BG60843B1 - Herbicide compositions based on metamitron/ethofumesate/phenmedifam/desmedifam - Google Patents

Abstract

The invention relates to ready-made new solid forms for application of the known herbicidally active compounds metamitron i of formula i and etofumesate of formula ii, indicated in the description, in a mixture with (a) phenmedipham iii or (b) phenmedipham iii and desmedipham iv or ( c) desmedipham iv, mainly in the form of water-dispersible powders (iv) or water-dispersible granules (vg). The weight ratio of the active compounds i:ii:iii:iv is 1:0.05 to 1:0.05 to 1:0.05 to 1, and the total content of the active compounds is between 20 and 75% by weight. The invention also relates to a method for obtaining the specified compounds.

Description

The invention relates to new solid formulations for the administration of the known herbicide-active compounds metamitron + ethofumesate + (A) phenmedipham or (B) phenmedipham + desmedipham or (B) desmedipham, preferably such as water-dispersible powders (granules) . The invention also relates to a method for the preparation of said compounds.

BACKGROUND OF THE INVENTION

Mixtures of these active compounds have been described previously, as well as reservoir mixtures of the solid form of ethofumesate + phenmedipham with metamitron (J. Marshall et al., 1987, British Crop Protection Conference Weeds (1), p.233- 240), which prove to be very suitable in the practice of selective weed control in beet crops.

The disadvantage of tank mixtures, however, is that when applying the spray mixture, the liquid formulation of ethofumesate + fenmedifam / trade name ® Betanal-Tandem, Fa must be mixed. Schering AG; emulsion concentrate (EC) with 94 g / l ethofumesate and 97 g / l phenmedifam / or ethofumesaz + phenmedifam + desmedifam / trade name ® Betanal-Progress, Fa. Schering AG, emulsion concentrate (EC) with 128 g / l ethofumesate, 62 g / l phenmedipham and 16 g / l desmedifam / and solid metamitron preparation / trade name Golrix, Fa Bayer AG; 70% of VG /.

Therefore, it is advantageous for the user to have a solid formulation ready with a combination of these active compounds. However, it is not known yet how such solid formulations can be formulated, as serious problems may arise due to the relatively low melting point of ethofumesate and the possibly necessary addition of liquid additives.

SUMMARY OF THE INVENTION

It is unexpectedly possible to prepare solid formulations for administration from the technically active compounds metamitron and ethofumesate and in admixture with:

And fenmedifam (III) and

B phenmedipham (III) and desmedipham (IV) or

In desmedifam (IV).

In part, by incorporating liquid emulsifiers, solid combination preparations were obtained. Especially suitable for agricultural practice are the new solid formulations in the form of water-dispersible granules (VG).

It is therefore an object of the present invention to provide herbicidal compositions in the form of solid formulations containing a combination of the active compounds metamitron (I) and ethofumesate (II) and

And phenmedipham (III) or

B phenmedipham (III) and desmedipham (IV) or

In desmedipham (IV), preferably in solid form, as water-dispersible powders (VP) or in the form of water-dispersible granules (VG), in admixture with auxiliary additives, wherein the weight ratio of the active compounds (I): (11) :( 111) ) in combination (A) is (1) :( 0.05 to 1) :( 0.05 to 1), mostly (1) :( 0.1 to 0.4) :( 0.1 to 0.4), and in particular (1) :( 0.1 to 0.35) :( 0.1 to 0.3), wherein the weight ratios of the active compounds (1) :( 11) :( III) :( IV) in combination (B) is (1) :( 0.05 to 1) :( 0.05 to 1) :( 0.05 to 1), mostly (1) :( 0.1 to 0.4) :( 0 , 1 to 0.4): 0.1 to 0.4) and in particular (1) :( 0.1 to 0.4) :( 0.1 to 0.35) :( 0.1 to 0 , 25), whereby the weight ratio of the active compounds (1) :( 11): (IV) in combination (B) is (1) :( 0.05 to 1) :( 0.05 to 1), mainly (1) :( 0,1 to 0.4) :( 0.1 to 0.4) and especially (1) :( 0.1 to 0.4) :( 0.1 to 0.3) and wherein the total content of active compounds as for combination (A), i.e. (1) + (II) + (111), as well as for combinations (B), i.e. (I) + (II) + (III) + (IV) and (B), i. (I) + (II) + (IV) is between 20 and 75%, preferably between 30 and 70%.

