hydroxide component or a fixed copper component, with a dry surfactant, plus a soluble iron component, plus a liquid surfactant, and plus an aggregation inhibitor, salt.
  • Zinc-doped CuO nanocomposites of a specific size are known for use in specific fields.
  • Eyal Malka et al., (small 2013, DOI:10.1002/smll.201301081 , www.small- journal.com) discloses, "eradication of multi-drug resistant bacteria by a novel zinc-doped CuO nanocomposite.”
  • Michal Eshed, et al., (Advanced Functional Materials 2014, pp.1382- 1390, www.afm-joumal.de) discloses, "a Zn-doped CuO nanocomposite shows enhanced anti-biofilm and antibacterial activities against Streptococcus lmitans compared to nanosized CuO.” They conclude, "the results ui uic picscm smu munu iiigmight the potential of these novel Zn:CuO np's as inliibitors of biofilm within the context of the oral niche.”
  • Richardson provides, "commercially produced cupric oxide (
  • Ploss et al United States Patent 7,105,136 B2 discloses that doping 5 wt % zinc metal into a copper salt composition intended for agricultural applications provided enhanced surface adhesion, as in the case of plants on leaf and fruit surfaces, thereby increasing the duration of the plant-protecting effects and also eliminating the expense and environmental emissions associated with the re-application of prior art compositions that would be required to provide the same level of protection.
  • Ploss's use of metallic zinc to provide enhanced surface adhesion does not teach any advantages with regard to pesticidal characteristics per se. For example, zinc is a metal, an element and is insoluble in water, with a small surface area.
  • Nufarm's Spraymate bond is a high quality sticker, deposition and retention agent for use with contact or protectant type fungicides or with contact and ingested insecticides. Spraymate bond increases adherence of spray droplets by sticking them firmly to target surfaces. This protects pesticides against wash-off by rain or sprinkler irrigation.
  • Spraymate bond also protects chemicals by slowing the rate of degradation immediately after application. Its key benefits are that it improves spray droplet deposition, retains and protects droplets on targets, improves the performance and life of protectant fungicides and contact insecticides. Furtheraiore, there is a world of difference between pure zinc metal, an element, and insoluble pesticidal zinc compounds.
  • This invention is directed to a pesticide, fungicidal, bactericidal, anti -pathogen or biocidal composition
  • a pesticide, fungicidal, bactericidal, anti -pathogen or biocidal composition including a) at least one biologically inert carrier and; b) at least one doped component comprising at least one fixed copper compound, such as copper hydroxide, doped with at least one compound selected from the group consisting of iron compounds, zinc compounds, magnesium compounds, calcium compounds, and combinations thereof.
  • the doped component only includes iron compounds and/or zinc compounds as the only doping compounds.
  • the doped component has a particle size of about 0.5 nm to 30 microns.
  • the iron compound and/or zinc compound are doped into the fixed copper compound, such as copper hydroxide, singly or together in combination, hi one embodiment a fixed copper compound is doped with an insoluble iron compound, such as, for example, where the fixed copper compound is copper hydroxide, and wherein the fixed copper compound is partially substituted by an insoluble iron compound.
  • a surfactant may be included in the composition to provide for a more efficacious formulation.
  • the composition includes doped components that contain both the fixed copper compounds and the iron, zinc, magnesium, and/or calcium compounds combined on the doped component.
  • the fixed copper compound such as copper hydroxide
  • doped with the iron compound and/or zinc compound is used in order to provide a more cost effective composition with increased activity as compared to copper hydroxide alone. Therefore, less copper is required with its resultant reduced runoff, and less pollution derived from copper.
  • iron is a plant micronutrient and the present composition would supply iron to plants as against copper hydroxide alone. It has been found that heavy use of copper compounds produces iron chlorosis.
  • copper hydroxide is a pesticide, fungicide bactericide that is so well established so that the present invention could be administered very similarly to the current methods of copper hydroxide administration with a straight substitution, more or less, except that the amount of elemental copper derived from the present invention will be reduced, as against stand-alone copper hydroxide, to achieve the same or greater control or pathogen reduction.
