MX2008006918A - Liquid formulations containing dialkyl sulfosuccinate and hydroxyphenylpyruvate dioxygenase inhibitors - Google Patents

Abstract

The invention relates to liquid formulations containing herbicide active ingredients from the group of HPPD inhibitors, dialkyl sulfosuccinates, surfactants and solvents. The invention also relates to liquid formulations containing A) at least one HPPD inhibitor, B) at least one dialkyl sulfosuccinate, C) at least one other surfactant, D) at least one solvent, E) other adjuvants and additives, and F) at least one agrochemical active ingredient different from A). The liquid formulations are suitable for using in the field of plant protection.

Description

LIQUID FORMULATIONS CONTAINING DIALKYL SULFOSUCCINATES AND INHIBITORS OF HYDROXYPHENILP1RUVATO-DIOXYGENASE DESCRIPTIVE MEMORY The present invention relates to the field of phyto-protective agent formulations. In particular, the invention relates to liquid formulations containing dialkyl sulfosuccinates and herbicidal active substances, which are known as hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors. Herbicidal active substances are usually not used in their pure form. Depending on the field of application and the mode of application, as well as physical, chemical and biological parameters, the active substances are used, in admixture with the usual additives and additives, as an active substance formulation. Also the combinations with other active substances for the extension of the spectrum of effects and / or for the protection of the cultivated plants (for example by means of insurers and antidotes). The formulations of herbicidal active substances should generally have a high chemical and physical stability, a good applicability and a favorable nature for the users and a broad biological effect together with a high selectivity.

From the series of the hydroxyphenylpyruvate-dioxygenase inhibitors, isoxaflutole, sulcotrione and mesotrione have been commercially available for some time. As formulations of these active substances, concentrates for suspension or water-dispersible granules are already known, see for example the "The Pesticide Manual" 13th edition (2003), The British Crop Protection Council. Depending on the purpose of application, liquid formulations are also requested by the users, in which the components are totally or almost totally dissolved. These, however, can not be prepared without difficulty from all active substances, since often a defective solubility in solvents and / or a defective chemical stability of the active substance do not allow a formulation as a liquid formulation to appear as possible. It was an object of the present invention to provide liquid formulations for active substances of the HPPD inhibitor series, which do not have the aforementioned disadvantages. The problem posed by this mission is solved by means of liquid formulations which, together with the HPPD inhibitors, also contain dialkyl sulfosuccinates, other additional surfactants and certain solvents. The present invention therefore relates to liquid formulations, which contain one or more active herbicidal substances taken among the group of HPPD inhibitors, one or more surfactants taken from the group of dialkyl sulphosuccinates, one or more other surfactants other than B), and one or more solvents, the molar ratio of the inhibitor being HPPD to dialkyl sulfosuccinate from less than or equal to 1 to 6. The liquid formulations according to the invention exhibit outstanding storage stability and have no tendency to form undissolved components. The liquid formulations according to the invention can optionally contain, together with components A) to D), additives and additives as well as other components, eg: E) customary formulating aids such as defoamers, evaporation inhibitors, perfumes, dyes, frost protection agents or preservatives, and F) one or more other agrochemical active substances other than A) such as herbicides, insecticides, fungicides, antidotes, growth regulators or fertilizing agents. Suitable liquid formulations are, for example, emulsifiable concentrates (EC), microemulsions, concentrates for microemulsions, concentrated emulsions (EW) such as emulsions of water-in-oil and oil-in-water types, solutions or emulsions, suspoemulsions, dispersions on the base oils (OD) and solutions miscible with oils (OL). Emulsifiable concentrates are preferred.

These types of formulations are known in principle and are described, for example, in the works of: Winnacker-Küchler, "Chemische Technologie" [Chemical Technology], volume 7, editorial C. Hauser Munich, 4th edition of 1986, Wade van Valkenburg, " Pesticide Formulations "[Pesticide Formulations, Marcel Dekker, NY, 1973; K. Martens, "Spray Drying" Handbook, 3rd edition, 1979, G. Goodwin Ltd. London. HPPD inhibitors have an acidic proton, which can be eliminated by a base. The salts thus obtainable from the HPPD inhibitors are also suitable in the liquid formulations according to the invention as component A). Suitable bases are for example ammonia, the hydroxides, carbonates and hydrogen carbonates of zinc and alkali and alkaline earth metals, such as sodium, potassium, calcium and magnesium, and organic bases of the formula NR1R2R3, wherein R1, R2 and R3 may in each case mean (C -? - C20) alkyl, (C2-C20) alkenyl or (C3-C20) alkynyl, and R2 and R3, in addition to this, may also mean hydrogen. The potassium, sodium and ammonium salts are preferred. In a preferred form of embodiment, these liquid formulations contain inhibitors of the HPPD of the formula (I), (i) wherein R means cyclohexane-1,3-dion-2-yl, 5-hydro-1 H -pyrazol-4-yl or isoxazol-4-yl, these three rings being unsubstituted or substituted with one or two radicals taken between the group consisting of methyl, ethyl, propyl and cyclopropyl; R 4 is methyl, methoxy, trifluoromethoxy, trifluoromethyl, methylsulfonyl, chlorine or bromine; R5 means hydrogen, methyl, methoxy, trifluoromethoxy, trifluoromethyl, chloro, bromo, 2,2,2-trifluoro-ethoxymethyl or 4,5-dihydro-isoxazol-3-yl; R6 is