MXPA00005224A - Surfactant systems for liquid aqueous preparations - Google Patents

Abstract

The invention relates to surfactant systems for liquid aqueous or aqueous-organic formulations containing a mixture comprised of one or several basic cosurfactants and one or several surfactants from the group of phosphoric acid esters. The surfactant systems enable the production of stable liquid formulations for active substances, whereby said formulations contain (a) one or several water soluble active substances (type (a)), (b) optionally one or several water-insoluble active substances (type (b)), optionally organic solvents and (d) the above-mentioned surfactant system and water. The formulations are either one-phase aqueous or aqueous-organic formulations of type (a) active substances, e.g. glufosinate-ammonium or glyphosate (salts) or microemulsions of type (a) and type (b) active substances, e.g. diphenyl ether herbicides.

Description

TENSIOACTIVE SYSTEMS FOR AQUEOUS LIQUID PREPARATIONS DESCRIPTIVE MEMORY The invention relates to the technical field of surfactant systems for aqueous or aqueous-organic liquid formulations (preparations), which preferably comprise an organic phase and an aqueous phase in the form of a microemulsion. The invention preferably relates to surfactant systems for formulations of one or more single-phase or multi-phase active compounds, wherein at least one of the active compounds is readily soluble in water. In this context, the active compounds may be, for example, active compounds from the fields of medicine or agriculture, or other substances having a particular technical function, such as, for example, dyes. In particular, the invention relates to microemulsions of culture protective agents with a combination of water-soluble active compounds and active compounds that are virtually insoluble in water, specifically micro-emulsions of glufosinate and oxyfluorfen or glyphosate and oxyfluorfen. Frequently, combinations of active compounds are used to use the properties of the individual active compounds together in the application, or also because the individual active compounds in combination are synergistic, ie they show increases in super-additive activity. Furthermore, the active compounds are not commonly used as pure substances, otherwise, depending on the area of application and the desired physical properties of the application form, in combination with certain auxiliaries, ie they are "formulated". In the case of a combination of active compounds of chemically different types, the person skilled in the art of formulations frequently encounters the problem of incompatibility of the individual active compounds with one another and with the auxiliaries in the joint formulation. In order to fully utilize the advantages of the combined active compounds, stable co-formulations are of particular interest. In principle, combinations of different active compounds can be formulated in different ways, depending on the prevailing biological and / or chemical-physical parameters. In general, the possibilities of appropriate formulation in this context are, for example: wettable powders (WP), oil in water or water in oil emulsions (EW and EO, respectively), suspensions (SC), suspo-emulsions (SE) or also granules for application in soil or application by dissemination, or granules that can be dispersed in water (WG). The aforementioned formulation types are known in principle and are described, for example, in: Winnacker-Küchier, "Chemische Technologie", [Chemical Technology], Volume 7, C. Hauser-Verlag, Munich, 4th edition 1986; van Valkenburg, "Pesticides Formulations", Marcel-Dekker N.Y., 1973; K.Martens, "Spray Drying Handbook", 3rd ed., 1979, G.Goodwin Ltd. London. If the active compounds to be combined are compounds having contrasting physicochemical properties, the possibilities for formulation are naturally limited. Thus, for example, the broad spectrum herbicides glufosinate and glyphosate, which have phosphinoyl or phosphono groups, and their salts belong to the polar hydrophilic active compounds which dissolve relatively well in water. In contrast, herbicides from the group of diphenyl ethers such as oxyfluorfen are virtually insoluble in water. The combined use of herbicides of the aforementioned type is known in advance. In DE-A-19501986 (WO 96/22692, ZA-A-96/0502), for example synergistic combinations of glufosinate-ammonium and salts thereof with oxyfluorfen are described, and wettable powders (WP), granules are mentioned. water dispersible (WDG) and oil-in-water (EW) emulsions as possible co-formulations. Other co-formulations of glufosinate-ammonium and oxyfluorfen are known from US-A-5324708 and Research Report 275 (1987), 154. In addition, the preparation of granules for such combinations of active compound has been described.; see EP-A-448538, EP-A-0394211. In addition, for example, aqueous dispersions with glufosinate or salts thereof and a water-insoluble herbicide (JP-A-07089817) are known. In particular, aqueous dispersions with glufosinate-ammonium and linuron, monolinuron, metolachlor or alachlor (EP-A-0244754) or with glufosinate-ammonium and diuron or simazine (EP-A-0499798) are known.

The combinations of glyphosate (salts) and oxyfluorfen are known from WO 84/03607 and EP-A-0143547. However, none of the aforementioned formulations is a microemulsion or comprises a microemulsion. In contrast to milky turbid suspensions and macroemulsions, microemulsions or micellar solutions are - due to the small particle size (<100 nm) - optically transparent. A particular advantage of microemulsions is their thermodynamic stability, due to which microemulsions theoretically have unlimited storage stability and shelf life. On the contrary, normally the macroemulsions or suspensions are only kinetically stable, and the phase separation and therefore the "decomposition" of the formulation can occur after a period which differs, depending on the individual case. Compared with the equally optically transparent emulsion concentrates (EC), the microemulsions also generally have a percentage of solvents reduced in weight. Also, due to the large reduction in the interfacial tension between the aqueous phase and the oil phase by means of the emulsifying system in question, the otherwise widely used thickeners can be excluded to stabilize the formulation. Additionally, due to the existence of a correlation between the surface tension and the interfacial tension (see Young's equations), said micellar solutions frequently do not require defoamers.

