WO2000003592A2 - Herbicidal agents with substituted phenoxysulfonylureas - Google Patents

Abstract

The invention relates to herbicidal agents containing A) one or more herbicidal active agents from the group of substituted phenoxysulfonylureas of formula (I) and their salts and B) one or more herbicidally active compounds from the following group of compounds: Ba) herbicides which are selectively active in rice, predominantly against grasses, chosen from the following group: fentrazamide (NBA 061), haloxyfop, sethoxydim, dithiopyr, etobenzanide clefoxidim, KIH 6127 and clethodim; Bb) herbicides which are selectively active in rice, predominantly against dicotyledonous harmful plants and cyperacaen, chosen from the following group: 2,4-D, MCPA, mecoprop, mecoprop-P, tritosulfuron, halosulfuron-methyl, dicamba, acifluorofen, carfentrazone, bentazone and triclopyr; Bc) herbicides which are selectively active in rice, predominantly against grasses and dicotyledonous harmful plants and cyperacaen, chosen from the following group: pendimethalin, clomazone, KIH 2023, oxadiargyl, cyclosulfamuron (AC 322, 140), azimsulfuron (DPX-A-8947), nicosulfuron, cinmethylin, indanofan, pentoxazone, pyribenzoxim, oxaziclomefone (MY-100), fluthiamide and mesotrione; preferably according to a weight ratio of compounds of formula (I) or their salts (type A compounds) and compounds from group B of 1:20000 to 200:1, preferably 1:8000 to 100:1, especially preferably 1:4000 to 50:1. The inventive herbicidal agents are suitable for use in combating undesirable harmful plants, preferably in rice crops.

Description

description

Herbicidal agents with substituted phenoxysulfonyl resins

The invention relates to the technical field of plant protection products, in particular the invention relates to herbicidal compositions containing certain phenoxysulfonylureas and / or their salts which are outstanding for combating weeds in rice, in particular grassy, dicotyledon, which have hitherto been difficult to control with individual herbicides and / or cyperaceae-like weeds in rice or transgenic rice cultures.

Herbicidal compositions are known from IT 1270985, characterized by an effective content of substituted phenoxysulfonylureas in combination with herbicidal active ingredients.

There are a number of economically very important monocotyledon weeds, especially in rice. B. primarily Echinochloa crus galli, Ischaemum ssp. or Leptochloa, which cannot be satisfactorily controlled alone with rice herbicides or mixtures thereof known to date. Harmful plants are also known from global rice cultivation systems, such as Sagittaria spp., Eleocharis spp., E.g. Eleocharis kuroguwai, Cyperus serotinus, Scirpus juπcoides, but also other harmful plants that mainly germinate from permanent organs in the soil and are therefore more difficult to control than weeds that germinate from seeds, and also broadleaved species that do not cover the whole spectrum of weeds are easy to control in an optimal way. Furthermore, more and more resistant species (including Cyperus ssp or Echinochloa ssp) are found, which are often no longer controllable with individual agents but also with conventional combinations.

In view of the prior art specified and discussed herein, it was therefore an object of the invention to provide mixtures with herbicidal activity, to enable the practitioner to control the weed spectrum or individual weed species that are difficult to control in rice with one application or a few applications of herbicides.

It has surprisingly been found that, among other things, these objects are achieved by herbicidal compositions having the features of claim 1. The present invention thus relates to herbicidal compositions comprising

A) one or more herbicidal active compounds from the group of the substituted phenoxysulfonylureas of the formula I and their salts

and

B) one or more herbicidally active compounds from the group of compounds which consists of

Ba) selectively in rice herbicides active mainly against grasses selected from the group consisting of

Fentrazamide (NBA 061), haloxyfop, sethoxydim, dithiopyr, etobenzanide., Clefoxidim, KIH 6127, and clethodim,

Bb) selectively in rice herbicides active mainly against dicotyledonous harmful plants and cyperaceae, selected from the group consisting of 2,4-D, MCPA, mecoprop, mecoprop-P, tritosulfuron, halosulfuron-methyl, dicamba, acifluorfen, carfentrazone, bentazoπ and triclopyr ,

Bc) selectively in rice, predominantly herbicides active against grass and dicotyledonous harmful plants and cyperaceae, selected from the group consisting of pendimethalin, clomazone, KIH 2023, oxadiargyl, cyclos ulfamuroπ (AC 322, 140), azimsulfuron (DPX-A-8947) , Nicosulfuron, cinmethylin, indanofan, pentoxazone,

Pyribeπzoxim, Oxaziclomefoπe (MY-100), Fluthiamid and Mesotrione.

The combinations of herbicidal active ingredients of types A and B according to the invention make it particularly advantageous to achieve the control of the weed spectrum required by the practitioner, individual species which are difficult to control also being recorded. In addition, the combinations of active ingredients in the individual combination partners contained in the combination can be significantly reduced with the combinations according to the invention, which allows more economical solutions on the part of the users.

Finally, surprisingly, increases in activity were achieved which go beyond what is to be expected, as a result of which the herbicidal compositions of the invention show synergistic activities to a large extent. In addition, many resistant species can be controlled in an excellent way.

The compounds of formula I can form salts in which the hydrogen of the -S0 ₂ -NH group is replaced by a cation suitable for agriculture. These salts are, for example, metal, in particular alkali salts (for example Na or K salts) or alkaline earth metal salts, or also ammonium salts or salts with organic amines. Salt formation can also take place by the addition of a strong acid to the heterocyclic part of the compounds of the formula I. Suitable for this are, for. B. HCl, HN0 ₃ , trichloroacetic acid, acetic acid or palmitic acid. Particularly advantageous compounds are those in which the salt of the herbicide of the formula (I) is formed by replacing the hydrogen of the —SO ₂ —NH groups with a cation from the group of the alkali metals, alkaline earth metals and ammonium, preferably sodium.

If the compounds of the formula I contain one or more asymmetric carbon atoms or else double bonds which are not indicated separately in the general formula, these nevertheless belong to the type A compounds. The through their Specific spatial forms of possible stereoisomers defined, such as enantiomeric diastereoisomers, Z and E isomers are all encompassed by the formula I and can be obtained from mixtures of the stereoisomers by customary methods or else be prepared by stereoselective reactions in combination with the use of stereochemically pure starting materials. The stereoisomers mentioned in pure form and their mixtures can thus be used according to the invention.

Phenoxysulfonylureas of the formula I are in principle, for. B. from general formula 1 from IT 127 09 85 and their suitability as a synergistic partner for herbicides to be used in crop plants is described there. The outstanding suitability of the special

However, group A phenoxysulfonylureas as combination partners in synergistic mixtures with other herbicides which can be used in rice cannot be found in the prior art. In particular, there is no evidence in the literature which has become known that combinations of compounds of group A) with the rice herbicides of group B have such an exceptional position in the control of the most important harmful plants in rice crops. Above all, it must also be taken into account that the use of a combination in other crops cannot be extrapolated to the effect in rice crops. Even if the compounds of group A) are only suitable for controlling harmful plants in rice, it cannot be predicted with a predominant or even some prospect of success whether combinations with other rice herbicides allow increases in effectiveness in combating harmful plants beyond the additive effect. The compound is a preferred combination partner from group A)

A1 (ethoxysulfuron): 1 - [2-ethoxy phenoxy ^. sulfonyl] -3- (4,6-dimethoxy-2-pyhmidyl) urea

among others is known from Pesticide Manual (publ. British Crop Protection Council), 11th edition, 1997, pp. 488-489. This compound is preferably used as the sole active ingredient of group A) and can be combined with one or more herbicidally active compounds of group B.

The special group A sulfonylurines, in particular the compound A1), in combination with other type B herbicides, are excellently suited to effectively control weed species which are difficult to control in rice crops. In particular, there are unexpected special effects against resistant harmful ^grasses.

The combination partners of type B are generally standard herbicides, but are selected based on certain criteria. Without exception, they are herbicides which are selective in rice against undesirable plants. The harmful plants to be controlled include above all grasses and dicotyledons / cyperaceae. The spelling “dicotyledons / cyperaceae” should express that the activity against dicotyledon and cyperaceae is given, but the effectiveness against dicotyledon is in the foreground.

With regard to the effectiveness of the standard herbicides of type B, in turn, a gradation can be made with regard to the focus of the plants being controlled. Part of the type B herbicides is predominantly, or almost exclusively, active against grasses (subgroup Ba)), another part is predominantly active against dicotyledons and cyperaceae (subgroup Bb)), while another group is active against both grasses and dicotyledons / cyperaceae (Subgroup Bc)) effectiveness developed.

For the combinations according to the invention, there is an optimized spectrum of activity by supplementing and intensifying the herbicidal properties of the compounds of type A, so that increases in activity against harmful plants in other target groups can also be achieved.

In a further particularly expedient embodiment, the herbicidally active mixture of the invention is characterized in that it contains, as herbicides of type B, one or more herbicides from the group Ba) which are active selectively in rice against grasses and which consists of

B1) NBA 061 - fentrazamide or BAY YRC 2388

4- (2-chlorophenyl) -5-oxo-4,5-dihydro-tetrazole-1-carboxylic acid cyclohexyl-ethyl-amide

Proceedings: The 1997 Brighton Crop Protection Conference, Weeds (publ.

