Title of Invention

HERBICIDAL COMPOSITION

Abstract HERBICIDAL COMPOSITION The invention relates to a herbicide agent containing A) at least one compound of formula (1) wherein Hal1 and Hal2 represent the same or different halogen atoms, and R1 represents H, a cation or a radical containing C1-C20 carbon; and B) at least one surfactant containing at least 12 alkylene oxide units as a structural element.
Full Text

Herbicidal composition
The present invention relates to the field of chemical crop protection, in particular to cojmbinations of specific herbicides of the hydroxybenzonitrile type with specific surfactants.
Herbicides of the hydroxybenzonitrile type, such as ioxynil or bromoxynil and derivatives thereof, such as salts or esters, are suitable for controlling undesirable vegetation, for example in crops such as corn or wheat.
It is also known that the abovementioned herbicidal compounds can be combined with surfactants for preparing standard formulations.
It was an object of the present invention to provide herbicidal compositions with particularly high herbicidal activity.
Surprisingly, it has now been found that this object is achieved by herbicidal compositions comprising herbicides of the hydroxybenzonitrile type of the formula (I) from below in combination with specific surfactants.
Accordingly, the present invention relates to herbicidal compositions, comprising

in which
Hal1 and Hal2 are identical or different halogen atoms such as F, CI, Br,
I, preferably Br or I, and
R1 is H, a cation or a CrC2o-carbon-containing radical, and B) one or more surfactants, comprising as structural elements at least 12



Compounds of the formula (1) are known, tor example, from C.D.S from the Pgsticide Manual", 12th edition (1999), The British Crop Protection Council, (ISBN 1 ^ 01 39 61 26); p. 110ff and p. 548ff.
Particularly preferred compounds of the formula (I) are, for example, bromoxynil (A1) arjd ioxynil (A5) and their salts and esters, such as bromoxynil-sodium (A2), brJDmoxynil-potassium (A3), bromoxynil-heptylcarbonyl (= bromoxynil-octanoate) (/^4), ioxynil-sodium (A6), ioxynil-potassium (A7), ioxynil-heptylcarbonyl (= ioxynil-odtanoate) (A8), bromoxynil-hexylcarbonyl (= bromoxynil-heptanoate) (A9). bromoxynil-propylcarbonyl (= bromoxynil-butyrate) (A10), ioxynil-hexylcarbonyl (= ioxynil-heptanoate) (A11) and ioxynil-propylcarbonyl (= ioxynil-butyrate) (A12) and mixtures thereof.
The surfactant B) preferably contains 12 - 200 alkylene oxide units, one or more CrC4cr-carbon-containing radicals and, if appropriate, one or more polar functional groups.
The term "alkylene oxide units" is preferably to be understood as meaning units of C2-C10-alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide or hexylene oxide, where the units within the surfactant may be identical or different from one another.
Suitable polar functional groups are, for example, anionic groups such as carboxylate, carbonate, sulfate, sulfonate, phosphate or phosphonate, cationic groups such as groups having a cationic nitrogen atom, for example a pyridinium group or an -NRya group, where Ry are identical or different radicals from the group consisting of H and unsubstituted or substituted C1-C10-hydrocarbon radicals such as (CrCio)-alkyl, electrically neutral polar groups, such as carbonyl, imine, cyano or sulfonyl, or betainic groups, such as

es
in which
Ed is an ethylene oxide unit,
PO is a propylene oxide unit,
X is an integer from 0 to 50, preferably from 1 to 50,
y; is an integer from 0 to 50,
z is an integer from 0 to 50,
where the sum (x+y+z) > 12 and














Unless specifically defined otherwise, the following definitions apply in general to the radicals in the formulae for (I) and (II) and in the formulae below.
If the term "acyl radical" is used in this description, this means the radical of an organic acid which is formally generated by removing an OH group from the organic acid, for example the radical of a carboxylic acid and radicals of acids derived therefrom, such as thiocarboxylic acid, unsubstituted or N-substituted imino carboxylic acids or the radicals of carbonic acid monoesters, unsubstituted or N-substituted carbaminic acids, sulfonic acids, sulfinic acids, phosphonic acids, phosphinic acids.
Preferred acyl radicals are formyl or acyl from the group consisting of CO-Rz CS-Rz CO-OR2 CS-ORz CS-SRz, SORz and S02Rz where Rz is in each case a C1-C10-hydrocarbon radical such as C1-C10-alkyl or C6-C10-aryl which is unsubstituted or substituted, for example by one or more substitutents from the group consisting of halogen, such as F, CI, Br, I, alkoxy, haloalkoxy, hydroxyl, amino, nitro, cyano or alkylthio, or R2 is aminocarbonyl or aminosulfonyl, where the two last-mentioned




substituted alkyl, alkenyl, alkynyl, or carbocyclic rings, such as cycloalkyi, cyicloalkenyl or aryl, and the hydrocarbonoxy radicals which correspond to these hydrocarbon radicals, such as alkoxy, alkenyloxy, alkynyloxy, cycloalkoxy, cyicioalkenyloxy or phenoxy, or substituted heterocyclyl radicals, are, for example, a siibstituted radical derived from the unsubstituted skeleton, where the substituents arte, for example, one or more, preferably 1, 2 or 3, radicals from the group consisting of halogen, alkoxy, haloalkoxy, alkylthio, hydroxyl, amino, nitro, carboxyl, cyano, azido, alkoxycarbonyl, alkylcarbonyl, formyl, carbamoyl, mono- and dialkylaminocarbonyl, substituted amino, such as acylamino, mono- and dialkylamino, and alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl and, in the case of cyclic radicals, also unsubstituted or substituted alkyl, such as haloalkyi, alkoxyalkyl, haloalkoxyaikyi, alkylthioalkyl, hydroxyalkyi, aminoalkyi, nitroalkyi, carboxyalkyi, cyanoalkyi or azidoalkyi, and also the unsaturated aliphatic radicals which correspond to the saturated hydrocarbon-containing radicals mientioned, such as alkenyl, alkynyl, alkenyloxy, alkynyloxy etc. Among the radicals having carbon atoms, preference is given to those having 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms. In general, preference is given to substituents from the group consisting of halogen, for example fluorine and chlorine, (C1-C4)-alkyl, preferably methyl or ethyl, (C1-C4)-haloalkyl, preferably trifluoromethyl, (CrC4)-alikoxy, preferably methoxy or ethoxy, (C1-C4)-haloalkoxy, nitro and cyano. Particular preference is given here to the substituents methyl, methoxy and chlorine.
The carbon-containing radicals, such as alkyl, alkoxy, haloalkyi, haloalkoxy, afkylamino and alkylthio, and the corresponding unsaturated and/or substituted radicals, can in each case be straight-chain or branched in the carbon skeleton. Unless specifically indicated othen^/ise, among these radicals, preference is given to the lower carbon skeletons, for example those having 1 to 6 carbon atoms or, in the case of unsaturated groups, those having 2 to 6 carbon atoms. Alkyl radicals, also in the composite meanings such as alkoxy, haloalkyi, etc., are, for example, methyl, ethyl, n- or isopropyl, n-, iso-, t- or 2-butyl, pentyls, hexyls, such as n-hexyi, i-hexyl ahd 1,3-dimethylbutyl, heptyls, such as n-heptyl, 1-methylhexyl and 1 4-dimethylpentyl; alkenyl and alkynyl radicals have the meaning of the possible

urisaturated radicals which correspond to the alkyl radicals; alkenyl is, for example, allyl, 1-methylprop-2-en-1-yl, 2-methyl-prop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, 1-hnethyl-but-3-en-1-yl and 1-methyl-but-2-en-1-yl; alkynyl is, for example, propargyl, bijt-2-in-1-yl, but-3-in-1-yl, 1-methyl-but-3-in-1-yl.
Cydoalkyl is preferably a cyclic alkyl radical having 3 to 8, preferably 3 to 7, particularly preferably 3 to 6, carbon atoms, for example cyclopropyl, cyclobutyl, cviclopentyl and cyclohexyl. Cycloalkenyl and cycloalkynyl denote the corresponding unsaturated compounds.
Halogen is fluorine, chlorine, bromine or iodine, haloalkyi, haloalkenyl and haloalkynyl are alkyl, alkenyl and alkynyl, respectively, which are partially or fully substituted by halogen, preferably by fluorine, chlorine and/or bromine, in particular by fluorine or chlorine, for example CF3, CHF2, CH2F, CF3CF2, CH2FCHCI, CCI3.
CHCI2, CH2CH2CI. Haloalkoxy is, for example, OCF3, OCHF2, OCH2F, CF3CF2O. OCH2CF3 and OCH2CH2CL This applies correspondingly to other halogen-substituted radicals.
A hydrocarbon radical can be an aromatic hydrocarbon radical, such as aryl, or an aliphatic hydrocarbon radical; an aliphatic hydrocarbon radical generally being a straight-chain or branched saturated or unsaturated hydrocarbon radical having prieferably 1 to 18, particularly preferably 1 to 12, carbon atoms, for example alkyl, alkenyl or alkynyl.
An aliphatic hydrocarbon radical is preferably alkyl, alkenyl or alkynyl having up to 12 carbon atoms; this applies correspondingly to an aliphatic hydrocarbon radical in a hydrocarbonoxy radical.
A ring is a carbocyclic or heterocyclic, mono-, bi-or polycyclic, unsubstituted or substituted ring system which is saturated, unsaturated or aromatic. Examples of carbocyclic rings are aryl, cycloalkyl or cycloalkenyl.

