EP0805627A1

EP0805627A1 - Synergistic herbicidal agents based on glufosinates and nitrodiphenyl ethers and their formulations

Info

Publication number: EP0805627A1
Application number: EP96900574A
Authority: EP
Inventors: Jürgen Cremer; Jean Kocur; Georges Krug
Original assignee: Hoechst Schering Agrevo GmbH
Current assignee: Bayer CropScience AG
Priority date: 1995-01-24
Filing date: 1996-01-10
Publication date: 1997-11-12
Also published as: CA2211200A1; KR19980701620A; CZ227897A3; JPH10512575A; HUP9702457A3; ZA96502B; MX9705604A; AU4437596A; DE19501986A1; CN1169099A; WO1996022692A1; HUP9702457A2; BR9606986A

Abstract

Herbicidal agents containing A) glufosinates or their salts or similar agents like bialophos, B) a nitrodiphenyl ether herbicide like oxyfluorophene and C) an alkyl polyglycol ether sulphate tenside have synergistic herbicidal effects. Components A, B and C can be jointly formulated in the form of an aqueous emulsion in which there are 1-15 % A), 0.1 to 5 % B), 1-15 % C), 3 to 30 % organic solvent, 40-60 % water, 2-10 % emulsifier and 0 to 20 % ordinary formulation auxiliaries.

Description

description

Synergistic herbicidal compositions based on giufosinate and nitrodiphenyl ethers and their formulations

The invention is in the field of crop protection agents which can be used against undesired plant growth, in particular the combinations of herbicides.

Glufosinate Ammonium (Phosphinothricin Ammonium) (1)

O

CH ₃ - P - CH ₂ - CH ₂ - CH - COO NH „(1),

OH NH-

i.e. the ammonium salt of 4- [hydroxy (methyl) phosphinoyl] -DL-homoalanine is a known herbicide which is taken up by the green parts of the plant (leaf herbicide); see "The Pesticide Manual" 9th Edition, British Crop Protection Council 1991, p. 458. Glufosinate-ammonium is mainly used in the post-emergence process to combat weeds and weeds in plantation crops and on non-cultivated land, as well as by means of special application techniques also for inter-row control in agricultural Area crops such as corn, cotton and others used. The compound of formula (1) contains an asymmetric carbon atom. The L enantiomer is considered the biologically active isomer.

Furthermore, it is known that the effect of glufosinate ammonium as well as that of its L-enantiomer can be significantly improved by surface-active substances, preferably by wetting agents from the series of alkyl polyglycol ether sulfates, for example in the form of their alkali metal or Ammonium salts, but also used as a magnesium salt, such as C ₂ / C ₁₄ - fatty alcohol diglycol ether sulfate sodium ( ^® Genapol LRO, Hoechst); see EP-A-0476555, EP-A-0048436, EP-A-03361 51 or US-A-4,400, 196 and Proc. EWRS Symp. "Factors Affecting Herbicidal Activity and Selectivity", 227-232 (1988). It is also known that alkyl polyglycol ether sulfates are also suitable as penetration aids and activity enhancers for a number of other herbicides, including herbicides of the diphenyl ether type; see EP-A-0476555.

Surprisingly, it has now been found that glufosinate-ammonium or related active ingredients can be advantageously combined as penetration aids together with certain herbicides of the nitrodiphenyl ether type and anionic surfactants from the series of alkyl polyglycol ether sulfates and result in synergistic increases in activity.

The invention thus relates to herbicidal compositions, characterized by an effective content of a combination of

A) one or more compounds of formula (A) or their salts

O 0

II II

H ₃ C - P - CH ₂ -CH ₂ - CH - C - Z (A)

I I

OH NH ₂ wherein

Z is a radical of the formula -OM, -NHCH (CH ₃ ) CONHCH (CH ₃ ) COOM or

-NHCH (CH ₃ ) CONHCH [CH ₂ CH (CH ₃ ) ₂ ] COOM, in which M is in each case hydrogen or an inorganic or organic cation,

B) one or more compounds from the group of the herbicides of the nitrodiphenyl ether type and

C) an anionic surfactant from the series of alkyl polyglycol ether sulfates. Formula (A) includes all stereoisomers and their mixtures, in particular the racemate and the biologically active enantiomer.

Examples of active substances of the formula (A) are as follows:

a1) the aforementioned glufosinate and its ammonium salt in racemic form,

a2) the L enantiomer of glufosinate and its ammonium salt,

a3) Bialaphos (or Bilanafos), i.e. L-2-Amino-4- [hydroxy (methyl) phosphinyl] butanoyl-L-alanyl-L-alanine and its sodium salt.

The racemate of glufosinate-ammonium is usually applied alone in doses between 200 and 1000 g a.i./ha (= grams of active ingredient per hectare). In these dosages, glufosinate ammonium is particularly effective when it is absorbed through green parts of plants. Since it degrades microbially in the soil within a few days, it has no permanent effect in the soil. The same applies to the related active ingredient bialaphos sodium; see "The Pesticide Manual" 9th Ed. British Crop Protection Council 1991. P. 75.