An additional advantage of microemulsions is the fact that the very small water or oil droplets that are present in the concentrate are conserved or converted into stable macroemulsion droplets when diluted with water. Dilution with water, which is customary before biological application, therefore results in spray solutions having small particle sizes, thus preventing clogging of the spray apparatus. In addition, the microemulsions can advantageously be prepared with very little energy expenditure and with technically simple agitators, that is to say even during production the advantages result, in comparison with the aforementioned thermodynamically unstable formulations, in terms not only of materials saved, not also in terms of reduced energy costs. Examples of preparation of pesticidal microemulsions are given, inter alia, in publications WO-A-9006681, WO-A-9314630, EP-A-0160182, EP-A-0533057, EP-A-499587, EP-A -500401, EP-A-432062, DE-A-3624910, DE-A-3235612, EP-A-648414 and EP-A-617894. However, the microemulsions in question do not contain glufosinate-ammonium or glyphosate (salts), and the emulsifiers, wetting and dispersing agents described in the aforementioned publications are in most cases unsuitable for preparing micro-emulsions containing glufosinate-and / or glyphosate; its use results in unstable formulations, characterized by strong turbidity and subsequent phase separation. It is further known that microemulsions with glyphosate (salts) and oxyfluorfen can be prepared using mixtures of fatty amine ethoxylates of various degrees of ethoxylation (GB-A-2267825) or fatty amine ethoxylates and quaternized cationic surfactants (US-A -5565409) in the presence of other surfactants or compatibility agents. The emulsifiers mentioned in the publications are exclusively basic or cationic in nature. In addition to the aforementioned general advantages of microemulsions, it is also known, however, that microemulsions are "critical" systems in that they are commonly sensitive to variations in temperature and / or in the exchange or addition of individual components. In most cases, modification by addition of other surfactants is not possible, which makes it more difficult to adapt the microemulsions to the active components and to the combinations of active compounds that are used in each case or to other application conditions, such as the ratio of the active compounds, temperature variations during storage, climatic zones, etc. . Until now, it has been difficult to predict whether stable microemulsions can be prepared for an individual case, and in most cases a special coordination of all components and relationships is required. There is therefore, in principle, a demand for surfactant systems that make it possible to prepare stable microemulsions. Additionally, it is known that the effect of pesticides can be increased considerably by the addition of certain surface active substances. Thus, for example, alkoxylated fatty amines have been proposed to increase the effect of glyphosate (salts) (EP-A-0290416). Moreover, the isopropylammonium salts of the orthophosphoric acid and triethoxylated butanol esters have been described as surfactant component (s) for increasing the biological activity of glyphosate (salts) (DE-A-4116516). Similarly, in the case of glufosinate-ammonium a strong increase in the activity is observed in the presence of diglycol ether ether sulphate of sodium C? 2 / C (EP-A-0476555, EP-A-0048436, EP-A). -0336151 or US-A-4400196). In general, alkyl polyglycol ether sulfates are also known additionally as penetration promoter auxiliaries and as activity enhancers for a number of other herbicides, including, among other things, diphenyl ether type herbicides (EP-A-0476555). Accordingly, there is a particular interest in formulations containing such activity enhancers either directly as auxiliaries, or allowing their "incorporation", to the detriment of the mixture of emulsifiers that is technically required. The person skilled in the art needs suitable surfactant systems, so that the application properties of the formulations can be fulfilled both with respect to their stability and in addition with respect to the desired activity. There continues to be an increased demand for surfactant systems that allow the effect of the formulated active compounds to be developed in an advantageous manner. The invention provides surfactant systems for aqueous or aqueous-organic liquid formulations (preparations), comprising a mixture of one or more basic surfactants (surfactant component 1) and * one or more anionic surfactants from the group of acid esters phosphoric (surfactant component 2). The invention also provides liquid aqueous or aqueous-organic formulations comprising the surfactant system according to the invention, in particular formulations comprising: (a) one or more water-soluble active compounds (active compounds of type (a)) and (b) ) optionally one or more water-insoluble active compounds (active compounds of type (b)), (c) optionally organic solvents, (d) the surfactant system according to the invention (mixtures of components (d)) and water. In addition, the surfactant system or the corresponding formulations may optionally contain additional components, for example other surfactants or other active compounds and / or auxiliaries customary for the protection of crops, such as inert materials, tackifiers, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreeze agents, solvents, fillers, vehicles, dyes, defoamers, evaporation inhibitors and regulators of pH and viscosity. In the context of the invention, a coagent surfactant of basic character is, in addition to its basic character, a component that is more soluble in an oil phase than in water, which is surface active and therefore reduces the internal tension between those phases, but that does not form any micellar structure in water, due to its insufficient amphiphilic character. The substances which are considered in the present invention as surfactant coagents are characterized in particular by the fact that they do not form any aggregate in aqueous solution, which can be detected, for example, by light scattering measurements or other methods. Suitable surfactant coagents of a basic nature (cation generators) (surfactant component 1) are, for example: (a1) N-alkylamines, such as primary, secondary or tertiary N-alkylamines, for example having in each case from 5 to 22 carbon atoms, preferably to 14 carbon atoms, for example n- or i-pentyl- or hexylamine, n-octylamine, n-decylamine, n-dodecylamine or n-tetradecylamine, or substituted or unsubstituted cycloalkylamines having preferably 5 to 12 carbon atoms , for example cyclohexylamine. (b1) alkoxylated products of the N-alkylamines, preferably fatty amine products (for example C8-C22 fatty amines) with ethylene oxide and / or propylene oxide, in particular fatty amine ethoxylates having from 8 to 18 carbon atoms in the fatty alkyl portion and from 1 to 6 ethyleneoxy units (EO), in which the EO units are present bound to one or two chains of the amino group. Examples are coconut fatty amine ethoxylates such as Genamin C-020® (Clariant), which can be formally considered as reaction products of N, N'-bis- (2-hydroxyethyl) -alkylamine with alkylene oxides, preferably ethylene oxide and / or propylene oxide; (d) alkylaminopolypropylene amines ("polyamines"), such as, for example, alkylpolypropylene diamines, -triamines or coconut polyamines (for example, Dinoram C, ®Trinoram C or © Polyram C, all from Elf Atochem), (d1) products alkoxylates of N-substituted amides or amides, such as carboxylic acid ethanolamides, preferably based on alkanocarboxylic acids having 8 to 18 carbon atoms and ethanolamine or diethanolamine, for example Comperlan LS® (Henkel), or N- (aminoalkyl) ) amides or alkoxylated N, N-bis (aminoalkyl) amides; (e1) alkylamidopropylamines, preferably those based on a C 8 -C 8 alkancarboxylic acid and diamines, such as DMAPA (= N, N-dimethylpropylamine), for example oleoylaminopropyldimethylamine (®Mackine 501, Me Intyre). The surfactants from the group of phosphoric acid esters (surfactant component 2) which can be used according to the invention are, for example, surface active compounds having one or more phosphate groups which are not completely esterified and in wherein the esterified acid radicals are esterified with compounds from the following group of alcohol components: (a2) alkanols (eg isoalkanols) having, for example, 1 to 22 carbon atoms, preferably 1 to 12 carbon atoms , in particular from 4 to 12 atoms or 4 to 8 carbon atoms, or unsubstituted or substituted cycloalkanols having preferably 5 to 12 carbon atoms, for example cyclohexanol, alkylcyclohexanols, cyclopentanol; (b2) alkoxylated alkanols having up to 24 carbon atoms in the alkyl radical and from 1 to 50 alkyleneoxy units in the alkyleneoxy or polyalkylenoxy portion, preferably those having from 4 to 22 carbon atoms, in particular 10 to 20 carbon atoms; carbon in the alkyl radical and from 1 to 60, in particular 3 to 30 alkyleneoxy units in the alkyleneoxy or polyalkylenoxy moiety; (c2) phenol or alkoxylated phenol, in which the phenyl radical is in each case unsubstituted or is substituted with one, two or three alkyl radicals preferably having in each case 4 to 12 carbon atoms or one, two or three aryl or arylalkyl radicals having 6 to 12 carbon atoms, and having, in the alkoxylated case, from 1 to 150 alkyleneoxy units in the alkyleneoxy or polyalkylenoxy moiety, preferably alkoxylated phenol having from 1 to 20 alkyleneoxy units or alkoxylated phenol which is substituted with 1 to 3 alkyl radicals having in each case 4 to 12 carbon atoms and having from 1 to 60, in particular from 4 to 30 alkyleneoxy units, or alkoxylated phenol, which is substituted with one , two or three aryl or arylalkyl radicals having from 6 to 12 carbon atoms and having from 1 to 100, in particular from 10 to 30 alkyleneoxy units, and (d2) alkoxylated alkylamines, having, for example, up to 24 carbon atoms in the alkyl portion and, for example, from 1 to 150 alkyleneoxy units in the polyalkylenoxy moieties such that the surfactants are alkoxylated phosphated alkylamines such as ethoxylated C8-C22 fatty amines. For the above-mentioned alkyleneoxy units, preference is given to C1-C4 alkyleneoxy units, for example ethyleneoxy, propyleneoxy and butyleneoxy units, in particular ethyleneoxy units. The phosphoric esters which are particularly preferred to be used are, for example: phosphated long-chain ethoxylated alcohols or fatty alcohols having from 10 to 18 carbon atoms in the alkyl radical and from 1 to 30 ethyleneoxy units in the polyethyleneoxy portion, example Rhodafac RS 710® (Rhone.Poulenc), Crodafos T 10 A® (Croda) or Crafol AP 240® (Henkel) or Servoxyl VPDZ 20 / 100® (Hüls); Phenol or ethoxylated phosphatized alkylphenol having from 4 to 12 carbon atoms in the alkyl radical and in each case from 1 to 30 ethyleneoxy units in the polyethyleneoxy portion, for example Rhodafac PA / 19 (Rhone-Poulenc); Ethoxylated ethoxylated tristyrylphenol and from 1 to 150 ethyleneoxy units in the polyethyleneoxy moiety, for example Soprophor 3D33® (Rhone-Poulenc). Additionally, the surfactant system may comprise other surfactants, without losing the aforementioned advantageous properties of the surfactant system. Therefore, it is optionally possible to incorporate into the formulations, for example, anion-generating surface-active agents such as alkyl polyglycol ether ether sulfates or alkyl polyglycol ether ether carboxylates. Examples of such anion-generating surfactants are Genapol LRO® (Clariant) and Marlowet 4538® (Hüls). By using the surfactant systems according to the invention, it is now possible surprisingly to prepare liquid pesticide microemulsions of hydrosoluble, thermodynamically stable and optically transparent active compounds such as glyphosate (salts) and / or glufosinate-ammonium in combination with water-soluble active compounds of the type ( b), such as for example oxyfluorfen, diclofop-methyl, fenoxaprop-ethyl or fenoxaprop-P-ethyl. In addition, the surfactant system according to the invention has a favorable influence on the herbicidal activity of the water-soluble active compounds such as glyphosate (salts) or glufosinate-ammonium in combination with the active compounds of type (b). The surfactant system according to the invention therefore also allows the microemulsification of oily phases or of fat soluble active compounds different from those listed in the present invention. In addition, it also provides access to microemulsions of active compounds other than the aforementioned water-soluble active compounds, for example of herbicides from the group of diphenyl ethers, carbamates, thiocarbamates, haloacetanilides, phenoxyphenoxycarboxylic acid derivatives and heteroaryloxyphenoxyalkanecarboxylic acid derivatives, such as quinolyoxy , quinoxalyloxy, pyridyloxy, benzoxalyloxy and benzothiazoleyloxyphenoxyalkanecarboxylic esters, which generally have adequate solubility in oil phase. In some cases, however, the liposoluble active compounds, virtually insoluble in water from the group usually comprising active compounds of variable solubility, are also suitable, for example active compounds from the group of cyclohexanedione derivatives, imidazoleinones, pyrimidyloxypyridinecarboxylic acid derivatives, pyrimidyloxybenzoic acid derivatives, sulfonylureas, triazoleopyrimidine sulfonamide derivatives, and also S- (N-aryl-N-alkylcarbamoylmethyl) dithiophosphoric esters. Correspondingly, the active compounds of the group of protectants, growth regulators, insecticides and fungicides are also suitable as component (b), or if these are readily soluble in water, as components (a). The fact that the surfactant system can be easily transferred to other combinations of water-insoluble compounds and water-soluble compounds demonstrates the flexibility of the surfactant system. This compatibility with other oil or aqueous phases is likewise a considerable practical advantage of the mixtures of components described. For the aforementioned reasons the invention in particular provides surfactant systems for liquid pesticidal compositions comprising a) one or more compound of the formula (1) or salts thereof O O OH NH. wherein Z- is a radical of the formula -OM, -NHCH (CH3) CONHCH (CH3) CO2M or -NHCH (CH3) CONHCH [CH2CH (CH3) 2] CO2M and M = H or a salt-forming cation , and / or one or more compounds of the formula (2) or salts thereof or R20. CH, NH CH 0R " wherein Z2 is a radical of the formula CN, or CO2R ?, in which R -? = Q or a salt-forming cation and Q = H, alkyl, alkenyl, alkoxyalkyl or C ar-C-aryl, the which is unsubstituted or substituted and is preferably unsubstituted or substituted with one or more radicals, selected from the group consisting of alkyl, alkoxy, halogen, CF3, NO2 and CN, and R2, R3 in each case independently one of the other are H, alkyl, C-β-C-io aryl, which is unsubstituted or substituted and is preferably unsubstituted or substituted with one or more radicals that are selected from the group consisting of alkyl, alkoxy, halogen, CF3, NO2 and CN, or are biphenyl or a salt-forming cation, and / or one or more compounds of the formula (3) wherein Z3 is a CN or CO2Q 'radical in which Q' = H, alkyl, alkenyl, alkoxyalkyl or C6-C10 aryl which is unsubstituted or substituted and is preferably unsubstituted or substituted by one or more radicals that are selected from the group consisting of alkyl, alkoxy, halogen, CF3, NO2 and CN and R4 and R5 are each H, alkyl or C6-C-? aryl which is unsubstituted or substituted and Preference is not substituted or is substituted with one or more radicals selected from the group consisting of alkyl, alkoxy, halogen, CF3, NO2 and CN and A is a salt-forming anion, and (b) optionally one or more insoluble active compounds water, in particular from the group of herbicides mentioned as preferred, (c) optionally one or more organic solvents, (d) the aforementioned surfactant system of one or more basic surfactant coagents and one or more surfactants from the group of what s esters of phosphoric acid. In the formulas (1) to (3) and in the formulas subsequently used in the present invention, the substituted alkyl, alkoxy and radical radicals can in each case be straight or branched chain carbon base structures. Unless specifically defined otherwise, for these radicals preference is given to lower carbon base structures, for example having 1 to 4 carbon atoms or, in the case of unsaturated groups, having 2 to 4 carbon atoms. carbon atoms. Alkyl radicals also in the compound meanings, such as alkoxy (alkanols) etc., are, for example, methyl, ethyl, n- or i-propyl, n-, i-, t- or 2-butyl, pentyl, hexyl , such as n-hexyl, i-hexyl and 1,3-dimethylbutyl, heptyl, such as n-heptyl, 1-methylhexyl, 2-ethylhex-1-yl and 1,4-dimethylpentyl. Halogen is, for example, fluorine, chlorine, bromine or iodine, haloalkyl, haloalkenyl and haloalkynyl are alkyl, alkenyl and alkynyl, respectively, which are partially or completely substituted by halogen, preferably with fluorine, chlorine, and / or bromine, in particular with fluorine or chlorine, for example CF3, CHF2, CH2F, CF3CF2, CH2FCHCI2, CCI3, CHCI2, CH2CH2CI; haloalkyl is, for example, OCF3) OCHF2, OCH2F, CF3CF2O, OCH2CF3 and OCH2CH2CI; this applies correspondingly to haloalkenyl and the other halogen-substituted radicals. Aryl is a monocyclic, carbocyclic aromatic ring, which, in the substituted case, also includes a bi- or polycyclic aromatic system containing at least one aromatic ring and optionally other aromatic rings or partially unsaturated or saturated rings; aryl is, for example, phenyl, naphthyl, tetrahydronaphthyl, indenyl, indanyl, pentanyl, fluorenyl and the like, preferably phenyl; Aryl is a mono- or polycyclic aromatic system, for example phenyl, naphthyl, tetrahydronaphthyl, indenyl, indanyl, pentalenyl, fluorenyl and the like, preferably phenyl; aryloxy is preferably an oxy radical corresponding to the aforementioned aryl radical, in particular phenoxy.