chlorine, bromine, trifluoromethoxy, trifluoromethyl or methylsulfonyl. In a particularly preferred embodiment, these liquid formulations contain the inhibitors A-1 through A-6 of the HPPD: The inhibitors of the HPPD, contained as component A), are known for example from the patent application documents WO1996 / 26206, WO 00/21924, WO 01/74785, from the "The Pesticide Manual" 13th edition (2003), The British Crop Protection Council and the website http: // www.hclrss.demon.co.uk and in part are already commercially available. In a preferred embodiment, the liquid formulations according to the invention contain from 0.1 to 50% of one or more inhibitors of HPPD, A) from 1 to 50% of one or more dialkyl sulfosuccinates, B) from 2 to 40. % of one or more other surfactants, C) from 5 to 80% of one or more solvents, D) from 0 to 25% of other additives and additives, and E) from 0 to 50% of one or more other substances active agrochemicals other than A). In a particularly preferred embodiment, these liquid formulations contain A) from 0.5 to 25% of one or more HPPD inhibitors, B) from 2 to 25% of one or more dialkyl sulfosuccinates, C) from 5 to 25% of one or more other surfactants, D) from 10 to 80% of one or more solvents, E) from 0 to 20% of other additives and additives, and F) from 0 to 40% of one or more other active substances agrochemicals different from A). All the data in% are so many percent in weight. Suitable dialkyl sulfosuccinates B) are those of the general formula (II): wherein R1, R2 independently of one another, the same or different, mean hydrogen, an unsubstituted or substituted hydrocarbyl radical CrC30, such as C3_3alkyl, or an adduct with an alkylene (poly) oxide, R3 + is a cation, eg a cation of a metal, such as a cation of an alkali metal or alkaline earth metal, an ammonium cation such as + NH, an alkyl-, alkylaryl cation or poly! (arylalkyl) phenyl-ammonium or its adducts with alkylene (poly) oxides, or an adduct with an amino-terminated (poly) alkylene oxide, and X, Y independently of one another, the same or different, mean O or + NR4, wherein R4 is hydrogen, an unsubstituted or substituted hydrocarbyl radical, such as C? -C30 alkyl, alkyl d-Cso-aryl C6 -C? 4 or poly (aryl C6-C1-CrC30 alkyl) phenyl, dicarboxyethyl or an adduct with a (poly) alkylene oxide. Examples of sulfosuccinates B), commercially available and preferred in the context of the present invention, are listed below: sodium dialkylsulfosuccinates, eg a diisooctyl sulfosuccinate of Na, commercially available, for example, in the form of the Aerosol® brands ( Cytec), from the Agrilan®- or Lankropol® (Akzo Nobel) brands, from the Empimin® brands (Albright &Wilson), Cropol® brands (Croda), Lutensit® brands (BASF) or Imbirol® brands, Madeol® or Polirol® (Cesalpinia), or di (2-ethylhexyl) sulfosuccinates from Triton® brands (Union Carbide) such as Triton® GR-5M and Triton® GR-7ME, an alcohol-poly (ethylene glycol) -ether-semisulfosuccinate sodium, commercially available for example in the form of Aerosol® (Cytec) brands Marlinat® or Sermul® (Condea), of the Empicol® (Albright &Wilson) brands, of the Secosol® (Stepan) brands, of the Geropon® brands (Rhodia), of the Disponil®- or Texapon® brands (Cognis) or of the Rolpon® brands (Cesalpinia), a disodium N-alkyl sulfosuccinamate, commercially available for example in the form of the Aerosol® (Cytec) brands, of the Rewopol® or Rewoderm® (Rewo) brands, of the Empimin® brands (Alb ght &Wilson; ), from Geropon® (Rhodia) or from the brands Polirol® (Cesalpinia), a (fatty acid amido) -poly (ethylene glycol) -disodium semisulfosuccinate, commercially available, for example, in the form of the Elfanol® brands. or Lankropol® (Akzo Nobel), of the brands Rewoderm®, Rewocid® or Rewopol® (Rewo), of the brands Emcol® (Witco), of the brands Standapol® (Cognis) or of the brands Rolpon® (Cesalpinia), and the N- (1,2-dicarboxy-ethyl) -N-octadecyl-tetrasodium sulfosuccinamate, commercially available for example in the form of Aerosol 22®- (Cytec). Suitable surfactants C) are, for example, surfactants on a non-aromatic base, for example on a base of heterocycles, olefins, aliphatic or cycloaliphatic compounds, for example surface-active compounds, pyridine, pyrimidine, triazine, pyrrole, pyrrolidine, furan, thiophene, benzoxazole, benzothiazole and triazole, substituted with one or more alkyl groups and then derivatized, eg alkoxylated, sulfated, sulphonated or phosphated, and / or surfactants on an aromatic base, eg benzenes or phenols substituted with one or more alkyl groups and subsequently derivatized, eg alkoxylated, sulphated, sulphonated or phosphated. The surfactants C) are generally soluble in the solvent phase and suitable for emulsifying them - in common with the dissolved active substances in it - in the case of dilution with water (to the broth to project). The formulations according to the invention may contain, for example, non-aromatic or aromatic surfactants, or mixtures of non-aromatic and aromatic surfactants. Examples of surfactants b), in which OE represents units of ethylene oxide, OP represents units of propylene oxide and OB represents butylene oxide units: C1) C10-C24 alcohols, which may be alkoxylated, are described below. eg with 1-60 units of an alkylene oxide, preferably 1-60 OE and / or 1-30 OP and / or 1-15 OB in any order of succession. The terminal hydroxy groups of these compounds can be closed by an alkyl, cycloalkyl or acyl radical with end groups of 1-24 carbon atoms. Examples of such compounds are: Genapol®C, L, O, T, UD, UDD, Clariant X products, Plurafac® - and Lutensol®A, AT, ON, TO products from BASF, Marlipal®24 and 013 products from Condea , Dehypon® products from Henkel, Ethylan® products from Akzo-Nobel such as Ethylan CD 120. C2) Anionic derivatives of the products described within C1), in the form of ether carboxylates, sulfonates, sulfates and phosphates and their inorganic salts ( eg alkaline and alkaline-earth metals) and organic salts (eg on the basis of amines or alkanol amines) such as Genapol® LRO, Sandopan® products, Hostafat / Hordafos® products by Clariant.