Aryl is generally a mono-, bi- or polycyclic aromatic hydrocarbon radical having preferably 6-20 carbon atoms, with preference 6 to 14 carbon atoms, particularly preferably 6 to 10 carbon atoms, which may be fused with mono-, bi- or polycyclic, urisubstituted or substituted, aromatic heterocyclyl or mono-, bi- or polycyclic, urisubstituted or substituted, saturated or unsaturated carbocyclyl, for example cyjcloalkyl or cycloalkenyl, or mono-, bi- or polycyclic, unsubstituted or substituted, saturated or unsaturated heterocyclyl. Examples of aryl radicals are phenyl, naphthyl, tetrahydronaphthyl, indenyl, indanyl, pentalenyl and fluorenyl, particularly preferably phenyl.
A heterocyclic ring, heterocyclic radical or heterocyclyl is a mono-, bi- or polycyclic unsubstituted or substituted ring system which is saturated, unsaturated and/or aromatic and contains one or more, preferably 1 to 4, heteroatoms, preferably from the group consisting of N, S and O.
Preference is given to saturated heterocycles having 3 to 7 ring atoms and one or two heteroatoms from the group consisting of N, O and S, where the chalcogens are not adjacent. Particular preference is given to monocyclic rings having 3 to 7 ring atoms and one heteroatom from the group consisting of N, O and S, and also to morpholine, dioxolane, piperazine, imidazoline and oxazolidine. Very particularly prieferred saturated heterocycles are oxirane, pyrrolidone, morpholine and tetrahydrofuran.
Preference is also given to partially unsaturated heterocycles having 5 to 7 ring atoms and one or two heteroatoms from the group consisting of N, O and S. Particular preference is given to partially unsaturated heterocycles having 5 or 6 ring atpms and one heteroatom from the group consisting of N, O and S. Very particularly prieferred partially unsaturated heterocycles are pyrazoiine, imidazoline and isoxazoline.
Preference is also given to heteroaryl, for example mono- or bicyclic aromatic heterocycles having 5 or 6 ring atoms which contain one to four heteroatoms from thje group consisting of N, O and S, where the chalcogens are not adjacent.

Particular preference is given to monocyclic aromatic heterocycles having 5 or 6 ring atoms including one heteroatom from the group consisting of N, O and S, and also to pyrimidine, pyrazine, pyridazine, oxazole, thiazole, thiadiazole, oxadiazole, pyrazole tricizole and isoxazole. Very particular preference is given to pyrazole, thiazole, tri4zole and furan.
Mono- or disubstituted amino is a chemically stable radical from the group of the substituted amino radicals which are N-substituted, for example, by one or two identical or different radicals from the group consisting of alkyl, alkoxy, acyl and aryl; preferably monoalkylamino, dialkylamino, acylamino, arylamino, N-alkyl-N-arylamino and N-heterocycles; here, preference is given to alkyl radicals having 1 to 4 carbon atoms; aryl is preferably phenyl or substituted phenyl; acyl corresponds to the definition given further below and is preferably formyl, (C1-C4)"alkylcarbonyl or (d-C4)-alkylsulfonyl. This applies correspondingly to substituted hydroxylamino or hydrazine.
Unsubstituted or substituted phenyl is preferably phenyl which is unsubstituted or mono- or polysubstituted, preferably up to trisubstituted, in the case of halogen such as CI and F also up to pentasubstituted, by identical or different radicals from the group consisting of halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkyl, (C1-C4)-haloalkoxy and nitro, for example 0-, m- and p-tolyl, dimethylphenyls, 2-, 3- and 4-chlorophenyl, 2-, 3- and 4-trifluoro- and -trichlorophenyl, 2,4-, 3,5-, 2,5- and 2,3-diahlorophenyl, o-, m- and p-methoxyphenyl.
Thie herbicidal compositions according to the invention comprising compounds of the fonmula (I) and surfactants B) have excellent herbicidal activity and, in a preferred embodiment, superadditive effects. Owing to the improved control of harmful plants by the herbicidal compositions according to the invention, it is possible to reduce the application rate and/or to increase the safety margin. Both make sense, both from an economical and an ecological point of view. The amounts of the components A) + B) to be employed and the ratio of the components A): B) depend on a whole range of factors.

In a preferred embodiment, the herbicidal compositions according to the invention are characterized in that they have a synergistically effective amount of a combination of the compounds of the formula (I) with surfactants B). Here, it has to be emphasized in particular that even in combinations where the application rates or weight ratios of A): B) are such that a synergism cannot be demonstrated clearly in eatch case - for example owing to the fact that the individual compounds are usually employed in the combination in very different application rates or else because the control of harmful plants by the individual compounds is already very good - a synergistic action is generally inherent to the herbicidal compositions of the invention.
Components A) and B) of the herbicidal compositions according to the invention can be formulated separately and applied by the tank mix method, or they can be contained together in a ready-to-use formulation which can then be applied in a customary manner, for example in the form of a spray liquor.
The herbicidal compositions according to the invention can be formulated in various ways depending on the prevailing biological and/or physical-chemical parameters. Examples of suitable formulation options are: wettable powders (WP), water-soluble powders (SP), water-soluble concentrates (SL), emulsifiable concentrates (EC), emulsions (EW), such as oil-in-water and water-in-oil emulsions, sprayable solutions, suspension concentrates (SC), oil- or water-based dispersions, oil-miscible solutions, capsule suspensions (CS), dusts (DP), granules for broadcasting and soil application, granules (GR) in the form of microgranules, spray granules, coating granules and adsorption granules, water-dispersable granules (WG), water-soluble grariules (SG), ULV formulations, microcapsules and waxes. These individual formulation types are known in principle and are described, for example, in: Wirinacker-Kijchler, "Chemische Technologie" [Chemical Technology], volume 7, C.Hauser Verlag Munich, 4th edition 1986, Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, N.Y., 1973; K. Martens, "Spray Drying" Handbook, 3rd;Ed. 1979, G. Goodwin Ltd. London.

The necessary formulation auxiliaries, such as inert materials, surfactants, solvents and other additives, are likewise known and are described, for example, in: Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell N.J.; H.v. Olphen, "Introduction to Clay Colloid Chemistry", 2nd Ed., J. wiey & Sons, N.Y.; C. Marsden, "Solvents Guide", 2nd Ed., Interscience, N.Y. 1963; McjCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood N.J.; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc.. N.Y. 1964; Schonfeldt, "Grenzflachenaktive Athylenoxidaddukte" [Surface-active ethylene oxide adducts], Wiss. VerlagsgeselL, Stuttgart 1976; Winnacker-Kuchler, "Chemische Technologie", Volume 7, C. Hauser Verlag Munich, 4th edition 1986.
Based on these formulations it is also possible to produce combinations with other agrochemically active compounds which differ from component A), such as insecticides, acaricides, herbicides, fungicides, safenerns, fertilizers and/or growth regulators, for example in the form of a ready-to-use formulation or as tank mix.
Wettable powders are preparations which are uniformly dispersable in water and which contain, in addition to the active compound A) and/or the surfactant B), and in addition to a diluent or inert substance, also surfactants of ionic and/or nonionic nature which are different from surfactant B) (wetting agents, dispersants), for example polyethoxylated alkylphenols, polyethoxylated fatty alcohols, polyethoxylated fatty amines, fatty alcohol polyglycol ether sulfates, alkane-sulfonates, alkylbenzenesulfonates, sodium lignosulfonate, sodium 2,2-dinaphthylmethane-6,6'-disuifonate, sodium dibutylnaphthalene sulfonate or else sodium oleoylmethyltaurinate. To prepare the wettable powders, the herbicidally active compounds A) and/or surfactants B) are finely ground, for example in customary apparatus such as hammer mills, fan mills and air-jet mills, and are mixed simultaneously or subsequently with the formulation auxiliaries.
Emsulsifiable concentrates are prepared by dissolving the active compound A) and/or the surfactant B) in an organic solvent, for example butanol, cyclohexanone,