  • Applicant submits that the present invention may be substituted for the copper hydroxide in PCT Patent Publication WO 2006028853 to Oberholzer.
  • the composition of the present invention also reverses resistance to copper so that copper resistant pathogens become sensitive to copper.
  • Applicant's present invention increases the activity of copper with respect thereto.
  • Applicant's present invention may be provided as a pesticide, fungicide, bactericide, anti-pathogen and biocidal nutrient spray with optional additional micronutrients and/or optionally macronutrients, so that there would be a combination copper based pesticide with micronutrients all in one formulation, h another embodiment, Applicant's present invention includes an insoluble copper pesticide, fungicide, bactericide, and anti-pathogen and biocidal capable of systemic uptake by foliar, root and/or trunk injection, and a plant protectorant, dual mode of action, all in one compound.
  • the prior art teaches various complexes of copper compounds, mixtures which are two or more substances that are not chemically combined, and chelates of copper compounds.
  • Compounds of the present invention are overwhelmingly, compellingly, and persuasively, distinguishable, as doped zinc compounds and doped iron compounds are internalized in the copper hydroxide or other fixed coppers. Complexes and chelates are joined so that they are externalized to the copper hydroxide or other fixed coppers. Moreover, being externalized to the copper hydroxide or other fixed copper produces larger particulates undesirable for systemic administration.
  • Applicant's doped components can also be sized at about 5m -10nm, and other larger particulates, in one embodiment, to provide both plant protectorant and systemic uptake to be earned internally through the plant phloem and xylem to kill systemic bacterial infections such as HLB, and Xylellafastidosa, and other systemic pathogenic fungi, or internal pathogens.
  • the Applicant's invention will decrease the breadth, depth and range of pesticides currently resistant to copper pesticides, restoring sensitivity and high activity. Moreover a Google search discloses over 52 million hits for the well-known established hamiful effects of pesticides. [0026] Moreover, Wikipedia discloses, "Environmental Impact of Pesticides" with one page and a half of harmful pesticide environmental effects of classes of pesticides. In contrast, the Applicant's present invention reduces the need for the quantity of copper currently being used as a pesticide and displaces and replace many current highly toxic poisonous pesticides currently being used. Copper is the lesser of the two evils as against synthetic agricultural chemical pesticides with their well-known toxicities and undesirable environmental effects.
  • FIG. 1 is a copy of an X-Ray Diffraction test showing copper hydroxide doped with 15 at% insoluble iron as a dopant in accordance with one embodiment of the present invention. There are no additional peaks proving that the iron is incorporated within the copper hydroxide.
  • FIG. 2 is a transmission electron microscopy (TEM) image of Applicant's iron doped copper hydroxide at 15 at% iron in accordance with one embodiment of the present invention.
  • the scale on the lower left of FIG. 2 shows a comparable length of 50 run.
  • the size of the iron doped 15 at% Fe copper hydroxide particulates is about 3.5 run to 9 nm, tested in quadruplicate and by transmission electron microscopy (TEM).
  • FIG.3 is an elemental analysis chart demonstrating the presence of both iron and copper in the iron doped copper hydroxide compound in accordance with one embodiment of the present invention of FIG.1 and FIG. 2 above.
  • FIG. 4 is the X-ray diffraction of 15 at% iron doped copper hydroxide with an additional 10 at% iron that the copper hydroxide is unable to incorporate, so that the final composition is 15 at% iron doped copper hydroxide + 10 at% unincorporated/free iron hydroxide and/or iron oxide.
  • the invention is a pesticide, fungicidal, bactericidal, anti-pathogen or biocidal composition
  • a pesticide, fungicidal, bactericidal, anti-pathogen or biocidal composition comprising a) at least one biologically inert carrier; and b) at least one doped component including at least one fixed copper compound doped with at least one compound selected from the group consisting of iron compounds, zinc compounds, magnesium compounds, calcium compounds and combinations thereof.
