DE19501986A1 - Synergistic herbicidal compositions based on glufosinates and nitrodiphenyl ethers and their formulations - Google Patents

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

The invention lies in the field of crop protection agents which are against unwanted plant growth can be used, especially the Combinations of herbicides.

Glufosinate Ammonium (Phosphinothricin Ammonium) (1)

d. H. is the ammonium salt of 4- [hydroxy (methyl) phosphinoyl] -DL-homoalanine a well-known herbicide that is absorbed through 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 for controlling weeds and weeds in plantation crops and on non-cultivated land as well as by means of special application techniques Inter-row control in agricultural crops such as maize, Cotton and a. used. The compound of formula (1) contains one asymmetric carbon atom. The L enantiomer is called the biologically active Viewed isomer.

It is also known that the effect of glufosinate ammonium as well that of its L-enantiomer clearly through surface-active substances can be improved, preferably by wetting agents from the series of alkyls polyglycol ether sulfates, for example in the form of their alkali or  Ammonium salts, but also used as a magnesium salt, such as C₁₂ / C₁₄- Fatty alcohol diglycol ether sulfate sodium (®Genapol LRO, Hoechst); see EP-A- 04 76 555, EP-A-00 48 436, EP-A-03 36 151 or US-A-44 00 196 and Proc. EWRS Symp. "Factors Affecting Herbicidal Activity and Selectivity", 227-232 (1988). It is also known that alkyl polyglycol ether sulfates as Penetration aids and potency enhancers for a number of other herbicides, is also suitable, inter alia, for herbicides of the diphenyl ether type; see EP- A-04 76 555.

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

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 wherein
  Z is a radical of the formula -OM, -NHCH (CH₃) CONHCH (CH₃) COOM or -NHCH (CH₃) CONHCH [CH₂CH (CH₃) 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 herbicides of the type the nitrodiphenyl ether 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), d. H. L-2-amino-4- [hydroxy (methyl) phosphinyl] butanoyl-L-alanyl-L-alanine and its sodium salt.

The racemate of glufosinate ammonium is usually alone in Doses applied that are between 200 and 1000 g a.i./ha (= grams Active substance per hectare). Glufosinate-ammonium is in these Dosages are particularly effective when it comes to green parts of plants is recorded. As it degrades in the soil microbially 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, d. H. 2-chloro-1- (3-ethoxy-4-nitro-phenoxy) -4-trifluoromethyl benzene, its use as a single active ingredient with 100-1000 g a.i./ha in Soy is known pre- and post-emergence or on non-cultivated land;
• b2) lactofen, d. H. 5- [2-chloro-4- (trifluoromethyl) phenoxy] -2-nitro-benzoic acid- 1- (ethoxycarbonyl) ethyl ester; the active ingredient is usually used alone 50-500 g a.i./ha in pre- and post-emergence in soy and cereals used;  
• b3) bifenox, i.e. H. 5- (2,4-dichlorophenoxy) -2-nitrobenzoic acid methyl ester; of the Active ingredient is usually alone with an application rate of 50 to 1000 g ai / ha in pre- and post-emergence in cereals, rice and corn used;
• b4) fluoroglycofen-ethyl, d. H. 5- [2-chloro-4- (trifluoromethyl) phenoxy] -2- nitrobenzoic acid ethoxycarbonylmethyl ester; the application is known as a single active ingredient with an application rate of 5 to 50 g ai / ha in advance and post-emergence in cereals and soybeans;
• b5) Acifluorfen, d. H. 5- [2-chloro-4- (trifluoromethyl) phenoxy] -2- nitrobenzoic acid or its salts such as the sodium salt; of the Single agent is usually with 100-500 g ai / ha in the pre and Post-emergence used in soy and cereals; and
• b6) Fomesafen, d. H. N-methylsulfonyl-5- [2-chloro-4- (trifluoromethyl) phenoxy] - 2-nitrobenzamide; the use as a single active ingredient at 50 is known up 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 1991 and the literature cited therein known as herbicides of the protoporphyrinogen oxidase inhibitor type.

The anionic surfactant (C) is, for example, a wetting agent from the group of Fatty alcohol polyglycol ether sulfates and their salts, preferably the C₁₀-C₁₈- Fatty alcohol polyglycol ether sulfates in the form of the alkali metal, alkaline earth metal or Ammonium salts or the substituted ammonium salts; substituted Examples of ammonium salts are primary, secondary, tertiary and quaternary Ammonium salts with substituents from the group consisting of alkyl or hydroxyalkyl, preferably with 1 to 4 carbon atoms.

