WO2002078442A2 - Co-formulation d'herbicide soluble dans l'huile et d'herbicide soluble dans l'eau - Google Patents

Co-formulation d'herbicide soluble dans l'huile et d'herbicide soluble dans l'eau Download PDF

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WO2002078442A2
WO2002078442A2 PCT/US2002/005734 US0205734W WO02078442A2 WO 2002078442 A2 WO2002078442 A2 WO 2002078442A2 US 0205734 W US0205734 W US 0205734W WO 02078442 A2 WO02078442 A2 WO 02078442A2
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composition
set forth
water
oil
soluble herbicide
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PCT/US2002/005734
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English (en)
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WO2002078442A3 (fr
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Ganiyu A. Jimoh
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Monsanto Technology Llc
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Priority to HU0303734A priority Critical patent/HUP0303734A2/hu
Priority to EP02728358A priority patent/EP1359800A2/fr
Priority to MXPA03007280A priority patent/MXPA03007280A/es
Priority to BR0207259-9A priority patent/BR0207259A/pt
Priority to CA002437741A priority patent/CA2437741A1/fr
Publication of WO2002078442A2 publication Critical patent/WO2002078442A2/fr
Publication of WO2002078442A3 publication Critical patent/WO2002078442A3/fr

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    • 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
    • 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
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals

Definitions

  • the present invention relates to compositions useful in agriculture comprising at least two herbicidal active ingredients, one of which is an oil-soluble herbicide and the other of which is a water-soluble herbicide. More particularly, the present invention relates to stable liquid concentrate compositions of such herbicidal active ingredients.
  • a common method of herbicidal treatment in agricultural endeavors is to treat a field to remove or control unwanted vegetation as preparation for planting a crop plant, a method otherwise known as "burndown."
  • single herbicides typically lack the weed control spectrum, e.g., the range of weed species effectively controlled by the herbicide, to fully control the diversity of weeds in a field. Therefore, it is common to apply two or more herbicides simultaneously in order to achieve the desired spectrum of control.
  • the different herbicides are packaged separately as concentrate formulations, which can be admixed with water in a spray tank by the end user, a method also known as tank-mixing. More conveniently, however, the different herbicides can be coformulated in a single concentrate formulation, requiring only dilution in water by the end user prior to application by spraying. Such a formulation is often known as a package-mix.
  • Package-mix formulations present numerous challenges to the formulator of agricultural chemicals such as herbicides.
  • the formulation should contain the herbicidal active ingredients at as high a total concentration as possible, for maximum convenience to the end user and to minimize packaging and shipping costs, while keeping the active ingredients within the desired weight ratios with respect to each other.
  • the package-mix formulation must exhibit sufficient physical and chemical stability to have an effective shelf life of at least a few months, preferably at least a year, and ideally at least two years.
  • the challenge of providing a storage-stable liquid concentrate formulation is particularly acute.
  • Water used as the solvent for the second herbicide acts as a degradation medium for the first herbicide.
  • hydrolysis is the most common water-mediated degradation mechanism; however, package-mix formulations with chemically unstable active ingredients are also subject to oxidation, dehalogenation, bond cleavage, Beckmann rearrangement and other forms of degradation.
  • Liquid concentrate coformulations of two herbicidal active ingredients are known in the art in the form of emulsions, most commonly oil-in-water type emulsions having a discontinuous oil phase dispersed in a continuous aqueous phase with the aid of one or more emulsifying agents.
  • the water-soluble active ingredient is contained predominantly in the aqueous phase and the oil-soluble active ingredient is contained predominantly in the oil phase.
  • the individual oil particles can be large enough to interfere with the transmission of light, giving rise to a cloudy or milky emulsion known as a macroemulsion.
  • the emulsion is clear, i.e., transparent, and is known as a microemulsion.
  • Microemulsions offer a number of practical advantages, one of the most important being that they typically remain homogeneous without agitation for long periods of time. In this respect, a microemulsion formulation can be handled by an agricultural technician or other user with the same ease and convenience as a simple aqueous solution.
  • selecting excipient ingredients for the preparation of a microemulsion is not necessarily straightforward or easy.
  • Difficulties in preparing stable microemulsions suitable for effective weed control and good crop safety are compounded when the active ingredients to be coformulated are a water-soluble herbicide and an oil-soluble herbicide.
  • the active ingredients to be coformulated are a water-soluble herbicide and an oil-soluble herbicide.
  • water-mediated chemical degradation, e.g., hydrolysis of the oil-soluble herbicide must be minimized. Minimizing hydrolysis is especially difficult in microemulsions, where the oil particles containing the oil-soluble herbicidal active are extremely small and therefore present a very large interfacial area with the aqueous phase.
  • microemulsions must contain surfactants, which tend to facilitate transfer of the oil-soluble herbicidal active across the large interface between the oil and aqueous phases, increasing the potential for chemical degradation.
  • surfactants are important to the microemulsion composition, functioning as emulsifying agents to physically stabilize the microemulsion, as dispersants to prevent aggregation of oil particles when the microemulsion is diluted in water for application to plants, and as adjuvants to enhance herbicidal efficacy of one or both active ingredients, for example by improving retention on or adhesion to foliar surfaces of the applied composition or by improving penetration of the active ingredient(s) into or through the cuticles of the plant foliage.
  • a novel liquid concentrate herbicidal composition useful in agriculture wherein at least two herbicidal active ingredients, one of which is a water-soluble herbicide and the other of which is an oil-soluble herbicide, can be coformulated; the provision of such a novel composition comprising a continuous aqueous phase having a discontinuous oil phase dispersed therein; the provision of such a novel composition having a broader weed control spectrum; the provision of such a novel composition that exhibits rapid burndown and early visual symptomology; the provision of such a novel composition that allows for higher loading of herbicidal active ingredients; and the provision of such a novel composition which has prolonged storage stability and is relatively easy to use.
  • the present invention is directed to a liquid concentrate herbicidal emulsion composition
  • a liquid concentrate herbicidal emulsion composition comprising a water-soluble herbicide in water and an oil- soluble herbicide.
  • the water-soluble herbicide and the oil-soluble herbicide are independently present in a concentration that is biologically effective when the composition is diluted in a suitable volume of water and applied to the foliage of a susceptible plant.
  • the composition further comprises a stabilizing amount of one or more water-soluble chlorides selected from hydrochloric acid, alkali metal chlorides, ammonium chloride, low molecular weight organic ammonium chlorides and quaternary ammonium chloride surfactants sufficient to inhibit substantial degradation of the oil- soluble herbicide; and one or more surfactants present in a concentration sufficient to provide acceptable physical stability of the emulsion and provide acceptable dispersion of the emulsion upon dilution thereof in a suitable volume of water for application to plants.
  • water-soluble chlorides selected from hydrochloric acid, alkali metal chlorides, ammonium chloride, low molecular weight organic ammonium chlorides and quaternary ammonium chloride surfactants sufficient to inhibit substantial degradation of the oil- soluble herbicide
  • surfactants present in a concentration sufficient to provide acceptable physical stability of the emulsion and provide acceptable dispersion of the emulsion upon dilution thereof in a suitable volume of water for application to plants.
  • composition is further characterized in that the oil-soluble herbicide is selected from the group consisting of acetochlor, alachlor, ametryn, amidosulfuron, anilofos, atrazine, azafenidin, azimsulfuron, benfluralin, benfuresate, bensulfuron-methyl, bensulide, benzfendizone, benzofenap, bromobutide, bromofenoxim, butachlor, butafenacil, butamifos, butralin, butylate, cafenstrole, carbetamide, chlorbromuron, chloridazon, chlorimuron-ethyl, chlorotoluron, chlorpropham, chlorsulfuron, chlorthal-dimethyl, chlorthiamid, cinidon-ethyl, cinmethylin, cinosulfuron, clomazone, clomeprop, cloransulam-methyl, cyanazine, cycl
  • the present invention is further directed to a liquid concentrate herbicidal emulsion composition comprising a water-soluble herbicide in water and an oil-soluble herbicide.
  • the water-soluble herbicide and the oil-soluble herbicide are independently present in a concentration that is biologically effective when the composition is diluted in a suitable volume of water and applied to the foliage of a susceptible plant.
  • the composition further comprises a substantially water-immiscible organic solvent; at least one emulsifying agent having a tertiary amine functionality; and a stabilizing amount of one or more water- soluble chlorides selected from hydrochloric acid, alkali metal chlorides, ammonium chloride, low molecular weight organic ammonium chlorides and quaternary ammonium chloride surfactants sufficient to inhibit substantial degradation of the oil-soluble herbicide.
  • composition is further characterized in that the oil-soluble herbicide is selected from the group consisting of acetochlor, alachlor, ametryn, amidosulfuron, anilofos, atrazine, azafenidin, azimsulfuron, benfluralin, benfuresate, bensulfuron-methyl, bensulide, benzfendizone, benzofenap, bromobutide, bromofenoxim, butachlor, butafenacil, butamifos, butralin, butylate, cafenstrole, carbetamide, chlorbromuron, chloridazon, chlorimuron-ethyl, chlorotoluron, chlorpropham, chlorsulfuron, chlorthal- dimethyl, chlorthiamid, cinidon-ethyl, cinmethylin, cinosulfuron, clomazone, clomeprop, cloransulam-methyl, cyanazine, cyclo
  • the present invention is further directed to a liquid concentrate herbicidal microemulsion composition having a continuous aqueous phase and a discontinuous oil phase.
  • the composition comprises a water-soluble herbicide in the aqueous phase present in a concentration that is biologically effective when the composition is diluted in a suitable volume of water and applied to the foliage of a susceptible plant.
  • the composition further comprises an oil-soluble herbicide in the oil phase present in a concentration that is biologically effective when the composition is diluted in a suitable volume of water and applied to the foliage of a susceptible plant; and at least one emulsifying agent having a tertiary amine functionality wherein the emulsifying agent is present in a concentration sufficient to provide acceptable physical stability of the microemulsion.
  • composition is further characterized in that the oil- soluble herbicide is selected from the group consisting of acetochlor, alachlor, ametryn, amidosulfuron, anilofos, atrazine, azafenidin, azimsulfuron, benfluralin, benfuresate, bensulfuron-methyl, bensulide, benzfendizone, benzofenap, bromobutide, bromofenoxim, butachlor, butafenacil, butamifos, butralin, butylate, cafenstrole, carbetamide, chlorbromuron, chloridazon, chlorimuron-ethyl, chlorotoluron, chlorpropham, chlorsulfuron, chlorthal-dimethyl, chlorthiamid, cinidon-ethyl, cinmethylin, cinosulfuron, clomazone, clomeprop, cloransulam-methyl, cyanazine,
  • the present invention is still further directed to a liquid concentrate herbicidal microemulsion composition having a continuous aqueous phase and a discontinuous oil phase.
  • the composition comprises a water-soluble herbicide in the aqueous phase and an oil-soluble herbicide in the oil phase.
  • the water-soluble herbicide and the oil-soluble herbicide are independently present in a concentration that is biologically effective when the composition is diluted in a suitable volume of water and applied to the foliage of a susceptible plant.
  • the composition further comprises a stabilizing amount of one or more water-soluble chlorides selected from hydrochloric acid, alkali metal chlorides, ammonium chloride, low molecular weight organic ammonium chlorides and quaternary ammonium chloride surfactants; and one or more surfactants present in a concentration sufficient to provide acceptable physical stability of the emulsion and provide acceptable dispersion of the emulsion upon dilution thereof in a suitable volume of water for application to plants.
  • water-soluble chlorides selected from hydrochloric acid, alkali metal chlorides, ammonium chloride, low molecular weight organic ammonium chlorides and quaternary ammonium chloride surfactants