Copolymers consisting of units of OE, OP and / or OB, such as for example block copolymers such as the Pluronic® products of BASF and the Synperonic® products of Uniquema with a molecular weight of 400 to 108. Adducts with oxides of alkylene of C1-C9 alcohols such as Atlox® 5000 from Uniquema or Hoe®-S3510 from Clariant. C3) Alkoxylated fatty acid and triglyceride compounds, such as Condea's Serdox®NOG products or alkoxylated vegetable oils such as soybean oil, rapeseed oil, corn germ oil, sunflower oil, cottonseed oil, oil flaxseed, coconut oil, palm oil, thistle oil, walnut oil, peanut oil, olive oil or castor oil, in particular rapeseed oil, including transesterification products within vegetable oils, p Alkaline esters such as rapeseed oil methyl ester or rapeseed oil ethyl ester, for example Clariant's Emulsogen® products, salts of carboxylic acids and polycarboxylic, aliphatic, cycloaliphatic and olefinic acids, as well as esters of alpha-sulfo-fatty acids such as those obtainable from Henkel. C4) Alkoxylated fatty acid amide compounds such as Henkel's Comperlan® products to the Amam® products of Rhodia. Adducts with alkylene oxides of alkynediols such as Surfynol® products from Air Products. Derivatives of sugars such as amino- and amido-sugars from Clariant, glucylates from Clariant, alkyl polyglycosides in the form of APG® products from Henkel or such as sorbitan esters in the form of the Span® or Tween® products from Uniquema, or Wacker's esters or cyclodextrin ethers. C5) Derivatives of cellulose and algin, pectin and guar, surface active, such as Clariant's Tylose® products, Manutex® products by Kelco and guar derivatives of Cesalpinia. Adducts with alkylene oxides based on polyols such as Polyglykol® products from Clariant. Interfacially active polyglycerides and their derivatives, by Clariant. C6) Alkanesulfonates, paraffin- and olefin sulfonates such as Netzer IS®, Hoe®S1728, Hostapur®OS, Hostapur® SAS from Clariant. C7) Alkylene oxide adducts of fatty amines, quaternary ammonium compounds with 8 to 22 carbon atoms (C8-C22) such as, for example, Geniant®C, L, O, T products by Clariant. C8) Surface-active hybrid ionic compounds, such as taurides, betaines and sulfo-betaines in the form of Tegotain® products from Goldschmidt, and Hostapon®T and Arkopon®T products from Clariant. C9) Surface-active compounds based on silicones or silanes, such as Tegopren® products Goldschmidt and Wacker SE® products, as well as Ralovia's Bevaloid®, Rhodorsil® and Silcolapse® products (Dow Corning, Reliance, GE, Bayer). C10) Per-or poly-fluorinated, surface active compounds, such as Clariant's Fluowet® products, Bayowet® products from Bayer, DuPont's Zonyl® products, and products from this type of Daikin and Asahi Glass. C11) Interfacially active sulfonamides, eg from Bayer. C12) Polyacrylic and polymethacrylic derivatives, interfacially active, such as Sokalan® products from BASF. C13) Surface-active polyamides, such as modified gelatins or poly (aspartic acids) derivatized from Bayer and its derivatives. C14) Polyvinyl surfactant compounds, such as a modified poly (vinyl pyrrolidone), such as Luviskol® products from BASF and ISR Agrimer® products or derivatized polyvinyl acetates such as Clariant's Mowilith® products or poly (vinyl butyrates) such as Lutonal® products from BASF, Vinnapas® products and Pioloform® from Wacker, or modified poly (vinyl alcohols) such as Mowiol® products from Clariant. C15) Surface-active polymers based on maleic anhydride and / or reaction products of maleic anhydride, as well as copolymers containing maleic anhydride and / or reaction products of maleic anhydride, such as the products Agrimer®-VEMA of ISP. C16) Surface-active derivatives of montaine, polyethylene and polypropylene waxes such as Hoechst® waxes or products Licowet® by Clariant.

C17) Surface-active phosphonates and phosphinates, such as Fluowet®-PL from Clariant. C18) Poly- or per-halogenated surfactants, such as, for example, Emulsogen®-1557 from Clariant. C19) Phenols, which may be alkoxylated, for example phenyl-alkyl (C -? - C4) -ethers or (poly) alkoxylated phenols [= phenol- (poly) alkylene glycol-ethers], for example with 1 to 50 alkyleneoxy units in the (poly) alkylenoxy part, the alkylene part preferably having in each case from 1 to 4 carbon atoms, preferably a phenol which has reacted with 3 to 10 moles of alkylene oxide, (poly) alkyl phenols or compounds alkoxylates of (poly) alkylphenols [= poly-alkylphenol- (poly) alkylene glycol ethers], for example with 1 to 12 C atoms for each alkyl radical and with 1 to 150 alkyleneoxy units on the poly (alkyleneoxy) part ), preferably tri-n-butyl-phenol or tri-isobutyl-phenol which has reacted with 1 to 50 moles of alkylene oxide, polyarylphenols or alkoxylated compounds of polyarylphenols [= polyarylphenol- (poly) alkylene glycol ethers], for example tristyryl -phenol-poly (alkylene glycol) -ethers with 1 to 150 alkyleneoxy units in the poly (alkyl) part enoxi), preferably tristyrylphenol which has reacted with 1 to 50 moles of ethylene oxide. C20) Compounds, which formally constitute the reaction products of the molecules described in C19), with sulfuric acid or phosphoric acid, and their salts neutralized with appropriate bases, for example the acid phosphoric acid ester of phenol three times ethoxylated , he acid phosphoric acid ester of a nonylphenol which has reacted with 9 moles of ethylene oxide, and the triethanolamine-neutralized phosphoric acid ester of the reaction product of 20 moles of ethylene oxide and 1 mole of tristyryl -phenol. C21) Benzene