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WO2000060940A1 - Dispersions aqueuses de produits chimiques agricoles - Google Patents

Dispersions aqueuses de produits chimiques agricoles Download PDF

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Publication number
WO2000060940A1
WO2000060940A1 PCT/US2000/009568 US0009568W WO0060940A1 WO 2000060940 A1 WO2000060940 A1 WO 2000060940A1 US 0009568 W US0009568 W US 0009568W WO 0060940 A1 WO0060940 A1 WO 0060940A1
Authority
WO
WIPO (PCT)
Prior art keywords
dispersion
pesticide
mill
weight
pesticidal
Prior art date
Application number
PCT/US2000/009568
Other languages
English (en)
Inventor
Robert M. Strom
D. Claude Price
Steven D. Lubetkin
Original Assignee
Dow Agrosciences Llc
The Dow Chemical Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Agrosciences Llc, The Dow Chemical Company filed Critical Dow Agrosciences Llc
Priority to AU42257/00A priority Critical patent/AU4225700A/en
Publication of WO2000060940A1 publication Critical patent/WO2000060940A1/fr

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P3/00—Fungicides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P7/00—Arthropodicides
    • A01P7/02—Acaricides

Definitions

  • the present invention relates to an aqueous dispersion of particles having pesticidal activity.
  • the present invention relates to dispersions of micron- or sub-micron- sized particles.
  • the present invention provides a stable, aqueous, pesticidal dispersion comprising from 1 to 60 percent by weight of the aqueous dispersion of a pesticide having a water solubility of less than 0.1 percent, having a crystalline phase, and having a melting point sufficiently high so as not to melt during milling, and from 1 to 30 percent by weight based on the weight of the pesticide of a surface active agent, wherein the dispersion has a volume mean diameter particle size of not greater than 500 nanometers (nm).
  • the present invention is a method of preparing a stable aqueous pesticidal dispersion comprising the steps of:
  • the present invention addresses a need in the art by providing aqueous dispersions of submicron-sized particles having high bioavailability and no or minimal amounts of an ancillary organic solvent.
  • the stable aqueous dispersion of the pesticide can be prepared by wet milling an aqueous dispersion of the pesticide in the presence of grinding media and a surface active agent.
  • a sur ace active agent means one or more surface active agents.
  • the preparation is carried out in such a manner so as to produce a dispersion of non-agglomerating or interacting particles having a volume median diameter of not greater than 500 nm, more preferably not greater than 400 nm, most preferably not greater than 200 nm, as measured by a Horiba model LA-700 particle size analyzer or an equivalent method.
  • An example of such preparation can be found in U.S. Patent 5,145,684.
  • the pesticide is a solid at ambient temperature, and has a melting point that is sufficiently high that the pesticide does not melt through the milling process.
  • the pesticide is preferably crystalline, and is substantially water insoluble.
  • substantially water insoluble is used herein to refer to a pesticide that has a solubility in water of less than 0.1 %, and most preferably less than 0.01 %. It is understood that the water solubilities of many pesticides are pH-dependent, as a result of the functional groups they contain. Thus, pesticides with carboxylic acid groups or with sulfonamide or sulfonylurea groups, for example, may meet the solubility requirements at low pH but may be too soluble at high pH. The pH of the aqueous dispersion can be adjusted to ensure substantial insolubility of these pesticides.
  • Pesticides include herbicides, insecticides, and fungicides.
  • classes of compounds that have herbicidal activity and meet the solubility, crystallinity and melting point requirements include, but are not restricted to, imidazolinones such as imazaquin, sulfonylureas such as chlorimuron-ethyl, triazolopyrimidine sulfonamides such as flumetsulam, aryloxyphenoxy propionates such as quizalofop ethyl, aryl ureas such as isoproturon and chlorotoluron, triazines such as atrazine and simazine, aryl carboxylic acids such as picloram, aryloxy alkanoic acids such as MCPA, chloroacetanilides such as metazachlor, dintroanilines such as oryzalin, pyrazoles such as pyrazolynate and diphenyl ethers such as bifenox.
