WO2012177851A1 - Herbicide granules with built-in adjuvant - Google Patents

Herbicide granules with built-in adjuvant Download PDF

Info

Publication number
WO2012177851A1
WO2012177851A1 PCT/US2012/043514 US2012043514W WO2012177851A1 WO 2012177851 A1 WO2012177851 A1 WO 2012177851A1 US 2012043514 W US2012043514 W US 2012043514W WO 2012177851 A1 WO2012177851 A1 WO 2012177851A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
herbicide
adjuvant
salt
butyl
Prior art date
Application number
PCT/US2012/043514
Other languages
French (fr)
Inventor
Hiteshkumar Dave
Lei Liu
David G. Ouse
Richard K. Mann
Raymond E. Boucher
Deborah G. Shatley
Toshiya Ogawa
Alan E. Haack
Original Assignee
Dow Agrosciences Llc
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
Priority to ES12802946.9T priority Critical patent/ES2627877T3/en
Application filed by Dow Agrosciences Llc filed Critical Dow Agrosciences Llc
Priority to UAA201400120A priority patent/UA112775C2/en
Priority to IN180DEN2014 priority patent/IN2014DN00180A/en
Priority to CN201280035287.0A priority patent/CN103687487B/en
Priority to AU2012272944A priority patent/AU2012272944B2/en
Priority to RU2013157759A priority patent/RU2610314C2/en
Priority to JP2014517151A priority patent/JP5980322B2/en
Priority to EP12802946.9A priority patent/EP2723175B1/en
Priority to NZ618961A priority patent/NZ618961B2/en
Priority to MX2013015320A priority patent/MX339351B/en
Priority to KR1020147000589A priority patent/KR102032204B1/en
Publication of WO2012177851A1 publication Critical patent/WO2012177851A1/en
Priority to IL230054A priority patent/IL230054B/en

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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • 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
    • A01N25/12—Powders or granules
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • 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
    • A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles

Definitions

  • This invention concerns granules containing a grass-active herbicide and non- petroleum derived built-in adjuvant. Such granules exhibit improved herbicidal efficacy on grass weeds in flooded paddy rice applications.
  • Agrochemical formulations are generally designed based on customer needs and the physiochemical properties of the active ingredients such as, for example, the solubility of the active ingredient in water or non-aqueous solvents. There are two major categories of formulations, solid formulations and liquid formulations.
  • Granule (GR) products containing agricultural active ingredients represent one class of solid formulations that are widely used because of their handling safety compared to liquid formulations and the advantages they offer with regard to cost savings in packaging and transportation.
  • Granule formulations are similar to powder or dust formulations except that the granule particles are larger (average particle size generally greater than about 100 micrometers) than the particles in powders or dusts (average particle size generally less than about 100 micrometers) and therefore present less of a respiratory hazard.
  • Granule products are generally produced from powders and may be used for insect, weed, fungal pathogen and nematode control and are often used in soil and aquatic environments. Because of the particle weight, granules used in aerial applications may pose a reduced hazard from off- target drift compared to aerial liquid spray applications.
  • Active ingredients in the form of solids or liquids, may be formulated as granules and include insecticides, herbicides, fungicides, nematicides and plant growth regulators.
  • Granule formulations usually contain a relatively small amount of the active ingredient since the granules are frequently not further diluted with a carrier solvent such as water prior to use, but are instead applied directly to the area of interest, such as for example, soil or water. Once applied, the active ingredient contained in the granule is released to the area of application, typically upon exposure to water.
  • a carrier solvent such as water prior to use
  • Agricultural granules containing active ingredients may also contain solid inert ingredients that serve as a diluent and/or carrier and may also help maintain the granules in a stable, solid state.
  • solid inert ingredients may include, for example, clays, starches, silicas, sulphates, chlorides, lignosulfonates, carbohydrates such as dextrines, alkylated celluloses, xanthum gums and guaseed gums, and synthetic polymers such as polyvinyl alcohols, sodium polyacrylates, polyethylene oxides, polyvinylpyrrolidones and
  • urea/formaldehyde polymers like PergoPak M® (registered trademark of Albemarle
  • the active ingredient(s) contained in a granule may be melted into a liquid, dissolved in a solvent or dispersed in a liquid, which may then be sprayed onto or absorbed into the solid inert ingredients.
  • dry granules may be physically unstable and, in the case of solid particles, slowly breakdown forming a dust or powder or, in the case of granules containing liquid built-in adjuvants, slowly breakdown forming large liquid droplets as a result of Ostwald Ripening.
  • Many solid inert ingredients used in agricultural granule formulations generally have good water solubility or dispersibility.
  • Adjuvants are important components of granules and are defined as substances which can increase the biological activity of the active ingredient, but are themselves not significantly biologically active. Adjuvants assist with the effectiveness of the active ingredient such as, for example, by improving the delivery and uptake of an herbicide into a target weed plant leading to improved biological control.
  • Adjuvants in the form of solids or liquids, can be added directly to a formulated agricultural product, such as a granule, to provide improved performance of the product upon application.
  • a formulated agricultural product such as a granule
  • Commonly used adjuvants may include, for example, surfactants, spreaders, petroleum and plant derived oils and solvents, and wetting agents.
  • adjuvants include, but are not limited to, paraffin oil, horticultural spray oils (e.g., summer oil), methylated rape seed oil, methylated soybean oil, highly refined vegetable oil and the like, polyol fatty acid esters, polyethoxylated esters, ethoxylated alcohols, alkyl polysaccharides and blends, amine ethoxylates, sorbitan fatty acid ester ethoxylates, polyethylene glycol esters, organosilicone based surfactants, ethylene vinyl acetate terpolymers, ethoxylated alkyl aryl phosphate esters and the like.
  • paraffin oil e.g., summer oil
  • methylated rape seed oil methylated soybean oil
  • highly refined vegetable oil and the like polyol fatty acid esters
  • polyethoxylated esters ethoxylated alcohols
  • alkyl polysaccharides and blends alkyl polysaccharides and
  • built-in adjuvant refers to one or more adjuvants that have been added to a particular formulation, such as a granule or liquid formulation, at the manufacturing stage of the product, rather than at the point of use of the product such as, for example, to a spray solution.
  • a particular formulation such as a granule or liquid formulation
  • the use of built-in adjuvants simplifies the use of agrochemical products for the end-user by reducing the number of ingredients that must be individually measured and applied.
  • Rice is an important cereal crop grown in many parts of the world and is cultivated under both wet and dry conditions. Control of weeds in rice is very important in order to maintain high levels of agricultural productivity. Use of herbicide granules for weed control in flooded paddy rice is a very common agronomic practice in many rice growing regions. New herbicide granule products that offer improved performance relative to current products are needed.
  • Cyhalofop-butyl (2/?)-2-[4-(4-cyano-2-fluorophenoxy)phenoxy]propanoic acid (CAS# 122008-78-0), is a member of the aryloxyphenoxypropionic acid class of herbicides which are known in the art as the fop herbicides and is used to control grass weeds in rice. Cyhalofop-butyl is marketed as Clincher ® herbicide (registered trademark of Dow
  • cyhalofop-butyl contains solid inert ingredients such as potassium chloride, clay or starch combined with built-in adjuvants derived from petroleum such as, for example, aromatic solvents. These built-in adjuvants consist of a maximum of from about 15 to about 20 per cent by weight relative to the total weight of the cyhalofop-butyl granule in currently marketed products.
  • the use of petroleum based built-in adjuvants in current granule products can limit the biological performance of cyhalofop-butyl herbicide due to a minimal herbicidal adjuvant effect.
  • the present invention provides an improvement to existing granules containing grass- active herbicides by the use of non-petroleum derived built-in adjuvants and thereby offer improved herbicidal efficacy on weeds in flooded paddy rice applications.
  • the present invention concerns an herbicide granule containing a built-in adjuvant which comprises: a) an aryloxyphenoxypropionic acid herbicide comprising, with respect to the total composition, from about 5 grams active ingredient per kilogram (gai/kg) to about 50 gai/kg; b) a non-petroleum derived built-in adjuvant comprising, with respect to the total composition, from about 20 g/kg to about 200 g/kg; c) a water soluble solid carrier comprising, with respect to the total
  • composition from about 700 g/kg to about 950 g/kg; and d) a surfactant comprising, with respect to the total composition, from about 1 g/kg to about 50 g/kg; wherein the weight ratio of the herbicide to the non-petroleum derived built-in adjuvant is from about 1:3 to about 1:40.
  • Another aspect of the present invention concerns a method of controlling undesirable vegetation in an aquatic environment which comprises broadcasting or adding the herbicide granule to an aquatic environment either before emergence or after emergence of the undesirable vegetation.
  • Agricultural active ingredients that have low water solubility can sometimes be difficult to effectively apply to crops to eliminate pests. This situation is particularly challenging when the active ingredients are not applied directly to plant foliage such as, for example, when herbicide granule products are used to control weeds in flooded paddy rice.
  • Herbicide granules applied to flooded paddy rice are normally added directly to the water in the paddy rice and have very little direct contact with plant foliage during application.
  • Cyhalofop-butyl is an herbicidal active ingredient that when applied to water in a granule, requires the use of a built-in adjuvant to provide the necessary delivery and uptake of the herbicide into the target weeds and expression of acceptable levels of weed control.
  • Cyhalofop-butyl granules that are currently marketed for the control of weeds in flooded paddy rice contain petroleum derived built-in adjuvants such as, for example, aromatic solvents or oils like ditridecyl phthalate.
  • Cyhalofop-butyl granules that contain non-petroleum derived built-in adjuvants such as, for example, plant-derived methylated seed oils and vegetable oil concentrates have surprising been found to offer improved weed control in aquatic environments such as, for example, flooded paddy rice when compared on a grams active ingredient per hectare (gai/ha) basis to cyhalofop-butyl granules containing petroleum derived adjuvants.
  • the improved weed control is dependent on the weight ratio of the herbicide active ingredient to the non- petroleum derived built-in adjuvant contained in the granule.
  • the granule of the present invention is comprised of an aryloxyphenoxypropionic acid herbicide active ingredient, a non-petroleum derived built-in adjuvant, a water soluble solid carrier and a surfactant.
  • the aryloxyphenoxypropionic acid herbicide active ingredient of the present invention may include, but is not limited to, cyhalofop-butyl, fenoxaprop-ethyl, fluazifop-P- butyl, haloxyfop-methyl, haloxyfop-R-methyl, metamifop, propaquizafop, quizalofop-P-ethyl and quizalofop-P-tefuryl.
  • Preferred aryloxyphenoxypropionic acid herbicide active ingredients of the present invention include cyhalofop-butyl, fenoxaprop-ethyl, haloxyfop- methyl, haloxyfop-R-methyl and metamifop.
  • the aryloxyphenoxypropionic acid herbicide active ingredient of the present invention comprises, with respect to the total composition, from about 5 gai/kg to about 50 gai/kg, preferably from about 10 gai/kg to about 30 gai/kg.
  • the non-petroleum derived built-in adjuvant of the present invention may be in the form of one or more of a naturally derived water immiscible liquid or solid, and a naturally or partially naturally derived non-ionic surfactant.
  • Water immiscible liquids or solids that may be used as the non-petroleum derived built-in adjuvant of the present invention generally have less than about 1 volume per cent solubility in water and may include one or more of a plant, algae or animal derived oil such as, but not limited to, seed oils, vegetable oils, animal oils and esters thereof.
  • Naturally or partially naturally derived non-ionic surfactants that may be used as built-in adjuvants of the present invention include, but are not limited to, polyol fatty acid esters, polyethoxylated naturally derived esters, polyethoxylated naturally derived alcohols, alkyl polysaccharides such as alkyl polyglycosides and blends thereof, fatty acid derived amine ethoxylates, sorbitan fatty acid ester ethoxylates and sucrose esters of fatty acids.
  • Preferred non-petroleum derived built-in adjuvants may include one or more plant derived oils such as soybean oil, rape seed oil, olive oil, castor oil, sunflower seed oil, coconut oil, corn oil, cotton seed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil and the like; Ci-Cio esters of plant derived oils such as methylated seed oils like methyl soyate, 2-ethyl hexyl stearate, n-butyl oleate, isopropyl myristate, propylene glycol dioleate and the like; polyol fatty acid esters; polyethoxylated esters derived from plant derived oils; polyethoxylated alcohols derived from plant derived oils; alkyl polysaccharides such as alkyl polyglycosides and blends thereof; amine ethoxylates derived from plant derived oils; sorbitan fatty acid este
  • the non- petroleum derived built-in adjuvant of the present invention comprises, with respect to the total composition, from about 20 g/kg to about 200 g/kg, preferably from about 50 g/kg to about 180 g/kg and most preferably from about 50 g/kg to about 150 g/kg.
  • the weight ratio of the herbicide active ingredient and the non-petroleum derived built-in adjuvant of the present invention has unexpectedly been found to affect the herbicidal efficacy of the granule when used to control weeds in paddy rice.
  • the weight ratio of the herbicide active ingredient to the non-petroleum derived built-in adjuvant offers improved herbicidal efficacy in the range from about 1 :3 to about 1 :40, and most preferably from about 1 :4 to about 1 :40.
  • the water soluble solid carrier of the present invention may include one or more of a salt of an inorganic or organic acid, a lignosulfonate, a carbohydrate, a fertilizer, a water soluble modified cellulose, a natural gum and a synthetic polymer.
  • Suitable salts of inorganic or organic acids may include alkali metal, magnesium, calcium or ammonium salts of inorganic and organic acids such as hydrochloric acid, sulphuric acid, nitric acid, carbonic acid or acetic acid.
  • Suitable solid carbohydrates may include, for example, glucose, fructose, sucrose, trehalose, lactose and maltose, dextrines, starches and water soluble modified starches.