British Crop Protection Council), pp. 67-68

B2) Haloxyfop

(±) -2- [4 - [[3-chloro-5- (trifluoromethyl) -2-pyridinyl] oxy] phenoxy] propionic acid, including the use form as haloxyfop-etotyl, haloxyfop-methyl, haloxyfop-methyl [(R ) -Isomer], the aforementioned compounds B2) being known from Pesticide Manual, 10th ed. 1994, pp. 551-554; B3) Sethoxydim

(±) - (EZ) -2- (1-ethoxyiminobutyl) -5- [2- (ethylthio) propyl] -3-hydroxycyclohex-2-enone,

Pesticide Mannual, 1 1st edition, 1997, p. 1 101 -1 103

B4) dithiopyr

S, 5. ^ι -dimethyi-2- (difluoromethyl-4-isobutyl-6-tπfluoromethyl-pyri, dine-3,5-dicarbothioate Pesticide Manual, 11th edition, 1997, pp. 442-443

B5) Etobenzanide = HM ^' -52

2 ^, 3'-dichioro-4-ethoxymethoxybenzaπilide Pesticide Manual, 11th edition, 1997, pp. 492-493

B6) Clefoxid- im = BAS 625 H

2- [1- (2- (4-chlorophenoxy) propoxyimino) butyl] -3-oxo-5-thione-3-ylcyclohex-1-enol

AG Chem, New Compouπd Review (publ. Agranova), Vol. 17, 1999, p. 26

B7) KIH 6127 = pyrimidobac-methyl

Methyl 2- (4,6-dimethoxy-2-pyrimidinyloxy) -6- (1-methoxyiminooethyl) benzoate, also as an acid or sodium salt

Pesticide Manual, 11th ed. 1997, p.1071-1072,

B7a) Clethodim

(±) -2 - [(E) -1 - [(E) -3-chloroallyloxyimiπo] propyl] -5- [2- (ethylthio) propyl] -

3-hydroxycyclohex-2-eπone

Pesticide Manual, 11th edition, 1997, pp. 250-251 Although the representatives of group Ba) also have relatively different chemical structures, they nevertheless form a related subgroup due to their spectrum of activity and the fact that they are synergists for the compounds of type A.

Also of particular interest are herbicidal compositions which, as a type B compound, contain one or more compounds which are selective in rice against dicotyledons and in some cases also cyperaceae (subgroup Bb)), which are selected from the group consisting of the herbicides

B8) 2,4-D

(2,4-dichloropheπoxy) acetic acid frequently used forms: 2,4-D-butotyl, 2,4-D-butyl, 2,4-D-dimethylammonium, 2,4-D-diolamine, 2,4-D- iso-octyl, 2,4-D-isopropyl, 2,4-D-trolamine,

Pesticide Manual, 10th ed. 1994, pp. 271-273,

B9) MCPA

(4-chloro-2-methylphenoxy) acetic acid, predominantly used forms are u. a. MCPA-butotyl, MCPA-dimethylammonium, MCPA-isoctyl, MCPA-potassium, MCPA-Nathum, Pesticide Manual, 10th ed. 1994, p.638-640,

B10) Mecoprop, Mecoprop-P

(RS) -2- (4-chloro-o-tolyloxy) propioic acid

(R) -2- (4-chloro-o-tolyloxy) propionic acid

Pesticide Manual, 10th ed. 1994, pp.646-647 and 647-648, B1 1) tritosulfuron

N - [[[4-methoxy-6- (trifluoromethyl) -1, 3,5-triazin-2-yl] amino] carbonyl] -2-

(trifluoromethylbenzenesulfonamide)

AG Chem, New Compound Review (publ. Agranova), Vol. 17, 1999 _, p _. 24

B12) Halosulfuron-methyl methyl3-chloro-5- (4,6-dimethoxypyrimidin-2-ylcarbamoylsulfamoyl) -1-methyIpyrazole-4-carboxylate

Pesticide Manual, 11th ed. 1997, pp. 657-659;

B13) Dicamba

3,6-dichloro-o-aisic acid used i.a. as dicamba-dimethylammonium, dicamba potassium, dicamba

Sodium, dicamba-trolamine,

Pesticide Manual, 10th ed. 1994, pp. 298-300,

B14) Acifluorfen

5- (2-chloro-α, α, α-trifluoro-p-tolyloxy) -2-nitrobenzoic acid, also used as acifluorfen sodium, Pesticide Manual, 10th ed. 1994, pp. 12-13,

B15) Carfeπtrazoπe ethyl (RS) -2-chloro-3- [2-chloro-5- (4-difiuoromethyl-4,5-dihydro-3-methyl-5-oxo

1 H-1, 2,4-triazol-1-yl) -4-fluorophenyl] propionate applied i.a. as Carfeπtrazone-ethyl (as indicated) or as

Acid, Pesticide Manual, 11th ed. 1997, p.191-193,

B16) bentazone

3-Isopropyl-1 H-2, 1, 3-beπzothiadiaziπ-4 (3H) -on-2,2-dioxide Pesticide Manual, 10th ed. 1994, p.90-91, B17) triclopyr

[(3,5,6-trichloro-2-pyridinyl) oxy] acetic acid, preferably as triclopyr, triclopyr-butotyl, triciopyr-triethylammonium,

Pesticide Manual, 10th ed. 1994, p.1015-1017.

In a further preferred embodiment of the present invention, the herbicidally active combinations contain, as herbicides of type B, one or more herbicides which are selectively active in rice, predominantly against grasses and dicotyledon / cyperaceae (subgroup Bc)) from the group consisting of

B18) Pendimethalin

N- (1-Ethylpropyl) -2,6-dinitro-3,4-xylidine Pesticide Manual, 10th ed. 1994, pp.779-780

B19) Clomazone

2 - [(2-chloropheny!) - 4,4-dimethyl-3-isoxazolidinone; Pesticide Manual, 10th ed. 1994, pp. 220-221

B20) KlH 2023

Sodium 2,6-bis [(4,6-dimethoxypyhmidin-2-yl) oxy] benzoate, preferred is the form as sodium salt Pesticide Manual, 10th ed. 1994, p.620,

B21) oxadiargyl

5-tert-butyl-3- [2,4-dichloro-5- (prop-2-ynyioxy) phenyl] -1, 3,4-oxadiazol-2 (3H) - one,

Pesticide Manual, 11th ed. 1997, p.904-905,

B22) AC 322.140 = Cyclosulfamuroπ

N - [[[2- (cyciopropylcarbonyl) phenyl] amino] sulfonyl] -N1 - (4,6- dimethoxypyrimidin-2-yl) urstoff, Pesticide Manual, 10th ed. 1994, p.8-9,

B23) azimsulfuron (DPX-A8947),

1 - (4,6-Dimethoxypyrimidin-2-yl) -3- [1-methyl-4- (2-methyl-2H-tetrazol-5-yl) pyrazol-5-ylsulfonylurea

Pesticide Manual, 11th edition, 1997, pp. 63-65

B24) Nicosulfuron

1 - (4,6-Dimethoxypyrimidin-2-yl) -3- (3-dimethylcarbamoyl-2-pyridylsuifonyl) urea

Pesticide Manual, 10th ed. 1994, pp.734-735,

B26) cinmethylin

(1 RS, 25R, 4SR) -1, 4-epoxy-p-menth-2-yl 2methylbenπzylether Pesticide Manual, 11th edition, 1997, pp. 246-248

B27) Indanofan

(RS) -2- [2- (3-chlorophenyl) -2,3-epoxypropyl] -ethyliπdan-1, 3-dione Pesticide Manual, 11th edition, p. 715

B 28) pentoxazones

3- (4-Chloro-5-cyclopentyloxy-2-fluorophenyl) -5-isoprpyIiden-1, 3-oxazolidiπ-2,4-dione, Pesticide Manual, 11th edition 1997, pp. 942-943 B29) LGC-40863 = pyribenzoxime

Beπzopheπone 0- [2,6-bis - [(4,6-dimethoxy-2-pyrimidinyl) oxy] benzoyl] oxime Daily volume: The 1997 Brightoπ Crop Protection Conference, Weeds (publ _. British Crop Protection Council) pp. 39-40

B30) Oxaziclomefoπe = MY100

3- [1 - (3,5-dichloropheπyl) -1-methylethyl] -2,3-dihydro-6-methyl-5-phenyl-4H-1,3-oxazim-4-one

Day volume: The 1997 Brighton Crop Protection Conference, Weeds (publ.

