Title of Invention	A HERBICIDAL EMULSIFIABLE CONCENTRATE COMPOSITION
Abstract	The present invention relates to a herbicidal emulsifiable concentrate composition which comprises, on a weight to weight basis, 15% to 40% of a dinitroaniline herbicide, 1 % to 10% of an oxyacetamide herbicide, 0.01 % to 1 % phosphoric acid, up to about 30% of an emulsifier or mixture of emulsifiers, up to about 1 % of an antifoaming agent, and an organic solvent or mixture of organic solvents.

Full Text

The invention relates to a herbicidal emulsifiable concentrate composition. Dinitroanihne herbicides such as pendimethalin and trifluralin, and oxyacetamide herbicides such as fluthiamid are known in the art. Combination treatments using these types of herbicides are disclosed in U.S. Patents 4,968,342 and 5,759,955; and in German Application No. 19720367. However, emulsifiable concentrate compositions comprising dinitroanihne and oxyacetamide herbicides are not known in the art. U.S. Patent 3,898,075 relates to stabilized liquid compositions containing m-biscarbamates and organic acids. U.S. Patent 2,954,396 describes a method for stabilizing carbamate esters with certain hydrolysis inhibitors. However, neither U.S. Patent 3,898,075 nor U.S. Patent 2,954,396 describe any method for the stabilization of oxyacetamide herbicides. It is therefore an object of the present invention to provide stable emulsifiable concentrate compositions of dinitroanihne herbicides and oxyacetamide herbicides. Other objects and advantages of the present invention will be apparent to those skilled in the art from the description below. SUMMARY OF THE INVENTION The present invention relates to a herbicidal emulsifiable concentrate composition comprising, on a weight to weight basis, about 15% to 40% of a dinitroaniline herbicide, about 1% to 10% of an oxyacetamide herbicide, about 0.01% to 1% phosphoric acid, up to about 30% of an emulsifier or mixture of emulsif iers, up to about: 1% of an antif earning agent, and an organic solvent or mixture of organic solvents. DETAILED DESCRIPTION OF THE INVENTION The herbicidal emulsifiable concentrate compositions of this invention comprise, on a weight to weight basis, about 15% to 40% of a dinitroaniline herbicide, about 1% to 10% of an oxyacetamide herbicide, about 0.01% to 1% phosphoric acid, up to about 30% of an emulsifier or mixture of emulsifiers, up to about 1% of an antifoaming agent, and an organic solvent or mixture of organic solvents. Preferred herbicidal emulsifiable concentrate compositions of the present invention are those comprising, on a weight to weight basis, about 15% to 40% of a dinitroaniline herbicide, about 1% to 10% of an oxyacetamide herbicide, about 0.01% to 1% phosphoric acid, about 2% to 10% of an alkylarylsufonate, about 0.5% to 5% of a polyalkylene glycol ether, about 1% to 5% of an ethoxylated fatty alcohol, up to about 1% of an antifoaming agent, and an aromatic hydrocarbon solvent having a distillation range of about 135°C to' 305°C. More preferred emulsifiable concentrate compositions* of this invention are those comprising, on a weight to weight basis, about 25% to 35% oendimethalin, about 4% to 8% fluthiamid, about 0.05% to 0.2% phosphoric acid, about 2% to 6% of a dodecylbenzenesulfonate, about 1% to 3% of an alkyl capped ethylene oxide/propylene oxide block copolymer, about 1% to 5% of an ethoxylated c10-C15 fatty alcohol having about 8 to 12 moles of ethylene oxide per mole, up to about 1% of an antifearning agent, and an aromatic hydrocarbon solvent having a distillation range of about 135° to 305°C. Phosphoric acid is an especially important element of rhe present compositions because it has been found that oxyacetamide herbicides are more stable in the phosphoric acid containing emulsifiable concentrate compositions of the present invention than m corresponding emulsifiable concentrate compositions which do not contain phosphoric acid. In a preferred embodiment of the present invention, the ratio of the oxyacetamide herbicide to the phosphoric acid, on a weight basis, is preferably about 30:1 to 100:1, and more preferably, is about 40:1 to 70:1. Dinitroaniline herbicides suitable for use in the compositions of this invention have the strucrural formula I wherein R is hydrogen, C2-C4alkyl or chloroethyl; R1 