LU82017A1 - HERBICIDE TREATMENTS AND FORMULATIONS - Google Patents

Description

♦ »t. 1 l, 1 [The present invention relates to a method for controlling weeds in grain crops, as well as herbicidal formulations which, inter alia, are useful in this method.

5 In order to control a wide range of weeds in crops, for example, grain crops, it is often necessary to use more than one herbicide. Despite the use of these mixtures, weeds still resist the herbicide treatment, thereby causing damage to the winter and spring grain crops, for example! wheat, barley, oats and rye.

| Now, it has been found that specific combinations of herbicides not only provide a broad spectrum of control, but unexpectedly are effective against weeds, in particular broadleaf weeds, in cereal crops.

Accordingly, the present invention provides a method for controlling weeds, in particular, broad weeds! leaves, in a cereal harvest field, this j process consisting in applying, to this field and after i; the emergence of the harvest, "bifenox" which is a

| 25 compound of formula I

j 0 CH30-C Cl j ", 'o - /” Va mi as well as one or more other active ingredients 1 chosen from: (1) a benzoic acid herbicide, namely "dicamba" or acid 2, 3,6-trichloroben-35 zoïque or one of their salts or esters, (2) a herbicide Z "'2

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μη phenoxy-acid, namely "dichlorprop" or [2,4-dichlorophenoxy) -butyric acid or one of their salts or esters, (3) a herbicide of dinitrophenol, namely 2-methyl-4,6 -dinitrophênol, "dinoterb" or 5 "dinoseb" or one of their salts or esters, (4) a benzonitrile herbicide, namely "ioxynil" or "bromoxynil" or one of their salts or esters , (5) benazoline or one of its salts or esters, (6) ben- * tazone and (7) 3,6-dichloropicolinic acid or one of its salts or esters.

It will be understood that, in the process of the invention, more than one of the active ingredients (1) to (7) can be used and that, in fact, other additional herbicidal compounds can be used in conjunction with these. ingredients (1) to (7). When the active ingredient is acidic or phenolic in nature, derivatives such as salts and esters can be used, provided of course that they are not phytotoxic to crops, that is to say say that they are not significantly more phytotoxic than free acid or phenol. The nature of these salts and esters is well known to those skilled in the art.

The preparation of "bifenox", ie methyl 5- (2,4-dichlorophenoxy) -2-nitrobenzoate, is described in British Patent 1,232,368 and its use as a herbicide is described in " Proc.

N.E. Weed Sci. Conf. "1973, 27, 31. Likewise," dicamba ", which is a herbicide of benzoic acid, namely 3,6-dichloro-2-methoxybenzoic acid, is described in the United States patent. United States of America No. 3,013,054, while 2,3,6-trichlorobenzoic acid is described in United States of America patents kn 2,848,470 and 3,081,162. Phenoxy-acid herbicides are part of a well known group of compounds which have long been widely available.

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I ’3" dichlorprop "is a common name for 2- (2,4-dichlorophenoxy) -propionic acid. The dinitro-phenol herbicide, namely 2-methyl-4,6-dinitrophenol, was the subject of British Patent 425,295; "dinoseb" 5 is the common name for 2-sec-butyl-4,6-dinitrophenol which is described in United States Patent No. 2,192,197, while "dinoterb" is 2-tert-butyl-4,6-dinitrophenol which has been described, for example, in British Patent No. 1,126,658.

• 10 The herbicides "ioxynil" (4-hydroxy-3,5-diiodobenzo-• nitrile) and "bromoxynil" (3,5-dibromo-4-hydroxybenzo-nitrile) are both described, for example, in the British patent 977,755. Benazoline (chemical structure: 4-chloro-2-oxo-3-benzothiazoline-acetic acid) is described in British Patent 862,226, while bentazone which is the common name for 3-isopropyl 2,2-dioxide - (1H) -benzo-2,1,3-thiadiazin-4-one, is described in US Patent No. 3,708,277. 3,6-20 dichloropicolinic acid is described in US Patent No. 3,317,549.