British Crop Protection Council) pp. 73-74

B31) Fluthiamid = BAY FOE 5043

4'-fluoro-N-isopropyl-2- (5-trifluoromethyl-1, 3,4-thiadiazol-2-yloxy) acetalide Pesticide Manual, 11th edition, 1997, pp. 82-83

B32) Mesotrione

2- [4- (methylsulfonyl) -2-nitrobenzoyl] -1, 3-cyclohexanediones

AG Chem, New Compound Review (publ. Agranova), Vol. 16, 1998, p. 51

Compounds B1) to B32) are, for example, herbicides which are known from the source indicated for the particular compound and are used specifically in combination with the compounds of group A) of the invention and are selective in rice and in transgenic rice. In addition to the basic substance, the formula of which is regularly given for clarification, in some cases it is also referred to modifications of the basic substances that are usually used, which can also be used in the context of the present invention. Insofar as optically active forms of type B compounds are customary, these are also part of the invention, and in some cases reference has also been made to these forms (for example mecoprop and mecoprop-P etc.). Combinations of the active ingredients A + B show superadditive effects, i _. H. with the same control of the harmful plants, the herbicidal compositions according to the invention make it possible to reduce the application rate and / or to increase the safety margin in rice crops. Both make economic and ecological sense. The choice of the amounts to be used by components A + B, the ratio of components A: B and the order in which they are applied, as well as the formulation to be chosen, depend on a whole series of factors.

In this context, not insignificant a. the type of mixing partner, the development stage of the weeds or grasses, the weed spectrum to be controlled, environmental factors, climatic conditions, soil conditions etc.

In a particularly preferred embodiment of the invention, herbicidal compositions according to the invention are characterized in that they have a synergistically active content of a combination of the compounds of the formula I or their salts (type A compounds) with compounds from group B. Above all, it should be emphasized that even in combinations with effort amounts or weight ratios of A: B, in which a synergism cannot be demonstrated in every case - for example because the individual compounds are usually used in combination in very different effort amounts or also because the Control of the harmful plants by the individual compounds is very good - the herbicidal compositions of the invention are generally inherent in a synergistic effect.

The application rates of type A herbicide are generally between 1 and 120 g ai / ha (ai = active ingredient, ie application rate based on the active ingredient), preferably between 5 and 90 g ai / ha. As mentioned, the weight ratios A: B of the combined herbicides and their application rates can vary within wide limits. A range according to the invention of the application rate ratios (wt / wt) comprises approximately A: B such as 1: 20,000 to approximately 200: 1. Agents which compounds of the formula I or their salts (type A compounds) and compounds are preferred in the context of the invention from group B in a weight ratio of about 1: 8000 to 100: 1. Means are particularly expedient with A: B ratio ratios between 1: 4000 and 50: 1. In detail, the following picture results for the various herbicides of group B, ie the following application rates and weight ratios (A: B) are preferably used:

The active compound combinations according to the invention can be present both as mixed formulations of the two components, which are then diluted with water in the customary manner, or else as So-called tank mixes can be prepared by diluting the separately formulated components together with water.

The active ingredients of types A and B can be formulated in different ways, depending on which biological and / or chemical-physical parameters are specified.

Examples of possible formulations are:

Wettable powder (WP), emulsifiable concentrates (EC), water-soluble powders (SP), water-soluble concentrates (SL), concentrated emulsions (EW) such as oil-in-water and water-in-oil emulsions, sprayable solutions or emulsions, capsule suspensions ( CS), oil or water-based dispersions (SC), Suspoemulsioπeπ, Suspensionskoπzeπtrate, dusts (DP), oil-miscible solutions (OL), pickling agents, granules (GR) in the form of micro, spray, elevator and adsorbent granules, granules for the soil or litter application, water-soluble granules (SG), water-dispersible granules (WG), ULV formulations, microcapsules and waxes.

Of these, water-soluble wettable powders (WP), water-dispersible granules (WG), water-emulsifiable granules (EC), suspoemulsions (SE) and oil suspension concentrates (SC) are preferred.

These individual types of formulation are known in principle and are described, for example, in: Winnacker-Küchler, "Chemical Technology" Volume 7, C. Hauser Verlag Munich, 4th ed. 1986; Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker N.Y., 1973; K. Marteπs, "Spray Drying Handbook", 3rd Ed. 1979, G. Goodwin Ltd. London.

The necessary formulation auxiliaries such as inert materials, surfactants, solvents and other additives are also known and are described, for example, in: Watkins, "Handbook of Insecticide Dust Diluents and Carriers ", 2nd Ed., Darland Books, Caldwell NJ; H. v. Olpheπ" Introduction to Clay Colloid Chemistry, 2nd Ed., J. Wiley & Sons, NY; Marsden "Solvents Guide, 2nd Ed., Interscience, NY 1963; McCutcheoπ ^'s " Detergents and Emulsifiers Annual ", MC Publ. Corp., Ridgewood NJ; Sisley and Wood," Encyclopedia of Surface Active Agents ", Chem. Publ. Co Inc., NY 1964; Schönfeldt, "interfacial ethylene oxide adducts", Scientific Publishing Company, Stuttgart 1976; Winnacker-Küchler "Chemical Technology", volume 7, C. Hauser Verlag Munich, 4th ed. 1986.

Based on these formulations, combinations with other pesticidally active substances, herbicides, insecticides, fungicides, and also antidotes, safeners, fertilizers and / or growth regulators can be prepared, for. B. in the form of a finished formulation or as a tank mix.

The herbicide combinations of the invention are produced particularly advantageously by combining the compounds of the formula I or their salts (type A compounds) with one or more compounds of the type B analogously to a conventional crop protection formulation from the group comprising water-soluble wettable powders (WP), water-dispersible granules (WDG), water-emulsifiable granules (WEG), suspoemulsions (SE) and oil suspension concentrates (SC).

Spray powders are preparations which are uniformly dispersible in water and, in addition to the active ingredients, in addition to a diluent or inert substance, are also surfactants of an ionic and / or nonionic type (wetting agents, dispersants), for. B. polyoxyethylated alkylphenols, polyoxyethylated fatty alcohols and Fettamiπe, fatty alcohol polyglycol ether, alkane, or Alkylarylsulfoπate, sodium ligninsulfonate, sodium ^{2,2'-dinaphthylmethane-6,6'} -disulfoπsaures sodium dibutylnaphthalenesulfonate or else sodium oleylmethyltaurate.

Emulsifiable concentrates are obtained by dissolving the active ingredient or ingredients in an organic solvent, e.g. As butanol, cyclohexanone, dimethylformamide, xylene or even higher aromaticsπ or Hydrocarbons with the addition of one or more surfactants of ionic and / or nonionic type (emulsifiers). Examples of emulators that can be used are: alkylarylsulfonic acid calcium salts such as cadodecylbenzenesulfonate or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products (e.g. block copolymers, or other polyether ethoxylate ethoxylate ethoxylate ethoxylate ethoxylate ethoxylates),

Dusts are obtained by grinding the active ingredient or ingredients with finely divided substances, e.g. B. talc, natural clays, such as kaolin, bentonite and pyrophyllite, or granules of diatomaceous earth can be prepared either by spraying the active ingredient or the active ingredients onto adsorbable, granulated inert material or by applying active ingredient concentrations by means of adhesives, e.g. As polyvinyl alcohol, sodium polyacrylic acid or mineral oils, on the surface of carriers such as sand, kaolinite or granulated inert material. Water-dispersible granules are generally produced using the customary methods, such as spray drying, fluidized bed granulation, plate granulation, mixing with high-speed mixers and extrusion without solid inert material. Suitable active ingredients can also be granulated in the manner customary for the production of fertilizer granules, if desired in a mixture with fertilizers.

The agrochemical preparations according to the invention generally contain 0.1 to 99% by weight, in particular 2 to 95% by weight, very particularly preferably 3 to 92% by weight, of active ingredients of types A and B, in addition to conventional formulation auxiliaries.

The concentrations of the active ingredients A + B can vary in the formulations. In Spritzpuivern the active ingredient concentration is z. B. about 10 to 95 wt .-%, the rest of 100 wt .-% consists of conventional Formulation components. In the case of emulsifiable concentrates, the active ingredient concentration can be about 1 to 85% by weight, preferably 5 to 80% by weight. Dust-like formulations contain about 1 to 25% by weight, mostly 5 to 20% by weight of active substances, sprayable solutions about 0.2 to 25% by weight _. -% _, preferably 2 to 20 wt .-% active ingredients. In the case of granules such as dispersible granules, the active ingredient content depends in part on whether the active compound is liquid or solid and which granulating agents and fillers are used. As a rule, the content of the water-dispersible granules is between 10 and 90% by weight.

In addition, the active ingredient formulations mentioned contain, if appropriate, the customary adhesives, wetting agents, dispersants, emulsifiers, penetration agents, preservatives, anti-freeze agents and solvents, fillers, dyes and carriers, defoamers, evaporation inhibitors and the pH and viscosity influencing means.

Because of the relatively low application rate of the combinations A + B according to the invention, their compatibility is generally very good. In particular, the combinations according to the invention achieve a reduction in the absolute application rate compared to the single application of a herbicidal active ingredient. In order to further increase the tolerance and / or selectivity of the herbicide combinations according to the invention, if desired, it is advantageous to use them together in a mixture or in succession in succession together with safeners or antidotes. Suitable safeners or antidots for the combinations according to the invention are, for. B. from 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-91/08202) and PCT / EP 90/02020 (WO-91/078 74) and the literature cited therein are known 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. The herbicidal mixtures or application combinations of the invention are advantageously characterized by an additional content of C) of one or more compounds which act as safeners.