is C2-C5alkyl, chloroethyl, 2 -methallyl or cycloprcpylmethyl, R1 is hydrogen, methyl or amino; and R3 iS trifluoromethyl, C1-C.alkyl, SO3NH. or SO-CH,. Preferred dinitroaniline herbicides for use in this invention include pendimethalin and trifluralin with pendimethalin being more preferred. Oxyacetamide herbicides suitable for use in the compositions of the present invention are those described in U.S. Patent Nos. 4,408,055; 4,509,971; 4,540,43 0; 4,54 9,8 99; 4,585,471; 4,645,525; 4,756,741; 4, 7 84, 682; 4,788,291; 4,833,243; 4, 968,342; 4,938,3 80; 5,090,991 and 5,234,896; EP Application Nos. 300344-A and 500934-Al; and WO 97/03160. Preferred oxyacetamide herbicides for use in the compositions of this invention have the structural formula II wherein R, is hydrogen, F, C1, 3r, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C^-C^alkylsulfonyl or C1-C4haloalkylsulfonyl; R3 is hydrogen or C1-C6alkyl; and R9 is phenyl optionally substituted with any combination of from one to three r, Cl, Br, CN, NO., C,-C,alkyl, C1-C4haloalkyl, C1-C4alkoxy or C1-C4,haloalkoxy groups. More preferred oxyacetamide herbicides for use in the emulsifiable concentrate compositions of this invention are those wherein R, is C1-C4haloalkyl; R5 IS C,-C,alkyl; and R5 is phenyl optionally substituted with any combination of one or two F, Cl or C1-C4alkyl groups. MOST: preferred oxyacetamide herbicides are rhose of formula II wherein R, is CF3, CHF. or CFCl,; R5 is isopropyl; and Re is selected from the group consisting of phenyl, 3-chlorophenyl, 4-chlorophenyl, 2 -fluorcphenyl, 4-fluorophenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl and 3,4-dimethylphenyl. An oxyacetamide herbicide which is especially suitable for use in the comDOsitions of this invention is 4'-fluoro-N-isopropyl-2-{[5-(trifluoromechyl;-1,3,4-thiadiazol-2-yl]oxy}acetanilide (fluthiamid). Emulsifiers suitable for use in the composirions of the present invention include, but are not limited tO; alkylarylsulfonates including C8-C1alkylbenzenesulfonates such as calcium dodecylbenzenesulfonate; polyalkylene glycol echers including alkyl capped ethylene oxide/propylene oxide block copolymers such as butyl capped ethylene oxide/propylene oxide block copolymers; and ethoxylaced fatty alcohols including ethoxylated C10-C16fatty alcohols having about 8 to 12 moles of ethylene oxide per mole; and mixtures thereof. Preferred emulsifiers include the alkali menal or alkaline earth mietal salts of dodecylbenzene sulfonic acid, such as calcium dodecylbenzenesulfonate including SOPROPHOR' 70 a 60% calcium dodecylbenzene sulfonate solution m isobutanol commercially available from Rhodia, Milan, Italy; butyl capped ethylene oxide/propylene oxide block copolymers including WITCONOL' NS 5 00K a butyl capped ethylene oxide/propylene oxide block copolymer commerically available from Witco SA, Saint-Pierre Les Elbeuf, France; and ethoxylated C10-C16fatty alcohols having about 8 to 12 moles of ethylene oxide per mole including RKODASURF' 870 a C,3 ethoxylated facty alcohol containing 10 moles of ethylene oxide per mole commercially available from Rhodia, Milan, Italy; and mixtures thereof. Organic solvents suitable for use in the compositions of this invention include aromatic, hydrocarbon solvents such as toluene, xylenes, polynuclear aromatic hydrocarbons such as naphthalenes and alkylnaphthalenes and mixtures thereof, many of which are available from the fractionation of crude oil and in general have distillation ranges in the temperature range of about 135°C to 3 05°C, with those having a distillation range of from about 183°C co 290°C being most preferred. These solvents are commercially available under a variety of tradenames, e.g. SOLVSSSO" 200 and AROMATIC' 200 both comm.ercially available from Exxon, rareham, Hants, United Kingdom. Antifoaming agents suitable for use in the compositions of the present invention include conventional antifoaming agents, with silicone based antifoaming agents such as those sold under the SILCOLAPSE' tradename commercially available from Rhodia, Lyon, France being preferred. In a preferred embodiment of this invention, an antifoaming agent is used at a level sufficient to prevent undesirable foaming during the preparation of tank mixes using the emulsion concentrates of the present