The cereal crop can be, for example, a wheat, barley, oat or rye crop and the process of the invention exerts its strongest action in the processing of wheat and barley crops , in particular the winter wheat crops, as well as the spring and winter barley crops. The sensitivity of the crop, as well as the severity of the weed problem, determines the amount of active ingredient to be applied. However, as a general rule, "bifenox" is applied at a rate of 0.25 to 3 kg / hectare, preferably at a rate of 0.5 to 1.5 kg / hectare and, in; particular, at a rate of 0.5 to 0.75 kg / hectare.

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The preferred application rates for the other active ingredients (1) to (7) are given below. When a component is derived from an acid or phenol, the amounts are based on the equivalent of free acid or phenol. Thus, when using a benzoic acid herbicide, namely "dicamba", or 2,3,6-trichlorobenzoic acid, it is preferably applied at a rate of 0.05 at 0.2 kg / hectare, the weight ratio between "bifenox" and the benzoic acid herbicide 40 advantageously being between 60: 1 and 1: 1, preferably between 30: 1 and 4: 1. The benzoic acid herbicide can be used in the form of one of its salts, in particular, in the form of one of its alkali metal salts such as a sodium or potassium salt, or alternatively in the form of one of its esters, for example, an alkyl ester containing 1 to 8 carbon atoms.

When a herbicide of a phenoxy acid, namely "dichlorprop" or 4- (2,4-dichlorophenoxy) -butyric acid, is used, it is preferably applied at a rate of 0 , 1 to 3.5 kg / hectare, the weight ratio between "bifenox" and the phenoxy-acid herbicide advantageously being between 30: 1 and 1:15, in particular, between 8: 1 and 1: 6. In a particularly preferred embodiment, "bifenox" is applied at the rate of 0.5 to 0.75 kg / hectare and the phenoxy acid herbicide at the rate of 1.5 to 3 kg / hectare. Advantageously, the herbicide of a phenoxy acid is used in the form of one of its salts, for example, in the form of one of its alkali metal salts, in particular in the form of a sodium salt. or potassium or in the form of an amine or ammonium salt.

Among the ester forms of the phenoxy acid herbicide, there may be mentioned those containing 1 to 8 carbon atoms in the ester group, for example, ethyl, isopropyl and butyl esters. When- /! · 5! ! i! that a dinitrophenol herbicide is used, namely 2-methyl-4,6-dinitrophenol, "dinoterb" or "dinoseb", it is preferably applied at a rate of 0.5 to 5 kg / hectare, better still and, in particular, 5 in the case of "dinoterb" or "dinoseb", at a rate of 0.5 to 2 kg / hectare. Preferably, the weight ratio „between" bifenox "and the herbicide dinitrophenol is between 6: 1 and 1:20, more preferably between 3: 1 and 1: 6. Among the suitable salt forms of the herbicide dinitrophenol, there may be mentioned, for example, those formed with both inorganic and organic bases, in particular the salts of amines and ammonium. Among the esters, mention may be made, for example, of those formed with organic acids, for example, carboxylic acids, especially acetal | "dinoseb" head.

i When using a benzonitrile herbicide, ie "ioxynil" or "bromoxynil", it is applied | that, preferably, at a rate of 0.05 to 0.5 kg / hectare, 120 more preferably, at a rate of 0.1 to 0.35 kg / hectare. Preferably, the weight ratio between "bifenox" and the benzonitrile herbicide is between 60: 1 and 1: 2, more preferably between 15: 1 and 2: 1. In a particular embodiment, "ioxynil" | 25 and "bromoxynil" are used together with "bifenox", in which case the preferred application rates and preferred weight ratios mentioned above are based on weight. total of "ioxynil" and "bromoxynil". Preferred salt forms of "ioxynil" and "bromoxynil" are alkali metal salts such as sodium and potassium salts. Among preferred esters , j there is the oxynyn octanoate and the bromo xynil octanoate.

