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US00945.1767B2

(12) United States Patent (10) Patent No.: US 9.451,767 B2 Nolte et al. (45) Date of Patent: Sep. 27, 2016

(54) AQUEOUS COMPOSITION COMPRISING (52) U.S. Cl. DCAMIBA AND A DRIFT CONTROL AGENT CPC ...... A0IN 33/04 (2013.01); A0IN 37/10 (2013.01); A0IN 37/40 (2013.01); A0IN (71) Applicant: BASF SE, Ludwigshafen (DE) 37/44 (2013.01) (58) Field of Classification Search (72) Inventors: Marc Nolte, Mannheim (DE); Wen Xu, CPC ...... AO1N 37/44 Cary, NC (US); Steven Bowe, Apex, USPC ...... 514/564 NC (US); Maarten Staal, Durham, NC See application file for complete search history. (US); Terrance M. Cannan, Raleigh, NC (US) (56) References Cited (73) Assignee: BASF SE, Ludwigshafen (DE) FOREIGN PATENT DOCUMENTS (*) Notice: Subject to any disclaimer, the term of this WO WO O2,34047 5, 2002 patent is extended or adjusted under 35 W. w838g 1239 U.S.C. 154(b) by 101 days. WO WO 2011/O19652 2, 2011 WO WO 2011/O102.11 9, 2011 (21) Appl. No.: 14/408,172 WO WO 2012/076567 6, 2012 (22) PCT Filed: Jun. 11, 2013 OTHER PUBLICATIONS International Search Report dated Jul. 12, 2013, prepared in Inter (86). PCT No.: PCT/EP2013/061962 national Application No. PCT/EP2013/061962. S 371 (c)(1), International Preliminary Report on Patentability dated Jun. 6. (2) Date: Dec. 15, 2014 2014, prepared in International Application No. PCT/EP2013/ O61962. (87) PCT Pub. No.: WO2013/189773 Primary Examiner — Raymond Henley, III PCT Pub. Date: Dec. 27, 2013 (74) Attorney, Agent, or Firm — Brinks Gilson & Lione (65) Prior Publication Data (57) ABSTRACT US 2015/O173354 A1 Jun. 25, 2015 The present invention relates to an aqueous composition comprising and a drift control agent; to a method O O for preparing a tank mix, which comprises the step of Related U.S. Application Data contacting water and said composition, and optionally fur (60) Provisional application No. 61/662,390, filed on Jun. ther pesticides; to a method of controlling phytopathogenic 21, 2012. fungi and/or undesired vegetation and/or unde-sired insect or mite attack and/or for regulating the growth of plants, (30) Foreign Application Priority Data wherein the composition is allowed to act on the respective pests, their environment or the plants to be protected from Jul. 5, 2012 (EP) ...... 12175090 the respective pest, on the soil and/or on undesired plants and/or the crop plants and/or their environment; and finally (51) Int. Cl. to a use of the alkoxylate of the formula (I) as defined below AOIN 37/44 (2006.01) for reducing the wind drift of an aqueous composition AOIN 33/04 (2006.01) comprising a pesticide. AOIN 37/40 (2006.01) AOIN 37/10 (2006.01) 19 Claims, No Drawings US 9,451,767 B2 1. 2 AQUEOUS COMPOSITION COMPRISING Solutions, LLC (Arrow four, Corral AMS, InterLock, Place DCAMIBA AND A DRIFT CONTROL AGENT ment Propak, PowerLock), and various other discontinued commercial products, such as Apasil, Bivert, Chem-Trol, This application is a National Stage application of Inter Confine, Corral Poly, Drifgon, Driftgard, Drop Zone, Intac national Application No. PCT/EP2013/061962, filed Jun. 11, Plus, Nalcotrol, Nalcotrol II, Nalduatic, Progacyl, Target, 2013, which claims the benefit of U.S. Provisional Appli TMP, Wind-Fall. cation No. 61/662,390, filed Jun. 21, 2012, the entire con Preferred examples of drift control agents are tents of which are hereby incorporated herein by reference. lecithin derivatives, This application also claims priority under 35 U.S.C. S 119 linear nonionic polymers with a molecular weight of at to European Patent Application No. 12175090.5, filed Jul. 5, 10 2012, the entire contents of which is hereby incorporated least 20 kDa, herein by reference. guar gum, The present invention relates to an aqueous composition fatty alcohol alkoxylates. Preferred drift control agents are the fatty alcohol alkoxy comprising dicamba and a drift control agent; to a method lates. for preparing a tank mix, which comprises the step of 15 contacting water and said composition, and optionally fur Suitable lecithin derivatives are lecithin or its chemically ther pesticides; to a method of controlling phytopathogenic modified derivatives. Such drift control agents are for fungi and/or undesired vegetation and/or undesired insect or example commercially available as Liberate(R) or Compa mite attack and/or for regulating the growth of plants, dre(R) from Loveland Products. wherein the composition is allowed to act on the respective Suitable linear nonionic polymers with a molecular pests, their environment or the plants to be protected from weight of at least 20 kDa, may be selected from polyacry the respective pest, on the soil and/or on undesired plants lamide, polyacrylate, or a polyethylene glycol. Preferred and/or the crop plants and/or their environment; and finally nonionic polymers are polyacrylamide and polyacrylate. to a use of the alkoxylate of the formula (I) as defined below The molecular weight of said nonionic polymers is usually for reducing the wind drift of an aqueous composition 25 at least 50 kDa, preferably at least 100 kDa, and in particular comprising a pesticide. The preferred embodiments of the at least 1000 kDa. invention mentioned herein below have to be understood as Suitable guar gums are for example described in being preferred either independently from each other or in EP0660999, or are commercially available as AGRHOR) combination with one another. DEP 775 or AGRHOR) DR 200 from Rhodia. The reduction wind drift is an important object in agro 30 Preferred fatty alcohol alkoxylates are fatty alcohol chemistry. Various drift control agents are known showing a ethoxylates. The fatty alcohol may comprise a C-, pref wide variety of different chemical compositions. Thus, it is erably a Co. and in particular a C-1s fatty alcohol. The very difficult to identify new drift control agents or opti fatty alcohol ethoxylate may comprise from 1 to 15, pref mizing structures of known drift control agents. erably from 1 to 8, and in particular from 2 to 6 equivalents Dicamba is an important , which requires high 35 of ethylene oxide. Especially suitable fatty alcohol ethoxy drift control to avoid damages in neighboring fields. late is a Cao fatty alcohol, which comprises from 2 to 6 Object of the present invention was to find a new drift equivalents of ethylene oxide. control agent with improved properties. These agents should The drift control agent may have a HLB value of 4.0 to be easily to prepare starting from cheap, industrially avail 11.0, preferably of 6.0 to 10.0 and in particular of 8.0 to 10.0. able compounds, which are easy to handle. Yet another 40 In another particular preferred form the drift control agent object was to find a dicamba composition, which allows a (such as the alkoxylate of the formula (I)) has a HLB of 5.0 high drift control. to 8.0, and most preferably from 6.0 to 7.0. The HLB may The object was solved by an aqueous composition com be determined according to Griffin. prising dicamba and a drift control agent. The object was In an especially preferred form the drift control agent is a also solved by a use of the alkoxylate of the formula (I) as 45 fatty alcohol alkoxylate. Such as an alkoxylate of the formula defined below for reducing the wind drift of aqueous com (I) position comprising a pesticide. Drift control agents may be understood as chemical agents, which reduce the wind drift when spraying an wherein R is C-C-alkyl and/or -alkenyl, m is 2, 3, 4 or aqueous tank mix composition. Drift control agents are 50 a mixture thereof, and n is from 1 to 15. The alkoxylates of commercially available from various companies (trade the formula (I) are obtainable by common alkoxylation of names of the products given in brackets): Ag Spray, Inc. alcohols R OH, e.g. with ethylene oxide (resulting in (Halt), Ashland Specialty Ingredients (Soilcare), Brewer m=2), propylene oxide, or butylene oxide. International Inc. (Poly Control 