Preferred solid forms for administration are forms such as water-dispersible powders (VP) and water-dispersible granules (VG). Particularly preferred solid formulations are water-dispersible granules (VG).

Solid forms of water-dispersible powders, as discovered, can be readily prepared by mixing the active compounds in the above weight ratio with the auxiliary additives suitable for one VP-formulation, grinding the mixture (for example with a conventional air-jet mill) and then homogenized by re-mixing.

The solid forms of (Br) are obtained by

(a) first prepare a premix of the active compounds (I), (II) and (III), respectively (I), (II), (III) and (IV), respectively (I), (II) and (iv) in the proportions indicated above and of the auxiliary additives suitable for one LH form by mixing, grinding (appropriate with an air-jet mill) and then re-mixing;

(b) this pre-mix is normally mixed with water in a fluidized bed granulator and then dried at an inlet air temperature of 50-90 ° C to a product temperature of 30-60 ° C; and

(c) the desired granulate (granule size between 200 and 1500 μιη) is separated by sieving, separating the fine granulate (size <200 pm) and coarse granulate (size> 1500 gm).

As discovered, one particular continuous implementation of the last described method for preparing the B-forms according to the invention is that:

-from the premix described in (a), by adding almost the same amount of water with vigorous stirring, a highly concentrated suspension is obtained,

-this slurry is then fed into a special pelletizer (as described in EP-A-0 163 863 or DE-A1-3 413 200), and at an inlet air temperature of about 100-125 ° C, obtained with the temperature of 30-60 ° C is removed continuously.

The very homogeneous product thus obtained (the granulate having a granule size of about 500 gm) does not require additional sieving.

The active compounds are administered in the form of technically active compounds for which the following melting points (mp) are determined:

metamitron (1) - mp 166 ° C, [3-methyl-4amino-6-phenyl-1,2,4-triazin-5 (4H) -one];

ethofumesate (II) -t.p. 69 ° C, [2-ethoxy-2,3-dihydro-3,3-dimethyl-5-benzofuranylmethanesulfonate];

phenmedipham (1 N) -p.144 ° C, [3-methoxycarbonylaminophenyl-N- (3'-methylphenyl) -carbamate];

desmedipham (IV) -t.t. 120 ° C, [3-ethoxycarbonylaminophenyl-N-phenyl carbamate].

All the basic technical characteristics of the active compounds can be taken from the relevant literature / see, e.g., The Pesticide Manual, 8.Ed, published by The British Crop Protection Counsel, 1987, pp. 353-354 for (II), p.536 for (I), pp.242-243 for (IV) /.

As auxiliary additives for the preparation of the formulations are used carriers, dispersers and optionally certain emulsifiers, respectively wetting agents.

Of interest are synthetic mineral flours such as aluminum oxide, silicates or silicic acids along with natural mineral flours such as kaolins, clays, quartz or attapulgite. Absorbing or precipitating silicic acids are particularly suitable for silicic acids.

Ligninsulfonates or alkyl arylsulfonates are used as the preferred dispersing agents.

As preferred additives, emulsifiers are used polyoxyethylenealkyl ethers, silicone surfactants or polyols, and, for example, condensation products of ethylene oxide with phenol may be used as wetting agents. The condensation products of ethylene oxide with phenol can also be used as emulsifiers.

All of these supplements are commercially available.

The VP forms of the invention (combination (A) and (B), respectively) preferably have the following composition by weight. by 1 parts by weight metamitron (I)

0.1-0.4 ethofumesate (II), 0.1-0.4 phenmedipham (III), 0.1-0.4 desmedipham (IV) respectively,

0.05-0.2 dispersant, 0.0-0.3 emulsifier, 0.00.1 wetting agent, 0.1-0.3 silicic acid and 0.05-0.2 kaolin.