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When using benazoline, it is preferably applied at a rate of 0.05 to 0.25

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L / 4 6 kg / hectare. Preferably, the weight ratio between MbifênoxM and benenazoline is between 60: 1 and 1: 1, better still, between 15: 1 and 5: 2. Among the suitable salt forms of benazoline are the alkali metal salts, in particular the sodium and potassium salts. The preferred esters are those containing 1 to 4 carbon atoms in the ester group, in particular the ethyl ester.

When bentazone is used, it is preferably applied at the rate of 0.1 to 1.5 kg / hectare, more preferably at the rate of 0.2 to 1.5 kg / hectare and most advantageously at a rate of 0.5 to 1.5 kg / hectare. The preferred weight ratio between "bifé-nox" and bentazone is between 6: 1 and 1: 6, better still, between 3: 1 and 1: 2.

When 3,6-dichloropicolic acid is used, it is preferably applied at the rate of 0.025 to 0.15 kg / hectare, more preferably at the rate of 0.05 to 0.1 kg /hectare. The preferred weight ratio between "bifenox" and 3,6-dichloropicolinic acid is between 30: 1 and 3: 1, more preferably, between 15: 1 and 5: 1.

Among the saline forms of 3,6-dichloropicolinic acid, there may be mentioned the alkali metal salts, for example, the sodium and potassium salts, as well as the amine and ammonium salts, for example , the monoethanolamine salt. As esters, mention may be made of those containing 1 to 8 carbon atoms in the ester group.

Preferably, the process of the present invention is carried out when the grain harvest is between the leaf stage and the appearance of the second node.

When "bifenox" is used with the benzoic acid herbicide, there is particularly good control of the following weed species:

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Stellaria media, Polygonum spp, Spergula arvensis, Tripleurospermum maritimum, Viola spp and Veronica spp.

When "bifenox" is used with the phenoxy acid herbicide, there is particularly good control of the following weed species: Galium aparine, Stellaria media and Veronica SPP "

When "bifenox" is used with dinitrophenol herbicide, there is particularly good control of the following 1.0 weed species: Galeopsis tetrahit, Fumaria officinalis, Polygo-num convolvulus and Galium aparine.

When "bifenox" is used with the benzonitrile herbicide, there is particularly good control of the following weed species: Matricaria spp, Polygonum spp and Galium aparine.

When using "bifenox" with bena-zoline, particularly good control of the following weed species is observed: Stellaria 20 media, Galium aparine and Viola spp.

When using "bifenox" with the benta-zone, we observe a particularly good control of the following weed species: Viola spp, Veronica spp and Matricaria spp.

When using "bifenox" with 3,6-dichloropicolinic acid, particularly good control of the following weed species is observed: Veronica spp and Matricaria spp.

Other additional herbicidal compounds which can be used with "bifenox" and components (1) to (7) above include, for example, "MCPA", "MCPB" and "mecoprop" which are all well known herbicides, of which there is an abundance of documentation in the literature and which are included in "Pesticide 1s 7v> /

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i '8 f à * i * ï i t |: Manual ”, Sixth edition, published by” British Crop Pro tection Council ".

The "bifenox" and the active ingredient (s) (1) to (7) above, as well as optionally an additional compound 5 with herbicidal activity can be applied to the field of the crop either simultaneously or separately. In this case, it is preferable to adopt a short time between applications, for example, one day or less, however, it is far better to apply the compounds * simultaneously as a single formulation. to simplify manufacturing, storage and transport, herbicide formulations are normally prepared in the form of concentrates which must be diluted to the required degree with water in order to be able to obtain the application rates mentioned above. above, this dilution: being generally calculated such that the formulation to be applied to the field of harvest contains 0.05 to 3% by weight of the active herbicidal ingredients. As a general rule, the formulations of! 1 to 90¾, preferably 15 to 851 of the active ingredients associated with one or more ί non-phytotoxic carriers or diluents.