2), Conklin Co. Inc. (Com R* may be an alkyl, alkenyl or a mixture thereof. Prefer plete), Helena Chemical Co. (AccuOuest WM. AccuZone 55 ably R' is an alkenyl or a mixture of an alkenyl with an alkyl. DC, Grounded. On-Line, Sta Put, Strike Zone, LineMan), In case R contains an alkenyl said alkenyl may comprise at Intracrop (Driftless), Kalo, Inc. (One AP XL, Spectra Tank least one double bond. R' is preferably a C-Co-alkyl Mix, Spectra Max), Loveland Products, Inc. (LI 700), Nalco and/or -alkenyl. More preferably R' is C-C-alkyl and/or Co. (Staput Plus), Precision Laboratories, Inc. (Border, -alkenyl. Especially preferred R is oleyl and/or cetyl. Border Xtra, Direct, Transport Plus), Rhodia Inc. (AgRHO 60 Preferably, m is 2, a mixture of 2 and 3, or a mixture of DEP, AgRHO DR), Sanitek Products, Inc. (SANAG Div.) 2 and 4. In particular, m is 2. (41-A, 38-F), Willowood USA (Willowood Driftguard), Preferably, n is from 2 to 8. In particular, n is from 2 to FORMULATORS TRADE NAMES: Brandt Consolidated, 5. Inc. (Drift Free), Custom Agricultural Formulators (Drifts In a very preferred form the drift control agent is an top), Loveland Products, Inc. (Compadre, Liberate, Reign, 65 alkoxylate of the formula (I), wherein R is C-Co-alkyl Reign LC, Weather Gard Complete), Wilbur-Ellis Co. and/or -alkenyl, m is 2, a mixture of 2 and 3, or a mixture (Bronc Max EDT, EDT Concentrate, In-Place), Winfield of 2 and 4, and n is from 2 to 8. In an even more preferred US 9,451,767 B2 3 4 form the drift control agent is an alkoxylate of the formula The dicamba polyamine salt usually comprises an anionic (I), wherein R is C-C-alkyl and/or -alkenyl, m is 2, and dicamba and a cationic polyamine. The term “cationic n is from 2 to 5. polyamine' refers to a polyamine, which is present as cation. The composition contains usually at least 1 wt %, pref Preferably, in a cationic polyamine at least one amino group erably at least 5 wt %, and in particular at least 10 wt % of 5 is present in the cationic form of an ammonium, Such as the drift control agent. The composition contains usually up R NH R NH, or R. N.H. An expert is aware 50 wt %, preferably up to 30 wt %, and in particular up to which of the amine groups in the cationic polyamine is 20 wt % of the drift control agent. preferably protonated, because this depends for example on The aqueous composition according to the invention the pH or the physical form. In aqueous solutions the comprises dicamba and a drift control agent. Dicamba is a 10 alkalinity of the amino groups of the cationic polyamine known herbicide, which may be present in form of an increases usually from tertiary amine to primary amine to protonated acid, in form of a salt, or a mixture thereof. secondary amine. Various dicamba salts may be used, such as dicamba In an embodiment the cationic polyamine has the formula Sodium, dicamba dimethylamine, dicamba diglyclolamine. 15 Dicamba is available in the commercial products like BAN (A1) VEL(R)+2,4-D, BANVEL HERBICIDER, BANVEL-K+ R R3 R ATRAZINER, BRUSH-MASTER(R), CELEBRITY PLUS(R, CIMARRON MAX(R), CLARITY HERBICIDER, Sh Sh Yx COOL POWER(R), DIABLO HERBICIDER, DICAMBA R2 R4 DMA SALT, DISTINCT HERBICIDER, ENDRUNR, HORSEPOWER*(R, LATIGOR), MARKSMAN HERBI wherein R', R. R. R. Rare independently H or C-C- CIDER, MACAMINE-DR, NORTHSTAR HERBICIDER, alkyl, which is optionally substituted with OH. Rand Rare OUTLAW HERBICIDE(R), POWER ZONER, PROKOZ independently C-Cio-alkylene, X is OH or NR'R'', and n is VESSEL(R), PULSARR, Q4 TURF HERBICIDER, RANG 25 from 1 to 20. R. R. R. Rand R7 are preferably indepen ESTARR, REQUIRE QR, RIFLE(R), RIFLE PLUSR, dently H or methyl. Preferably, R', R, R and R7 are H. R. RIFLE-D(R, SPEED ZONER), STATUS HERBICIDER, and Rare preferably identical to R' and R, respectively. R STER-LING BLUER, STRUTR), SUPER TRIMEC*(R), and Rare preferably independently C-C-alkylene, such as SURGE*R, TRIMEC BENTGRASS*(R, TRIMEC CLAS ethylene (—CH2CH2—). O n-propylene SIC*(R, TRIMEC PLUS*(R, TRIPLET SFR, TROOPER 30 ( CHCHCH ). Typically, R and R are identical. R EXTRAR, VANOUISHR, VETERAN 720R, VISION and R may be linear or branched, unsubstituted or substi HERBICIDER, WEEDMASTER(R), YUKON HERBI tuted with halogen. Preferably, R and Rare linear. Pref. CIDER). erably, R and Rare unsubstituted. X is preferably NR'R''. Preferably, dicamba is present in form of a dicamba Preferably, n is from 1 to 10, more preferably from 1 to 6, polyamine Salt and the polyamine has the formula (A1) 35 especially from 1 to 4. In another preferred embodiment, n is from 2 to 10. Preferably, R', R, and Rare independently H or methyl, Rand Rare independently C-C-alkylene, X (A1) is OH or NR'R'', and n is from 1 to 10. R R R The group X is bound to R, which is a C-Cio-alkylene st sh Nx 40 group. This means that X may be bound to any carbon atom R2 R4 of the C-Cio-alkylene group. Examples of a unit —R X are —CH, CH, CH, OH or —CH, CH(OH)—CH. wherein R", R. R. R. R7 are independently H or C-C-alkyl, R. R. R. R. and R7 are independently H or C-C- which is optionally substituted with OH. An example such alkyl, which is optionally substituted with OH, 45 a substitution is formula (B1.9), in which R is H or R and Rare independently C-Co-alkylene, C-C-alkyl substituted with OH (more specifically, R is X is OH or NR'R'', and C-alkyl substituted with OH. Preferably, R', R. R. R. R7 n is from 1 to 20; are independently H or C-C-alkyl. or the formula (A2) In another preferred embodiment the cationic polymer of 50 the formula (A1) is free of ether groups (—O ). Ether groups are known to enhance photochemical degradation resulting in exploxive radicals or peroxy groups. O 2 (A2) R R Examples for cationic polyamines of the formula (A1) n N 1n R13 wherein X is NRR" are diethylenetriamine (DETA, (A4) 55 with k=1, corresponding to (A1.1)), triethylenetetraamine RI (TETA, (A4) with k=2), tetraethylenepentaamine (TEPA, (A4) with k=3). Technical qualities of TETA are often wherein mixtures comprising in addition to linear TETA as main R'' and R'' are independently H or C-C-alkyl, component also tris-aminoethylamine TAEA, Piperazino R" is C-C2-alkylene, and 60 ethylethylenediamine PEEDA and Diaminoethylpiperazine R" is an aliphatic Cs-Cs ring system, which comprises DAEP. Technical qualities of TEPA a are often mixtures either nitrogen in the ring or which is substituted with comprising in addition to linear TEPA as main component at least one unit NR'R''. also aminoethyltris-aminoethylamine AE-TAEA, aminoeth The term “polyamine' within the meaning of the inven yldiaminoethylpiperazine AE-DAEP and aminoethylpiper tion relates to an organic compound comprising at least two 65 azinoethylethylenediamine AE-PEEDA. Such ethyleneam amino groups, such as an primary, secondary or tertiary ines are commercially available from Dow Chemical amino group. Company. Further examples are Pentamethyldiethylenetri US 9,451,767 B2 5 6 amine PMDETA (B1.3), N.N.N',N',N"-pentamethyl-dipro -continued pylenetriamine (B1.4) (commercially available as Jeffcat(R) (A1.9) ZR-40), N,N-bis(3-dimethylaminopropyl)-N-isopropa CH nolamine (commercially available as Jeffcat(R) ZR-50), N'- (3-(dimethylamino)propyl)-N,N-dimethyl-1,3-propanedi CH HO OH amine (A1.5) (commercially available as Jeffcat(R) Z-130), and N,N-Bis(3-aminopropyl)methylamine BAPMA (A1.2). HC1 N N-1N1 N CH Especially preferred are (A4), wherein k is from 1 to 10, ~s 3

(A1.2). (A1.4) and (A1.5). Most preferred are (A4), wherein 10 k is 1, 2, 3, or 4 and (A1.2). In particular preferred are (A1.1) In another embodiment the cationic polyamine has the and (A1.2), wherein the latter is most preferred. formula