Examples of compounds (B) of the nitrodiphenyl ether type are

b1) oxyfluorfen, i.e. 2-chloro-1 - (3-ethoxy-4-nitro-phenoxy) -4-trifϊuormethyl-benzene, the use of which as a single active ingredient with 100-1000 g a.i./ha in soy is known before and after emergence or on non-cultivated land;

b2) lactofen, ie 5- [2-chloro-4- (trifluoromethyl) phenoxy] -2-nitro-benzoic acid 1 - (ethoxycarbonyl) ethyl ester; the active ingredient is usually used alone with 50 - 500 g ai / ha pre- and post-emergence in soybeans and cereals; b3) bifenox, ie methyl 5- (2,4-dichlorophenoxy) -2-nitrobenzoate; the active ingredient is usually used alone with an application rate of 50 to 1000 g ai / ha before and after emergence in cereals, rice and corn;

b4) fluoroglycofen-ethyl, i.e. 5- [2-chloro-4- (trifluoromethyl) phenoxy] -2-nitrobenzoic acid ethoxycarbonylmethyl ester; it is known to be used as a single active ingredient at a rate of 5 to 50 g ai / ha in the pre- and post-emergence in cereals and soybeans;

b5) Acifluorfen, i.e. 5-t2-chloro-4- (trifluoromethyl) phenoxy] -2-nitrobenzoic acid or its salts such as the sodium salt; the single active ingredient is usually used with 100 - 500 g ai / ha pre- and post-emergence in soybeans and cereals; and

b6) Fomesafen, i.e. N-methylsulfonyl-5- [2-chloro-4- (trifluoromethyl) phenoxy] -2-nitrobenzamide; it is known to be used as a single active ingredient with 50 to 1000 g ai / ha pre- and post-emergence in soy or cereals.

The connections b1 to b6 are e.g. B. in "The Pesticide Manual" 9th Edition, British Crop Protection Council 1 991 and literature cited therein and known as herbicides of the protoporphyrinogen oxidase inhibitor type.

The anionic surfactant (C) is, for example, a wetting agent from the group of the fatty alcohol polyglycol ether sulfates and their salts, preferably the C ₁₀ -C ₁₈ fatty alcohol polyglycol ether sulfates in the form of the alkali metal, alkaline earth metal or ammonium salts or the substituted ammonium salts; Substituted ammonium salts are, for example, primary, secondary, tertiary and quaternary ammonium salts with substituents from the group alkyl or hydroxyalkyl, preferably with 1 to 4 carbon atoms.

C is preferably _{1 2} -C ₁₄ -fatty alcohol diethylenglykolethersulfat sodium salt (Genapol ^® LRO, Hoechst AG). From US-A-5, 324,708 it is already known to produce formulations containing a combination of the herbicides glufosinate-ammonium, in the form of a non-hygroscopic salt, and oxyfluorfen. Combinations of these herbicides with anionic wetting agents are not described therein. Biological examples of combinations of the herbicides are missing in US Pat. No. 5,324,708, as are indications of synergistic increases in activity for combinations of glufosinate-ammonium and oxyfluorfen.

Research Disclosure 275 (1987), 1 54 discloses combining the activity spectrum of glufosinate ammonium with other herbicides to supplement the spectrum of action. Among other things, the combination of glufosinate ammonium and oxyfluorfen for use in cotton is mentioned. There are no indications of synergistic increases in effectiveness for the combination of glufosinate ammonium and oxyfluorfen or for combinations with fatty alcohol polyglycol ether sulfates.

Surprisingly, it has been found that when herbicides of type A are used together with one or more active compounds from group B in the presence of surfactant C, superadditive (= synergistic) effects occur. The effect in the combinations is stronger than that of the individual herbicides used in the presence of wetting agent C when used alone. These effects allow a reduction in the application rate, the control of a broad spectrum of weeds and grasses, a faster use of the herbicidal action, a longer lasting effect, better control of the harmful plants with only one or a few applications and an expansion of the possible application period. These properties are required in practical weed control in order to keep agricultural crops free of undesired competing plants and thus to secure and / or increase the yields qualitatively and quantitatively. These new combinations significantly exceed the technical standard in terms of the properties described. The optimal choice of the weight ratio and the application rates depends, for example, on the mixing partners, the stage of development of the weeds or weeds, weed spectrum, environmental factors and climatic conditions.

