NZ618961B2 - Herbicide granules with built-in adjuvant - Google Patents

Abstract

Disclosed are 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. Preferred herbicides are cyhalofop-butyl, fenoxaprop-ethyl, fluazifop-P-butyl, haloxyfop-methyl, haloxyfop-R-methyl, metamifop, propaquizafop, quizalofop-P-ethyl, or quizalofop-P-tefuryl. Also disclosed are methods of controlling undesirable vegetation in an aquatic environment which comprises broadcasting or adding the herbicide granule composition into the aquatic environment before emergence or after emergence of the undesirable vegetation. For example this composition is useful for a rice paddy or field. -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. Preferred herbicides are cyhalofop-butyl, fenoxaprop-ethyl, fluazifop-P-butyl, haloxyfop-methyl, haloxyfop-R-methyl, metamifop, propaquizafop, quizalofop-P-ethyl, or quizalofop-P-tefuryl. Also disclosed are methods of controlling undesirable vegetation in an aquatic environment which comprises broadcasting or adding the herbicide granule composition into the aquatic environment before emergence or after emergence of the undesirable vegetation. For example this composition is useful for a rice paddy or field.

Description

PCT/U82012/043514 HERBICIDE GRANULES WITH BUILT—IN ADJUVANT Cross Reference to d Applications This application claims the benefit of US. Provisional ation No. 61/499,887, filed June 22, 2011, the entirety of which is incorporated herein by reference.

Field This invention concerns granules ning 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 ltural 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. e formulations are r 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 ge particle size generally less than about 100 micrometers) and therefore present less of a atory hazard. Granule products are generally produced from powders and may be used for insect, weed, fungal en 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 ations.

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 y 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 2012/043514 use, but are instead applied directly to the area of interest, such as for example, soil or water.

Once applied, the active ingredient ned 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 , 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 nyl alcohols, sodium polyacrylates, polyethylene oxides, polyvinylpyrrolidones and urea/formaldehyde polymers like PergoPak M® (registered ark of Albemarle Corporation). The active ingredient(s) contained in a granule may be melted into a , 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 e formulations lly 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 ing the ry and uptake of an herbicide into a target weed plant leading to ed 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 d oils and solvents, and wetting . Examples of ly used adjuvants include, but are not limited to, paraffin oil, horticultural spray oils (e.g., summer oil), ated rape seed oil, methylated soybean oil, highly refined vegetable oil and the like, polyol fatty acid esters, polyethoxylated esters, ethoxylated alcohols, alkyl ccharides 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 ndium (f ide Adjuvants, 9th Edition, " edited by Bryan Young, Dept. of Plant, Soil and ltural 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.corn/ .

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 mance relative to current products are needed. fop-butyl, (2/?)—2-[4-(4-cyanofluorophenoxy)phenoxy]propanoic acid (CAS# —78-0), is a member of the yphenoxypropionic acid class of herbicides which are known in the art as thefop 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 cial granule ations of cyhalofop-butyl contain solid inert ingredients such as ium chloride, clay or starch combined with built-in adjuvants derived from petroleum such as, for e, 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 ide due to a minimal herbicidal adjuvant effect.

The present invention provides an improvement to existing granules containing grass- active ides 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 abuilt-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 in adjuvant is from about 1:3 to about 1:40.

Another aspect of the present ion concerns a method of controlling undesirable vegetation in an aquatic environment which ses broadcasting or adding the ide e to an aquatic environment either before emergence or after emergence of the undesirable vegetation.

Detailed Description ltural active ingredients that have low water solubility can sometimes be difficult to ively apply to crops to eliminate pests. This ion 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 ly added directly to the water in PCT/U82012/043514 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, es 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 l.

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 n non-petroleum derived built-in adjuvants such as, for example, plant-derived methylated seed oils and ble oil concentrates have surprising been found to offer improved weed control in aquatic environments such as, for e, 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 ide active ient 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 nt, a water soluble solid carrier and a surfactant.

