CN106535640A - Potentiation of fixed coppers and other pesticides containing copper and supplementing plant nutrition - Google Patents
Potentiation of fixed coppers and other pesticides containing copper and supplementing plant nutrition Download PDFInfo
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- CN106535640A CN106535640A CN201580039745.1A CN201580039745A CN106535640A CN 106535640 A CN106535640 A CN 106535640A CN 201580039745 A CN201580039745 A CN 201580039745A CN 106535640 A CN106535640 A CN 106535640A
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- compound
- copper
- iron
- zinc
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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
-
- 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
-
- 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
Abstract
A pesticide, fungicidal, bactericidal, anti-pathogen or biocidal composition includes at least one biologically inert earner; and at least one ferrite or 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 and/or mixtures thereof. In one embodiment, the doped component has a particle size of about 0.5nm to about 30 microns. A method for the control of pests includes the step of applying to the pests or their growth habitat the aforementioned composition. The method also includes the control of disease in citrus plants caused by vectors such as Psyllid nymphs, by applying the aforementioned composition to their growth habitat in citrus groves.
Description
Invention field
The present invention relates to containing fixed copper in people, agricultural, antifungal, bactericidal, antipathogen and biocidal application
Pesticides are strengthened by the activity for improving its biocidal effect, so that using less contaminative copper.
Background
All patents, Science article and other documents being mentioned above are incorporated by reference into seemingly reproducing in full.
During 2 days 2015 California citrus of meeting that Florida Fort Pierce is held are puted on display, real is exhausted
Hope, it is apparent that because the most area of Florida is disclosed infected with yellow twig (HLB) bacterium, and do not exist to will
The good treatment of this destructive disease of California citrus industry is destroyed completely almost.Referring further to, Rusnak, " crew is urgent
Await orders to save California citrus (All Hands On Deck to Save Florida Citrus) ", 2015,
http://www.growingproduce.com/citrus/insect-disease-update/all-hands-on-deck-
to-save-florida-citrus/.Grower is almost crying bitterly, because they sell theirs in the orchard for abandoning them
Soil, implore scientist do something, anything, interim measure.In science narrative tense, scientist could not provide any at this moment
Substantial method.Made 5 years afterwards they may have some methods to resist the ambiguous promise of HLB etc..Actually institute
Some growers are adhered to trying one's best.Additionally, the reprint of the situation of Florida is in Italy's appearance, what is be there similar to is
System property bacterium is killing the Chinese olive tree of hundreds of age.The nature process of two kinds of diseases is similar to very much, it is impossible to escape ground to death
Progress, and there is no good treatment again.Unless solution was found in 7 years, otherwise in Florida or Italy
Oranges and tangerines or Chinese olive tree are there's almost no respectively.Additionally, with global warming and climate change, will have many plant pest lifes
Thing, insect, bacterium and fungi extend their scope to new ground Tape movement, have a strong impact on the life style and food of millions of people
Thing is supplied.
One example is difficult foster bacterium (Xylellafastidosa) sense of crushing xylem of Chinese olive tree in Italy
Dye, is discussed in " the difficult foster bacterium of xylem by J.D. Janse and A. Obradovic：Its biology, diagnosis, control and risk
(Xylellafastidosa:It's Biology, Diagnosis, Control, And Risks) " in.This infection is almost
It is the reprint of the HLB infection of oranges and tangerines.XyZella (Xylella) infection is Bacillus, inside dimension pipe of its perch in Chinese olive tree
Compartment xylem, and as HLB, cause plant to parch, it is dead, leave the withered stub that can not be born fruit.Also
Referring to Daily Mail (Daily Mail) published an article middle Hannah Roberts " olive oil is knocked down number by Italy
The bacterium threat of 100000 trees and (the Olive Oil Under Threat From Bacteria that can soar that fix a price
Which Is Hitting Hundreds Of Thousands Of Trees In Italy--And Could Set
Prices Soaring) " and Agro News on January 9th, 2015 " Italian government urge take action to resist Chinese olive tree
Infectious disease (Italian Government Urged To Take Action To Fight Against Olive Tree
Epidemic)”.As HLB, the treatment of skeleton inside targeting Chinese olive tree is there's almost no.
The HLB disease evil of oranges and tangerines is that crushing incurable bast limits to bacterium infection, and which is damaged/damaged in the whole world
Oranges and tangerines industry.Referring to " the novel bactericidal of control Citrus Huanglongbing pathogen disease of T.R. Gottwald, J.H. Graham et al.
Agent and methods for using them (Novel Bactericides and Application Methods to Control
Huanglongbing Disease of Citrus) ", it discuss that " nutrition treatment is to yellow twig control, fruit quality, bacterium
The general introduction of the inappreciable effect of potency and disease progress ".Referring further to the New York Times (New York Times) Lizette
Alvarez " citrus disease that cannot cure wreaks havoc Florida orchard (Citrus Disease with No Cure is
Ravaging Florida Groves) ", which provides：" we simply need someone to find out how we can kill these trees
In this bacterium ".Referring further to " oranges and tangerines greening forced Buddhist sieve to the Huffington Post (Huffington Post) August in 2013 on 30th
In trust controversial rescue method (Citrus Greening Forces Florida Growers To Trust up to grower
A Controversial Savior) ", it discloses most of commercial growers using foliar nutrition as temporary method come
Prevent their mandarin tree inevitably dead.Referring further to, Tim Spann " oranges and tangerines grower's nutrition spray composite
General introduction (Overview of Citrus Grower Nutritional Spray Compositions) ", it discloses " each
Production of manure business production now is directed to its own program of the foliar nutrition of HLB ".It is further disclosed that " Maury Boyd are mixed
Compound ", which is to do harm to the prototroph foliar spray supported for HLB disease.
Kocide SD (II), also referred to Kocide SD (cupric hydroxide) simultaneously have chemical formula Cu (OH)2, have
Various commercially important purposes, is used as mordant and pigment, for preparing in being included in dyed textiles and paper fiber
Catalyst and other copper compounds, for marine paint and it is used for fungicide and bactericide.Use all over the world every year
Tens million of pounds of Kocide SD pesticides, fungicide, bactericide and biocide, including only California one
Year just uses about 3,000,000 pounds.From fo environmental agriculture system centre (the Center for Environmental
Farming Systems) organic resource guide (the Organic Resource Guide) in " copper products " material
Bulletin, www.cefs.ncsu.edu/newsevents/...product06-copperproducts .pdf are public in page 93
Opened copper be marked on more than on 100 kinds of crops using controlling fungi and bacteriosis.Page 94 is disclosed and is designated as and " show still
Can or good effects copper research " chart.
Such as 2006028853 A1 of PCT Publication WO of Oberholzer, publication date on March 16th, 2006, for steady
Determine pointed by the method (Method for stabilizing copper hydroxide) of Kocide SD, the patent text
Offer the method for disclosing that the various business for Kocide SD (II) are manufactured.U.S. Patent number 2,924,505,3,428,731,3,
628,920 and RE 24,324 disclose and are related to phosphatic method.U.S. Patent number 4,490,337 and 4,808,406 is disclosed
It is related to the method for carbonate；Aftermentioned method is there is provided the product comprising a large amount of copper carbonates in addition to Kocide SD.The patent No. 1,
800,828th, 1,867,357,2,525,242,2,536,096 and 3,635,668 disclose the method for being related to ammonia.U.S. Patent number
2,525,242 and 2,536,096 method is related to the oxidation of copper metal in the presence of ammonia, and U.S. Patent number 4,944,
935 disclose the similar approach for replacing all or part ammonia with ammonium ion.Other methods are being usually the solvable of copper sulphate (II)
Mantoquita starts.U.S. Patent number 4,404,169, european patent number EP 80226 BI and PCT Publication WO 02/083566
A2 describes the method started with COPPER OXYCHLORIDE 37,5 (II).J. Komorowski-Kulik, Zeszyty, Naukowe
Politecniki Sitaskiej, Series:Chemistry 2001,142,59-66 disclose a kind of method, wherein chlorine oxygen
The aqueous suspension for changing copper (II) is contacted with aqueous NaOH in the presence of the glycerine as stabilizer.(referring to
2006028853 A1 of PCT Publication WO of Oberholzer, publication date on March 16th, 2006, for stabilizing copper hydroxide
Method).Oberholzer requires the PCT Publication WO of above-mentioned Oberholzer in U.S. Patent number 7,402,296
The priority of 2006028853 A1.