The weight ratios A: B of the combined herbicides of type A and type B can therefore vary within wide limits and are generally between 100: 1 and 1: 5, preferably between 10: 1 and 1: 1. The following weight ratios A: B are preferred for the combination of type A herbicides, in particular glufosinate-ammonium (racemic): with oxyfluorfen 10: 1 to 2: 1, in particular 8: 1 to 3: 1. with lactofen 10: 1 to 2: 1, especially 8: 1 to 3: 1. with Bifenox 10: 1 to 2: 1, especially 8: 1 to 3: 1. with fluoroglycofen 100: 1 to 10: 1, in particular 50: 1 to 10: 1. with acifluorfen 10: 1 to 2: 1, in particular 8: 1 to 3: 1. with fomesafen 10: 1 to 2: 1, especially 8: 1 to 3: 1.

The application rate of the respective herbicides in the combined application is substantially below the application rate for the individual application of the respective herbicide with the same herbicidal action. As a rule, application rates of 100 to 600 g a.i./ha herbicide of type A, preferably glufosinate-ammonium, and from 50 to 150 g a.i./ha of nitrodiphenyl ethers such as oxyfluorfen and lactofen are preferred.

In addition to the factors already mentioned, the optimum application rate of the type C anionic surfactant depends on the application rate of the herbicides and is generally between 100 and 2000 g surfactant per hectare, based on the detergent substance (WAS), preferably 500 to 1500 g WAS / Ha. The weight ratio of herbicide A to surfactant C is accordingly preferably 1: 1 to 1:10, in particular 1: 2 to 1: 5.

The agents according to the invention cover a wide range of chewing. They are suitable, for example, to combat annual and perennial Weeds such as Agropyron, Paspalum, Cynodon, Imperata, Pennisetum, Convolvulus, Cirsium, Rumex and others.

The agents according to the invention can be used for the selective control of annual and perennial harmful plants in plantation crops such as oil palm, coconut palm, rubber tree, citrus, pineapple, cotton, coffee, cocoa and others. as well as in fruit and wine growing. Likewise, the combinations according to the invention can be used in arable farming in the so-called "no till" or "zero tilP" process. However, they can also be used non-selectively on paths, squares, industrial plants, etc., in order to keep these areas free from undesired vegetation.

The herbicidal compositions according to the invention are notable for a rapid onset and long-lasting herbicidal action. The rain resistance of the active substances in the combinations according to the invention is favorable. A particular advantage is that the effective doses of compounds of the formula (A) and (B) used in the combinations are so low that their soil effect is considerably reduced. This makes their use not only possible in sensitive crops, but groundwater contamination is practically avoided. The combination of active ingredients and wetting agents according to the invention enables a considerable reduction in the amount of active ingredients required.

The invention therefore also relates to a process for combating undesirable plant growth, characterized in that one or more type A herbicides with one or more type B herbicides and an anionic type C surfactant are applied to the harmful plants, parts of plants thereof or the area under cultivation applied.

The active compound combinations according to the invention can be present both as mixed formulations of the three components, if appropriate with further customary formulation auxiliaries, which are then used in the usual manner Diluted water can be used, or can be produced as so-called tank mixes by jointly diluting the separately formulated or partially separately formulated components with water.

The compounds of type A and type B or their combinations, optionally together with the surfactant C, can be formulated in various ways, depending on which biological and / or chemical-physical parameters are specified. Examples of general formulation options are: wettable powder (WP), emulsifiable concentrates (EC), aqueous solutions (SL), emulsions (EW) such as oil-in-water and water-in-oil emulsions, sprayable solutions or emulsions, Oil- or water-based dispersions, suspoemulsions, dusts (DP), mordants, granules for soil or litter application or water-dispersible granules (WG), ULV formulations, microcapsules or waxes.

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

The necessary formulation aids such as inert materials, surfactants, solvents and other additives are also known and are described, for example, in: Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell NJ; Hv Olphen, "Introduction to Clay Colloid Chemistry"; 2nd Ed., J. Wiley & Sons, NY Marsden, "Solvent Guide," 2nd Ed., Interscience, NY 1,950; McCutcheon's, Detergents and Emulsifiers Annual, MC Publ. Corp., Ridegewood NJ; Sisley and Wood, "Encyclopedia of Surface Active Egents", Chem. Publ. Co. Inc., NY 1964; Schönfeldt, "Interface Active Äthylenoxidaddukte ", Wiss. Verlagsgesellschaft, Stuttgart 1976, Winnacker-Küchler," Chemical Technology ", Volume 7, C. Hauser Verlag Munich, 4th ed. 1986.

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

Spray powders (wettable powders) are preparations which are uniformly dispersible in water and which, in addition to the active substance, contain not only a diluent or inert substance, but also ionic or nonionic surfactants (wetting agents, dispersing agents), e.g. polyoxethylated alkylphenols, polyethoxylated fatty alcohols or fatty amines, alkanesulfonates or alkylbenzenesulfonates, ligninsulfonic acid sodium, 2,2'-dinaphthylmethane-6,6'-disulfonic acid sodium, dibutylnaphthalenesulfonic acid sodium or also oleoylmethyltauric acid sodium.