sulphonates such as alkyl or aryl benzene sulfonates, for example (poly) alkyl- and (poly) aryl-benzene sulphonates of acid character and neutralized with appropriate bases, for example with 1 to 12 carbon atoms per alkyl radical and respectively up to 3 styrene units in the polyaryl radical, preferably dodecyl benzene sulphonic acid (linear) and their oil-soluble salts, such as, for example, the calcium salt or the isopropanol-ammonium salt of dodecyl acid -benzene-sulphonic. In the cases of the alkylenoxy units, ethyleneoxy, propyleneoxy and butyleneoxy units are preferred, in particular ethyleneoxy units. Examples of surfactants, taken from the group of surfactants on a non-aromatic basis, are the surfactants of the groups C1) to C18) mentioned above, preferably of the groups C1), C2), C6) and C7). Examples of surfactants, taken from the group of surfactants on an aromatic basis, are the surfactants of the groups C19) to C21) mentioned above, preferably a phenol which has reacted with 4 to 10 moles of ethylene oxide, obtainable commercially for example in the form of Agrisol® products (Akcros), a triisobutyl-phenol which has reacted with 4 to 50 moles of ethylene oxide, commercially available for example in the form of the products Sapogenat® T (Clariant), a nonylphenol which has reacted with 4 to 50 moles of ethylene oxide, commercially available example in the form of Arkopal® products (Clariant), a tristyrylphenol which has reacted with 4 to 150 moles of ethylene oxide, for example taken from the Soprophor® series, such as Soprophor® FL, Soprophor® 3D33, Soprophor ® BSU, Soprophor® 4D-384, Soprophor® CY / 8 (Rhodia), and an acidic dodecyl benzene sulfonate (linear), commercially available, for example, in the form of Marion® products (Hüls). Preferred surfactants C) are, for example, C0-C24 alkoxylated alcohols (C1) and their anionic (C2) derivatives such as sulfates, sulphonates and phosphates, alkoxylated vegetable oils (C3), alkoxylated phenols (C19) and their products of reaction with sulfuric acid or phosphoric acid (C2o) and alkyl benzene sulfonates (C21). Suitable solvents D) are, for example, non-polar solvents, protic polar or dipolar aprotic solvents and their mixtures. Examples of such solvents are aliphatic or aromatic hydrocarbons, such as mineral oils, paraffins or toluene, xylenes and naphthalene derivatives, in particular 1-methyl-naphthalene, 2-methyl-naphthalene, mixtures of aromatic compounds C6-C? 6 such such as, for example, the Solvesso® series (ESSO) series with Solvesso® 100 types (eg 162-177 ° C), Solvesso® 150 (eg 187-207 ° C and Solvesso® 200 (pp. 219-282 ° C) and aliphatic compounds of 6-20 C, which can be linear or cyclic, such as the products of the Shellsol® series, types T and K or BP n-paraffins - halogenated aliphatic or aromatic hydrocarbons, such as methylene chloride or chlorobenzene respectively, - monobasic and / or polybasic esters such as, for example, triacetin (acetic acid triglyceride), butyrolactone, propylene carbonate, triethyl citrate and esters alkyl (C C22) of italic acid, especially alkyl esters (C-C8) of italic acid, ethers such as diethyl ether, tetrahydrofuran (THF), dioxane, monoalkyl ethers and dialkyl ethers of alkylene glycols such as eg monomethyl-propylene glycol ether, especially Dowanol® PM (propylene glycol monomethyl ether), propylene glycol monoethyl ether, monomethyl ether or ethylene glycol monoethyl ether, diglyme and tetraglimeketones, eg ketones miscible with water such as acetone, or ketones immiscible with water such as cyclohexanone or isophorone, nitriles such as acetonitrile, propionitrile, butyronitrile and benzonitrile sulfoxides and sulphones such as dimethyl sulfoxide (DMSO) ) and sulfolane as well as - oils of natural origin, eg vegetable oils, such as corn germ oil and rapeseed oil, and their transesterification products such as rapeseed oil methyl ester, and - water Other preferred organic solvents in the sense of the present invention are, in particular, aromatic solvents such as those from the Solvesso® series of Exxon and water-miscible ketones, such as acetone. The liquid formulations may also contain other agrochemical active substances E) such as herbicides, fungicides, insecticides, antidotes as well as fertilizing agents such as ammonium sulfate, hydrogen-ammonium sulfate, urea or mixtures thereof, and / or growth regulators. These active substances are known to a person skilled in the art, for example from the "The Pesticide Manual", 13th edition (2003), The British Crop Protection Council. Suitable agrochemical active substances other than component A), which may optionally be contained in the liquid formulations according to the invention as component E), are preferably herbicidally active substances, for example: EA) Herbicides of the type of phenoxyphenoxy- and heteroaryloxyphenoxy derivatives carboxylic acids, such as EA1) Derivatives of phenoxyphenoxy- and benzyloxyphenoxycarboxylic acids, for example 2- (4- (2,4-dichloro-phenoxy) -phenoxy) -propionic acid methyl ester (diclofop-methyl), 2- (4- (4-bromo-2-chloro-phenoxy) phenoxy) propionic acid methyl ester (German patent application DE-A-26.01.548), 2- (4- (4-methyl) methyl ester -bromo-2-fluoro-phenoxy) phenoxy) propionic (US-A-4,808,750), (4- (2-Chloro-4-trifluoromethyl-phenoxy) phenoxy) propionic acid methyl ester (DE-A-24,33,067) 2- (4- (2-fluoro-4-trifluoromethyl-phenoxy) methyl ester ) phenoxy) propionic (US-A-4,808,750), 2- (4- (2,4-dichloro-benzyl) phenoxy) propionic acid methyl ester (DE-A-24, 17,487), 4- (4- (4-trifluoromethyl-phenoxy) phenoxy) pent-2-enoic acid ethyl ester, 2- (4- (4-trifluoromethyl-) methyl ester phenoxy) phenoxy) propionic (DE-A-24 33 067); - EA2) "Mononuclear" derivatives of heteroaryloxyphenoxy-alkanecarboxylic acids, for example 2- (4- (3,5-dichloro-pyridyl-2-oxy) phenoxy) propionic acid ethyl ester (EP-A-0,002,925) , 2- (4- (3,5-dichloro-pyridyl-2-oxy) phenoxy) propionic acid propargyl ester (EP-A-0.003, 114), 2- (4- (3-chloro) methyl ester -5-trifluoromethyl-2-pyridyloxy) phenoxy) propionic (EP-A-0,003,890). 