dimethylformamide, xylene or else relatively high-boiling aromatic compounds or hydrocarbons or mixtures of the organic solvents with addition of one or more surfactants of ionic and/or nonionic nature differing from surfactant B) (emulsifiers). Suitable for use as emulsifiers are, for example: calcium alkylarylsulfonates, such as calcium dodecylbenzenesulfonate, or nonionic emulsifiers, such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide/ethylene oxide condensates, alkyl polyethers, sorbitan esters, for example sorbitan fatty acid esters, or polyoxyethylene sorbitan esters, for example polyoxyethylene sorbitan fatty acid esters.
Water-soluble concentrates are obtained, for example, by dissolving the active compound A) and/or the surfactant B) in water or a water-miscible solvent and adding, if appropriate, further auxiliaries such as water-soluble surfactants.
Dusts are obtained by grinding the active compound A) and/or the surfactant B) with finely divided solid substances, for example talc, natural clays, such as kaolin, b^ntonite and pyrophyllite, or diatomaceous earth.
Suspension concentrates can be water- or oil-based. They can be prepared, for example, by wet milling using commercially customary bead mills, with or without the addition of surfactants differing from surfactant B), as already mentioned above, for example, in the case of the other formulation types.
Eimulsions, for example oil-in-water emulsions (EW) can be prepared, for example, by means of stirrers, colloid mills and/or static mixers using aqueous organic solvents and, if appropriate, surfactants differing from surfactant B), as already mentioned above, for example, in the case of the other formulation types.
Granules can be prepared either by spraying the active compound A) and/or surfactant B) onto adsorptive, granulated inert material or by applying active-cpmpound concentrates to the surface of carriers such as sand, kaolinites or gjranulated inert material, by means of adhesive binders, for example polyvinyl

aldohol, sodium polyacrylate or else mineral oils. Suitable active compounds A) and/or surfactants B) can also be granulated in the manner which is customary for the preparation of fertilizer granules - if desired as a mixture with fertilizers.
Wkter-dispersable granules are generally prepared by the customary processes, sdch as spray-drying, fluidized-bed granulation, disk granulation, mixing using high-spleed mixers, and extrusion without solid inert material.
For the preparation of disk, fluidized-bed, extruder and spray granules, see, for example, processes in "Spray-Drying Handbook" 3rd ed. 1979, G. Goodwin Ltd., London; J.E. Browning, "Agglomeration", Chemical and Engineering 1967, pages 147 ff; "Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New York 1973, pp. 8-57.
For further details on the formulation of crop protection products, see, for example, G.C. Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961, pages 81-96 and J.D. Freyer, S.A. Evans, "Weed Control Handbook", 5th Ed., BJackwell Scientific Publications, Oxford, 1968, pages 101-103.
The herbicidal compositions according to the invention generally comprise from 0.01 to 99% by weight, in particular from 0.1 to 95% by weight, of one or more compounds of the formula (I).
In wettable powders, the concentration of active compound is, for example, from about 10 to 90% by weight, the remainder to 100% by weight consisting of customary formulation constituents and, if appropriate, surfactants B). In emulsifiable concentrates, the concentration of active compound can be from about 1 to 90, preferably from 5 to 80, % by weight. Formulations in the form of dusts comprise from 1 to 30% by weight of active compound, preferably most commonly from 5 to 20% by weight of active compound, while sprayable solutions comprise from about 0.05 to 80, preferably from 2 to 50, % by weight of active compound. In the case of water-dispersable granules, the content of active compound depends partly on

whether the active compound is in liquid or solid form and on the granulation auxiliaries, fillers, etc., that are used. In water-dispersabie granules the content of active compound is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.
Suitable further formulation forms are, for example, controlled-release formulations, in particular by incorporating the active compounds into carrier materials. The inciorporation of active compounds into carrier materials for providing formulations which allow controlled release is known in principle and can be found in the expert literature. Examples can be found in C. L. Foy, D. W. Pritchard, "Pesticide Formulation and Technology", CRC Press, 1996, page 273 ff. and literature cited therein, and in D. A. Knowles, "Chemistry and Technology of Agrochemical Formulations", Kluwer Academic Press, 1998, page 132 ff. and literature cited therein.
The carrier materials which surround or coat the active compounds are chosen such that they are solid in a suitable temperature range, preferably in a range of about 0-50°C. Solid materials are to be understood as meaning materials which are hard, resilient in a wax-like manner, amorphous or crystalline, but which are not or not yet present in the liquid state. The carrier materials can be of inorganic or organic nature arid of synthetic or natural origin.
Ohe possibility of incorporating the agrochemically active compounds into suitable carrier materials is, for example, microencapsulation. These microcapsules can consist of polymeric materials of synthetic and/or natural origin. Examples of suitable miaterials include polyureas, polyurethanes, polyamides, melamine resins, gelatin, wax and starch.
Microcapsules of some of these materials can be prepared, for example, by the interfacial polycondensation method. Particle size and wall thickness, and thus also thie release rates, can be controlled easily via the amount of monomers, the amount of active compound, the amounts of water and solvent and the process parameters.

In the case of microcapsules made of polyurethanes or polyureas, the method that is mjost frequently employed for constructing the capsule wall mentioned around the active compound to be coated is an interfacial polymerization with oil-in-water emulsions, where the organic phase contains an oil-soluble prepolymer with free ispcyanate groups, in addition to the active compound.
suitable prepolymers are the customary isocyanates known to the person skilled in the art, for example based on toluene 2,4-diisocyanate, toluene 2,6-diisocyanate, miethylene bis(phenyl 4-isocyanate) and hexamethylene diisocyanate. The polymerization, i.e. the synthesis of the mantle of the microcapsules, is generally carried out by customary methods known to the person skilled in the art.
The capsule-forming material from which the microcapsule mantles are constructed is preferably obtained from oil-soluble isocyanate group-containing prepolymers, which are a group of industrial mixed products, in each case consisting of pOlyisocyanates based on condensates of aniline and formaldehyde. These industrial mixed products differ from one another in the degree of condensation and, if appropriate, chemical modifications. For the user, important characteristics are viscosity and the content of free isocyanate groups. Typical commercial products are the Desmodur® brand (Bayer AG) and the Voranate® brand (Dow Chemicals). For the invention, the amount of prepolymer with isocyanate groups used is preferably The capsule-forming material is formed by curing the isocyanate prepolymer either in the presence of water at 0-95°C, preferably 20-65°C or, preferably, using the required amount of a dipolyamine.
If the microcapsules are formed using dipolyamines, suitable dipolyamines are, for example, alkylenediamines, dialkylenetriamines and trialkylenetetramines whose cajrbon chain units comprise between 2 and 8 carbon atoms. Preference is given to hexamethylenediamine. Here, it is possible to use amounts which are stoichiometric

to the amount of isocyanate prepolymer used, or, preferably, to use an excess of up to three times, particularly up to two times, the stoichiometric amount.
The literature discloses further methods for preparing microcapsules from pdlyurethanes or polyurea, which methods are likewise suitable for preparing the microcapsules according to the invention. These methods are listed below.
US-A-3 577 515 describes how, after introduction of water-soluble polyamines, the dr6plet surface in such emulsions cures as a result of addition to the prepolymers containing isocyanate groups. This forms a polyurea outer mantle.
US-A-4 140 516 discloses that, even in the absence of external water-soluble amines, microcapsules having an outer wall of the polyurea type can be produced by permitting partial hydrolysis in the emulsion of the prepolymer bearing isocyanate functions. In the course of this, some of the amino groups are reformed from the isocyanate groups and, as a result of internal polyaddition with subsequent curing, the desired capsule mantle is likewise formed. The use of tolylene diisocyanate, hexamethylene diisocyanate, methylenebis(phenyl isocyanate) and of its higher hornologues is described. If curing is to be performed using an external polyamine, this usually originates from the group consisting of ethylene diamine, propylene-diamine, hexamethylenediamine, diethylenetriamine and tetraethylenepentamine.
DS-A-2 757 017 discloses internally structured microcapsules whose wall material has the nature of a mixed polymer crosslinked by urea and urethane motifs. The active compound is situated in the interior of the capsule, dissolved in an organic solvent. Typically, to make up the capsule wall here, 10% of prepolymer, based on the total formulation, is required.
The same prepolymer is also used in WO-A-96/09760 to encapsulate, for example, endosulfan.