Emulsifiable concentrates are made by dissolving the active ingredient in an organic solvent, e.g. Butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons with the addition of one or more ionic or nonionic surfactants (emulsifiers). Examples of emulsifiers which can be used are: alkylarylsulfonic acid calcium salts, such as calcium dodecylbenzenesulfonate, or nonionic emulsifiers, such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan fatty acid ester sorbetyl ester, polyoxyethylene fatty acid sorbetyl ester, polyoxyethylene acid sorboxyl ester, polyoxyethylene acid sorbetyl ester, polyoxyethylene acid sorbetyl ester, polyoxyethylene ethoxylate, polyoxyethylene ethoxylate.

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

The agrochemical preparations generally contain 0.1 to 99 percent by weight, in particular 2 to 95 percent by weight, of active ingredients of types A and / or B, the following concentrations being customary depending on the type of formulation:

The active substance concentration in wettable powders is e.g. about 10 to 95 wt .-%, the rest of 100 wt .-% consists of conventional formulation components. In the case of emulsifiable concentrates, the active substance concentration can e.g. 5 to 80

% By weight.

Dust-like formulations usually contain 5 to 20% by weight of active ingredient, sprayable solutions about 0.2 to 25% by weight of active ingredient.

In the case of granules such as dispersible granules, the active ingredient content depends on

Part of whether the active compound is liquid or solid and which

Granulating agents and fillers can be used. As a rule, the

The content of the water-dispersible granules is between 10 and 90

% By weight.

In addition, the active ingredient formulations mentioned may contain the customary adhesives, wetting agents, dispersants, emulsifiers, preservatives, antifreezes and solvents, fillers, dyes and carriers, defoamers, Evaporation inhibitors and agents that affect pH or viscosity.

For use, the formulations present in the commercial form are optionally diluted in the customary manner, e.g. for wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules using water. Preparations in the form of dust, ground granules or granules for spreading, and sprayable solutions are usually no longer diluted with other inert substances before use.

The active compounds can be applied to the plants, parts of plants, plant seeds or the area under cultivation (arable soil), preferably to the green plants and parts of plants and, if appropriate, additionally to the arable soil.

One possible application is the joint application of the active ingredients in the form of tank mixes, the optimally formulated concentrated formulations of the individual active ingredients being mixed together with water in the tank and the spray liquor obtained being applied.

A common herbicidal formulation of the combination according to the invention of active ingredients A and B and surfactant C has the advantage of being easier to use because the amounts of the components have already been set in the correct ratio to one another. In addition, the auxiliaries in the formulation can be optimally coordinated with one another, while a tank mix of different formulations can result in undesired combinations of auxiliaries. However, because of the different physical properties of components A, B and C, most types of formulation are not suitable for a common formulation. Active substances of type A and surfactant C are hydrophilic and are usually formulated as a strongly salt-containing aqueous solution. Active ingredients B, on the other hand, are largely insoluble in water and are usually formulated as emulsifiable concentrates or granules. The common wording according to the type of said Individual formulations are not easily possible. Attempts to achieve the common formulation as emulsifiable suspensions, dispersions or emulsions usually do not lead to success and come up against narrow limits with regard to stability and desired application properties.

The invention therefore also relates to a special mixed formulation which does not have the disadvantages mentioned above, and to the use thereof. The mixed formulation is an oil-in-water emulsion (EW), characterized by the content of a) 1 to 15% by weight of active ingredient of the type A mentioned

(Glufosinate ammonium or analogous active ingredient) b) 0.1 to 5% by weight of active ingredient of the type B mentioned

(Nitrodiphenyl ether) c) 1 -1 5% by weight of anionic surfactant from the group of

Fatty alcohol polyglycol ether sulfates d) 3 to 30% by weight, preferably 3-20% by weight, in particular 3-1 5

% By weight of organic solvent, e) 40 to 60% by weight of water, f) 2 to 10% by weight of emulsifier or emulsifier mixture and g) 0 to 20% by weight of customary formulation auxiliaries.

Examples of suitable solvents are non-polar solvents, polar protic or aprotic dipolar solvents and mixtures thereof, the organic solvent forming an emulsified organic phase with the nitrodiphenyl ether herbicide in addition to the aqueous phase which contains the type A herbicide.

Examples of suitable solvents are aliphatic and aromatic hydrocarbons, such as. B. mineral oils or toluene, xylenes and naphthalene derivatives; halogenated aliphatic and aromatic hydrocarbons, such as methylene chloride or chlorobenzene; Ethers, such as diethyl ether, tetrahydrofuran (THF), dioxane,

Alkylene glycol monoalkyl ethers and dialkyl ethers such. B.