Substituted radicals, such as, for example, alkyl, aryl or substituted phenyl are, for example, a substituted radical obtained from an unsubstituted base structure, in which the substituents are, for example, one or more, preferably 1, 2 or 3, radicals selected from the group consisting of halogen, alkoxy, haloalkoxy , alkylthio, hydroxy, amino, nitro, cyano, azido, alkoxycarbonyl, alkylcarbonyl, formyl, carbamoyl, mono- and dialkylaminocarbonyl, substituted amino, such as acylamino, mono- or dialkylamino and alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl and, in the case of cyclic radicals, also alkyl and haloalkyl, and unsaturated aliphatic radicals corresponding to the aforementioned saturated hydrocarbon-containing radicals, such as alkenyl, alkenyl, alkynyl, alkenyloxy, alkynyloxy, etc. In the case of radicals having carbon atoms, preference is given to those having 1 to 4 carbon atoms, in particular 1 to 2 carbon atoms. Preference is generally given to substituents from the group consisting of halogen, for example fluorine and chlorine, C 1 -C 4 alkyl, preferably methyl or ethyl, C 1 -C 4 haloalkyl, preferably trifluoromethyl, C 1 -C 4 alkoxy, preferably methoxy or ethoxy, haloalkoxy of C1-C4, nitro and cyano. Particular preference is given in the present invention to methyl, methoxy and chloro substituents. The preferred compounds of formulas (1), (2) and (3) are those in which Z1 is a radical of the formula -OM and M = H or a salt-forming cation, Z2 is a radical of the formula CN or CO2R1 in which R1 = Q or a salt-forming cation in which Q = H, C-1-C12 alkyl, C2-C12 alkenyl, alkoxy (CrC6) -CrC6 alkyl or C6-C- aryl? 0 which is unsubstituted or substituted and is preferably unsubstituted or substituted by one or more radicals from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, CF 3, NO 2 and CN, R 2 , R3 in each case independently from each other are H, C 1 -C 4 alkyl, C 1 -C 10 aryl which is unsubstituted or substituted and is preferably unsubstituted or substituted by one or more radicals from the group consisting of C 1 -C 4 alkyl, alkoxy of C1-C4, halogen, CF3, NO2 and CN, or are biphenyl or a salt-forming cation, Z3 is a CN or CO2Q 'radical in which Q' = H, C1-C12 alkyl, C2-C12 alkenyl , alkoxy (C -? - C6) -alkyl (C -? - C6) or C6-C? aryl which is unsubstituted or substituted and is preferably unsubstituted or substituted by one or more radicals from of the group consisting of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, CF 3, NO 2 and CN, R 4 and R 5 are each H, C 1 -C 4 alkyl or C 6 -C 10 aryl which is unsubstituted or is substituted and is preferably unsubstituted or substituted with one or more radicals from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, CF 3, NO 2 and CN, and / or, A is an anion salt former , such as, for example, a halide, sulfate, nitrate, phosphate, carbonate, bicarbonate anion or an acid anion of a carboxylic acid or other organic acid.