  • Suitable modified celluloses may include, for example, water soluble alkylated and carboxyalkylated celluloses.
  • Suitable natural gums may include, for example, guar gums, xanthum gums and guarseed gums, and the like.
  • Suitable synthetic polymers may include, for example, polyvinyl alcohols, sodium polyacrylates, polyethylene oxides and
  • Preferred water soluble solid carriers of the present invention may include salts of inorganic acids such as, for example, potassium chloride, potassium sulfate, calcium carbonate and sodium sulfate, fertilizers such as, for example, ammonium sulfate and urea, and lignosulfonates such as, for example, calcium lignosulfonate and sodium lignosulfonate.
  • the water soluble solid carrier of the present invention comprises, with respect to the total composition, from about 700 g/kg to about 950 g/kg.
  • the surfactant of the present invention may be anionic, cationic or nonionic in character and can be employed as emulsifying agents, wetting agents, suspending agents, or for other purposes.
  • Surfactants conventionally used in the art of formulation and which may also be used in the present formulations are described, inter alia, in "McCutcheon's
  • Typical surface- active agents include salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; alkylarylsulfonate salts, such as calcium dodecylbenzenesulfonate;
  • alkylphenol-alkylene oxide addition products such as nonylphenol-Cis ethoxylate
  • alcohol- alky lene oxide addition products such as tridecyl alcohol-Ci6 ethoxylate
  • soaps such as sodium stearate
  • alkylnaphthalene-sulfonate salts such as sodium dibutyl- naphthalenesulfonate
  • dialkyl esters of sulfosuccinate salts such as sodium di(octyl) sulfo- succinate
  • sorbitol esters such as sorbitol oleate
  • quaternary amines such as lauryl trimethyl- ammonium chloride
  • polyethylene glycol esters of fatty acids such as polyethylene glycol stearate
  • salts of mono and dialkyl phosphate esters and mixtures thereof.
  • the surfactant of the present invention comprises, with respect to the total composition, from about 1 g/kg to about 50 g/kg.
  • a homogeneous oil phase is prepared by mixing together the aryloxyphenoxypropionic acid herbicide active ingredient, the non-petroleum derived built-in adjuvant and the surfactant, optionally with the use of heat as needed.
  • the oil phase is then combined with the granular solid carrier and mixed well to provide the granule of the present invention.
  • An example of an herbicide granule of the present invention containing a non- petroleum derived built-in adjuvant comprises: a) an aryloxyphenoxypropionic acid herbicide active ingredient comprising, with respect to the total composition, from about 5 gai/kg to about 50 gai/kg of cyhalofop-butyl; b) a non-petroleum derived built-in adjuvant comprising, with respect to the total composition, from about 20 g/kg to about 200 g/kg of methyl soyate; c) a water soluble solid carrier comprising, with respect to the total
  • composition from about 500 g/kg to about 950 g/kg of potassium chloride; and d) a surfactant comprising, with respect to the total composition, from about 1 g/kg to about 50 g/kg of sodium dioctyl sulfosuccinate; wherein the weight ratio of cyhalofop-butyl to methyl soyate is from about 1:3 to about 1:40.
  • Another aspect of the present invention concerns a method of controlling undesirable vegetation by broadcasting or adding the herbicide granule of the present invention into an aquatic environment such as rice paddys, ponds, lakes and streams and the like for the control of undesirable vegetation.
  • a herbicidally effective amount of the herbicide granules is applied to an area of water to provide suitable control of undesirable vegetation.
  • the herbicide granule of the present invention is particularly useful for the control of grass weeds in flooded rice paddys or fields and offers improved herbicidal performance relative to current granule products that contain petroleum derived adjuvants and are used to control grass weeds in flooded rice paddys or fields.
  • Granule formulations can be produced using one or more of the following processing methods: (1) pan granulation, (2) mixing agglomeration, (3) extrusion granulation, (4) fluid bed granulation or (5) spray drying granulation.
  • the physico-chemical properties of the active ingredient and additives are important to consider when choosing a process to use.
  • the present invention also embraces compositions containing one or more additional pesticide active ingredients, plant growth regulators or safeners that are added to the granule of the present invention.
  • pesticide active ingredients, plant growth regulators and safeners may include one or more of an herbicide, an insecticide, a fungicide, a plant growth regulator or an herbicide safener.
  • Suitable herbicides that may be added to the granule of the present invention include clodinafop-propargyl, clethodim, cycloxydim, diclofop-methyl, , fenoxaprop-ethyl + isoxidifen-ethyl, pinoxaden, profoxydim, propaquizafop, quizalofop-P-ethyl, quizalofop-P- tefuryl, sethoxydim, tepraloxydim, tralkoxydim, 2,4-D esters and salts, 2,4-MCPA, 2,4- MCPA esters and salts, acetochlor, acifluorfen, alachlor, amidosulfuron, aminopyralid, aminotriazole, ammonium thiocyanate, anilifos, azimsulfuron, benfuresate, bensulfuron- methyl, bentazon, bentazone-s
  • Ar is a polysubstituted phenyl group and R is H or halo and X is halo.
  • suitable herbicides that may be added to the granule of the present invention include penoxsulam and bensulfuron-methyl.
  • Suitable insecticides that may be added to the granule of the present invention include abamectin, acephate, acetamiprid, acrinathrin, ⁇ / ⁇ -cypermethrin, ⁇ / ⁇ ⁇ -endosulfan, azadirachtin, azinphos-ethyl, azinphos -methyl, bendiocarb, benfuracarb, bensultap, beta- cyfluthrin, ⁇ eto-cypermethrin, bifenthrin, bufencarb, buprofezin, butacarb, cadusafos, carbaryl, carbofuran, carbosulfan, cartap, cartap hydrochloride, chlorantraniliprole, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos- methyl, chromaf
  • pirimetaphos pirimicarb, pirimiphos-ethyl, pirimiphos-methyl, primidophos, profenofos, profluthrin, promecarb, propaphos, propoxur, prothiofos, pymetrozine, pyrafluprole, , pyridalyl, pyrifluquinazon, pyriprole, pyriproxyfen, spinetoram, spinosad, spirotetramat, sulfoxaflor, sulprofos, toi/-fluvalinate, tebufenozide, tebufenpyrad, teflubenzuron, tefluthrin, tetramethylfluthrin, ⁇ zeto-cypermethrin, thiacloprid, thiamethoxam, thicrofos, thiocyclam, thiocyclam oxa
  • Suitable fungicides that may be added to the granule of the present invention include tricyclazole, phthalide, carpropamide, pyroquilon, diclocymet, fenoxanil, probenazole, isoprothiolane, iprobenfos, isotianil, tiadinil, kasugamycin, flutolanil, mepronil, pencycuron, polyoxins, validamycin, toclophos-methyl, boscalid, penthiopyrad, thifluzamide, bixafen, fluopyram, isopyrazam, propiconazole, difenoconazole, fenbuconazole, ipconazole, triadimefon, hexaconazole, azoxystrobin, metaminostrobin, orysastrobin, trifloxystrobin and acibenzolar-S-methyl.
  • Some of these fungicides may not be effective for disease control when applied at the timing of an herbicide granule application because fungal disease propagation and growth cycles may not match the targeted weed growth cycles.
  • the effective use and application timing of these fungicides can be easily determined by one of normal skill in the art.
  • Suitable herbicide safeners that may be added to the granule of the present invention include benoxacor, benthiocarb, cloquintocet-mexyl, daimuron, dichlormid, dicyclonon, dimepiperate, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, furilazole, Harpin proteins, isoxadifen-ethyl, mefenpyr-diethyl, mephenate, MG 191, MON 4660, naphthalic anhydride (NA), oxabetrinil, R29148 and N-phenyl-sulfonylbenzoic acid amides.
  • benoxacor benthiocarb
  • cloquintocet-mexyl daimuron
  • dichlormid dicyclonon, dimepiperate
  • fenchlorazole-ethyl fenclorim
  • flurazole fluxofen
  • Suitable plant growth regulators that may be added to the granule of the present invention include 2,4-D, 2,4-DB, IAA, IB A, naphthaleneacetamide, a-naphthaleneacetic acid, kinetin, zeatin, ethephon, aviglycine, 1-methylcyclopropene (1-MCP), ethephon, gibberellins, gibberellic acid, abscisic acid, ancymidol, flurprimidol, mefluidide, paclobutrazol, tetcyclacis, uniconazole, brassinolide, brassinolide-ethyl and ethylene.
  • the present invention also embraces the composition and use of these herbicide granules in combination with one or more additional compatible ingredients which may include, for example, one or more agrochemical active ingredients, plant growth regulators or herbicide safeners, surfactants, dyes, fertilizers and micronutrients, growth regulators and pheromones and any other additional ingredients providing functional utility, such as, for example, stabilizers, fragrants, defoamers and dispersants.
  • the granule of the present invention may optionally be diluted in a spray tank containing water carrier and the resulting aqueous mixture used for spray application to control weeds.
  • compositions of the present invention When the compositions of the present invention are used in combination with additional active ingredients the presently claimed compositions can be formulated with the additional active ingredient or active ingredients as mixtures of granules, they may be tank mixed with the additional active ingredient or active ingredients for spray application or they may be applied sequentially with the additional active ingredient or active ingredients in separate spray or granule applications. It is usually desirable to incorporate one or more surface- active agents into the tank mixtures formed with the compositions of the present invention when used in conjunction with the additional active ingredients described herein. Such surface- active agents may advantageously be employed in both solid and liquid compositions, especially those designed to be diluted with carrier before application.
  • the surface-active agents can be anionic, cationic or nonionic in character and can be employed as emulsifying agents, wetting agents, suspending agents, or for other purposes.
  • Surfactants conventionally used in the art of formulation and which may also be used in the present formulations are described, inter alia, in "McCutcheon' s Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, New Jersey, 1998 and in "Encyclopedia of Surfactants", Vol. I-III, Chemical publishing Co., New York, 1980-81.
  • Typical surface-active agents include salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; alkylarylsulfonate salts, such as calcium dodecylbenzene- sulfonate; alky lphenol- alky lene oxide addition products, such as nonylphenol-Cis ethoxylate; alcohol- alky lene oxide addition products, such as tridecyl alcohol-Ci6 ethoxylate; soaps, such as sodium stearate; alkylnaphthalene-sulfonate salts, such as sodium dibutyl- naphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2-ethylhexyl) sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryl trimethylammonium chloride; poly
  • Potassium chloride (KC1) core granules were obtained from Nippon Kayaku Co., Ltd. (Japan) and used as received. Cyhalofop-butyl, methyl soyate and Polyglycol 26-2 (Dow Chemical) are melted together in a flask via a heated water bath controlled at 60-65 °C to give a homogeneous liquid oil phase. Then, the required amount of KC1 core granules is added to the liquid oil phase. The KC1 core granules and oil phase are mixed thoroughly to ensure uniform absorption of the molten oil phase into the KC1 core granules to provide Granule A of Table 1.
  • Simulated rice paddy preparation Two kg of mineral soil and 500 ml of distilled water were added to the container (4.163 L (1.1 gallon), 15 cm ht x 20.55 cm diameter, HDPE round container; for treatment purposes the surface area is calculated as 331 cm 2 with 1 hectare equivalent to 10 8 cm 2 ) and thoroughly mixed with a spatula for about 5 minutes to create a smooth mud mix. Once the mud is mixed, a 3 cm. furrow is made across the middle of the
  • Osmocote registered trademark of The Scotts Company LLC or its affiliates; 17:6: 10 N:P:K. The furrow is then sealed keeping the
  • the wrap is held in place by masking tape until the Leptochloa seed germinates, about 5 days.
  • the covered pots are kept in the greenhouse at a constant temperature of 18 to 22 °C and 50 to 60% relative humidity.
  • Natural light was supplemented with 1000- watt metal halide overhead lamps with an average illumination of 500 microeinsteins ( ⁇ ) m "2 s "1 photosynthetic active radiation (PAR). Day length was 16 hours.
  • barnyard grass seed is sprinkled along this trench and then covered with white sand.
  • the plants are allowed to grow until they reach 6-8 cm height in about 8 days.
  • Treatments were replicated 2-3 times. At intervals, percent visual injury and weed control assessments were made on a scale of 0 to 100% compared to the untreated control plants (where 0 is equal to no injury or control and 100 is equal to complete death of the plant).
  • ORYSJ Paddy rice, Oryza sativa subsp. japonica var. M202
  • LEFCH Chinese sprangletop, Leptochloa chinensis
  • ECHCG Barnyard grass, Echinochloa crus-galli
  • XGA-2444 is a C1 granule formulation containing 18 g/kg of cyhalofop-butyl and 115 g/kg of the petroleum derived adjuvant ditridecyl phthalate (Clincher 1 G from Nippon Kayaku Co., Ltd. of Japan)
  • Clincher CA (registered trademark of Dow AgroSciences LLC) is an EC formulation containing 285 grams per liter of cyhalofop-butyl and a petroleum derived adjuvant/solvent.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Agronomy & Crop Science (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Toxicology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