wjO-A-95/23506 discloses endosulfan-charged polyurea microcapsules in which the active compound is present as a cooled melt. As prepolymer, a mixture of methylenebis(phenyl isocyanate) and its higher homologues is described; the arjiount of prepolymer used is over 6%, based on the total formulation. Curing is
i
Performed using a mixture of polyamines.
T\\e content of the patents and patent applications listed above is, with respect to the materials of the microcapsule wall and the preparation processes, an important and integral part of the present invention and is included in the present application by way of reference.
A further possibility of encapsulation is capsule formation using, for example, melamine/formaldehyde or urea/formaldehyde.
To this end, melamine, or the abovementioned isocyanate prepolymers, is/are initially charged in water and admixed with the water-insoluble active compound. Priior to the addition, the active compound has been dispersed or dissolved in a water-insoluble solvent and emulsified. By establishing an acidic pH of about 3-5, preferably about 3-4, and stirring at elevated temperature between 30 and 60°C, preferably 50°C, for several hours, the capsule wall is formed by polycondensation. Examples are described in US 4,157,983 and US 3,594,328, the content of which, with respect to the preparation of the capsules, is included in the present application by way of reference.
Another suitable method for microencapsulation of the agrochemically active compounds is coacervation. To this end, the water-insoluble agrochemically active compound is dispersed in water and admixed with an anionic water-soluble polymer and a cationic material. The microcapsules formed by coacervation, containing the originally water-soluble polymer as wall material, are water-insoluble. In the last step, the capsule is then cured by condensation with aldehydes.-Suitable for this purpose is, for example, the combination gelatin/gum arabic (1:1) and formaldehyde. The projcess of microencapsulation by coacervation is known to the person skilled in the

art. The method is described in detail, for example, in J. A. Bahan "Microencapsulation using Coacervation/Phase Separation Techniques, Controlled Released Technology: Methods Theory and Application", Vol. 2, Kydoniens, A. F, Ejd. CRC Press, Inc., Boca Raton, FL. 1980, Chapter 4.
Fpr microencapsulation, it is finally possible, for example, to emulsify the active compound and the polymer which forms the capsule wall in water using a suitable surfactant. Here, polymer and active compound must not dissolve in each other. The solvent is then evaporated with stirring. When the water is removed, the polymer forms a layer on the surface of the emulsified drop.
Another suitable material for preparing microcapsules is wax. To this end, self-emulsifying waxes are dissolved in water by heating and applying shear forces, or are converted into an emulsion by adding surfactants and heating, whilst applying shear forces. Lipophilic agrochemically active compounds dissolve in molten and enhulsified wax. During cooling, the drops solidify, thus forming the wax dispersion.
Alternatively, it is possible to prepare wax dispersions by dispersing active compound/wax extrusion granules in water or oil, followed by fine grinding, for example to particle sizes of Suitable waxes are, for example, PEG 6000 in a mixture with non-hydrophilic waxes, Synchrowachs HGLC1, Mostermont® CAV2, Hoechst-Wachs OPS or combinations of these waxes.
An aqueous dispersion of the particles (microcapsules or wax particles) can be obtained similarly to the recipes for a CS formulation (capsule suspension).
The microcapsules obtained by the methods described above can be incorporated into various formulations mentioned above in the text. It is also possible to incorporate further active compounds into the formulation, for examole water-soluble

active compounds into the aqueous phase of the capsule dispersion, or, for example, solid active compounds into WG formulations.
After microencapsulation, the capsules can be freed from the solvent and dried by cijistomary methods, for example spray drying. In this state, the capsules can be
i
stjored and shipped. Prior to application to the crop in question, they are formulated, Of|)tionaliy with further active compounds, adjuvants and the customary additives.
However, the dispersion obtained after curing of the capsules can also be used for preparing suitable agrochemical formulations which comprise the abovementioned further components, without isolation of the capsules from the dispersions.
In these microcapsule dispersions, it is possible to use organic solvents or mixtures thereof, from the group of the N-alkyl fatty acid amides, N-alkyllactams, fatty acid esters, cyclohexanones, isophorones, phthalic esters and aromatic hydrocarbons, lower-alkyl-substituted naphthalene derivatives being particularly suitable.
Solvents which are suitable for the purpose of the invention and commercially available are, for example, Solvesso® 200, Solvesso® 150 and Solvesso® 100 (1), butyl digiycol acetate, Shellsol® RA (2), Acetrel® 400 (3), Agsolex® 8 (4), Agsolex® 12 (5), Norpar® 13 (6), Norpar® 15 (7), Isopar® V (8), Exsol® D 100 (9), Shellsol® K (10) and Shellsol® R (11), which are of the following composition:
(1) Mixtures of aromatic compounds; manufacturer: Exxon.
(2) Mixtures of alkylated benzenes, boiling range 183-312°C, manufacturer: Shell.
(3) High-boiling mixture of aromatic compounds, boiling range: 332-355°C, manufacturer: Exxon.
(4) N-Octylpyrrolidone, boiling point (0.3 mmHg) 100°C, manufacturer: GAF.
(5) N-Dodecylpyrrolidone, boiling point (0.3 mmHg) 145'C, manufacturer: GAF.
(6) Aliphatic hydrocarbons, boiling range: 228-243°C, manufacturer: Exxon.
(7) Aliphatic hydrocarbons, boiling range: 252-272°C, manufacturer: Exxon.
(8) Aliphatic hydrocarbons, boiling range: 278-305°C, manufacturer: Exxon.

(9) Aliphatic hydrocarbons, boiling range: 233-263°C, manufacturer: Exxon. (10) Aliphatic hydrocarbons, boiling range: 192-254°C, manufacturer: Shell. (11) Aliphatic hydrocarbons, boiling range: 203-267°C, manufacturer: Shell.
Also suitable are mixtures of these solvents with one another. Particularly suitable are butyl diglycol acetate, Acetrel® 400, Agsolex® 8 and Agsolex® 12. Particular pifeference is given to Solvesso® 200.
The aqueous phase of the dispersions according to the invention contains surface-active formulation auxiliaries from the group of the emulsifiers and dispersants. They originate from a group which comprises, for example, the compound families of the polyvinyl alcohols, the polyalkylene oxides, the condensates of formaldehyde with naphthalenesulfonic acids and/or phenols, the polyacrylates, the copolymers of maleic anhydride with alkylene alkyl ether, the lignosuifonates, and the polyvinylpyrrolidones. These substances are employed in an amount of from 0.2 to 10% by weight, preferably from 0.5 to 4% by weight, based in each case on the total dispersion.
In the case of polyalkylene oxides, preference is given to block copolymers whose mlolecular center and molecular periphery are formed by a polypropylene oxide block ahd polyethylene oxide blocks, respectively. Here, particular preference is given to siiJbstances in which the polypropylene oxide block has a molar mass of 2 000-3 000 and the percentage of the polyethylene oxide blocks is 60 to 80% of the total molar niass. Such a substance is available, for example, from BASF Wyandotte under the name Pluronic® F87.
Further suitable dispersants are calcium lignosulfonate, highly refined sodium lignosulfonate (for example Vanisperse® CB from Borregaard), dispersant S and dispersant SS from Clariant GmbH, naphthalene/sulfonic acid/formaldehyde condensate sodium salt (for example Monwet® D 425 from Witco or Tamol® NN 8906 from BASF), sodium polycarboxylate (for example Sopropan® T 36 from Rhodia GmbH).

Suitable polyvinyl alcohols are prepared by partial hydrolysis of polyvinyl acetate, they have a degree of hydrolysis of from 72 to 99 mor/o and a viscosity of from 2 to 1j8 cP (measured in 4% strength aqueous solution at 20°C, in accordance with DIN ^3 015). Preference is given to using partially hydrolyzed polyvinyl alcohols having a degree of hydrolysis of from 83 to 88 mol% and low viscosity, in particular from 3 to 5JcP.
If appropriate, the aqueous phase of the dispersions comprises at least one further formulation auxiliary from the group of the wetting agents, the antifreeze agents, the thickeners, the preservatives and viscosity-increasing components.
Suitable wetting agents are, for example, representatives from the substance groups of the alkylated naphthalenesulfonic acids, the N-fatty acyl N-alkyI taurides, the fatty acylamidoalkylbetaines, the alky! polyglycosides, the alpha-olefinsulfonates, the alkyibenzenesulfonates, the esters of sulfosuccinic acid and the fatty alkyl sulfates (Which may be modified by alkyleneoxy groups). Here, the percentage is between 0 and 5% by weight, preferably between 0 and 2% by weight, based on the total formulation.
suitable commercial products are, for example, Darvan® No. 3, Vanisperse® CB, Hoe S1728 (Clariant GmbH), Luviskol® K 30, Reserve C, Forianit® P, Sokalan® CP 10, Maranil A, Genapol® PF 40, Genapol® LRO, tributylphenol polyglycol ether, such as the Sapogenat T brands (Clariant GmbH), nonylphenol polyglycol ether, such as the Arkopal® N brands (Clariant GmbH) or tristyrylphenol polyglycol ether derivatives.
Preservatives which may be added to the aqueous dispersions are the following agents: formaldehyde or hexahydrotriazine derivatives, such as, for example, Mergal® KM 200 from Riedel de Haen or Cobate® C from Rhone Pouienc, isotlhiazolinone derivatives, such as, for example, Mergal® K9N from Riedel de Haen or Kathon® CG from Rohm and Haas, 1,2-benzisoth(azolin-2-ones, such as, for example, Nipacide® BIT 20 from Nipa Laboratorien GmbH or Mergal® K10 from