The compounds of the formula (1) contain an asymmetric carbon atom. The L-enantiomer is considered to be the biologically active isomer. Therefore, formula (1) encompasses all stereoisomers and mixtures thereof, in particular the racemate and the respective biologically active enantiomer. Examples of active compounds of the formula (1) are the following: * glufosinate and its ammonium salt in racemic form, the L-enantiomer of glufosinate and its ammonium salt, * Bilanafos / bialaphos, ie L-2-amino-4 - [hydroxy (methyl) -phosphinoyl] -butanoyl-L-alaninyl-L-alanine and its sodium salt. The glufosinate-ammonium racemate itself is usually applied in doses between 200 and 1,000 g of active ingredient (i.a.) / ha (= grams of active substance per hectare). At these doses, glufosinate-ammonium is effective in particular when it is consumed through the green parts of the plants; see "The Pesticide Manual" 10a. Edition, British Crop Protection Council 1994, page 541. Glufosinate-ammonium is mainly used to control broadleaf weeds and noxious grasses in plantation crops and on uncultivated land and, by means of special application techniques, also for the treatment between rows in furrowed agricultural crops such as corn, cotton and the like. The use in transgenic crops that are resistant to or tolerant to the active compound in question has become increasingly important. Since the glufosinate-ammonium active compound degrades microbiologically in the soil within a few days, no long-term action is observed. Similarly, this is also true for the related active compound bilanaphos / bialaphos; see "The Pesticide Manual" 10a. Edition, British Crop Protection Council 1994, page 98. The compounds of the formulas (2) and (3) are N- (phosphonoalkyl) glycine, and therefore derivatives of the amino acid glycine. The herbicidal properties of N- (phosphonomethyl) glycine ("glyphosate") are described, for example, in the US patent. No. 3799758. In the crop protection formulations, glyphosate is commonly used in the form of water soluble salts, the isopropylammonium salt ("IPA-glyphosate") being of particular importance in the context of the present invention. In general, the surfactant system according to the invention (mixture of component (d)) is suitable for the microemulsification of oil phases in water or, if the individual components are appropriately selected, from aqueous phases in oil. Depending on the composition, this gives access to microemulsions that can be diluted with water or with oil, while at the same time maintaining the micellar structure. Furthermore, in the absence of the oil phases comprising the liposoluble active compounds of type (b), thin aqueous solutions of the active compounds described in (a) are obtained. The invention therefore preferably provides the oil-in-water microemulsions with the components (a) to (d), in particular those with one or more diphenyl ethers dissolved in an organic solvent, a herbicide from the group of azol-type herbicides, phenoxyphenoxycarboxylic acid derivatives and heteroaryloxyphenoxycarboxylic acid derivatives. Here, the term "diphenyl ether" encompasses chemical compounds from the group of diphenyl ether-type herbicides, their equivalents, metabolites, salts, esters and derivatives. The diphenyl ether herbicides are composed of two substituted benzene rings which are linked by an oxygen atom. These are usually used to control broadleaf weeds and harmful grasses by means of the pre-emergence or postemergence method. Depending on the substitution and light supply, which is relevant to the herbicidal action, a distinction is made between the diphenylic ethers that are substituted in positions 2,4 or 2,4,6 and the diphenyl ethers that are substituted in position 3 or 3.5. The group of diphenyl ether herbicides include, in particular, acifluorfen and the corresponding alkali metal salts, aclonifen, bifenox, clometoxifen, fluorglycofen, fomesafen, lactofen, nitrophen, oxyfluorfen and mixtures of these compounds. The aforementioned compounds are described, for example, in "The Pesticide Manual" 10th edition, British Crop Protection Council 1994 and in the literature cited therein, and are known as herbicides of the protoporphyrinogen oxidase inhibitor type.