Particularly preferred antidots or safeners or groups of compounds which have proven themselves as safeners or antidots for the above-described product combinations of the invention include:

a) Compounds of the dichlorophenylpyrazoline-3-carboxylic acid type, preferably compounds such as 1 - (2,4-dichlorophenyl) -5- (ethoxycarbonyl) -5-methyl-2-pyrazoliπ- 3-carboxylic acid ethyl ester (compound C1-1) and related Compounds as described in international application WO 91/07874 (PCT / EP 90/02020);

b) derivatives of dichlorophenylpyrazole carboxylic acid, preferably compounds such as 1 - (2,4-dichlorohenyl) -5-methyl-pyrazole-3-carboxylic acid ethyl ester (compound C1 - 2), 1- (2,4-dichlorophenyl) -5-isopropyl- ethyl pyrazole-3-carboxylic acid ester (compound C1-3), 1- (2,4-dichlorophenyl) -5- (1, 1-dimethyl-ethyl) ethyl pyrazole-3-carboxylate (compound C1-4), 1- (2, 4-dichlorophenyl) -5-phenylpyrazole-3-carboxylic acid ethyl ester (compound C1-5) and related compounds as described in EP-A-0 333 131 and EP-A-0 269 806;

c) Compounds of the triazole carboxylic acid type, preferably compounds such as 1 - (2,4-dichlorophenyl) -5-trichloromethyl- (1 H) -1, 2,4-triazole-3-carboxylic acid ethyl ester (compound C1-6, fenchlorazole) 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 5- (2,4-dichlorobenzyl) - 2-isoxazolin-3- ethyl carboxylate (compound C1 -7) or 5-pheny [-2-isoxazoline-3-carboxylic acid ethyl ester (compound C1 -8) and related compounds as described in international patent application WO 91/08202 (PCT / EP 90/01966);

e) compounds of the 8-quinolinooxyacetic acid type, preferably compounds such as

(5-chloro-8-quinolinooxy) acetic acid (1-methyl-hex-1-yl) ester (C2-1), (5-chloro-8-quinolinoxy) acetic acid (1,3-dimethyl- but-1 -yl) -ester (C2-2), (5-chloro-8-quinolinoxy) -acetic acid-4-allyl-oxy-butyl ester (C2-3), (5-chloro-8-quinolinoxy) -acetic acid -1-Allyl-oxy-prop-2-yl ester (C2-4), (5-chloro-8-chiπoliπoxy) -acetic acid ethyl ester (C2-5), (5-chloro-8-quinolinoxy) -acetic acid methyl ester (C2-6 ), (5-chloro-8-quinolinoxy) allyl acetate (C2-7),

(5-Chloro-8-chiolinolin) acetic acid 2- (2-propylidene-iminoxy) -1-ethyl ester (C2-8), (5-chloro-8-quinolinoxy) acetic acid-2-oxo-prop-1 -ylester (C2-9) and related compounds as 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) Compounds of the type of (5-chloro-8-quinolinoxy) maleic acid, preferably compounds such as (5-chloro-8-quinolinoxy) malonic acid diethyl ester, (5-chloro-8-quinolinoxy) malonic acid diallyester, (5-chloro 8-Quinolinoxy) - methyl malonate and related compounds as described in the

Patent application EP-A-0 582 198 has been described and proposed;

g) active substances of the type of Pheπoxyessig- or -propioπsäurederivate or aromatic carboxylic acids, such as. B. 2,4-dichlorophenoxyacetic acid (ester) (2,4-D), 4-chloro-2-methylphenoxy-propionester (Mecoprop), MCPA or 3,6-dichloro-2-methoxy-benzoic acid (ester) ( Dicamba). h) Compounds of the 5,5-diphenyl-2-isoxazoiin-3-carboxylic acid type, preferably 5,5-diphenyl-2-isoxazoline-3-carboxylic acid ethyl ester (C3-1).

i) Compounds known as safeners for rice, such as fenclorim (= 4,6-dichloro-2-phenyipyrimidine, Pesticide Manual, 11th edition, 1997, pp. 511-512), dimepiperate (= piperidine-1 -thiocarboxylic acid- S-1-methyl-1-phenylethyl ester, Pesticide Manual, 11th edition, 1997, pp. 404-405), daimuron (= 1 - (1-methyl-1-phenylethyl) -3-p-tolylurea, pesticide Manual, 11th edition, 1997, p. 330), cumyluron (= 3- (2-chlorophenyimethyl) -1 - (1-methyl-1-phenyl-ethyl) -urea, JP-A-60/087254), methoxyphenoπ (= 3,3'-dimethyl-4-methoxy-beπzopheπon, COD (= 1 -Brom ^ - (chloromethylsulfonyl) -benzene, CAS-Reg. No. 54091 -06-4)

The compounds mentioned are also at least partially described in EP-A-0 640 587, to which reference is hereby made for the purposes of disclosure.

j) Another important group of compounds suitable as safeners and antidotes is known from WO 95/07897.

The safeners (antidotes) from groups a) to j) above reduce or prevent phytotoxic effects which can occur when the product combinations according to the invention are used in crops without impairing the effectiveness of the herbicides against harmful plants. As a result, the field of use of the mixtures of herbicides according to the invention can be expanded considerably and, in particular, the use of safeners enables the use of combinations which have hitherto been able to be used only to a limited extent or with insufficient success. H. of combinations which, without Safeπer in low dosages with little breadth effect, did not lead to adequate control of the harmful plants.

The herbicidal mixtures according to the invention and the safeners mentioned can be used together (as a finished formulation or in the Taπk-mix process) or in in any order. The weight ratio of safener: herbicide (group A, ie the compound of the formula I and its salts) can vary within wide limits and is preferably in the range from 1: 100 to 100: 1, in particular from 1: 100 to 50: 1. The optimum in each case Amounts of herbicides (type A and type B compounds) and safeners are usually dependent on the type of herbicide mixture used and / or on the safener used and on the type of crop to be treated.

Depending on their properties, the safeners of type C) can be used for pretreating the seed of the crop (dressing the seeds) or introduced into the seed furrows before sowing or used together with the herbicide mixture before or after emergence of the plants. Pre-emergence treatment includes both the treatment of the cultivated area before sowing and the treatment of the sown but not yet overgrown cultivated areas. Common use with the herbicide mixture is preferred. Tank mixes or ready formulations can be used for this.

Depending on the indication and the herbicide used, the required amounts of the Safeπer can vary within wide limits and are generally in the range from 0.001 to 1 kg, preferably 0.005 to 0.2 kg, of active ingredient per hectare. Particularly inexpensive herbicidal compositions which are outstandingly suitable for use in rice result in the context of the invention when herbicides from group A) are used in combination with type B compounds and the Safeπer C2-1 and / or C3-1.

For use, the formulations present in commercial form are optionally diluted in a customary manner, for example in the case of wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules, using water. Dust-like preparations, ground or scatter granules, as well as sprayable Solutions are usually no longer diluted with other inert substances before use.

The invention also relates to a process for controlling unwanted plants, which is characterized in that a herbicidally effective amount of a combination of active compounds A + B according to the invention is applied to this or the cultivated area. The active ingredients can be applied to the plants, parts of plants, plant seeds or the area under cultivation.

In a preferred process variant, the compounds of the formula (I) or their salts (type A compounds) are applied in amounts of from 1 to 120 g ai / ha, preferably from 5 to 90 g ai / ha, very particularly preferably between 6 and 60 g ai / ha, while the application rates for the compounds of type B are generally 1 to 5000 g ai / ha. It is preferred to apply the active ingredients of types A and B simultaneously or at different times in a weight ratio of 1: 20000 to 200: 1. Also particularly preferred is the joint application of the active ingredients in the form of sachet mixtures, the optimally formulated concentrated formulations of the individual active ingredients being mixed together with water in the tank and the spray liquor obtained being applied.

Since the crop tolerance of the combinations according to the invention is extremely good with very high control of the harmful plants at the same time, these can be regarded as selective. In a preferred process modification, herbicidal compositions with the active compound combinations according to the invention are therefore used for the selective control of undesired plants.

The process for the selective control of harmful plants is particularly favorable when the herbicidal compositions of the invention are used in rice. The combination partners of type A control a limited spectrum of annual and perennial weeds and cyperaceae when used alone in rice. The spectrum of activity of the type A compounds is, however, significantly improved further by the combination with the type B partners mentioned in the invention, individual type groups additionally being recorded. Depending on the nature of the combination partner B, the herbicidal combinations according to the invention can advantageously be used to control unwanted plants in transgenic rice crops.

Transgenic crops are those in which the plants are made resistant to herbicides or pesticides through genetic manipulation. Rice crops modified in this way then allow selective use.