Nufarm discloses the history of copper fungicide, and how the history of Kocide SD, Kocide SD work, and copper how
Work, the particle diameter of Kocide SD fungicide, and including with regard to its products C hamp Dry Prill, Champ
The more information of 2 Flowable and Champion WP of Formula is (referring to Nufarm Americas Inc., Nufarm
Agriculture Division, " The Copper Champs!”©2002).
DuPont discloses similar product, the DuPont Kocide Blue Xtra with similar information.(DuPont
(Australia) Ltd., the DuPont Kocide Blue Xtra 2006 with BioActive Copper.)
DuPont is disclosed and large quantities of crops treatments is made us using DuPont 3000 fungicides of Kocide/bactericide
A series of giddy many plant diseases.(E.I. DuPont de Nemours & Company Crop
Protection, DuPont 3000 fungicides of Kocide/bactericide, 2006-2011.)
Copper pesticides, fungicide and bactericide are extremely poisonous to fish and aquatile.(Nufarm Americas
Inc., Agt Division, Champ WG Specimen Label).From using copper fungicide, bactericide and killing algae
Agent is the well-known very serious pollution problem of those skilled in the art into the runoff on water route, underground water and ground.For example,
The science American of on March 18th, 2013 (Scientific American), Brian Bienkowski " fish is contaminated
Smell (Fish Cannot Smell In Polluted Waters) is lost in water " disclose：NOAA
(the National Oceanic and Atmospheric Administration, NOAA) northwest fishery science center
The excitology program administrator Nathaniel Scholz of (Northwest Fisheries Science Center) say
" copper is the typical thing of water pollution ", he further points out, and " copper is used intensively as pesticides, fungicide ... its quilt
It is found in automobile, in ship paint, therefore during dock is generally contaminated, and it is generally found in industrial discharge and leaves mining
Near operation.It is the pollutant in both rare agricultural and city." according to Scholz and colleague laboratory research, cruelly
The young age coho for being exposed to low-level copper does not escape predator mountain trout, almost as dog salmon is not exposed.According to
NOAA reports, the problem " may be extensive in many fresh water aquatic environment ".The copper target of low concentration is avoided to help fish
The neuron of predator, but at higher concentrations, copper loss evil smell of the fish to all things.
The Alabama water plan of Alabama water quality information system, FAQ results disclose agricultural and kill harmful organism
Agent is considered potential source of the copper to water pollution, and only has 10,000,000 pounds of copper to be used for agricultural in the U.S. in nineteen ninety to kill very
In microbial inoculum, " many copper are sprayed on plant and are intended to accumulate in direct soil environment, make soil environment to from agricultural
The stormwater runoff of operation is susceptible ".
" grower (the The Grower) " of the Tom Burfield of on January 1st, 2012 discloses that " now, the producer is copper
The impact that its orchard may be had of accumulation and increasingly worry, and they increasingly fear that pathogen shows that day of copper resistant will
Arrive.”
The U.S. Patent number 5 of Schroth in 1993,202,353, the iron increasing of copper-based antifungal and bactericidal and bactericidal composition
(Iron Enhancement of Copper Based Fungicidal and Bactericidal and by force
Bactericidal Compositions), disclose to Kocide SD fungicide addition soluble iron raising Kocide SD and kill
Epiphyte pharmaceutical bactericide activity and reverse the resistance to copper in vitro.Additionally, the U.S. Patent number 5 of nineteen ninety-five Schroth,
385,934, for preventing method (the Methods for Preventing of the copper-based bactericidal composition precipitates of iron content
Precipitation of Copper Based Bactericidal Compositions Containing Iron), it is open
Fe composition addition is added to suppress the salt of aggregation to copper, to prevent aggregation/or deposit from being formed when Fe+3 is added to composition.
Two patents of Schroth need five kinds of component Kocide SD components or fixed copper component altogether, with dry surface-active
Agent, plus soluble iron component, plus liquid surfactant, and addition polymerization collection mortifier salt.Do not receiving any particular theory
Or in the case that mechanism of action is limited, controls or constrained, applicant believes that because copper component and iron component are single, hydroxides
Copper is insoluble, iron components be soluble and it is insoluble have concurrently, the size of agglutination inhibitor, dry surfactant and liquid surfactant
It is extremely different, then it therefore follows that the rate of release and burst size and bioavilability of copper and iron ion be not on plant surface
It is identical or modulated, so that every kind of component may be discharged with different rates and disperse its ion, so as to damage killing for composition
Harmful organism, antifungal, bactericidal and biocidal effect.Additionally, being multiple with different 5 kinds of soluble different independent components
Miscellaneous；The component is copper component, iron component, two kinds of different surfactants and the component for suppressing aggregation.The iron of Schroth
Component is solvable, so that when being sprayed on plant leaf blade, would tend to disappear in rainwater, and therefore is hardly had
It is valuable.This forces Schroth to disclose, for example, page 1463 of paper in Lee and Schroth, discuss before sentence
In, " in these experiments, for persistent purpose is improved, the one of ferric chloride concn is replaced using insoluble iron oxide
Half." referring to Lee, Schroth et al., " the cupric bactericide of iron improvement is to the withered encephalapthy agent walnut ecliptic pole hair bacillus of English walnut
Toxicity improve (Increased Toxicity of Iron-Amended Copper-Containing Bactericides
To the Walnut Blight Pathogen Xanthomonascampestrispv. juglandis) ",
Phytopathology, Ecology ad Epidemiology, american plant pathology meeting (The American
Phytopathological Society), 1993, the 1460-1465 page (herein referred as " Schroth/Lee ").With
Champion to add and notice phytotoxicity on the tree of iron chloride and iron oxide treatment, although not existing between both treatments
The difference of effect.Page 1464 of Schroth/Lee is disclosed：" effect of the copper-iron mixture on nut droop is reduced is extremely
It is modern not yet significantly more preferable than only copper compound " and " although copper compound is highly effective in control leaf droop, they are right
Nut never shows this kind of validity ".On page 1464, Schroth/Lee also draws a conclusion, " although to fixed copper chemical combination
Thing addition iron chloride improves the concentration of free copper ion, but phytotoxicity is not yet observed on the spot.However, work as can not dissolved oxygen
Change when iron is combined with iron chloride and phytotoxicity occur.This reason is unknown, but the iron ion for being likely to and interacting with fixed copper
Long-term release has something to do.This afterclap shows, it is necessary to carries out many work and will lead in duration section to find
Cause bacterium maximum killing and while do not injure delicacy English walnut tissue optimal formulation.”
" effect of the iron on copper compound effect is improved there is provided the new development in the use that there is copper compound for a long time,
And the very big improvement to controlling the such as bacterium of walnut ecliptic pole hair bacillus (X.c.juglandis) should be caused.However, this is by pole
The earth depends on effect that the ecology and novel formulation of copper-resistant bacteria have been set up on population in elimination.”
By its soluble iron on plant leaf blade the failure of " persistence " and unacceptable phytotoxicity altogether, Schroth/
The patent of the paper and Schroth of Lee is substantially not implemented " novel formulation ".When Schroth/Lee is attempted using in its soluble iron
Add insoluble iron to improve during persistent shortage, their paper with disclose their invention if author oneself can not
Carry out.Their appealings to " novel formulation " and their statement " must also carry out many work " illustrate all.Due to which
The complicated property of practice and the problem that plasma diffusing W,Mo, phytotoxicity, persistence, activity lack, rain fastness and imperfection develop,
The disclosure of Schroth is never commercially popular.
Jim Graham, Megan Dewdney is in " the comparison that copper agent is controlled to the canker of Hanas Lake
(Comparison of Copper Formulations for Control of Canker on Hamlin Oranges)”
In disclose 11 kinds of different copper agents 14 kinds of various doses test.The never solvable copper compound of the scope of preparation, compound,
Chelate is to soluble copper chelate.Solid event when treating to harvesting without copper is highly effective.According to Graham, systematicness
The preferred size of intake is the nm of 5 nm to 10.Referring to September in 2014 23 days, Mexico's Jalisco Guadalajara city,
Four phytopathogen international symposium (IV International Symposium of Plant-Pathogenic
Bacteria), University of Florida, UF-IFAS, Graham, Jim control novel bactericide and the applying side of citrus disease
Method (Novel Bactericides and Application Methods to Control Disease of Citrus),
Especially from ending page three, entitled replacement bactericide must be plant-less toxicity and systematic, i.e. can be via leaf
Face applies to be loaded into bast.The insoluble copper tested by Graham does not have the particle diameter of 5-10 nanometers so that Graham is tested
All compounds be unable to carry out systemic administration in plant through pore.