  • composition is further characterized in that the oil-soluble herbicide is selected from the group consisting of acetochlor, alachlor, ametryn, amidosulfuron, anilofos, atrazine, azafenidin, azimsulfiiron, benfluralin, benfuresate, bensulfuron-methyl, bensulide, benzfendizone, benzofenap, bromobutide, bromofenoxim, butachlor, butafenacil, butamifos, butralin, butylate, cafenstrole, carbetamide, chlorbromuron, chloridazon, chlorimuron-ethyl, chlorotoluron, chlorpropham, chlorsulfuron, chlorthal-dimethyl, chlorthiamid, cinidon-ethyl, cinmethylin, cinosulfuron, clomazone, clomeprop, cloransulam-methyl, cyanazine,
  • the present invention is directed to a liquid concentrate herbicidal microemulsion composition having a continuous aqueous phase and a discontinuous oil phase.
  • the composition comprises a water-soluble herbicide in the aqueous phase and an oil-soluble herbicide in the oil phase.
  • the water-soluble herbicide and the oil-soluble herbicide are independently present in a concentration that is biologically effective when the composition is diluted in a suitable volume of water and applied to the foliage of a susceptible plant.
  • the composition further comprises a substantially water-immiscible organic solvent in the oil phase; at least one emulsifying agent having a tertiary amine functionality; a stabilizing agent present in a concentration sufficient to inhibit substantial degradation of the oil-soluble herbicide; and one or more dispersing agents present in a concentration sufficient to provide acceptable dispersion of the microemulsion upon dilution thereof in a suitable volume of water for application to plants, but not sufficient to destabilize the microemulsion prior to such dilution.
  • composition is further characterized in that the organic solvent is selected such that the oil-soluble herbicide has an organic solvent/water partition coefficient, expressed as a logarithm, of about 4 or greater; the emulsifying agent is present in a concentration sufficient to provide acceptable physical stability of the microemulsion; and the oil-soluble herbicide is selected from the group consisting of acetochlor, alachlor, ametryn, amidosulfuron, anilofos, atrazine, azafenidin, azimsulfuron, benfluralin, benfuresate, bensulfuron-methyl, bensulide, benzfendizone, benzofenap, bromobutide, bromofenoxim, butachlor, butafenacil, butamifos, butralin, butylate, cafenstrole, carbetamide, chlorbromuron, chloridazon, chlorimuron-ethyl, chlorotoluron, chlorpropham, chlorsul
  • the present invention is directed to a liquid concentrate herbicidal microemulsion composition.
  • the composition comprises a continuous aqueous phase comprising N-(phosphonomethyl)glycine or a salt thereof and a discontinuous oil phase comprising an oil-soluble protoporphyrinogen oxidase inhibitor (PPO) herbicide.
  • PPO protoporphyrinogen oxidase inhibitor
  • the N- (phosphonomethyl)glycine and the PPO herbicide are independently present in a concentration that is biologically effective when the composition is diluted in a suitable volume of water and applied to the foliage of a susceptible plant.
  • the composition further comprises a substantially water-immiscible organic solvent in the oil phase; at least one emulsifying agent having a tertiary amine functionality; a stabilizing agent present in a concentration sufficient to inhibit substantial degradation of the PPO herbicide; and one or more dispersing agents present in a concentration sufficient to provide acceptable dispersion of the microemulsion upon dilution thereof in a suitable volume of water for application to plants, but not sufficient to destabilize the microemulsion prior to such dilution.
  • composition is further characterized in that the organic solvent is selected such that the oil-soluble herbicide has an organic solvent/water partition coefficient, expressed as a logarithm, of about 4 or greater; the emulsifying agent is present in a concentration sufficient to provide acceptable physical stability of the microemulsion; and the PPO herbicide is selected from the group consisting of azafenidin, benzfendizone, butafenacil, cinidon-ethyl, fluazolate, flumiclorac-pentyl, flumioxazin, fluthiacet-methyl, oxadiargyl, oxadiazon, pentoxazone, profluazol, pyraflufen-ethyl, pyrazogyl, sulfentrazone and thidiazimin.
  • the organic solvent is selected such that the oil-soluble herbicide has an organic solvent/water partition coefficient, expressed as a logarithm, of about 4 or greater; the emulsifying agent is present in a
  • the present invention is further directed to a process for controlling the growth of or killing unwanted plants comprising diluting a liquid concentrate herbicidal composition comprising at least two or more herbicidal active ingredients, one of which is an oil-soluble herbicide and the other of which is a water-soluble herbicide, in a suitable volume of water to form a plant treatment composition; and, applying said plant treatment composition to the foliage of the unwanted plants.
  • the present invention is directed to compositions as described above that have a viscosity of not greater than about 1000 cPs at 10°C, that have a cloud point not lower than about 50°C and that exhibit substantially no crystallization or phase separation when stored at a temperature of from about 10° to about 30°C for a period of about 30 days.
  • the above compositions provide for high loading of water-soluble herbicides.
  • herbicidal effective concentrations of the water-soluble herbicide N-(phosphonomethy ⁇ )glycine can be as high as 360 to about 500 g a.e./l in the stable compositions of the invention.
  • a liquid composition of the invention comprises an oil-in-water microemulsion having a continuous aqueous phase and a discontinuous oil phase.
  • the water-soluble herbicide is present in solution in the continuous aqueous phase of the microemulsion, and the oil- soluble herbicide is present in solution in the discontinuous oil phase of the microemulsion.
  • Compositions of the present invention provide for an increased weed control spectrum, more rapid burndown, early symptomology and are relatively easy to use.
  • liquid concentrate compositions of the present invention can be oil-in-water macroemulsions or microemulsions, water-in-oil emulsions or water-in-oil-in-water multiple emulsions.
  • the composition is a herbicidal concentrate, i.e. , it is normally diluted in a suitable volume of water before application, for example, by spraying onto the foliage of plants.
  • a concentrate composition contains at least about 5% by weight and up to about 50% by weight of herbicidal active ingredients.
  • the combined concentration of the water-soluble herbicide and the oil-soluble herbicide comprises at least about 5% and up to about 50% by weight of the composition.
  • the combined concentration of the water-soluble herbicide and the oil-soluble herbicide comprises at least about 10% by weight of the composition, more preferably at least about 20% by weight.
  • compositions of the invention have a viscosity of not greater than about 1000 cPs at 10°C, more preferably, a viscosity of not greater than about 500 cPs at 10°C, even more preferably not greater than 250 cPs at 10°C.
  • compositions of the invention have a cloud point not lower than about 50°C and preferably exhibit substantially no crystallization or phase separation when stored at a temperature of from about 10° to about 30°C for a period of about 30 days. More preferably, a composition of the invention shows substantially no crystallization or phase separation for a period of at least about 180 days when stored at a temperature of about 10° to about 30°C.
  • substantially no crystallization or phase change occurs in a composition of the invention when stored for a period of at least about 30 days at storage temperatures of from about - 10° to about 40°C; most preferably for a period of at least about 180 days.
  • the aqueous phase of a composition of the invention comprises water having the selected water-soluble herbicide dissolved therein.
  • water-soluble as used herein in relation to a herbicide or salt thereof means having a solubility in deionized water at 20°C of not less than about 50 g/1.
  • Preferred water-soluble herbicides have a solubility in deionized water at 20°C of not less than about 200 g/1.
  • Particularly preferred water-soluble herbicides have a herbicidal active acid or anionic moiety and are most usefully present in a composition of the invention in the form of one or more water-soluble salts.
  • the aqueous phase can optionally contain, in addition to the water-soluble herbicide, other salts contributing to the ionic strength of the aqueous phase.
  • a particularly preferred group of water-soluble herbicides are those that are normally applied post-emergence to the foliage of plants. While the invention is not limited to any particular class of foliar-applied water-soluble herbicide, it has been found to provide useful benefits for compounds that rely at least in part for their herbicidal effectiveness on systemic movement in plants.
  • Systemic movement in plants can take place via apoplastic (non-living) pathways, including within xylem vessels and in intercellular spaces and cell walls, via symplastic (living) pathways, including within phloem elements and other tissues composed of cells connected symplastically by plasmodesmata, or via both apoplastic and symplastic pathways.
  • compositions of the invention can also be useful where the water- soluble herbicide is non-systemic, as in the case of paraquat.
  • Water-soluble herbicides suitable for use in compositions of the invention include acifluorfen, acrolein, amitrole, asulam, benazolin, bentazon, bialaphos, bromacil, bromoxynil, chloramben, chloroacetic acid, clopyralid, 2,4-D, 2,4-DB, dalapon, dicamba, dichlorprop, difenzoquat, diquat, endothall, fenac, fenoxaprop, flamprop, flumiclorac, fluoroglycofen, flupropanate, fomesafen, fosamine, glufosinate, glyphosate, imazameth, imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, ioxynil, MCPA, MCPB, mecoprop, methylarsonic acid, naptalam, nonanoic acid, paraquat, pic
  • Phloem-mobile herbicides that are preferred for use in compositions of the invention include but are not limited to aminotriazole, asulam, bialaphos, clopyralid, dicamba, glufosinate, glyphosate, imidazolinones such as imazameth, imazamethabenz, imazamox, imazapic, imazapyr, imazaquin and imazethapyr, phenoxies such as 2,4-D, 2,4- DB, dichlorprop, MCPA, MCPB and mecoprop, picloram and triclopyr.
  • a particularly preferred group of water-soluble herbicides are salts of bialaphos, glufosinate and glyphosate.
  • Another particularly preferred group of water-soluble herbicides are salts of imidazolinone herbicides.
  • Compositions of the invention can optionally contain more than one water-soluble herbicide in solution in the aqueous phase.
  • An especially preferred water-soluble herbicide useful in a composition of the present invention is glyphosate, the acid form of which is alternatively known as N-(phosphonomethyl)glycine.
  • glyphosate salts useful in compositions of the present invention are disclosed in U.S. Patents No. 3,799,758 and No. 4,405,531.
  • Glyphosate salts that can be used according to the present invention include but are not restricted to alkali metal, for example sodium and potassium, salts; ammonium salt; C,.
  • the N-phosphonomethylglycine molecule has three acid sites having different pKa values; accordingly mono-, di- and tribasic salts, or any mixture thereof, or salts of any intermediate level of neutralization, can be used.
  • the oil phase of a composition of the present invention comprises a solvent having an oil-soluble herbicidal active ingredient dissolved therein.
  • Oil-soluble herbicides suitable for use in compositions of the present invention include but are not limited to acetochlor, aclonifen, alachlor, ametryn, amidosulfuron, anilofos, atrazine, azafenidin, azimsulfuron, benfluralin, benfuresate, bensulfuron-methyl, bensulide, benzfendizone, benzofenap, bifenox, bromobutide, bromofenoxim, butachlor, butafenacil, butamifos, butralin, butroxydim, butylate, cafenstrole, carfentrazone-ethyl, carbetamide, chlomethoxyfen, chlorbromuron, chloridazon, chlorimuron-ethyl, chlorotoluron, chlornitrofen, chlorotoluron, chlorpropham, chlorsulfuron, chlorthal-dimethyl, chlorthi