(A4) 15 H (A2) N O 2 HN1\- N1,N1, RS-RS R13 (A1.1) R11 HN1\1 N1)NH, wherein R'' and R'' are independently H or C-C-alkyl, (A1.2) R" is C-C2-alkylene, and R' is an aliphatic Cs-Cs ring t system, which comprises either nitrogen in the ring or which 2N-1N-N-1-N-N2 is substituted with at least one unit NR'R''. 25 R" and R'' are preferably independently H or methyl, (A1.3) more preferably H. Typically R'' and R'' are linear or th branched, unsubstituted or substituted with halogen. Prefer HC N CH ably, R'' and R'' are unsubstituted and linear. More pref 3 ~ n- 3 30 erably, R'' and R'' are identical. CH CH R" is preferably C-C-alkylene, such as ethylene (A1.4) ( CH-CH ), or n-propylene ( CHCH-CH ). R' "N 1-1-1-1--" may be linear or branched, preferably it is linear. R' may be unsubstituted or substituted with halogen, preferably it is CH CH CH 35 unsubstituted. (A1.5) R" is an aliphatic Cs-Cs ring system, which comprises HC n N 1N1-1\1\N N 1. CH either nitrogen in the ring or which is substituted with at H least one unit NR'R''. Preferably, R' is an aliphatic Cs-Cs CH CH 40 ring system, which comprises nitrogen in the ring. The Cs-Cs ring system may be unsubstituted or Substituted with at least one C-C alkyl group or at least one halogen. Examples for polyamines of the formula (A1) wherein X Preferably, the C-C ring system is unsubstituted or sub is OH are N-(3-dimethylaminopropyl)-N,N-diisopropa stituted with at least one C-C alkyl group. Examples for an nolamine DPA (A1.9), N.N.N'-trimethylaminoethyl-etha 45 aliphatic Cs-Cs ring system, which comprises nitrogen in the nolamine (A1.7) (commercially available as Jeffcat(R) ring, are piperazyl groups. Examples for R' being an Z-110), aminopropylimonomethylethanolamine APMMEA aliphatic Cs-Cs ring system, which comprises nitrogen in the (A1.8), and aminoethylethanolamine AEEA (A1.6). Espe ring, are the compounds of the formulat (A2.11) and (A2.12) cially preferred is (A1.6). below. Examples for R' being an aliphatic Cs-Cs ring 50 system, which is substituted with at least one unit NR'R'' is the compound of the formula (A2.10) below. (A1.6) H More preferably, R'' and R'' are independently H or HN1,N1 N N1 No methyl, R' is C-C-alkylene, and R' is an aliphatic Cs-Cs. 55 ring system, which comprises oxygen or nitrogen in the ring. (A1.7) In another preferred embodiment the cationic polymer of the formula (A2) is free of ether groups (-O ). HC Nth 3 ~ N1 No Especially preferred cationic polyamines of formula (A2) 60 are isophorone diamine ISPA (A2.10), aminoethylpiperazine CH AEP (A2.11), and 1-methyl-4-(2-dimethylaminoethyl)pip erazine TAP (A2.12). These compounds are commercially (A1.8) available from Huntsman or Dow, USA. Preferred are t (A2.10) and (A2.11), more preferably (A2.11). In another N-1-N-N-1- OH 65 embodiment (A2.11) and (A2.12) are preferred. US 9,451,767 B2 7 8 point, e.g. kerosene, diesel oil; oils of vegetable or animal (A2.10) origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. NH2 toluene, paraffin, tetrahydronaphthalene, alkylated naphtha lenes; alcohols, e.g. ethanol, propanol, butanol, benzylalco hol, cyclohexanol; glycols; DMSO, ketones, e.g. cyclo hexanone; esters, e.g. lactates, carbonates, fatty acid esters, H3C NH2 gamma-butyrolactone; fatty acids; phosphonates; amines; H3C CH3 amides, e.g. N-methylpyrrolidone, fatty acid dimethylam (A2.11) ides; and mixtures thereof. / \ NH2 10 Suitable surfactants are Surface-active compounds, such HN 1N-1 as anionic, cationic, nonionic and amphoteric Surfactants, block polymers, polyelectrolytes, and mixtures thereof. (A2.12) Such surfactants can be used as emulsifier, dispersant, solu CH bilizer, wetter, penetration enhancer, protective colloid, or 15 adjuvant. Examples of surfactants are listed in McCutch HC-N N1\1 N Nchi, eons, Vol. 1: Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.). Suitable anionic Surfactants are alkali, alkaline earth or Dicamba is most preferred present in form of a N,N-bis ammonium salts of Sulfonates, Sulfates, phosphates, car (3-aminopropyl)methylamine (so called “BAPMA) salt. boxylates, and mixtures thereof. Examples of sulfonates are The composition contains usually at least 50 g/l, prefer alkylarylsulfonates, diphenylsulfonates, alpha-olefin Sul ably at least 300 g/l, more preferably at least 400 g/l, and in fonates, lignine Sulfonates, Sulfonates of fatty acids and oils, particular at least 450 g/l acid equivalents (AE) of dicamba. sulfonates of ethoxylated alkylphenols, sulfonates of The composition contains usually up to 800 g/l, preferably 25 alkoxylated arylphenols, Sulfonates of condensed naphtha up to 700 g/l, more preferably up to 650 g/l, and in particular lenes, Sulfonates of dodecyl- and tridecylbenzenes, Sul up to 600 g/l acid equivalents (AE) of dicamba. fonates of naphthalenes and alkylnaphthalenes, Sulfo Succi The composition according to the invention is usually nates or SulfoSuccinamates. Examples of Sulfates are Sulfates present in form of an homogenous solution, e.g. at 20° C. of fatty acids and oils, of ethoxylated alkylphenols, of Typically, the dicamba and the drift control agent are dis 30 alcohols, of ethoxylated alcohols, or of fatty acid esters. Solved in the aqueous composition. Examples of phosphates are phosphate esters. Examples of In a preferred form the aqueous composition contains at carboxylates are alkyl carboxylates, and carboxylated alco least 300 g/l acid equivalents of dicamba (e.g. as dicamba hol or alkylphenol ethoxylates. salt of the polyamine of the formula (A1), at least 5 wt % of Suitable nonionic surfactants are alkoxylates, N-substi the drift control agent (e.g. the alkoxylate of the formula (I)), 35 tuted fatty acid amides, amine oxides, esters, Sugar-based and water up to 100 wt %. Surfactants, polymeric Surfactants, and mixtures thereof. In a more preferred form the aqueous composition con Examples of alkoxylates are compounds Such as alcohols, tains at least 400 g/l acid equivalents of dicamba (e.g. as alkylphenols, amines, amides, arylphenols, fatty acids or dicamba BAPMA salt), at least 8 wt % of the drift control fatty acid esters which have been alkoxylated with 1 to 50 agent (e.g. the alkoxylate of the formula (I), wherein R is 40 equivalents. Ethylene oxide and/or propylene oxide may be C-Cls-alkyl and/or -alkenyl, m is 2, and n is from 2 to 5), employed for the alkoxylation, preferably ethylene oxide. and water up to 100 wt %. Examples of N-substituted fatty acid amides are fatty acid The aqeuous composition may comprise additional pes glucamides or fatty acid alkanolamides. Examples of esters ticides in addition to dicamba. Suitable additional pesticides are fatty acid esters, glycerol esters or monoglycerides. are pesticides as defined below. Preferred additional pesti 45 Examples of Sugar-based surfactants are Sorbitans, ethoxy cides are , such as lated Sorbitans. Sucrose and glucose esters or alkylpolyglu amino acid derivatives: bilanafos, (e.g. gly cosides. Examples of polymeric Surfactants are home- or phosate free acid, glyphosate ammonium salt, glypho copolymers of vinylpyrrolidone, vinylalcohols, or vinylac sate isopropylammonium salt, glyphosate trimethylsul etate. The alkoxylate of the formula (I) is not a nonionic fonium salt, glyphosate potassium salt, glyphosate 50 Surfactant within the meaning of this invention. dimethylamine salt), , Sulfosate; Suitable cationic Surfactants are quaternary Surfactants, imidazolinones: imazamethabenZ, imaZamox, , for example quaternary ammonium compounds with one or , imaZaquin, imazethapyr; two hydrophobic groups, or salts of long-chain primary phenoxy acetic acids: clomeprop, 2,4-dichlorophenoxy amines. Suitable amphoteric Surfactants are alkylbetains and acetic acid (2,4-D), 2,4-DB, , MCPA, 55 imidazolines. Suitable block polymers are block polymers of MCPA-thioethyl, MCPB, . the A-B or A-B-A type comprising blocks of polyethylene More preferred additional pesticides are glyphosate and oxide and polypropylene oxide, or of the A-B-C type com 2,4-D. Most preferred additional pesticide is glyphosate. prising alkanol, polyethylene oxide and polypropylene The aqueous composition may comprise auxiliaries, such oxide. Suitable polyelectrolytes are polyacids or polybases. as solvents, liquid carriers, Surfactants, dispersants, emulsi 60 Examples of polyacids are alkali salts of polyacrylic acid or fiers, wetters, adjuvants, solubilizers, penetration enhancers, polyacid comb polymers. Examples of polybases are poly protective colloids, adhesion agents, thickeners, humectants, vinylamines or polyethyleneamines. repellents, attractants, feeding stimulants, compatibilizers, Suitable adjuvants are compounds, which have a negli bactericides, anti-freezing agents, anti-foaming agents, colo gible or even no pesticidal activity themselves, and which rantS. 