2- (4- (3-Chloro-5-trifluoromethyl-2-pyridyloxy) phenoxy) propionic acid ethyl ester (EP-A-0,003,890). 2- (4- (5-Chloro-3-fluoro-2-pyridyloxy) phenoxy) propionic acid propargyl ester (EP-A-0,191, 736), 2- (4- (5-trifluoromethyl) butyl ester -2-pyridyloxy) phenoxy) propionic (fluazifop-butyl); EA3) "Binuclear" derivatives of heteroaryloxyphenoxy-alkanecarboxylic acids, eg - methyl ester and 2- (4- (6-chloro-2-quinoxalyloxy) phenoxy) -propionic acid ethyl ester (quizalofop-methyl and quizalofop-ethyl) ), 2- (4- (6-fluoro-2-quinoxalyloxy) phenoxy) propionic acid methyl ester (see J. Pest, Sci, Volume 10, 61 (1985)), 2-isopropylidene-aminooxyethyl-2-ethyl ester - (4- (6-chloro-2-quinoxaliloxi) phenoxy) -propionic (propaquizafop), 2- (4- (6-chloro-benzoxazol-2-yl-oxy) phenoxy) propionic acid ethyl ester (fenoxaprop-ethyl) ) and its D (+) isomer (fenoxaprop-P-ethyl, EX) and 2- (4- (6-chloro-benzothiazol-2-yloxy) phenoxy) propionic acid ethyl ester (DE-A-26,40,730 ) 2- (4- (6-chloro-quinoxalyloxy) phenoxy) propionic acid tetrahydro-2-furylmethyl ester (EP-A-0,323,727); - EB) Chloroacetanilides, eg N-methoxymethyl-2,6-diethyl-chloroacetanilide (alachlor); N- (3-methoxy-prop-2-yl) -2-methyl-6-ethyl-chloroacetanilide (metolachlor); N- (3-methyl-1, 2,4-oxadiazol-5-yl-methyl) -2,6-dimethyl-anilide of chloroacetic acid, N- (2,6-dimethyl-phenyl) -N- (1- pyrazolylmethyl) -amide of chloroacetic acid (metazachlor); EC) Thiocarbamates, eg S-ethyl-N, N-dipropyl thiocarbamate (EPTC), S-ethyl-N, N-diisobutyl thiocarbamate (butylate); ED) Cyclohexanedione oximes, e.g. - 3- (1-Allyloxyimino-butyl) -4-hydroxy-6,6-dimethyl-2-oxo-cyclohex-3-ene-carboxylic acid methyl ester (alloxidime), 2- (1-ethoxyimino-butyl) - 5- (2-ethylthio-propyl) -3-hydroxy-cyclohex-2-en-1 -one (sethoxydima), 2- (1-ethoxyimino-butyl) -5- (2-phenylthio-propyl) -3-hydroxy -cyclohex-2-en-1-one (cloproxidime), 2- (1- (3-chloro-allyloxy) imino-butyl) -5- (2-ethylthio-propyl) -3-hydroxy-cyclohex-2-en -1-one, 2- (1- (3-chloro-allyloxy) imino-propyl) -5- (2-ethylthio-propyl) -3-hydroxy-cyclohex-2-en-1-one, (clethodim) , 2- (1-ethoxyimino-butyl) -3-hydroxy-5- (thian-3-yl) -cyclohex-2-enone (cyclodexid), 2- (1-ethoxyimino-propyl) -5- (2 , 4,6-trimethyl-phenyl) -3-hydroxy-cyclohex-2-en-1-one (tralkoxidima), EE) benzoylcyclohexanediones, for example 2- (2-chloro-4-methylsulfonylbenzoyl) -cyclohexane-1, 3-dione (SC-0051, EP-A 0137963), 2- (2-nitro-benzoyl) -4,4-dimethyl-cyclohexane-1, 3-dione (EP-A 0274634) , 2- (2-nitro-4-methylsulfonyl-benzoyl) -4,4-dimethyl-cyclohexane-1,3-dione (WO 91/13548, mesot riona); EF) Esters S- (N-aryl-N-alkyl-carbamoílmetílicos) dithiophosphoric acid dithiophosphate such as S- [N- (4-chlorophenyl) -N-isopropyl-carbamoylmethyl] and 0,0-dimethyl ( anilofos).

EG) Alkylazines, eg as described in WO-A 97/08156, WO-A-97/31904, DE-A-19826670, WO-A-98/15536, WO-A- 98/15537, WO-A-98/15538, WO-A-98/15539 as well as DE-A-19828519, WO-A-98/34925, WO-A-98/42684, WO-A-99 / 18100, WO-A-99/19309, WO-A-99/37627 and WO-A-99/65882, preferably those of the formula (G) H wherein Rx means alkyl (C -? - C4) or haloalkyl (C C), R? means alkyl (CC), cycloalkyl (C3-C6) or cycloalkyl (C3-C6) -alkyl (C1-C4) and A means -CH2 -, - CH2-CH2 -, - CH2-CH2-CH2 -, - 0- , -CH2-CH2-0 -, - CH2-CH2-CH2-0-, especially those of the formulas G1-G7 Cl EH) Phosphorus-containing herbicides, eg of the glufosinate type, such as glufosinate in its strict sense, ie D, L-2-amino-4- [hydroxy (methyl) phosphinyl] -butanoic acid, salt monoammonium glufosinate, L-glufosinate, L- or (2S) -acetic 2-amino-4-4- [hydroxy (metl) phosphinyl] butanoic acid, monoammonium salt of L-glufosinate or bialaphos (or bilanafos ), ie L-2-amino-4- [hydroxy (methyl) phosphinyl] -butanoyl-L-alanyl-L-alanine, in particular its sodium salt, or the glyphosate type, such as glyphosate, ie N- (phosphonomethyl) glycine, salt of monoisopropyl ammonium glyphosate, the glyphosate sodium salt, or sulfosate, i.e. trimesium salt of N- (phosphonomethyl) glycine trimethylsulfoxonium salt = N- (phosphonomethyl) -glycine. The herbicides from sets EA to EH are known, for example, from the documents mentioned above in each case and from the "The Pesticide Manual" 13th edition, 2003, The British Crop Protection Council, "Agricultural Chemicals Book II - Herbicides- "[Book of Agricultural Chemicals II - Herbicides -], from WT Thompson, Thompson Publications, Fresno CA, USA 1990 and "Farm Chemicals Handbook '90" [Manual of Agricultural Chemicals of '90], Meister Pubiishing Company, Willoughby OH, USA. 1990. As the active substances E) other than component A) which are optionally contained, the known active substances mentioned below, as described, for example, in the liquid formulations according to the invention, are particularly suitable.