The CuO nano composite materials of the doping zinc with specific dimensions become known in specific area.Eyal Malka etc.
People, (Small 2013, DOI：10.1002/smll.201301081, www.small-journal.com) disclose " by new
The CuO nano composite materials of the doping zinc of grain husk are eradicating pluriresistant bacterium ".Michal Eshed et al., (Advanced
Functional Materials 2014, the 1382-1390 page, www.afm-journal.de) disclose " CuO of doping Zn
Nano composite material shows the streptococcic antibiont film of enhanced resistance to deformation and antibacterial activity compared to nanoscale CuO ".He
Draw a conclusion, " result of this research further emphasizes these novel Zn:CuO nano particles are in the case of microenvironment
As the possibility of biomembranous inhibitor." additionally, Richardson provide " due to little surface area, commodity production
Cupric oxide (cupric oxide (2)) be invalid as fungicide or bactericide；That is, compared to other alkaline coppers (2) chemical combination
Thing, dissolution time are very long ", referring to " copper compound and application manual (the Handbook Of of H. Wayne Richardson
Copper Compounds And Applications) " page 109.Malka and Eshed using this CuO be with above
Richardson indication identical copper.Although known dimensions are the Zn of 30 nm:CuO nano-components, but applicant propose close
Come, the biomembrane and flax dress material and antimicrobial bandage in microenvironment, they are related to agricultural never in any form and kill
Harmful organism agent and systemic plant protective material (protectorant).Additionally, previously the size of disclosed 30 nm is not inconsistent
Close the teaching of the 5-10 nm to citrus plants systemic administration of Graham.
Ploss et al. is disclosed in 7,105,136 B2 of United States Patent (USP) and is entered to apply for agricultural by 5 weight % zinc metal-doped
Plus mantoquita composition, as providing enhanced surface attachment in the case of in the leaves of plants and fruit surface, so as to increase plant
The duration of thing protected effect, and also eliminate and apply again to combine the prior art for needed for the identical level of protection of offer
The related expense of thing and environmental emission.Ploss provides enhanced surface attachment using metallic zinc and does not instruct harmful with regard to killing
Any advantage of biological nature itself.For example, zinc is metal, element and is insoluble in water, with little surface area.
Ploss does not provide teaching or the hint that its metallic zinc kills harmful organism, when " enhanced surface attachment " is substantially taught.This quilt
Personnel with ability domain knowledge are referred to as " assistant agent ".The illustrative examples of the excessive agriculture assistant agent of overwhelming are：Nufarm, it is " auxiliary
Agent product guide (Adjuvants Product Guide) " page 16；And Momentive, Momentive assistant agent, Silwet
With Agrospread assistant agents.The Spraymate adhesives of Nufarm are high-quality sticker, deposition agent and retention agents, are used for
With contact or protect formulation fungicide or with contact and the property taken in insecticide is used together.Spraymate adhesives pass through
Spray droplet is firmly sticked to target surface to increase its attachment.This protection pesticides avoids being washed off by rainwater or sprinkling irrigation.
Spraymate adhesives protect chemical substance also by slowing down degradation rate upon application immediately.Its key benefits are
It improves spray droplet deposition, preserves and protects the drop on target, improves protective agent fungicide and contact insecticide
Performance and life-span.Additionally, pure zinc metallic element and insoluble killing there is huge difference between harmful organism zinc compound.
The content of the invention
The present invention relates to pesticides, antifungal, bactericidal, antipathogen or biocidal composition, the combination
Thing includes：A) at least one biologically inert carrier and；B) at least one doping component, which includes at least the one of such as Kocide SD
Kind of fixed copper compound, the fixed copper is compound doped have selected from iron compound, zinc compound, magnesium compound, calcium compound,
And combinations thereof at least one compound.In preferred embodiments, the doping component only includes iron compound and/or zinc impregnation
Compound is used as only doped compound.Preferably, the doping component is with about 0.5 nm to 30 micron of particle diameter.Iron chemical combination
Thing and/or zinc compound arrive the fixed copper compound for being doped into such as Kocide SD together alone or in combination.In an embodiment party
In case, fixed copper is compound doped insoluble iron compound, such as, wherein fixed copper compound is Kocide SD, and its
Middle fixed copper compound is replaced by insoluble iron compound part.Optionally, surfactant can be included in the composition
In providing more effective preparation.
One advantage of the invention of applicant is that composition includes doping component, and the doping component contains fixed copper chemical combination
Thing and the iron combined on doping component, zinc, magnesium and/or calcium compound.Using doped with iron compound and/or zinc compound
The fixed copper compound of such as Kocide SD, puies forward highly active more cost efficient to provide to have compared to only Kocide SD
Composition.Accordingly, it would be desirable to less copper, obtains the thing reduction for flowing away therewith, and it is less from the pollution of copper.Additionally,
Iron is plant micronutrient, and this composition will supply iron to plant compared with only Kocide SD.Have found a large amount of uses
Copper compound produces Iron Deficiency Chlorosis.In addition, Kocide SD is pesticides, the fungicide/kill so being able adequately determines
Bacteriocin so that the method that the present invention can be applied with current Kocide SD is very similar, more or less directly instead applies,
Except, compared with independent Kocide SD, the amount from the elemental copper of the present invention will be reduced, so as to realize identical or bigger control
Pathogen processed is reduced.In one embodiment of the invention, applicant proposes that the present invention can replace the PCT of Oberholzer special
Kocide SD in the open WO 2006028853 of profit.The composition of the present invention also reverses the resistance to copper, so that anti-copper cause of disease
Body becomes sensitive to copper.
Although the material data list of copper products crop inventory disclosed using copper result badly of page 94, it is believed that application
The present invention of people is improved with regard to this copper activity.In one embodiment, the present invention of applicant may be provided as killing harmful
Biological agent, fungicide, bactericide, antipathogen and biocidal nutrition spraying, with optional extra micronutrient and/
Or optional macronutrient so that there will be the copper-based pesticides and micronutrient all in a kind of preparation
Combination.In another embodiment, the present invention of applicant includes insoluble copper pesticides, fungicide, kills thin
Microbial inoculum and antipathogen and biocide, which can carry out systemic intake by leaf, root and/or trunk injection；And plant
Protective substance, double action pattern is all in a kind of compound.
The teaching in prior art various compounds of copper compound, the mixing of not chemically combined two or more materials
The chelate of thing and copper compound.The compound of the present invention can overwhelming, noticeable and convictively distinguish because
The zinc compound of doping and the iron compound internalization (internalize) of doping are in Kocide SD or other fixed coppers.It is compound
Thing and chelate is combined so that their alienations (externalize) are in Kocide SD or other fixed coppers.Additionally, alienation in
Kocide SD or other fixed coppers generate the unacceptable bigger particulate of systemic administration.
In one embodiment, the doping component of applicant also can be about 5 nm-10 nm sizes and other are bigger micro-
Grain, to provide the plant protective material and systematicness intake thing two that need internally to be delivered through plant phloem and xylem
Person, so as to kill systemic bacterial infection and other systemic viral pathogenic fungis or interior of such as HLB and the difficult foster bacterium of xylem
Portion's pathogen.
The invention of applicant is not obviously replaced and is replaced the whole world of pesticides to use.However, applicant
Invention will be apparent from replacing and replace many current for resisting the height of the harmful organism resistant to existing copper pesticides
Toxicity pesticides.
Additionally, the invention of applicant will reduce the wide of currently resistant to copper pesticides pesticides
Degree, depth and scope, recover sensitiveness and high activity.Additionally, Google search is disclosed for it is known that what is determined kills harmful
Click of the biological agent ill-effect more than 52,000,000.