65 improve the biological performance of the compound I on Suitable solvents and liquid carriers are organic solvents, the target. Examples are Surfactants, mineral or vegetable Such as mineral oil fractions of medium to high boiling oils, and other auxilaries. Further examples are listed by US 9,451,767 B2 10 Knowles, Adjuvants and additives, Agrow Reports DS256, benzoic acid amides: flumetover, fluopicolide, fluopyram, T&F Informa UK, 2006, chapter 5. Zoxamide; Suitable thickeners are polysaccharides (e.g. Xanthan other carboxamides: carpropamid, dicyclomet, mandipro gum, carboxymethylcellulose), anorganic clays (organically amid, oxytetracyclin, silthiofarm and N-(6-methoxy modified or unmodified), polycarboxylates, and silicates. 5 pyridin-3-yl)cyclopropanecarboxylic acid amide: Suitable bactericides are bronopol and isothiazolinone C) azoles derivatives Such as alkylisothiazolinones and benzisothiaz triazoles: azaconazole, bitertanol, bromuconazole, cypro olinones. conazole, difenoconazole, diniconazole, diniconazole Suitable anti-freezing agents are ethylene glycol, propyl M, epoxiconazole, fenbuconazole, fluguinconazole, ene glycol, and glycerin. 10 flusilaZole, flutriafol, hexaconazole, imibenconazole, Suitable anti-foaming agents are silicones, long chain ipconazole, metconazole, myclobutanil, Oxpoconazole, alcohols, and salts of fatty acids. paclobutrazole, penconazole, propiconazole, prothio Suitable colorants (e.g. in red, blue, or green) are pig conazole, Simeconazole, tebuconazole, tetraconazole, ments of low water solubility and water-soluble dyes. 15 triadimefon, triadimenol, triticonazole, uniconazole; Examples are inorganic colorants (e.g. iron oxide, titan imidazoles: cyaZofamid, imazalil, pefurazoate, prochlo oxide, iron hexacyanoferrate) and organic colorants (e.g. raz, triflumizol; alizarin-, azo- and phthalocyanine colorants). benzimidazoles: benomyl, carbendazim, fuberidazole, The present invention further relates to a method for thiabendazole; preparing a tank mix, which comprises the step of contacting others: ethaboxam, etridiazole, hymexazole and 2-(4- water and the aqueous composition according to the inven chloro-phenyl)-N-4-(3,4-dimethoxy-phenyl)-isox tion, and optionally further pesticides. azol-5-yl)-2-prop-2-ynyloxy-acetamide; The tank mix may contain up to 10 wt %, preferably up D) heterocyclic compounds to 5 wt %, and in particular up to 2 wt % of the of the : fluaZinam, pyrifenox, 3-5-(4-chloro-phenyl)- aqueous composition. Usually, the tank mix contains at least 25 2,3-dimethyl-isoxazolidin-3-yl-, 3-5-(4- 0.1 wt % of the aqueous composition. methyl-phenyl)-2,3-dimethyl-isoxazolidin-3-yl-pyri The tank mix may contain up to 3.0 wt %, preferably up dine; to 0.5 wt %, and in particular up to 0.25 wt % of the of the pyrimidines: bupirimate, cyprodinil, diflumetorim, fena drift control agent. Usually, the tank mix contains at least rimol, ferimZone, mepanipyrim, nitrapyrin, nuarimol, 0.01 wt % of the drift control agent. 30 pyrimethanil; The further pesticides may be selected from any pesticide. piperazines: triforine; The term "pesticide” refers to at least one active substance pyrroles: fenpiclonil, fludioxonil; selected from the group of the fungicides, insecticides, morpholines: aldimorph, dodemorph, dodemorph-acetate, nematicides, herbicides, Safeners and/or growth regulators. fenpropimorph, tridemorph; Preferred pesticides are herbicides. Mixtures of pesticides of 35 two or more of the abovementioned classes may also be piperidines: fempropidin; used. The skilled worker is familiar with such pesticides, dicarboximides: fluoroimid, iprodione, procymidone, Vin which can be found, for example, in the Pesticide Manual, cloZolin; 15th Ed. (2009), The British Crop Protection Council, non-aromatic 5-membered heterocycles: famoxadone, London. The following list give examples of pesticides 40 fenamidone, flutianil, octhillinone, probenazole, which may be used as pesticide. Examples for fungicides 5-amino-2-isopropyl-3-oxo-4-ortho-tolyl-2,3-dihydro a. pyrazole-1-carbothioic acid S-allyl ester; A) strobilurins others: acilbenzolar-S-methyl, ametoctradin, amisulbrom, aZoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, anilazin, blasticidin-S, captafol, captan, chinomethio kresoxim-methyl, metominostrobin, orysastrobin, 45 nat, dazomet, debacarb, diclomeZine, difenZoquat, picoxystrobin, pyraclostrobin, pyrametostrobin, pyra difenZoquat-methyl-sulfate, fenoxanil, Folpet, OXolinic oxystrobin, pyribencarb, trifloxystrobin, methyl acid, piperalin, produinazid, pyroquilon, quinoxyfen, (2-chloro-5-1-(3-methylbenzyloxyimino)ethylben triazoxide, tricyclazole, 2-butoxy-6-iodo-3-propyl Zyl)carbamate and 2-(2-(3-(2,6-dichlorophenyl)-1- chromen-4-one, 5-chloro-1-(4,6-dimethoxy-pyrimidin methyl-allylideneaminooxymethyl)-phenyl)-2- 50 2-yl)-2-methyl-1H-benzoimidazole and 5-chloro-7-(4- methoxyimino-N-methyl-acetamide; methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-1.2.4 B) carboxamides carboxanilides: benalaxyl, benalaxyl-M, benodanil, bix triazolo 1.5-alpyrimidine; afen, boScalid, carboxin, fenfuram, fenhexamid, fluto E) carbamates lanil, furametpyr, isopyrazam, isotianil, kiralaxyl, 55 thio- and dithiocarbamates: ferbam, mancoZeb, maneb, mepronil, metalaxyl, metalaxyl-M (mefenoxam), ofu metam, methasulphocarb, metiram, propineb, thiram, race, oxadixyl, oxycarboxin, penflufen, penthiopyrad, Zineb, Ziram; sedaxane, tecloftalam, thifluZamide, tiadinil, 2-amino carbamates: benthiavalicarb, diethofencarb, iprovalicarb, 4-methyl-thiazole-5-carboxanilide, N-(3',4',5'-trifluo propamocarb, propamocarb hydrochlorid, Valifenalate robiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyra 60 and N-(1-(1-(4-cyano-phenyl)ethanesulfonyl)-but-2- Zole-4-carboxamide, N-(4-trifluoro yl) carbamic acid-(4-fluorophenyl) ester; methylthiobiphenyl-2-yl)-3-difluoromethyl-1-methyl F) other active substances 1H-pyrazole-4-carboxamide and N-(2-(1,3,3- guanidines: guanidine, dodine, dodine free base, guaza trimethyl-butyl)-phenyl)-1,3-dimethyl-5-fluoro-1H tine, guazatline-acetate, iminoctadine, iminoctadine-tri pyrazole-4-carboxamide: 65 acetate, iminoctadine-tris(albesilate); carboxylic morpholides: dimethomorph, flumorph, pyri antibiotics: kasugamycin, kasugamycin hydrochloride morph; hydrate, streptomycin, polyoxine, validamycin A; US 9,451,767 B2 11 12 nitrophenyl derivates: binapacryl, dinobuton, dinocap, Bipyridyls: diguat, ; nitrthal-isopropyl, tecnaZen, organometal compounds: (thio)carbamates: , butylate, carbetamide, desme fentin salts, such as fentin-acetate, fentin chloride or dipham, dimepiperate, eptam (EPTC), esprocarb, moli fentin hydroxide: nate, orbencarb, phenmedipham, prosulfocarb, pyribu Sulfur-containing heterocyclyl compounds: dithianon, 5 ticarb, thiobencarb, triallate: isoprothiolane; cyclohexanediones: butroxydim, clethodim, cycloxydim, organophosphorus compounds: edifenphos, fosetyl, fos profoxydim, , tepraloxydim, tralkoxydim; etyl-aluminum, iprobenfos, phosphorous acid and its dinitroanilines: , ethal fluralin, oryzalin, pendi salts, pyrazophos, tolclofoS-methyl; methalin, prodiamine, ; organochlorine compounds: chlorothalonil, dichlofluanid, 10 diphenyl ethers: , , , diclofop, dichlorophen, flusulfamide, hexachlorobenzene, pen ethoxyfen, , , oxyfluorfen: cycuron, pentachlorphenole and its salts, phthalide, hydroxybenzonitriles: bomoxynil, dichlobenil, ioxynil; quintoZene, thiophanate-methyl, tolylfluanid, N-(4- imidazolinones: imazamethabenz, imaZamox, imazapic, chloro-2-nitro-phenyl)-N-ethyl-4-methyl-benzenesul imazapyr, imaZaquin, imazethapyr; fonamide; 15 phenoxy acetic acids: clomeprop, 2,4-dichlorophenoxy inorganic active Substances: Bordeaux mixture, copper acetic acid (2,4-D), 2,4-DB, dichlorprop, MCPA, acetate, copper hydroxide, copper oxychloride, basic MCPA-thioethyl, MCPB, Mecoprop; copper Sulfate, Sulfur, pyrazines: chloridazon, flufenpyr-ethyl, fluthiacet, norflu others: biphenyl, bronopol, cyflufenamid, cymoxaniil, razon, pyridate; diphenylamin, metrafenone, mildiomycin, OXin-copper, pyridines: , , diflufenican, dithio prohexadione-calcium, Spiroxamine, tebufloquin, tolyl pyr, fluridone, , , picolinafen, thiaz fluanid, N-(cyclopropylmethoxyimino-(6-difluoro opyr; methoxy-2,3-difluoro-phenyl)-methyl)-2-phenyl acet Sulfonyl : amidosulfuron, azim Sulfuron, benSulfu amide, N'-(4-(4-chloro-3-trifluoromethyl-phenoxy)-2, ron, chlorimuron-ethyl, chlorSulfuron, cinosulfuron, 5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine, 25 cyclosulfamuron, ethoxysulfuron, , fluc N'-(4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dim etosulfuron, flupyrsulfuron, foramsulfuron, halosulfu ethyl-phenyl)-N-ethyl-N-methyl formamidine, N'-(2- ron, imaZoSulfuron, iodosulfuron, mesosulfuron, meta methyl-5-trifluoromethyl-4-(3-trimethylsilanyl Zosulfuron, metSulfuron-methyl, nicosulfuron, propoxy)-phenyl)-N-ethyl-N-methyl formamidine, N'- Oxasulfuron, primisulfuron, prosulfuron, pyrazosulfu (5-difluoromethyl-2-methyl-4-(3-trimethylsilanyl 30 ron, rimsulfuron, Sulfometuron, Sulfosulfuron, thifen propoxy)phenyl)-N-ethyl-N-methyl formamidine, sulfuron, triasulfuron, tribenuron, trifloxysulfuron, tri 2-1-2-(5-methyl-3-trifluoromethyl-pyrazole-1-yl)- flusulfuron, tritosulfuron, 1-((2-chloro-6-propyl acetyl-piperidin-4-yl)-thiazole-4-carboxylic acid imidazo[1,2-bipyridazin-3-yl)sulfonyl)-3-(4.6- methyl-(1,2,3,4-tetrahydro-naphthalen-1-yl)-amide, dimethoxy-pyrimidin-2-yl)urea; 2-1-2-(5-methyl-3-trifluoromethyl-pyrazole-1-yl)- 35 triazines: ametryn, , , dimethametryn, acetyl-piperidin-4-yl)-thiazole-4-carboxylic acid ethiozin, , metamitron, , prom methyl-(R)-1,2,3,4-tetrahydro-naphthalen-1-yl-amide, etryn, , terbuthylazine, terbutryn, triaziflam; methoxy-acetic acid 6-tert-butyl-8-fluoro-2,3-dim ureas: chlorotoluron, daimuron, diuron, fluometuron, iso ethyl-quinolin-4-yl ester and N-Methyl-2-1-(5- proturon, , methabenzthiazuron, ; methyl-3-trifluoromethyl-1H-pyrazol-1-yl)-acetyl-pi 40 other acetolactate synthase inhibitors: bispyribac-Sodium, peridin-4-yl)-N-(1R)-1,2,3,4-tetrahydronaphthalen-1- cloranSulam-methyl, dicloSulam, florasulam, flucarba yl-4-thiazolecarboxamide. Zone, flumetSulam, metoSulam, ortho-sulfamuron, Examples for growth regulators are: penoXSulam, propoxycarbazone, pyribambenZ-propyl. Abscisic acid, amidochlor, ancymidol, 6-benzylaminopu , pyriftalid, pyriminobac-methyl, pyrim rine, brassinolide, butralin, chlormeduat (chlormeduat chlo 45 isulfan, pyrithiobac, pyroxasulfone, pyroxSulam; ride), choline chloride, cyclanilide, daminozide, dikegulac, others: amicarbazone, aminotriazole, anilofos, beflubuta dimethipin, 2,6-dimethylpuridine, , flumetralin, mid, benazolin, bencarbazone, benfluresate, benzo flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid, fenap, bentaZone, benzobicyclon, bicyclopyrone, bro inabenfide, indole-3-acetic acid, maleic hydrazide, meflui macil, bromobutide, , butamifos, dide, mepiduat (mepiduat chloride), naphthaleneacetic acid, 50 cafenstrole, carfentraZone, cinidon-ethlyl, chlorthal, N-6-benzyladenine, paclobutraZol, prohexadione (pro cinmethylin, , cumyluron, cyprosulfamide, hexadione-calcium), prohydrojasmon, thidiaZuron, triapen dicamba, difenZoquat, diflufenZopyr, Drechslera thenol, tributyl phosphorotrithioate, 2,3,5-tri-iodobenzoic monoceras, endothal, ethofumesate, etobenzanid, acid, trinexapac-ethyl and uniconazole. fenoxasulfone, fentraZamide, flumiclorac-pentyl, flu Examples for herbicides are: 55 mioxazin, flupoxam, flurochloridone, flurtamone, acetamides: , , , dimethachlor, indanofan, isoxaben, isoxaflutole, lenacil, , , flufenacet, mefenacet, , propyZamide, , quinmerac, , metaZachlor, napropamide, naproanilide, pethoxamid, methyl arsonic acid, naptalam, oxadiargyl, oxadiazon, pretilachlor, , thenylchlor; oxaziclomefone, pentoxazone, pinoxaden, pyraclonil, amino acid derivatives: bilanafos, glyphosate (e.g. gly 60 pyraflufen-ethyl, pyrasulfotole, pyrazoxyfen, pyra phosate free acid, glyphosate ammonium salt, glypho Zolynate, quinoclamine, , Sulcotrione, sate isopropylammonium salt, glyphosate trimethylsul , terbacil, tefuryltrione, tembotrione, fonium salt, glyphosate potassium salt, glyphosate thiencarbazone, toprameZone, (3-2-chloro-4-fluoro-5- dimethylamine salt), glufosinate, Sulfosate; (3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydro aryloxyphenoxypropionates: clodinafop, cyhalofop-bu 65 2H-pyrimidin-1-yl)-phenoxy-pyridin-2-yloxy)-acetic tyl, fenoxaprop, , haloxyflop, metamifop, acid ethyl ester, 6-amino-5-chloro-2-cyclopropyl-py propaquizafop, quizalofop, quizalofop-P-tefuryl; rimidine-4-carboxylic acid methyl ester, 6-chloro-3-(2- US 9,451,767 B2 13 14 cyclopropyl-6-methyl-phenoxy)-pyridazin-4-ol. The compositions according to the invention are Suitable 4-amino-3-chloro-6-(4-chloro-phenyl)-5-fluoro-pyri as herbicides. They are Suitable as such or as an appropri dine-2-carboxylic acid, 4-amino-3-chloro-6-(4-chloro ately formulated composition. The compositions according 2-fluoro-3-methoxy-phenyl)-pyridine-2-carboxylic to the invention control vegetation on non-crop areas very acid methyl ester, and 4-amino-3-chloro-6-(4-chloro efficiently, especially at high rates of application. They act 3-dimethylamino-2-fluoro-phenyl)-pyridine-2-carbox against broad-leafed weeds and grass weeds in crops such as ylic acid methyl ester. wheat, rice, corn, soybeans and cotton without causing any Examples for insecticides are: significant damage to the crop plants. This effect is mainly organo (thio)phosphates: acephate, azamethiphos, azin observed at low rates of application. phos-methyl, chlorpyrifos, chlorpyrifos-methyl, chlo 10 rfenvinphos, diazinon, dichlorvos, dicrotophos, dime Depending on the application method in question, the thoate, disulfoton, ethion, fenitrothion, fenthion, compositions according to the invention can additionally be isoxathion, malathion, methamidophos, methidathion, employed in a further number of crop plants for eliminating methyl-parathion, mevinphos, monocrotophos, undesirable plants. Examples of suitable crops are the fol Oxydemeton-methyl, paraoxon, parathion, phenthoate, 15 lowing: Allium cepa, Ananas comosus, Arachis hypogaea, phosalone, phosmet, phosphamidon, phorate, phoxim, Asparagus officinalis, Avena sativa, Beta vulgaris spec. pirimiphos-methyl, profenofos, prothiofos, Sulprophos, altissima, Beta vulgaris spec. rapa, Brassica napus var. tetrachlorvinphos, terbufos, triazophos, trichlorfon; napus, Brassica napus var. napobrassica, Brassica rapa Var. carbamates: alanycarb, aldicarb, bendiocarb, benfuracarb, silvestris, Brassica oleracea, Brassica nigra, Brassica jun carbaryl, carbofuran, carbosulfan, fenoxycarb, fura cea, Brassica campestris, Camelia sinensis, Carthamus thiocarb, methiocarb, methomyl, oxamyl, pirimicarb, tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, propoXur, thiodicarb, triazamate; Coffea arabica (Coffea Canephora, Coffea liberica), Cucu pyrethroids: allethrin, bifenthrin, cyfluthrin, cyhalothrin, mis sativus, Cynodon dactylon, Daucus carota, Elaeis cyphenothrin, cypermethrin, alpha-cypermethrin, beta guineensis, Fragaria vesca, Glycine max, Gossypium hir cypermethrin, Zeta-cypermethrin, deltamethrin, esfen 25 sutum, (Gossypium arboreum, Gossypium herbaceum, Gos Valerate, etofenproX, fenpropathrin, fenvalerate, imi sypium vitifolium), Helianthus annuus, Hevea brasiliensis, prothrin, lambda-cyhalothrin, permethrin, prallethrin, Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Jug