The aryloxyphenoxypropionic acid herbicide active ingredient of the t invention may include, but is not limited to, cyhalofop-butyl, fenoxaprop-ethyl, fluazifop-P- butyl, haloxyfop—methyl, haloxyfop-R-methyl, fop, propaquizafop, quizalofop-P—ethyl and ofop-P-tefuryl. Preferred aryloxyphenoxypropionic acid herbicide active ingredients of the present invention include cyhalofop-butyl, fenoxaprop-ethyl, haloxyfop- , haloxyfop-R-methyl and metamifop. The aryloxyphenoxypropionic acid herbicide active ingredient of the present invention ses, 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 PCT/USZOIZ/043514 oils and esters thereof. Naturally or partially naturally derived non-ionic surfactants that may be used as built—in nts of the present invention include, but are not limited to, polyol fatty acid esters, polyethoxylated lly derived esters, hoxylated naturally derived alcohols, alkyl polysaccharides such as alkyl polyglycosides and blends f, fatty acid derived amine ethoxylates, sorbitan fatty acid ester lates and sucrose esters of fatty acids.

Preferred non-petroleum derived built-in adjuvants may include one or more plant d 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 ccharides such as alkyl polyglycosides and blends thereof; amine ethoxylates d from plant derived oils; sorbitan fatty acid ester ethoxylates; and sucrose esters of fatty acids. The non- petroleum derived built-in nt 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 troleum 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 d celluloses may e, for example, water soluble alkylated and PCT/U82012/043514 yalkylated celluloses. Suitable natural gums may e, for e, guar gums, xanthum gums and ed 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 e, fertilizers such as, for example, ammonium sulfate and urea, and ulfonates such as, for e, calcium lignosulfonate and sodium lignosulfonate.

The water soluble solid carrier of the present invention comprises, with t 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 cheon's Detergents and Emulsifiers ", MC hing Corp, Ridgewood, New Jersey, 1998 and in "Encyclopedia of Surfactants", Vol. I-III, Chemical publishing C0., 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 ts, such as nonylphenol—Cis ethoxylate; alcohol-alkylene oxide addition products, such as tridecyl alcohol-Ci6 ethoxylate; soaps, such as sodium stearate; alkylnaphthalene-sulfonate salts, such as sodium dibutyl- naphthalenesulfonate; l esters of sulfosuccinate salts, such as sodium di(octy1) 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 ate esters; and mixtures thereof. The surfactant of the t ion 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. 2012/043514 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 e 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 fop-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 e 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 l of grass weeds in flooded rice paddys or fields and offers improved herbicidal performance relative to current granule products that contain petroleum derived nts and are used to control grass weeds in flooded rice paddys or fields.

Granule ations can be produced using one or more of the following processing methods: (1) pan granulation, (2) mixing eration, (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 er when choosing a process to use. G.