Propylene glycol monomethyl ether, propylene glycol monoethyl ether,

Ethylene glycol monomethyl ether or monoethyl ether, diglyme and

Tetraglyme;

Amides such as dimethylformamide (DMF), dimethylacetamide and N-

Methyl pyrrolidone;

Ketones such as acetone and cyclohexanone;

Nitriles such as acetonitrile, propionitrile, butyronitrile and benzonitrile;

Sulfoxides and sulfones such as dimethyl sulfoxide (DMSO) and sulfolane;

Oils, e.g. B. plant-based such as corn oil and rapeseed oil. Especially in combinations of solvents, alcohols such as the alkanols methanol, ethanol, n- and i-propanol, n-, i-, t- and 2-butanol can often be used. Preferred organic solvents are aromatic hydrocarbons, such as. B. toluene, xylenes and naphthalene derivatives.

Suitable emulsifiers are ionic surfactants and nonionic surfactants, for example as ionic emulsifiers: alkylarylsulfonic acid calcium salts such as Ca-dodecylbenzenesulfonate, phosphated

Propylene oxide-ethylene oxide condensation products such as phosphated PO-EO

Block copolymers or phosphated tristyrylphenol polyglycol ethers; and for example as nonionic emulsifiers:

Fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers,

Propylene oxide-ethylene oxide condensation products such as PO-EO-

Block copolymers, alkyl polyethers, polyols such as polyvinyl alcohol,

Sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters or

Polyoxethylene sorbitol ester.

Emulsifier mixtures of modified polyvinyl alcohol (for example ^® Mowiol 3/83, ^® Mowiol 4/88; Hoechst), phosphated PO-EO block copolymer (for example Hoe S 361 8, Hoechst), dodecylbenzenesulfonate calcium and Fatty alcohol polyglycol ether. Typical formulation aids (g) are e.g. B. the usual formulation aids already mentioned above; preferred tools are

Antifreeze and evaporation inhibitors, such as glycerin, e.g. B. in one

Amount from 2 to 10% by weight,

Preservatives, e.g. B. ^® Mergal K9N (Riedel) or ^® Cobate C, in the usual application concentrations for the particular used

Medium,

Defoamers, e.g. B. silicone defoamers such as anti-foam emulsion SRE, in the usual application concentrations.

Preferred mixed formulations are EW formulations, characterized by a) 5 to 1 2% by weight glufosinate ammonium, b) 1 to 4% by weight nitrodiphenyl ether, c) 5 to 1 2% by weight fatty alcohol polyglycol ether sulfate, d ) 3 to 20% by weight, preferably 3-15% by weight, in particular 5 to 10

% By weight of organic solvent, e) 45 to 55% by weight of water, f) 4 to 8% by weight of emulsifier or emulsifier mixture and g) 0 to 10% by weight of customary formulation auxiliaries.

Mixed formulations are preferred which contain 6 to 1 8% by weight of a herbicide combination of glufosinate-ammonium (racemic) and oxyfluorfen or lactofen in a weight ratio A: B of 10: 1 to 2: 1 and 5 to 1 2% by weight C. Contain _{1 2} -C ₁₄ fatty alcohol diethylene glycol ether sulfate sodium salt as anionic surfactant C in the weight ratio herbicide A: wetting agent C from 1: 1 to 1:10.

The EW mixed formulations are characterized by good physical and chemical storage stability. The handling of the formulations is simplified compared to that of a tank mix. When using the mixed formulations, biological results are obtained which are comparable to those of one Tank mix from the separately formulated components do not lag behind, but usually surpass them.

A. General wording examples:

a) A dusting agent is obtained by mixing 10 parts by weight of an active ingredient combination according to the invention and 90 parts by weight of talc as an inert substance and comminuting them in a hammer mill.

b) A wettable powder which is readily dispersible in water is obtained by adding 25 parts by weight of active compounds A + B, 64 parts by weight of kaolin-containing quartz as an inert substance, 10 parts by weight of lignosulfonic acid potassium and 1 part by weight of oleoylmethyl tauric acid sodium mixes as a wetting and dispersing agent and grinds in a pin mill.

c) A dispersion concentrate which is readily dispersible in water is obtained by mixing 20 parts by weight of active compounds A + B with 6 parts by weight of alkylphenol polyglycol ether ( ^® Triton X 207), 3 parts by weight of isotridecanol polyglycol ether (8 EO) and 71 parts by weight. Parts of paraffinic mineral oil (boiling range approx. 255 to 277 ° C) and ground in a friction ball mill to a fineness of less than 5 microns.

d) An emulsifiable concentrate is obtained from 1 5 parts by weight of cyclohexanone as solvent and 10 parts by weight of oxyethylated nonylphenol as emulsifier.

e) A water-dispersible granulate is obtained by adding 75 parts by weight of active ingredients A + B,

10 parts by weight of calcium lignosulfonate, 5 parts by weight of sodium lauryl sulfate, 3 parts by weight of polyvinyl alcohol and 7 parts by weight of kaolin mixes, grinds on a pin mill and granulates the powder in a fluidized bed by spraying water as granulating liquid.