pyrethrin I and II, resmethrin, silafluofen, tau-fluvali lans regia, Lens culinaris, Linum usitatissimum, Lycopersi nate, tefluthrin, tetramethrin, tralomethrin, transflu con lycopersicum, Malus spec. Manihotes-culenta, Med thrin, profluthrin, dimefluthrin; 30 icago sativa, Musa spec. Nicotiana tabacum (N. rustica), insect growth regulators: a) chitin synthesis inhibitors: Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus benzoylureas: chlorfluaZuron, cyramazin, difluben vulgaris, Picea abies, Pinus spec., Pistacia vera, Pisum Zuron, flucycloxuron, flufenoXuron, hexaflumuron, sativum, Prunus avium, Prunus persica, Pyrus communis, lufenuron, novaluron, teflubenZuron, triflumuron; Prunus armeniaca, Prunus cerasus, Prunus dulcis and buprofezin, diofenolan, hexythiaZOX, etoxazole, clofen 35 prunus domestica, Ribes Sylvestre, Ricinus communis, Sac tazine; b) ecdysone antagonists: halofenozide, charum officinarum, Secale cereale, Sinapis alba, Solanum methoxyfenozide, tebufenozide, azadirachtin; c) tuberosum, Sorghum bicolor (S. vulgare). Theobroma cacao, juvenoids: pyriproxyfen, methoprene, fenoxycarb; d) Trifolium pratense, Triticum aestivum, Triticale, Triticum lipid biosynthesis inhibitors: spirodiclofen, spirome durum, Vicia faba, Vitis vinifera, Zea mays. Sifen, spirotetramat; 40 Preferred crops are: Arachis hypogaea, Beta vulgaris nicotinic receptor agonists/antagonists compounds: cloth spec. altissima, Brassica napus var. napus, Brassica olera ianidin, dinotefuran, imidacloprid, thiamethoxam, cea, Brassica iuncea, Citrus limon, Citrus sinensis, Coffea nitenpyram, acetamiprid, thiacloprid, 1-(2-chloro-thi arabica (Coffea canephora, Coffea liberica), Cynodon dac azol-5-ylmethyl)-2-nitrimino-3,5-dimethyl-1,3,5 tri tylon, Glycine max, Gossypium hirsutum, (Gossypium aZinane; 45 arboreum, Gossypium herbaceum, Gossypium vitifolium), GABA antagonist compounds: endosulfan, ethiprole, Helianthus annuus, Hordeum vulgare, Juglans regia, Lens fipronil, Vaniliprole, pyrafluprole, pyriprole, 5-amino culinaris, Linum usitatissimum, Lycopersicon lycopersicum, 1-(2,6-dichloro-4-methyl-phenyl)-4-sulfinamoyl-1H Malus spec. Medicago sativa, Nicotiana tabacum (N. rus pyrazole-3-carbothioic acid amide; tica), Olea europaea, Oryza sativa, Phaseolus lunatus, macrocyclic lactone insecticides: abamectin, emamectin, 50 Phaseolus vulgaris, Pistacia vera, Pisum sativum, Prunus milbemectin, lepimectin, spinosad, spinetoram; dulcis, Saccharum officinarum, Secale cereale, Solanum mitochondrial electron transport inhibitor (METI) I aca tuberosum, Sorghum bicolor (s. vulgare), Triticale, Triticum ricides: femaZaquin, pyridaben, tebufenpyrad, tolfen aestivum, Triticum durum, Vicia faba, Vitis vinifera and Zea pyrad, flufenerim; mayS METI II and III compounds: acequinocyl, fluacyprim, 55 The compositions according to the invention can also be hydramethylnon, used in genetically modified plants, e.g. to alter their traits Uncouplers: chlorfenapyr; or characteristics. The term “genetically modified plants' is oxidative phosphorylation inhibitors: cyhexatin, diafen to be understood as plants, which genetic material has been thiuron, fenbutatin oxide, propargite; modified by the use of recombinant DNA techniques in a moulting disruptor compounds: cryomazine; 60 way that under natural circumstances it cannot readily be mixed function oxidase inhibitors: piperonyl butoxide: obtained by cross breeding, mutations, natural recombina Sodium channel blockers: indoxacarb, metaflumizone; tion, breeding, mutagenesis, or genetic engineering. Typi others: benclothiaz, bifenazate, cartap, flonicamid, cally, one or more genes have been integrated into the pyridalyl pymetrozine, Sulfur, thiocyclam, flubendi genetic material of a genetically modified plant in order to amide, chlorantraniliprole, cyazypyr (HGW86), cyen 65 improve certain properties of the plant. Such genetic modi opyrafen, flupyrazofos, cyflumetofen, amidoflumet, fications also include but are not limited to targeted post imicyafos, bistrifluron, and pyrifluquinazon. transtional modification of protein(s), oligo- or polypeptides US 9,451,767 B2 15 16 e.g. by glycosylation or polymer additions such as pre saporin or bryodin; steroid metabolism enzymes, such as nylated, acetylated or famesylated moieties or PEG moi 3-hydroxy-steroid oxidase, ecdysteroid-IDP-glycosyl-trans eties. ferase, cholesterol oxidases, ecdysone inhibitors or HMG Plants that have been modified by breeding, mutagenesis CoA-reductase; ion channel blockers, such as blockers of or genetic engineering, e.g. have been rendered tolerant to Sodium or calcium channels; juvenile hormone esterase; applications of specific classes of herbicides, are particularly diuretic hormone receptors (helicokinin receptors); stilben useful with the compositions according to the invention. synthase, bibenzyl synthase, chitinases or glucanases. In the Tolerance to classes of herbicides has been developed such context of the present invention these insecticidal proteins or as herbicides such as dicamba or 2,4-D, bleacher toxins are to be under-stood expressly also as pre-toxins, herbicides Such as hydroxyphenylpyruvate dioxygenase 10 hybrid proteins, truncated or otherwise modified proteins. (HPPD) inhibitors or phytoene desaturase (PDS) inhibitors: Hybrid proteins are characterized by a new combination of acetolactate synthase (ALS) inhibitors such as Sulfonyl ureas protein domains, (see, e. g. WO 02/015701). Further or imidazolinones; enolpyruvylshikimate 3-phosphate Syn examples of Such toxins or genetically modified plants thase (EPSP) inhibitors such as glyphosate; glutamine syn capable of synthesizing Such toxins are dis-closed, e.g., in thetase (GS) inhibitors such as glufosinate; protoporphy 15 EP-A374. 753, WO 93/007278, WO95/34656, EP-A 427 rinogen-IX oxidase (PPO) inhibitors; lipid biosynthesis 529, EP-A 451878, WO 03/18810 and WO 03/52073. The inhibitors such as acetyl CoA carboxylase (ACCase) inhibi methods for producing Such genetically modified plants are tors; or oxynil (i.e. or ioxynil) herbicides as a generally known to the person skilled in the art and are result of conventional methods of breeding or genetic engi described, e.g. in the publications mentioned above. These neering. Furthermore, plants have been made resistant to insecticidal proteins contained in the genetically modified multiple classes of herbicides through multiple genetic plants impart to the plants producing these proteins tolerance modifications, such as resistance to both glyphosate and to harmful pests from all taxonomic groups of athropods, glufosinate or to both glyphosate and a herbicide from especially to beetles (Coeloptera), two-winged insects (Dip another class such as ALS inhibitors, HPPD inhibitors, auxin tera), and moths (Lepidoptera) and to nematodes (Nema herbicides, or ACCase inhibitors. These herbicide resistance 25 toda). Genetically modified plants capable to synthesize one technologies are, for example, described in Pest Manage or more insecticidal proteins are, e. g., described in the ment Science 61, 2005, 246; 61, 2005, 258; 61, 2005, 277: publications mentioned above, and some of which are com 61, 2005, 269: 61, 2005, 286; 64, 2008, 326; 64, 2008, 332; mercially available such as YieldGard(R) (corn cultivars Weed Science 57, 2009, 108: Australian Journal of Agricul producing the Cry1Ab toxin), YieldGard(R) Plus (corn cul tural Research 58, 2007, 708; Science 316, 2007, 1185; and 30 tivars producing Cry1Ab and Cry3Bb1 toxins), Starlink(R) references quoted therein. Examples of these herbicide resis (corn cultivars producing the Cry9c toxin). Herculex(R) RW tance technologies are also described in US 2008/0028482, (corn cultivars producing Cry34Ab1, Cry35Ab1 and the US2009/0029891, WO 2007/143690, WO 2010/080829, enzyme Phosphino-thricin-N-Acetyltransferase PATI); U.S. Pat. No. 6,307,129, U.S. Pat. No. 7,022,896, US NuCOTNR 33B (cotton cultivars producing the Cry1Ac 2008/0015110, U.S. Pat. No. 