Additionally, wikipedia discloses " ambient influnence (the Environmental Impact of of pesticides
Pesticides) ", wherein one page is partly the horrible pesticides environmental effect of pesticides classification.By contrast,
The present invention of applicant reduces the needs to being currently used as the amount of the copper of pesticides, and replaces and replace many current
The current high toxicity pesticides being currently in use.With the synthesis agriculture with its well-known toxicity and horrible environmental effect
Industry chemistry pesticides are compared, copper is lesser extent among two kinds of crimes (evils) person.
Brief description：
The preferred embodiments of the invention can combine accompanying drawing and carry out best understanding.It should be noted that the invention is not restricted to shown in accompanying drawing
Definite embodiment, in the accompanying drawings：
Fig. 1 be show an embodiment of the invention doped with the insoluble iron of 15 atom % as dopant hydroxide
The copy of the X-ray diffraction test of copper.There is no extra peak, it was demonstrated that iron is blended in Kocide SD.
Fig. 2 is the saturating of the Kocide SD with 15 atom % Fe2O3 doping iron of an embodiment applicant of the invention
Penetrate electron microscope (TEM) image.The scale of Fig. 2 lower lefts shows the comparable length of 50 nm.The doping iron of 15 atom %Fe
The size of copper hydroxide particulates be for about the nm of 3.5 nm to 9, it is quadruplicate and by transmission electron microscope (TEM) test.
Fig. 3 is the Kocide SD of the doping iron for being illustrated in the one embodiment of the invention according to figure 1 above and Fig. 2
The elementary analysis chart that iron and copper are present in compound.
Fig. 4 is that the Kocide SD of the 15 atom % iron of doping of the extra 10 atom % iron that can not be blended with Kocide SD is caused
Final composition is the X that+10 atom % of Kocide SD of 15 atom % iron of doping did not blended/dissociated iron hydroxide and/or iron oxide
X ray diffraction.
Detailed description of the invention
The present invention is pesticides, antifungal, bactericidal, antipathogen or biocidal composition, and the composition is included：
A) at least one biologically inert carrier；And b) at least one doping component, which is included doped with least one compound at least
A kind of fixed copper compound, at least one compound selected from iron compound, zinc compound, magnesium compound, calcium compound and
Its combination.In preferred embodiments, the doping component only includes iron compound and/or zinc compound as only doping
Compound.For example, Kocide SD can be doped with iron hydroxide, FeOOH or other iron compounds as a kind of doping group
Point.In one embodiment, the fixed copper is compound doped insoluble iron compound, wherein fixed copper compound is not by
Solvable iron compound part replaces.Fixed copper compound of the present invention also comprising the such as Kocide SD doped with zinc compound.
Additionally, the fixed copper compound of such as Kocide SD can be doped with both iron compound and zinc compound.The invention bag of applicant
At least one doping component is included, containing the fixed copper compound doped with iron compound and/or zinc compound, which can be with use only
The method of Kocide SD is similarly used.In one embodiment of the invention, iron compound is entrained on Kocide SD, zinc
It is compound doped on Kocide SD, zinc compound and iron compound are entrained on Kocide SD, individually and are optionally combined
To together, and/or add to other pesticides.Doping component is prepared according to method described herein and to ability
It is easy to understand for field technique personnel.Composition can be resistant to copper with current in the application of many current utilization Kocide SDs
It is many newly kill harmful organism indication (indications) used in.See, e.g., WO2006028853.In preferred embodiment
In, doped with iron hydroxide to provide 15 atom % iron to doping component, this produces black doping component to Kocide SD.Another
In individual preferred embodiment, in doping component, less than 15 atom %, more preferably less than 10 is former for the atomic percentage (atom %) of iron
Sub- %.Due to the biocidal activity for improving, the preferred Kocide SD-iron hydroxide doping component prepared by this method especially may be used
As the active component in pesticides, fungicide, bactericide and biocide.This biocidal activity for improving subtracts
The quantity of few current pathogen resistant to copper pesticides, so as to increase copper resist other bacteriums, fungi, virus,
The scope and range of the activity of mycoplasma and other pathogenic organisms.
Preferably, composition by selected from spreading, spill, spraying, brushing, dipping in, smearing, impregnating, injectable composition to plant vasular ties
In structure and the method for root system system is put on being applied to plant.
Definition
In the context of this application, several terms are by following utilization：
The definition of " pesticides " that use in this application refers to www.epa.gov/agriculture/
The U.S. EPA of tpes.html defines page 1, and which is：" pesticides are for preventing, eliminating, beat back or mitigate any
Any material or the mixture of material of harmful organism.Harmful organism can be insect and class insect biology, mouse and other vertebras
Animal, unwanted plant (weeds), or fungi, bacterium and the virus for causing plant disease.Kill although being generally misinterpreted as only referring to
Insect agent, but term pesticides are also applied to herbicide, fungicide and for controlling the various other of harmful organism
Material.”
The definition of " mixture "：Mixture contains not chemically combined two or more materials.Mixture is different from compound,
Because：Material in mixture can be separated using such as filtration and the physical method for distilling.Mixture has variable composition,
And compound has fixed determination molecular formula.When mixing, individual material keeps its property in the mixture, and if they
Compound is formed, then its property can change.Referring to http://www.chemicool.com/definition/
mixture.html).The example of mixture is 30/30 wg of NORDOX, by NORDOX AS c/o Monterey
AgResources is manufactured, EPA number of registration 48142-7), which is cuprous oxide and zinc oxide mix.
The definition of " element " and " compound "：" element and compound are the pure chemicals found in nature.Element with
Difference between compound be element be by the material of same type atomic building, and compound by determine ratio difference unit
Element is constituted.The example of element includes iron, copper, zinc, hydrogen and oxygen.The example of compound includes water (H2O) and salt (sodium chloride-
NaCl)." referring to http://www.diffen.com/difference/Compound_vs_Element.
The definition of " compound "：" compound is that (ion is not charged by two or more component molecular entities are related to
Lotus), or correspondence chemical species loose association formed molecular entity.Between component bonding generally than in covalent bond more
It is weak.In inorganic chemistry, it is proposed that with term " coordination entity " rather than " compound " (IUPAC inorganic matters name (nineteen ninety).”
Referring to http://www.chemicool.com/definition/complex.html.
The definition of " chelate "：" in fact, chelate is to be bound to the anion (band with more than one attachment site
The group of negative electrical charge) any metal.Chelant means that anion is bonded with the independent site of metal with two or more.Ginseng
See, www.jostchemical.com.
The definition of " dopant "：Dopant is " generally micro to add to pure material to change the impurity of its property." referring to,
www.merriam-webster.com/dictionary/dopant.According to www.freedictionary.com, in " medical science "
Under, term " doping " is used as verb in material science, it is intended that " is added material or other additives or is blended to target
Compound, it is intended that improve or change performance parameter.”
The definition of " fixed copper "：Insoluble or height is insoluble in the copper compound in water.Fixed copper is by H. Wayne
Richardson is further disclosed in the 3rd section of page 97 of " copper compound and application manual ", and " suitable copper compound includes
Fixed copper [Cu+ (OH) 2], Bordeaux mixture (Bordeaux), and other well-known fixed copper compositions, including being disclosed in
Agricultural pest management CRV handbooks (CRV Handbook of Pest Management in Agriculture), the 3rd
Volume, David Pimentel (eds.), those in CRC Press, Boca Raton, FL (1981), the publication is drawing
Mode is expressly incorporated herein " and further disclosed by 196 patents of Sabin ', such as cupric oxide/cuprous oxide, COPPER OXYCHLORIDE 37,5,
Three basic copper sulfate (CuSO4 3Cu(OH)2), diamino oxalic acid copper composition and/or currently used or previously have been used as killing harmful
Any other well-known fixation of biological agent, fungicide, bactericide and algicide or insoluble copper composition.Example
Property example is Kocide SD, cupric oxide/cuprous oxide, copper carbonate, COPPER OXYCHLORIDE 37,5, subcarbonate, copper carbonate particularly including three
The basic copper sulfate of basic copper sulfate, COPPER OXYCHLORIDE 37,5, and its mixture, ammonia formula copper carbonate, basic copper chloride, and other, and its
Mixture.
Term " Kocide SD of doping iron " refers to the copper hydroxide compound doped with iron compound.It is appreciated that
In alternate embodiment, copper hydroxide compound can be replaced by another kind of fixed copper compound as provided herein.