Weed Research 26, 441-445 (1986), or in "The Pesticide Manual", 13th edition, The British Crop Protection Council, 2003, and the bibliography cited therein, eg in mixtures formulations or as participants in mixtures in Deposit. Compounds are designated either with the "common name" in accordance with the International Organization for Standardization (ISO) or with the chemical name, possibly in common with a usual code number and always include all forms of application such as acids, salts, esters and isomers such as stereoisomers and optical isomers: acetochlor; acifluorfen; Aclonifen; AKH 7088, ie [[[1- [5- [2-chloro-4- (trifluoromethyl) -phenoxy] -2-nitro-phenyl] -2-methoxyethylidene] -amino] -oxy] -acetic acid and its ester methyl; Alachlor aloxidime; ametryn; Amitrol; AMS, ie ammonium sulphamate; anilophos; asulam; atrazine; azaphenidine (DPX-R6447), aziprotrine; barban BAS 516 H, ie 5-fluoro-2-phenyl-4H-3,1-benzoxazin-4-one; benazoline; benfluralin; benfuresate; bensulide; bentazone; benzofluoro; benzoylprop-ethyl; benzothiazuron; bialaphos; bifenox; bispyribac-sodium (KIH-2023), bromacil; bromobutide; bromophenoxime; bromoxynil, in particular bromoxynil octanoate and bromoxynil heptanoate; butachlor; butamiphos; butenachlor; butidazole; butralin; butroxydim (ICI-0500), butylate; cafenstrole (CH-900); carbetamide; Cafentrazone; CDAA, i.e. 2-chloro-N, N-di-2-propenyl acetamide; CDEC, ie 2-chloro-allyl ester of diethyldithiocarbamic acid; clometoxifene; chloramben; cloransulam-methyl (XDE-565), clorazifop-butyl, chlorobromuron; chlorobufam; chlorofenac; chlorofluorol-methyl; chloridazone; chloronitrofen; chlorotoluron; Chloroxuron; chloroprofam; clortal-d imethyl; Chlorotiamide; cinidón-etil, cinmetilina; clethodima; clodinafop and its ester derivatives (eg clodinafop-propargyl); clomazone; clomeprop; cloproxidime; Clopyraide; cumiluron (JC 940); cyanazine; cycloate; cycloxydime; Cyclone; cyhalofop and its ester derivatives (eg butyl ester, DEH-112); cyperquat; ciprazine; ciprazole; 2,4-D; 2,4-DB; dalapon; desmedifam; desmethrin; di-alato; dicamba; diclobenil; dichlorprop; diclofop and its esters such as diclofop-methyl; diclosulam (XDE-564), dietyl; difenoxuron; difenzoquat; diflufenican; diflufenzopyr-sodium (SAN-835H), dimefuron; dimethachlor; dimethamethrin; dimethenamid (SAN-582H); dimidazone, methyl 5- (4,6-dimethyl-pyrimidin-2-yl-carbamoyl sulfamoyl) -1- (2-pyridyl) -pyrazole-4-carboxylic acid methyl ester (NC-330); triaziflam (IDH-1105), cyosulfon; dimetipine, dinitramine; dinoseb; dinoterb; diphenamide; dipropetrin; diquat; ditiopir; diuron; DNOC; eglinazine-ethyl; HE 177, i.e. 5-cyano-1- (1,1-dimethyl-ethyl) -N-methyl-1 H-pyrazole-4-carboxamide; endotal; indanofano (MK-243), EPTC; esprocarb; etalfluralin; etidimuron; etiozine; ethofumesate; F5231, ie N- [2-chloro-4-fluoro-5- [4- (3-fluoro-propyl) -4,5-dihydro-5-oxo-1 H-tetrazol-1-yl] -phenyl] -etanosulfonamide; ethoxyfen and its esters (e.g. ethyl ester, HN-252); etobenzanide (HW 52); 3- (4-Ethoxy-6-ethyl-1, 3,5-triazin-2-yl) -1- (2,3-dihydro-1,1-dioxo-2-methyl-benzo [b] -thiophen- 7-sulfonyl) -urea (EP-A 079,683); 3- (4-ethyl-6-methoxy-1, 3,5-triazin-2-yl) -1 - (2,3-dihydro-1,1-dioxo-2-methyl-benzo [b] thiophen-7) -sulfonyl) urea (EP-A 079,683); fenoprop; clomazone, fenoxaprop and fenoxaprop-P as well as their esters, e.g., fenoxaprop-P-ethyl and fenoxaprop-ethyl; butroxydima-fenuron; flamprop-methyl; flufenacet (BAY-FOE-5043), fluazifop and fluazifop-P and their esters, eg fluazifop-butyl and fluazifop-P-butyl, florasulam (DE-570); flucloraline; flumetsulam; fluometuron; flumicyraco and its esters (e.g., pentylester, S-23031); flumioxazine (S-482); flumipropin; flupoxam (KNW-739); fluoroglyphene-ethyl fluorodifen; flupropacil (UBIC-4243); fluridone; flurocloridone fluroxypyr; flurtamone; flutiacet-methyl (KIH-9201), fomesafen; Furanyl Fosiloxifene; glufosinate; glyphosate; halosafeno; halosulfuron and its esters (e.g., methyl ester, NC-319); haloxifop and its esters; haloxifop-P (= R-haloxifop) and its esters; hexazinone; imazametabenz-methyl; imazamox (AC-299263), imazapyr; imazaquin and its salts such as the ammonium salt; imazapic; imazethapyr; imazosulfuron; Oxinyl; isocarbamide; isopropaline; isoproturon; isourón; isoxabeno; isoxapirifop; karbutylate; lactofen; lenacilo; linuron; MCPA; MCPB; mecoprop; mefenacet; mefluidide; metamitron; metazachlor; metabenzothiazuron; metam; metazole; methoxyphenone; metildimron; methobenzuron, Mesosulfuron-methyl, mesosulfuron-methyl (WO document) 95/10507); methobromuron; metolachlor; S-metolachlor, metosulam (XRD 511); methoxuron; metribuzin; maleic hydrazide; molinate; monalid; monocarbamide dihydrogen sulfate; monolinuron; Monuron MT 128, ie 6-chloro-N- (3-chloro-2-propenyl) -5-methyl-N-phenyl-3-pyridazinamine; MT 5950, i.e. N- [3-chloro-4- (1-methyl-ethyl) -phenyl] -2-methylpentanamide; foramsulfuron (WO 95/01344); naproanilide; napropamide; naptalam; NC 310, that is 4- (2,4-dichloro-benzoyl) -1-methyl-5-benzyloxy-pyrazole; neburon; nipiraclofen; nitraline; nitrophen; nitrofluorfen; norflurazone; orbencarb; Orizalina; Oxadiargyl (RP-020630); oxadiazone; oxaziclomene (MY-100), oxyfluorfen; paraquat; pebble pendimethalin; pentoxazone (KPP-314), perfluidone; fenisofam; fenmedifam; picloram; pinoxadene; piperophos; pyributicarb; pirifenop-butyl; pretilachlor; procyanine; prodiamine; profluralin; proglinazine-ethyl; prometona; prometryn; propachlor; propanil; propaquizafop and its esters; propazine; profam; propischlorine; propizamide; prosulfaline; prosulfocarb; prinachlor; pyraflufen-ethyl (ET-751), chloridazone; pyrazoxyphene; piribenzoxime, pyridate; pyriminobacco-methyl (KIH-6127), piritiobaco (KIH-2031); piroxofop and its esters (e.g. propargyl ester); quincloraco; quinmeraco; quizalofop, quizalofop and quizalofop-P and their ester derivatives eg quizalofop-ethyl; quizalofop-P-tefuril and -ethyl; S 275, i.e. 