The VP forms of the invention (combination (A)) have in particular the following composition in parts by weight of 1 parts by weight. metamitron (I):

0.1-0.35 ethofumesate (II), 0.1-0.3 phenmedipham (III), 0.05-0.2 dispersant, 0.0-0.3 emulsifier, 0.0-0.1 wetting agent , 0.1-0.3 silicic acid and 0.05-0.2 kaolin.

The VP forms of the invention (combination (B)) have in particular the following composition by weight. by 1 parts by weight metamitron (I):

0.1-0.4 ethofumesate (II), 0.1-0.3 desmedifam (IV), 0.05-0.2 dispersant, 0.0-0.3 emulsifier, 0.0-0.1 wetting agent , 0.1-0.3 silicic acid and 0.05-0.2 kaolin.

The VP forms of the invention (combination (B)) preferably have the following composition by weight. by 1 parts by weight metamitron (I):

0.1-0.4 ethofumesate (II), 0.1-0.4 phenmedipham (III), 0.1-0.4 parts by weight desmedipham (IV), 0.05-0.2 dispersant, 0.0-0.3 emulsifier, 0.00.1 wetting agent, 0.1-0.3 silicic acid and 0.05-0.2 kaolin.

The VP forms of the invention (combination (B)) have in particular the following composition by weight. by 1 parts by weight metamitron (I):

0.1-0.4 ethofumesate (II), 0.1-0.35 phenmedipham (III), 0.1-0.25 desmedifam (IV), 0.050.2 dispersant, 0.0-0.3 emulsifier, 0.0-0.1 wetting agent, 0.1-0.3 silicic acid and 0.050.2 kaolin.

The formulations of the invention (combination (A)) and (B), respectively, preferably have the following composition by weight. by 1 parts by weight metamitron (1):

0.1-0.4 ethofumesate (II), 0.1-0.4 phenmedipham (III), 0.1-0.4 desmedifam (IV), 0.2-0.5 dispersant, 0.0- 0.3 emulsifier, 0.1-0.3 silicic acid and 0.0-0.2 kaolin.

The formulations of the invention (combination (A)) have in particular the following composition by weight. by 1 parts by weight metamitron (I):

0.1-0.35 ethofumesate (II), 0.1-0.3 phenmedipham (III), 0.2-0.5 dispersant, 0.0-0.3 emulsifier, 0.1-0.3 silica acid and 0.0-0.2 kaolin.

The formulations of the invention (combination (B)) have in particular the following composition by weight. by 1 parts by weight metamitron (I):

0.1-0.4 ethofumesate (II) 0.1-0.3 desmedi fam (IV), 0.2-0.5 dispersant, 0.0-0.3 emulsifier, 0.1-0.3 silicon acid and 0.0-0.2 kaolin.

The formulations of the invention (combination (B)) preferably have the following composition of 1 parts by weight. metamitron (I):

0.1-0.4 ethofumesate (II), 0.1-0.4 phenmedipham (III), 0.1-0.4 desmedipham (IV), 0.2-0.5 dispersant, 0.0-0 , 3 emulsifiers, 0.1-0.3 silicic acid and 0.0-0.2 kaolin.

The formulations of the invention (combination (B)) have in particular the following composition of 1 parts by weight. metamitron (I):

0.1-0.4 ethofumesate (II), 0.1-0.35 phenmedipham (III), 0.1-0.25 desmedifam (IV), 0.20.5 dispergator, 0.0-0.3 emulsifier, 0.1-0.3 silicic acid and 0.0-0.2 kaolin.

More details are given in the Examples of Preparation.

In view of the technical difficulties of a fundamental nature that must be overcome in the preparation of the new solid formulations, and above all of the water-dispersible granules, the results obtained should be regarded as surprising.