Term " Kocide SD of doping zinc " refers to the copper hydroxide compound doped with zinc compound.It is appreciated that
In alternate embodiment, copper hydroxide compound can be replaced by another kind of fixed copper compound as provided herein.
Term " Kocide SD of doping zinc and iron " refers to the hydroxide doped with both iron compound and zinc compound
Copper compound.It is appreciated that copper hydroxide compound can be by another kind fixed copper as provided herein in an alternate embodiment
Compound replaces.
The example of iron compound includes any insoluble or generally insoluble iron compound.Further example includes
But be not limited to selected from iron hydroxide, FeOOH, iron oxide, glucoferrum, ironic citrate, ferritin, ferrous fumarate and
The iron compound of ferrous sulfate.Most preferably, the iron compound is iron hydroxide and/or FeOOH.
The example of zinc compound includes any insoluble or generally insoluble zinc compound.Further example includes
But it is not limited to the zinc compound selected from zinc hydroxide and zinc oxide.
In preferred embodiments, there is used herein term " insoluble or generally insoluble ".However, being based on industry mark
Standard, applicant propose when being used by those skilled in the art do not exist for such term and do not allow what is changed quantitatively to determine
Justice.Therefore, the term of " indissoluble ", " insoluble ", " highly insoluble ", " slightly soluble ", (" negligible ") etc. is by this area
Technical staff has used decades.See, e.g. at 5,385,934 the 1st hurdle 28-38 rows of US, wherein Emeritus
Milton N. professors Schroth provide " these copper-based compositions of copper-based composition typically aqueous " fixation ", because at this
Solubility of the copper compound used in a little compositions generally with the free Cu+2 of about 1 to 30 ppm in aqueous, and copper
Remainder (and be most) it is insoluble or in chelated forms (that is, " fixed ").1 in such Aquo-composition
Cu+2 to 30 ppm is commonly known as " free copper ", to differentiate it from chelant Cu+2 in these fixed copper compositions or not
Solvable Cu+2." similarly, Santra professors disclose in 8221791 B1 of US " important Consideration be whether by
" solvable " or " insoluble " copper (Cu) is protected for long-term antifungal or bactericidal." solvable " Cu refers to Cu bases salt (such as
Copper sulphate), its complete hydrolysis in water produces ion Cu." insoluble (indissoluble) Cu compounds serve as deposit, and Cu ions are from which
In discharge to plant surface, apply when Cu ions deposit on a surface." in addition, professor Santra is there is provided " currently used
Cu compounds there is the unique set of physics and chemical property.They have difference in the total amount and water solubility of its Ni metal content
It is different.What is fully understood is antibacterial activity by the utilizability depending on solvable (free and reactivity) the Cu ions in preparation.
In existing Cu compounds, three basic copper sulfates and cuprous oxide are least solvable, and Kocide SD is more solvable than COPPER OXYCHLORIDE 37,5.”
And professor Santra further provides for that " several Cu compounds register for management in the U.S. that almost 50 kinds of cereal crops exceed
100 kinds of diseases.Cu compounds represent different degrees of validity biological to any target on any given host.It is full in various degree
The most common form of the Cu of foot these conditions is normal hydrolysate (also referred to " fixation Cu " compound of Cu (1) and Cu (2) salt
" insoluble Cu "：Cupric oxide (1), (Cu2O), COPPER OXYCHLORIDE 37,5 (2) (CuCl2.3Cu(OH)2), three basic copper sulfates (2)
(CuSO43Cu(OH)2), and Kocide SD (Cu (OH)2)." in agricultural chemicals and pesticides security manual
In (Agrochemical and Pesticide Safety Handbook), Michael F Waxman are disclosed " because copper
It is poisonous to plant, so it must be used with low-level or with insoluble form.Due to this reason, using relatively insoluble or
" fixation " mantoquita.These compounds are planted with the low-down speed enough to Fungicidally active rather than will injure or kill host
The concentration of thing is discharging copper ion." Richardson disclose " substitute products are mainly developed in the '20s and the '30s,
And the low soluble copper or fixed copper by applying as powder or suspension " and " must select to have weathering relatively
Resistance the copper compound for tackling fungal spore and the toxic enough copper without adverse effect host of bacterial cell.It is different
Degree meets the normal hydrolysate that the most common form of the copper of these conditions is copper (1) and copper (2) salt：Cupric oxide (1)
(Cu2) (cuprous oxide), COPPER OXYCHLORIDE 37,5 (2) (CuCl2.3Cu(OH)2), three basic copper sulfates (2) (CuSO4.3Cu(OH)2、
With Kocide SD (Cu (OH)2).These " fixed coppers " provide the plant of the applying and reduction better than classical bohr mixture of liquids thing
The advantage of toxicity." these are the terms that Richardson is used below：Page 85, Copper phosphate (Cu3(PO4)2) trihydrate (2) " is insoluble in cold water
In ", page 55, cupric oxide (1), " hardly in water soluble " cupric oxide (2), " are substantially insoluble in water at page the 57th, 58
In ", page 61, Kocide SD (2), " hardly in water soluble ", page 63, basic copper carbonate (2) " is almost insoluble in
In water ", page 69, COPPER OXYCHLORIDE 37,5 (2), " being substantially insoluble in water ", page 79, basic copper sulfate (2) " is insoluble in
In water ", page 83, copper gluconate (2), " in water soluble." Richardson discloses a large amount of copper compounds and such as top exhibition
That what is shown describes its soluble descriptive term.
Those skilled in the art can easily and easily test the invention to determine applicant and realize needed for Disease management
Relatively low-dose, and test to determine the dosage for realizing antagonism copper pathogen Disease management by standard normal.
The Fe2O3 doping of Kocide SD nano particle be from less than 0.01 atom % trace iron pollution to about 40 atom % iron, its
In preferably from about 5-15 atoms % elemental irons, wherein most preferably amount is about 15 atom % elemental irons.Other fixed coppers can be blended and are more than
40 atom % iron and/or zinc.Although can be manufactured using various methods the present invention doping component, applicant used as
The wet chemistry method for indicating in further detail below.It will be understood by those skilled in the art that method disclosed herein is can to put by ratio
It is used for greatly commodity production.Product is dried by the method well-known to chemical art/is evaporated, and is needed
When can be cladded with stabilizer by the well-known method of chemical field personnel." it is used for for example, with reference to Ploss et al. is entitled
The United States Patent (USP) 4,404 of the method (Process For Producing Cupric Hydroxide) of production Kocide SD ",
169.The preferred size of the Kocide SD nano particle of doping iron is submicron order, for about 0.5 nm to 30 micron.More preferably
Size is about 3.5 nm to 15 micron, and another preferred size is about 3.5 nm of nm to 200.Most preferably size is about 3.5 nm
To 10 nm, especially for the particle that leaf protective substance and system activity are integrated.Different size in the practice of the invention
Can be admixed together.
Additionally, the fixed copper compound of such as Kocide SD is general insoluble or height is insoluble in water.Although not receiving
Any particular theory or mechanism of action are limited, control or are constrained, it is generally understood that " free copper penetrates into bacterium and/or fungi
To play its poisonous effect in microorganism." (referring to the U.S. Patent number 5 of Schroth, 202,353, it is copper-based antifungal and kill
The iron of bacterium and bactericidal composition strengthens, 1993).In addition, applicant believes that, active oxygen is generated by fixed copper compound
(ROS) and using addition iron compound come additionally increase ROS generate kill harmful organism.Although additionally, not by any specific
Theoretical or mechanism of action is limited, controls or is constrained, but thinks that the exudate on the surface of plant leaf blade is closed with rainfall and acid rain
Get up to produce the fixed copper compound of dissolving and discharge the sour environment of free copper, this is very active for opposing pathogen.
Therefore, in the case where not limited, controlling or being constrained by these disclosed plant diseases, exist thousands of
Plant disease obeys the control of copper pesticides, and the invention of applicant must strengthen the opposing of copper pesticides
The biocidal effect of these harmful organisms.The composition of the present invention can be used together with any known biologically inert carrier, described
Carrier includes but is not limited to liquid diluent, solid diluent and/or the surfactant of such as water.The combination of the design present invention
Thing is compatible with the physical property of Kocide SD and any other active component, applying method and environmental factor, the environmental factor
May include soil types, moisture and temperature, organic matter, soil texture, current trophic level and chemistry and agriculture field personnel
It is well-known more.