2- [4-chloro-2-fluoro-5- (2-propynyloxy) -phenyl] -4,5,6,7-tetrahydro-2H-indazole; secbumetone; Sethoxydim; siduron; simazine; symmetry; SN 106279, ie 2 - [[7- [2-chloro-4- (trifluoro-methyl] -phenoxy] -2-naphthalene] -oxi] -propanoic acid and its methyl ester; flazasulfuron (FMC-97285, F-6285); sulfazuron; glyphosate-trimesium (ICI-A0224); TCA; tebutam (GCP-5544); tebutyuron; tepraloxidime (BAS-620H), terbacillus; terbucarb; terbucloro; terbumetone; terbuthylazine; terbutrin; TFH 450, that is N, N-diethyl-3 - [(2-ethyl-6-methyl-phenyl) -sulfonyl] -1H-1, 2,4-triazole-1-carboxamide; Tenilchlor (NSK-850); thiazafluron; thiazopyr (Mon-13200); thidiazimine (SN-124085); thiobencarb; thiocarbazyl; trakoxidime; tri-alato; triazophenamide; triclopyr; tridifan; trietazine; trifluralin; trimeturon; vernolate; WL 110547, ie 5-phenoxy-1- [3- (trifluoromethyl) -phenyl] -1 H-tetrazole; UBH-509; D-489; LS 82-556; KPP-300; KPP-421, MT-146, NC-324; butenachlor (KH-218); DPX- N8189; haloxifop-etotyl (DOWCO-535); DK-8910; flumioxazine (V-53482); PP-600; MBH-001, amicarbazone, aminopyralide, beflubutamide, benzobicyclone, benzophenap, benzophenone, butafenacil, chlorophenprop, cloprop, daimuron, dichlorprop-P, dimethopentate, dimethenamid-P, phentrazamide, flamprop-M, fluazolate, indanofan, isoxaclortol, isoxaflutole, MCPA- thioethyl, mecoprop-P, mesotrione, metamifop, penoxsulam, petoxamide, picolinafen, profluazol, profoxidime, pyraclonil, pyrazolinate, pyridafol, piriftalide, sulcotrione, thidiazuron. Suitable antidotes are, for example, the following groups of compounds: 1) Compounds of the dichlorophenylpyrazoline-3-carboxylic acid type, preferably compounds such as the ethyl ester of 1- (2,4-dichloro-phenyl) -5- (ethoxycarbonyl) -5-methyl-2-pyrazoline-3-carboxylic acid (S1-1, mefenpyr-diethyl, MW, pages 781-782), and related compounds, as described in WO 91/07874, 2) Derivatives of dichlorophenylpyrazole-carboxylic acid, preferably compounds such as the ethyl ester of 1- (2,4-dichloro-phenyl) -5-methyl-pyrazole-3-carboxylic acid (S1-2), the ethyl ester of acid 1 - (2,4-dichloro-phenyl) -5-isopropyl-pyrazole-3-carboxylic acid (S1-3), the ethyl ester of 1- (2,4-dichloro-phenyl) -5- (1, 1-) dimethyl-ethyl) pyrazole-3-carboxylic acid (S1-4), the ethyl ester of 1- (2,4-dichloro-phenyl) -5-phenyl-pyrazole-3-carboxylic acid (S1 -5) and related compounds, as described in EP-A-333,131 and EP-A-269,806. 3) Compounds of the triazole carboxylic acid type, preferably compounds such as phenclorazol, ie the ethyl ester of 1- (2,4-dichloro-phenyl) -5-trichloromethyl- (1 H) -1, 2,4-triazole-3-carboxylic acid (S1 -6), and related compounds (see EP-A-174,562 and EP-A-346,620; 4) Compounds of the type of 5-benzyl- or 5-phenyl acids -2-isoxazoline-3-carboxylic acids, or 5,5-diphenyl-2-isoxazoline-3-carboxylic acid, preferably compounds such as the 5- (2,4-dichloro-benzyl) -2-ethyl ester -isoxazoline-3-carboxylic acid (S1-7) or the 5-phenyl-2-isoxazoline-3-carboxylic acid ethyl ester (S1-8) and related compounds, as described in WO 91/08202, or the ethyl ester of 5,5-diphenyl-2-isoxazoline-carboxylic acid (S1-9, isoxadifen-ethyl) or the n-propyl ester of this (S1-10) or the ethyl ester of 5- (4-fluoro) phenyl) -5-phenyl-2-isoxazoline-3-carboxylic acid (S1-11), as described in the document patent application (WO-A-95/07897). 5) Compounds of the type of 8-quinolinoxy-acetic acids (S2), preferably the ester (1-methyl-hex-1-yl) of (5-chloro-8-quinolinoxy) -acetic acid (S2-1 cloquintocet-mexyl PM, 263-264), the ester ( 1, 3-dimethyl-but-1-yl) of (5-chloro-8-quinolinoxy) -acetic acid (S2-2), the 4-allyl-oxy-butyl ester of (5-chloro-8-quinolinoxy) ) -acetic (S2-3), the 1-allyloxy-prop-2-yl ester (5-chloro-8-quinolinoxy) -acetic ester (S2-4), the ethyl ester of (5-chloro-8-quinolinoxy) ) -acetic (S2-5), the methyl ester of (5-chloro-8-quinolinoxy) -acetic acid (S2-6), the allyl ester of (5-chloro-8-quinolinoxy) -acetic acid (S2-) 7), the 2- (2-propylidene-iminooxy) -1-ethyl ester of acid (5-chloro-8-quinolinoxy) -acetic (S2-8), the 2-oxo-prop-1-yl ester of (5-chloro-8-quinolinoxy) -acetic acid (S2-9) and related compounds, as described in EP-A-86, 750, EP-A-94,349 and EP-A-191, 736 or EP-A-0,492,366. 6) Compounds of the (5-chloro-8-quinolinoxy) -malonic acid type, preferably compounds such as the diethyl ester of (5-chloro-8-quinolinoxy) -malonic acid, the diallyl ester of the acid (5- chloro-8-quinolinoxy) -malonic, the methyl and ethyl ester of (5-chloro-8-quinolinoxy) -malonic acid and related compounds, as described in EP-A-0,582,198. 7) Active substances of the phenoxy acetic or propionic acid derivatives or of aromatic carboxylic acids, for example (an ester of) 2,4-dichloro-phenoxyacetic acid (2,4- D), an ester of 4-chloro-2-methyl-phenoxy-propionic acid (mecoprop), MCPA or (an ester of) 3,6-dichloro-2-methoxy-benzoic acid (dicamba). 