: Concentrate formulations are part of the present invention. Therefore, a concentrated herbicidal formulation is provided which can be used! in particular, but not exclusively, in the process of the invention, this formulation comprising I v "bifenox", one or more other active ingredients _ "| 30 chosen from (1) a benzoic acid herbicide, namely "dicamba" or 2,3,6-trichlorobenzoic acid I or one of their salts or esters, (2) a herbicide I of a phenoxy -acid, namely "dichlorprop" or] 4- (2,4-dichlorophenoxy) -butyric acid or alternatively 35 | one of their salts or esters, (3) a herbicide of dini- / 9 trophenol, namely 2-methyl-4,6-dinitrophenol, Mdinoterb "or" dinoseb "or also one of their salts or esters, ( 4) a benzonitrile herbicide, namely "ioxynil" or "bromoxynil" or one of their 5 salts or esters, (5) benazoline or one of its salts or esters, (6) bentazone and (7 ) 3,6-dichloro-picolinic acid or one of its salts or esters, in combination with one or more non-phytotoxic carriers or diluents.

In this formulation, the weight ratios between the "bifenox" and each of the ingredients (1) to (7) are preferably those indicated above with respect to the process of the invention.

The concentrate formulations according to the invention are usually in the form of a wettable powder, an emulsifiable concentrate or an aqueous suspension. Formulations in aqueous suspensions and in wettable powders are preferred for the process of the invention because they are much less phytotoxic to cereal crops than emulsifiable concentrates.

The wettable powders comprise an intimate mixture of the active ingredients, one or more inert carriers and suitable surfactants.

The inert support can be chosen, for example, from attapulgite clays, montmoril-lonite clays, diatomaceous earth, kaolins, micas, talcs and purified silicates. We can find

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surfactants effective among sulfonated lignins, naphthalene sulfonates and condensed naphthalene sulfonates, alkyl succinates, alkylbenzene sulfonates, alkyl sulfates and nonionic surfactants such as the products I of addition of phenol to ethylene oxide.

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10 \ i it ii i? Ά || Emulsifiable concentrates include the active ingredients dissolved in one or more suitable solvents, together with a surfactant. Suitable surfactants can be selected, for example, from those mentioned above in connection with wettable powders. Among the suitable solvents are benzene substituted with an alkyl group, o-chlorotoluone, heavy aromatic naphthalene, glycol ethers and the like. 10 cyclic ketones.

! * Suspensions and aqueous solutions com-! take the active ingredients in suspension or in solution in water or suitable solvents together with any desired surfactant, thickening agent, antifreeze agent or preservative. Appropriate surfactants | may be chosen from those mentioned above in connection with wettable powders. When used, the thickeners are normally selected from suitable cellulosic materials and natural gums, while glycols will generally be used when an antifreeze agent is required. Preservatives can be selected from a wide range of materials such as the various "paraben" antibacterial agents, phenol, o-chlorocresol, phenyl mercury nitrate and formaldehyde.

P Alternatively, herbicidal formulations can be formed by mixing the two active ingredients 30 or more with water in a spray tank i immediately before use, thereby providing water- | non-phytotoxic support. These formulations

Are called "tank mixes" and they constitute another aspect of the invention. In these tank mixtures, the weight ratios between the "bifenox" and the i / (11 other ingredients (1) to (7) are again, preferably, those indicated above for the process of l 'invention.

The following examples illustrate concentrated herbicidal formulations according to the invention.

When a herbicidal ingredient is a derivative of an acid or phenol, the amount is based on the acid or phenolic equivalent.

EXAMPLES 1 to 10 The following wettable powders are prepared in each case with the ingredients indicated.

