KR20010079532A - 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

Herbicides containing substituted phenoxysulfonylureas {HERBICIDAL AGENTS WITH SUBSTITUTED PHENOXYSULFONYLUREAS}

Italian Patent No. 127 09 85 discloses a herbicide composition comprising an effective amount of substituted phenoxysulfonylurea combined with a herbicide active ingredient.

In particular rice has some economically important monocotyledonous weeds, for example mainly Echinoloclus crs-Gali, which cannot be controlled to a satisfactory level using the currently known rice herbicides alone or in mixtures thereof. ( Echinochloa crus-galli ), Ischaemum species or Leptochloa . Also from the world's rice cultivation systems, by sprouting mainly from perennial organs in the soil, harmful plants are more difficult to control than weeds germinating from seeds, eg Sagittaria spp., Eleocharis Species (e.g., Eleocharis kuroguwai ), Cyperus serotinus , Scirpus juncoides and other harmful plants, and also optimal across the entire species range It is known that broad-leaved weed species are not easy to exhibit control effects. In addition, resistant species (eg Cyperus species or Echinochloa species) that are often no longer controlled using individual active ingredients or even conventional combinations are on the rise.

In the context of the prior art indicated and discussed herein, it is an object of the present invention to control a range of weeds or individual weed species that are difficult to control in rice by one application of the herbicide to be herbicide or a small number of applications. It is to provide a mixture having a herbicidal activity to enable.

FIELD OF THE INVENTION The present invention relates to the technical field of crop protection compositions, and in particular to weeds, in particular weed grass, dicotyledonous weed and / or cyperaceous, found in rice, which has been difficult to control using individual herbicides to date in rice or genetically modified cultivated rice. A herbicidal composition comprising certain phenoxysulfonylureas and / or salts thereof which are very suitable for controlling weeds.

Surprisingly, it has been found that this object is achieved in particular by a herbicide composition having the features of claim 1 below. Therefore, the present invention

(A) at least one herbicide component selected from the group consisting of substituted phenoxysulfonylureas of formula (I) and salts thereof:

; And

(B) (Ba) fentrazamid (NBA 061), haloxyfop, sethoxydim, dithiopyr, etobenzanid, clepoxydim ( clefoxidim, KIH 6127 and herbicides selectively effective against weed grass, mainly in rice, selected from the group consisting of clethodim,

(Bb) 2,4-D, MCPA, mecoprop, mecoprop-P, tritosulfuron, halosulfuron-methyl, dicamba, acifluorfen, carpent Herbicides selectively effective against harmful dicotyledonous plants and harmful roomworm plants in rice, selected from the group consisting of carfentrazone, bentazon and triclopyr, and

(Bc) pendimethalin (pendimethalin), clomazone, KIH 2023, oxadiargyl, cyclosulfamuron (AC 322, 140), azimsulfuron (DPX-A -8947), nicosulfuron, cinmethylin, indanofan, indanofan, pentoxazone, pyribenzoxim, oxaziclomefone (MY-100), Selectively effective herbicides for weeds, harmful dicotyledonous plants, and harmful roomworm plants in rice, selected from the group consisting of fluthiamid and mesotrione

It provides a herbicide composition comprising at least one herbicide active compound selected from the group consisting of.

By using a novel combination of herbicide active ingredients of the above groups (A) and (B), it is very advantageous for those who wish to weed a certain kind of weeds, including individual species that are difficult to control, to a very favorable level.

In addition, this combination of the invention provides a more economical solution for the user because it can significantly reduce the spread of the individual co-components present in the formulation.

Finally, the herbicidal compositions of the present invention may surprisingly exhibit significant levels of synergistic activity as they exhibit increased activity above expected levels. In addition, it can exhibit excellent control effects against a number of resistant species.

Compounds of formula (I) may be formed into salts by replacing the hydrogen of the —SO ₂ —NH— group with an agriculturally appropriate cation. Examples of such salts include metal salts, in particular alkali metal salts (eg Na or K salts), alkaline earth metal salts, or other ammonium salts or salts of organic amines. Salts can also be formed by adding strong acids to the heterocyclic moieties of the compound of formula (I). Examples of suitable acids include HCl, HNO ₃ , trichloroacetic acid, acetic acid and palmitic acid. As a particularly advantageous compound, the salts of the herbicides of formula (I) are formed by replacing the hydrogen of the -SO ₂ -NH- group with a cation, preferably sodium, selected from the group consisting of alkali metals, alkaline earth metals and ammonium.

Although the compounds of the formula (I) are not individually indicated in the formula, if they contain one or more asymmetric carbon atoms or double bonds, these compounds also belong to the group (A) compounds. Possible stereoisomers, such as enantiomers, diastereomers and Z and E isomers, defined by their particular spatial form, are all included in the compounds of Formula (I), obtained from conventional mixtures of these stereoisomers or Or alternatively it can be prepared by stereoselective reaction with a stereochemically pure starting material. Thus, according to the invention, the stereoisomers or mixtures thereof in pure form can be used.

The phenoxysulfonylurea of the general formula (I) is generally included in, for example, the general formula I disclosed in Italian Patent No. 127 09 85, which also discloses that the phenoxysulfonylurea is a herbicide for use in agricultural plants. Is said to be suitable as a synergistic partner. However, the fact that certain phenoxysulfonylureas of group (A) is well suited as co-components in synergistic mixtures with other herbicides that may be used in rice cannot be derived from the prior art. In particular, the cited patent document does not mention at all that the combination of the compound of the group (A) and the herbicides for the rice of the group (B) shows a surprising effect in controlling the major harmful plants in cultivated rice. In this connection, it should also be particularly noted that the activity of the formulation in cultivated rice cannot be deduced from the effects of the use of the formulation in other cultivated plants. Although the compounds of group (A) are suitable for themselves to control harmful plants in rice, it is predictable whether the combination of these compounds with other rice herbicides will show an increase in weed control activity that exceeds the additional activity. Is impossible at all.

Preferred co-components belonging to the (A) group are described in particular in Pesticide Manual, British Crop Protection Council, 11th Ed., Pp. 488-489, 1997, an ethoxysulfuron of formula A1, i.e. 1- (2-ethoxyphenoxysulfonyl) -3- (4,6-dimethoxy-2-pyrimidinyl) urea:

The compound is preferably used as the sole active ingredient of group (A) and may be combined with one or more herbicide active compounds of group (B).

Certain sulfonylureas of group (A), in particular compounds of formula (A1) in combination with other herbicides of group (B), are well suited for effectively controlling weed species in cultivated rice that is difficult to control. In this regard, certain unintended effects are obtained, in particular in terms of activity against resistant weeds.

However, the co-components of group (B) are typically herbicides, selected according to certain criteria. For example, they all contain herbicides that have a selective effect on unwanted plants in rice. Harmful plants to be controlled in this regard include, in particular, weed grass and dicotyledonous / animalous plants. As used herein, the expression "dicotyledonous / arachnoidaceae" is intended to indicate the fact that it has activity against both dicotyledonous and astrocytes but is better at dicotyledonous plants.

Conventional herbicides of group (B) can be classified based on the plants to be controlled according to their activity. That is, one subgroup of herbicides of group (B) is mainly or almost exclusively active against weed grass (subgroup (Ba)), and another subgroup is mainly active against dicotyledonous and roomy plants (sub) Group (Bb)), another subgroup, shows activity against both weed grass and dicotyledonous / animalous plants (subgroup (Bc)).

The optimum range of activity of the combinations of the present invention is obtained by enhancing the herbicide properties of the compounds of the group (A) and adding other properties, thus increasing the activity on harmful plants belonging to different target groups. have.

Also in a particularly advantageous embodiment, the herbicide active mixtures of the present invention are herbicides of group (B), which are selectively active against weeds in rice and are (B1), (B2), (B3), (B4), ( At least one herbicide selected from the group (Ba) consisting of B5), (B6), (B7) and (B7a):

(B1) NBA 061-pentrazamide or BAY YRC 2388

4- (2-Chlorophenyl) -5-oxo-4,5-dihydrotetrazole-1-carboxylic acid cyclohexylethyl amide (Conference volume: The 1997 Brighton Crop Protection Conference, Weeds, Brithsh Crop Protection Council, pp 67-68);

(B2) halooxypop

(±) -2- [4-[[3-chloro-5- (trifluoromethyl) -2-pyridinyl] oxo] phenoxy] propionic acid, in particular halox-ethyl, halox-methyl, halo Use forms of oxypop-methyl [(R) isomers) (known from Pesticide Manual, 10th Ed., Pp. 551-554, 1994);

(B3) cetoxydim

(±)-(EZ) -2- (1-ethoxyiminobutyl) -5- [2- (ethylthio) propyl] -3-hydroxycyclohex-2-enone (Pesticide Manual, 11th Ed. , pp. 1101-1103, 1997);

(B4) dithiopyr

S, S'-dimethyl 2-difluoromethyl-4-isobutyl-6-trifluoromethylpyridine-3,5-dicarbothioate (Pesticide Manual, 11th Ed., Pp. 442-443, 1997);

(B5) etobenzanide = MY-52

2 ', 3'-dichloro-4-ethoxymethoxybenzanilide (see Pesticide Manual, 11th Ed., Pp. 492-493, 1997);

(B6) clepoxysid = BAS 625 H

2- [1- (2- (4-chlorophenoxy) propoxyimino) butyl] -3-oxo-5-thione-3-yl-cyclohex-1-enol (AG Chem, New Compound Review, Agranova, vol. 17, p. 26, 1999);

(B7) KIH 6127 = pyriminobak-methyl

Methyl 2- (4,6-dimethoxy-2-pyrimidinyloxy) -6- (1-methoxyiminoethyl) benzoate, also present as an acid or sodium salt (Pesticide Manual, 11th Ed., pp. 1071-1072, 1997); And

(B7a) Cletodim

(±) -2-[(E)-[(E) -3-chloroallyloxyimino] propyl] -5- [2- (ethylthio) propyl] -3-hydroxycyclohex-2-enone (Pesticide Manual, 11th Ed., Pp. 250-251, 1997).