  • classes of compounds that have insecticidal activity and meet the solubility, crystallinity and melting point requirements include, but are not restricted to, benzoyl ureas such as hexaflumuron, diacylhydrazines such as tebufenozide, carbamates such as carbofuran, pyrethroids such as a/p/?a-cypermethrin, organophosphates such as phosmet, triazoles, and natural products such as spinosyns.
  • classes of compounds that have fungicidal activity and meet the solubility, crystallinity and melting point requirements include, but are not restricted to, morpholines such as dimethomorph, phenylamides such as benalaxyl, azoles such as hexaconazole, strobilurins such as azoxystrobin, phthalonitriles such as chlorothalonil and phenoxyquinolines such as quinoxyfen.
  • the surface active agent may be anionic, cationic, or nonionic, or combinations of cationic and nonionic or anionic and nonionic. Generally, and to a point, higher concentrations of surface active agent result in smaller particle size.
  • suitable classes of surface active agents include, but are not limited to, anionics such as alkali metal fatty acid salts, including alkali metal oleates and stearates; alkali metal lauryl sulfates; alkali metal salts of diisooctyl sulfosuccinate; alkyl aryl sulfates or sulfonates, alkali metal alkylbenzene sulfonates, such as dodecylbenzene sulfonate; and alkali metal soaps; cationics such as long chain alkyl quaternary ammonium surfactants including cetyl trimethyl ammonium bromide; or nonionics such as ethoxylated derivatives of
  • the concentration of the surface active agent is not less than 1 %, and not more than 30% by weight, based on the total weight of the pesticide and the surface active agent.
  • the surface active agent is preferably adsorbed onto the surface of the pesticide particle in accordance with U.S. Patent 5,145,684.
  • the stable aqueous dispersions of the present invention can be prepared in the following manner. First, the pesticide is dispersed, preferably as a relatively coarse material having a particle size of less than 100 ⁇ m.
  • Such a degree of coarseness can be achieved, for example, by sieving.
  • the coarse material is dispersed in an aqueous solution containing the surface active agent and preferably an antifoaming agent such as Antifoam B (Dow Corning) to form a premix.
  • the premix can then be ground mechanically to reduce further the particle size of the pesticide.
  • the concentration of the pesticide is in the range of from 1 % to 60%, more preferably to 30%, by weight based on the weight of the pesticide and the water. Attrition time can vary widely depending on the mechanical means used and the choice and concentration of surfactant.
  • Examples of mechanical means to reduce the size of the agricultural product include a ball mill, a roller miller, an attritor mill, a sand mill, a bead mill, and a Cowles type mixer.
  • the grinding media used for particle size reduction preferably include substantially spheroidal shaped particles having an average size of less than 3 mm.
  • suitable media material include ZrO stablized with magnesia, zirconium silicate, glass, stainless steel, polymeric beads, alumina, and titania, although nature of the material is not believed to be critical.
  • the particles are reduced in size at any suitable temperature where the agricultural product is stable. Typically, processing temperatures are not greater than the boiling point of water and below the melting point of the solid, but ambient temperature is preferred.
  • the final volume mean diameter particle size is less than 500 microns, more preferably less than 400 nm, and most preferably less than 200 nm.
  • the stable aqueous dispersions are preferably diluted with water, then applied to a site in a pesticidally effective amount.