Additionally, in the case where control not being limited by any particular theory or mechanism of action or being constrained, more iron are added
To Kocide SD or other fixed coppers, the present invention will biocidal for harmful organism/firm pesticides.
Additionally, in this paper one embodiment of the invention, the Kocide SD or doping zinc of the doping iron of applicant
The Kocide SD of Kocide SD or doping zinc and iron, can be stablized or overcoating in optional embodiment.U.S. of Ploss et al.
The method that state's patent 4,404,169 discloses the compound of stable applicant's invention.The release of overcoating adjustable activity composition.
In an alternate embodiment, the insoluble iron compound of such as iron hydroxide or FeOOH can be added to hydrogen
Cupric oxide causes the presence of two kinds of single components.In another alternate embodiment, can be by iron hydroxide or other are insoluble
Iron compound adds to the Kocide SD of doping iron, therefore there is also two kinds of single components.In each case, all things
It is combined together for agricultural use in aerosol can.
Additionally, because iron and copper are by agronomy committee of the U.S. (American Society of Agronomy) and Soil Loss section
The generally acknowledged micronutrient that association (Soil Science Society of America) is approved, then it follows that can remain
Remaining micronutrient boron, chlorine, manganese, molybdenum and zinc are easily added to the Kocide SD of doping iron or zinc or iron and zinc, and which will
Iron and/or zinc are used as dopant to produce the doping hydroxide copper and iron fungicide/bactericide/nutrition with micronutrient
Element, applies and/or is injected in the trunk or branch of plant for leaf, trunk, branch and/or root.Additionally, can also individually or
It is grouped together and adds the secondary nutrient of such as calcium, magnesium and sulphur.
The invention of applicant is only known foliar nutrition bactericidal preparation, and which is into bast and kill causes
Candidatus liberibacter category (Candidatus Liberibacter, CLas) bacterium of HLB disease evil.
Because zinc has the determination antimicrobial acivity of opposing bacterium, fungi and other pathogen, applicant suggests that passing through
Further adulterate Kocide SD to strengthen, improve the activity of the Kocide SD of doping iron required for protection with zinc compound, make
It will be doping iron, the Kocide SD of doping zinc or other fixed coppers to obtain finished product.It is appreciated that using the doping of zinc be by zinc impregnation
Compound rather than by using simple metal Zn-ef ficiency providing.
The preferred embodiments of the invention include the hydroxide of the Kocide SD of doping zinc compound and doping iron compound
Both copper.Zinc sulfate is considered as the illustrative examples of the zinc salt of the compound that can be used to manufacture the present invention.Sulphur in zinc sulfate
And nutrient for plants.Applicant is also claimed the Kocide SD for being adulterated with both iron compound and zinc compound together.
In the preparation of the Kocide SD of doping iron, the excessive iron that will be blended more than Kocide SD is left in preparation so that in its preparation
Middle result is the Kocide SD of the doping iron with extra iron hydroxide.It is that hydroxyl is blended during doping that possibility is extraordinary
Iron oxide or other iron compounds.
Have in preparation and do not have extra unblended iron hydroxide doping iron Kocide SD can with have and
The Kocide SD combination of the doping zinc with extra unblended zinc hydroxide or other zinc compounds, and have additionally not
The Kocide SD of doping both the zinc and iron of the zinc and iron of blending also all can be used with its combination or form of mixtures.Other
Available compound is ferrite, and which can be the other alternative compounds that independently use, or can be combined to the doping for also using
The Kocide SD of iron and/or zinc.Ferrite is a class ceramic compound, its by chemical combination with a kind of or other metal
Iron oxide (the Fe that element is combined2O3) composition.Referring to Encyclopaedia Britannica (Encyclopedia Britannica).Referring to Wiki
Encyclopaedia.Illustrative examples are copper zinc-iron oxides (CuZnFe2O4).Referring to Sigma acknowledgements of orders, Order Date April 6 in 2015
Day, O/No. 3013972345.This order also contains copper and iron oxide ferrite (CuFe2O4).Referring to Jeanne Harrell
Sigma technological services reply, " X-ray diffraction result ", the date be on April 14th, 2015.Other ferrites include zinc-iron oxygen
Compound nanometer powder (ZnFe2O4).Referring to American Elements 150416RP03, the date is on April 14th, 2015.Separately
A kind of ferrite is cu ferrite (CuFe2O4).Referring to data sheets of the American Elements to cu ferrite, the date is
On April 16th, 2015.Manganese be there may be in available ferritic composition.It is although not limited, controlling or being constrained, front
It is to think available illustrative examples in the practice of the invention to state ferrite, and can with its own or be previously disclosed in this
Any combinations of other compounds in the practice of invention are combining.Preferably, ferritic size is up to 30 for 0.5 nm
Micron.
These combinations or its mixture are surveyed by routine that is rapid, being able adequately determines well known to the skilled person
Examination, such as in vitro the laboratory high flux screening and/or chamber planting of the compound of enormous amount come directed toward bacteria, fungi,
Virus, mycoplasma and other pathogen are easily tested for.
The composition of the invention of applicant especially orient and be fine suitable as oranges and tangerines yellow twig (HLB) disease and
The treatment of other citrus diseases of citrus bacterial canker disease and such as greasy spot, melanose and Alternaria brown spot, wherein current profit
Use copper.
Additionally, the blade face that the small size of the invention of applicant will improve leaf covers, little particulate as is commonly known in the art
There is provided to plant leaf blade and evenly and preferably cover.The key and distinctive feature of applicant's invention is in preferred embodiment
In its can be extra small insoluble copper and iron compound.Additionally, another critical aspects of the invention of applicant are mixing for applicant
The size of the Kocide SD of miscellaneous iron so that realize the systematicness intake of copper and iron.Applicant is known, applicant this
Particle size is different from any size of any business fixed copper, so as to promotion system is applied.About 90+% in the particulate of applicant
Particulate is for about the nm of 3.5 nm to 10, used as leaf protective substance and systemic pesticides and bactericide.Previous
Insoluble or fixed copper is due to its large scale for most fractional part rather than systematic.The particulate of applicant about 90
+ % is of about the nm of 3.5 nm to 10, to avoid aggregation, and there is optimal probability to carry out promotion system intake.Preferably, Shen
Invention assistant agent/the surfactant to be utilized asked someone is applying.Transmission electron microscope (TEM) figure of the applicant of this paper Fig. 2
Seem to utilize surfactants to what is tested, to guarantee good separation.Think that the typical surface that can be used for applicant's invention is lived
Property agent in the Momentive publications of the Momentive Performance Materials Inc. of New York Albany send out
The Silwet assistant agents applied for agricultural of table and SAG defoamers (Silwet Adjuvants and SAG Antifoams
For Agricultural Applications), described in " the assistant agent product guide " of (2012) and Nufarm.
In description above, preferred embodiment is illustrated using some terms and visual depiction.However, without not
It is necessary limit will exceed it is shown in prior art, by used term or described diagram explaining because term and figure
Show exemplary only, and be not intended to limit the scope of the present invention.Other fixed coppers may also be combined with, doped with iron compound
And/or zinc compound is implementing the present invention.It is understood, therefore, that the Kocide SD that applicant is used for fixed copper compound
Easily can be replaced by other known fixed copper compound.Kocide SD and other fixed coppers can be doped with insoluble iron chemical combination
Thing, and/or doped with insoluble zinc compound.
Further, since in applicant's invention doping component about 3.5-10 nm super-small, shown that Kocide SD adds
Assistant agent/super agent Silwet-77 that disseminates is to Asia diaphorina citri larva --- and the medium (vector) of bacillary HLB is poisonous.
It is considered as further enhancing Kocide SD with applicant's invention that zinc (Zn) and iron (Fe) add or other fixed coppers resists this
Pesticides effect of the adult of the medium/carrier and medium of HLB bacteriums/carrier wood louse larva.