  • Preferred oil-soluble herbicides for use in a composition of the invention include but are not limited to acetochlor, aclonifen, alachlor, ametryn, amidosulfuron, anilofos, atrazine, azafenidin, azimsulfuron, benfluralin, benfuresate, bensulfuron-methyl, bensulide, benzfendizone, benzofenap, bromobutide, bromofenoxim, butachlor, butafenacil, butamifos, butralin, butroxydim, butylate, cafenstrole, carfentrazone-ethyl, carbetamide, chlorbromuron, chloridazon, chlorimuron-ethyl, chlorotoluron, chlornitrofen, chlorotoluron, chlorpropham, chlorsulfuron, chlorthal-dimethyl, chlorthiamid, cinidon-ethyl, c
  • PPO herbicides are known to affect plants by inhibiting protoporphyrinogen oxidase in chloroplasts, thereby disrupting photosynthesis and other biological processes and causing early symptoms of tissue necrosis in plants.
  • PPO herbicides include diphenylether herbicides (e.g., bifenox, chlomethoxyfen, fluoroglycofen-ethyl, fomesafen, halosafen, lactofen and oxyfluorfen); phenylpyrazoles (e.g., fluazolate and pyraflufen-ethyl); N- phenylphthalimides (e.g., cinidon-ethyl, flumioxazin and flumiclorac-pentyl); thiadiazoles
  • diphenylether herbicides e.g., bifenox, chlomethoxyfen, fluoroglycofen-ethyl, fomesafen, halosafen, lactofen and oxyfluorfen
  • phenylpyrazoles e.g., fluazolate and pyraflufen-ethyl
  • oxadiazoles e.g., oxadiazon and oxadiargyl
  • triazolinones e.g., azafenidin, carfentrazone-ethyl and sulfentrazone
  • oxazolidinediones e.g., pentoxazone
  • pyrimidindiones e.g., benzfendizone and butafencil
  • pyrazogyl and profluazol e.g., fluthiacet-methyl and thidiazimin
  • oxadiazoles e.g., oxadiazon and oxadiargyl
  • triazolinones e.g., azafenidin, carfentrazone-ethyl and sulfentrazone
  • oxazolidinediones e.g., pentoxazone
  • pyrimidindiones e.g.,
  • Triazolinone herbicides are known to provide good control of broadleaf weeds but are less efficacious in controlling grasses. Suitable triazolinone herbicides for use in compositions of the invention are described generally in U.S. Patent Nos. 5,217,520 and 5,125,958 to Poss and U.S. Patent No. 4,818,275 to Theodoridis, all of which are hereby incorporated herein by reference.
  • a triazolinone herbicide suitable for use in a composition of the invention can be a compound of the structure shown in the following formula:
  • R 1 is haloalkyl
  • R 2 is halogen or lower alkyl
  • R 3 is -CH 2 CHClCO 2 R 4 or — NHSO 2 R 5
  • R 4 is alkyl, alkoxycarbonylalkyl, cycloalkyl, benzyl, chlorobenzyl, alkylbenzyl, or haloalkylbenzyl
  • R 5 is alkyl, haloalkyl, dialkylamino, carboxymethyl, hydroxy, or aryl
  • X is hydrogen, halogen, alkyl, alkoxy, haloalkyl, or nitro
  • Y is hydrogen, halogen, alkyl, alkoxy, haloalkyl, haloloweralkylsulfinyl, or haloloweralkoxy.
  • R 1 is difluoromethyl and R 2 is lower alkyl, more preferably C, to about C 5 alkyl, and still more preferably methyl.
  • R 4 is preferably alkyl or alkoxy, more preferably alkyl, still more preferably C, to about C 5 alkyl, and most preferably ethyl.
  • R 5 is preferably alkyl, more preferably C, to about C 5 alkyl, and most preferably methyl.
  • X is preferably a halogen and more preferably X is fluoro or chloro.
  • Y is preferably a halogen, more preferably chloro.
  • the triazolinone herbicide is a triazolinone acid ester herbicide.
  • a particularly preferred triazolinone herbicide is carfentrazone-ethyl having a structure as follows:
  • the triazolinone herbicide is a triazolinone sulfonamide herbicide.
  • Another particularly preferred triazolinone herbicide is sulfentrazone having the following structure:
  • the herbicidal active ingredients are generally present in an amount which is biologically effective when the composition is diluted in a suitable volume of water and applied to the foliage of a susceptible plant.
  • the oil-soluble herbicide is present in a concentration such that the weight ratio of water- soluble herbicide to oil-soluble herbicide ranges from about 190:1 to about 1 :1.
  • the oil-soluble herbicide is a PPO herbicide such as a triazolinone
  • the weight ratio of triazolinone to water-soluble herbicide ranges from about 190:1 to about 19:1.
  • the concentration of the oil-soluble herbicide in the composition as a whole is about 0.1 % to about 25% by weight.
  • the concentration of the oil-soluble herbicide is about 0.1 % to about 5% by weight, for example about 0.2% to about 2%, by weight.
  • a key to the present invention is to select as the solvent for the oil-soluble herbicide, i.e., as the basis for the oil phase, an organic liquid having the following properties. First, the solvent must be substantially immiscible with water. Second, the affinity of the solvent for the oil-soluble herbicide in question must be such that substantially all of the oil-soluble herbicide is partitioned in the oil phase and substantially none is partitioned in the aqueous phase.
  • one such test procedure comprises the following steps.
  • a solution of the oil-soluble herbicide is prepared in the organic solvent at as high a concentration as possible up to 15% by weight.
  • Subsamples of the resulting oil and water phases are taken and analyzed by HPLC to determine concentrations C 0 and C w in the oil and water phases respectively.
  • the subsample of the water phase is preferably centrifuged before analysis to remove traces of organic solvent.
  • a partition coefficient, analogous to octanol-water partition coefficient P, is calculated as C ( C w .
  • the partition coefficient is conveniently expressed as a logarithm.
  • the concentration of the oil-soluble herbicide in the water phase will be below the detection limit of the HPLC method.
  • traces of the organic solvent are found in the water phase, even after centrifugation, so that the apparent concentration of oil-soluble herbicide observed in the water phase is misleadingly high.
  • a published value for solubility in water of the oil-soluble herbicide in question can be used in place of C w for calculation of the partition coefficient.
  • the organic solvent is selected such that the oil-soluble herbicide exhibits a partition coefficient such that log( ) is about 4 or greater, preferably about 5 or greater.
  • the oil-soluble herbicide is soluble in the organic solvent by at least about 5% by weight, more preferably by at least about 10% by weight and most preferably by at least about 15%> by weight.
  • organic solvents having a higher solubility of the oil-soluble herbicide therein are more suitable, provided the organic solvent is substantially immiscible with water.
  • Organic solvents useful in compositions of the present invention preferably have a flash point above about 35°C, more preferably above about 90°C, and are preferably not antagonistic to the herbicidal effectiveness of any of the herbicidal active ingredients of the composition.
  • suitable solvents for use in the present invention include naphthalenic aromatic solvents such as Aromatic 100, Aromatic 150 or Aromatic 200, commercially available from Exxon Mobil Chemical of Houston, TX or Sure Sol 225, commercially available from Koch Specialty Chemical Co. of Houston, TX; and alkyl acetates with high solvency, such as ExxateTM 1000, also available from Exxon Mobil Chemical.
  • naphthalenic aromatic solvents such as Aromatic 100, Aromatic 150 or Aromatic 200, commercially available from Exxon Mobil Chemical of Houston, TX or Sure Sol 225, commercially available from Koch Specialty Chemical Co. of Houston, TX
  • alkyl acetates with high solvency such as ExxateTM 1000, also available from Exxon Mobil Chemical.
  • an aromatic solvent is especially preferred.
  • Useful aromatic solvents include benzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, naphthalene, bis-( ⁇ - methylbenzyl)xylene, phenylxylene and combinations thereof.
  • Other useful solvents include substituted aromatic solvents such as chlorobenzene or ortho-dichlorobenzene.
  • the amount of the selected organic solvent to be used is important. Clearly the amount must be sufficient to completely dissolve the oil-soluble herbicide. Even for an organic solvent in which the oil-soluble herbicide is highly soluble, the weight ratio of organic solvent to oil-soluble herbicide should not be less than about 3:1.
  • a composition of the invention further comprises one or more surfactants. As indicated above, these surfactants can function as emulsifying agents, dispersing agents and/or adjuvants for enhancing herbicidal efficacy.
  • compositions of the invention contain one or more surfactants present in a concentration sufficient to provide acceptable physical stability of the composition, and provide acceptable dispersion of the composition upon dilution thereof in a suitable volume of water for application to plants.
  • chemical degradation can be kept to an acceptable minimum by including less than about 10% by weight of the emulsifying agent(s) and less than about 5% of the dispersing agent(s) in the composition.
  • the amount of all surfactants in the composition is less than about
  • the amount of surfactants included is not substantially more than the minimum needed for acceptable physical stability and acceptable dispersibility in water. Minimum levels of emulsifying and dispersing agents can readily be determined by one skilled in the art as indicated above.
  • a composition of the invention includes at least one surfactant which is an emulsifying agent.
  • the emulsifying agent preferably has a tertiary amine functionality.
  • Preferred tertiary amine surfactants have a hydrophobic moiety comprising a linear or branched saturated or unsarurated aliphatic hydrocarbyl group having about 8 to about 22 carbon atoms, this moiety being referred to herein as an "alkyl” group consistent with conventional use of the term "alkyl” in surfactant-related literature.
  • Such tertiary amine surfactants typically also enhance the herbicidal effectiveness of the composition by various means, including assisting adherence to, and thereby retention on, plant foliage of the spray composition obtained by diluting the composition in water, and facilitating penetration of the active ingredients through cuticles on the surface of plant foliage. This is especially true where the water-soluble herbicide is a salt of glyphosate.
  • Quaternary ammonium surfactants can also be effective emulsifiers and provide good herbicidal efficacy enhancement; however, quaternary ammonium surfactants are not preferred in compositions of the invention because, at least when present in large amounts, they promote increased rates of chemical degradation of the oil-soluble herbicide. Without being bound to a particular theory, it is believed that the increased chemical degradation associated with the presence of quaternary ammonium surfactants results from their effectiveness in facilitating transfer of the oil-soluble herbicide from the oil phase to the aqueous phase.
  • compositions of the invention preferably contain no substantial amount of quaternary ammonium surfactants that are water-insoluble.
  • Tertiary amine surfactants for use as the emulsifying agent(s) are preferably selected from polyoxyethylene (2-20) tertiary alkylamines and polyoxyethylene (2-20) tertiary alkyletheramines.
  • the alkyl chains of these surfactants have about 12 to about 18 carbon atoms.
  • the alkyl chains are derived from natural oils or fats such as coconut oil, soybean oil or beef tallow, and the resulting surfactants therefore typically contain a variety of alkyl chain lengths and degrees of unsaturation.
  • Preferred tertiary alkylamines for use in the present invention include polyoxyethylene (2-10) cocoamine and polyoxyethylene (2-10) tallowamine, which are commercially available from many surfactant suppliers.
  • EthomeenTM C15 polyoxyethylene (5) cocoamine
  • EthomeenTM T15 polyoxyethylene (5) tallowamine
  • Suitable polyoxyethylene alkyletheramines for use in compositions of the invention are disclosed in U.S. Patent No. 5,750,468 to Wright et al.
  • the minimum amount of emulsifying agent(s) required to provide acceptable physical stability depends, among other things, on the amount of organic solvent present, which depends in turn on the amount of oil-soluble herbicide present.
  • the amount of emulsifying agent(s) in compositions of the invention ranges from about 3%o to about 10% by weight, more preferably about 3% to about 8% by weight, and even more preferably about 3% to about 6% by weight.
  • quaternary alkylammonium chloride surfactants are more effective emulsifying agents than the corresponding tertiary alkylamines.