Representative compounds of the above (Ba) group have somewhat different chemical structures, but nevertheless they are in close subgroups based on their range of activity and the fact that they act as synergists for the compounds of the (A) group To form.

It is also selectively active against dicotyledonous plants and, in some cases, room plants, in the rice plants, and the following (B8), (B9), (B10), (B11), (B12), (B13), (B14), (B15), Of particular note is a herbicide composition comprising at least one compound selected from the group consisting of (B16) and (B17) (compounds of subgroups (Bb)) as compounds of group (B):

(B8) 2,4-D

(2,4-dichlorophenoxy) acetic acid, a frequently used form is 2,4-D-butotyl, 2,4-D-butyl, 2,4-D-dimethylammonium, 2,4-D-diolamine , 2,4-D-isooctyl, 2,4-D-isopropyl, 2,4-D-trolamine (see Pesticide Manual, 10th Ed., Pp. 271-273, 1994);

(B9) MCPA

(4-Chloro-2-methylphenoxy) acetic acid, mainly used forms include MCPA-butotyl, MCPA-dimethylammonium, MCPA-isoctyl, MCPA-potassium, MCPA-sodium (Pesticide Manual, 10th Ed., Pp. 638-640, 1994);

(B10) mekoplop, mekoplop-P

(RS) -2- (4-chloro-o-tolyloxy) propionic acid, (R) -2- (4-chloro-o-tolyloxy) propionic acid (Pesticide Manual, 10th Ed., Pp. 646-647 And 647-648, 1994);

(B11) tritosulfuron

N-[[[4-methoxy-6- (trifluoromethyl) -1,3,5-triazin-2-yl] amino] carbonyl] -2- (trifluoromethylbenzenesulfonamide) ( See AG Chem, New Compound Review, Agranova, vol. 17, p. 24, 1999);

(B12) halosulfuron-methyl

Methyl 3-chloro-5- (4,6-dimethoxypyrimidin-2-ylcarbamoylsulfamoyl) -1-methylpyrazole-4-carboxylate (Pesticide Manual, 11th Ed., Pp. 657 -659, 1997);

(B13) Dicamba

3,6-dichloro-O-anisic acid, in particular dicamba-dimethylammonium, dicamba-potassium, dicamba-sodium, dicamba-trolamine (Pesticide Manual, 10th Ed., Pp. 298- 300, 1994);

(B14) acifluorfen

It is also used as 5- (2-chloro-α, α, α-trifluoro-p-tolyloxy) -2-nitrobenzoic acid, asifluorophene-sodium (Pesticide Manual, 10th Ed., Pp. 12- 13, 1994);

(B15) carpentrazone

Ethyl (RS) -2-chloro-3- [2-chloro-5- (4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-tria Zol-1-yl) -4-fluorophenyl] propionate, in particular carpentrazone-ethyl (as indicated) or else as an acid (Pesticide Manual, 11th Ed., Pp. 191-193 , 1997);

(B16) Ventazone

3-isopropyl-1H-2,1,3-benzothiadiazine-4 (3H) -one 2,2-dioxide (see Pesticide Manual, 10th Ed., Pp. 90-91, 1994); And

(B17) triclopyr

[(3,5,6-trichloro-2-pyridyl) oxy] acetic acid, preferably in the form of triclopyr, triclopyr-butotyl, triclopyr-triethylammonium (Pesticide Manual, 10th Ed., Pp. 1015-1017, 1994).

In another preferred embodiment of the present invention, the herbicide active combination is (B18), (B19), (B20), (B21), (B22), (B23), (B24), (B26), (B27) At least one herbicide selectively active against weeds and dicotyledonous / animalous plants in rice, selected from the group consisting of (B28), (B29), (B30), (B31) and (B32) As herbicides include:

(B18) pendimethalin

N- (1-ethylpropyl) -2,6-dinitro-3,4-xyldine (see Pesticide Manual, 10th Ed., Pp. 779-780, 1994);

(B19) clomazone

2- (2-chlorophenyl) -4,4-dimethyl-3-isoxazolidinone (see Pesticide Manual, 10th Ed., Pp. 220-221, 1994);

(B20) KIH 2023

Sodium 2,6-bis [(4,6-dimethoxypyrimidin-2-yl) oxy] benzoate, preferred form is sodium salt (see Pesticide Manual, 10th Ed., P. 620, 1994) );

(B21) oxadiaryl

5-tert-butyl-3- [2,4-dichloro-5- (prop-2-ynyloxy) phenyl] -1,3,4-oxadiazol-2 (3H) -one (Pesticide Manual, 11th Ed., Pp. 904-905, 1997);

(B22) AC 322,140 = cyclosulfamuron

N-[[[2- (cyclopropylcarbonyl) phenyl] amino] sulfonyl] -N1- (4,6-dimethoxypyrimidin-2-yl) urea (Pesticide Manual, 10th Ed., Pp 8-9, 1994);

(B23) Azimsulfuron (DPX-A8947)

1- (4,6-dimethoxypyrimidin-2-yl) -3- [1-methyl-4- (2-methyl-2H-tetrazol-5-yl) pyrazol-5-yl] sulfonyl Urea (see Pesticide Manual, 11th Ed., Pp. 63-65, 1997);

(B24) Nicosulfuron

1- (4,6-dimethoxypyrimidin-2-yl) -3- (3-dimethylcarbamoyl-2-pyridylsulfonyl) urea (Pesticide Manual, 10th Ed., Pp. 734-735, 1994);

(B26) cinmethylline

(1RS, 25R, 4SR) -1,4-ethoxy-p-ment-2-yl 2-methylbenzyl ether (see Pesticide Manual, 11th Ed., Pp. 246-248, 1997);

(B27) indanopan

(RS) -2- [2- (3-chlorophenyl) -2,3-epoxypropyl] ethylindan-1,3-dione (see Pesticide Manual, 11th Ed., P. 715, 1997);

(B28) pentoxazone

3- (4-chloro-5-cyclopentyloxy-2-fluorophenyl) -5-isopropylidene-1,3-oxazolidine-2,4-dione (Pesticide Manual, 11th Ed., Pp 942-943, 1997);

(B29) LGC-40863 = pyribensimsim

Benzophenone O- [2,6-bis [(4,6-dimethoxy-2-pyrimidinyl) oxy] benzoyl] oxime (Conference volume: The 1997 Brighton Crop Protection Conference, Weeds, British Crop Protection Council, pp. 39-40);

(B30) Oxazillomethone = MY100

3- [1- (3,5-dichlorophenyl) -1-methylethyl] -2,3-dihydro-6-methyl-5-phenyl-4H-1,3-oxazim-4-one [Conference volume : The 1997 Brighton Crop Protection Conference, Weeds, British Crop Protection Council, pp. 73-74);

(B31) flutiamide = BAY FOE 5043

4'-fluoro-N-isopropyl-2- (5-trifluoromethyl-1,3,4-thiadiazol-2-yloxy) acetanilide (Pesticide Manual, 11th Ed., Pp 82-83, 1997); And

(B32) mesotrione

2- [4- (methylsulfonyl) -2-nitrobenzoyl] -1,3-cyclohexanedione (see AG Chem, New Compound Review, Agranova, vol. 16, p. 51, 1998).

The compounds of the above (B1) to (B24) and (B26) to (B32) are known, for example, from the references indicated for the respective compounds, and are specifically combined with the compounds of the group (A) of the present invention. And herbicides having selective activity in rice, including genetically modified rice. In some cases, in addition to the base material in which the formula is illustrated, variants of the base material which are likewise modified in a manner which can be used in the present invention are commonly used. Where their optically active forms in the compounds of group (B) are conventional, those forms of the compounds likewise fall within the scope of the invention, and in some cases these forms are shown together (methopprop and mecoprop-P). Etc).

The combination of the active ingredients of group (A) + group (B) shows a hyperadditive effect. In other words, in controlling harmful plants to a certain level, the use of the herbicide compositions of the present invention can reduce the spread and / or increase the stability limit for cultivated rice. These effects are both economically and environmentally significant. The content of the components of group (A) and of the components of group (B) to be used, the ratio of the components of (A) :( B), and their sequential spreading order depend on a wide range of factors, for example, the formulation selected. Is selected.