  • the stable aqueous dispersion of the present invention provides a means to prepare one-part formulations of different pesticides which are not only compatible with each other, but incompatible or unstable in each other's presence as well. For example, it may be desirable to combine a certain pesticide with a certain herbicide for a particular application but for the fact that the two (in solution, for example) react with each other faster than they can be applied to the desired site.
  • these different and incompatible pesticides can coexist, at least temporarily, since they are shielded from each other from reacting rapidly, so that an end user can mix the incompatible pesticides together and apply them to a site before their efficacy is significantly diminished.
  • the fine particle size suspensions prepared according to the methods of the present invention have enhanced biological efficacy as a result of their increased surface area as compared to suspensions of greater particle size.
  • Enhanced biological efficacy is particularly important in cases where pesticide solubility is very low and thus, biological availability is restricted.
  • the sample was milled for 90 minutes and the particle size (pre-mill) was measured to be 1520 nm.
  • a portion of the pre- mill (1 g) was removed and added to a fresh vial, at which time 1 drop of the antifoaming agent was added. Milling was continued for 3 hours, after which the particle size was determined to be 183 nm.
  • Example 1 was repeated except that styrene/divinylbenzene copolymer beads (475 ⁇ m diameter) were used instead of stainless steel beads. After the pre-mill was subjected to 120 minutes of additional milling, the particle size was determined to be 148 nm.
  • Example 3 Preparation of a Stable Aqueous Nano-Dispersion Using Alternative Surfactant Package Example 1 was repeated except that the aqueous phase was prepared using Atlox 4991 surfactant (6%), Atlox 4913 surfactant (12%), deionized water (78%) and Antifoam B (4%). After the pre-mill was subjected to 270 minutes of additional milling, the particle size was determined to be 163 nm.
  • Example 1 Spinosad insecticide was milled. Again, Example 1 conditions were used except that the dispersion was prepared using the surfactant package described in Example 3. After the pre-mill was subjected to 195 minutes of additional milling, the particle size was determined to be 297 nm.
  • Example 1 The conditions of Example 1 were repeated except the Spinosad was used instead of the triazole. After the pre-mill was subjected to 315 minutes of additional milling, the particle size was found to be 281 nm.
  • Atrazine herbicide (1 g) was placed in a 20 mL polyethylene scintillation vial along with an aqueous phase (9 g) prepared by combining lconol TD-6 surfactant (0.5 g) deionized water (8 g) and Antifoam B (0.5 g). About 10 g of 1/8" stainless steel ball bearings were added, and the vial was sealed and placed on the mill. The particles were milled for 30 minutes, after which time a portion of the pre-mill (1 g) was removed and placed in a fresh vial along with fresh ball bearings (10 g) and 1 drop of Antifoam B. The vial was sealed and subjected to milling for an additional 105 minutes. Then Nipol 2782 surfactant (0.2 g) was added and milling was continued for an additional 2 hours. The particle size was measured to be 167 nm.
  • Epoxiconazole was placed in a 20 mL polyethylene scintillation vial along with an aqueous phase prepared from Soprophor FL surfactant (0.2 g), Empicol LX 28 (0.3 g), deionized water (8.45 g), and Antifoam B agent (0.05 g). About 10 g of 1/8" steel ball bearings were added, and the vial was sealed and placed on the mill for 30 minutes, after which time, a portion of the pre-mill (1 g) was removed and placed in a fresh vial along with fresh ball bearings (10 g) and 1 drop of Antifoam B. The vial was sealed and subjected to milling for an additional 405 minutes. The particle size was measured to be 314 nm.
  • the amount required to kill 50% of the spider mites is substantially reduced at smaller VMD.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Environmental Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Zoology (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Insects & Arthropods (AREA)
  • Microbiology (AREA)
  • Mycology (AREA)
  • Dispersion Chemistry (AREA)
  • Agronomy & Crop Science (AREA)
  • Toxicology (AREA)
  • Dentistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