A water-dispersible granulate is also obtained by

25 parts by weight of active ingredients A + B,

5 parts by weight of 2,2'-dinaphthylmethane-6,6'-disulfonic acid sodium,

2 parts by weight of sodium oleoylmethyl taurine,

1 part by weight of polyvinyl alcohol, 17 parts by weight of calcium carbonate and 50 parts by weight of water homogenized and pre-comminuted on a colloid mill, then ground on a bead mill and the suspension thus obtained is atomized and dried in a spray tower using a single-component nozzle.

B. Formulation Examples for Emulsions (EW)

B1. EW formulation with 10% glufosinate ammonium, 3.3% oxyfluorfen and 10% fatty alcohol polyglycol ether sulfate

To an aqueous solution

10.00% by weight glufosinate ammonium,

14.29% by weight of «Genapol LRO paste (70% = 10% WAS),

0.75% by weight ^® Mowiol 3/83,

1.00% by weight ^® Mowiol 4/88,

0.20% by weight ^® Mergal K9N,

1.50% by weight propylene glycol monomethyl ether,

5.50 wt% glycerin and

50.86 wt% water

a solution is slowly let out with stirring at 20 ° C.

3.47% by weight oxyfluorfen 95% (= 3.3% a. I.),

1.00% by weight Hoe S 361 8.

2.00% by weight of phenyl sulfonate CA,

1.30% by weight of SRE antifoam emulsion,

0.25% by weight ^® Arlypon F,

7.88% by weight of ^® Solvesso 200 run and let stir for an hour. The emulsion formed is physically and chemically stable between -10 ° C and + 50 ° C.

B2. EW formulation with 9.5% glufosinate ammonium, 1.95% oxyfluorfen and 10% fatty alcohol polyglycol ether sulfate

4

To an aqueous solution

9.50% by weight glufosinate ammonium,

14.29% by weight of ^® Genapol LRO paste (70% = 10% WAS),

0.20% by weight ^® Mergal K9N, 1.50% by weight propylene glycol monomethyl ether,

5.50 wt% glycerin and

53.44 wt% water

a solution is slowly let out with stirring at 20 ° C.

2.00% by weight oxyfluorfen 95% (= 1.95% a. IJ,

1.00% by weight Hoe S 3618,

2.00% by weight of phenyl sulfonate CA,

1.30% by weight of SRE antifoam emulsion,

0.25% by weight ^® Arlypon F,

9.02% by weight of ^® Solvesso 200 run and let stir for an hour. The emulsion formed is physically and chemically stable between -10 ° C and +40 ° C.

B3. EW formulation with 10% glufosinate ammonium, 2% oxyfluorfen and 10% fatty alcohol polyglycol ether sulfate

To an aqueous solution of 10.00% by weight glufosinate ammonium,

34,50 wt .-% Genapol ^® LRO paste (28% = 9.66% WAS), 0.20 wt .-% Mergal K9N ^®, 4.00 wt .-% glycerol,

4.88% by weight of Hoe S 3618 Na salt (20.8% strength), 1.21% by weight of antifoam emulsion SRE and 24.91% by weight of water are slowly allowed to dissolve with stirring at 20 ° C from 2.05% by weight oxyfluorfen 94% (= 2.0% ai),

16.00% by weight ^® Solvesso 200, 2.00% by weight phenylsulfonate CA,

0.25% by weight of ^® Arlypon F, run and let stir for one hour. The emulsion formed is physically and chemically stable between -10 ° C and + 50 ° C. B4. EW formulation with 10% glufosinate ammonium, 2% oxyfluorfen and 10% fatty alcohol polyglycol ether sulfate

To an aqueous solution

10.00% by weight glufosinate ammonium,

34.50% by weight of ^® Genapol LRO paste (28% = 9.66% WAS),

0.20% by weight ^® Mergal K9N,

4.00% by weight glycerin,

4.88% by weight Hoe S 3618 Na salt (20.8%),

1, 21 wt .-% SRE and

24.91% by weight of water is slowly allowed to stir at 20 ° C., a solution of 2.05% by weight of 94% oxyfluorfen (= 2.0% a. I.),

10.00% by weight ^® Solvesso 200,

6.00 wt% cyclohexanone

2.00% by weight of phenyl sulfonate CA,

0.25% by weight of ^® Arlypon F, run and let stir for one hour. The emulsion formed is physically and chemically stable between -10 ° C and + 40 ° C.

B5. EW formulation with 14% glufosinate ammonium, 2.8% oxyfluorfen and 10% fatty alcohol polyglycol ether sulfate

To an aqueous solution of 14.00% by weight glufosinate ammonium,

9.76% by weight of Hoe S 3618 Na salt (20.8%),

1, 21 wt .-% SRE and

1 6, 14% by weight of water is slowly let out of a solution while stirring at 20 ° C. 2.89% by weight oxyfluorfen 94% (= 2.0% a. IJ,

1 5.00 wt .-% Solvesso 200 ^®, 2.00 wt .-% Phenylsulfonat CA, 0.25 wt .-% ^® Arlypon F, run and then stirred for one hour. The emulsion formed is physically and chemically stable between -10 ° C and +40 ° C.