  • polyoxyethylene (2-5) N-methyl alkylammonium chlorides are very effective emulsifiers.
  • these quaternary ammonium surfactants are unacceptable at relatively high concentration because they promote chemical degradation of the oil-soluble herbicide.
  • tertiary amines alone are used, acceptable physical stability is not always achievable.
  • a solution to this problem lies in the surprising discovery that inclusion of a stabilizing agent, such as a water-soluble chloride surfactant, substantially dispersed in and associated with the aqueous phase can provide enhanced physical stability when tertiary amine surfactants are used as emulsifiers.
  • a stabilizing agent such as a water-soluble chloride surfactant
  • water-soluble quaternary ammonium chloride surfactants such as benzalkonium chloride are preferred.
  • water-soluble quaternary ammonium chloride surfactants have a lesser tendency to promote chemical degradation of the oil-soluble herbicide than other, less water-soluble quaternary ammonium chlorides such as polyoxyethylene (2-5) N-methyl alkylammonium chlorides and thus, are acceptable ingredients in compositions of the invention.
  • the amount of the stabilizing agent does not exceed about 6% by weight of the composition.
  • a minimum effective stabilizing amount of a stabilizing agent can be determined by routine evaluation of physical stability in any particular situation.
  • Preferred amounts of such a stabilizing agent, for example benzalkonium chloride are about 1% to about 6%, more preferably about 1% to about 4%, by weight of the composition.
  • non-surfactant stabilizing agent that is substantially dispersed in and associated with the aqueous phase of compositions of the invention.
  • a non-surfactant stabilizing agent that is substantially dispersed in and associated with the aqueous phase of compositions of the invention.
  • low molecular weight (C 6 ) organic ammonium halides preferably (C, .6 ) organic ammonium chlorides such as isopropylamrnonium chloride
  • Alkali metal halides preferably alkali metal chlorides such as sodium chloride or potassium chloride are also effective, as is hydrochloric acid.
  • preferred water-soluble chlorides are ammonium chloride, sodium chloride and hydrochloric acid.
  • Hydrochloric acid can be especially useful where a downward adjustment of the pH of the aqueous phase is desired.
  • An effective stabilizing amount of a water-soluble chloride in any particular situation can be determined by routine evaluation of physical stability as indicated previously.
  • preferred amounts of low molecular weight organic ammonium chlorides, ammonium chloride, alkali metal chlorides and/or hydrochloric acid are those providing about 0.5% to about 2.5% chloride ion by weight of the composition.
  • compositions of the invention may further contain one or more dispersing agents.
  • any nonionic surfactant known to be effective as a dispersing agent for liquid concentrate herbicidal formulations can be used as a dispersing agent in a composition of the invention.
  • the dispersing agent is preferably one or more surfactants selected from polyoxyethylene (2-20) alkylethers and alkylphenylethers, the term "alkyl" having the same meaning as in the context of the tertiary amine surfactants described above.
  • the amount of dispersing agents in a composition of the invention range from about 0.5%) to about 5% by weight, and more preferably from about 0.5% to about 3% by weight, of the composition.
  • compositions having differing amounts of the emulsifying agent(s) can be readily determined by one of skill in the art by routine evaluation of a range of compositions having differing amounts of the emulsifying agent(s). Typically, physical stability of the composition is acceptable if no significant phase separation is evident following storage for at least 7 days at any temperature in the range from about 0°C to about 40°C. Where the composition is one that additionally requires the presence of a water-soluble chloride for acceptable physical stability, routine evaluation of differing amounts of the emulsifying agent(s) is conducted in the presence of such water-soluble chloride.
  • a "stabilizing" amount of one or more selected water-soluble chlorides as used above is an amount that provides acceptable physical stability of the compositions as defined above, when present along with an emulsifying agent(s) in an amount insufficient on its own to provide such stability.
  • One of skill in the art can readily determine such a stabilizing amount by routine evaluation of a range of compositions having differing amounts of the selected chloride(s).
  • an amount of the selected dispersing agent(s) "sufficient to provide acceptable dispersion of the composition upon dilution thereof in a suitable volume of water for application to plants” can readily be determined by one of skill in the art by routine evaluation of a range of compositions having differing amounts of the selected dispersing agent(s).
  • a suitable volume of water is that which upon dilution of the composition provides an application treatment composition having a concentration of active ingredients adequate to kill or control susceptible plants if applied to foliage of such plants. Dispersion of the composition in such a volume of water is acceptable if no visible aggregation or flocculation of water-insoluble ingredients is observed. Therefore, an amount of the selected dispersing agent(s) "not sufficient to destabilize the composition" is an amount lower than that which results in the composition losing the acceptable physical stability it has in the absence of the dispersing agent(s). Such an amount can readily be determined by one of skill in the art by routine evaluation of a range of compositions having differing amounts of the selected dispersing agent(s).
  • compositions of the invention can optionally contain additional desired agriculturally acceptable ingredients, including surfactants of classes other than those defined above.
  • surfactants of classes other than those defined above.
  • Standard reference sources from which one of skill in the art can select suitable surfactants, without limitation to the above mentioned classes, include Handbook of Industrial Surfactants, Second Edition (1997) published by Gower, McCutcheon 's Emulsifiers and Detergents, North American and International Editions (1997) published by MC Publishing Company, and International Cosmetic Ingredient Dictionary, Sixth Edition (1995) Volumes 1 and 2, published by the Cosmetic, Toiletry and Fragrance Association.
  • compositions of the invention include agents to modify color, viscosity, gelling properties, freezing point, hygroscopicity, caking behavior, dissolution rate, dispersibility, or other formulation characteristics.
  • the pH of the aqueous phase of the composition is in a range that is minimally conducive to chemical degradation of the oil-soluble herbicide.
  • the water-soluble herbicide can, in some cases, naturally provide a pH in the desired range; in other cases an acid, e.g., hydrochloric acid, or base, e.g., potassium hydroxide or isopropylamine, can be added to adjust the pH.
  • an acid e.g., hydrochloric acid, or base, e.g., potassium hydroxide or isopropylamine
  • the effect of pH on degradation of the particular oil-soluble herbicide of choice can be determined by empirical testing, but is often known and available in standard reference sources such as
  • a process of preparing a composition of the invention comprises mixing the various ingredients in a suitable vessel. It is important to note that mixing is not critical to the invention and any order of addition of ingredients is suitable. However, experience to date suggests that certain orders of addition in preparing compositions of the invention require less reaction time. Therefore, a presently preferred order of addition of the ingredients involves adding all required surfactants to a concentrated aqueous solution of the water-soluble herbicide along with an acid or base for pH adjustment, if desired, to form a first mixture. The oil-soluble herbicide is added to the organic solvent with agitation to form a second mixture. The second mixture is then added to the first mixture with agitation to form the finished composition.
  • An alternative order of addition involves mixing a concentrated aqueous solution of the water-soluble herbicide together with other, optional, water-soluble ingredients including an acid or base for pH adjustment, with agitation to form a first mixture.
  • the oil-soluble herbicide is then added to the organic solvent with agitation to form a second mixture.
  • the second mixture is added to the first mixture with agitation, then the surfactants are added. Agitation is continued until a physically stable composition is formed.
  • the oil-soluble herbicide is carfentrazone-ethyl, a PPO herbicide of the triazolinone class, and the water-soluble herbicide is a salt of N-(phosphonomethyl)glycine ("glyphosate").
  • N-(phosphonomethyl)glycine is a widely-used broad-spectrum herbicide that does not necessarily provide early symptomology. Therefore, coformulations of carfentrazone-ethyl and N-(phosphonomethyl)glycine can benefit from the broad spectrum of control of the N-(phosphonomethyl)glycine while the early symptoms caused by the carfentrazone-ethyl can serve as a marker indicating whether a given plant has been treated with the combination.
  • Contemplated compositions of the invention comprising a salt of glyphosate and an oil-soluble triazolinone such as carfentrazone-ethyl typically contain about 50 to about 500 grams per liter of glyphosate, expressed as acid equivalent (g a.e./l). Higher glyphosate concentrations within this range, for example, about 300 to about 500 g a.e./l are preferred, even more preferably about 360 to about 500 g a.e./l.
  • Glyphosate N-phosphonomethylglycine in its strict sense is an acid compound, but the word "glyphosate” is used herein in a less restrictive sense, except where the context dictates otherwise, to encompass not only glyphosate acid but also salts, adducts and esters thereof, and compounds which are converted to glyphosate in plant tissues or which otherwise provide glyphosate ions.
  • the glyphosate is present as a water-soluble salt.
  • glyphosate is typical of most exogenous chemical substances that are acids or that form anions.
  • Herbicidal salts of glyphosate are disclosed, for example, in U.S. Patent No. 3,799,758 to Franz, U.S. Patent No. 3,853,530 to Franz, U.S. Patent No. 4,140,513 to Prill,
  • salts are alkali metal, for example sodium and potassium, salts; ammonium salt; and salts having an ammonium, sulfonium or sulfoxonium cation substituted with 1-3 organic groups containing in total 1-6 carbon atoms, for example dimethylammonium, isopropylammonium, ethanolammonium and trimethylsulfonium salts.
  • glyphosate salts include, for example, Roundup® brand, Accord® brand, Roundup® Ultra brand and Roundup® Xtra brand herbicides of
  • Monsanto Company which contain the isopropylammonium salt, Roundup® Dry brand and Rival® brand herbicides of Monsanto Company, which contain the ammonium salt, Roundup® Geoforce brand herbicide of Monsanto Company, which contains the sodium salt, and Touchdown® brand herbicide of Zeneca, which contains the trimethylsulfonium salt.
  • compositions of the invention containing a glyphosate salt can be applied to any and all plant species on which glyphosate is biologically effective. Therefore, for example, compositions of the invention containing glyphosate as an herbicidal active ingredient can be applied to a plant in a herbicidally effective amount, and can effectively control one or more plant species of one or more of the following genera without restriction: Abutilon, Amaranthus, Artemisia,
  • Particularly important annual broadleaf species for which glyphosate compositions are used are exemplified without limitation by the following: velvetleaf (Abutilon theophrasti), pigweed (Amaranthus spp.), buttonweed (Borreria spp.), oilseed rape, canola, indian mustard, etc. (Brassica spp.), commelina (Commelina spp.), filaree (Erodium spp.), sunflower (Helianthus spp.), morningglory (Ipomoea spp.), kochia (Kochia scoparia), mallow (Malva spp.), wild buckwheat, smartweed, etc.