The term "azole-type herbicides" includes chemical compounds that comprise one or more substituted heterocycles having one or more nitrogen atom. Depending on the number of nitrogen atoms in the original heterocycle, these compounds are known as mono-, di- or triazole herbicides. The group of "azole-type herbicides" includes in particular oxadiazone. Similarly, this compound is described in "The Pesticide Manual" 10th edition, British Crop Protection Council 1994 and in the literature cited therein, and is known as a herbicide of the type of protoporphyrinogen oxidase inhibitors. Suitable liposoluble herbicides from the group of herbicides of the phenoxyphenoxycarboxylic acid and heteroaryloxyphenoxycarboxylic acid derivatives are, for example: a) phenoxyphenoxycarboxylic acid derivatives, for example, 2- (4- (2,4-dichlorophenoxy) phenoxy) propionate methyl (diclofop-methyl) -2- (4- (4-cyano-2-fluorophenoxy) phenoxy) butyl propionate and its 2- (R) enantiomer (cyhalofop-butyl); - methyl 2- (4- (2-chloro-4-trifluoromethylphenoxy) phenoxy) propionate (see DE-A-2433067) - methyl 2- (4-fluoro-4-trifluoromethylphenoxy) phenoxy) propionate (cf. US-A-4808750) - methyl 2- (4- (trifluoromethylphenoxy) phenoxy) propionate (see DE-A-2433067) b) "mononuclear" heteroaryloxyphenoxyalkanecarboxylic acid derivatives, for example - 2 (4- (3) ethyl 5-dichloropyridyl-2-oxy) phenoxy) propionate (see EP-A-2925) - methyl 2- (4- (3-chloro-5-trifluoromethyl-2-pyridyloxy) phenoxy) propionate and its (R) -enantiomer (haloxifop-methyl or haloxifop-P-methyl, see EP-A-3890) and the corresponding ethoxyethyl ester (haloxifop-etotyl or haloxifop-P-etotyl), - 2- (4- ( Propargyl-5-chloro-3-fluoro-2-pyridyloxy) phenoxy) propionate and its (R) -enantiomer (EP-A-191736, clodinafop-propargyl), 2- (4- (5-trifluoromethyl-2-pyridyloxy) phenoxy) ) butyl propionate and its (R) -enantiomer (fluazip-butyl or fluazifop-P-butyl), c) deri "dinuclear" heteroaryloxyphenoxyalkanecarboxylic acid radicals, for example, methyl (ethyl) - (R) -2- (4- (6-chloro-2-quinoxalyloxy) phenoxy) propionate (quizalofop-P-methyl and quizalofop-P-ethyl, respectively) or the corresponding 2-isopropylidenamino-oxyethyl ester (propaquizafop), ethyl 2- (4- (6-chlorobenzoxazol-2-yl-oxy) phenoxy) propionate (fenoxaprop-ethyl), its (R) -enantiomer (fenoxaprop -P-ethyl), tetrahydrof ur-2-ylmethyl-2- (4- (6-chloroquinoxalyloxy) phenoxy) propionate and its (R) -enantiomer (see EP-A-323727). The compounds mentioned under the common name are also described in "The Pesticide Manual" 11th edition, British Crop Protection Council 1997, and in most cases they are known as inhibitors of fatty acid biosynthesis in plants. The weight ratios of (a) :( b) of the combined active compounds of type (a) and (b) can vary within wide limits and depends in particular on the activity or the common application rate of the active compounds used. The weight ratios are generally between 1000: 1 and 1: 1, preferably from 100: 1 to 1: 1, in particular from 50: 1 to 1: 1, and in the case of the herbicides of the formula (1) , (2) or (3) and the diphenyl ether herbicides are preferably between 10: 1 and 1: 1. For combinations of herbicides of the diphenyl ether type with herbicides of the type (a) in particular glufosinate-ammonium, the following weight ratios of (a) :( b): * are preferred with acifluorfen, 10: 1 to 2: 1, in particular 8: 1 to 3: 1 with bifenox, 10: 1 to 2: 1, in particular 8: 1 to 3: 1 * with fluoroglycofen, 100: 1 to 10: 1, in particular 50: 1 to 10: 1 * with fomesafen, 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 oxyfluorfen, 10: 1 to 2 : 1, in particular 8: 1 to 3: 1. In general, application regimes can be used from 100 to 600 g of i.a./ha of herbicide of type (a), preferably glufosinate-ammonium, and from 50 to 150 g.i./ha of the active compounds of type (b), in particular oxyfluorfen or lactofen.