Explanations / abbreviations for examples B1 and B5:

^® Genapol LRO (Hoechst):

C _{1 2} -C ₁₄ fatty alcohol diethylene glycol ether sulfate sodium salt,

^® Mowiol 3/83 (Hoechst):

Polyvinyl alcohol produced by partial saponification of polyvinyl acetate with a viscosity of 3 cP, measured in a 4% strength aqueous solution at 20 ° C., and a degree of hydrolysis of 83 mole percent.

^® Mowiol 4/88 (Hoechst):

Polyvinyl alcohol produced by partial saponification of polyvinyl acetate and having a viscosity of 4 cP, measured in a 4% strength aqueous solution at 20 ° C., and a degree of hydrolysis of 88 mole percent.

Hoe S 3618 (Hoechst):

Bis-monophosphoric acid ester of a PO / EO block copolymer

Phenylsulfonate CA (Hoechst): C ₁₂ alkyl benzenesulfonate calcium

^® Mergal K9N (Riedel de Haen): mixture of isothiazolinones

^® Arlypon F (Hoechst): C ₁₂ -C ₁₄ fatty alcohol ethoxylate (2.5 EO)

^® Solvesso 200 (ESSO): aromatic solvent

Antifoam emulsion SRE (Wacker): antifoam based on silicone oil Biological examples

Various economically important weeds and grasses are grown under natural outdoor conditions. After certain development stages have been reached (expressed by the number of unfolded leaves or by the height), a tank mix of the respective herbicides with the surfactant C or a tank mix of the herbicide mixtures and the surfactant C are applied under standard conditions, i.e. H. with a plot sprayer with a water application rate of 300-400 liters of water per hectare. In the period of 1 to 3 weeks after application, the herbicidal activity of the active compounds or mixtures of active compounds is visually assessed on the basis of the treated plots in comparison to untreated control plots. Damage and development of all parts of the plant above ground are recorded.

In the majority of cases the synergistic increase in activity is so high that the effect of the combination clearly exceeds the formal (numerical) sum of the effects of the individual substances. Such a high increase in activity was not expected due to the known effects of the individual active substances. It should be particularly pointed out that an assessment of the synergism with the active ingredients used here must take into account the widely differing application rates of the individual active ingredients. It is therefore not sensible to compare the effects of the active ingredient combinations and the individual active ingredients in each case at the same application rates. The amounts of active ingredient to be saved according to the invention can only be recognized by the superadditive increase in activity when the combined application rates are used or by the reduction in the application rates of both individual active ingredients in the combination in comparison to the individual active ingredients with the same effect in each case. Another advantage of the active ingredient combinations is the faster onset or longer-lasting effect on a wide range of economically relevant harmful plants. Some biological results are shown in Tables 1 to 3. Table 1: Herbicidal activity (abbreviations are given in Table 3)

Dose of herbicidal effect in% of harmful I

[g a.i./ha or. after plant g WHAT / ha] 14 days 28 days

A1 + C1 450 + 450 76.0 45.5 Mix

B1 + C1 90 + 450 15.0 3.7 ••

A1 + B1 + C1 450 + 90 + 450 86.8 55.0 π

A1 + C1 450 + 450 60.0 10.0 GERSP

B1 + C1 90 + 450 12.5 22.5

A1 + B1 + C1 450 + 90 + 450 72.5 55.0 n

A1 + C1 450 + 450 60.0 10.0 GERSP

B2 + C1 90 + 450 40.0 7.5

A1 + B2 + C1 450 + 90 + 450 90.0 42.5

Table 2: Herbicidal activity (see Table 3 for abbreviations)

Dose of herbicidal effects in% harmful

[g a.i./ha or after plant g WHAT / ha] 7 days 28 days

A1 + C1 450 + 450 50 6 SONAS

B1 + C1 90 + 450 15 4

A1 + B1 + C1 450 + 90 + 450 85 40

A1 + C1 450 + 450 50 6 SONAS

B2 + C1 90 + 450 6 5

A1 + B2 + C1 450 + 90 + 450 85 20

A1 + C1 450 + 450 48 18 CONAR

B1 + C1 90 + 450 56 4

A1 + B1 + C1 450 + 90 + 450 97 28 Table 3: Herbicidal activity

Dose herbicidal activity in% harmful

[g a.i./ha or after plant g WHAT / ha] 7 days 14 days

A1 + C1 450 + 450 49 51 CONAR

B2 + C1 90 + 450 6 26

A1 + B2 + C1 450 + 90 + 450 93 80

A1 + C1 450 + 450 13 88 ERISP

B2 + C1 90 + 450 3 29

A1 + B2 + C1 450 + 90 + 450 75 93

A1 + C1 450 + 450 13 88 ERISP

B2 + C1 90 + 450 1 21

A1 + B2 + C1 450 + 90 + 450 75 95

A1 + C1 450 + 450 48 18 CONAR

B1 + C1 90 + 450 56 4

A1 + B1 + C1 450 + 90 + 450 97 28

Abbreviations in tables 1 to 3:

A1 = glufosinate ammonium (rac.)