Overall, the invention thus also relates to the use of herbicidal compositions comprising

A) one or more herbicidal active compounds from the group of the substituted phenoxysulfonylureas of the formula I and their salts

and

B) one or more herbicidally active compounds from the group of

Compounds which consists of Ba) selectively in rice herbicides active mainly against grasses selected from the group consisting of

Fentrazamide (NBA 061), haloxyfop, sethoxydim, dithiopyr, etobenzaπid

(MY-52), Clefoxidim, KIH 6127 and Clethodim, Bb) selectively in rice herbicides active mainly against dicotyledonous harmful plants and cyperaceae, selected from the group consisting of 2,4-D, MCPA, Mecoprop, Mecoprop-P, Tritosulfuroπ, Halosulfuron-methyl, Dicamba, Acifluorfen, Carfentrazone, Bentazon and Triclopyr ,

Bc) selectively in rice, predominantly herbicides active against grass and dicotyledonous harmful plants and cyperaceae, selected from the group consisting of pendimethalin, clomazone, KIH 2023, oxadiargyl, cycloslulfamuron (AC 322, 140), azimsulfuron (DPX-A-8947), nicosulfuro , Cinmethylin, Indanofan, Pentoxazone,

Pyribenzoxim, oxaziclomefone (MY-100), fluthiamide and mesotrione,

to combat unwanted harmful plants, preferably in plant crops such as rice crops. The weight ratio of compounds of the formula I or their salts (type A compounds) and compounds from group B is generally in the range from 1: 20,000 to 200: 1, preferably 1: 8,000 to 100: 1, particularly preferably 1: 4000 to 50: 1.

A preferred use relates to the use of combinations which have contents of A and B compounds in a synergistically effective amount.

Also preferred is the use of mixtures with combinations of A) and Ba) for the selective control of grasses in rice. It is also preferred to use mixtures with combinations of A) and Bb) for the selective control of dicotyledons and cyperaceae in rice. It is further preferred to use mixtures with combinations of A) and Bc) for the selective control of grasses, dicotyledons and cyperaceae in rice.

The invention also includes mixtures of one or more combination partners A), preferably only A1 (ethoxysulfuron), and one or several combination partnersπ B), optionally in combination with one or more Safeπem C).

The following combinations of A1 (ethoxysulfuron) with mixture partners B1 -B32 may be mentioned as preferred examples of the active compound mixtures according to the invention, without any intention that this should restrict the combinations explicitly mentioned:

A1 + B1: Fentrazamide, A1 + B2: Haloxyfop, A1 + B3: Sethoxydim, A1 + B4: Dithiopyr, A1 + B5: Etobenzaπid, A1 + B6: Clefoxidim, A1 + B7: KIH 6127, A1 + B7a: Clethodim, A1 + B8: 2,4-D, A1 + B9: MCPA, A1 + B10: Mecoprop Mecoprop-P, A1 + B11: Tritosulfuron, A1 + B12: Halosulfuron-methyl, A1 + B13: Dicamba, A1 + B14: Acifluorfen, A1 + B15: Carfentrazone, A1 + B16: Bentazon, A1 + B17 Triclopyr, A1 + B18: Pendi-methalin, A1 + B19: Clomacone, A1 + B20: KIH 2023, A1 + B21 Oxadiargyl, A1 + B22: Cyclosulfamuron, A1 + B23: Azimsulfuron, A1 + B24: Nicosulfuron, A1 + B25: Thenylchlor, A1 + B26: Sinmethylin, A1 + B27: Indanofan, A1 + B28: Pentoxazone, A1 + B29: Pyribenzoxim, A1 + B30: Oxaziclomefone, A1 + B31 : Fluthiamid, A1 + B 32: Mesotrione.

The mixtures described above can expediently be used together with one or more safeners. Examples of preferred safeners are (5-chloro-8-quinolinooxy) acetic acid (1-methyl-hex-1-yl) ester (C2-1) and 5,5-diphenyl-2-isoxazoline-3-carboxylic acid methyl ester ( C3-1).

In the combinations listed, the use of a safener offers considerable advantages, since this reduces possible damage to the crop, such as rice, which can arise from sulfonylurea derivatives or other herbicidally active compounds.

Furthermore, the Safeπer C2-1 and C3-1 can advantageously be replaced by one or more compounds from the following group of safeners or used together with one or more of the following compounds: 1 - (2,4-dichlorophenyl) -5- (ethoxycarbonyl) -5-methyl-2-pyrazoliπ-3-carboxylic acid ethyl ester (C1 -1),

1 - (2,4-dichlorophenyl) -5-methyl-pyrazole-3-carboxylic acid ethyl ester (C1 -2), 1 - (2,4-dichlorophenyl) -5-isopropyl-pyrazole-3-carboxylic acid ethyl ester (C1 -3),

1 - (2,4-dichlorophenyl) -5- (1, 1-dimethyl-ethyl) pyrazole-3-carboxylic acid ethyl ester (C1 -4),

1 - (2,4-dichlorophenyl) -5-phenyl-pyrazole-3-carboxylic acid ethyl ester (C1 -5), 1 - (2,4-dichlorophenyl) -5-trichloromethyl- (1 H) -1, 2,4- triazole-3-carboxylic acid ethyl ester (C1-6, fenchlorazole)

5- (2,4-dichlorobenzyl) -2-isoxazoline-3-carboxylic acid ethyl ester (C1 -7), 5-pheny! -2-isoxazoline-3-carboxylic acid ethyl ester (C1 -8), (5 - chloro-8-quinolinoxy ) -acetic acid- (1,3-dimethyl-but-1-yl) ester (C2-2), (5-chloro-8-chiolinolinoxy) -acetic acid ^ -allyl-oxy-butyl ester (C2-3), ( 5-chloro-8-quinolinoxy) -acetic acid-1-allyl-oxy-prop-2-yl ester (C2-4), (5-chloro-8-quinolinoxy) -acetic acid ethyl ester (C2-5), (5-chloro 8-quinolinoxy) -acetic acid methyl ester (C2-6), (5-chloro-8-quinolinoxy) -acetic acid allyl ester (C2-7),

(5-Chloro-8-quinolinooxy) acetic acid 2- (2-propylidene-iminoxy) -1-ethyl ester (C2-8), (5-chloro-8-quinolinoxy) acetic acid-2-oxo-prop-1 -ylester (C2-9), (5-chloro-8-quinolinoxy) -malonic acid diethyl ester, (5-chloro-8-quinolinooxy) -malonic acid diallyester, (5-chloro-8-quinolinoxy) -malonic acid methyl ester 2,4-dichlorophenoxyacetic acid (ester ) (2,4-D), 4-chloro-2-methyl-pheπoxy-propioπester (Mecoprop), MCPA, 3,6-dichloro-2-methoxy-benzoic acid (ester) (Dicamba).