As a result it is that the doping component that applicant invents at least hits the bacterium reason that HLB disease does harm at least three kinds modes as follows
With the difficult foster bacterium infection of xylem and other outer/inner phytopathogens of Chinese olive tree：
A) as the leaf protective substance with above-mentioned fine particle size, i.e. 3.5-10 nm；
B) as leaf and systemic pesticides bactericide/fungicide；That is, 3.5-10 nm；And,
C) as the opposing medium/carrier of HLB bacteriums, Asia diaphorina citri larva and adult and leafhopper, froth worm and foam
The pesticides of the medium of the difficult foster bacterium of cicada, xylem.In addition, the invention of applicant simultaneously treat citrus bacterial canker disease and
Other citrus diseases.
In one embodiment of the invention, the doping component is the fixed copper compound doped with magnesium and/or calcium.
Additionally, the compound of the invention of applicant can strengthen copper with the current collaboration of such as Regalia biology fungicides
The medicament and horticultural oils and such as Silwet-L77 of administration kill harmful organism assistant agent and other pesticides together
Use.
The compound of the present invention is suitable for usual coating, the coating include but is not limited to surfactant, wetting agent,
Stabilizer, dispersant and defoamer.
Applicant claims the iron compound for being doped into Kocide SD of preferred iron hydroxide, preferred zinc hydroxide and mixes
It is miscellaneous enter the zinc compound of Kocide SD, the iron compound being entrained in Kocide SD together and zinc compound.The hydrogen of these doping
Copper oxide compound can be combined with any combinations or its mixture, and can add the extra iron compound of such as iron hydroxide
Or the zinc compound of such as zinc hydroxide.For example, the Kocide SD of the doping iron hydroxide of 15 atom % iron can have free not mixing
The iron hydroxide of conjunction, concentration are the iron hydroxide or more of 5,10,15,20,25,30,35 atom %, together with 15 atom % hydrogen of doping
The Kocide SD of iron oxide.Applicant claim for agricultural kill harmful organism purposes it is all doped with iron compound and/
Or the fixed copper compound of zinc compound.
Embodiment
Following examples illustrate the present invention in the case where the present invention is not limited.It is except having at other instruction, shown
Part and percentage are represented by percentage (atom %).
Embodiment 1：The synthesis of the Kocide SD of doping iron
Carry out the Kocide SD (Fe-Cu (OH) of synthesizing blender iron using wet chemistry method2) composite powder.For the starting material of synthesis
It is six nitric hydrate copper (Cu (NO3)2.6H2O), iron chloride (FeCl3), NaOH (NaOH) and deionized water (H2O).In order to
The Cu (OH) of about 15 atom %Fe of synthesizing blender2, will be 2.43 g, six nitric hydrate copper and 0.4 g iron chloride molten in round-bottomed flask
Solution is in 75 mL deionized waters.Solution is flowed back 3 hours.Once solution is cooled to room temperature, that is, add 0.25 M of 102.2 mL
NaOH.In this stage pH between 10 and 11.Subsequently, solution is transferred to into beaker, and adds the NaOH of another 102.2 mL,
Simultaneously using the high-shear mixer agitating solution under about 1000 rpm.After addition NaOH, pH is between 11 and 12.Use
Once and most which is dried deionized water washing precipitation in atmosphere at last.Synthesize iron-Kocide SD using similar approach multiple
The amount of condensation material, wherein iron is changed to 50 atom % from 20 atom %.
Fig. 1 is the X-ray diffraction test for confirming Kocide SD doped with insoluble iron.Associated system, in Fig. 2 of this paper
In, applicant proposed the data sheet of the Kocide SD of the doping iron of the applicant of the analysis of the 15 atom % ferro elements with Fig. 3.
Fig. 2 discloses the invention of the applicant of the about 90%+ particulates fully tested by TEM, and the invention is produced different from any other business
Product, are very narrow Particle Distributions between 3.5 nm and 10 nm.Fig. 4 is that doping 15 atom % iron+Kocide SD can not be blended
Extra 10 atom % iron cause final prepared product be adulterate 15 atom % iron+10 atom % of Kocide SD do not blend/dissociate hydrogen-oxygen
Change the X-ray diffraction of iron and/or iron oxide.
Embodiment 2：The synthesis of the Kocide SD of doping iron-zinc
Carry out the Kocide SD (Fe-Zn-Cu (OH) of synthesizing blender iron-zinc using wet chemistry method2) composite powder.Rising for synthesis
Beginning material is six nitric hydrate copper (Cu (NO3)2.6H2O), iron chloride (FeCl3), Zinc vitriol (ZnSO4.7H2O), hydrogen-oxygen
Change sodium (NaOH) and deionized water (H2O).For the Cu (OH) of about 7.5 atom %Fe-7.5 atom % Zn of synthesizing blender2, in round bottom
2.43 g, six nitric hydrate copper, 0.21 g Zinc vitriols and 0.19 g iron chloride are dissolved in into 75 mL deionizations in flask
In water.Solution is flowed back 3 hours.Once solution is cooled to room temperature, that is, add the 0.25 M NaOH of 102.2 mL.Subsequently, will be molten
Liquid is transferred to beaker, and adds the NaOH of another 102.2 mL, while being stirred using the high-shear mixer under about 1000 rpm
Mix solution.Once and most which is dried in atmosphere at last to make to be washed with deionized precipitation.Synthesized using similar approach iron-
Other modifications of zinc-Kocide SD composite.
Embodiment 3：The synthesis of the Kocide SD of doping zinc
Carry out the Kocide SD (Zn-Cu (OH) of synthesizing blender zinc using wet chemistry method2) composite powder.For the starting material of synthesis
It is six nitric hydrate copper (Cu (NO3)2.6H2O), Zinc vitriol (ZnSO4.7H2O), NaOH (NaOH) and deionized water
(H2O).For the Cu (OH) of about 15 atom %Zn of synthesizing blender2, by 2.43 g, six nitric hydrate copper, 0.42 g in round-bottomed flask
Zinc vitriol is dissolved in 75 mL deionized waters.Solution is flowed back 3 hours.Once solution is cooled to room temperature, that is, add
The 0.25 M NaOH of 102.2 mL.Subsequently, solution is transferred to into beaker, and adds the NaOH of another 102.2 mL, while making
With the high-shear mixer agitating solution under about 1000 rpm.Make to be washed with deionized precipitation once and most at last its in sky
It is dried in gas.Synthesize other modifications of zinc-Kocide SD composite using similar approach.
Although disclosing the present invention according to a preferred embodiment, in situation without departing from the spirit and scope of the present invention
Under, further know to carry out the present invention other modifications.
Claims (30)
1. one kind kills harmful organism, antifungal, bactericidal, antipathogen or biocidal composition, and which includes：
A) at least one biologically inert carrier；With
B) at least one ferrite, which contains copper, zinc or iron, individually or with any combinations, and,
C) optionally, at least one doping component, which includes at least one fixed copper chemical combination doped with least one compound
Thing, at least one compound is selected from iron compound, zinc compound, magnesium compound, calcium compound and combinations thereof；
D) wherein described ferrite and the optionally doped component are with about 0.5 nm to 30 micron of particle diameter.
2. the composition described in claim 1, wherein the fixed copper compound selected from Kocide SD, COPPER OXYCHLORIDE 37,5, cupric oxide,
Basic copper carbonate, basic copper sulfate, three basic copper sulfates, cuprous oxide, copper citrate, cupric phosphate, cuprobam, covellite, ore deposit
Thing warringtonite, langite, malachite, cornetite, liebethenite, pseudolibethenite, pseudomalachite, antleritel, covellite, iodine copper
Ore deposit, cuprite, vitreous copper, Rogojski salt, warringtonite, chalcocyanite, nantokite, dolerophanite, ammonia formula copper carbonate, alkali formula chlorine
Change copper, and combinations thereof.
3. the composition described in claim 2, wherein the fixed copper compound is Kocide SD.
4. the composition described in claim 1, wherein the iron compound is insoluble or generally insoluble iron compound.
5. the composition described in claim 4, wherein the iron compound is selected from iron hydroxide, FeOOH, iron oxide, Portugal
People's Holo-transferrin of grape sugar iron, ironic citrate, ferritin, ferrous fumarate, ferrous sulfate and iron saturation.
6. the composition described in claim 1, wherein the zinc compound is insoluble or generally insoluble zinc compound.
7. the composition described in claim 6, wherein the zinc compound is selected from zinc hydroxide and zinc oxide.
8. the composition described in claim 1, wherein the fixed copper compound is Kocide SD and the iron compound is
Iron hydroxide and/or FeOOH.