The optimal choice of weight ratios and application regimes depends, in particular, on the stage of development of broadleaf weeds or harmful grasses in question, prevailing weed ranges, environmental factors and climatic conditions , so that the aforementioned weight ratios and the application regimes have to be verified in the individual case. For combined use, the application rate of the herbicides in question is considerably below the application regimes for the individual application to obtain the same herbicidal effect, so that the thermodynamically stable formulations containing both active compound components give as resulting in a particularly high biological activity, and a reduced content of active compound. In the context of the present invention, the term "organic solvents" (components (c)) indicates for example, non-polar solvents, polar protic or polar aprotic solvents and mixtures thereof. Examples of solvents in the context of the invention are: aliphatic or aromatic hydrocarbons, such as, for example, mineral oils, or toluene, xylenes or naphthalene derivatives, * halogenated aliphatic or aromatic hydrocarbons, such as methylene chloride or chlorobenzene; ethers, such as diethyl ether, tetrahydrofuran, (THF), dioxane, monoalkyl ethers and alkylene glycol dialkyl ethers, such as, for example, propylene glycol monomethyl ether, propylene glycol monoethyl ether, monomethyl ether or ethylene glycol monoethyl ether, diglyme and tetraglim; * amides, such as dimethylformamide (DMF), dimethylacetamide, dimethylcaprylamide, dimethylcaprinamide (®Hallcowide) and N-alkylpyrrolidones; * ketones, such as acetone; * esters based on carboxylic acids and glycerol, such as glycerol mono-, di- and triacetate; * Italic esters; * lactams, * carbon diesters; * nitriles, such as acetonitrile, propionitrile, butyronitrile and benzonitrile; * sulfoxides and sulfones, such as dimethyl sulfoxide (DMSO) and sulfolane; * oils, for example based on vegetables, such as corn oil and rapeseed oil. In many cases, combinations of different solvents are also suitable which additionally contain alcohols, such as methanol, ethanol, n- and i-propanol, n-, i-, t- and 2-butanol. In the case of monobasic aqueous-organic solutions, solvents or mixtures of solvents completely or substantially miscible in water are suitable. To prepare the microemulsions, essentially those solvents are suitable which predominantly become a component of the organic phase, ie solvents or solvent mixtures which are not miscible, or are poorly miscible with water, Furthermore, it is possible to mix, if it is considered convenient, solvents that are partially or indefinitely water soluble. In the context of the present invention, the preferred organic solvents are aromatic solvents, such as toluene, o-, m- or p-xylene and mixtures thereof, 1-methylnaphthalene, 2-methylnaphthalene, aromatic mixtures of 6-16 C , such as, for example, the Solvesso® (ESSO) series including the Solvesso® 100 (Pe162-177 ° C), Solvesso® 150 (Pe187-207 ° C) and Solvesso® 200 (Pe 219-282 °) types. C), alkylphthalates (1-12C), specifically alkylphthalates (4-8C), ketones immiscible in water, such as, for example, cyclohexanone or isophorone, or aliphatics of 6-20C, which may be linear or cyclic, such as the products of the Shellsol® series, types T and K, or BP-n paraffins, esters, such as glycerol triacetate, and the polar organic solvents N-methylpyrrolidone and Dowanol® PM (propylene glycol monomethyl ether). The components which may additionally be present as formulation aids in the formulations according to the invention are, for example, solid inert solvents which are not soluble in water., which frequently make a beneficial contribution to the stability of the formulation. This can prevent or delay, for example, the formation of macro-phases, the sedimentation of solid phases and the like. In this context, suitable inert materials are resins or substances in the form of resins of natural or synthetic origin which are soluble in the oil phase, for example natural resins such as rosin (rosin, turpentine gum) and tannin. Resins can be added, for example, in amounts up to 30% by weight, preferably up to 20% by weight, in particular up to 5% by weight, based on the weight of the formulation. The auxiliary materials that are required to prepare the aforementioned formulations, such as, in particular, surfactants and surfactant coagents, are known in principle and are described, for example, in: McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood N.J.; Sisley and Wood, "Encyclopedia of Surface Active Agents," Chem. Publ.Co.Inc, N.Y. 1964; Schonfeld, "Grenzfláchenaktive Áthylenioxidaddukte" [adducts of active surface ethylene oxide], Wiss. Verlagsgesellschaft, Stuttgart 1976; Winnacker-Küchier, "Chemische Technologie", Volume 7, C. Hauser-Verlag, Munich, 4th edition 1986, and the literature cited in these publications. Although the chemical "structure" of the individual usable components is sufficiently described therein, the properties of the mixtures of said components for the formulation of a certain system of active compounds, of the aforementioned manuals, can not be predicted. This is typical, even if mixtures of components are used with microemulsions that have been obtained for other active compounds - as illustrated in Table 1 (see below). If, for example, in this case, a surfactant or combination of surfactants is used with which the microemulsions for other active compounds have been obtained and described (cf. DE-A-36234910), it is precisely the case that for the combinations of glufosinate-ammonium and oxyfluorfen, microemulsions are not discovered, but unstable multiple phase systems (see examples 1 and 4). Similarly, if instead of the ethoxylated fatty amine used as "co-emulsifier" in Examples 1 and 4, compounds which have been described as co-surfactants in another context- such as, for example, n-butanol (Example 2) are used. ) - they also give a multiple phase system instead of a microemulsion. Moreover, it is not correct to assume that n-butanol is just as hydrophobic as to be suitable for use as a co-surfactant for the formation of a microemulsion, in this case. As shown in Example 3 of Table 1, a microemulsion is not obtained, even if the HLB value has been increased. In addition, in the case of glufosinate-ammonium and oxyfluorfen to obtain neutralized phosphoric esters in the presence of basic surfactant coagents (examples 5-7), phase separation is observed. Starting from these mixtures of components, which do not give a stable microemulsion of the combination of active compounds (a) and (b), it was not expected, therefore, that the microemulsions for the active compounds described according to (a) and (b) ) could be prepared using the surfactant system of the invention. This is a fact, particularly for mixtures of basic surfactant coagents (cationogenic components) and acid phosphoric esters (anionogenic components): specifically for said mixtures of "cationogenic" surfactants, crystal precipitates insoluble in water are expected. Therefore, from the cause to the effect, they seemed totally unsuitable for use as emulsifiers. Surprisingly, however, they are particularly suitable for microemulsifying the active compounds described according to (a) and (b). This is illustrated by the examples shown in Table 2 (see below) that give an idea of the chemical flexibility of the described component mixtures. Therefore, acidic phosphoric esters of various chemical origins can be used, such as ethoxylated phosphated fatty alcohols based on various fatty alcohols (example I and example III), ethoxylated nonylphenol phosphates (example IV) or in addition, ethoxylated tristyrylphenol phosphates (example V). Apparently, even the degree of ethoxylation of the phosphoric esters plays only a lower role, as can be seen in Example II. In addition, it is also possible to use chemically different components as basic surfactant coagents, such as alkylamines with base of various alkyls (example I and example VI), or aminoethylates (example VII). Finally, example VIII illustrates that even basic carboxamides can be used as surfactant coagents, or acid ethoxylated aryl phosphates as surfactant. The chemical diversity that is possible, allows the optimal adaptation of the system of surfactants used for the technical requirements that have to be met in the individual case. However, it should be taken into account that the mixtures according to component (d) are particularly effective precisely when they contain an excess basic surfactant (examples I-VII, IX-XIV) or an excess acid phosphoric ester (Example VIII). Preferred molar ratios (based on the equivalents of the acidic or basic groups) of the acidic: basic surfactant components are in particular 1: 1.01-1: 100 or 1: 0.01-1: 0.99, preferably a ratio from 1: 2 to 1: 4, for example, approximately 1: 2, 1: 3 or 1: 4, or from about 1: 05 to 1: 0.25, for example 2: 1, 3: 1 or 4: 1 . As a consequence, mixtures comprising the two surfactant components (1) and (2) in non-equimolar amounts are particularly suitable for microemulsification. The pH of the formulation is preferably established in such a way that the phase separation described above does not occur, in the case of glufosinate-ammonium preferably on the scale near pH = 7. If the pH from the beginning is not within the neutral scale, as in the case of examples VII and VIII, it can be adjusted, for example, using acetic acid (examples I-VI, IX and XII-XIV). The anionogenic surfactants, such as alkyl polyglycol ether sulfates or alkyl polyglycol ether carboxylates, which by themselves, ie without the surfactant system according to the invention, do not give microemulsions for the mixtures of (a) and (b), its presence as a "destabilizing" effect. The use of such anionogenic surfactants alone, for the mixtures of (a) and (b) generally results in thermodynamically unstable systems, such as the macroemulsions described in DE-A-19501986. Surprisingly, however, even ether alkyl polyglycol sulfates or alkyl polyglycol ether carboxylates give, in combination with sufficient hydrophobic primary N-alkylamines as the basic component, acid phosphoric esters as the anionogenic component according to the mixture of components (d), finished formulations thermodynamically stable (examples IX and X). As can be further appreciated from example XI, the mixtures of components described according to (d) can be used to microemulsify active compounds that are insoluble in water, such as oxyfluorfen, in the presence of glyphosate. N-alkylpyrrolidones are described as insecticidal microemulsion components, in U.S. Patent Nos. 5338762, U.S-A-5326789, U.S.-A-5317042, U.S-A-5298529, U.S.-A-5300529 and WO-A-9213454. The surfactant system (d) according to the invention allows the microemulsification of combinations of active compounds (a) and (b) even independently of the presence of the component N-methylpyrrolidone (NMP). This is immediately evident from Example XII. Microemulsions or micellar solutions, which are prepared according to the present invention, include water. Some of the water originates from the wastewater that is present in commercially available surfactants or surfactant mixtures, and another part originates from the aqueous solution of the herbicides of type (a); In order to truly obtain a microemulsion with the mixtures of surfactants described, additional water is generally required. Even in the absence of an organic phase or in the presence of polar solvents which are indefinitely miscible with water, such as, for example, N-pyrrolidone (NMP), the surfactant system (d) according to the invention, gives in combination with active compounds of type (a) stable single-phase aqueous solutions. This is illustrated by the examples in Table 3. Therefore, with the aid of the mixtures of components (d), it is possible to prepare preferably liquid preparations of glufosinate or glyphosate or salts thereof or of other substances which are readily soluble in water. water, comprising a) 1 to 50% by weight, preferably 5 to 20%, of the active compound of the aforementioned type (a). b) 0 to 70% by weight, preferably 0 to 10%, of the active compound of the aforementioned type (b). c) 0 to 60% by weight, preferably 0 to 30%, of organic solvents, d) 3 to 70% by weight, preferably 10 to 40%, of the mixture of components (d) according to the invention (system of surfactants), e) O at 20% by weight, preferably 0 to 15%, of other anionogenic surfactants, such as alkyl polyglycol ether sulfates or alkyl polyglycol ether carboxylates, f) 0 to 20% by weight, preferably 0 to 15% by weight weight, of customary formulation auxiliaries, g) 0.1 to 60% by weight, preferably 10 to 40%, of water, where the weight ratio of the herbicides (a) to the surfactants mentioned in (e) - based on the detergent surfactant in question - is preferably 1: 1 to 1:10, in particular 1: 1 to 1: 5. Particular preference is given to microemulsions having a content of a) 5 to 20% by weight of active compound of the aforementioned type (a), b) 1 to 10% by weight of the active compound of the aforementioned type (b) , d) 5 to 30% by weight of organic solvents forming a phase with active compound (b), c2) 0 to 30% by weight of water-soluble organic solvents, where the total proportion of solvents (d) + (c2) is preferably 5 to 30% by weight, d) 10 to 40% by weight of the mixture of components (d) according to the invention (system of surfactants) e) 0 to 20% by weight, preferably 0 to 15% , of other anionogenic surfactants, such as alkyl polyglycol ether sulfates or alkyl polyglycol ether carboxylates, f) 0 to 20% by weight, preferably 0 to 10% by weight of customary formulation auxiliaries, g) 10 to 40% by weight of water. In addition, preference is also given to the aqueous single-phase solutions of the herbicides (a), which have a content of the surfactant system (d) according to the invention. These solutions represent a favorable form of application of herbicides (a). In the present, preference is given to single-phase aqueous herbicidal solutions having a content of a) 1 to 50%, by weight, preferably 5 to 20% by weight, of the active compound of the aforementioned type (a) , d) 3 to 70%, preferably 5 to 50%, of the mixture of components (d) according to the invention (system of surfactants) c) 0 to 40% by weight of organic solvents that can be mixed without separation of phases, e) 0 to 20% by weight, preferably 0 to 15%, of other anionogenic surfactants, such as alkyl polyglycol ether sulfate or alkyl polyglycol ether carboxylates f) 0 to 20% by weight, preferably 0 to 15% by weight of customary formulation aids, g) 10 to 40% water. The solvents that can be mixed to prepare the solution of a single aqueous phase, are in particular, indefinitely or substantially organic solvents miscible in water, such as for example, N-methylpyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMA) or propylene glycol monomethyl ether. The customary formulation aids (f) are, for example, the aforementioned inert materials, antifreeze agents, evaporation inhibitors, preservatives, dyes, antifoams and the like.; Preferred formulation auxiliaries (f) are • water-insoluble inert materials (for example oil-soluble resins) up to 30% by weight, • antifreeze agents and evaporation inhibitors, such as glycerol or ethylene glycol, for example in an amount of 2 to 10% by weight, and • preservatives, for example Mergal K9N® (Riedel) or Cobate C®, • antifoams, such as ®Fluowet PL 80 (Clariant) in amounts from 0.001 to 1% by weight at customary concentrations for the agents that are used specifically in each case. The liquid formulations according to the invention can be prepared by methods which are customary in principle, that is, by mixing the components with stirring, liquefying or by means of static mixing procedures. The resulting liquid formulations are stable and have good storage stability. Additionally, liquid formulations, in many cases, have favorable properties and applications. As can be seen, for example, from Table 4 (see below), the measurable herbicidal effect of the active compounds glufosinate-ammonium and oxyfluorfen formulated according to the invention, in the form of a microemulsion according to the formulation I, is clearly higher than the effect of the same active compounds, which are formulated, however, in the form of a macroemulsion. In general, this applies correspondingly also to other formulations according to the invention. Accordingly, the formulations according to the invention are particularly suitable for controlling the undesirable growth of plants. Unless defined otherwise, the amounts provided in the examples below are based on weight. The examples in Table 1 relate to the comparative examples (= examples not in accordance with the invention) that do not give microemulsions. Examples of microemulsions according to the invention are listed in table 2. Table 2 further mentions examples of single-phase systems according to the invention. Table 4 contains the comparative biological results of the herbicidal activity of the formulations described.