R|iedel de Haen or 5-bromo-5-nitro-1,3-dioxane (Bronidox® LK from Henkel). The percentage of these preservatives is at most 2% by weight, based on the total formulation.
j SJjitable antifreeze agents are, for example, mono- or polyhydric alcohols, glycol etihers or urea, in particular calcium chloride, glycerol, isopropanol, propylene glycol mbnomethyl ether, di- or tripropylene glycol monomethyl ether or cyclohexanol. The percentage of these antifreeze agents is at most 20% by weight, based on the total dispersion.
Thickeners may be of inorganic or organic nature; they can also be combined. Suitable thickeners are, for example, those based on alumosilicate, xanthane, methylcellulose, polysaccharide, alkaline earth metal silicate, gelatin and polyvinyl alcpohol, such as, for example, Bentone® EW, Vegum®, Rodopol® 23 or Kelzan® S. Their percentage is 0-0.5% by weight, preferably 0.3% by weight, based on the total dispersion.
The invention also relates to a process for preparing the microcapsule dispersions according to the invention, which comprises initially preparing a crude preemulsion of organic and aqueous phases (without diamine) and then subjecting this preemulsion to shear forces by passing it through a mixer, which preferably operates continuously, for example a static mixer, a toothed colloid mill or the like. Only in this step is the fineness required for later microcapsule formation of the emulsified oil droplets achieved. Finally, if appropriate after addition of a diamine, the entire sulbstance volume is cured by polyreaction. Alternatively, the addition of water-soliuble polyamine is dispensed with, and the finished emulsion is stirred for a certain period of time at a suitable temperature, for example for 6 h at 70°C.
For preparing a controlled release combination it is also possible, instead of microencapsulation, to introduce the active compound into an organic matrix, such as,ifor example, wax. It is also possible to use inorganic matrices, for example silicates, alumosilicates or aluminum oxides or minerals based on these

abovementioned materials. Incorporation into such an organic or inorganic matrix results in physical binding of the agrochemically active compounds.
Possible release mechanisms are, for example, abiotic and/or biotic degradation (w|eathering), bursting of the matrix or the capsule walls, or diffusion or dissolution of the active compound from the matrix or the capsules. This may take place de|pending on the contact with liquids, for example water, or depending on the terlnperature.
In general, the major amount of active compound is released from the matrix or the microcapsules within the first 4 weeks after application, preferably within the first 7 days.
In addition, said formulations of active compound may comprise the auxiliaries such asitackifiers, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreeze agents, solvents, fillers, carriers, colorants, antifoams, adjuvants such as mirtieral or vegetable oils and derivatives thereof, evaporation inhibitors and pH and viscosity regulators which are customary in each case.
The herbicidal compositions according to the invention can be prepared by customary processes, for example by mixing the components with the aid of stirrers, shakers or (static) mixers.
In $ preferred embodiment of this invention, the formulations comprising compounds of tihe formula (I) are mixed in the spray tank with surfactants B) and/or formulations thereof. To this end, the compounds of the formula (I) can be formulated, for example on the basis of kaolin, as water-dispersible granules, where the content of corhpounds of the formula (I) may vary within wide limits between 0.01 and 99% by weijght, preferably between 0.5 and 80% by weight. In addition to the compounds of the formula (I), these formulations may comprise further agrochemically active


pure substances or in formulated form, preferably as a liquid product, such as a water-soluble concentrate or an emulsifiable concentrate.
Ready-to-use formulations can be obtained by preparing, for example, aqueous concentrates, aqueous dispersions, emulsifiable concentrates or oil dispersions of compounds of the formula (1), surfactants B) and further auxiliaries. In the ready-to-use formulations, the amount of compounds of the formula (I) can vary within wide limits and is generally between 0.01 and 99% by weight, preferably between 0.1 and 30% by weight. The amount of surfactants B) can also vary within wide limits and is generally between 1 and 80% by weight, as a rule between 5 and 50% by weight. Finally, the ready-to-use formulations may also comprise further agrochemically active compounds such as safeners, for example in an amount of from 0.01 to 60% oy weight, preferably from 0.1 to 40% by weight.
If appropriate, the formulations may comprise auxiliaries such as solvents, for example aromatic solvents, such as xylenes or mixtures of aromatic compounds from the Solvesso® series such as Solvesso® 100, Solvesso® 150 or Solvesso® 200 from Exxon; aliphatic or isoparaffinic solvents, such as products from the Exxol®-D or Isopur® series from Exxon; oils of vegetable, mineral or animal origin and derivatives thereof, such as rapeseed oils or rapeseed oil methyl esters; esters, such as butyl acetate; ethers, such as diethyl ether, THF or dioxane. The solvent content is preferably 1-95% by weight, particularly preferably 5-80% by weight. Further suitable auxiliaries are, for example, emulsifiers (preferred content: 0.1-10% by weight), dispersants (preferred content: 0.1-10% by weight) and thickeners (preferred content: 0.1-5% by weight), and, if appropriate, stabilizers, such as antifoams, agents for reducing drift, fertilizers, for example nitrogen-containing fertilizers, water scavengers, acid scavengers and crystallization inhibitors.
The herbicidal compositions according to the invention can be used pre- or post-emergence, preferably post-emergence, for example by spraying. The use of the ntiixtures allows the amount of preparation required for controlling weeds to be reduced considerably.

The surfactants B) to be used according to the invention are generally applied together with the compound(s) A) or immediately afterward, preferably in the form of a spray liquor which comprises effective amounts of surfactants B) and compounds A) jand, if appropriate, further customary auxiliaries. The spray liquor is preferably prepared based on water and/or an oil, for example a high-boiling hydrocarbon such as kerosene or paraffin. Here, the herbicidal compositions according to the invention call be realized as a tank mix or via a "ready-to-use formulation".
The weight ratio of compounds A) to surfactant B) can vary within a wide range and depends, for example, on the efficacy of the herbicide. It is generally in a range of from 10:1 to 1:5000, preferably from 4:1 to 1:2000.
The application rates of the compound(s) of the formula (I) are generally between 10 and 2000 g of AS/ha (AS = active substance, i.e. application rate based on the active compound), preferably between 50 and 1000 g of AS/ha. The application rates of suirfactants B) are generally between 1 and 5000 g of surfactant/ha; preference is given to from 10 to 2000 g of surfactant/ha, in particular from 50 to 1000 g of suirfactant/ha.
The concentration of the surfactants B) to be used according to the invention in a spray liquor is generally from 0.05 to 4% by weight, preferably 0.1 to 1% by weight, in iparticular from 0.1 to 0.3% by weight, of surfactant.
The herbicidal compositions according to the invention may, as additional components, also comprise agrochemically active compounds different from component A), such as herbicides, fungicides, insecticides or safeners.
The herbicidally active compounds which are present in the herbicidal compositions according to the invention are, for example, ALS inhibitors (acetolactate synthetase inhibitors) or herbicides other than ALS inhibitors, such as herbicides from the group of the carbamates, thiocarbamates, haloacetanilides, substituted phenoxy-, naphthoxy- and phenoxyphenoxycarboxylic acid derivatives and heteroaryloxy-

phenoxyalkanecarboxylic acid derivatives such as quinolyloxy-, quinoxalyloxy-, pyridyloxy-, benzoxazolyloxy- and benzothiazolyloxyphenoxyaikanecarboxylic acid esters, cyclohexanedione derivatives, imidazolinones, phosphorus-containing herbicides, for example of the glufosinate type or the glyphosate type, pyj-imidinyioxypyridinecarboxylic acid derivatives, pyrinnidyloxybenzoic acid deHvatives, triazolopyrimidinesulfonamide derivates and S-(N-aryl-N-all^ylcarbamoylmethyl)dithiophosphoric acid esters.
Preferred ALS inhibitors are from the series of the sulfonylureas and/or their salts, for example pyrimidinyl- or triazinylaminocarbonyl[benzene-, pyridine-, pyrazole-, thiophene- and (alkylsulfonyl)alkylamino]sulfamides. Preferred as substituents on the pyrimidine ring or triazine ring are alkoxy, alkyl, haloalkoxy, haloalkyi, halogen or dimethylamino, it being possible for all substituents to be combined independently of one another. Preferred substituents in the benzene-, pyridine-, pyrazole-, thiophene-orj(alkylsulfonyl)alkyiamino moiety are alkyl, alkoxy, halogen, amino, alkylamino, dialkylamino, nitro, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkoxyaminocarbonyl, haloalkoxy, haloalkyi, alkylcarbonyl, allkoxyalkyi, (alkanesulfonyl)alkyiamino. Examples of such suitable sulfonylureas are