Of particular importance among these factors are the nature of the co-components, the stage of development of broad-leaved weeds or weeds, the types of weeds to be controlled, environmental factors, climatic conditions and soil conditions.

In a particularly preferred embodiment according to the invention, the herbicide composition of the invention comprises a synergistically effective amount of a compound of formula (I) or a salt thereof (a compound of group (A)) and a combination of a compound of group (B). In this regard, among other things, synergistic effects are readily demonstrated in all cases, for example for the reason that individual compounds are usually used in the formulation in very different spreads or that harmful plants are already very well controlled by the individual compounds. It is important to note that the herbicidal compositions of the present invention generally exhibit synergistic activity, even in the case of formulations with inadequate spread or weight ratios of (A) :( B).

The spraying dose of the herbicides belonging to the group (A) is generally 1 to 120 g ai / ha (where ai = the spraying amount based on the active ingredient, ie the active ingredient), preferably 5 to 90 g ai / ha.

As with the above spreading amount, the weight ratio of (A) :( B) in the blended herbicide may vary within a wide range as described above. The range (weight / weight) of the spraying ratio of (A) :( B) according to the present invention is from 1: 20,000 to about 200: 1. In the context of the present invention, a composition comprising a compound of formula (I) or a salt thereof (a compound of group (A)) and a compound of group (B) in a weight ratio of 1: 8,000 to 100: 1 is preferred. Particularly preferred compositions are compositions having a spreading ratio of (A) :( B) in a ratio of 1: 4,000 to 50: 1. (B) Details of the various herbicides of the group are as follows. That is, the following spraying quantity and weight ratio ((A) :( B)) are used preferably.

The active ingredient combination of the present invention is present as a blended blend of the two ingredients and is then usually sprayed with aqueous dilution or as a tank mix prepared by diluting the individually formulated ingredients together with water. Can be. The active ingredients of groups (A) and (B) can be formulated in a variety of ways depending on the prevailing biological and / or physicochemical parameters.

The following are examples of possible suitable formulations:

Wettable powder (WP), emulsifiable concentrate (EC), water soluble powder (SP), water soluble concentrate (SL), concentrated emulsion (EW) (e.g. oil-in-water emulsion and water-in-oil emulsion), spray solutions Or spray emulsions, capsule suspensions (CS), oil-based or aqueous dispersions (SC), suspoemulsions, suspension concentrates, dust (DP), oil-miscible solutions (OL), dressing agents (dressing agent), granules (GR) (eg granules in the form of microgranules, spray granules, coated granules and adsorbent granules), granules for spraying or soil application, water soluble granules (SG), water dispersible granules (WG) , Thickening agent (ULV) formulations, microcapsules and waxes.

Of these, water-soluble wettable powder (WP), water dispersible granules (WG), water-soluble granules (EC), suspo emulsions (SE) and oil suspension concentrates (SC) are preferred.

Individual types of such formulations are generally known and described, for example, in Vinnacker-Kuchler, "Chemische Technologie", Vol. 7, C. Hauser Verlag Munich, 4th Edition, 1986, by Wade van Valkenburg ("Pesticide Formulations", Marcel Dekker, NY, 1973) and by K. Martens [" Spray Drying Handbook ", 3rd Ed., G. Goodwin Ltd., London, 1979.

Essential formulation aids such as inerts, surfactants, solvents and other additives are also known and described, for example, in Watkins, "Handbook of Insecticide Dust Diluents and Carriers," 2nd Ed., Darland Books, Caldwell, NJ. ], Hv Olphen, "Introduction to Clay Colloid Chemistry", 2nd Ed., J. Wiley & Sons, NY, C. Marsden, "Solvents Guide", 2nd Ed., Interscience, NY, 1963, McCutcheon, "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", Wiss. Verlagsgesellschaft, Stuttgart, 1976 and by Binnacker-Quickler, "Chemische Technologie", Vol. 7, C. Hauser Verlag Munich, 4th Ed., 1986.

Based on these formulations, but also in ready-to-apply formulations or in tank mixes, other pesticides, herbicides, insecticides, fungicides and detoxifiers, and also emollients, fertilizers and Combinations with growth regulators may also be prepared.

Particularly advantageously the herbicide compositions of the present invention comprise one or more compounds of formula (I) or salts thereof (compounds of group (A)) together with one or more compounds of group (B), which are water soluble wettable powders (WP), water dispersible granules (WDG). ), Water-emulsifiable granules (WEG), suspo-emulsions (SE), and oil suspension concentrates (SC).

Wettable powders may be uniformly dispersed in water and, in addition to the active compounds and diluents or inerts, to ionic and / or nonionic surfactants (wetting agents, dispersants), for example polyethoxylated alkyl phenols, poly Toxylated Fatty Alcohols, Polyethoxylated Fatty Amines, Fatty Alcohol Polyglycol Ether Sulfates, Alkalsulfonates, Alkylarylsulfonates, Sodium Ligninsulfonates, Sodium 2,2'-Dinaphthylmethane-6,6'-Di Preparations comprising sulfonate, sodium dibutylnaphthalenesulfonate or sodium oleoylmethyltaurate.

Emulsifiable concentrates may contain organic solvents such as butanol, cyclohexanone, dimethylformamide, xylene or other high boiling aromatic compounds or hydrocarbons with the addition of one or more ionic and / or nonionic surfactants (emulsifiers). It is prepared by dissolving the active ingredient in the. Examples of emulsifiers that can be used are calcium alkylarylsulfonates such as Ca dodecylbenzenesulfonate, or fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide concentrated products (e.g. Non-ionic emulsifiers such as block copolymers), alkyl polyethers, sorbitan fatty acid esters, polyoxyethylene sorbitan esters or other polyoxyethylene sorbitan esters.

Dust is obtained by grinding the active ingredient or ingredients together with finely ground material, such as talc, natural clays (eg kaolin, bentonite and pyrophyllite) or diatomaceous earth.

The granules are evenly sprayed onto the adsorbent granulated inert material or the concentrate of the active ingredient is sand, kaolinite or granules in the presence of a binder such as, for example, polyvinyl alcohol, sodium polyacrylate or mineral oil. It can be prepared by applying to the surface of the carrier such as oxidized inert material. Water dispersible granules are generally prepared by conventional methods such as spray drying, fluid bed granulation, disk granulation, mixing using a high speed mixer, and extrusion without solid inertness. Suitable active ingredients can also be granulated in a conventional manner for preparing fertilizer granules, optionally in the form of a mixture with fertilizers.

The agrochemical formulations of the present invention generally contain, in addition to conventional formulation aids, from 0.1 to 99% by weight, in particular from 2 to 95% by weight, very preferably from 3 to 92% by weight of the active ingredients of groups (A) and (B) Contains them.

Depending on the dosage form, the concentrations of the active ingredients (A) + (B) may be different. The concentration of the active ingredients in the wettable powder is, for example, about 10 to 95% by weight and makes up 100% by weight with other ingredients consisting of conventional formulation components. In emulsifiable concentrates, the concentration of the active ingredients is about 1 to 85% by weight, preferably 5 to 80% by weight. The dust formulation comprises about 1 to 25% by weight, typically 5 to 20% by weight of active ingredient and the spray solution comprises about 0.2 to 25% by weight, preferably 2 to 20% by weight of active ingredient. In the case of granules such as water dispersible granules, the content of the active ingredient depends in part on whether the active compound is in liquid form or in solid form, and in part also on the granulation aids, fertilizers and the like used. In the case of water dispersible granules, the content of the active ingredient is generally from 10 to 90% by weight.

In addition, the formulations of the active ingredients may each comprise conventional tackifiers, wetting agents, dispersants, emulsifiers, penetrants, preservatives, cryoprotectants, solvents, fillers, colorants, carriers, antifoams, evaporation inhibitors, pH regulators and viscosity regulators.

Since the compounding quantity of the compound (A) compound + (B) of this invention has a comparatively small spreading amount, these compatibility is generally very favorable. In particular, the spraying amount of the combination of the present invention is absolutely less than the spraying amount of the individual spraying of the herbicide active ingredient. However, in some cases, it is advantageous to spray the formulations of the invention as a mixture with emollients or antidotes over time to further increase the safety and / or selectivity of the herbicide formulations of the invention. Compounds suitable as emollients or detoxifiers in the formulations of the invention are described, for example, in EP-A-333 131 (ZA-89 / 1960), EP-A-269 806 (US Pat. No. 4,891,057). ) And EP-A-346 620 (Australian Patent Application No. 89/34951), and International Patent Application No. PCT / EP90 / 01966 (Patent Publication WO91 / 08202) and International Patent Application No. PCT / EP90 / 02020 (Patent Publication WO 91/07874), and the documents cited therein, or can be prepared by the methods disclosed in these patent documents. Other suitable emollients are EP-A-94 349 (US Pat. No. 4,902,304), EP-A-191 736 (US Pat. No. 4,881,966) and EP-A-0 492 366, and Known from the documents cited therein.