TABLE 1 Examples of formulations that do not give microemulsions (comparative examples) or TABLE 2 Examples of microemulsion formulation TABLE 3 Examples of single-phase aqueous formulations EXAMPLE OF USE Seeds or fragments of rhizomes of harmful monoeotyledonous and dicotyledonous grasses are placed in sandy loam soil in thick cardboard pots, covered with soil and grown in a greenhouse under good growing conditions. Three weeks after sowing, the test plants are treated in the three-leaf stage with the formulations and dosages according to Table 4 with an application rate of 300 I of water / ha. After the test plants have been kept in the greenhouse for 28 days under optimal growth conditions, one can visually record the effect of the preparations compared to the controls without treatment. The results are summarized in table 4.

TABLE 4 Biological results for herbicidal activity a) Formulation in accordance with DE-A-18501986 b) Microemulsion in Table 2 c) Herbicidal effect in% after 28 days Abbreviations and footnotes for tables 1, 2, 3, and 4: n in the formulas n = 0-3, that is, it is in each case a mixture of the phosphoric esters where n = 1, 2 and 3, the acid proportions where n = 1 and 2 is essential; numbers all percentages are percentages determined in percent by weight, based on the weight of the formulation (= 100 percent by weight); the rest at 100 percent by weight is the percentage of water 1-C-I3- = isotridecyl Cs / C-is- or C12 / C-18- or C12 / C14, are mixtures of fatty alkyl radicals having chain lengths in the scale of the chain lengths given in atoms of -C (Tri-sty-) fe- = tristyrylphenol-EO = "ethylene oxide", that is, a group of formula -CH2-CH2-O - (ethyleneoxy) or, if terminal, -CH2-CH2-OH (hydroxyethyl) TEA = triethanolamine MEA = monoethanolamine NP = nonylphenyl Explanations of the index numbers 1) to 13)): 1) ethoxylated phosphate isotridecyl alcohol (specifically Rhodafac RS 710®, (Rhone-Poulenc)) 2) ethoxylated phosphated fatty alcohol (specifically Crafol AP 240 ®, Henkel) 3) ethoxylated phosphated tristyrylphenol, neutralized with TEA (specifically Soprophor FL®, Rhone-Poulenc); it is not according to the invention, because it is not acidic; 4) ethoxylated isotridecyl alcohol (specifically Genapol X-060®, Clariant) 5) coconut fat amine ethoxylate (specifically Genamin C-200®, Clariant); it is not coagent surfactant in the context of the invention; form molecular aggregates (micelles); 6) ethoxylated phosphate isotridecyl alcohol (specifically Servoxil VPDZ 20 / 100®, Hüls) 7) ethoxylated phenol phosphate having the following percentages in the mixture: 7.5-8.5% by weight n = 0.1 1-10% by weight C6H5-O- (EO) 4H, 80-90% by weight n = 1 and approximately 2% by weight n = 2 8) nonylphenol phosphate ethoxylate (specifically Rhodafac PA / 19®, Rhone-Poulenc) 9) tristyrylphenol phosphate ethoxylate (specifically Soprophor 3D33® (Rhone-Poulenc)) 10) Fatty alcohol diethylene glycol ether sulfate (specifically Genapol LRO®, Clariant) 11) 2- (isotridecyloxypolyethyleneoxy) ethyl carboxymethyl ether (specifically Marlowet 4538®, Hüls) 12) fatty amine ethoxylate. coconut (specifically Genamin C-020®, Clariant) 13) fatty amide ethoxylate (specifically Comperlan LS®, Henkel)