Provided herein are herbicide granules containing non-petroleum derived built-in adjuvant.

Description

HERBICIDE GRANULES WITH BUILT-IN ADJUVANT
Cross Reference to Related Applications
This application claims the benefit of U.S. Provisional Application No. 61/499,887, filed June 22, 2011, the entirety of which is incorporated herein by reference.
Field
This invention concerns granules containing a grass-active herbicide and non- petroleum derived built-in adjuvant. Such granules exhibit improved herbicidal efficacy on grass weeds in flooded paddy rice applications.
Background
Agrochemical formulations are generally designed based on customer needs and the physiochemical properties of the active ingredients such as, for example, the solubility of the active ingredient in water or non-aqueous solvents. There are two major categories of formulations, solid formulations and liquid formulations.
Granule (GR) products containing agricultural active ingredients represent one class of solid formulations that are widely used because of their handling safety compared to liquid formulations and the advantages they offer with regard to cost savings in packaging and transportation. Granule formulations are similar to powder or dust formulations except that the granule particles are larger (average particle size generally greater than about 100 micrometers) than the particles in powders or dusts (average particle size generally less than about 100 micrometers) and therefore present less of a respiratory hazard. Granule products are generally produced from powders and may be used for insect, weed, fungal pathogen and nematode control and are often used in soil and aquatic environments. Because of the particle weight, granules used in aerial applications may pose a reduced hazard from off- target drift compared to aerial liquid spray applications.
Active ingredients, in the form of solids or liquids, may be formulated as granules and include insecticides, herbicides, fungicides, nematicides and plant growth regulators.
Granule formulations usually contain a relatively small amount of the active ingredient since the granules are frequently not further diluted with a carrier solvent such as water prior to use, but are instead applied directly to the area of interest, such as for example, soil or water. Once applied, the active ingredient contained in the granule is released to the area of application, typically upon exposure to water.
Agricultural granules containing active ingredients may also contain solid inert ingredients that serve as a diluent and/or carrier and may also help maintain the granules in a stable, solid state. These solid inert ingredients may include, for example, clays, starches, silicas, sulphates, chlorides, lignosulfonates, carbohydrates such as dextrines, alkylated celluloses, xanthum gums and guaseed gums, and synthetic polymers such as polyvinyl alcohols, sodium polyacrylates, polyethylene oxides, polyvinylpyrrolidones and
urea/formaldehyde polymers like PergoPak M® (registered trademark of Albemarle
Corporation). The active ingredient(s) contained in a granule may be melted into a liquid, dissolved in a solvent or dispersed in a liquid, which may then be sprayed onto or absorbed into the solid inert ingredients. In the absence of effective solid inert ingredients, dry granules may be physically unstable and, in the case of solid particles, slowly breakdown forming a dust or powder or, in the case of granules containing liquid built-in adjuvants, slowly breakdown forming large liquid droplets as a result of Ostwald Ripening. Many solid inert ingredients used in agricultural granule formulations generally have good water solubility or dispersibility.
Adjuvants are important components of granules and are defined as substances which can increase the biological activity of the active ingredient, but are themselves not significantly biologically active. Adjuvants assist with the effectiveness of the active ingredient such as, for example, by improving the delivery and uptake of an herbicide into a target weed plant leading to improved biological control.
Adjuvants, in the form of solids or liquids, can be added directly to a formulated agricultural product, such as a granule, to provide improved performance of the product upon application. Commonly used adjuvants may include, for example, surfactants, spreaders, petroleum and plant derived oils and solvents, and wetting agents. Examples of commonly used adjuvants include, but are not limited to, paraffin oil, horticultural spray oils (e.g., summer oil), methylated rape seed oil, methylated soybean oil, highly refined vegetable oil and the like, polyol fatty acid esters, polyethoxylated esters, ethoxylated alcohols, alkyl polysaccharides and blends, amine ethoxylates, sorbitan fatty acid ester ethoxylates, polyethylene glycol esters, organosilicone based surfactants, ethylene vinyl acetate terpolymers, ethoxylated alkyl aryl phosphate esters and the like. These and other adjuvants are described in the "Compendium of Herbicide Adjuvants, 9th Edition, " edited by Bryan Young, Dept. of Plant, Soil and Agricultural Systems, Southern Illinois University MC-4415, 1205 Lincoln Drive, Carbondale, IL 62901, which is available for viewing on the internet at http://www.herbicide-adjuvants.com/.
The term "built-in adjuvant" refers to one or more adjuvants that have been added to a particular formulation, such as a granule or liquid formulation, at the manufacturing stage of the product, rather than at the point of use of the product such as, for example, to a spray solution. The use of built-in adjuvants simplifies the use of agrochemical products for the end-user by reducing the number of ingredients that must be individually measured and applied.
Rice is an important cereal crop grown in many parts of the world and is cultivated under both wet and dry conditions. Control of weeds in rice is very important in order to maintain high levels of agricultural productivity. Use of herbicide granules for weed control in flooded paddy rice is a very common agronomic practice in many rice growing regions. New herbicide granule products that offer improved performance relative to current products are needed.
Cyhalofop-butyl, (2/?)-2-[4-(4-cyano-2-fluorophenoxy)phenoxy]propanoic acid (CAS# 122008-78-0), is a member of the aryloxyphenoxypropionic acid class of herbicides which are known in the art as the fop herbicides and is used to control grass weeds in rice. Cyhalofop-butyl is marketed as Clincher® herbicide (registered trademark of Dow
AgroSciences LLC) and is sold in granule (GR), oil in water (EW) and emulsifiable concentrate (EC) formulations and exhibits good selectivity to rice when used in both dry land and flooded paddy applications. Existing commercial granule formulations of cyhalofop-butyl contain solid inert ingredients such as potassium chloride, clay or starch combined with built-in adjuvants derived from petroleum such as, for example, aromatic solvents. These built-in adjuvants consist of a maximum of from about 15 to about 20 per cent by weight relative to the total weight of the cyhalofop-butyl granule in currently marketed products. The use of petroleum based built-in adjuvants in current granule products can limit the biological performance of cyhalofop-butyl herbicide due to a minimal herbicidal adjuvant effect. The present invention provides an improvement to existing granules containing grass- active herbicides by the use of non-petroleum derived built-in adjuvants and thereby offer improved herbicidal efficacy on weeds in flooded paddy rice applications.
Summary
The present invention concerns an herbicide granule containing a built-in adjuvant which comprises: a) an aryloxyphenoxypropionic acid herbicide comprising, with respect to the total composition, from about 5 grams active ingredient per kilogram (gai/kg) to about 50 gai/kg; b) a non-petroleum derived built-in adjuvant comprising, with respect to the total composition, from about 20 g/kg to about 200 g/kg; c) a water soluble solid carrier comprising, with respect to the total
composition, from about 700 g/kg to about 950 g/kg; and d) a surfactant comprising, with respect to the total composition, from about 1 g/kg to about 50 g/kg; wherein the weight ratio of the herbicide to the non-petroleum derived built-in adjuvant is from about 1:3 to about 1:40.
Another aspect of the present invention concerns a method of controlling undesirable vegetation in an aquatic environment which comprises broadcasting or adding the herbicide granule to an aquatic environment either before emergence or after emergence of the undesirable vegetation.
Detailed Description
Agricultural active ingredients that have low water solubility can sometimes be difficult to effectively apply to crops to eliminate pests. This situation is particularly challenging when the active ingredients are not applied directly to plant foliage such as, for example, when herbicide granule products are used to control weeds in flooded paddy rice. Herbicide granules applied to flooded paddy rice are normally added directly to the water in the paddy rice and have very little direct contact with plant foliage during application.
Cyhalofop-butyl is an herbicidal active ingredient that when applied to water in a granule, requires the use of a built-in adjuvant to provide the necessary delivery and uptake of the herbicide into the target weeds and expression of acceptable levels of weed control.
Cyhalofop-butyl granules that are currently marketed for the control of weeds in flooded paddy rice contain petroleum derived built-in adjuvants such as, for example, aromatic solvents or oils like ditridecyl phthalate.
Cyhalofop-butyl granules that contain non-petroleum derived built-in adjuvants such as, for example, plant-derived methylated seed oils and vegetable oil concentrates have surprising been found to offer improved weed control in aquatic environments such as, for example, flooded paddy rice when compared on a grams active ingredient per hectare (gai/ha) basis to cyhalofop-butyl granules containing petroleum derived adjuvants. The improved weed control is dependent on the weight ratio of the herbicide active ingredient to the non- petroleum derived built-in adjuvant contained in the granule. The granule of the present invention is comprised of an aryloxyphenoxypropionic acid herbicide active ingredient, a non-petroleum derived built-in adjuvant, a water soluble solid carrier and a surfactant.
The aryloxyphenoxypropionic acid herbicide active ingredient of the present invention may include, but is not limited to, cyhalofop-butyl, fenoxaprop-ethyl, fluazifop-P- butyl, haloxyfop-methyl, haloxyfop-R-methyl, metamifop, propaquizafop, quizalofop-P-ethyl and quizalofop-P-tefuryl. Preferred aryloxyphenoxypropionic acid herbicide active ingredients of the present invention include cyhalofop-butyl, fenoxaprop-ethyl, haloxyfop- methyl, haloxyfop-R-methyl and metamifop. The aryloxyphenoxypropionic acid herbicide active ingredient of the present invention comprises, with respect to the total composition, from about 5 gai/kg to about 50 gai/kg, preferably from about 10 gai/kg to about 30 gai/kg.