% by weight (1) "Bifenox" 25

Bentazone 25 15 Sodium alkyl ether sulfate 3

Sulfonated lignin 2

Precipitated silica 6

Talc, to complete 100 20 (2) "Bifenox" 50 "Ioxynil" 5

Sodium salt of condensed naphthalene sulfonic acids 2

Ethoxylated alkylphenol 4 25 Pyrogenic silica 5

Montmorillonite, to complete 100 (3) "Bifenox" 42 "Bromoxynil" 6 30 Sodium lauryl sulfate 5

Sodium lignosulfonate 3

Precipitated silica 8

Kaolin, to supplement £ 100 35

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r 12 i (4) "Bifenox" 48 Bénazoline (ethyl ester) 4

Nonylphenol ethoxylate 4

Sulfite washing powder 4 5 Pyrogenic silica 5

Attapulgite to complete at 100 (5), TBifenox "40

3,6-dichloropicolinic acid ’10 (monoethanolamine salt) 4

Sodium lauryl sulfate 4

Sodium lignosulfonate. 3

Precipitated silica 8

Kaolin, to complete 100 15 (6) "Bifénox'1 20

4- (2,4-Dichlorophenoxy) -butyric acid (potassium salt) 30

Ethoxylated alkylphenol 2 20 Sulfite washing powder 4

Pyrogenic silica 5

Attapulgite, to complete 100 (7) "Bifenox" 20 25 "Dichlorprop" (potassium salt) 40

Sodium dialkylsulfosuccinate 3

Lignosulfonate 2

Micronized silica 7

Land of dippers, for 30 to complete 100! (8) "Bifenox" 45 "Ioxynil" 2.5 I "Bromoxynil" 3 13, »

Sodium lignosulfonate ‘3

Precipitated silica 5

Montmorillonite, to complete 100 5 (9) "Bifénox" 40

2,3,6-trichlorobenzoic acid - (sodium salt) 5

Sodium lauryl sulfate 3 ► Sodium lignosulfonate 3 10 Precipitated silica 4

Kaolin, to complete 100 (10) "Bifenox" 40 "Dicamba" (sodium salt) 4 15 Alkylphenol ethoxylated 4

Lignosulfonate 2

Pyrogenic silica 3

Sodium aluminosilicate, to make up to 100.

In each example, the active ingredients are carefully mixed with the specified excipients in conventional mixing equipment. Then, the mixture is kneaded further in a fluidization kneader to a granularity of 1 to 10 microns.

25 EXAMPLES 11 to 22

The following emulsifiable concentrates containing the constituents indicated are prepared: (11) "Bifenox" 25 "Ioxynil" (octanoate) 3 30 Dodecyl-benzene-calcium sulfonate 4

Alkylphenoxy-polyoxyethylene-ethanols 2] Cyclohexanone ’35 35 —jy. Xylene, to complete to 100 / (! T - 14 (12) '' Bifenox "20 d" Bromoxynil "(octanaote) 4 iSel of dodecylbenzene-sulfonic acid amine 3 5 Polyoxyethylene triglyceride 3

Cyclohexanone 30

Orthochlorotoluene, to complete 100 10 (13) "Bifenox” 20 Bénazoline (ethyl ester) 2

Calcium dodecyl-benzene-sulfonate 2

Ethoxylated alkylphenol 4 15 Isophorone 35

Heavy aromatic naphtha, to complete at 100 days (14) "Bifenox" 6 20 2-methyl-4,6-dinitrophenol 20

Calcium dodecyl-benzene-sulfonate 3

Ethoxylated alkylphenol 3 I Cyclohexanone 25 25 Heavy aromatic naphtha, to I complete to 100 | '(15) "Bifenox” 20 | v "Dinoterb" 10 | J 30 Alkyl aryl sulfonate 2 j Alkylphenoxy-polyoxyethylene- j ethanols 4 j Isophorone 30 i Orthochlorotoluene to complete at 100' 35 * 5 ^ (15 "Bifenox "15" Dinoseb "15

Amine salt of dodecylbenzene sulfonic acid 4 5 Polyoxyethylene triglyceride 3

Isophorone 20

Heavy aromatic naphtha, to complement 100 .10 (17) "Bifénox" 20

3,6-dichloropicolinic acid 4

Calcium dodecyl benzene sulfonate 4

Ethoxylated alkylphenol 4 15 Isophorone 30

Heavy aromatic naphtha, to complement 100 (18) "Bifenox" 15 20 4- (2,4-Dichlorophenoxy) - butyric acid (isopropyl ester) 30