Generally, the preparation of a ground mixture of the active compound ethofumesate is difficult because of its low melting point of about 69 ° C. In an air-jet mill, nozzles or jams in the mill chamber are clogged. So far, the active compound is commercially available in liquid form only. However, in the mixtures described herein, the active compound ethofumesate in combinations (A), (B) and (B) can be digested without problems. The ability to grind the herbicidal mixture is retained above all when an additional liquid emulsifier is added to the formulations up to about 10%.

Granulation of an active compound with a low melting point is generally problematic. Surprisingly, however, the premix with the active compounds can be granulated without significant problems. Surprisingly, the premix can be granulated even when there is a liquid emulsifier in it.

The resulting granulate is completely redispersed, although up to 10% of highly dispersed silicic acid is added to it. Usually, after granulation, this part of silicic acid is not completely redispersed.

Surprisingly, the same premix can be granulated by conventional methods, preferably by a powder method, such as fluidized bed granulation or the like. A slurry method, such as spray drying. ("Slurry" means "concentrated aqueous suspension").

Surprisingly, the (premixed) mixture can be ground and then granulated, if necessary, when the liquid emulsifier is previously melted together with the active compound metamitron (I) at 160 ° C without degradation of the active compound.

Furthermore, it has been found that the solid formulations according to the invention, especially the new LH forms, are extremely suitable for selective weed control, especially in beet crops.

The new solid formulations are proving to be well-practiced, high-quality, broad-spectrum preparations for combating monocotyledonous and dicotyledonous harmful plants, including problem weeds such as Mercurialis annua u Galium aparine in beet crops.

In the relevant comparative trials, it was surprisingly found that the BH forms according to the invention outperformed known tank mixtures, in part by action and in part by tolerance, and thus offer additional advantages over the prior art.

In addition, the new solid formulations can be used as selective herbicides in beet, strawberry, spinach, spinach and other fruit and vegetable crops.

Other typical weeds that can be found in said crops and successfully destroyed by the agents of the invention are the following:

Bi-weekly weeds of the genera: Sinapis, Lepidum, Stlarria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirschus, Rorippus, Sonus, Carduan , Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum.

Monocotyledonous weeds of the genera: Echinochloa. Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon,

Monochoria, Fimbristylis, Saggitaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactiloctenium, Agrostis, Alopecurus, Apera.

Consumption amounts of active compounds per unit area correspond to consumed amounts of active compounds of known tank mixtures used in the art.

Of particular importance to consumers in agricultural practice is that new HC forms have significant technical advantages over other forms of the same active compounds:

for example, the packaging is simplified (emptied without residue and thus secured without problems with a significantly reduced amount of packaging material); the granules can be dosed by volume and no powder is emitted or concentrate is sprayed in the preparation of the spray suspension; Compared to known emulsion concentrates (ECs), the new solid forms are completely solvent-free.

The activity of a herbicide agent acting through the leaves can be increased by the addition of an emulsifier. Such an additive is usually added in large quantities to the tank mixture. Surprisingly, only a small fraction of about 510% of the emulsifier used in the solid formulations of the invention is sufficient to increase the activity of the formulations described herein.

The following preparation and administration examples serve to further illustrate the invention.

EXAMPLES FOR THE IMPLEMENTATION OF THE INVENTION

a) Examples of preparation

Examples for the preparation of solid solid formulations of the invention according to the invention from metamitron & ethofumesate & phenmedifam.

The constituents listed in the following Table 1 obtain the premix by mixing, grinding with an air-jet mill and re-blending.

Each of these premixes was mixed in the usual way in a fluid bed granulator of Aeromatic (Strea 1) with water and then dried at a supply air temperature of 68 ° C to a product temperature of 40 ° C. The resulting product was then separated by sieving the fine granulate (<200 μιη) and the coarse granulate (> 1500 pm).

In the preparation of the solid forms Br3, Br-5 and Br-7, a suspension of 3.0 kg pre-mix and 3.0 l water, respectively. This suspension is fed to a device described in patent DE-A-3 413 200, respectively EP-A-0 163 863. At an inlet air temperature of 110 ° C, the resulting product is removed at 10 ° C repeatedly. The product thus obtained, with a pellet size of about 500 μπι due to the apparatus, does not require additional sieving.