Advantageously, the herbicide mixtures or combinations of the present invention further comprise one or more compounds (C) which act as emollients.

Particularly preferred antidotes or emollients, or groups of compounds suitable as emollients or detoxifiers in the aforementioned product combinations of the present invention, include the compounds of (a) to (i):

(a) a compound of the dichlorophenylpyrazoline-3-carboxylic acid type, preferably ethyl 1- (2,4) as described in WO 91/07874 (Patent Application PCT / EP90 / 02020) Compounds such as -dichlorophenyl) -5- (ethoxycarbonyl) -5-methyl-2-pyrazoline-3-carboxylate (Compound C1-1) and related compounds;

(b) derivatives of dichlorophenylpyrazolecarboxylic acid as described in EP-A-0 333 131 and EP-A-0 269 806, preferably ethyl 1- (2,4- Dichlorophenyl) -5-methylpyrazole-3-carboxylate (Compound C1-2), ethyl 1- (2,4-dichlorophenyl) -5-isopropylpyrazole-3-carboxylate (Compound C1-3) , Ethyl 1- (2,4-dichlorophenyl) -5- (1,1-dimethylethyl) pyrazole-3-carboxylate (compound C1-4), ethyl 1- (2,4-dichlorophenyl) -5 Compounds such as -phenylpyrazole-3-carboxylate (compound C1-5) and related compounds;

(c) compounds of the triazolecarboxylic acid type as described in EP-A-0 174 562 and EP-A-0 346 620, preferably ethyl 1- (2,4-dichlorophenyl Compounds such as) -5-trichloromethyl- (1H) -1,2,4-triazole-3-carboxylate (compound C1-6, fenchlorazole) and related compounds;

(d) compounds of the dichlorobenzyl-2-isoxazolin-3-carboxylic acid type, 5-benzyl-2- as described in WO 91/08202 (patent application PCT / EP90 / 01966); Isoxazolin-3-carboxylic acid type or 5-phenyl-2-isoxazolin-3-carboxylic acid type compound, preferably ethyl 5- (2,4-dichlorobenzyl) -2-isoxazolin-3-carboxyl Compounds such as late (compound C1-7) or ethyl 5-phenyl-2-isoxazolin-3-carboxylate (compound C1-8) and related compounds;

(e) as described in European Patent Application EP-A-0 086 750, EP-A-0 094 349, EP-A-0 191 736 or EP-A-0 492 366 Compounds of the 8-quinolinoxyacetic acid type, preferably 1-methylhex-1-yl (5-chloro-8-quinolinoxy) acetate (C2-1), 1,3-dimethylbut-1-yl (5- Chloro-8-quinolinoxy) acetate (C2-2), 4-allyloxybutyl (5-chloro-8-quinolinoxy) acetate (C2-3), 1-allyloxyprop-2-yl (5-chloro -8-quinolineoxy) acetate (C2-4), ethyl (5-chloro-8-quinolineoxy) acetate (C2-5), methyl (5-chloro-8-quinolineoxy) acetate (C2-6), allyl (5-chloro-8-quinolineoxy) acetate (C2-7), 2- (2-propylideneiminooxy) -1-ethyl (5-chloro-8-quinolineoxy) acetate (C2-8), 2 Compounds such as oxoprop-1-yl (5-chloro-8-quinolinoxy) acetate (C2-9) and related compounds;

(f) a compound of the (5-chloro-8-quinolineoxy) malonic acid type as described and presented in EP-A-0 582 198, preferably diethyl (5-chloro-8-quinoline Compounds such as oxy) malonate, diallyl (5-chloro-8-quinolineoxy) malonate, methyl ethyl (5-chloro-8-quinolineoxy) malonate and related compounds;

(g) phenoxyacetic acid derivatives, phenoxypropionic acid derivatives and active ingredients of the aromatic carboxylic acid type, for example 2,4-dichlorophenoxyacetic acid (ester), (2,4-D), 4-chloro-2-methyl Phenoxypropionic acid ester (methoplop), MCPA or 3,6-dichloro-2-methoxybenzoic acid (ester) (dicamba);

(h) a compound of the 5,5-diphenyl-2-isoxazolin-3-carboxylic acid type, preferably ethyl 5,5-diphenyl-2-isoxazolin-3-carboxylate (C3-1); And

(i) compounds known as emollients for rice, for example phenchlorine (= 4,6-dichloro-2-phenylpyrimidine, Pesticide Manual, 11th Ed., pp. 511-512, 1997) Dimepiperate (= S-1-methyl-1-phenylethylpiperidine-1-thiocarboxylate, see Pesticide Manual, 11th Ed., Pp. 404-405, 1997), die Muron (= 1- (1-methyl-1-phenylethyl) -3-p-tolylurea, see Pesticide Manual, 11th Ed., P. 330, 1997), cumyluron (= 3- (2 -Chlorophenylmethyl) -1- (1-methyl-1-phenylethyl) urea, Japanese Patent Application No. JP-A-60 / 087,254), methoxyphenone (= 3,3'-dimethyl-4-methoxy -Benzophenone), and CSB (= 1-bromo-4- (chloromethylsulfonyl) benzene, CAS Registry No. 54091-06-4).

Compounds of at least some of these compounds are also described in EP-A-0 640 587, incorporated herein by reference.

(j) Another important group of compounds suitable as emollients and detoxifiers known from WO 95/07897 are also included in these compounds.

The emollients (detoxifiers) of groups (a) to (j) above have no adverse effect on the activity of herbicides on harmful plants, and have no phytotoxic effect that may occur when the resulting combinations of the present invention are used in useful agricultural plants. Reduce or prevent. In this way, the field of use of the herbicidal mixtures of the present invention can be greatly extended, especially in combination with the use of emollients, which have never been used with limited use or without success, i. E. Low levels have a narrow range of action, allowing the use of formulations that have not been able to adequately control harmful plants.

The herbicide mixtures according to the invention and the emollients may be sprayed together (spread as ready-to-applied formulations or tank mixes) or in any order. The weight ratio of emollient: herbicide (group (A), i.e., a compound of formula (I) or a salt thereof) may vary within a wide range and is preferably from 1: 100 to 100: 1, in particular from 1: 100 to 50: 1. . In each case the optimal amount of herbicide (compounds in groups (A) and (B)) and emollients will typically depend on the type of herbicide mixture and / or emollient used and the nature of the root of the plant to be treated.

Depending on this property, the laxatives of group (C) can be used for pretreatment (seed dressing) of the seeds of agronomic plants, introduced into the seed furrows before sowing, or with or without herbicide mixture before or after the plants sprout. Can be sprayed together. Treatments before sprouting include both treatment of arable land before sowing and treatment of cropland that has been sown but not yet sprouted. Preference is given to spraying with the herbicide mixture. Tank mixes or ready-to-use formulations can be used for this purpose.

The required spreading amount of the emollient can vary within a wide range depending on the usage and the herbicide used and is generally from 0.001 to 1 kg, preferably from 0.005 to 0.2 kg of active ingredient per hectare. Within the scope of the present invention, herbicide compositions which are very suitable and particularly advantageous for use in rice are prepared by combining herbicides of group (A) with compounds of group (B) and emollients (C2-1 and / or C3-1) It is obtained when used.

Upon sparging, formulations in commercially available form are usually diluted, for example, with water, for example wettable powders, emulsifiable concentrates, dispersions and water dispersible granules. Preparations in the form of dust, soil-coated granules, sparged granules and spray solutions are usually not further diluted with other inert materials prior to sparging.

The present invention also provides a method for controlling unwanted plants, comprising spraying a new combination of active ingredients (A) + (B) on the plants or farmland in an effective amount of herbicide. Active ingredients can be applied to plants, parts of plants, plant seeds or cropland.

In a preferred variant of the process, the compound of formula (I) or a salt thereof (compound of group (A)) is 0.1 to 20 g ai / ha, preferably 5 to 90 g ai / ha, particularly preferably 6 to 60 g ai / It is sprayed at a spraying rate of ha, and the compound of group (B) is generally sprayed at a spraying amount of 1 to 5000 g ai / ha. The active ingredients of group (A) and group (B) are preferably sprayed simultaneously or at a time difference in a weight ratio of 1: 20,000 to 200: 1. It is also particularly desirable to spray the active ingredients together in the form of a tank mix, in which case the optimally formulated concentrated formulation of the individual active ingredients is mixed with water in the tank and the resulting spray mixture is then sprayed do.

Since the novel formulations of the present invention are very safe for crops and at the same time can control harmful plants at very high levels, they can be regarded as selective formulations. Thus, in a preferred variant of the method, herbicide compositions comprising a combination of the active ingredients of the invention are used to selectively control unwanted plants.

The method of the invention for selectively controlling harmful plants is a particularly advantageous embodiment when the herbicide composition of the invention is used in rice.

Co-components of group (A), when used alone in rice, control a limited range of annual and perennial broad-leaved weeds and roomworm plants. However, the range of action of the compounds of the group (A) can be further improved by combining with the partners of the group (B) as specifically disclosed herein, to control a broader range of weed species. Depending on the nature of the co-component of the group (B), the herbicide combinations of the invention can also be used to control unwanted plants also in genetically modified cultivated rice.