  • glyphosate compositions are used are exemplified without limitation by the following: mugwort (Artemisia spp.), milkweed (Asclepias spp.), Canada thistle (Cirsium arvense), field bindweed (Convolvulus arvensis) and kudzu (Pueraria spp.).
  • brachiaria particularly important perennial narrowleaf species for which glyphosate compositions are used are exemplified without limitation by the following: brachiaria
  • glyphosate/triazolinone compositions of the present invention can be useful on any of the above species.
  • a plant treatment composition is formed by diluting a composition of the invention in a suitable volume of water for application to a field.
  • a plant treatment composition comprising glyphosate and a triazolinone herbicide such as carfentrazone-ethyl is formed by diluting a composition of the present invention in water and the plant treatment composition is applied to weeds or undesired plants for burndown.
  • the role of the triazolinone in a glyphosate/triazolinone composition is especially to control broadleaf weeds and to act as a marker in providing rapid burndown and early visual symptoms of treatment.
  • compositions of the present invention can be used in precision farming techniques, in which apparatus is employed to vary the amount of exogenous chemical substance applied to different parts of a field, depending on variables such as the particular plant species present, plant growth stage, soil moisture status, etc.
  • a global positioning system operated with the spraying apparatus can be used to apply the desired amount of the composition to different parts of a field.
  • a plant treatment composition is preferably dilute enough to be readily sprayed using standard agricultural spray equipment. Suitable application rates for the present invention vary depending upon such factors as the type and concentration of active ingredient and the plant species involved. Useful rates for applying an aqueous composition to a field of foliage can range from about 25 to about 1,000 liters per hectare (1/ha), preferably about 50 to about 300 1/ha, by spray application.
  • Examples 1 through 12 utilized Formulation L, available from Monsanto Company as MON 0139, which consists of 62% by weight of glyphosate isopropylammonium salt (IP A) in aqueous solution with no surfactant as a starting ingredient.
  • Formulation L contains 570 g a.e./l of glyphosate.
  • Example 1 A microemulsion composition was prepared having the following ingredients: glyphosate IPA salt solution (MON 0139) 67.37% 1 ammonium chloride 1.11 %
  • Emulsifier (Ethomeen T/l 5) 3.07%
  • Emulsifier (Ethomeen C/l 5) 2.95%
  • Ammonium chloride (0.45 g) was dissolved in 2N hydrochloric acid (4.60 g) and the resulting solution was mixed with MON 0139 (27.41 g) to form a first mixture.
  • Carfentrazone-ethyl (0.0739 g) was dissolved in Aromatic 150 (4.85 g) to form a second mixture, which was then added to the first mixture with agitation.
  • surfactants Ethomeen T/15 (1.25 g), Ethomeen C/15 (1.20 g) and Surfonic L12-6 (0.85 g) were added and the whole composition was stirred, using an overhead electric stirrer, under moderate agitation for 30 minutes.
  • Example 2 A microemulsion composition was prepared having the following ingredients: glyphosate IPA salt solution (MON 0139) 67.48%' ammonium chloride 0.27% water 3.62%
  • Emulsifier (Ethomeen TV 15) 3.27% Emulsifier (Ethomeen C/15) 1.26%
  • Dispersant (Surfonic L12-6) 2.07% > 1 Equivalent to 41.84% glyphosate IPA active ingredient.
  • Ammonium chloride (0.11 g) was dissolved in water (1.47 g) and 2N hydrochloric acid (4.60 g) and the resulting solution was mixed with MON 0139 (27.41 g) to form a first mixture.
  • Carfentrazone-ethyl (0.0739 g) was dissolved in Aromatic 150 solvent (4.27 g) to form a second mixture, which was then added to the first mixture with agitation.
  • surfactants Ethomeen T/15 (1.33 g), Ethomeen C/15 (0.51 g) and Surfonic LI 2-6 (0.84 g) were added and the whole composition was stirred, using an overhead electric stioer, under moderate agitation for 30 minutes.
  • the composition was a clear amber microemulsion that was physically stable at -10°C, room temperature (approximately 22°C) and 60°C.
  • the microemulsion exhibited good dispersion in water.
  • Example 3 A microemulsion composition was prepared having the following ingredients: glyphosate IPA salt solution (MON 0139) 68.29%' water 3.31% 2N hydrochloric acid 11.53%
  • Emulsifier (Ethomeen T/l 5) 4.36%
  • Emulsifier (Ethomeen C/15) 0.00% Dispersant (Surfonic L12-6) 1.67%
  • MON 0139 (27.42g) was mixed with water (1.33 g) and 2N hydrochloric acid (4.63 g) to form a first mixture.
  • Carfentrazone-ethyl (0.0740 g) was dissolved in Aromatic 150 solvent (4.28 g) to form a second mixture, which was then added to the first mixture with agitation.
  • surfactants Ethomeen T/15 (1.75 g) and Surfonic L12-6 (0.67 g) were added and the whole composition was stioed, using an overhead electric stirrer, under moderate agitation for 30 minutes.
  • the composition was a clear amber microemulsion that was physically stable at -10°C, room temperature (approximately 22°C) and 60°C.
  • the microemulsion exhibited good dispersion in water.
  • Example 4 A microemulsion composition was prepared having the following ingredients: glyphosate IPA salt solution (MON 0139) 67.79%' water 4.10%
  • Emulsifier (Ethomeen T/15) 4.33% Emulsifier (Ethomeen C/15) 0.00%
  • MON 0139 (27.42 g) was mixed with water (1.66 g) and 2N hydrochloric acid (4.60 g) to form a first mixture.
  • Carfentrazone-ethyl (0.0740 g) was dissolved in Aromatic 150 solvent (4.28 g) to form a second mixture, which was then added to the first mixture with agitation.
  • surfactants Ethomeen T/15 (1.75 g), and Surfonic LI 2-6 (0.67 g) were added and the whole composition was stirred, using an overhead electric stirrer, under moderate agitation for 30 minutes.
  • composition was a clear amber microemulsion that was physically stable at -10°C, room temperature (approximately 22°C) and 60°C.
  • the microemulsion exhibited good dispersion in water.
  • a microemulsion composition was prepared having the following ingredients: glyphosate IPA salt solution (MON 0139) 67.84%' water 2.47%
  • Emulsifier (Ethomeen T/15) 4.33%
  • Emulsifier (Ethomeen C/l 5) 0.00%
  • Dispersant (Surfonic L12-6) 1.76% ' Equivalent to 42.06%> glyphosate IPA active ingredient.
  • MON 0139 (27.42 g) was mixed with water (1.00 g) and 2N hydrochloric acid (4.61 g) to form a first mixture.
  • Carfentrazone-ethyl (0.0740 g) was dissolved in Aromatic 150 solvent (4.86 g) to form a second mixture, which was then added to the first mixture with agitation.
  • surfactants Ethomeen T/15 (1.75 g) and Surfonic L12-6 (0.71 g) were added and the whole composition was stirred, using an overhead electric stirrer, under moderate agitation for 30 minutes.
  • composition was a clear amber microemulsion that was physically stable at -10°C, room temperature (approximately 22°C) and 60°C.
  • the microemulsion exhibited good dispersion in water.
  • Example 6 A microemulsion composition was prepared having the following ingredients: glyphosate IPA salt solution (MON 0139) 67.71%' water 2.30% 2N hydrochloric acid 11.43%)
  • Emulsifier (Ethomeen T/15) 6.27%>
  • microemulsion exhibited good dispersion in water.
  • Example 7 A microemulsion composition was prepared having the following ingredients: glyphosate IPA salt solution (MON 0139) 67.89%' water 1.91% 2N hydrochloric acid 11.41%
  • Emulsifier (Ethomeen T/l 5) 5.00%
  • surfactants Ethomeen T/15 (2.02 g) and Surfonic L12-6 (0.48 g) were added and the whole composition was stirred, using an overhead electric stirrer, under moderate agitation for 30 minutes.
  • the composition was a clear amber microemulsion that was physically stable at
  • microemulsion exhibited good dispersion in water.
  • Example 8 A microemulsion composition was prepared having the following ingredients: glyphosate IPA salt solution (MON 0139) 67.82%' water 3.76% 2N hydrochloric acid 10.39%
  • Emulsifier (Ethomeen T/15) 4.01%
  • microemulsion exhibited good dispersion in water.
  • Example 9 A microemulsion composition was prepared having the following ingredients: glyphosate IPA salt solution (MON 0139) 67.72%' water 5.39% 2N hydrochloric acid 10.38%
  • Emulsifier (Ethomeen T/15) 4.00%
  • microemulsion exhibited good dispersion in water.
  • Example 10 A microemulsion composition was prepared having the following ingredients: glyphosate IPA salt solution (MON 0139) 67.37%' ammonium chloride 1.11% 2N hydrochloric acid 11.31%
  • Emulsifier (Ethomeen T/15) 3.07%
  • Emulsifier (Ethomeen C/15) 2.95% Dispersant (Surfonic L12-6) 2.09%
  • Ammonium chloride (0.11 g) was dissolved in water (1.47 g) and 2N hydrochloric acid (4.60 g) and the resulting solution was mixed with MON 0139 (27.41 g) to form a first mixture.
  • Carfentrazone-ethyl (0.07 g) was dissolved in Aromatic 150 solvent (4.27 g) to form a second mixture, which was then added to the first mixture with agitation.
  • surfactants Ethomeen T/15 (1.33 g), Ethomeen C/15 (0.51 g) and Surfonic L12-6 (0.84 g) were added and the whole composition was stirred, using an overhead electric stirrer, under moderate agitation for 30 minutes.
  • the composition was a clear amber microemulsion that was physically stable at
  • microemulsion exhibited good dispersion in water.
  • Example 11 The following example demonstrates the effect of varying the amount of solvent used in the formulation on the stability of carfentrazone-ethyl in compositions of the present invention. All compositions were prepared as in the Examples above using the glyphosate IPA salt solution MON 0139 and carfentrazone-ethyl. The amount and type of solvent was varied as in the following Table 1. For all of the compositions prepared, five aliquots were taken and stored in capped glass bottles. Aliquots were stored at 0°C, Room Temperature (approximately 22°C), 40°C, 50°C and 60°C to accelerate any chemical degradation of the carfentrazone-ethyl that might occur.
  • Example 12 This example demonstrates the effect of compositions of the invention for controlling broadleaf weeds and grasses. Test were conducted by preparing a microemulsion composition (Formulation MON 78402) as in Example 1 having the following ingredients: glyphosate IPA salt solution (MON 0139) 67.80% ammonium chloride/sodium chloride 1.53%
  • Emulsifiers (Ethomeen T/15 and C/15) 6.06%
  • Dispersant (Surfonic LI 2-6) 1.58% The microemulsion composition was applied to a field (1.0 lb a.i./a) having 4-8 inch weeds actively growing. As a comparison, a separate field test was conducted wherein 0.25% of non-ionic surfactant was added to the microemulsion composition MON 78402 and applied to a field (1.0 lb a.i./a). The formulations were applied to the field using a CO 2 backpack with 3 replications per treatment at a spray volume of 10 gallons per acre. Burndown was evaluated at 2 to 4 days after treatment with a final control evaluation at 21 to 28 days after treatment.
  • the test was evaluated for control of broadleaf weeds and grasses in comparison to standard burndown data for formulations of Roundup® Ultra brand herbicide comprising glyphosate IPA salt as the only herbicidal active ingredient.
  • Broadleaf weed species evaluated included p. lettuce, mustard, w. mustard, f. pennycress, dandelion, c. chickweed, sowthistle, c. primrose, w. buckwheat, henbit, cidweed, c. geranium, horseweed, bittercress, shepardspurse, velvetleaf, r. thistle, p. sida, h. sesbania, p.
  • Example 13 A microemulsion composition (MON 78481) was prepared having the following composition: glyphosate potassium salt solution (MON 78623) 76.27%>' sodium chloride 0.36% phosphoric acid 2.87% Solvent (Aromatic 150) 10.38% carfentrazone-ethyl (92.2% active) 0.21% Emulsifier (Ethomeen T/15) 1.98% Emulsifier (Ethomeen C/12) 2.03% Dispersant (Surfonic LI 2-6) 1.57% Water 4.31%
  • the composition was a clear amber microemulsion that was physically stable at -10°C, room temperature (approximately 22°C) and 60°C.
  • the microemulsion exhibited good dispersion in water.
  • Example 14 A microemulsion composition (MON 78482) was prepared having the following composition: glyphosate potassium salt solution (47.8% a.e.) 76.56%' sodium chloride 0.42% phosphoric acid 2.88% Solvent (Aromatic 150) 10.51% carfentrazone-ethyl (92.2% active) 0.11%
  • Emulsifier (Ethomeen T/l 5) 1.98%
  • Emulsifier (Ethomeen C/12) 2.01%