The B-forms described in Table 1 have weight ratios of the active compounds.

(1): (11) :( 111) = 1: 0,132: 0,136 for VG 1 to 10 (1) :( 11) :( 111) = 1: 0,272: 0,279 for VG 11. The same is true for all the following examples of application.

Table 1.

Composition of the obtained VG forms

Form No Active compound ¹ Disperser ² Emulsifier ³ Carriers ⁴ (I) (II) (III) Silicon resort Kaolin (%) (%) (%) (%) (%) (%) (%) VG-1 50.0 6,60 6.80 20,0 0.0 5.0 about 11.6 VG-2 50.0 6,60 6.80 20,0 5.0 7.5 about 4.10 VG-3 50.0 6,60 6.80 20,0 5.0 7.5 about 4.10 VG-4 45.0 5.94 6.12 20,0 7.5 7.5 about 7.94 VG-5 45.0 5.94 6.12 20,0 7.5 7.5 about 7.94 VG-6 45.0 5.94 6.12 20,0 10,0 10,0 about 2.94 VG-7 45.0 5.94 6.12 20,0 10,0 10,0 about 2.94 VG-8 ⁵⁾ 45.0 5.94 6.12 20,0 10,0 10,0 about 2.94 VG-9 50.0 6,60 6.80 20,0 7.0 7.0 about 2.60 VG-10 ⁶ ' 50.0 6,60 6.80 20,0 7.0 about 9.6 0.0 VG-11 23.3 6.30 6.50 15.0 5.0 5.0 38,9

Notes:

1) active compound (I) = metamitron technically active compound (II) = ethofumesate technically active compound (III) = phenmedipham technical

2) dispersant: alkylaryl sulfonate

3) emulsifier: polyoxyethylene- (6) -tridecyl ether

For preparations containing an emulsifier, a 50% pre-mix with silicic acid was prepared.

4) carriers: highly dispersed silicic acid for precipitation + kaolin W

5) the specified amount of active compound metamitron (I) and the specified amount of emulsifier are fused together at

160 ° C and cooled. The waxy mass is mixed with silicic acid.

6) 60% emulsifier with 40% silicic acid is used as premix; this premix is prepared by mixing 4Q of the two ingredients. Kaolin is not added.

B) Examples of application of preparations used in the experiments:

(a) according to the prior art, a (res45 ervoir) mixture such as etharone consisting of ®GOLTIX /: Metamitron (I), Bayer AG, 70% B-form;

© TRAMAT / ETHOFUMESAT (II), Shering AG, liquid form, content of 5Q active compound 200 g / l;

© BETANAL / Phenmedipham (III), Shering AG, emulsion concentrate, containing 157 g / l active compound.

b) according to the invention described in the preparation examples, solid form BH-1 to BH-10 of metamitron & ethofumesate & phenmedifam.

Conducting experiments:

Preparation of active compound preparations: weigh the required amounts of the finished formulations, respectively, weigh and prepare with water in spray suspensions.

Post-emergence method: test plants are grown in a greenhouse under controlled conditions (standard soil / normal soil, temperature, moisture, light) up to a size of 5 to 10 cm and then treated with herbicides in a spray booth.

The concentration of the spray suspensions is selected so that the corresponding desired amounts of active compound per unit area are applied with 500 Ι / ha of water.

After treatment, the pots with the experimental plants are kept in the greenhouse until the values are taken into account. Two to three weeks after treatment, the degree of plant damage in% relative to untreated control plants is estimated.

Designation:

= no impact / damage (as untreated plants)

100 = complete destruction / damage The following tables A through G give the forms, expenditures, test plants and impacts.

Abbreviations used in the tables: WST = active compound, BEAVA = Beta vulgaris (beet), AMARE = Amaranthus retroflexus, GALAP = Galium apparatus, MATIN = Matricaria inodora, MERAN = Mercurialis annua, POLCO = Polygonum convolvulus, SINAL = Sinapis alba.