The non-petroleum derived built-in adjuvant of the present invention may be in the form of one or more of a naturally derived water immiscible liquid or solid, and a naturally or partially naturally derived non-ionic surfactant. Water immiscible liquids or solids that may be used as the non-petroleum derived built-in adjuvant of the present invention generally have less than about 1 volume per cent solubility in water and may include one or more of a plant, algae or animal derived oil such as, but not limited to, seed oils, vegetable oils, animal oils and esters thereof. Naturally or partially naturally derived non-ionic surfactants that may be used as built-in adjuvants of the present invention include, but are not limited to, polyol fatty acid esters, polyethoxylated naturally derived esters, polyethoxylated naturally derived alcohols, alkyl polysaccharides such as alkyl polyglycosides and blends thereof, fatty acid derived amine ethoxylates, sorbitan fatty acid ester ethoxylates and sucrose esters of fatty acids.
Preferred non-petroleum derived built-in adjuvants may include one or more plant derived oils such as soybean oil, rape seed oil, olive oil, castor oil, sunflower seed oil, coconut oil, corn oil, cotton seed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil and the like; Ci-Cio esters of plant derived oils such as methylated seed oils like methyl soyate, 2-ethyl hexyl stearate, n-butyl oleate, isopropyl myristate, propylene glycol dioleate and the like; polyol fatty acid esters; polyethoxylated esters derived from plant derived oils; polyethoxylated alcohols derived from plant derived oils; alkyl polysaccharides such as alkyl polyglycosides and blends thereof; amine ethoxylates derived from plant derived oils; sorbitan fatty acid ester ethoxylates; and sucrose esters of fatty acids. The non- petroleum derived built-in adjuvant of the present invention comprises, with respect to the total composition, from about 20 g/kg to about 200 g/kg, preferably from about 50 g/kg to about 180 g/kg and most preferably from about 50 g/kg to about 150 g/kg.
The weight ratio of the herbicide active ingredient and the non-petroleum derived built-in adjuvant of the present invention has unexpectedly been found to affect the herbicidal efficacy of the granule when used to control weeds in paddy rice. The weight ratio of the herbicide active ingredient to the non-petroleum derived built-in adjuvant offers improved herbicidal efficacy in the range from about 1 :3 to about 1 :40, and most preferably from about 1 :4 to about 1 :40. The water soluble solid carrier of the present invention may include one or more of a salt of an inorganic or organic acid, a lignosulfonate, a carbohydrate, a fertilizer, a water soluble modified cellulose, a natural gum and a synthetic polymer. Suitable salts of inorganic or organic acids may include alkali metal, magnesium, calcium or ammonium salts of inorganic and organic acids such as hydrochloric acid, sulphuric acid, nitric acid, carbonic acid or acetic acid. Suitable solid carbohydrates may include, for example, glucose, fructose, sucrose, trehalose, lactose and maltose, dextrines, starches and water soluble modified starches. Suitable modified celluloses may include, for example, water soluble alkylated and carboxyalkylated celluloses. Suitable natural gums may include, for example, guar gums, xanthum gums and guarseed gums, and the like. Suitable synthetic polymers may include, for example, polyvinyl alcohols, sodium polyacrylates, polyethylene oxides and
polyvinylpyrrolidones . Preferred water soluble solid carriers of the present invention may include salts of inorganic acids such as, for example, potassium chloride, potassium sulfate, calcium carbonate and sodium sulfate, fertilizers such as, for example, ammonium sulfate and urea, and lignosulfonates such as, for example, calcium lignosulfonate and sodium lignosulfonate. The water soluble solid carrier of the present invention comprises, with respect to the total composition, from about 700 g/kg to about 950 g/kg.
The surfactant of the present invention may be anionic, cationic or nonionic in character and can be employed as emulsifying agents, wetting agents, suspending agents, or for other purposes. Surfactants conventionally used in the art of formulation and which may also be used in the present formulations are described, inter alia, in "McCutcheon's
Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, New Jersey, 1998 and in "Encyclopedia of Surfactants", Vol. I-III, Chemical publishing Co., New York, 1980- 81. Typical surface- active agents include salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; alkylarylsulfonate salts, such as calcium dodecylbenzenesulfonate;
alkylphenol-alkylene oxide addition products, such as nonylphenol-Cis ethoxylate;
alcohol- alky lene oxide addition products, such as tridecyl alcohol-Ci6 ethoxylate; soaps, such as sodium stearate; alkylnaphthalene-sulfonate salts, such as sodium dibutyl- naphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(octyl) sulfo- succinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryl trimethyl- ammonium chloride; polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; salts of mono and dialkyl phosphate esters; and mixtures thereof. The surfactant of the present invention comprises, with respect to the total composition, from about 1 g/kg to about 50 g/kg.
In a typical procedure for preparing the granule of the present invention a homogeneous oil phase is prepared by mixing together the aryloxyphenoxypropionic acid herbicide active ingredient, the non-petroleum derived built-in adjuvant and the surfactant, optionally with the use of heat as needed. The oil phase is then combined with the granular solid carrier and mixed well to provide the granule of the present invention. An example of an herbicide granule of the present invention containing a non- petroleum derived built-in adjuvant comprises: a) an aryloxyphenoxypropionic acid herbicide active ingredient comprising, with respect to the total composition, from about 5 gai/kg to about 50 gai/kg of cyhalofop-butyl; b) a non-petroleum derived built-in adjuvant comprising, with respect to the total composition, from about 20 g/kg to about 200 g/kg of methyl soyate; c) a water soluble solid carrier comprising, with respect to the total
composition, from about 500 g/kg to about 950 g/kg of potassium chloride; and d) a surfactant comprising, with respect to the total composition, from about 1 g/kg to about 50 g/kg of sodium dioctyl sulfosuccinate; wherein the weight ratio of cyhalofop-butyl to methyl soyate is from about 1:3 to about 1:40.
Another aspect of the present invention concerns a method of controlling undesirable vegetation by broadcasting or adding the herbicide granule of the present invention into an aquatic environment such as rice paddys, ponds, lakes and streams and the like for the control of undesirable vegetation. In this aspect, a herbicidally effective amount of the herbicide granules is applied to an area of water to provide suitable control of undesirable vegetation. The herbicide granule of the present invention is particularly useful for the control of grass weeds in flooded rice paddys or fields and offers improved herbicidal performance relative to current granule products that contain petroleum derived adjuvants and are used to control grass weeds in flooded rice paddys or fields.
Granule formulations can be produced using one or more of the following processing methods: (1) pan granulation, (2) mixing agglomeration, (3) extrusion granulation, (4) fluid bed granulation or (5) spray drying granulation. The physico-chemical properties of the active ingredient and additives are important to consider when choosing a process to use. G. A. Bell and D. A. Knowles in, "Chemistry and Technology of Agrochemical Formulations," D. A. Knowles, editor, (Kluwer Academic Publishers, 1998), pages 41-114, describe the types of granules used in agricultural chemical formulations and provide many references to the production of these solid formulations.
In addition to the compositions set forth above, the present invention also embraces compositions containing one or more additional pesticide active ingredients, plant growth regulators or safeners that are added to the granule of the present invention. These pesticide active ingredients, plant growth regulators and safeners may include one or more of an herbicide, an insecticide, a fungicide, a plant growth regulator or an herbicide safener.
Suitable herbicides that may be added to the granule of the present invention include clodinafop-propargyl, clethodim, cycloxydim, diclofop-methyl, , fenoxaprop-ethyl + isoxidifen-ethyl, pinoxaden, profoxydim, propaquizafop, quizalofop-P-ethyl, quizalofop-P- tefuryl, sethoxydim, tepraloxydim, tralkoxydim, 2,4-D esters and salts, 2,4-MCPA, 2,4- MCPA esters and salts, acetochlor, acifluorfen, alachlor, amidosulfuron, aminopyralid, aminotriazole, ammonium thiocyanate, anilifos, azimsulfuron, benfuresate, bensulfuron- methyl, bentazon, bentazone-sodium, benthiocarb, benzobicyclon, benzofenap, bifenox, bispyribac-sodium, bromobutide, butachlor, cafenstrole, carfentrazone-ethyl, chlorimuron, chlorpropham, cinosulfuron, clomazone, clomeprop. clopyralid, cloransulam-methyl, cyclosulfamuron, cumyluron, daimuron, diclosulam, diflufenican, dimepiperate,
dimethametryn, diquat, dithiopyr, EK2612, EPTC, esprocarb, ET-751, ethoxysulfuron, ethbenzanid, fenoxasulfone, fentrazamide, flazasulfuron, florasulam, fluazifop,
flucetosulfuron, flufenacet, flufenpyr-ethyl, flumetsulam, flumioxazin, flupyrsulfuron, fluroxypyr, fluroxypyr esters and salts, fomesafen, foramsulfuron, glufosinate, glufosinate-P, glyphosate, halosulfuron-methyl, imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, indanofan, ioxynil, ipfencarbazone, MCPB, mefenacet, mesosulfuron, mesotrione, metazosulfuron, metolachlor, metosulam, metsulfuron, molinate, monosulfuron, MSMA, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxazichlomefone, oxyfluorfen, pendimethalin, penoxsulam, pentoxazone, pethoxamid, picloram, piperophos, pretilachlor, primisulfuron, prohexadione-calcium, propachlor, propanil, propisochlor, propyrisulfuron, prosulfuron, pyrabuticarb, pyraclonil, pyrazogyl, pyrazolynate, pyrazosulfuron-ethyl, pyrazoxyfen, pyribenzoxim, pyridate, pyriftalid, pyriminobac-methyl, pyrimisulfan, pyroxsulam, quinoclamine, quinclorac, S-3252, simazine, simetryne, s-metolachlor, sulcotrione, sulfentrazone, sulfosate, tefuryltrione, thenylchlor, thiazopyr, thiobencarb, triclopyr esters and salts, triafamone, trifluralin, trinexapac-ethyl, tritosulfuron and compounds of the following generic structures and their derivatives as disclosed in US7314849 B2 and US7300907 B2
Figure imgf000011_0001
wherein Ar is a polysubstituted phenyl group and R is H or halo and X is halo. Especially suitable herbicides that may be added to the granule of the present invention include penoxsulam and bensulfuron-methyl.