In addition, one or two or more of the following pesticides (herbicides, insecticides, fungicides, etc.) may additionally be present in the mixtures of the invention in order to round off the properties, usually in minor amounts: abamectin, AC94377, AC263222, AC3-103630, acephate, acloπifen, acrinathrin, acypectas, AKH-7088, alachlor, alanycarb, aldicarb, aldoxycarb, allethrin, alloxydim, alpha-cypermethriπ, ametryn, amidosulfymolate, amidosulfymolate , aπilaziπe, aπthraquinoπe, asulam, atrazine, azaconazole, azadirachtin, azamethiphos, azinphos-ethyl, aziπphos-methyl, azocyclotin, BAS480F, BAS490F, benalaxyl, benazoliπ, bendiocarb, beanflarboxin, beta, benapfluralapin, beta, beniflurapin, beta, benifluraphenon, beta, benxflurapin, beta, beniflurapin, beta, beniflurapin, beta, beniflurapin, beta, beniflurapenin -cyfluthrin, beta-cypermethrin, bifenox, bifenthrin, bilanafos, bioallethriπ, bioallethrin (S-cyclopentenyl isomer), bioresmethriπ, biphenyl, bitertaπol, blasticidin-S, borax, Bordeaux mixture, brodifacoum, bromachalo, bromiolomo, bromiolomo, bromiolomo, bromiolo, bromomolomone, bromiolomo, bromomomilomine, bromiolo, bromomomino, bromolomo, bromomomino, bromiolo, bromomomino, bromiolo, bromomolomone, bromiolo, bromomomyl, bromomolomone, bromolomo, bromomomino, bromomomino, bromolomo, bromomomilomone, bromolomo, bromomolomone, bromiolo, bromomolomone, bromiolo, bromomolomone, bromolomo, bromomethoxin, bromomethoxin bromoxynil, bromuconazole, bronopol, bupirimate, buprofezin, butamifos, butocarboxim, butoxycarboxim, butralin, butylamine, butylate, cadusafos, calcium polysulfide, captafol, captan, ca rbaryl, carbendazim, carbetamide, carbofuran, carbosulfan, carboxiπ, cartap, CGA50439, CGA183893, CGA219417, chinomethioπat, chlomethoxyfeπ, chloralose, chloramben, chlorbromuron, chlorbufam, chlordane, chlorethoxyfos, chlαrfenviπphos, chlorfluazuron, chlorflurenol, chloridazon, chlormephos, chiormequat, chlornitrofen, chloracetic acid, chlorobenzilate, chloroneb, chlorophacinone, chloropicriπ, chlorothalonil, chlorotoluron, chlorophonium, chlorpropham, chlorpyrifos, chlorpyrifos-methyl, chlorsulfuron, chlorthal, chlorthiamid, chiozolinate, CL26691, CL30afid, cloprofin, clocobid, cl304415, cloafin, cl304415 , cloxyfonac, copper hydroxide, copper oxychloride, copper sulfate, coumaphos, coumatetralyl, 4-CPA, cuprous oxide, cyanamide, cyanazine, cyanophos, cycloate, cycloprothriπ, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda- cyhalothrymethrin, cyanamide , alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin, cyphenotri n, cyproconazole, cyromazine, daminozide, dazomet, 2,4-DB, DCIP, debacarb, decan-1 -ol, deltamethriπ, demeton- S-methyl, desmedipham, desmetryπ, diafenthiuroπ, diazinoπ, dichlobeπil, dichlofluanid, dichlone, dichlone dichlorophen, 1, 3-dichloropropeπe, dichlorprop, dichlorprop-P, dichlorvos, diclofop, diclomezine, dicloran, diclofol, dicrotophos, dienochlor, diethofeπcarb, diethyltoluamide, difenacoum, diefenoconazole, difeπzoquat, difethialone, diflubenzuron, diflufeπican, dikegulac, dimefuron, dimethachlor, dimethametryn, dimethenamid, dimethipin, dimethirimol, _dimethoate, dimethomorph, dimethyl phthalate, dimethylviπphos, diniconazole, dinitramine, dinocap, dinoterb, diofenolan , dioxabeπzofos, diphacinone, diphenamide, diphenyiamiπe, dipropyl pyridine-2,5-dicarboxylate, diquat, disulfutoπ, dithianon, diuron, DKA-24, DNOC, dodemorph, dodine, edifeπphos, empenthrin, eπdosulfan, EP818, EPH4DOTHAL ergocalciferol, esfenvalerate, esprocarb, ET751, ethalfluraliπ, ethametsulfuron-methyl, ethephon, ethiofencarb, ethioπ, ethirimol, ethofumesate, ethoprophos, ethoxyquin, ethychlozate, ethylene dibromide, ethylene dichloride, etofenprox, Fetr42imphenolam, fetr42azamam, fetr42azolam, fetr42azolamif, etridazamam, 8 fenbuconazole, fenbutatin oxide, fenchlorazole, fenclorim, fenfuram, feπitrothion, fenobucarb, fenothiocarb, fen oxycarb, fenpiclonil, fenpropathrin, fenpropidin, fenpropimorph, fenpyroximate, fenthioπ, feπtin, fenuroπ, feπvalerate, ferbam, ferbam, ferimzone, fipronil, flamprop, fiamprop-M, flazasulfuron, flocoumafen, fluamopazalone, fluazopalin, fluazopalin, fluazopalin, fluazopalin flucycloxuroπ, flucythrinate, fludioxonil, flufenoxuron, flumetralin, flumetsulam, flumiclorac, flumioxazin, fluometuron, fluoroacetamide, fluoroglycofen, fluoromide, flupoxam, flupropaπam, fluridololurol, flurinololoxurol, flurinololoxurol flutriafol, tau- fluvalinate, fluxofeπim, folpet, fomesafen, fonofos, forchlorfenuron, formetanate, formothion, fosamine, fosetyl, fosthiazate, fuberidazole, furalaxyl, furathiocarb, furilazole, gibberellic acid, gibberellinxA, gibberellinin A4, gibberellin A4, gibberellin A4 halosulfuron, HC-252, gamma-HCH, heptachlor, heptenophos, hexachlorobenzene, hexaconazole, hexaflumuron, hexazinone, hexythiazox, hydramethylnon, 2-hydrazinoethanol, hydroprene, 8-hydroxyquinoline sulfate, hymexazol, 1C1A0858, ICIA5504, imazalil, imazamethabenz, imazapyr, imazaquin, imazethapyr, imibenconazole, imidacloprid, iminofideπi, 3-imidol-3-yl-iodide-4-yl, 3-iodide 3-ylbutyric acid, ipconazole, iprobenfos, iprodione, isazofos, isofenphos, isopamphos, isoprocarb, isoprothiolane, isoproturon, isouron, isoxaben, isoxapyrifop, isoxathion, kasugamycin, KIH9201, cyhalhalothrin, i lenacil, liπuroπ, lufenuron, malathioπ, maleic hydrazide, mancopper, mancozeb, maneb, MCPA-thioethyl, MCPB, mecarbam, mefluidide, mepanipyrim, mephosfolan, mepiquat, meproπil, metalaxyl, metaldehitone, metπ, methamazazamethaz, methamazazamethaz, methamazazole, methamazazole, methamazazole , methamidophos, methasulfocarb, methidathion, methiocarb, methomyl, methoprene, methoxychlor, methylarsonic acid, methyl bromide, methyldymroπ, methyl isothiocyanate, metiram, metobeπzuron, metobromuroπ, metolcarb, metoxuron, metribuziπ, meviectphini, MK-rot3nphini, MK-rotbiectin, MK muscalure, myclαbutaπil, πabam, naled, naphthenic acid, 2- (1 -πaphthyl) acetamide, (l -naphthyl) acetic acid, (2-naphthoyloxy) acetic acid, napropamide, πaptalam, natamycin, NC-330, neburon, NI- 25, πickel bis (dimethyldithiocarbamate), niclosamide, nicotine, nitenpyram, nithiazine, πitrapyrin, nitrothal-isopropyl, norflurazon, πuarimol, octhilinone, 2- (octylthio) ethanol, ofurace, omethoate, orbencarb, ory zaliπ, oxabetrinil, oxadixyl, oxamyl, oxine-copper, oxoliπic acid, oxycarboxin, oxydemeton-methyl, paclobutrazol, paraquat, parathion, parathion-methyl, pebulate, pefurazoate, peπconazole, peπcycuron, pentachanhrinophenol, pentetan chlorophenol, pentetan chlorophenol, pentetan chlorophenol, , 2-phenylphenol, N-phenylphthalamic acid, phorate, phosalone, phosdiphene, phosmet, phosphamidon, phoxim, phthalide, pindone, piperalin, piperonyl butoxide, pirimicarb, pirimiphos-ethyl, pirimiphos-methyl, polyoxins, prallethrin.pretoleuron, probazole-π-sulfole-chlorine , prochloraz, procymidone, prodiamiπe, profenofos, prohexadioπe, prometon, propachlor, propamocarb, propaphos, propaquizafop, propargite, propazine, propetamphos, propham, propiconazole, propineb, propisochlor, propoxur, propyzamide, prosulfon, pyrofosine, prosofonos, pyrofosine, prosofonosulfon, pyrofosine, prosulfon, pyrofosine, prosulfon, pyrofosine, prosulfon, pyrofosine, prosulfon, pyrofosine, prosulfon, pyrofosine, prosulfon, pyrofosine, prosulfon, pyrofosine, prosulfon, pyrofosine, prosulfon, pyrofosine, prosulfon, pyrofins, pro , pyridabeπ, pyridaphenthion, pyridate, pyrifenox, pyrimethanil, pyrimidifen, pyriproxyfen, pyrithiobac-sodium, pyroquiloπ, quinalo phos, quiπmerac, quinoclamine, quintozeπe, quizalofop, quizalofop-P, resmethriπ, rimsulfuron, roteπone, RU15525, S421, siduroπ, silafluofen, smaziπe, sodium fluoroacetate, SSF-109, SSI-stryurnurone, sulfonomycin, sulfonomycin, sulphuroncinol, sulfur , sulfometuron, sulfotep, sulfur, sulprofos, tar oils, 2,3,6-TBA, TCA-sodium, tebucoπazole, tebufenozide, tebufeπpyrad, tebutam, tebuthiuron, tecloftalam, tecnazeπe, teflubenzuron, tefluthrin, temephos, terbacil, terbufos, terbumeton, terbuthylazine, terbutryn, tetrachlorvinphos, tetraconazole, tetradifon, tetramethrin, tetramethrin [(1 R) -thidonon, thifuzon, thifuzon, thiifonazole, thifiazon thiometone, thiophanate-methyl, thiram, tiocarbazil, tolclofos-methyi, tolylfluanid, tralkoxydim, tralomethrin, transfluthriπ, triadimefon, triadimenol, tri-allate, triazamate, triazophos, triazoxide, tribenlorioz , tridemorph, trietazine, triflumizole, triflumuron, trifluralin, triflusulfuron, triforine, trimethacarb, trinexapac, triticonazole, uπicoπazole, validamycin, vamidothion, vernolate, viπclozoliπ, warfarin, XDE5iebirMCarb, XDE5iyirMC, XDE5yiMirC, XDE5yiMirCM

This results in numerous possibilities for combining several active ingredients with one another and using them together for weed control in rice culture without deviating from the concept of the invention.

The herbicidal compositions (combinations) according to the invention have excellent herbicidal activity against a broad spectrum of economically important mono- and dicotyledonous harmful plants. Perennial weeds that are difficult to control and that sprout from seeds or rhizomes, rhizomes or other permanent organs are also well captured by the active ingredient combinations. It does not matter whether the substances are applied by pre-sowing, pre-emergence or post-emergence.