Alkylaryl sulfonate 4

Polyoxyethylene 2 triglyceride

Cyclohexanone 25 25 Xylene, to complete to 100 (19) "Bifenox" 15 "Dichlorprop" (butyl ester) 45

Dodecylbenzene sulfonate 3 amine salt

Alkylphenoxy-polyoxyethylene-ethanols 3

Cyclohexanone 25

Heavy aromatic naphtha, to 35 complete to 100

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L / 16 i \ (20) "Bifënox" 20 "Ioxynil" (octanoate) 1.5 "Bromoxynil" (octanoate) 2

Dodecylbenzene sulfonate 5 calcium 3

Alkylphenoxy-polyoxyethylene-ethanols 4

Isophorone 30

Orthochlorotoluene, for 10 complete with 100 (21) "Bifënox" 25

2,3,6-trichlorobenzoic acid (ester) 3 15 Dodecyl-benzene-calcium sulfonate 3

Alkylphenol ethoxylated 3

Isophorone 30

Orthochlorotoluene, to complete 20 to 100 (22) "Bifënox" 20 "Dicamba" 2

Alkylaryl sulfonate 4 25 * Alkylphenoxy-polyoxyethylene-ethanols 2

Cyclohexanone 25 I - Xylene, to make up to 100.

The active ingredients are added to the appropriate solvent (s) while stirring and optionally! by heating to facilitate the solubilization of the active ingredients. Next, the surfactants are added. After solubilization, the so- is filtered; fj lution to remove insoluble impurities.

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"17 EXAMPLES 25 to 26

The following aqueous suspensions are prepared from the indicated components:% w / v 5 (23) "Bifenox" 20

Bentazone 20

Alkylaryl sulfonate 2

Phosphate ester of an ethoxylated polyarylphenol, neutralized with, triethanolamine 2

0.2 xanthan gum

Silicone antifoaming agent 0.1

Formaldehyde 0.2 15 Water, to complete 100 (24) "Bifenox" 40 "Ioxynil" (sodium salt) 4

Ethoxylated nonylphenol 3 20 Hydroxymethyl cellulose 2

Silicone antifoaming agent 0.1

Water, to make up to 100 (25) "Bifenox" 35 25 "Bromoxynil" (potassium salt) 3.5

2.5 ethoxylated nonylphenol

Hydroxymethyl cellulose 1.7

Silicone antifoaming agent 0.1

Water, to make up to 100 30 (26) "Bifenox" 48 Bénazoline (potassium salt) 8

Sodium lauryl sulfate 3

Attapulgite 1.5 35 Silicon defoaming agent 0.15 | Water, to make up to 100.

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The herbicidal ingredients are mixed with the surfactants and the anti-foaming agent, then; stirred vigorously in water to form an aqueous suspension in large particles. Then, the latter is kneaded wet to reduce the particle size of the active ingredients to 0.5-20 microns. To this preparation kneaded by; wet, then an aqueous suspension of the thickening agent or suspending agent (hydrated) is added.

Example 27 below illustrates the test method adopted to determine the effectiveness of the method and of the formulation of the invention.

EXAMPLE 27 - TEST PROCEDURE

115 Add the appropriate amount of the formulated product (for example, one of the concentrated formulations of Examples 1 to 26 above) to an amount of water in a micropulverizer which is then stirred to disperse . We settle it; 20 sprayer to obtain a volume equivalent to 200 liters / hectare under a pressure of about 2.72 atmospheres. To the sprayer, we adapt a typical nozzle (Allman N ° 0) distributing a fan fan.

} ί The application is made post-emergence i 25 on both the crop and the weeds, the! harvest varying, for different applications, between the three-leaf stage and the start of stem extension. The stage reached by the bad; herbs at the time of application can also vary I 30 between the cotyledon stage and the stage of a small! plant.