Suitable insecticides that may be added to the granule of the present invention include abamectin, acephate, acetamiprid, acrinathrin, α/ρΛα-cypermethrin, α/ρ ζα-endosulfan, azadirachtin, azinphos-ethyl, azinphos -methyl, bendiocarb, benfuracarb, bensultap, beta- cyfluthrin, ^eto-cypermethrin, bifenthrin, bufencarb, buprofezin, butacarb, cadusafos, carbaryl, carbofuran, carbosulfan, cartap, cartap hydrochloride, chlorantraniliprole, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos- methyl, chromafenozide, clothianidin, cyantraniliprole, cyfluthrin, cyhalothrin, cypermethrin, deltamethrin, diazinon, dicrotophos, diflubenzuron, dimethoate dinotefuran, disulfoton, emamectin, emamectin benzoate, endosulfan, endothion, endrin, EPN, esfenvalerate, etaphos, ethiofencarb, ethion, ethiprole, ethoate-methyl, etofenprox, fenamiphos, fenazaflor, fenethacarb, fenitrothion, fenobucarb, fenpropathrin, fensulfothion, fenthion, fenthion-ethyl, fenvalerate, fipronil, flonicamid, flubendiamide, flucythrinate, fonofos, fufenozide, furathiocarb, gamma-cyhalothrin, gamma-HCH, halfenprox, halofenozide, heptenophos, hyquincarb, imidacloprid, indoxacarb, isazofos, isobenzan, isocarbophos, isofenphos, isofenphos -methyl, isoprocarb, isothioate, isoxathion, kinoprene, /amMa-cyhalothrin, lepimectin, lufenuron, malathion, methamidophos, methomyl, methoxyfenozide, mevinphos, mexacarbate, milbemectin, monocrotophos, nitenpyram, novaluron, omethoate, oxamyl, oxydemeton-methyl, oxydeprofos, oxydisulfoton, parathion, parathion-methyl, penfluron, permethrin, phenthoate, phorate, phosalone, phosfolan, phosmet, phosphamidon,
pirimetaphos, pirimicarb, pirimiphos-ethyl, pirimiphos-methyl, primidophos, profenofos, profluthrin, promecarb, propaphos, propoxur, prothiofos, pymetrozine, pyrafluprole, , pyridalyl, pyrifluquinazon, pyriprole, pyriproxyfen, spinetoram, spinosad, spirotetramat, sulfoxaflor, sulprofos, toi/-fluvalinate, tebufenozide, tebufenpyrad, teflubenzuron, tefluthrin, tetramethylfluthrin, ί zeto-cypermethrin, thiacloprid, thiamethoxam, thicrofos, thiocyclam, thiocyclam oxalate, thiodicarb, thiometon, thiosultap, thiosultap-disodium, thiosultap- monosodium, thuringiensin, tolfenpyrad, triazophos, triflumuron and zeto-cypermethrin.
Suitable fungicides that may be added to the granule of the present invention include tricyclazole, phthalide, carpropamide, pyroquilon, diclocymet, fenoxanil, probenazole, isoprothiolane, iprobenfos, isotianil, tiadinil, kasugamycin, flutolanil, mepronil, pencycuron, polyoxins, validamycin, toclophos-methyl, boscalid, penthiopyrad, thifluzamide, bixafen, fluopyram, isopyrazam, propiconazole, difenoconazole, fenbuconazole, ipconazole, triadimefon, hexaconazole, azoxystrobin, metaminostrobin, orysastrobin, trifloxystrobin and acibenzolar-S-methyl. Some of these fungicides may not be effective for disease control when applied at the timing of an herbicide granule application because fungal disease propagation and growth cycles may not match the targeted weed growth cycles. The effective use and application timing of these fungicides can be easily determined by one of normal skill in the art. Suitable herbicide safeners that may be added to the granule of the present invention include benoxacor, benthiocarb, cloquintocet-mexyl, daimuron, dichlormid, dicyclonon, dimepiperate, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, furilazole, Harpin proteins, isoxadifen-ethyl, mefenpyr-diethyl, mephenate, MG 191, MON 4660, naphthalic anhydride (NA), oxabetrinil, R29148 and N-phenyl-sulfonylbenzoic acid amides. Suitable plant growth regulators that may be added to the granule of the present invention include 2,4-D, 2,4-DB, IAA, IB A, naphthaleneacetamide, a-naphthaleneacetic acid, kinetin, zeatin, ethephon, aviglycine, 1-methylcyclopropene (1-MCP), ethephon, gibberellins, gibberellic acid, abscisic acid, ancymidol, flurprimidol, mefluidide, paclobutrazol, tetcyclacis, uniconazole, brassinolide, brassinolide-ethyl and ethylene. In addition to the compositions and uses set forth above, the present invention also embraces the composition and use of these herbicide granules in combination with one or more additional compatible ingredients which may include, for example, one or more agrochemical active ingredients, plant growth regulators or herbicide safeners, surfactants, dyes, fertilizers and micronutrients, growth regulators and pheromones and any other additional ingredients providing functional utility, such as, for example, stabilizers, fragrants, defoamers and dispersants. In addition to broadcast application, the granule of the present invention may optionally be diluted in a spray tank containing water carrier and the resulting aqueous mixture used for spray application to control weeds.
When the compositions of the present invention are used in combination with additional active ingredients the presently claimed compositions can be formulated with the additional active ingredient or active ingredients as mixtures of granules, they may be tank mixed with the additional active ingredient or active ingredients for spray application or they may be applied sequentially with the additional active ingredient or active ingredients in separate spray or granule applications. It is usually desirable to incorporate one or more surface- active agents into the tank mixtures formed with the compositions of the present invention when used in conjunction with the additional active ingredients described herein. Such surface- active agents may advantageously be employed in both solid and liquid compositions, especially those designed to be diluted with carrier before application. The surface-active agents can be anionic, cationic or nonionic in character and can be employed as emulsifying agents, wetting agents, suspending agents, or for other purposes. Surfactants conventionally used in the art of formulation and which may also be used in the present formulations are described, inter alia, in "McCutcheon' s Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, New Jersey, 1998 and in "Encyclopedia of Surfactants", Vol. I-III, Chemical publishing Co., New York, 1980-81. Typical surface-active agents include salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; alkylarylsulfonate salts, such as calcium dodecylbenzene- sulfonate; alky lphenol- alky lene oxide addition products, such as nonylphenol-Cis ethoxylate; alcohol- alky lene oxide addition products, such as tridecyl alcohol-Ci6 ethoxylate; soaps, such as sodium stearate; alkylnaphthalene-sulfonate salts, such as sodium dibutyl- naphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2-ethylhexyl) sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryl trimethylammonium chloride; polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; salts of mono and dialkyl phosphate esters. The following examples are presented to illustrate the various aspects of this invention and should not be construed as limitations to the claims. Example 1 Preparation of Granules of the Present Invention
Potassium chloride (KC1) core granules were obtained from Nippon Kayaku Co., Ltd. (Japan) and used as received. Cyhalofop-butyl, methyl soyate and Polyglycol 26-2 (Dow Chemical) are melted together in a flask via a heated water bath controlled at 60-65 °C to give a homogeneous liquid oil phase. Then, the required amount of KC1 core granules is added to the liquid oil phase. The KC1 core granules and oil phase are mixed thoroughly to ensure uniform absorption of the molten oil phase into the KC1 core granules to provide Granule A of Table 1.
Table 1. Composition of Granules of the Present Invention
Figure imgf000014_0001
Example 2 Use of Granules of the Present Invention for Weed Control in Simulated Rice
Paddys
Simulated rice paddy preparation: Two kg of mineral soil and 500 ml of distilled water were added to the container (4.163 L (1.1 gallon), 15 cm ht x 20.55 cm diameter, HDPE round container; for treatment purposes the surface area is calculated as 331 cm2 with 1 hectare equivalent to 108 cm2) and thoroughly mixed with a spatula for about 5 minutes to create a smooth mud mix. Once the mud is mixed, a 3 cm. furrow is made across the middle of the
®
container to which is added 18 g (0.6 oz.) Osmocote (registered trademark of The Scotts Company LLC or its affiliates; 17:6: 10 N:P:K). The furrow is then sealed keeping the
®
Osmocote below the surface of the soil. Plant propagation
Weed Plant - Chinese sprangletop, Leptochloa chinensis (LEFCH): In a small container, 80 grams of mineral soil is mixed with 40 milliliters (mL) of distilled water to make a viscous slurry. ¼ tsp (2-4000) of Leptochloa seed is added to the slurry and thoroughly mixed to evenly distribute the seed. Approximately 3 grams of this slurry is placed atop the prepared mud on one side of each container and spread thinly in a 1-2 cm band across the container. This yields 25-50 plants per pot. Clear shrink wrap is used to cover the containers acting as a terrarium. The wrap is held in place by masking tape until the Leptochloa seed germinates, about 5 days. The covered pots are kept in the greenhouse at a constant temperature of 18 to 22 °C and 50 to 60% relative humidity. Natural light was supplemented with 1000- watt metal halide overhead lamps with an average illumination of 500 microeinsteins (μΕ) m"2 s"1 photosynthetic active radiation (PAR). Day length was 16 hours. Weed Plant - Barnyard grass, Echinochloa crus-galli (ECHCG): Once the sprangletop seed has germinated, a shallow depression is made in the mud parallel to the sprangletop. Barnyard grass seed is sprinkled along this trench and then covered with white sand. This yields approximately 20-30 plants per pot. At this stage, the plant material is top-watered with distilled water and kept very moist. Pots are moved to a warmer greenhouse where the temperature is kept at 26 to 28 ° C with the same lighting parameters as described for the Chinese sprangletop.
Crop Plant - Paddy rice, Oryza sativa subsp. japonica var. M202 (ORYSJ): On the same day that the barnyard grass is planted, the rice is also directly seeded into the pot mud following the same methodology. A shallow depression is made in the mud parallel to the Chinese sprangletop and Barnyard grass and the seed is sprinkled along this trench then covered with white sand. This should also yield approximately 5-8 plants per pot.
The plants are allowed to grow until they reach 6-8 cm height in about 8 days.
Flooding and paddy application methods for herbicide evaluations Once the plants have reached the proper size (the growth stage of the various species ranged from 2 to 4 leaves) the containers are flooded with distilled water to a depth of 3 cm leaving 1-2 cm of each plant above the surface. Herbicide treatments are applied directly to the paddy water as granular or liquid formulations at rates adjusted to the surface area.
Treatments were replicated 2-3 times. At intervals, percent visual injury and weed control assessments were made on a scale of 0 to 100% compared to the untreated control plants (where 0 is equal to no injury or control and 100 is equal to complete death of the plant).
Table 2. Crop Tolerance and Percent Weed Control with Cyhalofop-butyl Granules of the Present Invention 14 days After Application in a Simulated Rice Paddy Trial in the Greenhouse
Figure imgf000016_0001
1 ORYSJ = Paddy rice, Oryza sativa subsp. japonica var. M202
LEFCH = Chinese sprangletop, Leptochloa chinensis
ECHCG = Barnyard grass, Echinochloa crus-galli
2 XGA-2444 is a C1 granule formulation containing 18 g/kg of cyhalofop-butyl and 115 g/kg of the petroleum derived adjuvant ditridecyl phthalate (Clincher 1 G from Nippon Kayaku Co., Ltd. of Japan)
Clincher CA (registered trademark of Dow AgroSciences LLC) is an EC formulation containing 285 grams per liter of cyhalofop-butyl and a petroleum derived adjuvant/solvent.