Genetically modified crops are crops in which plants have become resistant to herbicides or insecticides by genetic engineering. Rice plants modified in this way can then be used for selective use.

Therefore, most importantly, the present invention additionally

(A) at least one herbicide component selected from the group consisting of substituted phenoxysulfonylureas of formula (I) and salts thereof:

Formula I

; And

(B) (Ba) selected from the group consisting of pentrazamide (NBA 061), haloxop, cetoxydim, dithiopyr, etobenzanide (MY-52), clepoxydim, KIH 6127 and cletodim Herbicide, selectively effective against weeds, mainly in rice

(Bb) selected from the group consisting of 2,4-D, MCPA, mecoprop, mecoprop-P, tritosulfuron, halosulfuron-methyl, dicamba, acifluorfen, carpentrazone, bentazone and triclopyr , Herbicides selectively effective against harmful dicotyledonous plants and harmful algae plants in rice, and

(Bc) pendimethalin, clomazone, KIH 2023, oxadisarzyl, cyclosulfamuron (AC 322, 140), azisulsulfuron (DPX-A-8947), nicosulfuron, synmethyline, indanopan, Selectively effective herbicides against weeds, harmful dicotyledonous plants, and harmful algae plants in rice, selected from the group consisting of pentoxazone, pyribenzime, oxazilomethone (MY-100), flutiamide, and mesotrione

It is to provide a use of a herbicide composition comprising at least one herbicide active compound selected from the group consisting of for controlling unwanted harmful plants in a cultivated plant, preferably in cultivated rice. The weight ratio of the compound of formula (I) or a salt thereof (a compound of group (A)) and a compound of group (B) is generally from 1: 20,000 to 200: 1, preferably from 1: 8,000 to 100: 1, more preferably In the range from 1: 4,000 to 50: 1.

Preferred uses are the use of combinations comprising a synergistically effective amount of a compound of groups (A) and (B).

Preference is also given to the use of a mixture comprising a combination of compounds of the (A) and (Ba) groups for the selective control of weeds in rice. Preference is also given to the use of mixtures comprising a combination of compounds of the (A) and (Bb) groups for the selective control of dicotyledonous and asteraceae plants in rice. Also preferred is the use of a mixture comprising a combination of the compounds of the (A) and (Bc) groups for the selective control of weeds, dicotyledonous plants and asteraceae plants in rice.

The present invention also comprises, alone or one or more co-components of the (A) group, preferably a mixture of only one compound (ethoxysulfuron) of the (A1) and one or more co-components of the (B) group, or It is contained in the mixture mix | blended with the above emollient (C).

Preferred examples of the mixture of the active ingredients of the present invention include the following combinations of the compound of (A1) (ethoxysulfuron) with the co-components of (B1) to (B32) above, but one example of such a combination of the present invention It is not intended to be limited to the following combinations:

(A1) + (B1): pentrazamide, (A1) + (B2): halooxypop, (A1) + (B3): cetoxydim, (A1) + (B4): dithiopyr, (A1 ) + (B5): etobenzanide, (A1) + (B6): clepoxysid, (A1) + (B7): KIH 6127, (A1) + (B7a): cletodim, (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): carpentrazone, (A1) + (B16): Ventazone, (A1) + (B17): Triclopyr, (A1) + (B18): Fendimethalin, (A1) + (B19): Clomazone, (A1) + (B20): KIH 2023, (A1) + (B21): oxadiargyl, (A1) + (B22): cyclosulfamuron, (A1) + (B23): azimsulfuron, (A1) + (B24): nicosulfuron , (A1) + (B25): tenylchlor, (A1) + (B26): citmethyline, (A1) + (B27): indanophan, (A1) + (B28): pentoxazone, (A1) + (B29): pyribenzone sim, (A1) + (B30): oxazilomethone, (A1) + (B31): flutiamide, (A1) + (B32): mesotrione.

The aforementioned mixtures can advantageously be used with one or more emollients. Examples of preferred emollients are 1-methylhex-1-yl (5-chloro-8-quinolinoxy) acetate (C2-1) and methyl 5,5-diphenyl-2-isoxazolin-3-carboxylate (C3 -1)

The use of emollients in these combinations provides a significant advantage since the damage to agricultural plants such as rice is reduced by sulfonylurea derivatives or other herbicide active ingredients.

In addition, emollients (C2-1) and (C3-1) may be advantageously replaced by one or more compounds from the group consisting of the following emollients or used with one or more of the following compounds:

Ethyl 1- (2,4-dichlorophenyl) -5- (ethoxycarbonyl) -5-methyl-2-pyrazoline-3-carboxylate (C1-1),

Ethyl 1- (2,4-dichlorophenyl) -5-methylpyrazole-3-carboxylate (C1-2),

Ethyl 1- (2,4-dichlorophenyl) -5-isopropylpyrazole-3-carboxylate (C1-3),

Ethyl 1- (2,4-dichlorophenyl) -5- (1,1-dimethylethyl) -pyrazole-3-carboxylate (C1-4),

Ethyl 1- (2,4-dichlorophenyl) -5-phenylpyrazole-3-carboxylate (C1-5),

Ethyl 1- (2,4-dichlorophenyl) -5-trichloromethyl-1H-1,2,4-triazole-3-carboxylate (C1-6, fenchlorazole),

Ethyl 5- (2,4-dichlorobenzyl) -2-isoxazolin-3-carboxylate (C1-7),

Ethyl 5-phenyl-2-isoxazolin-3-carboxylate (C1-8),

1,3-dimethylbut-1-yl (5-chloro-8-quinolinoxy) acetate (C2-2),

4-allyloxybutyl (5-chloro-8-quinolineoxy) acetate (C2-3),

1-allyloxyprop-2-yl (5-chloro-8-quinolinoxy) acetate (C2-4),

Ethyl (5-chloro-8-quinolineoxy) acetate (C2-5),

Methyl (5-chloro-8-quinolineoxy) acetate (C2-6),

Allyl (5-chloro-8-quinolineoxy) acetate (C2-7),

2- (2-propylideneiminooxy) -1-ethyl (5-chloro-8-quinolineoxy) acetate (C2-8),

2-oxoprop-1-yl (5-chloro-8-quinolinoxy) acetate (C2-9),

Diethyl (5-chloro-8-quinolineoxy) malonate,

Diallyl (5-chloro-8-quinolineoxy) malonate,

Methyl ethyl (5-chloro-8-quinolineoxy) malonate,

2,4-dichlorophenoxyacetic acid (ester) (2,4-D),

4-chloro-2-methylphenoxypropionic acid ester (mecoprop),

MCPA, and

3,6-dichloro-2-methoxybenzoic acid (ester) (dicamba).

In addition to these, the mixtures of the present invention may typically further comprise one or two or more of the following pesticides (herbicides, insecticides, fungicides, etc.), usually in small amounts, to complete the properties:

Abamectin, AC94377, AC263222, AC3-103630, Acetate, Acloniphene, Acrinatrin, Apsifectas, AKH-7088, Alachlor, Alanicarb, Aldicarb, Aldoxicarb, Altrerin, Aloxydim , Alpha-cypermethrin, amethrin, amidosulfuron, amitraz, amitrol, ammonium sulfamate, ansimidol, anilazin, anthraquinone, asulam, atrazine, azaconazole, azadirachtin, aza Methyphos, Ajinfoss-ethyl, Ajinfoss-methyl, Azocyclotin, BAS480F, BAS490F, Benalacyl, Benazoline, Bendiocarb, Benfluraline, Benfuracarb, Benomil, Benoxacor, Bensulfide, Ben Sultapes, benzoxmate, beta-cifluthrin, beta-cypermethrin, biphenox, bifenthrin, villanafos, bioallrethrin, bioaltrerin (S-cyclopentenyl isomer), bioresmethrin, b Phenyl, Vitertanol, Blastisidin-S, Borax, Bordu Mixture, Bro Paccomum, bromasil, bromadiolone, bromethalin, bromophenoxime, bromopropylate, bromocinyl, bromuconazole, bronopol, butypyrimate, buprofezin, butamiphos, butocacarsim , Butoxycarboxime, butraline, butylamine, butyrate, cardusafos, calcium polysulfide, captapol, captan, carbaryl, carbendazim, carbetamid, carbofuran, carbosulphan, carboxycin, cartop, CGA50439 , CGA183893, CGA219417, chinomethionate, chlormethoxyphene, chloralose, chlorambene, chlorbromuron, chlorbufam, chlordan, chlorethoxyphosphate, chlorfenbinfos, chlorfluazuron, chlorflurenol, Chloridazone, Chlormephos, Chlormekuat, Chlornitropen, Chloracetic Acid, Chlorobenzylate, Chloronep, Chlorofacinone, Chloropicrine, Chlorotalonyl, Chlorotoluron, Chlorofonium, Chlorprofam, Chlorpyripo , Chlorpyriphos-methyl, Chlorsulfuron, Chlortal, Chlortiamide, Clozolinate, CL26691, CL304415, Clodinapop, Cloetocarb, Clopentezin, Clomeprop, Cloprop, Clopyralide, Cloquinto Set, K. cyphonacna, copper hydroxide, copper sulphate, copper sulfate, coomafoss, coumatetralyl, 4-CPA, cuprous oxide, cyanamide, cyanazine, cyanophosph, cycloate, cycloprotrin, seaco Flutrin, beta-cifluthrin, sihalothrin, lambda-sihalothrin, cyhexatin, cymoxanyl, cypermethrin, alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin, cifenotrine, Ciproconazole, cyromazine, daminozide, azomet, 2,4-DB, DCIP, devacarb, decan-1-ol, deltamethrin, demethone-S-methyl, desmediphamm, desmetrin, Diafenthiuron, diazinon, diclobenyl, diclofloanide, diclones, dichlormid, Dichlorophene, 1,3-dichloropropene, dichloroprop, dichloroprop-P, dichlorbos, diclopop, diclomezin, dichloran, dichloropol, dicrotophos, dienochlor, die Tofencarb, diethyltoluamide, dipenacoum, diefenoconazole, dipfenkuart, dipetialone, diflubenzuron, diflufenican, dikegulac, dimethuron, dimethaclor, dimethamethine, Dimethenamid, dimethipine, dimethymol, dimethoate, dimethomorph, dimethyl phthalate, dimethylvinforce, diconazole, dinitramine, dinocap, dinotub, diophenolane, dioxabenzoforce, Difacinone, diphenamide, diphenylamine, dipropyl pyridine-2,5-dicarboxylate, diquat, disulfutone, dithianon, diuron, DKA-24, DNOC, dodemorph, dodine, edifeneforce , Empentrin, Endosulfan, Endortal, ENT8184, EPN, EPTC, Ergocalciferol, Espenvalate, Esp Carb, ET751, etafluralline, etamethsulfuron-methyl, etepon, ethofenecarb, ethion, etirimole, etofumesate, etoprofos, ethoxyquine, ethoxylozate, ethylene dibromide, ethylene di Chloride, Etopenprox, Etridazole, F8426, Pamper, Phenamiphos, Phenarimol, Penazaquin, Fenbuconazole, Penbutatin Oxide, Fenchlorazole, Fenchlorim, Fenfuram, Phenythrothion, Phenyl Nobucarb, phenothiocarb, phenoxycarb, fenpiclonyl, phenpropartin, fenpropidine, fenpropormoff, fenpyroximate, pention, fentin, phenuron, fenvallate, ferbam, fen Rimzone, Fipronil, Flamprop, Flamprop-M, Plazasulfuron, Plocoumafen, Fluazipone, Fluazip-P, Fluazinam, Fluazuron, Fluchlorinline, Flucycloroxulin, Flucitrinate, fludioxonyl, flufenoxuron, flumetraline, flumetsulam, Flumichlorac, flumioxazine, fluoromethuron, fluoroacetamide, fluoroglycopene, fluoromide, flupoxam, flupropanate, fluquinconazole, flurazole, flurenol, flulidone, Flulochloridone, fluoxirpyre, fluprimidol, flutarmone, flusilazole, flusulfamide, flutolanil, flutriafol, tau-fluvalinate, fluxofenam, polpet, pomesafen , Phonophos, forchlorfenuron, formethanate, formomothione, fosamine, pocetyl, phosphthiazate, fuberidazole, furalacyl, furateocarb, furilazol, gibberelic acid, gibberellin A4, Gibberellin A7, Guazatin, GY-81, Halfenprox, Halosulfuron, HC-252, Gamma-HCH, Heptachlor, Heptenophosphate, Hexachlorobenzene, Hexaconazole, Hexaflumuron, Hexazinone, Hexa Citiazox, Hydramethylnon, 2-Hydrinoethanol, Hydroprene, 8-Hy Roxyquinoline sulfate, hymexazole, ICIA0858, ICIA5504, imazaryl, imazamethabenz, imazaphyr, imazaquin, imazetapyr, imibenconazole, imidacloprid, iminoctadiene, inabenpid, indole-3- Monoacetic acid, 4-indole-3-ylbutyric acid, ifconazole, isprobenfoss, isprodione, isozofos, isopenfos, isophamphos, isoprocarb, isoprothiolane, isoproturon, isourone, Isoxaben, isoxatipyripop, isoxation, kasugamycin, KIH9201, lactofen, lambda-sihalothrin, lenacil, linuron, lufenuron, malathion, maleic hydrazide, mancopper, manco 젭, manep, MCPA-thioethyl, MCPB, mechabam, mefluidide, mepanipyrim, mephospolan, mepicuat, mepronyl, petalacyl, metaldehyde, metham, metamitrone, metaza Chlor, Metconazole, Metabenzthiazuron, Metacripos, Metamidose, Meme Sulfocarb, metidathione, methiocarb, metomil, methoprene, methcyclocyclo, methylarsonic acid, methyl bromide, methyldimron, methyl isothiocyanate, metiram, methopenzuron, methopromurone, Mettolcarb, methoxuron, metribuzin, mevinphos, milbectin, MK-243, monoclotophos, monolinuron, muscalurele, myclobutanyl, nabam, naled, naphthenic acid, 2- (1- Naphthyl) acetamide, (1-naphthyl) acetic acid, (2-naphthoyloxy) acetic acid, naprofamide, naphthalam, natamycin, NC-330, neburon, NI-25, nickel bis (dimethyldithio Carbamate), niclosamide, nicotine, nitenpyram, nithiazine, nitrapyrin, nitrotal-isopropyl, norflurazone, nourimol, octylinone, 2- (octylthio) ethanol, opurase, ometo 8, orbencarb, oryzaline, oxavetrinyl, oxadixyl, oxamyl, auxin-copper, oxolinic acid, oxycarboxycin, ox Demethone-methyl, paclobutrazole, paraquat, parathion, parathion-methyl, pebulate, pefurazoate, fenconazole, pensicuron, pentachlorophenol, pentanochlor, fermethrin, phenmedipham , Phenotrine, pentoate, 2-phenylphenol, N-phenylphthalamic acid, forrate, phosphonone, phosphodiphene, phosphmet, phosphamidone, bombardment, phthalide, pindon, piperaline, piperonyl butoxide , Pyrimicab, pyrimifos-ethyl, pyrimifos-methyl, polyoxine, praletrin, pretilachlor, primisulfuron, probenazole, prochloraz, procimidon, prodiamine, propeno Phos, prohexadione, promethone, propachlor, propamocarb, propaphos, propaquizapop, propargite, propazine, propapefoss, propfam, propiconazole, propineb, propiso Chlorine, propoxur, propizamide, prosulfocarb, prosulfuron, Thiophos, pymetrozine, pyraclophos, pyrethrins, pyridaben, pyridapentione, pyridate, pyriphenox, pyrimethanyl, pyrimidipene, pyriproxyfen, pyrithiobac-sodium, pyriquilon , Quinalofos, quinmerac, quinoclamin, quintogen, quizolopop, quizolopop-P, resmethrin, rimsulfuron, rotenone, RU15525, S421, siduron, silafluorene, smazine, sodium Fluoroacetate, SSF-109, SSI-121, Streptomycin, Strycnin, Sulfurfuron, Sulfentrazone, Sulfluamide, Sulfomethuron, Sulpotep, Sulfur, Sulprophos, Tar Oil, 2,3,6- TBA, TCA-sodium, tebuconazole, tebufenozide, tebufenpyrad, tebutam, tebutiuuron, teclophthalam, technazen, teflubenzuron, tefluthrin, temephos, terbasil, terbu Phosph, terbumetone, terbutylazine, terbutrin, tetrachlorbinfos, tetraconazole, tetradipon, tetramethrin, Tramethrin [(1R) -isomer], thibendazole, thidiazuron, thifensulfuron, tifluzamide, thiocyclam, thiodicarb, thiophanox, thiomethone, thiophanate-methyl, tiram , Thiocarbasil, tollclofos-methyl, tolylufluoride, tralcoxysid, tralomethrin, transfluthrin, triadimefon, triadimenol, tri-allate, triamate, triazofos, Triaside, tribenuron, S, S, S-tributyl phosphorotrithioate, trichlorphene, tricyclazole, tridemorph, triethazine, triflumizole, triflumuron, trituralin , Triflusulfuron, tripolin, trimetacarb, trinexa park, triticonazole, uniconazole, validamycin, bamidothione, vernolate, vinclozoline, warfarin, XDE537, XMC, xylylcarb , Jeanne and Zeal.

Thus, there are numerous possible combinations which are prepared by combining two or more active ingredients with another without departing from the scope of the present invention and which can be used to control weeds in cultivated rice.

The herbicide compositions (combinations) of the present invention exhibit excellent herbicide activity against a broad range of economically important harmful monocotyledonous and dicotyledonous plants. Combinations of the active ingredients of the invention also effectively control difficult to control perennial broad-leaved weeds that sprout from seeds or rhizomes, rhizomes or other perennial organs. In this regard, the timing of the application, such as whether the material is sprayed before planting seeds or perennial organs, before sprouting or after sprouting, is not critical.

Among monocotyledonous weed species, for example, annual and genus species, and perennial species, are effectively controlled.