La biodisponibilité d'un pesticide peut être accrue par la formulation du pesticide sous la forme d'une dispersion aqueuse de particules présentant un diamètre moyen maximal de 500 nm. Une telle formulation procure l'avantage supplémentaire de réduire sensiblement ou d'éliminer le recours à des solvants organiques. Par ailleurs, la dispersion aqueuse stable procure un moyen de préparation d'une simple formulation d'une pluralité de pesticides qui auraient été instables en présence des uns et des autres.
PCT/US2000/009568 1999-04-12 2000-04-10 Dispersions aqueuses de produits chimiques agricoles WO2000060940A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU42257/00A AU4225700A (en) 1999-04-12 2000-04-10 Aqueous dispersions of agricultural chemicals

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US12899499P 1999-04-12 1999-04-12
US60/128,994 1999-04-12

Publications (1)

Publication Number Publication Date
WO2000060940A1 true WO2000060940A1 (fr) 2000-10-19

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2000/009568 WO2000060940A1 (fr) 1999-04-12 2000-04-10 Dispersions aqueuses de produits chimiques agricoles

Country Status (3)

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AR (1) AR023447A1 (fr)
AU (1) AU4225700A (fr)
WO (1) WO2000060940A1 (fr)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6664237B1 (en) 1999-08-12 2003-12-16 Eli Lilly And Company Oral treatment of companion animals with ectoparasiticidal spinosyns
US6727228B2 (en) 2001-04-25 2004-04-27 Johnson & Johnson Consumer Companies, Inc. Pediculicidal and ovacidal treatment compositions and methods for killing head lice and their eggs
US6927210B1 (en) 1999-08-12 2005-08-09 Eli Lilly And Company Ectoparasiticidal aqueous suspension formulations of spinosyns
US6933318B1 (en) 1999-08-12 2005-08-23 Eli Lilly And Company Topical organic ectoparasiticidal formulations
US6955818B1 (en) 1999-12-02 2005-10-18 Eli Lilly And Company Pour-on formulations
WO2007130548A3 (fr) * 2006-05-05 2008-03-20 Phibro Tech Inc Procédé de traitement de cultures à l'aide de chlorthalonil submicronique
EP1987716A1 (fr) * 2007-05-04 2008-11-05 Troy Technology Corporation, Inc. Concentrés de dispersion, activés de façon antimicrobienne et à base d'eau
US7652048B2 (en) 2007-05-04 2010-01-26 Troy Corporation Water-based, antimicrobially active, dispersion concentrates
US7772194B2 (en) 2001-09-17 2010-08-10 Eli Lilly And Company Pesticidal formulations
CN101984814A (zh) * 2010-12-17 2011-03-16 沈阳市和田化工有限公司 多杀菌素水剂型农药
EP2255621A3 (fr) * 2004-03-14 2012-05-30 Makhteshim Chemical Works Limited Procédé permettant de préparer des compositions pésticides contenant des nanoparticules et composition obtenue selon ce procédé
US8871277B2 (en) 2003-06-17 2014-10-28 Osmose, Inc. Particulate wood preservative and method for producing the same
US9314030B2 (en) 2004-05-17 2016-04-19 Koppers Performance Chemicals Inc. Particulate wood preservative and method for producing same
EP3081084A1 (fr) * 2015-04-16 2016-10-19 Rotam Agrochem International Company Limited Compositions submicroniques comprenant de l'imidaclopride et de l'abamectine
US9775350B2 (en) 2004-10-14 2017-10-03 Koppers Performance Chemicals Inc. Micronized wood preservative formulations in organic carriers

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4430336A (en) * 1979-12-04 1984-02-07 Basf Aktiengesellschaft N-Substituted 2-methylnaphthylamides, their preparation and fungicides containing these compounds
US4832950A (en) * 1984-08-29 1989-05-23 Kao Corporation Antimicrobial suspensions and antimicrobial hair treatment compositions
EP0499299A2 (fr) * 1991-01-25 1992-08-19 NanoSystems L.L.C. Nanoparticules de médicaments à surface modifiée
GB2267825A (en) * 1992-05-26 1993-12-22 Dowelanco Herbicide microemulsion concentrate
WO1995007614A1 (fr) * 1993-09-15 1995-03-23 Dowelanco Stockage et dilution de dispersions aqueuses stables
EP0683979A2 (fr) * 1994-05-25 1995-11-29 American Cyanamid Company Suspension concentrée des arylpyrroles insecticides et acarizides
WO1999048359A1 (fr) * 1998-03-20 1999-09-30 Dow Agrosciences Llc Adjuvants pesticides