B1 = oxyfluorfen

B2 = lactofen

C1 = C ₁₂ / C ₁₄ fatty alcohol diethylene glycol ether sulfate Na ( ^® Genapol LRO)

CONAR = Convolvulus arvensis

ERISP = Erigeron sp.

GERSP = Geraniu sp.

SONAS = Sonchus asper

Mix = harmful plants mix from CONAR, ERISP, GERSP, SONAS a. i. = based on pure herbicidal active substance

WHAT = based on pure surfactant (= detergent substance)

= not tested

Claims

claims

1 . Herbicidal agent, characterized by an effective content of a combination of

A) one or more compounds of formula (A) or their salts

O O

II II

H ₃ C - P - CH ₂ -CH ₂ - CH - C - Z (A)

I I

OH NH ₂ wherein

Z is a radical of the formula -OM, -NHCH (CH ₃ ) CONHCH (CH ₃ ) COOM or

C) an anionic surfactant from the series of alkyl polyglycol ether sulfates.

2. Herbicidal composition according to claim 1, characterized in that it

A) a herbicide from group D, L-glufosinate, D, L-glufosinate-ammonium, L-glufosinate, L-glufosinate-ammonium, bialaphos and bialaphos-sodium,

B) a nitrodiphenyl ether herbicide from the group oxyfluorfen, lactofen, bifenox, fluoroglycofen-ethyl, acifluorfen and fomesafen and

C) contain an anionic wetting agent from the group of C ₁₀ -C ₁₈ fatty alcohol polyglycol ether sulfates in the form of the alkali metal, alkaline earth metal or ammonium salts or the substituted ammonium salts.

3. Herbicidal composition according to claim 1 or 2, characterized in that the weight ratios A: B of the combined herbicides of type A and type B are between 100: 1 and 1: 5.

4. Herbicidal composition according to one of claims 1 to 3, characterized in that it

A) Glufosinate-ammonium (racemic) and

B) Oxyfluorfen or lactofen in the weight ratio A: B from 10: 1 to 2: 1.

5. Herbicidal composition according to claim 4, characterized in that the weight ratio A: B is from 8: 1 to 3: 1. '

6. Herbicidal composition according to one of claims 1 to 5, characterized in that the weight ratio of herbicide A to wetting agent C is 1: 1 to 1:10.

7. A method for controlling unwanted vegetation, characterized in that one or more herbicides of type A with one or more herbicides of type B and an anionic wetting agent of type C are applied to the harmful plants, parts of plants thereof or the area under cultivation, the types A, B and C are as defined in any one of claims 1 to 6.

8. Use of a combination of a) one or more herbicides of type A, b) one or more herbicides of type B and c) an anionic wetting agent of type C as a herbicidal agent for controlling unwanted vegetation, types A, B and C are as defined in any one of claims 1 to 6.

9. Herbicidal formulation based on aqueous emulsions (EW), characterized by the content of a) 1 to 15% by weight of type A herbicide, b) 0.1 to 5% by weight of type B herbicide, c) 1-15% by weight of type C anionic surfactant, d) 3 to 30% by weight of organic solvent, e) 40 to 60% by weight of water, f) 2 to 10% by weight of emulsifier or emulsifier mixture and g) 0 to 20% by weight of customary formulation auxiliaries, the types A), B) and C) in components a), b) and c) as defined in claim 1.

10. Herbicidal formulation according to claim 9, characterized in that it contains a) 5 to 12% by weight glufosinate ammonium, b) 1 to 4% by weight nitrodiphenyl ether, c) 5 to 12% by weight fatty alcohol polyglycol ether sulfate, d) 3 to 20% by weight of organic solvent, e) 45 to 55% by weight of water, f) 4 to 8% by weight of emulsifier or emulsifier mixture and g) 0 to 10% by weight of customary formulation auxiliaries.

1 1. Herbicidal formulation according to claim 9 or 10, characterized in that it contains

6 to 18 wt .-% of a herbicide combination of glufosinate-ammonium

(racemic) and oxyfluorfen or lactofen in the weight ratio A: B from 10: 1 to 2: 1 and

5 to 12 wt .-% C _{1 2} -C ₁₄ fatty alcohol diethylene glycol ether sulfate sodium salt as anionic surfactant C in the weight ratio herbicide A: wetting agent C from 1: 1 to 1:10.