Combinations of active ingredients according to the invention is the broad-leaved weeds may appear according to the specific cultivation conditions of rice, for example, Sagittaria trifolia in species, Alismataceae speed (Alisma) species, word kkotsok (Rotala) species, mulokjam in (Monochoria) species, Eleanor It exhibits excellent control effects against the species of Ocaris, Scirpus and the genus Sardin.

When the herbicide composition of the present invention is sprayed before germination, the weed seeds do not germinate completely, or grow up to the stage of leaf formation, but after that, growth stops and eventually wither and dies completely after 3-4 weeks.

When the combination of the active ingredients of the present invention is applied to the green areas of the sprouted weeds, the weeds likewise stop growing rapidly in a very short time after application. These weed plants exist only in the growth phase at the time of spraying or die a little faster after some time, so that the weed plants compete with the agro plants to harm them and consequently lose a qualitative and quantitative harvest. Possessions that may result are initially removed in a continuous manner.

Although the compositions of the present invention exhibit good herbicide activity against monocotyledonous and dicotyledonous weeds, they do only minimally harming or no detrimental effects on agricultural plants. For this reason, the compositions of the present invention are well suited for selectively inhibiting the growth of unwanted plants in rice.

The harmful plants to be controlled specifically include, as already mentioned above, weeds, dicotyledonous plants and / or roomworm plants, which are particularly difficult to control in other ways. Harmful plants which can be preferably controlled using novel combinations of the compounds of groups (A) and (B) are, in particular, Echinochloa colonum , Echinolocaa chinese belonging to the weeds Echinochloa chinesis , Echinochloa crus -Gali, Leptochloa chin./fil. , Paspalum distichum , Brachiaria platyphylla , Barranquilla is in kind (Digitaria spp.), soebori speed, rear-cyano-hexane drive (Leersia hexandra), Come and sativa (Oryza sativa) (red rice), Sen Cruz station or Bluetooth (Cenchrus echinatus), Lot Bo Elia eksal Rottboellia exaltata , Leersia , and the like; Monochoria vaginalis belonging to the broad-leaved weed, Potamogeton dis. , Rotala indica , Marsilea crenata , Ludwigia . ad. ), Salvina mol. , Ipomoea , Sesbania ex. , Heteranthera , Commelinia , Butomus , Buttercup in (Aeschynomene), Alice Do Plane ride (Alisma plantago), the clip other (Eclypta), mureuda California (Murdania), Xanthium strumarium in (Xanthium), Alter is Terah (Alteranthera.) species, Spain Notre Boutique J.. (Spenodea zey ), Haricot , Iuncus species, Polygonum , Ammania ind . ; Cyperus difformis , Cyperus iria , Fimbristylis litt. , Cyperus ferax , Cyperus esculentes Cyperus esculentes ); And also Eleocharis species, Lycoris species, Scirpus mucronatus and Cyperus rotundus belonging to the perennial farniaceae family.

In summary, it can be said that when the sulfonylurea of formula (I) and / or its salts are sparged with one or more active ingredients of group (B), a hyperadditive (ie synergistic) effect is seen. The activity of the combinations of the present invention is much better than the activity of individual products sprayed alone.

By this effect, in particular, it is possible to: 1) reduce the spread, 2) control a broader range of broad-leaved weeds and weeds, and 2) eliminate the requirements for lowering activity, including those associated with resistant species. 3) faster and more reliable activity can be obtained, 4) longer lasting action, 5) complete control of harmful plants with only one or less recovery, and 6) combinations May increase the useful life of the active ingredients.

The above-mentioned characteristics are required when weeds are controlled to protect and / or increase the quality and quantity of the harvest by keeping free of plant competitors who do not actually want cropland. The formulations of the present invention significantly outperform the art in the art with respect to the above-mentioned properties.

In addition, the formulations of the present invention can excellently control harmful plants that are resistant to other methods.

The following examples are intended to illustrate the invention but not to limit it.

1. Formulation Example

a) Dust was obtained by mixing 10 parts by weight of the combination of the active ingredients according to the invention and 90 parts by weight of talc as an inert material and grinding the mixture in a hammer mill.

b) Easily dispersible wettable powders comprise 25 parts by weight of active ingredients (A) + (B), 64 parts by weight of kaolin-containing quartz as inert material, 10 parts by weight of potassium ligninsulfonate as wetting agent and dispersant and sodium oleoyl 1 part by weight of methyltautinate was mixed and obtained by grinding in a disk mill with pin holes.

c) Easily dispersible dispersion concentrates comprise 20 parts by weight of active ingredients (A) + (B), 6 parts by weight of alkylphenol polyglycol ether (Triton® X 207), isotridecanol poly 3 parts by weight of glycol ether (8 EO) and 71 parts by weight of paraffin mineral oil (eg, mineral oil having a boiling point range of about 255 to 277 ° C.), and the mixture is milled to a fineness of less than 5 microns. Obtained by grinding in a (ball mill).

d) Emulsifiable concentrates were obtained from 15 parts by weight of cyclohexanone as solvent and 10 parts by weight of ethoxylated nonylphenol as emulsifier.

e) the water dispersible granules are mixed with 75 parts by weight of the active ingredients (A) + (B), 10 parts by weight of calcium ligninsulfonate, 5 parts by weight of sodium lauryl sulfate, 3 parts by weight of polyvinyl alcohol and 7 parts by weight of kaolin, This mixture was obtained by pulverizing in a disk mill with pin holes and then granulating the powder by spraying water as granulation liquid in the fluidized bed.

f) The water dispersible granules also contain 25 parts by weight of the active ingredients (A) + (B), 5 parts by weight of sodium 2,2'-dinaphthylmethane-6,6'-disulfonate, sodium oleoylmethyltauri After homogenizing and initial milling in a colloid mill 2 parts by weight, 1 part by weight of polyvinyl alcohol, 17 parts by weight of calcium carbonate and 50 parts by weight of water, the mixture was ground in a bead mill and the resulting suspension was mono- Obtained by miniaturization and drying in a spray tower using a material nozzle.

g) The extruded granules are mixed with 20 parts by weight of the active ingredients (A) + (B), 3 parts by weight of sodium lignansulfonate, 1 part by weight of carboxymethylcellulose and 76 parts by weight of kaolin, and the mixture is triturated and then watered. Obtained by wetting. The mixture was extruded and dried in air.

2. Biological Example

The following examples were performed in the greenhouse, and some were performed in the field field test site.

i) control of weeds before sprouting

Seed or rhizome fragments of monocotyledonous and dicotyledonous weed plants were placed in sandy loam in a plastic container 9 cm in diameter and covered with soil. The broad-leaved weeds from rice cultivation were grown in water-filled soils, where the amount of water filled in the containers was up to the soil surface or up to a few millimeters from the soil surface. The combination of the active ingredients of the invention formulated in the form of a wettable powder or emulsifiable concentrate, and the corresponding active ingredients formulated in similar tests are then sprayed onto the surface of the soil covered with different dosages as an aqueous suspension or emulsion. Or, in the case of rice, the spraying amount (based on water) corresponding to 300 to 600 l / ha was poured into the irrigation water.

After treatment, the containers were placed in a greenhouse and kept under good growth conditions (temperature, atmospheric humidity, water supply) for broadleaf weeds. After sprouting from the test plants after the test period of 3-4 weeks, the adverse effects on the sprouting of these plants were visually evaluated in comparison to the untreated control group. This test was repeated multiple times (up to 5 times) to obtain statistically significant results. The herbicide compositions of the present invention showed good herbicide activity upon spraying against a wide range of weeds and broadleaf weeds before they sprouted.

ii) control of weeds after sprouting

Seeds or rhizome pieces of monocotyledonous and dicotyledonous weed plants were placed on sandy loam in plastic containers, covered with soil and grown in greenhouses under good growth conditions (temperature, atmospheric humidity, water supply). The broad-leaved weeds from rice cultivation were grown in containers filled with water 2 cm above the soil surface. Three weeks after seed or rhizome pieces were planted, the test plants were treated at three leafy stages. Formulations of the active ingredients of the invention formulated as wettable powders or emulsifiable concentrates, and spraying amounts corresponding to 300 to 600 l / ha in varying dosages of the correspondingly formulated individual active ingredients in similar tests (based on water Application by spraying the green areas of the plant, and after about three to four weeks in a greenhouse under optimal growth conditions (temperature, atmospheric humidity, water supply), the activity of the preparations compared to the untreated control group. Was evaluated visually. In the case of rice, or in the case of broad-leaved weeds appearing in rice cultivation, the active ingredients were also added directly to the irrigation water (applied in a manner similar to so-called granulation application) or sprayed on plants and irrigation water. This test was repeated multiple times (up to 5 times) to obtain statistically significant results. The herbicide compositions of the present invention also exhibited good herbicide activity when applied to a wide range of economically important weeds and broadleaf weeds after they sprout.

iii) outdoor field test site

Field field test sites were prepared on conventional farmland containing natural sand. After seeding or rhizome pieces were planted and sprouted by agri-plants / leaves weeds / weeds, it was sprayed 2 to 4 times repeatedly on the ground of about 20 to 10 m 2 using a ground sprayer. The effectiveness of the herbicide / blend of the present invention was assessed visually 1-8 weeks after sparging and the effect was determined as a percentage (0-100%) compared to the untreated control ground. The results are shown as averages repeated 2-4 times for each broad weed species / weed grass species.

iv) evaluation of the effects exhibited by the formulation in the examples.