Claims (15)

NOVELTY OF THE INVENTION CLAIMS

1. - A thermodynamically stable aqueous or aqueous-organic liquid formulation comprising a surfactant of one or more basic surfactant coagents and one or more surfactants of the group of acid phosphoric esters.

2. The formulation according to claim 1, further characterized in that the surfactants of the group of acid phosphoric esters used are those in which the esterified acid radicals are esterified with one or more compounds from the group of alcohol components (a2) a (d2), wherein: (a2) are alkanols having 1 to 22 carbon atoms, or unsubstituted or substituted cycloalkanols having preferably 5 to 12 carbon atoms, (b2) are alkoxylated alkanols having up to 24 carbon atoms. carbon in the alkyl radical and from 1 to 50 alkyleneoxy units in the alkylenoxy portion or polyalkylenoxy moiety and (c2) is phenol or alkoxylated phenol, in which the phenyl radical is in each case unsubstituted or is substituted with one, two or three alkyl radicals having in each case 4 to 12 carbon atoms or one, two or three aryl or arylalkyl radicals having 6 to 12 carbon atoms, and having, in the alkoxylated case, 1 to 150 alkyleneoxy units in the alkyleneoxy or polyalkylenoxy moiety, and (d2) are alkoxylated alkylamines.

3. - The formulation according to claim 1 or 2, further characterized in that the acid phosphoric ester surfactants are phosphated long chain ethoxylated alcohols or fatty alcohols having from 10 to 18 carbon atoms in the alkyl radical and from 1 to 30 ethyleneoxy units in the polyethyleneoxy moiety; ethoxylated phenol or alkylphenol phosphate having from 4 to 12 carbon atoms in the alkyl radical and in each case from 1 to 30 ethyleneoxy units in the polyethyleneoxy portion, or ethoxylated phosphated tristyrylphenol having from 1 to 150 ethyleneoxy units in the polyethyleneoxy moiety; or a mixture of surfactants. 4. The formulation according to any of claims 1 to 3, further characterized in that the basic surfactant coagents are selected from the group of (a1) N-alkylamines or substituted or unsubstituted cycloalkylamines, (b1) alkoxylated products of the N- alkylamines, (d) alkylaminopropylenamines, (d1) alkoxylated products of N-substituted amides or amides, (e1) alkylamidopropylamines. 5. The formulation according to any of claims 1 to 4, wherein the formulations comprise: a) one or more water-soluble active compounds (type (a)) and b) optionally one or more water insoluble active compounds (type (b)) )), optionally organic solvents. 6. The formulation according to claim 5, further comprising as water-soluble active compounds one or more compounds of the formula (1) or salts thereof, O O where Zi is a radical of the formula -OM,

NHCH (CH3) CONHCH (CH3) CO2M or NHCH (CH3) CONHCH [CH2CH (CH3) 2] CO2M and M = H or a salt-forming cation, or one or more compounds of the formula (2) or salts thereof , O

R20 CH. NH CH OR. wherein Z2 is a radical of the formula CN, or CO2R ?, in which R? = Q or a salt-forming cation and Q = H, alkyl, alkenyl, alkoxyalkyl or C6-C? 0 aryl, which is not substituted or substituted, and R2, R3 in each case independently of one another are H, alkyl, C6-C ar aryl, which is unsubstituted or substituted or biphenyl or a salt-forming cation, or one or more compounds of the formula (3),

H i

ORc in which Z3 is a radical CN or CO2Q 'in which Q' = H, alkyl, alkenyl, alkoxyalkyl or C6-C- aryl which is unsubstituted or substituted and R and R5 are each H , C 1 -C 12 alkyl or aryl which is unsubstituted or substituted, and A is a salt-forming anion, or mixtures of two or more of the compounds defined above. 7. The formulation according to claim 5 or 6, which comprises as compounds insoluble in water, compounds selected from the group of diphenyl ether herbicides.

8. The formulation according to any of claims 5 to 7, comprising a) 1 to 50% by weight, of the active compound of type (a), b) 0 to 60% by weight, of the active compounds of the type (b), c) 0 to 60% by weight of organic solvents, d) 3 to 70% by weight, of the surfactant system of one or more basic surfactant coagents and one or more surface active agents of the phosphoric ester group acids ((mixture of components (d)), e) 0 to 20% by weight, of other anionogenic surfactants, f) 0 to 20% by weight, of customary formulation auxiliaries, g) 0.1 to 60% by weight of Water.

9. The formulation according to any of claims 5 to 8, further characterized in that the formulations are microemulsions comprising a) 5 to 20% by weight, of the active compound of type (a), b) 1 to 10% by weight weight, of the active compound of type (b), d) 5 to 30% by weight, of organic solvents forming a phase with the active compound (b), c2) 0 to 30% by weight of water-soluble organic solvents, d) 10 to 40% by weight, of the surfactant system of one or more basic surfactant coagents and one or more surfactants of the group of acid phosphoric esters ((mixture of components (d)), e) 0 to 20% by weight, of other anionogenic surfactants, f) 0 to 20% by weight, of customary formulation auxiliaries, g) 10 to 40% by weight of water.

10. The formulation according to claim 5 or 6, further characterized in that the formulation is a solution of a single aqueous phase of active compounds of type (a) comprising a) 1 to 50% by weight of the active compound of type (a), d) 3 to 70% by weight, of the surfactant system of one or more basic surfactant coagents and one or more surfactants of the group of acid phosphoric esters ((mixture of components (d)), c) 0 to 40% by weight, of organic solvents that can be mixed without phase separation, e) 0 to 20% by weight, of customary formulation auxiliaries, g) 10 to 40% by weight of water.

11. A process for preparing a formulation as defined in one or more of claims 1 to 10, which comprises mixing the components that are part of the formulation.

12. A method for controlling the undesirable growth of plants, comprising applying an effective amount of a formulation as claimed in claim 6, on the plants, parts of the plants or the growing area.

13. The use of a formulation, according to claim 6, as a herbicide.

14. - The use of a surfactant system according to claim 1 for preparing liquid aqueous or aqueous-thermonidamically stable organic formulations.

15. The use according to claim 14 for preparing aqueous microemulsions.