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4430336A (en) * 1979-12-04 1984-02-07 Basf Aktiengesellschaft N-Substituted 2-methylnaphthylamides, their preparation and fungicides containing these compounds
US4832950A (en) * 1984-08-29 1989-05-23 Kao Corporation Antimicrobial suspensions and antimicrobial hair treatment compositions
EP0499299A2 (fr) * 1991-01-25 1992-08-19 NanoSystems L.L.C. Nanoparticules de médicaments à surface modifiée
GB2267825A (en) * 1992-05-26 1993-12-22 Dowelanco Herbicide microemulsion concentrate
WO1995007614A1 (fr) * 1993-09-15 1995-03-23 Dowelanco Stockage et dilution de dispersions aqueuses stables
EP0683979A2 (fr) * 1994-05-25 1995-11-29 American Cyanamid Company Suspension concentrée des arylpyrroles insecticides et acarizides
WO1999048359A1 (fr) * 1998-03-20 1999-09-30 Dow Agrosciences Llc Adjuvants pesticides

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6927210B1 (en) 1999-08-12 2005-08-09 Eli Lilly And Company Ectoparasiticidal aqueous suspension formulations of spinosyns
US6933318B1 (en) 1999-08-12 2005-08-23 Eli Lilly And Company Topical organic ectoparasiticidal formulations
US6664237B1 (en) 1999-08-12 2003-12-16 Eli Lilly And Company Oral treatment of companion animals with ectoparasiticidal spinosyns
US6955818B1 (en) 1999-12-02 2005-10-18 Eli Lilly And Company Pour-on formulations
US6727228B2 (en) 2001-04-25 2004-04-27 Johnson & Johnson Consumer Companies, Inc. Pediculicidal and ovacidal treatment compositions and methods for killing head lice and their eggs
US7030095B2 (en) 2001-04-25 2006-04-18 Johnson & Johnson Consumer Companies, Inc. Pediculicidal and ovacidal treatment compositions and methods for killing head lice and their eggs
US7772194B2 (en) 2001-09-17 2010-08-10 Eli Lilly And Company Pesticidal formulations
US8048861B2 (en) 2001-09-17 2011-11-01 Eli Lilly And Company Pesticidal formulations
US8871277B2 (en) 2003-06-17 2014-10-28 Osmose, Inc. Particulate wood preservative and method for producing the same
EP2255621A3 (fr) * 2004-03-14 2012-05-30 Makhteshim Chemical Works Limited Procédé permettant de préparer des compositions pésticides contenant des nanoparticules et composition obtenue selon ce procédé
US9314030B2 (en) 2004-05-17 2016-04-19 Koppers Performance Chemicals Inc. Particulate wood preservative and method for producing same
US9775350B2 (en) 2004-10-14 2017-10-03 Koppers Performance Chemicals Inc. Micronized wood preservative formulations in organic carriers
WO2007130548A3 (fr) * 2006-05-05 2008-03-20 Phibro Tech Inc Procédé de traitement de cultures à l'aide de chlorthalonil submicronique
US7652048B2 (en) 2007-05-04 2010-01-26 Troy Corporation Water-based, antimicrobially active, dispersion concentrates
EP1987716A1 (fr) * 2007-05-04 2008-11-05 Troy Technology Corporation, Inc. Concentrés de dispersion, activés de façon antimicrobienne et à base d'eau
CN101984814A (zh) * 2010-12-17 2011-03-16 沈阳市和田化工有限公司 多杀菌素水剂型农药
EP3081084A1 (fr) * 2015-04-16 2016-10-19 Rotam Agrochem International Company Limited Compositions submicroniques comprenant de l'imidaclopride et de l'abamectine

Also Published As

Publication number Publication date
AR023447A1 (es) 2002-09-04
AU4225700A (en) 2000-11-14

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