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  • Agronomy & Crop Science (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
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Abstract

La présente invention concerne une composition herbicide stable se présentant sous forme de concentré liquide. Cette composition comprend un herbicide soluble dans l'eau se trouvant dans une phase continue aqueuse et un herbicide soluble dans l'huile se trouvant dans une phase discontinue huileuse.
PCT/US2002/005734 2001-02-14 2002-02-14 Co-formulation d'herbicide soluble dans l'huile et d'herbicide soluble dans l'eau WO2002078442A2 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
HU0303734A HUP0303734A2 (hu) 2001-02-14 2002-02-14 Olajban oldható herbicidet és vízben oldható herbicidet tartalmazó készítmények
EP02728358A EP1359800A2 (fr) 2001-02-14 2002-02-14 Co-formulation d'herbicide soluble dans l'huile et d'herbicide soluble dans l'eau
MXPA03007280A MXPA03007280A (es) 2001-02-14 2002-02-14 Co-formulacion de herbicida oleosoluble y un herbicida hidrosoluble.
BR0207259-9A BR0207259A (pt) 2001-02-14 2002-02-14 Coformulação de um herbicida solúvel em óleo e um herbicida solúvel em água
CA002437741A CA2437741A1 (fr) 2001-02-14 2002-02-14 Co-formulation d'herbicide soluble dans l'huile et d'herbicide soluble dans l'eau