On the side of the monocotyledon weed species, for example Echinochloa and Cyperus species from the aπnuelien group on the part of the perennial species persistent Cyperus species are well recorded.

The weeds occurring in rice under specific cultivation conditions, such as Sagittaria, Alisma, Rotala, Monochoria, Eleocharis, Scirpus, Cyperus etc., are combated excellently by the active compound combinations according to the invention. If the herbicidal compositions according to the invention are applied before germination, either the emergence of the weed seedlings is prevented completely, or the weeds grow to the cotyledon stage, but then stop growing and finally die completely after three to four weeks.

When the active ingredient combination of the invention is applied to the green plant parts in the post-emergence process, a drastic growth stop also occurs rapidly after the treatment. The weed plants remain in the growth stage available at the time of application or die more or less quickly after a certain time, so that weed control which is harmful to crop plants can be prevented very early and sustainably by the use of the novel agents according to the invention and also connected therewith quantitative and qualitative loss of earnings.

Although the compositions according to the invention have excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, the crop is only insignificantly or not at all damaged. For this reason, the agents are particularly suitable, particularly in rice, for the selective control of undesired plant growth.

In particular, the harmful plants to be controlled include, as already mentioned, grasses, dicotyledons and / or cyperaceae which are otherwise difficult to control. Harmful plants to be controlled preferably with the combinations of type A and type B compounds according to the invention include, among others, Echinochloa colonum, Echinochloa chinese, Echinochloa crus galli, Leptochloa chin./fil., Paspalum dis., Brachiaria platyphylla, Digitaria spp., Ischaemum , Leersia hexandra, Oryza sativa (Red rice), Cenchrus echinatus, Rottboellia exaltata, Leersia and the like on the side of the grasses, Monochoria vag., Potamogeton dis., Rotala indica, Marsilea crenata, Ludwigia ad., Salviπa mol., Ipomoea, Sesbania ex., Heteranthera, Commelinia, Butomus, Aeschynomene, Alisma plantago, Eclypta, Murdania, Xanthium, Alteranthera spp., Spenodea zey., Sagittaria, luncus spp., Polygonum, Ammania ind. on the side of the weeds and Cyperus diff., Cyperus iria, Fimbristylis litt, Cyperus ferax, Cyperus esculentes on the side of the annual Cyperaceae as well as Eleocharis spp., Scirpus spp., Scirpus mucronatus and Cyperus rotundus on the side of the perennial Cyperaceae.

In summary, it can be said that when sulfonylureas of the formula I and / or their salts are used together with one or more active substances from group B, superadditive (= synergistic) effects occur. The effect in the combinations is stronger than that of the individual products used when used alone.

These effects allow, among other things, a reduction in the application rate, the control of a broader spectrum of weeds and grasses, the closing of gaps in activity, also with regard to resistant species, a faster and safer effect, a longer lasting effect, complete control of the harmful plants with only one or a few Applications, and an extension of the application period of the active ingredients in combination.

The properties mentioned are required in practical weed control in order to keep agricultural crops free of undesired competing plants and thus to secure and / or increase the yields qualitatively and quantitatively. The technical standard is clearly exceeded by the combinations according to the invention with regard to the properties described.

In addition, the combinations according to the invention permit the control of otherwise resistant harmful plants in an excellent manner.

The following examples serve to illustrate the invention without being limiting: 1. Formulation examples a) A dusting agent is obtained by mixing 10 parts by weight of an active compound combination according to the invention and 90 parts by weight of talc as an inert substance and comminuting them in a hammer mill. b) A water-dispersible, wettable powder is obtained by adding 25 parts by weight of active compounds A + B, 64 parts by weight of kaolin-containing quartz as an inert substance, 10 parts by weight of lignosulfonic acid potassium and 1 part by weight of oleoylmethyl tauric acid sodium mixes as a wetting and dispersing agent and grinds in a pin mill. c) A dispersion concentrate which is readily dispersible in water is obtained by mixing 20 parts by weight of active compounds A + B with 6 parts by weight of alkylphenol polyglycol ether (© Triton X 207), 3 parts by weight of isotridecanol polyglycol ether (8 EO) and 71 parts by weight. Parts of paraffinic mineral oil (boiling range e.g. approx. 255 to 277 ° C.) and ground in a attritor to a fineness of less than 5 microns. d) An emulsifiable concentrate is obtained from 15 parts by weight of cyclohexanone as solvent and 10 parts by weight of oxyethylated nonylphenol as emulsifier. e) A water-dispersible granulate is obtained by adding 75 parts by weight of active compounds A + B,

10 parts by weight of calcium lignosulfonate,

5 parts by weight of sodium auryl sulfate,

3 parts by weight of polyvinyl alcohol and

7 parts by weight of kaolin are mixed, ground on a pin mill and the powder is granulated in a fluidized bed by spraying water as the granulating liquid. f) A water-dispersible granulate is also obtained by adding 25 parts by weight of active ingredients A + B

5 parts by weight of 2,2 ^{'-dinaphthylmethan-6,6'} disulfonate sodium, 2 parts by weight of sodium oleoylmethyltaurinate, 1 part by weight of polyvinyl alcohol, 17 parts by weight of calcium carbonate and 50 parts by weight of water were homogenized and pre-comminuted on a colloid mill, then ground on a bead mill and the suspension thus obtained was atomized and dried in a spray tower using a single-component nozzle.

Extruder granules are obtained by mixing 20 parts by weight of active ingredients A ₊ B, 3 parts by weight of sodium lignosulfonate, 1 part by weight of carboxymethyl cellulose and 76 parts by weight of kaolin, and grinding and moistening them with water. This mixture is extruded and then dried in an air stream.

2. Biological examples

The following examples were developed in the greenhouse and partly in field trials.

i) weed action in the pre-emergence

Seeds or rhizome pieces of monocotyledonous and dicotyledonous herb plants are placed in sandy loam in plastic pots 9 cm in diameter and covered with earth. Weeds found in rice cultivation are cultivated in soil saturated with water, with enough water being poured into the pots that the water is up to the surface of the soil or a few millimeters above it. The active compound combinations according to the invention formulated in the form of wettable powders or emulsion concentrates and, in parallel experiments, the correspondingly formulated individual active compounds are then applied as aqueous suspensions or as emulsions with a water application rate of the equivalent of 300 to 600 l / ha, in different dosages to the surface of the covering earth or poured into the irrigation water for rice. After the treatment, the pots are placed in the greenhouse and kept under good growth conditions (temperature, humidity, water supply) for the weeds. After the test plants had emerged, the plants or the damage caused by emergence were assessed visually after a test period of 3 to 4 weeks in comparison to untreated controls. The experiments are statistically repeated with multiple, up to five times. The herbicidal compositions according to the invention have good herbicidal pre-emergence activity against a broad spectrum of grasses and weeds.

ii) Post-emergence weed action

Seeds or rhizome pieces of monocotyledonous and dicotyledonous herb plants are placed in plastic pots in sandy loam soil, covered with soil and grown in the greenhouse under good growth conditions (temperature, air humidity, water supply). Weeds found in rice cultivation are cultivated in pots in which water is up to 2 cm above the surface of the soil. Three weeks after sowing, the test plants are treated at the three-leaf stage. The active compound combinations according to the invention formulated as wettable powder or emulsion concentrates and, in parallel tests, the correspondingly formulated individual active compounds are sprayed onto the green plant parts in various dosages with a water application rate of the equivalent of 300 to 600 l / ha, and after about 3 to 4 weeks of the test plants in the greenhouse under optimal conditions Growth conditions (temperature, humidity, water supply) rated the effect of the preparations visually in comparison to untreated controls. In the case of rice or weeds that occur in rice cultivation, the active ingredients are also added directly to the irrigation water (application in analogy to the so-called granulate application) or sprayed onto plants and the irrigation water. The experiments are repeated several times, up to five times. The herbicidal compositions according to the invention also have good post-emergence properties herbicidal activity against a broad spectrum of economically important grasses and weeds.

iii) field trials

Field trials are carried out on areas that are cultivated in practice with natural changes. After sowing or emergence of the culture / weeds / grasses, plots with about 20 to 1 Om ² and 2 to 4 repetitions are applied. Plot sprayers are used for this. The effects of the herbicide / combinations are assessed visually in the period from 1 to 8 weeks after application and the effects are recorded as a percentage (0-100%) compared to untreated control plots. The results represent mean values of the 2 to 4 repetitions for the respective herb / grass species.

iv) Evaluation of the combination effects in the examples

When evaluating the combination effects, the effect of the individual components is added and compared with the effectiveness of the mixtures of the same dosage. It was often found that the combinations showed higher efficiencies than the sum of the individual effects.

In cases with less clear effects, the expected value is calculated using the COLBY formula and compared with the empirically determined result. The calculated, theoretically expected efficiency of a combination is determined using the formula by SR Colby: "Calculation of synergistic and antagonistic responses of herbicide combinations", Weeds 15 (1967), pages 20 to 22. The formula for combinations of two is: XY E = X + Y

100

Synergistic effects can be assumed here if the empirical value is greater than the expected value. In the case of combinations with individual components of the same active ingredient, comparisons can also be made using the empirical formula.