Claims

What is claimed:
1. A herbicide granule composition comprising: a) from about 5 grams active ingredient per kilogram (gai/kg) to about 50 gai/kg, with respect to the composition, of an
aryloxyphenoxypropionic acid herbicide; b) from about 20 g/kg to about 200 g/kg, with respect to the composition, of a non-petroleum derived built-in adjuvant; c) from about 700 g/kg to about 950 g/kg, with respect to the composition, a water soluble solid carrier; and d) from about 1 g/kg to about 50 g/kg, with respect to the composition, a surfactant; wherein the weight ratio of the herbicide to the non-petroleum derived built-in adjuvant is from about 1 :3 to about 1 :40.
2. The composition of claim 1, wherein the aryloxyphenoxypropionic acid herbicide is cyhalofop-butyl, fenoxaprop-ethyl, fluazifop-P-butyl, haloxyfop-methyl, haloxyfop-R-methyl, metamifop, propaquizafop, quizalofop-P-ethyl, or quizalofop-P-tefuryl.
3. The composition of claim 1, wherien the aryloxyphenoxypropionic acid herbicide is cyhalofop-butyl.
4. The composition of claim 1, wherein the composition comprises from about 10 g/kg to about 30 g/kg of the aryloxyphenoxypropionic acid.
5. The composition of claim 1 , wherein the non-petroleum derived built-in adjuvant is a water-immiscible organic liquid or solid.
6. The composition of claim 5, wherein the water-immiscible organic liquid or solid is at least one of a plant, algae or animal derived oil or a Ct-Cio ester of a plant, algae or animal derived oil.
7. The composition of claim 6 in which the Ci-Cio ester of a plant, algae or animal derived oil is methyl soyate.
8. The composition of claim 1, wherein the composition comprises from about 50 g/kg to about 150 g/kg of the non-petroleum derived built-in adjuvant.
9. The composition of claim 1 , wherein the weight ratio of the herbicide to the non-petroleum derived built-in adjuvant is from about 1 :4 to about 1 :40.
10. The composition of claim 1, wherein the water soluble solid carrier is at least one of an inorganic compound, a Hgnosulfonate, a carbohydrate, a fertilizer, a, a natural gum and a synthetic polymer.
11. The composition of claim 1 , wherein the water soluble solid carrier is potassium chloride, potassium sulfate, ammonium sulfate, sodium sulfate, calcium carbonate, urea, calcium Hgnosulfonate or sodium Hgnosulfonate.
12. The composition of claim 1, wherein the composition comprises from about 700 g/kg to about 950 g/kg of the water soluble solid carrier.
13. The composition of claim 1, wherein the surfactant is an alkyl sulfate salt, alkylarylsulfonate salt, alkylphenol-alkylene oxide addition product, soap, alkylnapfhalene- sulfonate salt, salt of a dialkyl ester of a sulfosuccinate, sorbitol ester, quaternary amine, polyethylene glycol ester of a fatty acid, block copolymer of ethylene oxide and propylene oxide, salt of a mono or dialkyl phosphate ester, or mixture thereof.
14. The composition of claim 1, wherein:
(a) the aryloxyphenoxypropionic acid herbicide is cyhalofop-butyl, fenoxaprop- ethyl, fluazifop-P-butyl, haloxyfop-methyl, haloxyfop-R-methyl, metamifop, propaquizafop, quizalofop-P-ethyl, or quizalofop-P-tefuryl;
(b) the non-petroleum derived built-in adjuvant is a water-immiscible organic liquid or solid;
(c) the water soluble solid carrier is at least one of an inorganic compound, a Hgnosulfonate, a carbohydrate, a fertilizer, a, a natural gum and a synthetic polymer; and (d) the surfactant is an alkyl sulfate salt, alkylarylsulfonate salt, alkylphenol- alkylene oxide addition product, soap, alkylnapthalene-sulfonate salt, salt of a dialkyl ester of a sulfosuccinate, sorbitol ester, quaternary amine, polyethylene glycol ester of a fatty acid, block copolymer of ethylene oxide and propylene oxide, salt of a mono or dialkyl phosphate ester, or mixture thereof.
15. The composition of claim 1, wherein the aryloxyphenoxypropionic acid herbicide is cyhalofop-butyl; the non-petroleum derived built-in adjuvant is methyl soyate, the water soluble solid carrier is potassium chloride, and the surfactant is sodium dioctyl sulfosuccinate.
16. The composition of claim 1, wherein the composition further comprises one or more additional pesticides.
17. The composition of claim 1, wherein the composition further comprises one or more herbicide safeners.
18. A method of controlling undesirable vegetation in an aquatic environment which comprises broadcasting or adding the herbicide granule composition of claim 1 into the aquatic environment before emergence or after emergence of the undesirable vegetation.
19. The method of claim 18 in which the aquatic environment is a flooded rice paddy or field.
PCT/US2012/043514 2011-06-22 2012-06-21 Herbicide granules with built-in adjuvant WO2012177851A1 (en)

Priority Applications (12)

Application Number Priority Date Filing Date Title
RU2013157759A RU2610314C2 (en) 2011-06-22 2012-06-21 Granular herbicidal composition containing built-in adjuvant and method of control of undesired vegetation
UAA201400120A UA112775C2 (en) 2011-06-22 2012-06-21 HERBICIDAL PELLETS WITH BUILT-IN ADJUST
IN180DEN2014 IN2014DN00180A (en) 2011-06-22 2012-06-21
CN201280035287.0A CN103687487B (en) 2011-06-22 2012-06-21 Herbicide granules with built-in adjuvant
AU2012272944A AU2012272944B2 (en) 2011-06-22 2012-06-21 Herbicide granules with built-in adjuvant
ES12802946.9T ES2627877T3 (en) 2011-06-22 2012-06-21 Herbicide granules with adjuvant incorporated
JP2014517151A JP5980322B2 (en) 2011-06-22 2012-06-21 Herbicide granules containing built-in adjuvant
MX2013015320A MX339351B (en) 2011-06-22 2012-06-21 Herbicide granules with built-in adjuvant.
NZ618961A NZ618961B2 (en) 2011-06-22 2012-06-21 Herbicide granules with built-in adjuvant
EP12802946.9A EP2723175B1 (en) 2011-06-22 2012-06-21 Herbicide granules with built-in adjuvant
KR1020147000589A KR102032204B1 (en) 2011-06-22 2012-06-21 Herbicide granules with built-in adjuvant
IL230054A IL230054B (en) 2011-06-22 2013-12-19 Herbicide granules with built-in adjuvant

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201161499887P 2011-06-22 2011-06-22
US61/499,887 2011-06-22

Publications (1)

Publication Number Publication Date
WO2012177851A1 true WO2012177851A1 (en) 2012-12-27

Family

ID=47422940

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2012/043514 WO2012177851A1 (en) 2011-06-22 2012-06-21 Herbicide granules with built-in adjuvant

Country Status (21)

Country Link
US (1) US9055742B2 (en)
EP (1) EP2723175B1 (en)
JP (1) JP5980322B2 (en)
KR (1) KR102032204B1 (en)
CN (1) CN103687487B (en)
AR (1) AR086727A1 (en)
AU (1) AU2012272944B2 (en)
BR (1) BR102012017793B1 (en)
CL (1) CL2013003676A1 (en)
CO (1) CO6852092A2 (en)
ES (1) ES2627877T3 (en)
IL (1) IL230054B (en)
IN (1) IN2014DN00180A (en)
MX (1) MX339351B (en)
MY (1) MY161752A (en)
PE (1) PE20141327A1 (en)
PT (1) PT2723175T (en)
RU (1) RU2610314C2 (en)
TW (1) TWI568351B (en)
UA (1) UA112775C2 (en)
WO (1) WO2012177851A1 (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013112675A1 (en) * 2012-01-25 2013-08-01 Dow Agrosciences Llc Improved solid herbicide compositions with built-in adjuvant
JP2015007004A (en) * 2013-06-25 2015-01-15 日本曹達株式会社 Preparation composition for horticultural or industrial use
KR101735427B1 (en) 2015-02-17 2017-05-16 충남대학교 산학협력단 Herbicides for weed control composition comprising Sorghum bicolor aerial part extract and Adjuvant
US11612164B2 (en) 2016-12-30 2023-03-28 Winfield Solutions, Llc Drift reduction adjuvant compositions and methods of using same
US11678660B2 (en) 2016-12-30 2023-06-20 Winfield Solutions, Llc Drift reduction adjuvant compositions and methods of using same
US11910793B2 (en) 2019-01-24 2024-02-27 Winfield Solutions, Llc Multifunctional agricultural adjuvant compositions