  • the doped component only includes iron compounds and/or zinc compounds as the only doping compound.
  • copper hydroxide may be doped with iron hydroxide, iron oxyhydroxide or other iron compound as one doped component.
  • the fixed copper compound is doped with an insoluble iron compound, wherein the fixed copper compound is partially substituted by the insoluble iron compound.
  • the invention also comprises a fixed copper compound, such as copper hydroxide, doped with a zinc compound.
  • the fixed copper compound such as copper hydroxide
  • Applicant's invention includes at least one doped component containing both the fixed copper compound doped with an iron compound and/or a zinc compound that can be used similarly to how copper hydroxide alone is used.
  • an iron compound is doped on copper hydroxide
  • a zinc compound is doped on copper hydroxide
  • a zinc compound and an iron compound are doped on copper hydroxide, singly and optionally combined together, and or added to other pesticide agents.
  • the doped component is prepared according to methods described herein and readily understood to those of skill in the art.
  • the composition can be used in many of the applications that copper hydroxide is currently utilized, and many new pesticidal indications which are currently resistant to copper. See, for example, WO2006028853.
  • copper hydroxide is doped with iron hydroxide to provide 15at% iron to the doped component, which results in a black doped component.
  • the atomic percentage (at%) of iron in the doped component is less than 15 at%, more preferably less than 10 at%.
  • the preferred copper hydroxide-iron hydroxide doped component prepared by the present method is especially useful as an active ingredient in pesticides, fungicides, bactericides and biocides. This increased biocidal activity reduces the number of pathogens currently resistant to copper pesticides, increasing the range and breath of activity of copper against other bacteria, fungi, viruses, mycoplasma, and other pathogenic organisms.
  • the composition is administered to plants by a method selected from the group consisting of dusting, sprinkling, spraying, brushing, dipping, smearing, impregnating, injection of the composition into plant vasculature, and application to a root system.
  • Pests can be insects and insect-like organisms, mice and other vertebrate animals, unwanted plants (weeds), or fungi, bacteria and viruses that cause plant diseases. Though often misunderstood to refer only to insecticides, the term pesticide also applies to herbicides, fungicides, and various other substances used to control pests.”
  • a mixture contains 2 or more substances that are not chemically combined. Mixtures are unlike chemical compounds, because: the substances in a mixture can be separated using physical methods such as filtration and distillation. Mixtures have variable compositions while compounds have a fixed definite formula. When mixed, individual substances keep their properties in a mixture, while if they form a compound their properties can change. See http://www.chemicool.coni/definition/mixtL re.html).
  • An example of a mixture is NORDOX 30/30 wg, manufactured by NORDOX AS c/o Monterey
  • Elements and compounds are pure chemical substances found in nature. The difference between an element and a compound is that an element is a substance made of the same type of atoms, whereas a compound is made of different elements in definite proportions. Examples of elements include iron, copper, zinc, hydrogen and oxygen. Examples of compounds include water (H 2 0) and salt (sodium chloride-NaCl) . " S ee, http://www.diffen.com/difference/ Compound_vs_Element.
  • complex is a molecular entity formed by loose association involving two or more component molecular entities (ionic or uncharged), or the corresponding chemical species. The bonding between the components is normally weaker than in a covalent bond.
  • coordination entity In inorganic chemistry the term "coordination entity" is
  • chelate In reality, a chelate is any metal that is attached to an anion (negatively charged group) with more than one attachment site. Chelation means that the anion has two or more separate sites to which the metal is bonded.” See,
  • dopant a dopant is "an impurity added usually in minute amounts to a pure substance to alter its properties.” See, www.merriam- webster.com/dictionary/dopant. According to www.freedictionary.com, under “medical” the term “to dope” is used in materials sciences as a verb which means "To add or incorporate a substance or other additive to a chemical compound of interest, with the intent of improving or altering performance parameters.”