invention. Typically, less than 1% by weight of a defoamer is sufficient, with amounts of about 0.01 to about 0.1% by weight being preferred. The herbicidal emulsifiable concentrate compositions of the present invention may be prepared by admixing all of the ingredients in the organic solvent. In a preferred embodiment: of this invention, the composicions are prepared by: (a) admaxing an alkylarylsulfonate, an ethoxylated fatty alcohol, an ancifearning agent and an organic solvent to obtain a first homogeneous mixture; (b) adding a molten dinitroaniline and a molten polyalkylene glycol ether to the first homogenous mixture of seep (a) with scirring to obtain a second homogenous mixture; (c) adding an oxyacetamide herbicide to the second homogenous m.ixture of step (b) with stirring to obtain a third homogenous mixture; and (d) adding phosphoric acid to the chird homogenous mixture of step (c) with stirring. The emulsifiable concentrate compositions of this invention are diluted with water and applied as dilute, aqueous emulsions to the locus where weed control is desired. Typical dilution rates are in the range of about 1 L of concentrace per 400 L of water to 4 L of concentrate per 100 L of water. While the compositions of this invention are effective for controlling weeds when employed alone, they may also be used in conjunction with or in combination with other biological chemicals, including other herbicides. In order to facilitate a further understanding of the invention, the following examples are presented primarily for the purpose of illustrating more specific details thereof. The scope of the invention should not be deemed limited by the examples, but encompasses the entire subject matter defined m the claims. EXAMPLE 1 Preparation of emulsifiable concentrate compositions A mixture of a 60% calcium dodecylbenzene sulfonate solution in isobutanol commercially available as SOPROPHOR' 70 from Rhodia, Milan, Italy (53. Og, 5.00% on a weight basis), a C12 ethoxylated fatty alcohol containing 10 moles of ethylene oxide per mole commercially available as RHODASURF" 870 from Rhodia, Milan, Italy (32.Og, 3.00% on a weight basis), a silicone antifcam commercially available as SILCCLAFSE' 431 from Rhodia, Lyon, France (O.lg, 0.01% on a weight basis) , and an aromatic hydrocarbon mixture (C10-C13) aromatics having a distillation range of abouc 22 6-279°C commercially available as SOLVSSSO 200 from Exxon, Fareham, Hants, United Kingdom (557.0g, 52.29% on a weight basis) is stirred until homogeneous. Molten pendimethalin (333.3g, 90% real, 31.33% on a weight basis) and a molten butyl capped ethylene oxide/propylene oxide block copolymer commercially available as WITCONOL' NS 500K from Witco SA, Saini:-Pierre Les Elbeuf, France (21.Og, 2.00% on a weight basis) are added to the mixture with stirring. Solid fluthiamid (66.7g, 90% real, 6.27% on a weight basis) is then added to the mixture and the mixture is scirred until all of the solids dissolve. An 85% phosphoric-acid solution (l.Og, 0.10% on a weight basis) is added to the mixture, with stirring until homogeneous, zo obtain the emulsifiable concentrate composition identified as composition number 1 in Table I. Using essentially the same procedure, the emulsifiable concentrate compositions identified as composition numbers 2 to 14 in Table I are obtained. EXAMPLE 2 Evaluation of storage stability of test compositions Samples of test compositions identified in Table I and a comparative composition identified below are placed in glass bottles. The bottles are capped and placed in a temperature controlled storage incubator. After completing the required storage period; the samples are removed and assayed for pendimethalin and fluthiamid content. The active ingredient content: is expressed as a percentage relative to the active ingredient content prior to storage (% Initial Content). The results are summarized in Table II. As can be seen from the data in Table II, fluthiamid is more stable in the emulsifiable concentrate compositions of the present invention which contain phosphoric acid than the comparative emulsifiable concentrate composition which does net contain phosphoric acid. COMPARATIVE COMPOSITION Ingredient %w/w Pendimethalin (90% real) 32.00 Fluthiamid (90% real) 6.40 SOPROPHOR® 70 3.84 RHODASURF® 87 0 2.60 WITCONOL® NS 500K 1.06 SILCOLAPSE® 431 0.01 SOLVESSO® 200 54.09 "Prepared according to the procedure described m Example 1 except that the 85% phosphoric acid solution iS not added. WE CLAIM: 1. A herbicidal emulsifiable concentrate composition which comprises, on a weight to weight basis, 15% to 40% of a dinitroaniline herbicide, 1% to 10% of an oxyacetamide herbicide, 0.01% to 1% phosphoric acid, up to about 30%) of an emulsifier or mixture of emulsifiers, up to about 1% of an antifoaming agent, and an organic solvent or mixture of organic solvents. 