Tyipical representatives of these active substances are, inter alia, the compounds listed hereinbelow: amidosulfuron, azimsulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfannuron, ethametsulfuron-methyl, et(ioxysulfuron, flazasulfuron, flupyrsulfuron-methyl-sodium, halosulfuron-methyl, imjazosulfuron, metsulfuron-methyl, nicosulfuron, oxasulfuron, primisulfuron-methyl, prjosulfuron, pyrazosulfuron-ethyl, rimsulfuron, sulfometuron-methyl, sulfosulfuron, thifensulfuron-methyl, triasulfuron, tribenuron-methyl, triflusulfuron-methyl, ioiilosulfuron-nnethyl and its sodium salt (WO 92/13845), mesosulfuron-methyl and its sodium salt (Agrow No. 347, March 3, 2000, page 22 (PJB Publications Ltd. 2000)) and foramsulfuron and its sodium salt (Agrow No. 338, October 15, 1999, page 26 (PJB Publications Ltd. 2000)).
The active substances listed hereinabove are known, for example, from C.D.S. Tomin, The Pesticide Manual", 12th Edition (1999), The British Crop Protection Council, or the references cited after the individual active substances.
The herbicidal active substances which are present in the herbicidal compositions according to the invention and which differ from the ALS inhibitors are, for example, herbicides from the group of the carbamates, thiocarbamates, haloacetanilides, sijjbstituted phenoxy-, naphthoxy- and phenoxyphenoxycarboxylic acid derivatives, ahd heteroaryloxyphenoxyalkanecarboxylic acid derivatives such as quinolyloxy-, qyinoxalyloxy-, pyridyloxy-, benzoxazolyloxy- and benzothiazolyloxyphenoxyalkane-c^rboxylic esters, cyclohexanedione derivatives, imidazolinones, phosphorus-containing herbicides, for example of the glufosinate type or of the glyphosate type, pyrimidinyloxypyridinecarboxylic acid derivatives, pyrimidyloxybenzoic acid derivatives, triazolopyrimidinesulfonamide derivatives and S-(N-aryl-N-alkylcarbamoylmethyl)dithiophosphoric esters. Preferred in this context are phenoxyphenoxy- and heteroaryloxyphenoxycarboxylic acid esters and salts, irhidazolinones and herbicides such as bentazone, cyanazine, atrazine, dicamba or hydroxybenzonitriles such as bromoxynil and ioxynil and other foliar-acting herbicides.

Suitable herbicidal active substances A) which may be present as component A) in the herbicidal compositions according to the invention and which differ from ALS
inhibitors are, for example:
i
B) I Herbicides of the phenoxyphenoxy- and heteroaryloxyphenoxycarboxylic
aciy derivatives type, such as
Blj) Phenoxyphenoxy- and benzyloxyphenoxycarboxylic acid derivatives, for
example methyl 2-(4-(2,4-dichlorophenoxy)phenoxy)propionate (diclofop-methyl),
mdthyl 2-(4"(4-bromo-2-chlorophenoxy)phenoxy)propionate (DE-A 26 01 548),
methyl 2-(4-(4-bromo-2-fluorophenoxy)phenoxy)propionate (US-A 4,808,750),
methyl 2-(4-(2-chloro-4-trifluoromethylphenoxy)phenoxy)propionate
(DE-A 24 33 067),
methyl 2-(4-(2-fluoro-4'-trifluoromethylphenoxy)phenoxy)propionate
(US-A 4,808,750),
methyl 2-(4-(2,4-dichloroben2yl)phenoxy)propionate (DE-A 24 17 487),
ethyl 4-(4-(4-trifluoromethylphenoxy)phenoxy)pent-2-enoate,
methyl 2-(4-(4-trifluoromethylphenoxy)phenoxy)propionate (DE-A 24 33 067);
82) "Mononuclear" heteroaryloxyphenoxyalkanecarboxylic acid derivatives, for
exiample
ethyl 2-(4-(3,5-dichloropyridyl-2-oxy)phenoxy)propionate (EP-A 0 002 925),
propargyl 2-(4-(3,5-dichloropyridyl-2-oxy)phenoxy)propionate (EP-A 0 003 114),
methyl 2-(4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenoxy)propionate
(EP-A 0 003 890),
ethyl 2-(4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenoxy)propionate
(EP-A 0 003 890),
prbpargyl 2-(4-(5-chloro-3-fluoro-2-pyridyloxy)phenoxy)propionate (EP-A 0 191 736),
butyl 2-(4-(5-trifluoromethyl-2-pyridyloxy)phenoxy)propionate
(flUazif op-butyl);
83) "Binuclear" heteroaryloxyphenoxyalkanecarboxylic acid derivatives, for
example











N-phosphonomethy)glycine trimesium salt = N-(phosphonomethyl)glycine trimethylsulfoxonium salt.
i i
The herbicides of groups B to L are known, for example, from each of the specification£ stated above and from "The Pesticide Manual", 12th Edition. 1999, The British Crop Protection Council, "Agricultural Chemicals Book II - Herbicides -", by W.T. Thompson, Thompson Publications, Fresno CA, USA 1990 and "Farm dhemicals Handbook '90", Meister Publishing Company, Willoughby OH, USA,1990.
The herbicidal compositions according to the invention have excellent herbicidal activity against a broad spectrum of economically important monocotyledonous and dicotyledonous harmful plants. The active compounds also act efficiently on perennial weeds which produce shoots from rhizomes, root stocks or other perennial organs and which are difficult to control. In this context, it is generally immaterial whether the substances are applied pre-sowing, pre-emergence or post-emergence. Specifically, examples may be mentioned of some representatives of the nhonocotyledonous and dicotyledonous weed flora which can be controlled by the herbicidal compositions according to the invention, without this being a restriction to certain species.
Examples of weed species on which the active compounds act efficiently are, from amongst the monocotyledons, Avena, Lolium, Alopecurus, Phalaris, Echinochloa,
Digitaria, Setaria and also Cyperus species from the annual sector and, from
«
amongst the perennial species, Agropyron, Cynodon, Imperata and Sorghum, and allso perennial Cyperus species.
In the case of the dicotyledonous weed species, the spectrum of action extends to sipecies such as, for example, Galium, Viola, Veronica, Lamium, Stellaria, Amaranthus, Sinapis, Ipomoea, Matricaria, Abutilon and Sida from amongst the annuals, and Convolvulus, Cirsium, Rumex and Artemisia in the case of the perennial weeds.

The compositions according to the invention also effect outstanding control of harmful plants which occur under the specific conditions of rice-growing such as, for example, Echinochloa, Sagittaria, Alisma, Eleocharis, Scirpus and Cyperus.
If the herbicidal compositions according to the invention are applied to the soil surface prior to germination, then the weed seedlings are either prevented ccfrnpletely from emerging, or the weeds grow until they have reached the cotyledon st^ge but then their growth stops, and, eventually, after three to four weeks have elapsed, they die completely.
If the herbicidal compositions according to the invention are applied post-emergence to the green parts of the plants, growth also stops drastically a very short time after the treatment and the weed plants remain at the developmental stage of the point in time of application, or they die completely after a certain time, so that in this manner competition from the weeds, which is harmful to the crop plants, is eliminated at a very early point in time and in a sustained manner.
Although the herbicidal compositions according to the invention have an excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, in particular against dicotyledonous weeds, crop plants of economically important crops, for example dicotyledonous crops such as soya, cotton, oilseed rape, sugar beet, in particular soya, or gramineous crops such as wheat, barley, rye, rice or corn, are not damaged at all, or only to a negligible extent. For these reasons, the present compounds are highly suitable for selectively controlling undesired plant growth in plantings of agriculturally useful plants or of ornamental plants.
In addition, the herbicidal compositions according to the invention have outstanding growth-regulating properties in crop plants. They engage in the plant metabolism in a regulating manner and can thus be employed for the targeted control of plant constituents and for facilitating harvesting, such as for example by provoking desiccation and stunted growth. Furthermore, they are also suitable for generally regulating and inhibiting undesirable vegetative growth, without destroying the plants in|the process. Inhibition of vegetative growth plays an important role in many

monocotyledonous and dicotyledonous crops because lodging can be reduced hereby, or prevented completely.
Owing to their herbicidal and plant-growth-regulatory properties, the herbicidal compositions according to the invention can also be employed for controlling harmful plants in crops of known or still to be developed genetically engineered plants. The transgenic plants generally have particularly advantageous properties, for example resistance to certain pesticides, in particular certain herbicides, resistance to plant diseases or causative organisms of plant diseases, such as certain insects or microorganisms such as fungi, bacteria or viruses. Other particular properties relate, for example, to the quantity, quality, storage stability, composition and to specific ingredients of the harvested product. Thus, transgenic plants having an increased st$rch content or a modified quality of the starch or those having a different fatty acid composition of the harvested product are known.
The use of the compositions according to the invention in economically important transgenic crops of useful and ornamental plants, for example of cereals, such as wheat, barley, rye, oats, millet, rice, manioc and corn, or else in crops of sugar beet, cotton, soya, oilseed rape, potatoes, tomatoes, peas and other vegetable species is preferred. The compositions according to the invention can preferably be used as herbicides in crops of useful plants which are resistant or which have been made resistant by genetic engineering toward the phytotoxic effects of the herbicides.
When using the herbicidal compositions according to the invention in transgenic crops, in addition to the effects against harmful plants which can be observed in other crops, there are frequently effects which are specific for the application in the respective transgenic crop, for example a modified or specifically broadened spectrum of weeds which can be controlled, modified application rates which can be us0d for the application, preferably good combinability with the herbicides to which the transgenic crop is resistant, and an effect on the growth and the yield of the trahsgenic crop plants.
The invention therefore also provides for the use of the compositions according to the invention as herbicides for controlling harmful plants, preferably in crop plants,

where the crop plants may also be transgenic crop plants, for example
bromoxynil-tolerant cotton.