Table A-l

Post-emergence / greenhouse test (standard soil)

form *) Exp. qty. experienced plants g / ha damage, respectively. WST influence in% BEAVA AMARE (a) according to the prior art (tank mixture): 2000+ 264 + 272 0 70 metamitron + ethofumesate + phenmedipham (b) according to the invention: VG-2 2000 +264 +272 0 100 metamitron & ethofumesate & fenmedifam VG-4 2000+ 264+ 272 0 90 metamitron & ethofumesate & phenmedipham VG-7 2000 +264 + 272 0 90 metamitron & ethofumesate & fenmedifam

*) for (b) cp8. relevant receipt examples (applies to all Tables A through G).

Table A-2

Post-emergence / greenhouse test (normal soil)

form *) Exp. qty. experienced plants g / ha damage respectively. WST influence in% BEAVA AMARE (a) according to the prior art (tank mix): 500+ 66 + 68 0 80 metamitron + ethofumesate + phenmedipham (b) according to the invention: VG-1 500+ 66+ 68 0 100 metamitron & ethofumesate & phenmedipham VG-2 500 + 66 +68 10 100 metamitron & ethofumesate & phenmedipham VG-7 500 + 66 +68 0 100 metamitron & ethofumesate & phenmedipham VG-8 500 + 66 +68 0 90 metamitron & ethofumesate & fenmedifam

Table B

Post-emergence / greenhouse test (normal soil)

form *) Exp. qty. experienced plants g / ha damage respectively. WST influence in% (a) according to the level of 1000 + 132 + 136 BEAVA 10 GALAP 80 technique (tank mix): metamishron + ethofumesate + phenmedipham (b) according to the invention: 1000. +132 +136 10 80

VG-8 Metamitron & Ethofumesate & Phenmedifam

Table C

Post-emergence / greenhouse test (standard soil)

form *) Exp. qty. experienced plants g / ha damage respectively. WST influence in% BEAVA GALAP (a) according to the prior art (tank mixture): 4000 + 528 + 544 20 90 metamishron + ethofumesate + phenmedipham (b) according to the invention: VG-1 4000 * 528 + 544 10 100 metamitron & ethofumesate & fenmedifam

Table D

Post-emergence / greenhouse test (standard soil) shape *) ext. qty. test plants g / ha damage resp.

WST influence in%

BEAVA MERAN (a) according to the level of 4000 + 528 + 544 20 technique (tank mix):

metamitron + ethofumzate + phenmedipham (b) according to the invention: 4000 +528+ 544 0 '

VG-3 metamitron & ethofumzat & phenmedipham

Table D-1

Post-emergence test1 Orujukery (standard finger) shape * Exp. qty. g / ha WST test plants damage resp. influence in% BEAVA POLCO (a) according to the level of 4000 + 528+ 544 20 technique (tank mix): metamitron + ethofumesate + phenmedipham (b) according to the invention:

VG-5 Metamitron & Ethofumesate & Phenmedifam

VG-6

4000. + 528 +544 0

4000 +528 +544 10

100 Metamitron & Ethofumesate & Phenmedifam

Table D-2

Post-emergence / greenhouse test (normal soil) shape * ext. qty. g / ha WST test plants damage resp. influence in% BEAVA POLCO (a) according to the prior art 2000+ 264+ 272 10 technique (tank mix): metamitron + ethofumesate + phenmedipham (b) according to the invention:

VG-9 Metamitron & Ethofumesate & Phenmedifam

VG-10

2000 + 264 + 272 0

2000 + 264+ 272 0

100

100 Metamitron & Ethofumesate & Phenmedifam

Table F

Post-emergence / greenhouse test (standard soil)

form *) Exp. qty. g / ha WST experienced plants damage resp. influence in% BEAVA SINAL (a) according to the prior art 4000+ 528 + 544 20 90 (tank mix): metamitron + ethofumesate + phenmedipham (b) according to the invention: VG-5 4000+ 528 +544 0 90 metamitron & ethofumesate & fenmedifam 11