9. the composition described in claim 1, wherein the doping component is included from being entrained in the fixed copper compound
The iron compound about 15 atom % iron.
10. the composition described in claim 1, wherein the particle diameter of the doping component is for about the nm of 3.5 nm to about 200.
Composition described in 11. claims 10, wherein the particle diameter of the doping component is for about the nm of 3.5 nm to about 10.
A kind of 12. methods for controlling bacterium in plant, methods described include；
Apply bactericidal composition according to claim 1 to the bacterium.
Method described in 13. claims 12, wherein the bactericidal composition includes consolidating for the particle diameter with about 3.5-10 nm
Determine copper compound.
Method described in 14. claims 13, which includes applying yellow twig (HLB) of the bactericidal composition for oranges and tangerines
The treatment of disease and citrus bacterial canker disease and other citrus diseases.
Method described in 15. claims 13, which includes applying xylem hardly possible of the bactericidal composition for Chinese olive tree
The treatment of foster bacteriosis.
A kind of 16. methods for controlling harmful organism, methods described include；
Apply according to claim 1 to kill pest composition to the harmful organism or its growth habitat.
Method described in 17. claims 12, wherein the bactericidal composition by selected from spreading, spill, spraying, brushing, dipping in, smearing,
Dipping, inject the composition into plant vasular structure and apply to root system system method come be applied to the bacterium or its
Growth habitat.
Composition described in 18. claims 1, wherein the doping component is only doped with iron compound and/or zinc compound.
Composition described in 19. claims 1, which is further comprising c)：With at least one iron compound for a) and b) mixing.
Composition described in 20. claims 19, wherein the iron compound is at least one insoluble or generally insoluble
Iron compound.
Composition described in 21. claims 20, wherein the iron compound is iron hydroxide.
Composition described in 22. claims 1, which is further comprising d)：Close with least one zinc impregnation for a), b) and c) mixing
Thing.
Composition described in 23. claims 22, wherein at least one zinc compound is insoluble or generally insoluble
Zinc compound.
Composition described in 24. claims 23, wherein at least one zinc compound is zinc hydroxide or zinc oxide.
Composition described in 25. claims 1, which is further comprising d)：With at least one zinc compound for a) and b) mixing.
Composition described in 26. claims 25, wherein at least one zinc compound is insoluble or generally insoluble
Zinc compound.
Composition described in 27. claims 26, wherein at least one zinc compound is zinc hydroxide or zinc oxide.
28. claims 16 for the method that controls harmful organism, wherein the harmful organism is at least one fungi, and
The step of methods described is included to the fungi or its growth habitat applying Fungicidal composition according to claim 1.
29. claims 16 for the method that controls harmful organism, wherein the harmful organism is at least one to carry disease
Medium, and methods described includes to the growth habitat of the carrier applying according to claim 1 to kill harmful
The step of biological composition.
Method described in 30. claims 29, wherein the medium for carrying disease is wood louse.
Applications Claiming Priority (17)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201462002330P | 2014-05-23 | 2014-05-23 | |
| US62/002330 | 2014-05-23 | ||
| US201462003528P | 2014-05-27 | 2014-05-27 | |
| US62/003528 | 2014-05-27 | ||
| US201462020247P | 2014-07-02 | 2014-07-02 | |
| US62/020247 | 2014-07-02 | ||
| US201462021819P | 2014-07-08 | 2014-07-08 | |
| US62/021819 | 2014-07-08 | ||
| US201462094775P | 2014-12-19 | 2014-12-19 | |
| US62/094775 | 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 |
| US14/625405 | 2015-02-18 | ||
| US14/674607 | 2015-03-31 | ||
| 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 |
| US14/689675 | 2015-04-17 | ||
| PCT/US2015/031702 WO2015179478A1 (en) | 2014-05-23 | 2015-05-20 | Potentiation of fixed coppers and other pesticides containing copper and supplementing plant nutrition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106535640A true CN106535640A (en) | 2017-03-22 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580039745.1A Pending CN106535640A (en) | 2014-05-23 | 2015-05-20 | Potentiation of fixed coppers and other pesticides containing copper and supplementing plant nutrition |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP3145314A4 (en) |
| CN (1) | CN106535640A (en) |
| AU (1) | AU2015264306B2 (en) |
| EA (1) | EA033186B1 (en) |
| MA (1) | MA40010A (en) |
| MX (1) | MX358397B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024008221A1 (en) * | 2022-07-04 | 2024-01-11 | Agra Group A.S. | Fertilizer containing a source of copper |
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| US5202353A (en) * | 1991-01-22 | 1993-04-13 | The Regents Of The University Of California | Iron enhancement of copper based fungicidal and bactericidal compositions |
| US7105136B2 (en) * | 2001-09-28 | 2006-09-12 | Spiess-Urania Chemicals Gmbh | Controlled morphogenesis of copper salts |
| US20130189364A1 (en) * | 2004-07-09 | 2013-07-25 | Robert Sabin | Compositions and methods of potentiating adjuvant pharmaceuticals targeting latent viral infections |
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| DE4142432A1 (en) * | 1991-12-20 | 1993-06-24 | Wacker Chemie Gmbh | METHOD FOR PRODUCING COPPER POWDER |
| JPH08290990A (en) * | 1995-04-19 | 1996-11-05 | Hitachi Metals Ltd | Magnetized fertilizer |
| 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 (en) * | 1997-05-02 | 2008-01-23 | 澄男 宮川 | Plant disease control agent and plant disease control method using ferrite suspension |
| JP2001269051A (en) * | 2000-03-27 | 2001-10-02 | Hida Sangyo Kk | Culture soil, and apparatus and method for manufacture thereof |
| US6877275B2 (en) * | 2002-02-19 | 2005-04-12 | Engelhard Corporation | Method of weed control |
| 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 |
| WO2011017137A2 (en) * | 2009-08-03 | 2011-02-10 | Alnylam Pharmaceuticals, Inc. | Methods and compositions for treating insects |
| WO2012135016A2 (en) * | 2011-03-25 | 2012-10-04 | North Carolina State University | Inhibition of bacterial biofilms and microbial growth with imidazole derivatives |
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2015
- 2015-05-20 CN CN201580039745.1A patent/CN106535640A/en active Pending
- 2015-05-20 EP EP15796119.4A patent/EP3145314A4/en not_active Withdrawn
- 2015-05-20 AU AU2015264306A patent/AU2015264306B2/en not_active Ceased
- 2015-05-20 MA MA040010A patent/MA40010A/en unknown
- 2015-05-20 MX MX2016015322A patent/MX358397B/en active IP Right Grant
- 2015-05-20 EA EA201692393A patent/EA033186B1/en not_active IP Right Cessation
Patent Citations (3)
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|---|---|---|---|---|
| US5202353A (en) * | 1991-01-22 | 1993-04-13 | The Regents Of The University Of California | Iron enhancement of copper based fungicidal and bactericidal compositions |
| US7105136B2 (en) * | 2001-09-28 | 2006-09-12 | Spiess-Urania Chemicals Gmbh | Controlled morphogenesis of copper salts |
| US20130189364A1 (en) * | 2004-07-09 | 2013-07-25 | Robert Sabin | Compositions and methods of potentiating adjuvant pharmaceuticals targeting latent viral infections |
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| LEE ET AL.: "Increased Toxicity of Iron-Amended Copper-Containing Bactericides to the Walnut Blight Pathogen Xanthomonas campestris pv.juglandis", 《ECOLOGY AND EPIDEMIOLOGY》 * |
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|---|---|---|---|---|
| WO2024008221A1 (en) * | 2022-07-04 | 2024-01-11 | Agra Group A.S. | Fertilizer containing a source of copper |
Also Published As
| Publication number | Publication date |
|---|---|
| MX358397B (en) | 2018-08-17 |
| MX2016015322A (en) | 2017-05-10 |
| EA033186B1 (en) | 2019-09-30 |
| AU2015264306A1 (en) | 2016-12-15 |
| EP3145314A4 (en) | 2017-05-17 |
| MA40010A (en) | 2015-11-26 |
| EP3145314A1 (en) | 2017-03-29 |
| EA201692393A1 (en) | 2017-05-31 |
| AU2015264306B2 (en) | 2017-07-27 |
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