The herbicidal compositions according to the invention can also be used in a non-selective manner for controlling undesirable vegetation, for example on paths, open spjaces, industrial sites or rail tracks.
owing to the relatively low application rate of the herbicidal compositions according to the invention, they are, as a rule, already well tolerated. In particular, the combinations according to the invention lead to a reduction in the absolute application rate in comparison with the individual application of a herbicidal active compound.
If, if desired, the tolerance and/or selectivity of the herbicidal compositions according to the invention are to be increased further, it may be advantageous to apply them jointly as a mixture or staggered in time one after the other together with safeners or antidotes.
Compounds which are suitable as safeners or antidotes for the herbicidal compositions according to the invention are disclosed, for example, in EP-A-333 131 (ZA-89/1960), EP-A-269 806 (US-A-4,891,057), EP-A-346 620 (AU-A-89/34951) and the international patent applications PCT/EP 90/01966 (WO-91108202) and PCT/EP 90102020 {WO-911078474) and the literature cited therein or can be prepared by the processes described therein. Other suitable safeners are known from EP-A-94 349 (US-A-4,902,304), EP-A-191 736 (US-A.4,881,966) and EP-A-0 492 366 and the literature cited therein.
In & preferred embodiment, the herbicidal compositions of the present invention therefore additionally comprise C) one or more compounds which act as safeners or antidotes.

a) i Compounds of the dichlorophenylpyrazoline-3-carboxylic acid type, preferably compounds such as ethyl 1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylate (compound C1-1, mefenpyr-diethyl) and related compounds as they are described in the international application WO 91/07874 (PCT/EP 90102020);
b): Dichlorophenylpyrazolecarboxylic acid derivatives, preferably compounds such as ethyl 1-(2,4-dichlorophenyl)-5-methylpyrazole-3-carboxylate (compound CI-2), ethyl 1-(2,4-dichlorophenyl)-5-isopropylpyrazole-3-carboxylate (compound CI-3), ethyl 1-(2,4-dichlorophenyl)-5-(1,1-dimethylethyl)pyrazole-3-carboxylate (compound CI-4), ethyl 1-(2,4-dichlorophenyl)-5-phenylpyrazole-3-carboxylate (compound C1-5) and related compounds as are described in EP-A-0 333 131 and EP-A-0 269 806;
c) Compounds of the triazolecarboxylic acid type, preferably compounds such as
ethyl 1 -(2,4-dichlorophenyl)-5-trichloromethyl-(1 H)-1,2,4-triazole-3-carboxylate
(compound C1-6, fenchlorazole-ethyl) and related compounds (see
EP-A-0 174 562 and EP-A-0 346 620);
d) Compounds of the dichlorobenzyl-2-isoxazoline-3-carboxylic acid type, compounds of the 5-benzyl- or 5-phenyl-2-isoxazoline-3-carboxylic acid type, preferably compounds such as ethyl 5-(2,4-dichlorobenzyl)-2-isoxazoline-3-carboxylate (compound C1-7) or ethyl 5-phenyl-2-Jsoxazoline-3-carboxylate (compound CI-8) and related compounds as they are described in the international patent application WO 91/08202 (PCT/EP 90/01966);
e) Compounds of the 8-quinolinoxyacetic acid type, preferably compounds such as 1-methylhex-1-yl 5-chloro-8-quinolinoxyacetate (cloquintocet-mexyl, C2-1), 1,3-dimethylbut-1-yl 5-chloro-8-quinolinoxyacetate (C2-2), 4-allyloxybutyl 5-chloro-8-quinolinoxyacetate (C2-3), 1-allyloxyprop-2-yl 5-chloro-8-quinolinoxyacetate (C2-4), ethyl 5-chloro-8-quinolinoxyacetate (C2-5), methyl 5-chloro-8-quinolinoxyacetate (C2-6), allyl 5-chloro-

8-quinolinoxyacetate (C2-7), 2-(2-propylidene-iminooxy)-1-ethyl 5-chloro-8-quinolinoxyacetate (C2-8), 2-oxoprop-1-yl 5-chloro-8-quinolinoxyacetate (C2-9) and related compounds as they are described in EP-A-0 086 750, EP-A-0 094 349 and EP-A-0 191 736 or EP-A-0 492 366;
f)i Compounds of the 5-chloro-8-quinolinoxymalonic acid type, preferably
compounds such as diethyl 5-chloro-8-quinolinoxymalonate, diallyl 5-chloro-i 8-quinolinoxymalonate, methyl ethyl 5-chloro-8-quinolinoxymalonate and
related compounds as they have been described and proposed in the German patent application EP-A-0 582 198;
g) Active compounds of the type of the phenoxyacetic- or -propionic acid derivatives or of the aromatic carboxylic acids, such as, for example, 2,4-dichlorophenoxyacetic acid (and its esters) (2,4-D), 4-chloro-2-methylphenoxypropionic ester (mecoprop), MCPA or 3,6-dichloro-2-methoxybenzoic acid (and its esters) (dicamba);
h) Compounds of the 5,5-diphenyl-2-isoxazoline-3-carboxylic acid type,
preferably ethyl 5,5-diphenyl-2-isoxa2oline-3-carboxylate (C3-1, isoxadifen-ethyl);
i) Compounds known as safeners, for example for rice, such as fenclorim (= 4,6-dichloro-2-phenylpyrimidine, Pesticide Manual, 12th Edition, 1999, pp. 386/387), dimepiperate (= S-(l-methyl-l-phenylethyl) 1-piperidinecarbothioate, Pesticide Manual, 12th Edition, 1999, pp. 302/303), daimuron (= 1-(1-methyl-1-phenylethyl)-3-p-tolylurea, Pesticide Manual, 12th Edition, 1999, p. 247), cumyluron (= 3-(2-chlorophenylmethyl)-1-(1-methyl-1-phenyl-ethyl)urea, JP-A-60/087254), methoxyphenone (= 3,3'-dimethyl-4-methoxybenzophenone), CSB (= 1-bromo-4-(chloromethylsulfonyl)benzene, CAS Reg. No. 54091-06-4).

In addition, at least some of the compounds mentioned are descnbed in EP-A-0 640 587, which is herewith referred to for publication purposes.
j)j A further important group of compounds which are suitable as safeners and antidotes is disclosed in WO 95107897.
The safeners (antidotes) of the above groups a) to j) reduce or contain phytotoxic effects which may occur in crops of useful plants when employing the herbicidal compositions according to the invention without adversely affecting the efficacy of thie herbicides against harmful plants. This allows the field of application of the herbicidal compositions according to the invention to be widened considerably, and, in particular, the use of safeners allows combinations to be employed whose use has prieviously only been possible with limitations or with insufficient success, i.e. combinations which, without safeners, had a poor spectrum of action and led to insufficient control of harmful plants when applied at low dosage rates.
The herbicidal compositions according to the invention and the abovementioned safeners can be applied together (as a ready-to-use formulation or by the tank mix method) or in succession in an arbitrary sequence. The weight ratio of safener:herbicide (compound(s) of the formula (1) and/or the salts thereof) may vary within wide limits and is preferably in the range of 1:100 to 100:1, in particular 1:10 to 10:1. The amounts of herbicide(s) and safener(s) which are optimal in each case deipend usually on the type of the herbicidal composition and/or on the safener used and on the nature of the plant stand to be treated.
Depending on their properties, the safeners of type C) may be used for pretreating the seed of the crop plant (seed dressing) or incorporated into the seed furrow prior to sowing or applied together with the herbicide mix before or after emergence of the plants.
Thje pre-emergence treatment includes not only the treatment of the area under cultivation before sowing, but also the treatment of the areas under cultivation where

sped has been sown but the plants have not yet emerged. The joint application together with the herbicide mix is preferred. To this end, tank mixes or ready-to-use formulations may be employed.
The required application rates of the safeners may vary within wide limits, depending o|i the indication and the herbicide used, and are, as a rule, in the range of 0.001 to 1 kg, preferably 0.005 to 0.2 kg, of active compound per hectare.
The present invention also relates to a method of controlling undesired plants, preferably in crop plants, which comprises applying a herbicidally active amount of the herbicidal composition according to the invention, for example to the plants, the parts of the plants, the seeds of the plants or the area under cultivation.
In la preferred variant of the method the herbicidal compositions according to the invention are applied in the form of tank mixes, the individual components, for exiampie in the form of formulations, jointly being mixed in the tank with water or an oil and the resulting spray liquor being applied. Since the crop plant tolerance of the cojmbinations according to the invention is decidedly good while simultaneously effecting very good control of the harmful plants, the combinations can be cohsidered as selective. In a preferred modification of the method, herbicidal cohipositions are therefore employed for the selective control of undesired plants.
Thie herbicidal compositions can be applied in the customary manner, for example with water and/or oil as carrier in amounts of approximately 0.5-4000, preferably 100 to 1000, liters of spray liquor/ha. The compositions may also be applied by the low-volume and ultra-low-volume (ULV) methods and in the form of granules and microgranules.
A preferred application relates to the use of herbicidal compositions which comprise components A) and B) in a synergistically effective amount.
The invention also includes herbicidal compositions which comprise mixtures of one