Claims (10)

Claims A herbicidal agent comprising a combination of the active compounds metamitron (I) and ethofumesate (II) and the combinations: 5 (A) phenmedipham (III) or (B) phenmedipham (III) and desmedifam (IV) or (B) desmedifam (IV), together with ancillary additives, characterized in that it is in the form of a solid form of administration, wherein the weight ratio of the active compounds (1) :( 11) :( 111) in combination (A) is (1) :( 0.05 to 1) :( 0.05 to 1), the weight ratio of the active compounds (1) :( 11) :( 111): (IV) in combination (B) is (1) :( 0.05 to 1) :( 0.05 to 1) :( 0.05 to 1) and the weight ratio of the active compounds inenium (1) :( 11): (IV) in combination (B) is (1) :( 0.05 to 1): (0.05 to 1), having the total content of 20 active compounds in combinations (A) , (B) and (B) is between 20 and 75% by weight. A herbicidal agent according to claim 1, characterized in that the weight ratio of the active compounds 25 (1) :( 11) :( 111) is (1) :( 0,1 to 0,4) :( 0,1 to 0.4), of the active compounds (1) :( 11) :( III) :( IV) is (1) :( 0.1 to 0.4) :( 0.1 to 0.4) :( 0.1 to 0.4) and the active compounds (1) :( 11): (IV) is (1) :( 0.1 to 0.4) :( 0.1 to 0.4). 30 A herbicidal agent according to claim 1, characterized in that the weight ratio of the active compounds (1) :( 11) :( 111) is (1) :( 0.1 to 0.35) :( 0.1 to 0.3) of the active compounds (I): (II): (1II): (1V) is 35 (1) :( 0.1 to 0.4): (0.1 to 0.35) :( 0.1 to 0.25) and the active compounds (I) :( II) :( IV) is (1) :( 0.1 to 0.4) :( 0.1 to 0.3). A herbicidal agent according to claim 1, characterized in that the total 40 content of active compounds in combinations (A), (B) and (B) is between 30 and 70%. The herbicidal agent according to claims 1 to 4, characterized in that it comprises, as auxiliary additives, a carrier, a dispersant and, if necessary, an emulsifier and / or a wetting agent. The herbicidal agent according to claim 1, characterized in that it is in the form of water-dispersible granules. A herbicidal agent according to claim 1, characterized in that it is in the form of a water-dispersible powder. 8. A herbicide agent in the form of water-dispersible granules according to claims 1 and 6, characterized in that it contains 1 parts by weight. metamitron (I) additionally in parts by weight: 0.2 - 0.5 dispersant, 0.0 - 0.3 emulsifier, 0.1 - 0.3 silicic acid and 0.0 - 0.2 kaolin. A herbicide agent in the form of a water-dispersible powder according to claims 1 and 7, characterized in that it contains, in 1 parts by weight, metamitron (I) in addition in parts by weight: 0.05 - 0.2 dispersant, 0.00 - 0.3 emulsifier, 0.00 - 0.1 wetting agent, 0.10 - 0.3 silicic acid and 0.05 - 0.2 kaolin. 10. A process for preparing a herbicide agent in solid form according to claim 1, characterized in that the water-dispersible powder form is obtained by mixing the active compounds in the respective weight ratios according to claim 1 with auxiliary additives, grinding the resulting mixture. and subsequent homogenization by re-mixing and that the water-dispersible granulate is obtained by: a) preparation of a preliminary mixture of the active compounds (I), (II) and (III) or (I), (I), (III) and (IV) or (I), (II) and (IV) in the corresponding weight ratios according to claim 1 and auxiliary additives suitable for water-dispersible granules, by mixing, grinding and subsequent re-mixing, (b) treating this premix with water in a fluid bed granulator in the usual manner, followed by drying at an inlet air temperature of 50-90 ° C to a product temperature of 30-60 ° C; and c) separating the desired granulate (granule size between 200 and 1500 gm) by sieving whereby small granules (<200 gm in size) and coarse granules (larger than 1500 gm in size) are separated.