When evaluating the effectiveness of the combinations, the activities of the individual components were combined and compared with the activity of their mixtures at the same dose. It has often been found that the combinations of the invention exhibit higher activity than the sum of the activities of the individual components.

For effects where the difference was not apparent, the expected value was calculated using the SR Colby equation and compared with the experimentally determined results. The theoretically expected calculated efficacy of the combination was determined using Colby's equation (Calculation of synergistic and antagonistic responses of herbicide combinations, Weeds , 15, pp. 20-22, 1967).

In the case of a combination of two active ingredients, the Colby equation is given by Equation 1:

Synergy can be assumed to occur when the experimental value exceeds the expected value. In the case of a combination of individual components having the same active ingredients, the values of Equation 1 of the individual components can be summed and compared.

In most cases, however, the synergistic increase in activity is so large that Colby's criterion cannot be applied, and even in this case it is clear that the activity of the combination exceeds the Colby formula (calculated) summation of the activities of the individual components. .

Particular attention should be paid to the fact that when evaluating the synergy between the active ingredients used in the present invention, differences in very different spreads between the individual active ingredients must be taken into account. Thus, it is not reasonable to compare the activity of a combination of active ingredients with the activity of each individual active ingredient at the same spread. The fact that the application rate can be saved only by the present invention indicates that an increase in hyperadditional activity is observed in the present invention when a combination of the individual active ingredients of each application amount is used, or the combination of the present invention and the individual active ingredients. If their activity is the same, it is demonstrated from the fact that their spreading amount is further reduced when used in the combination than when the two active ingredients are used separately.

Specific Experimental Example

In Tables 1 to 11, g ai / ha is g of active ingredient per hectare, and the expected values of the herbicide combinations are given in parentheses.

Ethoxysulfuron + pentrasamide (B1) g ai / ha rice plant % Damage to Sagittaria pygmaea (A) ethoxysulfuron 30 6 85 (B) pentrazamide 200 0 80 100 0 40 50 0 0 (A) + (B) 30 + 50 2 93 (85 + 0) Greenhouse Trials: Treated at 1 to 2 leafing stages. Assessment: Evaluated 20 days after application.

Ethoxysulfuron + Azimsulfuron (B23) g ai / ha rice plant Cyperrus serotonin damage rate (%) (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 Field Test: Field Treatment in two to three leafing stages. Assessment: Evaluated 28 days after application.

Ethoxysulfuron + pentoxazone (B28) g ai / ha rice plant % Damage to Lindernia pyxidaria (A) ethoxysulfuron 20 4 60 (B) pentoxazone 150 6 25 (A) + (B) 20 + 150 5 90 (60 + 25) Field Field Test: Field Treatment in one leafing step. Assessment: Assessment 43 days after application.

Ethoxysulfuron + oxazillomepon (B30) g ai / ha rice plant Cyperrus serotonin damage rate (%) (A) ethoxysulfuron 60 20 85 30 5 75 (B) Oxazillomethone 200 5 95 100 0 80 50 0 10 (A) + (B) 30 + 50 5 98 (75 + 10) Greenhouse test: treated at 2-4 leafy stages. Assessment: Assessment 20 days after application.

Ethoxysulfuron + Clepoxydim (B6) g ai / ha rice plant % Weed Damage (A) ethoxysulfuron 30 7 55 15 6 50 7.5 5 35 (B) clepoxydim 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 test: treated at 2-4 leafy stages. Assessment: Assessment 20 days after application.

Ethoxysulfuron + KIH 2023 (B20) g ai / ha rice plant % Damage to Echinochloa gens-galli (A) ethoxysulfuron 30 6 55 15 5 50 7.5 5 35 (B) KIH 2023 75 5 30 38 0 15 18 0 0 9 0 0 (A) + (B 7.5 + 9 0 55 (35 + 0) Greenhouse Trials: Treated at 2 leafy stages. Assessment: Evaluated 22 days after application.

Ethoxysulfuron + oxadiargyl (B21) g ai / ha rice plant Cyperrus serotonin damage rate (%) (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 Trials: Treated at 1 to 2 leafing stages. Assessment: Evaluated 21 days after application.

Ethoxysulfuron + KIH 6127 (B7) g ai / ha rice plant Cyperrus serotonin damage rate (%) (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 + 45) Greenhouse Trials: Treated at 1 to 2 leafing stages. Assessment: Evaluated 21 days after application.

Ethoxysulfuron + tritosulfuron (B11) g ai / ha rice plant % Of damage caused by Mono Korea's trousers (A) ethoxysulfuron 7.5 0 32 15 0 96 (B) trisulfuron 37.5 0 26 75 0 38 (A) + (B) 7.5 + 37.5 0 98 (32 + 26) Field Field Test: Field Treatment in two to four leafy stages. Assessment: Assessment 28 days after application.

Ethoxysulfuron + Chromazone (B19) g ai / ha rice plant % Damage to 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 Field Test: Field treatment before sprouting. Assessment: Assessment on day 53 after application.

Ethoxysulfuron + Nicosulfuron (B24) g ai / ha rice plant % Of Echinoloclus Cress-Gali damage (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 Field Test: Field Treatment in two to four leafy stages. Assessment: Assessment 28 days after application.

It can be seen from the above examples that the individual active ingredients show an effective control effect against the individual harmful plants only at high doses. When applied at low dosages, co-components generally exhibited only low activity, well below the actual required activity. Excellent effects on all harmful plants tested could only be obtained if the active ingredients were applied together. In addition, this effect far exceeded the additional activity of the individual components. That is, the required level of control can be obtained using less spreading amount. This effect extends the range of activity considerably.

Evaluation of the type of damage did not adversely affect the safety of the crop. In other words, the blend of the present invention can be said to be a blend with complete selectivity.

Claims (10)

(A) at least one herbicide component selected from the group consisting of substituted phenoxysulfonylureas of formula (I) and salts thereof: Formula I ; And (B) (Ba) fentrazamid (NBA 061), haloxyfop, sethoxydim, dithiopyr, clefoxidim, KIH 6127 and cletodim herbicide selectively effective against weed grass, mainly in rice, selected from the group consisting of (clethodim), (Bb) 2,4-D, MCPA, mecoprop, mecoprop-P, tritosulfuron, halosulfuron-methyl, dicamba, acifluorfen, carpent Herbicides selectively effective against harmful dicotyledonous and harmful cyperaceous plants, mainly in rice, selected from the group consisting of carfentrazone, bentazon and triclopyr, and (Bc) pendimethalin (pendimethalin), clomazone, KIH 2023, oxadiargyl, cyclosulfamuron (AC 322, 140), azimsulfuron (DPX-A -8947), nicosulfuron, cinmethylin, indanofan, indanofan, pentoxazone, pyribenzoxim, oxaziclomefone (MY-100), Selectively effective herbicides for weeds, harmful dicotyledonous plants, and harmful roomworm plants in rice, selected from the group consisting of fluthiamid and mesotrione A herbicide composition comprising at least one herbicide active compound selected from the group consisting of: The method of claim 1, A herbicidal composition comprising a synergistically effective amount of a compound of formula (I) or a salt thereof (a compound of group (A)) and a combination of a compound of group (B). The method according to claim 1 or 2, A compound of formula (I) or a salt thereof (a compound of group (A)), and a compound of group (B) are 1: 20,000 to 200: 1, preferably 1: 8,000 to 100: 1, more preferably 1: 4,000 Herbicide composition comprising in a weight ratio of 50 to 50: 1. The method according to any one of claims 1 to 3, A herbicide composition comprising one or more additional ingredients selected from the group consisting of other plant protection active ingredients, emollient active ingredients, formulation aids and conventional plant protection additives. The herbicides in the herbicide composition as defined in any one of claims 1 to 4 are sprayed together or individually before or after the shoots are sprouted on the plants, parts of the plants, seeds or crops of the plants. A method of controlling harmful plants, including spraying both before and after sprouting. The method of claim 5, A method for selectively controlling harmful plants from cultivated plants. The method of claim 6, Method for controlling harmful plants in rice. Use of herbicide composition as defined in any of claims 1 to 4 for controlling harmful plants. The method of claim 8, For controlling harmful plants in cultivated rice. A compound of formula (I) or a salt thereof (compound of group (A)) together with one or more compounds of group (B), wettable powder, emulsifiable concentrate, aqueous solution, emulsion, spray solution (tank mix), Conventional dispersions selected from the group consisting of oil-based dispersions, aqueous dispersions, suspoemulsion, dust, soil application or spraying granules, water dispersible granules, thickening agent (ULV) formulations, microcapsules and waxes A method of making a herbicide composition as defined in any of claims 1 to 4, comprising formulating analogously to a plant protection formulation.