2. The composition according to claim 1 wherein the emulsifier or mixture of emulsifiers comprises 2%) to 10% of an alkylarylsulfonate such as herein described, 0.5% to 5% of a polyalkylene glycol ether such as herein described and 1% to 5% of an ethoxylated fatty alcohol such as herein described, and the orgainc solvent or mixture of organic solvents is an aromatic hydrocarbon solvent such as herein described having a distillation range of 135°C to 3 05°C. 3. The composition according to claim 1 which comprises, on a weight to weight basis, 25% to 35%) pendimethalin, 4% to 8% fluthiamid, 0.05%) to 0,2% phosphoric acid, 2% to 6% of a dodecylbenzenesulfonate, 1% to 3%o of an alkyl capped ethylene oxide/propylene oxide block copolymer, 1% to 5% of an ethoxylated C10-C16 fatty alcohol having 8 to 12 moles of ethylene oxide per mole, up to l%o of an antifoaming agent, and an aromatic hydrocarbon solvent having a distillation range of 135°C to 305°C. 4. The composition according to claim 1 wherein the ratio of the oxyacetamide herbicide to the phosphoric acid on a weight basis is 30:1 to 100:1. 5. The composition according to claim 4 wherein the ratio is 40:1 to 70:1. 6. The composition according to claim 1 wherein the emulsifier is selected from the group consisting of an alkylarylsufonate, a polyalkylene glycol ether, and an ethoxylated fatty alcohol, and mixtures thereof 7. The composition according to claim 6 wherein the alkylarylsulfonate is a C8-C18 alkylbenzenesulfonate; the polyalkylene glycol ether is an alkyl capped ethylene oxide/propylene oxide block copolymer and the ethoxylated fatty alcohol is an ethoxylated C10-C16 fatty alcohol having 8 to 12 moles of ethylene oxide per mole. 8. The composition according to claim 1 wherein the antifoaming agent is present. 9. The composition according to claim 1 wherein the dinitroaniline herbicide has the structural formula I wherein R is hydrogen, C2-C4alkyl or chloroethyl; Ri is C2-C5 alkyl chloroethyl, 2-methallyl or cyclopropylmethyl; R2 is hydrogen, methyl or amino; and R3 is trifluoromethyl, C1-C3-alkyl, SO2NH2 or SO2CH3. 10. The composition according to claim 1 wherein the dinitroaniline herbicide is selected from the group consisting of pendimethalin and trifluralin. 11. The composition according to claim 1 wherein the dinitroaniline herbicide is pendimethalin. 12. The composition according to claim 1 wherein the oxyacetamide herbicide has the structural formula II wherein R4 is hydrogen, F, CI, Br, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylsulfonyl or C1-C4 haloalkylsulfonyl; Rs is hydrogen or C1-C4alkyl; and R6 is phenyl optionally substituted with any combination of from one to three F, CI, Br,CN,N02, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy or C1-C4haloalkoxy groups. 13. The composition according to claim 12 wherein R4 is C1-C4haloalkyl; R5 is C1-C4alkyl; and Re is phenyl optionally Substituted with any combination of one or two F, CI or C1 C4alkyl groups. 14. The composition according to claim 13 wherein R4 is CF3, CHF2 or CFCl2; R5 is isopropyl; and R6 is selected from the group consisting of phenyl, 3-chlorophenyl, 4-chlorophenyl, 2-fluorophenyl, 4- fluorophenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl and 3,4-dimethylphenyl. 15. The composition according to claim 1 wherein the oxyacetamide herbicide is fluthiamid. 16. The composition according to claim 1 wherein the organic solvent is an aromatic hydrocarbon solvent having a distillation range of 135°C to 305°C. 17. The composition according to claim 16 wherein the distillation range is 183°C to 290X. 18. An aqueous tank mixture which comprises water and a composition as claimed in claim 1.

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