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130334537A1 (en) * 2012-06-14 2013-12-19 The Curators Of The University Of Missouri Optically Controlled Power Devices
BR112016028368B8 (en) * 2014-06-10 2022-08-23 Dow Agrosciences Llc SOLID HERBICIDAL COMPOSITIONS CONTAINING A PROTECTIVE AGENT, AND ITS PREPARATION METHOD
EP3247212A4 (en) * 2015-01-20 2018-08-15 Everris International B.V. Synergistic granular herbicidal compositions
US9627275B1 (en) * 2015-10-30 2017-04-18 Taiwan Semiconductor Manufacturing Company Ltd. Hybrid semiconductor structure on a common substrate
CN109379920B (en) * 2018-09-21 2021-11-02 湖南省植物保护研究所 Method for rapidly breaking barnyard grass seed dormancy and improving germination rate

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7300907B2 (en) 2006-01-13 2007-11-27 Dow Agrosciences Llc 2-(Poly-substituted aryl)-6-amino-5-halo-4-pyrimidinecarboxylic acids and their use as herbicides
US7314849B2 (en) 2006-01-13 2008-01-01 Dow Agrosciences Llc 6-(poly-substituted aryl)-4-aminopicolinates and their use as herbicides
US20080254983A1 (en) * 2005-09-16 2008-10-16 Nufarm Australia Limited Herbicide Composition
US20100304967A1 (en) * 2007-11-01 2010-12-02 Syngenta Crop Protection, Inc. Method of protecting rice crops
US20110098181A1 (en) * 2009-10-28 2011-04-28 Dow Agrosciences Llc. Synergistic herbicidal composition containing fluroxypyr and cyhalofop, metamifop or profoxydim

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3779427D1 (en) 1985-03-25 1992-07-02 Dowelanco METHOD FOR PRODUCING PHOSPHORTHIOATS AND PHOSPHATES.
GB9016783D0 (en) * 1989-09-01 1990-09-12 Ici Plc Agrochemical compositions
WO2000025586A1 (en) * 1998-11-04 2000-05-11 Syngenta Participations Ag Herbicidal composition
DE10020671A1 (en) * 2000-04-27 2001-11-08 Aventis Cropscience Gmbh Liquid formulations
WO2003014159A1 (en) * 2001-08-03 2003-02-20 Commonwealth Scientific And Industrial Research Organisation Methods of screening based on the egf receptor crystal structure
US20080248955A1 (en) * 2003-11-17 2008-10-09 Jeffrey David Fowler Emulsifiable Concentrates Containing Adjuvants
CN1968604A (en) * 2004-06-18 2007-05-23 辛根塔参与股份公司 Herbicidal composition
US20070184980A1 (en) 2006-01-25 2007-08-09 Helena Holding Company Manufacture and use of herbicide chlorinated phenoxy formulation
US8822443B2 (en) * 2006-03-02 2014-09-02 Ishihara Sangyo Kaisha, Ltd. Solid herbicidal composition
CA2694662C (en) 2007-08-30 2014-04-29 Lei Liu Stable emulsion formulation hindering interaction across the water-oil interface
CA2730571A1 (en) * 2008-08-12 2010-02-18 E. I. Du Pont De Nemours And Company Method for controlling undesired mimosoideae vegetation
CN101601403B (en) * 2009-07-23 2013-06-26 江苏辉丰农化股份有限公司 Weeding composition containing cyhalofop-butyl and bensulfuron-methyl for paddy field
CN101953340A (en) * 2010-06-03 2011-01-26 深圳诺普信农化股份有限公司 Cyhalofop-butyl-containing weed oil suspension composition
CN102047877A (en) * 2010-12-17 2011-05-11 上海生农生化制品有限公司 Cyhalofop-butyl water-dispersible granule and preparation method thereof
RU2606771C2 (en) * 2011-06-22 2017-01-10 Доу Агросаенсиз Ллк Herbicide emulsifiable concentrates with auxiliary substance

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080254983A1 (en) * 2005-09-16 2008-10-16 Nufarm Australia Limited Herbicide Composition
US7300907B2 (en) 2006-01-13 2007-11-27 Dow Agrosciences Llc 2-(Poly-substituted aryl)-6-amino-5-halo-4-pyrimidinecarboxylic acids and their use as herbicides
US7314849B2 (en) 2006-01-13 2008-01-01 Dow Agrosciences Llc 6-(poly-substituted aryl)-4-aminopicolinates and their use as herbicides
US20100304967A1 (en) * 2007-11-01 2010-12-02 Syngenta Crop Protection, Inc. Method of protecting rice crops
US20110098181A1 (en) * 2009-10-28 2011-04-28 Dow Agrosciences Llc. Synergistic herbicidal composition containing fluroxypyr and cyhalofop, metamifop or profoxydim

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"Encyclopedia of Surfactants", vol. I-III, 1980, CHEMICAL PUBLISHING CO.
"McCutcheon's Detergents and Emulsifiers Annual", 1998, MC PUBLISHING CORP.
See also references of EP2723175A4

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013112675A1 (en) * 2012-01-25 2013-08-01 Dow Agrosciences Llc Improved solid herbicide compositions with built-in adjuvant
US9445591B2 (en) 2012-01-25 2016-09-20 Dow Agrosciences Llc Solid herbicide compositions with built-in adjuvant
EA025293B1 (en) * 2012-01-25 2016-12-30 ДАУ АГРОСАЙЕНСИЗ ЭлЭлСи Improved solid herbicide compositions with built-in adjuvant
JP2015007004A (en) * 2013-06-25 2015-01-15 日本曹達株式会社 Preparation composition for horticultural or industrial use
KR101735427B1 (en) 2015-02-17 2017-05-16 충남대학교 산학협력단 Herbicides for weed control composition comprising Sorghum bicolor aerial part extract and Adjuvant
US11612164B2 (en) 2016-12-30 2023-03-28 Winfield Solutions, Llc Drift reduction adjuvant compositions and methods of using same
US11678660B2 (en) 2016-12-30 2023-06-20 Winfield Solutions, Llc Drift reduction adjuvant compositions and methods of using same
US11910793B2 (en) 2019-01-24 2024-02-27 Winfield Solutions, Llc Multifunctional agricultural adjuvant compositions

Also Published As

Publication number Publication date
CL2013003676A1 (en) 2014-10-03
JP5980322B2 (en) 2016-08-31
UA112775C2 (en) 2016-10-25
TW201309196A (en) 2013-03-01
ES2627877T3 (en) 2017-07-31
CN103687487B (en) 2017-03-22
MY161752A (en) 2017-05-15
NZ618961A (en) 2015-07-31
CO6852092A2 (en) 2014-01-30
US9055742B2 (en) 2015-06-16
BR102012017793B1 (en) 2019-06-18
TWI568351B (en) 2017-02-01
KR102032204B1 (en) 2019-10-15
MX2013015320A (en) 2014-02-17
IN2014DN00180A (en) 2015-06-05
EP2723175B1 (en) 2017-05-17
AU2012272944A1 (en) 2014-01-30
AR086727A1 (en) 2014-01-15
RU2610314C2 (en) 2017-02-09
EP2723175A1 (en) 2014-04-30
US20130023414A1 (en) 2013-01-24
JP2014517073A (en) 2014-07-17
CN103687487A (en) 2014-03-26
EP2723175A4 (en) 2014-11-26
PT2723175T (en) 2017-08-29
MX339351B (en) 2016-05-19
IL230054B (en) 2018-02-28
RU2013157759A (en) 2015-07-27
PE20141327A1 (en) 2014-10-03
BR102012017793A2 (en) 2014-01-14
KR20140041704A (en) 2014-04-04
AU2012272944B2 (en) 2016-03-10

Similar Documents

Publication Publication Date Title
EP2592929B1 (en) Solid herbicide compositions with built-in adjuvant
AU2012272944B2 (en) Herbicide granules with built-in adjuvant
US9456603B2 (en) Aryloxyphenoxypropionic acid herbicide emulsifiable concentrates with non-petroleum derived built-in adjuvant
US9445591B2 (en) Solid herbicide compositions with built-in adjuvant
NZ618961B2 (en) Herbicide granules with built-in adjuvant

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12802946

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 002855-2013

Country of ref document: PE

Ref document number: MX/A/2013/015320

Country of ref document: MX

ENP Entry into the national phase

Ref document number: 2014517151

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 2013003676

Country of ref document: CL

NENP Non-entry into the national phase

Ref country code: DE

REEP Request for entry into the european phase

Ref document number: 2012802946

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2012802946

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 20147000589

Country of ref document: KR

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: A201400120

Country of ref document: UA

WWE Wipo information: entry into national phase

Ref document number: 14004178

Country of ref document: CO

ENP Entry into the national phase

Ref document number: 2013157759

Country of ref document: RU

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 2012272944

Country of ref document: AU

Date of ref document: 20120621

Kind code of ref document: A