A. Bell and D. A. s in, "Chemistry and Technology of Agrochemical Formulations," D. A. Knowles, , (Kluwer Academic Publishers, 1998), pages 41-114, describe the 2012/043514 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 ion. 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 e of the present invention include clodinafop-propargyl, clethodim, cycloxydim, diclofop—methyl, ,fenoxaprop-ethyl + isoxidifen-ethyl, pinoxaden, profoxydim, propaquizafop, quizalofop-P-ethyl, quizalofop-P- l, sethoxydim, tepraloxydim, tralkoxydim, 2,4-D esters and salts, PA, 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, ibac-sodium, bromobutide, butachlor, cafenstrole, carfentrazone-ethyl, chlorimuron, chlorpropham, cinosulfuron, clomazone, clomeprop. alid, cloransulam-methyl, cyclosulfamuron, cumyluron, daimuron, diclosulam, diflufenican, dimepiperate, dimethametryn, diquat, dithiopyr, EK2612, EPTC, esprocarb, ET-751, ethoxysulfuron, ethbenzanid, sulfone, zamide, flazasulfuron, florasulam, fluazifop, sulfuron, flufenacet, flufenpyr-ethyl, flumetsulam, flumioxazin, flupyrsulfuron, fluroxypyr, fluroxypyr esters and salts, fen, foramsulfuron, glufosinate, glufosinate-P, glyphosate, halosulfuron—methyl, ethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, indanofan, ioxynil, ipfencarbazone, MCPB, cet, mesosulfuron, mesotrione, metazosulfuron, chlor, metosulam, metsulfuron, molinate, monosulfuron, MSMA, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxazichlomefone, oxyfluorfen, ethalin, penoxsulam, pentoxazone, pethoxamid, picloram, piperophos, pretilachlor, primisulfuron, prohexadione-calcium, propachlor, propanil, propisochlor, propyrisulfuron, prosulfiaron, pyrabuticarb, pyraclonil, pyrazogyl, pyrazolynate, pyrazosulfuron-ethyl, pyrazoxyfen, pyn'benzoxim, te, pyriftalid, pyriminobac—methyl, pyrimisulfan, ulam, quinoclamine, quinclorac, 8-3252, simazine, simetryne, lachlor, sulcotrione, sulfentrazone, sulfosate, tefuryltrione, thenylchlor, thiazopyr, thiobencarb, triclopyr esters and salts, triafamone, trifluralin, trinexapac-ethyl, W0 2012/177851 PCT/U82012/043514 tritosulfuron and compounds of the following generic structures and their derivatives as disclosed in US73 14849 B2 and US7300907 B2 NH2 NH2 R CI x | N; \ / / Ar N COOH Ar/kN COOH 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 ulam and bensulfuron-methyl.

Suitable insecticides that may be added to the granule of the present invention e abamectin, acephate, acetamiprid, acrinathrin, alpAa-cypermethrin, alpha-endosulfan, azadirachtin, azinphos-ethyl, os -methyl, bendiocarb, benfuracarb, bensultap, beta- cyfluthrin, "eto-cypermethrin, bifenthrin, bufencarb, buprofezin, rb, cadusafos, carbaryl, carbofuran, carbosulfan, cartap, cartap hloride, chlorantraniliprole, chlorfenapyr, envinphos, chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos- , chromafenozide, clothianidin, cyantraniliprole, cyfluthrin, thrin, cypermethrin, deltamethrin, diazinon, dicrotophos, diflubenzuron, dimethoate dinotefuran, disulfoton, emamectin, emamectin benzoate, endosulfan, endothion, endrin, EPN, esfenvalerate, etaphos, ethiofencarb, ethion, ole, ethoate-methyl, etofenprox, fenamiphos, flor, fenethacarb, fenitrothion, fenobucarb, pathrin, 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 -methy1, isoprocarb, isothioate, isoxathion, kinoprene, /amMa-cyhalothrin, lepimectin, lufenuron, malathion, methamidophos, methomyl, yfenozide, mevinphos, mexacarbate, milbemectin, monocrotophos, nitenpyram, novaluron, omethoate, oxamyl, oxydemeton-methyl, rofos, 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, ole, pyriproxyfen, spinetoram, spinosad, spirotetramat, sulfoxaflor, fos, uvalinate, tebufenozide, tebufenpyrad, teflubenzuron, tefluthrin, tetramethylfluthrin, t/zeto-cypermethrin, thiacloprid, thiamethoxam, thicrofos, thiocyclam, clam oxalate, thiodicarb, ton, ltap, thiosultap-disodium, thiosultap- monosodium, giensin, tolfenpyrad, triazophos, triflumuron and zeto-cypermethrin.