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US33134801P 2001-02-14 2001-02-14
US60/331,348 2001-02-14
US26919301P 2001-02-15 2001-02-15
US60/269,193 2001-02-15

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WO2002078442A2 true WO2002078442A2 (fr) 2002-10-10
WO2002078442A3 WO2002078442A3 (fr) 2003-01-03

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PCT/US2002/005734 WO2002078442A2 (fr) 2001-02-14 2002-02-14 Co-formulation d'herbicide soluble dans l'huile et d'herbicide soluble dans l'eau
PCT/US2002/005144 WO2002063955A2 (fr) 2001-02-14 2002-02-14 Coformulation de carfentrazone-éthyle et d'un herbicide hydrosoluble

Family Applications After (1)

Application Number Title Priority Date Filing Date
PCT/US2002/005144 WO2002063955A2 (fr) 2001-02-14 2002-02-14 Coformulation de carfentrazone-éthyle et d'un herbicide hydrosoluble

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EP (1) EP1359800A2 (fr)
CN (1) CN1514686A (fr)
AR (2) AR032691A1 (fr)
AU (1) AU2002245479A1 (fr)
BR (1) BR0207259A (fr)
CA (1) CA2437741A1 (fr)
CZ (1) CZ20032183A3 (fr)
HU (1) HUP0303734A2 (fr)
MX (2) MX237457B (fr)
PL (1) PL364247A1 (fr)
RU (1) RU2003127742A (fr)
WO (2) WO2002078442A2 (fr)

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EP1722628A2 (fr) * 2004-03-12 2006-11-22 Fmc Corporation Composition de glyphosate
WO2007082769A1 (fr) * 2006-01-23 2007-07-26 Syngenta Limited Formule herbicide
US20100041553A1 (en) * 2006-11-13 2010-02-18 Bayer Cropscience Ag Herbicide combinations with particular sulphonyl ureas
WO2011051969A3 (fr) * 2009-10-29 2011-06-16 United Phosphorus Limited Combinaison d'herbicides
CN102334485A (zh) * 2011-11-04 2012-02-01 利尔化学股份有限公司 增效除草农药组合物
CN102428935A (zh) * 2011-12-14 2012-05-02 安徽科立华化工有限公司 一种丙炔噁草酮和丁草胺水乳剂及其制备方法
US8293683B2 (en) 2006-12-06 2012-10-23 Akzo Nobel N.V. Alkylamidopropyl dialkylamine surfactants as adjuvants
CN104430464A (zh) * 2014-11-13 2015-03-25 山东胜邦绿野化学有限公司 一种玉米田复合除草剂及其制备方法
US9012365B2 (en) 2006-12-06 2015-04-21 Akzo Nobel N.V. Compatibility agents for herbicidal formulations comprising 2,4-(Dichlorophenoxy) acetic acid salts
CN104522031A (zh) * 2014-12-29 2015-04-22 陕西上格之路生物科学有限公司 一种含噻酮磺隆的玉米田除草剂组合物
CN105145656A (zh) * 2015-08-31 2015-12-16 潍坊友容实业有限公司 一种抑芽剂及其在盐柏盆景培育中的应用
US9930889B2 (en) 2012-12-12 2018-04-03 Dow Agrosciences Llc Synergistic weed control from applications of penoxsulam and mefenacet
US10085451B2 (en) 2010-08-30 2018-10-02 Dow Agrosciences Llc Synergistic herbicidal composition containing penoxsulam and bentazon
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JP2007528905A (ja) * 2004-03-12 2007-10-18 エフ　エム　シー　コーポレーション グリホセート組成物
EP1722628A4 (fr) * 2004-03-12 2009-04-22 Fmc Corp Composition de glyphosate
EP1722628A2 (fr) * 2004-03-12 2006-11-22 Fmc Corporation Composition de glyphosate
WO2007082769A1 (fr) * 2006-01-23 2007-07-26 Syngenta Limited Formule herbicide
US20100041553A1 (en) * 2006-11-13 2010-02-18 Bayer Cropscience Ag Herbicide combinations with particular sulphonyl ureas
US8883680B2 (en) * 2006-11-13 2014-11-11 Bayer Cropscience Ag Herbicide combinations with particular sulphonyl ureas
US8293683B2 (en) 2006-12-06 2012-10-23 Akzo Nobel N.V. Alkylamidopropyl dialkylamine surfactants as adjuvants
US9012365B2 (en) 2006-12-06 2015-04-21 Akzo Nobel N.V. Compatibility agents for herbicidal formulations comprising 2,4-(Dichlorophenoxy) acetic acid salts
US8815773B2 (en) 2009-07-29 2014-08-26 Upl Limited Herbicidal combination
WO2011051969A3 (fr) * 2009-10-29 2011-06-16 United Phosphorus Limited Combinaison d'herbicides
AU2010313076B2 (en) * 2009-10-29 2014-07-31 Upl Limited Herbicidal combination
CN102595906A (zh) * 2009-10-29 2012-07-18 联合磷业有限公司 除草组合
CN102595906B (zh) * 2009-10-29 2014-12-03 Upl有限公司 除草组合
US10085451B2 (en) 2010-08-30 2018-10-02 Dow Agrosciences Llc Synergistic herbicidal composition containing penoxsulam and bentazon
CN102334485A (zh) * 2011-11-04 2012-02-01 利尔化学股份有限公司 增效除草农药组合物
CN102428935A (zh) * 2011-12-14 2012-05-02 安徽科立华化工有限公司 一种丙炔噁草酮和丁草胺水乳剂及其制备方法
US9930889B2 (en) 2012-12-12 2018-04-03 Dow Agrosciences Llc Synergistic weed control from applications of penoxsulam and mefenacet
CN104430464A (zh) * 2014-11-13 2015-03-25 山东胜邦绿野化学有限公司 一种玉米田复合除草剂及其制备方法
CN104430464B (zh) * 2014-11-13 2015-11-25 山东胜邦绿野化学有限公司 一种玉米田复合除草剂及其制备方法
CN104522031A (zh) * 2014-12-29 2015-04-22 陕西上格之路生物科学有限公司 一种含噻酮磺隆的玉米田除草剂组合物
CN105145656A (zh) * 2015-08-31 2015-12-16 潍坊友容实业有限公司 一种抑芽剂及其在盐柏盆景培育中的应用
JP2018154623A (ja) * 2017-03-15 2018-10-04 日産化学株式会社 水性除草剤組成物

Also Published As

Publication number Publication date
CA2437741A1 (fr) 2002-10-10
EP1359800A2 (fr) 2003-11-12
HUP0303734A2 (hu) 2004-03-29
WO2002063955A2 (fr) 2002-08-22
AR035747A1 (es) 2004-07-07
PL364247A1 (en) 2004-12-13
AR032691A1 (es) 2003-11-19
MXPA03007280A (es) 2003-12-04
WO2002063955A3 (fr) 2003-03-20
WO2002078442A3 (fr) 2003-01-03
RU2003127742A (ru) 2005-03-10
MX237457B (es) 2006-06-02
CN1514686A (zh) 2004-07-21
BR0207259A (pt) 2004-02-10
AU2002245479A1 (en) 2002-08-28
CZ20032183A3 (cs) 2004-02-18
MXPA03007371A (es) 2003-12-04

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