C₁₂-C₁₄ fatty alcohol diethylene glycol ether sulfate sodium salt is preferred (®Genapol LRO, Hoechst AG) used.  

From US-A-53 24 708 it is already known formulations containing a combination of the herbicides glufosinate-ammonium, in the form of a non-hygroscopic salt, and oxyfluorfen. Combinations 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 well as indications of synergistic increases in effectiveness for Combinations of glufosinate ammonium and oxyfluorfen.

Research Disclosure 275 (1987), 154 is known to supplement the Spectrum of activity of glufosinate-ammonium the latter with other herbicides to combine. Among other things, the combination of glufosinate ammonium and oxyfluorfen mentioned for use in cotton. Hints on synergistic increases in effectiveness for the combination of glufosinates ammonium and oxyfluorfen or in combinations with Fatty alcohol polyglycol ether sulfates are missing.

Surprisingly, it has been shown that when Type A herbicides with one or more active ingredients from group B. in the presence of surfactant C, superadditive (= synergistic) effects occur. The effect in the combinations is stronger than that of the ones used Individual herbicides in the presence of wetting agent C when used alone. These Effects allow a reduction in the application rate, the fight against broader spectrum of weeds and grasses, faster use the herbicidal effect, a longer lasting effect, better control of the Harmful plants with only one or a few applications and one Extension of the possible application period. These properties are in of practical weed control called for agricultural crops to keep free from undesirable competing plants and thus the yields to secure and / or increase qualitatively and quantitatively. The technical These new combinations standardize the described ones Properties clearly exceeded.  

The optimal choice of the weight ratio and the application rates is for example from the mixing partners, from the development stage of the Weeds or weeds, weed spectrum, environmental factors and Depending on 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 usually between 100: 1 and 1: 5, preferably between 10: 1 and 1: 1. For the Combination of type A herbicides, especially glufosinate ammonium (rac), the following weight ratios A: B are preferred:

• with oxyfluorfen, 10: 1 to 2: 1, in particular 8: 1 to 3: 1.
• - with lactofen, 10: 1 to 2: 1, in particular 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 significantly below the application rate for the individual application of respective herbicide with the same herbicidal activity. Usually are 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 ether such as Oxyfluorfen and lactofen preferred.

The optimal application rate of the type C anionic surfactant depends on The factors already mentioned depend on the application rate of the herbicides usually between 100 and 2000 g surfactant per hectare, based on wash-active substance (WAS), preferably 500 to 1500 g WAS / ha. The weight ratio of herbicide A to surfactant C is therefore preferred 1: 1 to 1:10, in particular 1: 2 to 1: 5.

The agents according to the invention cover a broad spectrum of weeds. You 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 the like. a. as well as in fruit and wine growing. Likewise, the invention Combinations in arable farming in the so-called "no till" or "zero till" process be used. But you can also non-selectively on paths, places, Industrial plants etc. are applied to these areas of to keep unwanted vegetation free.

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 are favorable. As a special one The advantage is that the used in the combinations and effective doses of compounds of formula (A) and (B) so low are that their soil impact is significantly reduced. Thus their use not only possible in sensitive cultures, but groundwater Contamination is practically avoided. By the invention Combining active ingredients and wetting agents will result in a significant reduction enables the necessary application rate of the active ingredients.

The invention therefore also relates to a method for combating undesirable plant growth, characterized in that one or several type A herbicides with one or more type B herbicides and an anionic surfactant of type C on the harmful plants, parts of plants of it or the acreage applied.

The active compound combinations according to the invention can be used both as Mixed formulations of the three components, optionally with further ones usual formulation aids are present, which then in the usual way  Diluted water can be used, or as so-called Tank mixes by diluting the separately formulated or partially separately formulated components can be produced with water.