  • fixed copper a copper compound which is insoluble or highly insoluble in water. Fixed Coppers are further disclosed by H. Wayne Richardson in the "Handbook Of Copper Compounds And Applications", page 97 third paragraph, "suitable copper compounds include fixed coppers [Cu+(OH)2], Bordeaux, as well as other well known fixed copper compositions including those disclosed in CRV Handbook of Pest Management in Agriculture, Vol.
  • Exemplary examples are copper hydroxide, copper/cuprous oxide, copper carbonate, copper oxychloride, basic carbonate, copper carbonate, basic copper sulfates including particularly tribasic copper sulfate, copper oxychlorides, and mixtures thereof, ammonia copper carbonate, basic copper chloride, and others, and mixtures thereof.
  • iron doped copper hydroxide refers to a copper hydroxide compound that is doped with an iron compound. It is understood in alternate embodiments that the copper hydroxide compound may be substituted with another fixed copper compound as provided herein.
  • zinc doped copper hydroxide refers to a copper hydroxide compound that is doped with a zinc compound. It is understood in alternate embodiments that the copper hydroxide compound may be substituted with another fixed copper compound as provided herein.
  • iron and iron doped copper hydroxide refers to a copper hydroxide compound that is doped with both an iron compound and a zinc compound. It is understood in alternate embodiments that the copper hydroxide compound may be substituted with another fixed copper compound as provided herein.
  • iron compounds include any insoluble or substantially insoluble iron compound. Further examples include, but are not limited to iron compounds selected from the group consisting of iron hydroxide, iron oxyhydroxide, iron oxide, iron glucose, ferric citrate, Ferritin, ferrous fumarate, and ferrous sulfate. Most preferably the iron compound is iron hydroxide and/or iron oxyhydroxide.
  • Examples of zinc compounds include any insoluble or substantially insoluble zinc compound. Further examples include, but are not limited to zinc compounds selected from the group consisting of zinc hydroxide and zinc oxide.
  • insoluble or substantially insoluble is used herein.
  • Applicant submits that there is not a hard and fast quantitative definition for such terms as used by those of skill in the art. Accordingly, terms such as “sparingly soluble”, “insoluble”, “highly insoluble”, “slightly soluble”,
  • Cuirently used Cu compounds possess unique set of physical and chemical properties. They differ in their total amount of metallic Cu content and aqueous solubility. It is well understood that the antibacterial activity will depend upon the availability of soluble (free and reactive) Cu ions in the formulation. Among the existing Cu compounds, tribasic Cu sulphates and cuprous oxide are least soluble, whereas Cu hydroxides are more soluble than Cu
  • copper copper (1) oxide(Cu2), cuprous oxide), copper(2) oxychloride(CuCl 2 .3Cu(OH) 2 , tribasic copper(2)sulphate(CuS0 4 .3Cu(OH) 2 , and copper hydroxides(Cu(OH) 2 ).
  • copper(2) oxychloride(CuCl 2 .3Cu(OH) 2 copper(2) oxychloride(CuCl 2 .3Cu(OH) 2
  • tribasic copper(2)sulphate CuS0 4 .3Cu(OH) 2
  • copper hydroxides Copper(OH) 2 ).
  • the iron doping of the copper hydroxide nanoparticles is from a trace contamination of iron, less than .01 at%, to about 40 at% iron with abovat 5-15 at% elemental iron preferred, with about 15 at% elemental iron the most preferred quantity.
  • Other fixed coppers may incorporate more than 40 at% iron and/or zinc.
  • Applicant has used a wet chemical process as further indicated in detail below. It is understood to those of skill in the art that the process disclosed herein is scalable for commercial production.
  • the product is dried/evaporated by methods well known to those skilled in the chemical art, and may be overcoated, if desired, with a stabilizer by methods well known to those in the chemical art.
  • the preferred size of an iron doped copper hydroxide nanoparticle is sub-micron, from about 0.5nm to 30 microns. A more preferred size is from about 3.5nm to 15 microns, an additional preferred size is from about 3.5mn to 200mn. A most preferred size is from about 3.5nm to 1 Onm, especially for both leaf protectorant and systemic activity all in one. Different sizes may be mixed together in the practice of the invention.
  • fixed copper compounds such as copper hydroxide