7,632,985, U.S. Pat. No. 7,105, 35 toxin), Bollgard(R) I (cotton cultivars producing the Cry1Ac 724, and U.S. Pat. No. 7,381,861, each herein incorporated toxin), Bollgard(R) II (cotton cultivars producing Cry1Ac and by reference. Cry2Ab2 toxins); VIPCOTR) (cotton cultivars producing a Several cultivated plants have been rendered tolerant to VIP-toxin); New Leaf R (potato cultivars producing the herbicides by conventional methods of breeding (mutagen Cry3A toxin); Bt-Xtra R, NatureGard(R), Knock-Out(R), Bite esis), e. g. Clearfield(R) summer rape (Canola, BASF SE. 40 Gard(R), ProtectaR), Bt11 (e. g. Agrisure R. CB) and Bt176 Germany) being tolerant to imidazolinones, e.g. imaZamox, from Syngenta Seeds SAS, France, (corn cultivars produc or ExpressSunR) sunflow-ers (DuPont, USA) being tolerant ing the Cry1Ab toxin and PAT enyzme), MIR604 from to Sulfonyl ureas, e. g. tribenuron. Genetic engineer-ing Syngenta Seeds SAS, France (corn cultivars producing a methods have been used to render cultivated plants such as modified version of the Cry3A toxin, c.f. WO 03/018810), Soybean, cotton, corn, beets and rape, tolerant to herbicides 45 MON 863 from Monsan-to Europe S.A., Belgium (corn Such as glyphosate, dicamba, imidazolinones and glufosi cultivars producing the Cry3Bb1 toxin), IPC 531 from nate, Some of which are under development or commercially Monsanto Europe S.A., Belgium (cotton cultivars producing available under the brands or trade names RoundupReady(R) a modified version of the Cry1Ac toxin) and 1507 from (glyphosate tolerant, Monsanto, USA), Cultivance(R) (imi Pioneer Overseas Corporation, Belgium (corn cultivars pro dazolinone tolerant, BASF SE, Germany) and LibertyLink R. 50 ducing the Cry1F toxin and PAT enzyme). (glufosinate tolerant, Bayer CropScience, Germany). Furthermore, plants are also covered that are by the use of Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or recombinant DNA techniques capable to synthesize one or more proteins to increase the resistance or tolerance of those more insecticidal proteins, especially those known from the plants to bacterial, viral or fungal pathogens. Examples of bacterial genus Bacillus, particularly from Bacillus thuringi 55 Such proteins are the so-called “pathogenesis-related pro ensis, such as ?-endotoxins, e.g. CryIA(b), CryIA(c), Cry IF, teins’ (PR proteins, see, e.g. EP-A 392 225), plant disease CryIF(a2), CryIIA(b), CryIIIA, CryIIIB(b1) or Cry9c; veg resistance genes (e. g. potato culti-vars, which express etative insecticidal proteins (VIP), e.g. VIP1, VIP2, VIP3 or resistance genes acting against Phytophthora infestans VIP3A; insecti-cidal proteins of bacteria colonizing nema derived from the mexican wild potato Solanum bulbo todes, e.g. Photorhabdus spp. or Xenorhabdus spp., toxins 60 castanum) or T4-lyso-Zym (e.g. potato cultivars capable of produced by animals, such as Scorpion toxins, arachnid synthesizing these proteins with increased resistance against toxins, wasp toxins, or other insect-specific neurotoxins: bacteria such as Erwinia amylvora). The methods for pro toxins produced by fungi, Such Streptomy-cetes toxins, plant ducing Such genetically modified plants are generally known lectins, such as pea or barley lectins; agglutinins; proteinase to the person skilled in the art and are described, e.g. in the inhibitors, such as trypsin inhibitors, serine protease inhibi 65 publications mentioned above. tors, patatin, cyStatin or papain inhibitors; ribosome-inacti Furthermore, plants are also covered that are by the use of vating proteins (RIP), such as ricin, maize-RIP. abrin, luffin, recombinant DNA techniques capable to synthesize one or US 9,451,767 B2 17 18 more proteins to increase the productivity (e.g. bio mass seed comprises essentially all procedures familiar to the production, grain yield, starch content, oil content or protein person skilled in the art (seed dressing, seed coating, seed content), tolerance to drought, Salinity or other growth dusting, seed soaking, seed film coating, seed multilayer limiting environ-mental factors or tolerance to pests and coating, seed encrusting, seed dripping and seed pelleting) fungal, bacterial or viral pathogens of those plants. based on the compounds of the formula I according to the Furthermore, plants are also covered that contain by the invention or the compositions prepared therefrom. Here, the use of recombinant DNA techniques a modified amount of herbicidal compositions can be applied diluted or undiluted. Substances of content or new Substances of content, specifi The term seed comprises seed of all types, such as, for cally to improve human or animal nutrition, e.g. oil crops example, corns, seeds, fruits, tubers, seedlings and similar that produce health-promoting long-chain omega-3 fatty 10 forms. Here, preferably, the term seed describes corns and acids or unsaturated omega-9 fatty acids (e. g. Nexera R. seeds. rape, DOW Agro Sciences, Canada). The seed used can be seed of the useful plants mentioned Furthermore, plants are also covered that contain by the above, but also the seed of transgenic plants or plants use of recombinant DNA techniques a modified amount of obtained by customary breeding methods. Substances of content or new Substances of content, specifi 15 cally to improve raw material production, e.g. potatoes that The rates of application of the active compound are from produce increased amounts of amylopectin (e.g. Amflora R. 0.0001 to 3.0, preferably 0.01 to 1.0 kg/ha of active sub potato, BASF SE, Germany). stance (a.s.), depending on the control target, the season, the Furthermore, it has been found that the compositions target plants and the growth stage. To treat the seed, the according to the invention are also suitable for the defolia compounds I are generally employed in amounts of from tion and/or desiccation of plant parts, for which crop plants 0.001 to 10 kg per 100 kg of seed. Such as cotton, potato, oilseed rape, Sunflower, soybean or The present invention also relates to a use of the alkoxy field beans, in particular cotton, are Suitable. In this regard late of the formula (I) for reducing the wind drift of an compositions have been found for the desiccation and/or aqueous composition comprising a pesticide (e.g. dicamba). defoliation of plants, processes for preparing these compo 25 The present invention offers various advantages: it sitions, and methods for desiccating and/or defoliating reduced spray drift fines and off-target movement of pesti plants using the compositions according to the invention. cide (e.g. dicamba) applications compared to current avail As desiccants, the compositions according to the inven able formulations, while maintaining use friendly handling tion are suitable in particular for desiccating the above and use characteristics, and without adversely affecting their ground parts of crop plants such as potato, oilseed rape, 30 pesticidal activity. The compositions reduced driftable fines Sunflower and soybean, but also cereals. This makes pos at a lower adjuvant use rate in the spray tank in comparison sible the fully mechanical harvesting of these important crop to commercial standard applied as a tank mix. Further plants. advantages of the invention are good adhesion of the pes Also of economic interest is the facilitation of harvesting, ticide on the Surface of the treated plants, increased perme which is made possible by concentrating within a certain 35 ation of the pesticides into the plant and, as a result, more period of time the dehiscence, or reduction of adhesion to rapid and enhanced activity. An advantage is the low toxicity the tree, in citrus fruit, olives and other species and varieties of the alkoxylates, in particular the low aquatic toxicity. of pomaceous fruit, stone fruit and nuts. The same mecha Another advantage is the low harmful effect against crop nism, i.e. the promotion of the development of abscission plants, i.e., low phytotoxic