In the majority of cases, however, the synergistic increase in activity is so high that the Colby criterion can be dispensed with; the effect of the combination then clearly exceeds the formal (numerical) sum of the effects of the individual substances.

It should be particularly pointed out that an assessment of the synergism with the active ingredients used here must take into account the widely differing application rates of the individual active ingredients. It is therefore not sensible to compare the effects of the active ingredient combinations and the individual active ingredients in each case with the same expenditure. The amounts of active ingredient to be saved according to the invention can only be recognized by the superadditive increase in activity when the combined application rates are used or by the reduction in the amount of expenditure of both individual active ingredients in the combinations in comparison to the individual active ingredients with the same effect in each case.

Special test examples

In the tables below, the following applies: g ai / ha = grams of active ingredient per hectare

Expected values for the herbicide combinations are given in brackets. Table 1: Ethoxysulfuron + fentrazamide (B1)

Damage (%) in g ai / ha rice Sagittaria pygmaea

A) Ethoxysulfuron 30 6 85

B) fentrazamide 200 0 80

100 0 40

50 0 0

A + E i) 30 + 50 2 9 933 (85 + 0)

Greenhouse trial: treatment in 1-2 leaf stages. Rating: 20 days after application

Table 2: Ethoxysulfuron + Azimsulfuron (B23)

Damage (%) in g ai / ha rice Cyperus serotinus

A) Ethoxysulfuron 21 5 0

42 8 40

B) Azimsulfuron 6 8 30

12 10 40

A + B 21 +6 8 75 (0 + 30)

Field trial: treatment in 2 -3 leaf stage. Rating: 28 days after application Table 3: Ethoxysulfuron + (Pentoxazone) (B 28)

Damage (%) in g ai / ha rice Lindernia pyxidaria

A) Ethoxysulfuron 20 4 60

B) Pentoxazone 150 6 25

A + B) 20 + 150 5 90 (60 + 25)

Field trial: Treatment in 1 leaf stage. Rating: 43 days after application

Table 4: Ethoxysulfuron + Oxaziclomefone (B 30)

Damage (%) in g ai / ha rice Cyperus serotinus

A) Ethoxysulfuron 60 20 85

30 5 75

B) Oxaziclomefone200 5 95

100 0 80

50 0 10

A + B 30 + 50 5 98 (75 + 10)

Greenhouse trial: Treatment in 2 - 4 leaf stage Rating: 20 days after application Table 5: Ethoxysulfuron + Clefoxidim (B6)

Damage (%) in g ai / ha rice Echinochloa

A) Ethoxysulfuron 30 7 55

15 6 50

7.5 5 35

B) Clefoxidim 75 0 83

37 0 10

18 0 0

A + B) 7.5 + 18 5 45 (35 + 0)

30 + 18 6 75 (55 + 0)

7.5 + 37 5 80 (35 + 10)

30 + 37 6 85 (55 + 10)

Greenhouse trial: Treatment in 2 - 4 leaf stage Rating: 20 days after application

Table 6: Ethoxysulfuron + KIH 2023 (B 20)

Damage (%) in g ai / ha rice Echinochloa gens galli

A) Ethoxysulfuron 3 300 6 6 55 1 155 5 5 50 7 7., 55 5 5 35

B) KIH 2023 7 755 5 5 30 3 388 0 0 15

1 188 0 0 0 9 9 0 0 0

A + B) 77 7 ,,, 555 +++ 999 00 0 5555 (35 + 0)

Greenhouse trial: treatment in 2 leaf stages. Rating: 22 days after application

Table 7: Ethoxysulfuron + Oxadiargyl (B21)

Damage (%) in g ai / ha rice Cyperus serotinus

A) Ethoxysulfuron 30 7 80

15 6 70

7.5 5 35

B) Oxadiargyl 50 3 45

A + B) 7.5 + 50 4 85 (35 + 45) Greenhouse trial: Treatment in 1 - 2 leaf stage Rating: 21 days after application

Table 8: Ethoxysulfuron + KIH 6127 (B7)

Damage (%) in g ai / ha rice Cyperus serotinus

A) Ethoxysulfuron 30 7 80

15 6 70

7.5 5 35

B) KIH 6127 30 4 55

A + B) 7.5 5 93 (35 + 55)

Greenhouse trial: Treatment in 1 - 2 leaf stage Rating: 21 days after application

Table 9: Ethoxysulfuron + Tritosulfuron (B11)

Damage (%) in g ai / ha rice Monocharia vaginalis

A) ethoxysulfuron 7.5 0 32

15 0 96

B) Tritosulfuron 37.5 0 26

75 0 38

A + B) 7.5 + 37.5 0 98 (32 + 26) Field trial: Treatment in 2 - 4 leaf stage Rating: 28 days after application

Table 10: Ethoxysulfuron + Clomazone (B19)

Damage (%) in g ai / ha rice Aeschynomene rudis

A) Ethoxysulfuron 45 0 50

60 0 57

B) Clomazone 200 0 10

400 0 20

800 0 45

A + B 60 + 200 0 75 (57 + 10)

60 + 400 0 80 (57 + 20)

45 + 800 0 97 (50 + 15)

Field trial: pre-emergence rating: 53 days after application

Table 1 1: Ethoxysulfuron + Nicusulfuron (B24)

Damage (%) in

g ai / ha rice Echinochloa crus galli

A) Ethoxysulfuron 45 0 25

22.5 0 0

B) Nicosulfuron 30 15 83

15 12 65

A + B 45 + 15 12 93 (25 + 65)

27.5 +30 15 91 (0 + 83)

Field trial: Treatment in the 2-4 leaf stage Rating: 28 days after application

The examples show that the individual active ingredients can only be used to combat harmful plants with high doses. The combination partners applied in low doses usually show only a small, far from the effectiveness required in practice. Good effects against all tested harmful plants can only be achieved by using the active ingredients together. The additive effect from the individual components was clearly exceeded, i. that is, the required level of control is achieved by significantly lower application rates. These effects make the spectrum of activity significantly wider.

The cultural compatibility, assessed in the form of damage, is not adversely affected, i. H. that the combinations can be rated as fully selective.

Claims

claims 1. Containing herbicidal compositions A) one or more herbicidal active compounds from the group of the substituted phenoxysulfonylureas of the formula I and their salts

and B) one or more herbicidally active compounds from the group of Connections, which consists of Ba) selectively in rice herbicidal herbicides selected from the group consisting of fentrazamide (NBA 061), haloxyfop, setoxydim, dithiopyr, clefoxidim, KIH 6127 and clethodim, Bb) selectively in rice herbicides active mainly against dicotyledonous harmful plants and cyperaceae, selected from the group consisting of 2,4-D, MCPA, mecoprop, mecoprop-P, tritosulfuron, halosulfuron-methyl, dicamba, acifluorfen, carfentrazone, bentazone and triclopyr , Bc) selectively in rice, predominantly herbicides active against grasses and dicotyledonous harmful plants and cyperaceae, selected from the group consisting of pendimethalin, clomazone, KIH 2023, oxadiargyl, cyclosulfamuron (AC 322, 140), azimsulfuron (DPX-A-8947), nicosulfuron , Ciπmethylin, Indanofan, Pentoxazone, Pyribenzoxim, Oxaziclomefone (MY-100), Fluthiamid and Mesotrione. _Second Herbicidal agents after. Claim 1, characterized in that they have a synergistically effective content of a combination of the compounds of the formula I or their salts (type A compound) with compounds from group B. 3. Herbicidal compositions according to one or more of the preceding claims, characterized in that they contain the compounds of formula 1 or their salts (type A compounds) and the compounds from group B in a weight ratio of 1: 20000 to 200: 1 , preferably 1: 8000 to 100: 1, particularly preferably 1: 4000 to 50: 1. 4. Herbicidal compositions according to one or more of the preceding claims, characterized in that they contain one or more further components from the group comprising other types of pesticide active ingredients, safener active ingredients, additives and formulation auxiliaries customary in crop protection. 5. A method of combating harmful plants, characterized in that the herbicides of the herbicidal compositions, defined according to one or more of claims 1 to 4, together or separately in the pre-emergence, post-emergence or in the pre-and post-emergence on the plants, plant parts, plant seeds or applied the acreage. 6. The method according to claim 5 for the selective control of harmful plants in plant crops. 7. The method according to claim 6 for controlling harmful plants in rice. 8. Use of the herbicidal compositions according to one of claims 1 to 4 for controlling harmful plants. 9. Use according to claim 8 for combating harmful plants in rice culture. 10. A process for the preparation of herbicidal compositions, defined according to one or more of claims 1 to 4, wherein the compound (eπ) of formula I or its salts (type A compounds) with one or more compounds of type B analogous to a conventional crop protection formulation from the group containing wettable powders, emulsifiable concentrates, aqueous solutions, emulsions, sprayable solutions (tank mix), dispersions based on oil or water, suspoemulsions, dusts, granules for soil or litter application, water-dispersible granules, ULV formulations, microcapsules and waxes , be formulated.