  • copper hydroxide are generally insoluble or highly insoluble in water. While not being limited, held or bound to any particular theory or mechanism of action, it is generally thought that "The free copper penetrates into the bacterial and/or fungal micro-organism in order to exert its toxic effect.”
  • ROS reactive oxygen species
  • composition of the present invention may be used with any known biologically inert carrier, including, but not limited to, a liqxxid diluent, e.g., water, a solid diluent and/or a surfactant.
  • a liqxxid diluent e.g., water, a solid diluent and/or a surfactant.
  • composition of the present invention is designed to be compatible with the physical properties of copper hydroxide and any other active ingredients, method of application and environmental factors which may include soil type, moisture and temperature, organic matter, soil structure, current nutrient levels and more, well known to those in the chemical and agricultural art.
  • Applicant's iron doped copper hydroxide, or zinc doped copper hydroxide, or zinc and iron doped copper hydroxide in an optional embodiment, may be stabilized or overcoated.
  • United States Patent 4,404,169 Ploss et al. discloses methods of stabilizing compounds of the applicant's invention.
  • Overcoating can modulate release of the active ingredient.
  • insoluble iron compounds such as iron hydroxide or iron oxyhydroxide
  • copper hydroxide may be added to copper hydroxide so that there are two separate components.
  • iron hydroxide or other insoluble iron compounds may be added to the iron doped copper hydroxide, so there are also two separate components, hi each case, everything goes together in the spray tank for agricultural uses.
  • iron and copper are recognized micronutrients, recognized by the American Society of Agronomy and the Soil Science Society of America, then it follows that the remaining micronutrients boron, chloride, manganese, molybdenum and zinc, can easily be added to the iron or zinc or iron and zinc doped copper hydroxide, which uses iron and or zinc as a dopant to produce a doped copper hydroxide iron nmgicide actericide/nutrient with micronutrients for foliar, trunk, branch and/or root application and/or injection in the trunk or branches of the plant.
  • secondary nutrients such as calcium, magnesium and sulfur may also be added, singly or together in combination.
  • Applicant's invention is the only known foliar nutritional bactericidal fomiulation that enters the phloem and kills the HLB disease causing CandidatusLiberibacter (CLas) bacteria.
  • Applicant proposes to potentiate, increase activity of the claimed iron doped copper hydroxide by further doping the copper hydroxide with a zinc compound so that the end product will be an iron doped, zinc doped copper hydroxide or other fixed copper. It is understood that the doping with zinc is provided by a zinc compound and not by the use of pure metallic zinc, an element.
  • Preferred embodiments of this invention include both a zinc compound doped copper hydroxide and an iron compound doped copper hydroxide.
  • Zinc sulfate is an exemplary example of a zinc salt thought to be useful in the manufacture of compounds of the invention.
  • the sulfur in zinc sulfate is also a plant nutrient.
  • Applicant also claims copper hydroxide which is both doped with an iron compound and a zinc compound together. In the preparation of the iron doped copper hydroxide, excess iron more than that the copper hydroxide will incorporate, is left in the preparation, so that the upshot is iron doped copper hydroxide, with additional iron hydroxide, in the preparation thereof. It may very well be an iron
  • Iron doped copper hydroxide with and without additional unincorporated iron hydroxide in the preparation, may be combined with zinc doped copper hydroxide with and without additional unincorporated zinc hydroxide or other zinc compounds, and both zinc and iron doped copper hydroxide with both additional unincorporated zinc and iron may also all be used in combinations or mixtures thereof.
  • Other useful compounds are fenites, which may be an additional alternate compound to be used stand alone, or may be combined as the iron and/or zinc doped copper hydroxide is also used.
  • a ferrite is a type of ceramic compound composed of iron oxide (Fe 2 0 3 ) combined with one or additional metallic elements in chemical combination. See Encyclopedia Britannica. See Wikipedia. Exemplary examples are copper zinc iron oxide (CuZnFe 2 0 4 ).
  • the aforesaid fenites are exemplary examples thought to be useful in the practice of the invention, and may be combined in any combination with themselves or other compounds previously disclosed in the practice of the invention.