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Claims (12)

1. A method for combating weeds in a cereal harvest field, characterized in that it consists in applying, to this field and after the emergence of the harvest, "bifenox" which is a compound of formula I 0 ch3o-c Cl lo o2n - ^) - 0- ^ ^ -Cl (I) and one or more other active ingredients chosen from: (1) a benzoic acid herbicide, 15. ie "dicamba ”Or 2,3,6-trichlorobenzoic acid or one of their salts or esters, (2) a herbicide of a phenoxy acid, namely" dichlorprop "or 4- (2, 4-dichlorophenoxy) -butyric acid or one of their salts or esters, (3) a herbicide of dinitro-phenol, namely 2-methyl-4,6-dinitrophenol, "dinoterb" or "dinoseb" or one of their salts or esters, C4) a benzonitrile herbicide, namely "ioxynil" or "bromoxynil" or also one of their salts or esters, (5) benazoline or one of its salts or esters, ( 6) bentazone and (7) 3,6-dichloropicolinic acid or one of its s els or esters. 2. Method according to claim 1, characterized in that the "bifenox" is applied at a rate of 0.25 to 3 kg / hectare of the field. 3. Method according to claim 2, ca characterized in that the application rate is between 0.5 and 1.5 kg / hectare. 4. Method according to claim 3, characterized in that the application rate is 35 I between 0.5 and 0.75 kg / hectare. A * 20 * • fc 5. Method according to any one of claims 1 to 4, characterized in that the benzoic acid herbicide is applied at a rate of 0.05 to 0.2 kg / hectare, the phenoxy-acid herbicide, at a rate of 0.1 to 3.5 kg / hectare, the dinitrophenol herbicide, at a rate of 0.5 to 5 kg / hectare, the benzonitrile herbicide, at a rate of 0.05 at 0.5 kg / hectare, benazoline, at a rate of 0.05 to 0.25 kg / hectare, bentazone, at a rate of 0.1 to 1.5 kg / hectare and „10 acid 3, 6-dichloropicolinique, at a rate of 0.025 to * 0.15 kg / hectare. 6. Method according to any one of claims 1 to 7, characterized in that the "bifenox" is applied at a rate of 0.5 to 0.75 kg / hectare and the herbicide of phenoxy-acid, to 1.5 to 3 kg / hectare. 7. Method according to any one of i claims 1 to 5, characterized in that one applies "bifenox" with both "ioxynil" and "bromo-20 xynil". 8. Herbicidal formulation, characterized in that it is a concentrate or a tank-mix comprising "bifenox", as well as one or more of the active ingredients (1) to (7) indicated in claim 1, in combination with one or more non-phytotoxic diluents or carriers. 9. Herbicide formulation according to resale; - indication 8, characterized in that the weight ratio between "bifenox" and the benzoic acid herbicide 30 is between 60: 1 and 1: 1, the weight ratio between "bifenox" and phenoxy herbicide -acid is between 30: 1 and 1:15, the weight ratio between "bifenox" and the herbicide of dinitrophenol is between 6: 1 and 1:20, the weight ratio between "bifé-35 I nox" and the benzonitrile herbicide is between 60: 1 At 21 and 1: 2, the weight ratio between "bifenox" and benazoline is between 60: 1 and 1: 1, the weight ratio between "bifenox" and bentazone is between 6: 1 and 1: 6, while the weight ratio between 5 "bifenox" and 3,6-dichloropicolinic acid is between 30: 1 and 3: 1. 10. Herbicide formulation according to any one of claims 8 and 9, characterized in that it is a concentrate formulation containing y e10 15 to 851 of active ingredients. * 11. Herbicidal formulation according to claim 10, characterized in that it is an emulsifiable concentrate, an aqueous suspension or a wettable powder. 12. herbicidal formulation according to any of the conchs of claims 8 to 11, characterized in that it is used in the process according to any one of claims 1 to 7. Y)