Suitable fungicides that may be added to the granule of the present invention e tricyclazole, phthalide, carpropamide, pyroquilon, diclocymet, fenoxanil, probenazole, isoprothiolane, iprobenfos, isotianil, tiadinil, kasugamycin, flutolanil, mepronil, uron, 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 e control when applied at the timing of an herbicide granule ation because fungal disease propagation and growth cycles may not match the targeted weed growth cycles. The effective use and application timing of these ides can be easily determined by one of normal skill in the art.

Suitable herbicide safeners that may be added to the granule of the t invention include benoxacor, benthiocarb, cloquintocet-mexyl, daimuron, dichlorrnid, dicyclonon, dimepiperate, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, furilazole, Harpin ns, isoxadifen-ethyl, mefenpyr-diethyl, mephenate, MG 191, MON 4660, naphthalic anhydride (NA), oxabetrinil, R29148 and N-phenyl-sulfony1benzoic 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, IBA, naphthaleneacetamide, a-naphthaleneacetic acid, kinetin, zeatin, on, cine, 1-methylcyclopropene (l-MCP), ethephon, gibberellins, gibberellic acid, abscisic acid, ancymidol, midol, mefluidide, paclobutrazol, tetcyclacis, uniconazole, brassinolide, brassinolide-ethyl and ethylene.

In addition to the compositions and uses set forth above, the present invention also es the composition and use of these herbicide granules in combination with one or more additional ible 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.

PCTfU82012/043514 In addition to ast 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 ated with the additional active ingredient or active ingredients as es of granules, they may be tank mixed with the additional active ingredient or active ingredients for spray application or they may be d 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 r before application. The surface-active agents can be anionic, cationic or nonionic in character and can be ed 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 bed, inter alia, in "McCutcheon‘ s Detergents and Emulsifiers Annual", MC hing 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 m dodecylbenzene- sulfonate; alkylphenol- alkylene oxide on products, such as nonylphenol-Cis late; alcohol- alkylene oxide addition products, such as tridecyl alcohol-Ci6 ethoxylate; soaps, such as sodium te; aphthalene-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 tions to the claims.

PCT/U82012/043514 Example 1 Preparation of Granules of the t Invention ium chloride (KCl) 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 KC] core granules is added to the liquid oil phase, The KC] core granules and oil phase are mixed thoroughly to ensure uniform absorption of the molten oil phase into the KCl core granules to provide Granule A of Table 1.

Table 1. Composition of Granules of the Present Invention Ingredients Example 2 Use of es of the Present Invention for Weed l in Simulated Rice Paddys Simulated rice paddy preparation: Two kg of l 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 re 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; 17:6210 N:P:K). The furrow is then sealed keeping the Osmocote®below the surface of the soil, PCT/U82012/043514 Plant propagation Weed Plant - Chinese sprangletop, Leptochloa chinensz's (LEFCH): In a small container, 80 grams of mineral soil is mixed with 40 milliliters (mL) of distilled water to make a viscous slurry. % tsp (2-4000) of Leptochloa seed is added to the slurry and thoroughly mixed to evenly bute 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 hloa 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 e illumination of 500 microeinsteins (uE) m'2 s'] photosynthetic active radiation (PAR). Day length was 16 hours.

Weed Plant - rd 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 tered 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, 0ryza sativa subsp. japom'ca var. M202 (ORYSJ): On the same day that the barnyard grass is planted, the rice is also directly seeded into the pot mud ing the same methodology. A shallow depression is made in the mud el 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 WO 77851 PCT/U52012/043514 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 l 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 nce 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 Herbicide Application Average % Injury to Plantsx Active Ingredient. . ent . Rate D t' (a) 6“”W10n (ganm) ORYSJ LEFCH: ECHCG c halofop—butyl Granule A 45 4 5 ‘- i90 10 3 0 IA!“180 65 85 360 100 cyhalofo—butyl 44 45 0%0I IIIIIIIIIIIIHEIIIII 3 43 40 360 3 93 33 cyhalofop-butyl ClincherCA3 45 m IIIIlflIIIIIIIIlIIIIIIIIflIIIIIIIIJIIII IIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIEEEIIIIIIIIIIIIIIIIIHIIIIIIIEEIIII 360 (/1 O\O 0\w 1ORYSJ = Paddy rice, Oryza sativa subspjaponica var. M202 LEFCH = Chinese sprangletop, Leptochloa chinensz's ECHCG = Barnyard grass, Echinochloa crus-galli 2 XGA-2444 is a KCl granule formulation containing 18 g/kg of cyhalofop—butyl and 115 g/kg of the petroleum derived adjuvant ditridecyl phthalate (Clincher®lKG from Nippon Kayaku Co., Ltd. of Japan) 3 Clincher®CA tered trademark ofDow AgroSciences LLC) is an EC ation containing 285 grams per liter of cyhalofop—butyl and a petroleum derived adjuvant/solvent.