The connections of type A and type B or their combinations, optionally together with the surfactant C, can in various ways be formulated, depending on which biological and / or chemical physical parameters are specified. As a general Formulation options are possible, for example: 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, suspo emulsions, Dusts (DP), pickling agents, 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 will described for example in: Winnacker-Küchler, "Chemical Technology", Volume 7, C. Hauser Verlag Munich, 4th ed. 1986; van Valkenburg, "Pesticides 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 will be described, for example, in: Watkins, "Handbook of Insecticide Dust Diluents and Carriers ", 2nd Ed., Darland Books, Caldwell N.J .; H.v. Olphen," Introduction to Clay Colloid Chemistry "; 2nd Ed., J. Wiley & Sons, N.Y. Marsden," Solvents Guide ", 2nd Ed., Interscience, N.Y. 1950; McCutcheon's," Detergents and Emulsifiers Annual ", MC Publ. Corp., Ridegewood N.J .; Sisley and Wood, "Encyclopedia of Surface Active Egents", Chem. Publ. Co. Inc., N.Y. 1964; Schönfeldt, "Interface Active  Ethylene Oxide Adducts ", Scientific Publishing Company, Stuttgart 1976, Winnacker- Küchler, "Chemical Technology", Volume 7, C. Hauser Verlag Munich, 4th ed. 1986.

Based on these formulations, combinations can also be made with other pesticidal substances, such as other herbicides, fungicides or Insecticides, as well as safeners, fertilizers and / or growth regulators produce, e.g. B. in the form of a finished formulation or as a tank mix.

Spray powders (wettable powders) are evenly dispersible in water Preparations in addition to the active ingredient other than a diluent or inert still ionic or non-ionic surfactants (wetting agents, dispersing agents), e.g. B. polyoxethylated alkylphenols, polyethoxylated fatty alcohols or - Fatty amines, alkanesulfonates or alkylbenzenesulfonates, ligninsulfonic acid Sodium, 2,2'-dinaphthylmethane-6,6'-disulfonic acid sodium, dibutylnaphthalene contain sulfonic acid sodium or oleoylmethyltaurinic sodium.

Emulsifiable concentrates are made by dissolving the active ingredient in one organic solvents, e.g. B. butanol, cyclohexanone, dimethylformamide, Xylene or even higher-boiling aromatics or hydrocarbons Addition of one or more ionic or non-ionic surfactants (Emulsifiers). For example, emulsifiers can be used are: Alkylarylsulfonic acid calcium salts such as Ca-dodecylbenzenesulfonate or nonionic emulsifiers such as fatty acid polyglycol esters, Alkylaryl polyglycol ether, fatty alcohol polyglycol ether, propylene oxide-ethylene oxide Condensation products, alkyl polyethers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid ester or polyoxethylene sorbitol ester.

Dusts are obtained by grinding the active ingredient with finely divided solids, e.g. B. talc, natural clays such as kaolin, bentonite and Pyrophyllite, or diatomaceous earth.  

Granules can either by spraying the active ingredient adsorbable, granulated inert material or by Applying active ingredient concentrates using adhesives, e.g. B. Polyvinyl alcohol, polyacrylic acid sodium or mineral oils on which Surface of carriers such as sand, kaolinite or granulated Inert material. Suitable active ingredients can also be used in the production of Fertilizer granules in the usual way - if desired in a mixture with Fertilizers - be granulated. Water-dispersible granules are used in the Rule according to processes such as spray drying, fluidized bed granulation, plate Granulation, mixing with high speed mixers and extrusion without solid inert material.

The agrochemical preparations usually contain 0.1 to 99 % By weight, in particular 2 to 95% by weight, of active compounds of types A. and / or B, the following concentrations being customary, depending on the type of formulation are:

In wettable powders, the active ingredient concentration is e.g. B. about 10 to 95% by weight, the rest of 100% by weight consists of customary formulation components. At emulsifiable concentrates, the active ingredient concentration z. B. 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 wt .-% 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 Granulation aids 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 optionally contain the usual adhesive, wetting, dispersing, emulsifying, preserving, Antifreeze and solvents, fillers, dyes and carriers, defoamers,  Evaporation inhibitors and agents that control pH or viscosity influence.

Those available in the commercial form are used Formulations optionally diluted in a conventional manner, e.g. B. at Wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules using water. Dust-like preparations, Soil or scatter granules, as well as sprayable solutions are before the Application usually no longer diluted with other inert substances.

The active ingredients can be applied to the plants, parts of plants, plant seeds or the Cultivated area (arable soil) are spread, preferably on the green Plants and parts of plants and, if necessary, additionally on the soil.