effects. Another advantage is that tissue between fruit part or leaf part and shoot part of the 40 the volatility of pesticides (e.g. auxin herbicides like plants is also essential for the controlled defoliation of useful dicamba, or 2,4-D) is reduced; or that no additional drift plants, in particular cotton. Moreover, a shortening of the control agent needs to be added to the tank mix, thus time interval in which the individual cotton plants mature allowing an easy and safe preparation of the tank mix. leads to an increased fiber quality after harvesting. The invention is further illustrated but not limited by the The compositions according to the invention are applied 45 following examples. to the plants mainly by spraying the leaves. Here, the application can be carried out using, for example, water as carrier by customary spraying techniques using spray liquor EXAMPLES amounts of from about 100 to 1000 l/ha (for example from 300 to 400 l/ha). The herbicidal compositions may also be 50 Antidrift A: Ethoxylated Cetyl/Oleylalcohol (degree of applied by the low-volume or the ultra-low-volume method, ethoxylation about 3), HLB about 6.6 according to Griffin. or in the form of microgranules. Antifoam: Aqueous, nonionic silicone emulsion, Solid con The herbicidal compositions according to the present tent about 32%. invention can be applied pre- or post-emergence, or together with the seed of a crop plant. It is also possible to apply the 55 Example 1 compounds and compositions by applying seed, pretreated with a composition of the invention, of a crop plant. If the active compounds A and C and, if appropriate C, are less Preparation of SL Formulation well tolerated by certain crop plants, application techniques may be used in which the herbicidal compositions are 60 A clear, homogenous aqueous formulation was prepared sprayed, with the aid of the spraying equipment, in Such a by mixing 84 wt % of an aqueous Solution containing 600 g/1 way that as far as possible they do not come into contact with of dicamba BAPMA salt (resulting in 480 aeg/l dicamba), the leaves of the sensitive crop plants, while the active 13.2 wt % Antidrift A, 0.05 wt % Antifoam, and water up to compounds reach the leaves of undesirable plants growing 100 wit 9%. underneath, or the bare soil Surface (post-directed, lay-by). 65 The formulation was storage stable for at least three In a further embodiment, the composition according to the months at 25°C., 40°C. and 50° C. and through 5 cycles of invention can be applied by treating seed. The treatment of freeze that -20 to 5° C. US 9,451,767 B2 19 20 Example 2 R" is an aliphatic Cs-Cs ring system, which comprises either nitrogen in the ring or which is substituted Sprayable Tank Mix with at least one unit NR'R''; and wherein the drift control agent is an alkoxylate of the A sprayable tank mix was prepared by mixing 84.0 ml 5 formula (I) Roundup WetherMax(R) from Monsanto (aqueous SL formu lation containing 49 wt % potassium glyphosate), 47.2 ml of the dicamba formulation of Example 1, and 3.671 of water. wherein R is Cs-C2-alkyl and/or -alkenyl, m is 2, 3, 4 or The amount of spray drift is influenced by the amount of a mixture thereof, and n is from 1 to 15. fine particles from the spray nozzle tip. Typically, spray 10 2. The composition as claimed in claim 1, wherein particles of less than 150 um in size have a significant higher dicamba is present in form of a N,N-bis(3-aminopropyl) potential to remain in the air and to be less affected by wind methylamine salt. to be carried off-site. 3. The composition as claimed in claim 1, wherein the The tank mix was sprayed at 40 psi through a TeeJet drift control agent is an alkoxylate of the formula (I), AIXR11004 spray nozzle at field dilution rate of 10 gallons 15 wherein R is C-Co-alkyl and/or -alkenyl, m is 2, a per acre (GPA). A laser diffraction setup (SprayTec, Malvern mixture of 2 and 3, or a mixture of 2 and 4, and n is from Instruments, 750 mm lens) was used to measure the volume 2 to 8. fraction of droplets less than 150 um in diameter. The laser 4. The composition as claimed in claim 1, wherein the was positioned perpendicular to the plane of the liquid sheet drift control agent is an alkoxylate of the formula (I), produced by the spray noZZle. The spray sheet was moved wherein R is C-Cls-alkyl and/or -alkenyl, m is 2, and n is through the laser beam at a constant speed of 4.5 m/s to from 2 to 5. enable measurements covering the complete width of the 5. The composition as claimed in claim 1, containing at spray pattern at a distance of 12" below the nozzle tip. The least 300 g/l acid equivalents of dicamba. cabinet in which the experiment was carried out was ven 6. The composition as claimed in claim 1, containing from tilated at the bottom resulting in a downward air flow of 5.5 25 5 to 30 wt % of the drift control agent. km/h. Each sample was passed through the laser three times. 7. The composition as claimed in claim 1 in form of an Before each pass a new background was collected. The data homogenous Solution. from the three passes was averaged. The percentage of fines 8. A method for preparing a tank mix, which comprises (particle size below 150 um) was 5%. the step of contacting water and the composition according For comparison, the dicamba formulation of Example 1 30 to claim 1, and optionally further pesticides. was prepared without the addition of Antidrift A and used for 9. The method according to claim 7, wherein the tank mix preparing a sprayable tank mix as described above. The contains up to 3 wt % of the aqueous composition. percentage of fines (particle size below 150 um) was 10.5%. 10. The method according to claim 8, wherein the tank Thus, the percentage of fines was reduced by 50% by the 35 mix contains up to 0.5 wt % of the drift control agent. addition of Antidrift A. 11. A method of controlling undesired vegetation, wherein the composition according to claim 1 is allowed to act on the We claim: respective pests, their environment or the plants to be 1. An aqueous composition comprising dicamba and a protected from the respective pest, on the Soil and/or on drift control agent, wherein dicamba is present in form of a 40 undesired plants and/or the crop plants and/or their envi dicamba polyamine salt and the polyamine has the formula rOnment. (A1) 12. The method of claim 11, wherein in the alkoxylate of the formula (I),

(A1) 45 R R R wherein R is Cs-C2-alkyl and/or -alkenyl, m is 2, 3, 4 or st Sh Nx a mixture thereof, and n is from 1 to 15, for reducing R2 R4 the wind drift of an aqueous composition comprising a pesticide. wherein 50 13. The method of claim 11, wherein in the alkoxylate of R", R. R. R. and R7 are independently H or C-C- the formula (I), R is C-Co-alkyl and/or -alkenyl, m is 2. alkyl, which is optionally substituted with OH, a mixture of 2 and 3, or a mixture of 2 and 4, and n is from R and Rare independently C-Co-alkylene, 2 to 8. X is OH or NR'R'', and 14. The method of claim 11, wherein in the alkoxylate of 55 the formula (I), R is C-Cls-alkyl and/or -alkenyl, m is 2. n is from 1 to 20; and n is from 2 to 5. or the formula (A2) 15. The method of claim 11, wherein dicamba is present in form of a N,N-bis(3-aminopropyl)methylamine salt. A2 16. The method of claim 15, wherein the drift control RQ R2 ( ) 60 agent is an alkoxylate of the formula (I), wherein R is n N1 NR 13 C-Co-alkyl and/or -alkenyl, m is 2, a mixture of 2 and 3. or a mixture of 2 and 4, and n is from 2 to 8. RI 17. The method of claim 15, wherein the drift control agent is an alkoxylate of the formula (I), wherein R is wherein 65 C-Cls-alkyl and/or -alkenyl, m is 2, and n is from 2 to 5. R'' and R'' are independently H or C-C-alkyl, 18. The method of claim 15, wherein dicamba is present R" is C-C2-alkylene, and in at least 300 g/l acid equivalents of dicamba. US 9,451,767 B2 21 22 19. The method of claim 15, wherein the composition contains from 5 to 30 wt % of the drift control agent. k k k k k