SUBSTITUTE SHEET (RULE 26) 1001135440

Claims (20)

What is claimed 1.:

1. A herbicide granule ition comprising: a) from about 5 grams active ingredient per kilogram (gai/kg) to about 50 gai/kg, with t 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 adj uvant; c) from about 700 g/kg to about 950 g/kg, with t to the composition, a water soluble solid carrier; and 10 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 ition of claim 1, wherein the aryloxyphenoxypropionic acid 15 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, wherein the aryloxyphenoxypropionic acid herbicide is cyhalofop-butyl.

4. The composition of any one of claims 1 to 3, n the composition 20 comprises from about 10 g/kg to about 30 g/kg of the aryloxyphenoxypropionic acid.

5. The composition of any one of claims 1 to 4, wherein the non-petroleum d built-in adjuvant is a water-immiscible organic liquid or solid.

6. The composition of claim 5, wherein the immiscible organic liquid or solid is at least one of a plant, algae or animal derived oil or a C1-C10 ester of a plant, algae or 25 animal derived oil. 1001 135440

7. The composition of claim 6 in which the C1-C10 ester of a plant, algae or animal derived oil is methyl soyate.

8. The composition of any one of the preceding claims, wherein the composition ses from about 50 g/kg to about 150 g/kg of the non-petroleum derived built-in adjuvant.

9. The composition of any one of the preceding , 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 any one of the preceding claims, wherein the water soluble solid carrier is at least one of an inorganic compound, a lignosulfonate, a carbohydrate, a fertilizer, a natural gum and a synthetic polymer. 10

11. The composition of any one of claims 1 to 9, wherein the water soluble solid carrier is potassium chloride, potassium sulfate, ammonium sulfate, sodium sulfate, calcium ate, urea, calcium lignosulfonate or sodium lignosulfonate.

12. The composition of any one of the preceding claims, wherein the composition comprises about 860g/kg of the water soluble solid carrier. 15

13. The composition of any one of the ing , wherein 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 f. 20

14. The composition of claim 1, wherein: (a) the yphenoxypropionic acid herbicide is cyhalofop-butyl, fenoxaprop- ethyl, op-P-butyl, haloxyfop-methyl, haloxyfop-R—methyl, metamifop, propaquizafop, quizalofop—P—ethyl, or quizalofop-P-tefuryl; (b) the troleum d in adjuvant is a water-immiscible organic 25 liquid or solid; (0) the water soluble solid carrier is at least one of an inorganic compound, a lignosulfonate, a carbohydrate, a fertilizer, a, a natural gum and a synthetic polymer; and 1001 135440 (d) the surfactant is an alkyl e salt, alkylarylsulfonate salt, alkylphenol- alkylene oxide on 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 l 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. 1O

16. The ition of any one of the preceding claims, wherein the composition further comprises one or more additional ides.

17. The composition of any one of the preceding claims, wherein the composition further comprises one or more ide safeners.

18. A method of controlling undesirable vegetation in an aquatic environment 15 which comprises broadcasting or adding the herbicide e composition of any one of the preceding claims 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. 20

20. The composition of claim 1, substantially as hereinbefore described.