One possibility of 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 together in the tank Water mixed and the spray mixture obtained is 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 lighter Applicability because the quantities of the components are already correct Relationship to each other are set. In addition, the tools in the Formulation can be optimally coordinated with one another during a tank mix of different formulations undesirable combinations of Excipients can result. However, most of the wording types are due to the different physical properties of components A, B and C not suitable for a common formulation. Type A and Surfactant C are hydrophilic and are usually considered to be highly saline aqueous Solution formulated. In contrast, active ingredients B are largely insoluble in water and are commonly used as emulsifiable concentrates or granules formulated. The common wording according to the type of said  Individual formulations are not easily possible. Also attempts that common formulation as emulsifiable suspensions, dispersions or Achieving emulsions usually does not lead to success and comes up against tight ones Limits in terms of stability and desired application properties.

The invention therefore also relates to a special mixed formulation which Does not have the above disadvantages, and their application. 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 analog active substance)
• b) 0.1 to 5% by weight of active ingredient of the type B mentioned (Nitrodiphenyl ether)
• c) 1-15 wt .-% anionic surfactant from the group of Fatty alcohol polyglycol ether sulfates
• d) 3 to 15 wt .-% organic solvent
• e) 40 to 60% by weight of water,
• f) 2 to 10 wt .-% emulsifier or emulsifier mixture and
• g) 0 to 20% by weight of customary formulation auxiliaries.

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

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;
• 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, deploy. 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 calcium 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 esters.

Emulsifier mixtures of modified polyvinyl alcohol are preferred (e.g. ®Mowiol 3/83, ®Mowiol 4/88; Hoechst), phosphated PO-EO- Block copolymer (e.g. Hoe S 3618, Hoechst), dodecylbenzenesulfonate Calcium and fatty alcohol polyglycol ether.  

Typical formulation aids (g) are e.g. B. the above in general usual formulation aids mentioned; preferred tools are

• - Antifreeze and evaporation inhibitors, such as glycerin, e.g. B. in one Amount of 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 content of

• a) 5 to 12% by weight of glufosinate ammonium,
• b) 1 to 4% by weight of nitrodiphenyl ether,
• c) 5 to 12% by weight of fatty alcohol polyglycol ether sulfate,
• d) 5 to 10% by weight of organic solvent,
• e) 45 to 55% by weight of water,
• f) 4 to 8 wt .-% emulsifier or emulsifier mixture and
• g) 0 to 10% by weight of customary formulation auxiliaries.

Mixed formulations which contain 6 to 18% by weight of one are preferred 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 % By weight of C₁₂-C₁ Fett fatty alcohol diethylene glycol ether sulfate sodium salt anionic surfactant C in the weight ratio herbicide A: wetting agent C from 1: 1 to 1:10 included.

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 will get biological results that one Tank mix from the separately formulated components do not lag behind, but instead usually surpass them.

A. General wording examples

• a) A dusting agent is obtained by adding 10 parts by weight of a active ingredient combination according to the invention and 90 parts by weight of talc as Mixes inert material and crushes it in a hammer mill.
• b) a wettable powder which is readily dispersible in water is obtained, by 25 parts by weight of active ingredients A + B, 64 parts by weight of kaolin Quartz as an inert substance, 10 parts by weight of potassium lignosulfonate and 1 part by weight Part of oleoylmethyl tauric acid sodium as wetting and dispersing agent mixes 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 ingredients A + B with 6 parts by weight Alkylphenol polyglycol ether (®Triton X 207), 3 parts by weight Isotridecanol polyglycol ether (8 EO) and 71 parts by weight paraffinic Mineral oil (boiling range e.g. approx. 255 to 277 ° C) mixes and in one Grinding ball mill ground to a fineness of less than 5 microns.
• d) An emulsifiable concentrate is obtained from 15 parts by weight Cyclohexanone as solvent and 10 parts by weight of ethoxylated Nonylphenol as an emulsifier.
• e) A water-dispersible granulate is obtained by:
  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.
• f) 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 on a colloid mill and pre-comminuted, 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
is slowly let out of a solution with stirring at 20 ° C.
3.47% by weight oxyfluorfen 95% (= 3.3% ai),
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,
7.88 wt% ® 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

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% by weight of water
is slowly let out of a solution with stirring at 20 ° C.
2.00% by weight oxyfluorfen 95% (= 1.95% ai),
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 ® Solvesso 200
run and let stir for an hour. The emulsion formed is physically and chemically stable between -10 ° C and +40 ° C.