  • the size of the fenites are from 0.5 nm up to 30 microns.
  • compositions of the Applicant's invention are especially directed and extraordinarly suited as a treatment for Huanglongbing (HLB) disease of citrus, and citrus canker, and other citrus diseases, such as Greasy Spot, Melanose, and Alternaria Brown Spot, where copper is currently utilized.
  • HLB Huanglongbing
  • Applicant's invention will improve foliage coverage of leaves, which is well known in the art, that small particulates provide more uniform and superior coverage to leaves of plants.
  • a critical and distinguishing feature of the Applicant's invention is that in preferred embodiments it can be an ultra-small insoluble copper and iron compound.
  • another critical aspect of Applicant's invention is the size of
  • Applicant's iron doped copper hydroxide such that it is enabled for systemic uptake of the copper and iron.
  • This size of Applicant's particles is unlike any size of any commercial fixed copper, so far as the Applicant is aware of, to facilitate systemic administration.
  • Applicant's particulate at about 90+% particulate is about 3.5 to lOmn, as both a leaf protectorant and a systemic pesticide, and bactericide. Previous insoluble or fixed coppers are not systemic due to their large size for the most part. Applicant's particulate is about 90+% approximately 3.5 to 10 ran, in order to avoid aggregation, and has the best chance to facilitate systemic uptake.
  • Applicant's invention is to be administered with adjuvants/surfactants.
  • Applicant's Transmission Electron Microscopy (TEM) image of FIG.2 herein was tested with a surfactant, to insure good separation.
  • Typical surfactants thought to be useful for the Applicant's invention are described in Silwet Adjuvants and SAG Antifoams for Agricultural
  • the upshot is that doped components of the Applicant's invention hits the bacterial causes of HLB disease and XyellaFastidiosa infection of Olive Trees, and other
  • Applicant's invention simultaneously treats citrus canker and other citrus diseases.
  • the doped component is a fixed copper compound doped with magnesium and/or calcium.
  • compounds of the Applicant's invention may be used with agents which currently synergizes with copper administration, such as for example Regalia biofungicide, and horticultural oils, and pesticidal adjuvants such as Silwet-L77, and other pesticides.
  • agents which currently synergizes with copper administration such as for example Regalia biofungicide, and horticultural oils, and pesticidal adjuvants such as Silwet-L77, and other pesticides.
  • Compounds of the present invention are suitable for the customary coatings, which include but not limited to surfactants, wetting agents, stabilizers, dispersants and anti-foam agents.
  • Iron-doped Copper Hydroxide (Fe-Cu (OH) 2 ) composite powder is synthesized using a wet chemical process.
  • the starting materials for the synthesis were copper nitrate hexahydrate(Cu(N0 3 )2.6H 2 0), iron chloride (FeCl 3 ), sodium hydroxide (NaOH) and deionized water (H 2 0).
  • To synthesize -15 at% Fe-doped- Cu (OH) 2 2.43g of copper nitrate hexahydrate and 0.4 g of iron cliloride were dissolved in 75 niL of deionized water in a round bottom flask. The solution was refiuxed for 3 hours.
  • FIG. 1 is an X-ray diffraction test verifying that copper hydroxide is doped with an insoluble iron, hi connection therewith, in FIG.2 herein, Applicant submits a data sheet of Applicant's iron doped copper hydroxide with 15 at% iron elemental analysis of FIG.3.
  • FIG. 2 discloses Applicant's invention tested out by TEM at about 90%+ particulates, which is a very narrow particulate distribution unlike any other commercial product, between 3.5nm and lOnm.
  • Fig.4 is the X-ray diffraction of 15 at% Iron doped+ additional 10 at% Iron that the copper hydroxide is unable to incorporate, so that the final preparation is 15 at% Iron doped copper hydroxide+ 10 at% unincorporated/free Iron Hydroxide and or Iron Oxide.
  • Iron-Zinc-doped Copper Hydroxide (Fe-Zn-Cu (OH) 2 ) composite powder is synthesized using a wet chemical process.
  • the starting materials for the synthesis is copper nitrate hexahydrate (Cu (N0 3 ) 2 .6H 2 0), iron chloride (FeCl 3 ), ziiic sulfate heptahydrate (ZnS0 4 .7H 2 0), sodium hydroxide (NaOH) and deionized water (H 2 0).
  • Zinc-doped Copper Hydroxide (Zn-Cu(OH) 2 ) composite powder is synthesized using a wet chemical process.
  • the starting materials for the synthesis is copper nitrate hexahydrate (Cu(N0 3 ) 2 .6H 2 0), zinc sulfate lieptahydrate (ZnS0 4 .7H 2 0), sodium hydroxide (NaOH) and deionized water (H 2 0).