or more combination partners A), preferably A1, A2, A3, A4, A5, A6, A7, A8, A9 and/or A10 and one or more combination partners B), if appropriate in combination with one or more safeners C).
Preferred examples of the herbicidal compositions according to the invention which may be mentioned are the following combinations of A1, A2, A3, A4, A5, A6, A7, A8, A9 and/or A10 with surfactants B), without the combinations being limited to those mjentioned explicitly:
Ai in combination with one of the surfactants of group B1 to B65 (see
Table 1)
A2 in combination with one of the surfactants of group B1 to B65 (see
Table 1)
A3 in combination with one of the surfactants of group B1 to B65 (see
Table 1)
A4 in combination with one of the surfactants of group B1 to B65 (see
Table 1)
A5 in combination with one of the surfactants of group B1 to B65 (see
Table 1)
A6 in combination with one of the surfactants of group B1 to B65 (see
Table 1)
A7 in combination with one of the surfactants of group B1 to B65 (see
Table 1)
A8 in combination with one of the surfactants of group B1 to B65 (see
Table 1)
A9 in combination with one of the surfactants of group B1 to 865 (see
Table 1)
A10 in combination with one of the surfactants of group B1 to 865 (see
Table 1)
A11 in combination with one of the surfactants of group B1 to B65 (see
Table 1)
A12 in combination with one of the surfactants of group B1 to B65 (see

Table 1)
In addition, the herbicidal compositions of the present invention may comprise, to refund off the properties, additionally, in most cases in minor amounts, one, two or rrjore agrochemically active compounds differing from component A) (for example herbicides, insecticides or fungicides).
Thus, there are numerous possibilities of combining a plurality of active compounds with one another and using them jointly for controlling harmful plants, preferably in crop plants, without deviating from the essence of the invention.
To summarize, it can be-said that, when compounds of the formula (I) are used together with one or more surfactants B), an excellent herbicidal activity is obtained. The activity of the herbicidal compositions according to the invention in a preferred enjibodiment is more pronounced than the activity of the individual components enjiployed when used on their own. These effects permit, inter alia, a reduction of the application rate, the control of a broader spectrum of broad-leafed weeds and weed grasses, the closure of activity gaps, also with respect to resistant species, a more rapid and safer action, a complete control of the harmful plants with only one or a few applications, and a widening of the period of use.
The abovementioned properties are needed in practical control of weeds to keep agricultural crops free of undesirable competing plants and thus to secure and/or increase the quality and quantity of the yields. With respect to the described prdperties, the prior art is considerably surpassed by these novel combinations. In addition, the combinations according to the invention permit, in an excellent manner, the control of harmful plants which are othenwise resistant.


An example of a combination according to the invention of compounds of the formula (l)iWith surfactants is an SL formulation which comprises 5% bromoxynil-potassium, 10% Genapol®-X-150, 84.8% of water and 0.2% of Biozid Mirgal® A. This is obtained byl| introducing the substances successively with stirring into water. In an analogous manner, it is possible to prepare formulations with other surfactants, where the ratio of lactive compound/surfactant may vary within wide ranges.
Fcjrmulation example 2
In a 1 I four-necked flask, an aqueous phase comprising 57.9% by weight of water, 5.0% by weight of Atlox® Metasperse 550 S, 1.0% by weight of polyethylene glycol (molecular weight: 4000), 5.0% by weight of Emulsogen® EL 400 and 0.1% by weight of Rhodorsil®432 is stirred at 60°C. An organic phase comprising 11.1% by weight of brpmoxynil-octanoate, 10.0% by weight of Solvesso® 200 and 1.0% by weight of Voiranate® M 220 is likewise heated to 60°C and introduced with vigorous stirring (300 rpm) into the aqueous phase. The mixture is then sheared at a high rotational spfeed (1500 - 2000 rpm) until the desired particle size is obtained (up to 1 minute) and then stirred at a rotational speed of about 50-100 rpm for another 6 hours. This gives a microcapsule suspension (CS) having an average capsule diameter of 2 - 20 mictrometers.
Biological examples
Seeds or rhizome pieces of monocotyledonous and dicotyledonous weeds were placed in sandy loam soil in plastic pots, covered with soil and grown in a grelenhouse under good growth conditions. Three weeks after seeding, the test plants were treated in the three-leaf stage. The compositions of the invention, foriinulated as wettable powders or as emulsion concentrates, were sprayed onto the greien parts of the plants at various application rates of 600 - 8001 of water/ha (co)nverted). The test plants were allowed to stand in the greenhouse under optimum growth conditions for about 3 to 4 weeks, and the effect of the preparations was then rat^d visually in comparison to untreated controls. The compositions according to the

invention have good herbicidal activity against harmful plants of economic importance. The activity of bromoxynil-Na (300 g/ha) in combination with a surfactant such as Genapol® X 150, Genapol® X 200, Sapogenat® T130, Sapogenat® T 200, Sipogenat® T 300, Sapogenat® T 400, Sapogenat® T 500 or Genapol® O 200 at apiplication rates of, for example, 50 g/ha, 100 g/ha, 300 g/ha and 60 g/ha is, for e>iample, considerably higher than, for example, bromoxynil-Na applied with a surfactant having a lower content of ethylene oxide units, such as Genapol® X 060 (eiethylene oxide units).
Bnomoxynil-octanoate (300 g of AS/ha and 600 g of AS/ha), formulated according to Formulation Example 2 as a microcapsule suspension (10%) and applied together with a surfactant such as Genapol® X 150, Genapol® X 200, Sapogenat® T130. Sapogenat® T 200, Sapogenat® T 300, Sapogenat® T 400, Sapogenat® T 500 or Genapol® O 200 at application rates of 150 g of surfactant/ha, 300 g of surfactant/ha arid 600 g of surfactant/ha showed a herbicidal activity which was considerably higher than a commercial formulation of bromoxynil-octanoate.




in which
Haf and Hal are identical or different halogen atoms,
R1 is H, a cation or a C1-C20-carbon-containing radical and
B) one or more surfactants, comprising as structural element at least 12 alkylene oxide units.
2. \ The microcapsule as claimed in claim 1, comprising as component B) one or more surfactants of the formula (II)



5. ; A method for controlling harmful plants, which comprises applying
microcapsules defined according to one or more of claims 1 to 4 by the pre-emergence method, the post-emergence method or the pre- and postemergence method to the plants, parts of plants, plant seeds or the area under cultivation.
6. The method as claimed in claim 5 for the selective control of harmful plants in
crop plants.
7. The use of microcapsules defined in any of claims 1 to 4 for controlling
harmful plants.
8. A process for preparing microcapsules defined according to one or more of
claims 1 to 4, which comprises mixing the compound(s) of the formula (I) with
one or more surfactants B) and one or more polymer materials.
Intermational file reference: PCT/EP01/13787; WO 02/49432; AGR 2000/M239

8. A microcapsule made from polymer material substantially as herein
described and exemplified.
9. A method for controlling harmful plants substantially as herein
described and exemplified.


Documents:

959-chenp-2003-abstract.pdf

959-chenp-2003-claims duplicate.pdf

959-chenp-2003-claims original.pdf

959-chenp-2003-correspondnece-others.pdf

959-chenp-2003-correspondnece-po.pdf

959-chenp-2003-description(complete) duplicate.pdf

959-chenp-2003-description(complete) original.pdf

959-chenp-2003-form 1.pdf

959-chenp-2003-form 18.pdf

959-chenp-2003-form 26.pdf

959-chenp-2003-form 3.pdf

959-chenp-2003-form 5.pdf

959-chenp-2003-pct.pdf


Patent Number 209660
Indian Patent Application Number 959/CHENP/2003
PG Journal Number 50/2007
Publication Date 14-Dec-2007
Grant Date 05-Sep-2007
Date of Filing 17-Jun-2003
Name of Patentee M/S. BAYER CROPSCIENCE GMBH
Applicant Address Bruningstrasse 50, D- 65929 Frankfurt
Inventors:
# Inventor's Name Inventor's Address
1 KOCUR, Jean Eichendorffstraße 1 65719 Hofheim
PCT International Classification Number A01N 37/40
PCT International Application Number PCT/EP2001/013787
PCT International Filing date 2001-11-27
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 100 63 960.7 2000-12-20 Germany