Explanations / abbreviations for examples B1 and B2:
®Genapol LRO (Hoechst):
C₁₂-C₁₄ 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): C₁₂-alkyl-benzenesulfonal-calcium
®Mergal K9N (Riedel de Haen): mixture of isothiazolinones
®Arlypon F (Hoechst): C₁₂-C₁₄ 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 under natural outdoor conditions. After reaching certain Stages of development (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 below Standard conditions applied, d. H. with a plot sprayer a water application rate of 300-400 liters of water per hectare. In the period of 1 to 3 weeks after application, the herbicide Effectiveness of the active ingredients or active ingredient mixtures based on the treated Plots visually rated in comparison to untreated control plots. Damage and development of all aerial parts of plants detected.

In the majority of cases the synergistic increase in effectiveness is so high that the effect of the combination clearly the formal (numerical) sum of the Effects of the individual substances exceeds. Such a high increase in effectiveness is not to be expected due to the known effects of the individual active substances been. It should be noted that an assessment of the Synergism with the active ingredients used here the very different The application rates of the individual active ingredients must be taken into account. So it is not sensible, the effects of the active ingredient combinations and the individual active ingredients to compare in each case with the same application rates. The invention The amount of active ingredient to be saved is only due to the super-additives Increased effectiveness when using the combined application rates or through 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. Another advantage of the active ingredient combinations is shown in a faster Onset or a longer lasting effect on a wide range of economically relevant harmful plants. Some biological results are in Tables 1 to 3 listed.  

Table 1

Herbicidal activity (see Table 3 for abbreviations)

Table 2

Herbicidal activity (see Table 3 for abbreviations)

Table 3

Herbicidal effects

Abbreviations in tables 1 to 3:
A1 = glufosinate ammonium (rac.)
B1 = oxyfluorfen
B2 = lactofen
C1 = C₁₂ / C₁₄ fatty alcohol diethylene glycol ether sulfate Na (®Genapol LRO)
CONAR = Convolvulus arvensis
ERISP = Erigeron sp.
GERSP = Geranium sp.
SONAS = Sonchus asper
Mix = mix of harmful plants from CONAR, ERISP, GERSP, SONAS
ai = based on pure herbicidal active substance
WHAT = based on pure surfactant (= detergent substance)
- = not tested.

Claims (15)

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

• A) one or more compounds of formula (A) or their salts wherein
  Z is a radical of the formula -OM, -NHCH (CH₃) CONHCH (CH₃) COOM or -NHCH (CH₃) CONHCH [CH₂CH (CH₃) 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.

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) an anionic wetting agent from the group of C₁₀-C₁₈ fatty alcohol polyglycol ether sulfates in the form of the alkali metal, alkaline earth metal or ammonium salts or the substituted ammonium salts

contain. 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 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

contained 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 compositions according to one of claims 1 to 5, characterized characterized in that the weight ratio of herbicide A to wetting agent C 1: 1 to 1:10. 7. Process for combating undesirable plant growth, thereby characterized in that one or more type A herbicides with one or several type B herbicides and a type C anionic wetting agent applied to the harmful plants, parts of them or the area under cultivation, wherein types A, B and C are as defined in any one of claims 1 to 6. 8. Use a combination of

• a) one or more type A herbicides,
• b) one or more type B herbicides and
• c) an anionic wetting agent of type C.

as a herbicidal agent to combat unwanted plant growth, wherein 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 herbicidal active ingredient
• b) 0.1 to 5% by weight of type B herbicidal active ingredient
• c) 1-15% by weight of type C anionic surfactant
• d) 3 to 15 wt .-% organic solvent
• e) 40 to 60% by weight of water,
• f) 2 to 10 wt .-% emulsifier or emulsifier mixture and
• g) 0 to 20% by weight of customary formulation auxiliaries,

where types A), B) and C) in components a), b) and c) are like Claim 1 are defined. 10. Herbicidal formulation according to claim 9, characterized by a content of

• a) 5 to 12% by weight of glufosinate ammonium,
• b) 1 to 4% by weight of nitrodiphenyl ether,
• c) 5 to 12% by weight of fatty alcohol polyglycol ether sulfate,
• d) 5 to 10% by weight of organic solvent,
• e) 45 to 55% by weight of water,
• f) 4 to 8 wt .-% emulsifier or emulsifier mixture and
• g) 0 to 10% by weight of customary formulation auxiliaries.

11. Herbicidal formulation according to claim 9 or 10, characterized by a content of
6 to 18% by weight of a herbicide combination of glufosinate-ammonium (racemic) and oxyfluorfen or lactofen in the weight ratio A: B of 10: 1 to 2: 1 and
5 to 12% by weight of C₁₂-C₁₄ 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
contains.