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Catching Or Destruction (AREA)

Abstract

L'invention concerne une composition pesticide, fongicide, bactéricide, anti-pathogène ou biocide comprenant au moins un support biologiquement inerte; et au moins une ferrite ou au moins un composant dopé comprenant au moins un composé de cuivre insoluble dopé avec au moins un composé choisi dans le groupe constitué de composés de fer, de composés de zinc, de composés de magnésium, de composés de calcium, et de leurs combinaisons et/ou mélanges. Dans un mode de réalisation, le composant dopé a une taille de particule d'environ 0,5 nm à environ 30 microns. L'invention concerne également un procédé de lutte contre les nuisibles, qui comprend l'étape consistant à appliquer sur les nuisibles ou sur leur habitat de croissance la composition susmentionnée. Le procédé comprend également la lutte contre les maladies dans des plantes d'agrumes provoquées par des vecteurs comme les nymphes de psylle, par application de la composition susmentionnée à leur habitat de croissance dans des plantations d'agrumes.
EP15796119.4A 2014-05-23 2015-05-20 Potentialisation de cuivres insolubles et d'autres pesticides contenant du cuivre et supplémentation de la nutrition des végétaux Withdrawn EP3145314A4 (fr)

Applications Claiming Priority (9)

Application Number Priority Date Filing Date Title
US201462002330P 2014-05-23 2014-05-23
US201462003528P 2014-05-27 2014-05-27
US201462020247P 2014-07-02 2014-07-02
US201462021819P 2014-07-08 2014-07-08
US201462094775P 2014-12-19 2014-12-19
US14/625,405 US9247734B2 (en) 2014-05-23 2015-02-18 Potentiation of fixed coppers and other pesticides containing copper and supplementing plant nutrition
US14/674,607 US9718739B2 (en) 2014-05-23 2015-03-31 Potentiation of fixed coppers and other pesticides containing copper and supplementing plant nutrition
US14/689,675 US9271502B2 (en) 2014-05-23 2015-04-17 Potentiation of fixed coppers and other pesticides containing copper and supplementing plant nutrition
PCT/US2015/031702 WO2015179478A1 (fr) 2014-05-23 2015-05-20 Potentialisation de cuivres insolubles et d'autres pesticides contenant du cuivre et supplémentation de la nutrition des végétaux

Publications (2)

Publication Number Publication Date
EP3145314A1 true EP3145314A1 (fr) 2017-03-29
EP3145314A4 EP3145314A4 (fr) 2017-05-17

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EP15796119.4A Withdrawn EP3145314A4 (fr) 2014-05-23 2015-05-20 Potentialisation de cuivres insolubles et d'autres pesticides contenant du cuivre et supplémentation de la nutrition des végétaux

Country Status (6)

Country Link
EP (1) EP3145314A4 (fr)
CN (1) CN106535640A (fr)
AU (1) AU2015264306B2 (fr)
EA (1) EA033186B1 (fr)
MA (1) MA40010A (fr)
MX (1) MX358397B (fr)

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Publication number Priority date Publication date Assignee Title
CZ2022298A3 (cs) * 2022-07-04 2023-10-04 Agra Group A.S. Použití Chevreulovy soli jako hnojiva a hnojivo tuto sůl obsahující

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5202353A (en) * 1991-01-22 1993-04-13 The Regents Of The University Of California Iron enhancement of copper based fungicidal and bactericidal compositions
DE4142432A1 (de) * 1991-12-20 1993-06-24 Wacker Chemie Gmbh Verfahren zur herstellung von kupferpulver
JPH08290990A (ja) * 1995-04-19 1996-11-05 Hitachi Metals Ltd 磁化肥料
US6139879A (en) * 1997-06-25 2000-10-31 Foliar Nutrients, Inc. Fungicidal and bactericidal compositions for plants containing compounds in the form of heavy metal chelates
JP4037936B2 (ja) * 1997-05-02 2008-01-23 澄男 宮川 フェライト懸濁液を用いた植物の病害防除剤及び植物の病害防除方法
JP2001269051A (ja) * 2000-03-27 2001-10-02 Hida Sangyo Kk 培養土及びその製造装置、方法
EP1298092A1 (fr) * 2001-09-28 2003-04-02 Spiess -Urania Chemicals GmbH Morphogénèse controllée de sels de cuivre
US6877275B2 (en) * 2002-02-19 2005-04-12 Engelhard Corporation Method of weed control
US20130189364A1 (en) * 2004-07-09 2013-07-25 Robert Sabin Compositions and methods of potentiating adjuvant pharmaceuticals targeting latent viral infections
TW201041508A (en) * 2009-04-30 2010-12-01 Dow Agrosciences Llc Pesticide compositions exhibiting enhanced activity
TW201041507A (en) * 2009-04-30 2010-12-01 Dow Agrosciences Llc Pesticide compositions exhibiting enhanced activity and methods for preparing same
TW201041510A (en) * 2009-04-30 2010-12-01 Dow Agrosciences Llc Pesticide compositions exhibiting enhanced activity
CA2806295A1 (fr) * 2009-08-03 2011-02-10 Alnylam Pharmaceuticals, Inc. Procedes et compositions de traitement d'insectes
WO2012135016A2 (fr) * 2011-03-25 2012-10-04 North Carolina State University Inhibition de biofilms bactériens et croissance microbienne avec des dérivés d'imidazole

Also Published As

Publication number Publication date
MX358397B (es) 2018-08-17
EA033186B1 (ru) 2019-09-30
MX2016015322A (es) 2017-05-10
AU2015264306A1 (en) 2016-12-15
CN106535640A (zh) 2017-03-22
EA201692393A1 (ru) 2017-05-31
EP3145314A4 (fr) 2017-05-17
MA40010A (fr) 2015-11-26
AU2015264306B2 (en) 2017-07-27

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