8) Active substances of the pyrimidine type, such as phenchlorima (MW, pages 512-511) (= 4,6-dichloro-2-phenyl-pyrimidine), 9) Active substances of the dichloroacetamide type, which are frequently used as antidotes for pre-emergence (effective antidotes in the soil), such as eg "dichloromide" (PM, pages 363-364) (= N, N-diallyl-2,2-dichloro-acetamide), "R -29148"(= 3-dichloroacetyl-2,2,5-trimethyl-1,3-oxazolidone from Stauffer), "benoxacor" (MW, pages 102-103) (= 4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine), "PPG-1292" (= N-allyl-N- [ (1,3-dioxolan-2-yl) -methyl] -dichloroacetamide from PPG Industries), "DK-24" (= N-allyl-N - [(allylaminocarbonyl) -methyl] -dichloroacetamide from Sagro- Chem), "AD-67" or "MON 4660" (= 3-dichloroacetyl-1-oxa-3-aza-spiro [4,5] decane from the entity Nitrokemia or Monsanto), "diclonone" or "BAS145138" or "LAB145138" (= (= 3-dichloroacetyl-2,5,5-trimethyl-1,3-diaza-bicyclo [4.3.0] nonane from BASF) and "furilazole" or "MON 13900" (see PM , pages 637-638) (= (RS) -3-dichloroacetyl-5- (2-furyl) -2,2-dimethyl-oxazolidone) 10) Active substances of the dichloroacetone derivative type, such as eg " MG 191"(CAS-N0 of Reg. 96420-72-3) (= 2-dichloromethyl-2-methyl-1,3-dioxolane of the entity Nitrokemia), 11) Active substances of the oxyimino-compound type, which they are known as seed disinfectants, such as, for example, "oxabetrinyl" (PM, p. inas 902-903) (= (Z) -1, 3-dioxolan-2-yl-methoxyimino (phenyl) -acetonitrile), which is known as antidote and seed disinfectant agent for millet against damage caused by metolachlor, "fluxofenima" (MW, pages 613-614) (= 0- (1,3-dioxolan-2-ylmethyl) -oxime of 1- (4-chloro-phenyl) -2,2,2-trifluoro-1-ethanone , which is known as antidote and seed disinfectant agent for millet against damage caused by metolachlor, and "cyometrinyl" or "-CGA-43089" (PM, page 1304) (= (Z) -cyanomethoxyimino (phenyl) -acetonitrile) , which is known as antidote and seed disinfectant agent against damage caused by metolachlor, 12) Active substances of the thiazole carboxylic acid esters, which are known as seed disinfectants, such as, for example, "flurazole" (PM, pages 590-591) (= benzyl ester of 2-chloro acid) -4-trifluoromethyl-1,3-thiazole-5-carboxylic acid), which is known as an antidote and seed disinfecting agent against damage caused by alachlor and metolachlor, 13) Active substances of the naphthalene dicarboxylic acid type, which are known as seed disinfectants, such as, for example, "naphthalic anhydride" (PM, page 1, 342) (= 1,8-naphthalene dicarboxylic acid anhydride), which is known as an antidote and disinfectant of seeds for corn against damage caused by herbicides of the thiocarbamate type, 14) Active substances of the chromanoacetic acid derivatives type, such as eg "CL 304415" (CAS-N0 of Reg. 31541-57-8) (= 2- (4-carboxy-chroman-4-yl) -acetic acid of the American entity Cyanamid), ) Active substances, which together with a herbicidal effect against harmful plants also have an antidotal effect in the presence of cultivated plants, such as, for example, "dimepiperate" or "MY-93" (PM, pages 404-405) ( = S-1-methyl-1-phenyl-ethyl ester of piperidine-1-thio-carboxylic acid), "daimuron" or "SK 23" (MW, page 330) (= 1- (1-methyl-1-phenyl) -ethyl) -3-p-tolyl-urea), "cumiluron" = "JC-940" (= 3- (2-chloro-phenylmethyl) -1- (1-methyl-1-phenyl-ethyl) -urea, see Japanese patent application JP-A-60087254), "methoxyphenone" or "NK 049" (= 3,3'-dimethyl-4-methoxy-benzophenone), "CSB" (= 1- bromo-4- (chloromethylsulfonyl) -benzene) (CAS-N0 of Reg. 54091-06-4 of Kumiai), 16) Compounds of the amide type of acylsulphamoylbenzoic acids, eg of the following formula (VIII), which are known, for example, from WO 99/16744.

Preferred antidotes are mefenpir, fenchlorazole, isoxadifen, cloquintocet and their C1-C-10 alkyl esters, in particular mefenpyr-diethyl (S1-1), fenchlorazole-ethyl (S1-6), isoxadifen-ethyl (S1 -9), cloquintocet -mexyl (S2-1), and (S3-1). The usual adjuvants and additives F) optionally contained in the liquid formulations according to the invention are known in principle and are described, for example, in the classics of: "Detergents and Emulsifiers Annual" by McCutcheon, MC Publ. Corp., Ridgewood N.J .; Sisley and Wood, "Encyclopedia of Surface Active Agents" surfactants), Chem. Publ. Co. Inc., N.Y. 1964; Schonfeldt, "Grenzfláchenaktive Áthylenoxidaddukte" (Adducts with interfacially active ethylene oxide), Wiss. Verlagsgesell., Stuttgart 1976; Winnacker-Küchler, "Chemische Technologie" (Chemical Technology), volume 7, C. Hauser Munich publishing house, 4th edition, 1986. As usual adjuvants and additives F) may still be present in the formulations according to the invention, eg: thixotropic agents, wetting agents, anti-drift agents, adhesives, penetrants, preservatives and frost protectors, anti-oxidants, fillers and fillers, support materials, dyes, perfumes, defoamers, fertilizers, evaporation inhibitors, agents which influence the pH value and the viscosity as well as agents that positively influence the stability, in particular on the stability against hydrolysis. Suitable antifreeze agents are those taken from the group of ureas, diols and polyols, such as ethylene glycol and propylene glycol. Suitable defoamers are those based on silicones. Appropriate structure-forming substances are those taken among the group of xanthans. Suitable preservatives, dyes and perfumes are known to one skilled in the art. Especially preferred forms of embodiment are liquid formulations containing (A) pyrasulfotol (A-5), sodium salt of pyrasulfotol (A-5Na), poasium salt of pyrasulfotol (A-5K), (B) sodium bis-2-ethyl-hexyl sulfosuccinate (B-1), (C) Emulsogen® EL 400 (C-1), Genapol® X-060 (C-2), Genapol® X-150 (C-3), (D) Solvesso® 100 (D-1), Solvesso® 200 ND (D-2), (E) mefenpyr-diethyl (E-1), fenoxaprop-P-ethyl (E-2), bromoxynil (E-3) Especially preferred forms of modality are liquid formulations containing the components : A-5 + B-1 + C-1 + D-1, A-5 + B-1 + C-2 + D-1, A-5 + B-1 + C-3 + D-1, A -5Na + B-1 + C-1 + D-1, A-5Na + B-1 + C-2 + D-1, A-5Na + B-1 + C-3 + D-1, A-5K + B-1 + C-1 + D-1, A-5K + B-1 + C-2 + D-1, A-5K + B-1 + C-3 + D-1, A-5 + B-1 + C-1 + D-2, A-5 + B-1 + C-2 + D-2, A-5 + B-1 + C -3 + D-2, A-5Na + B-1 + C-1 + D-2, A-5Na + B-1 + C-2 + D-2, A-5Na + B-1 + C-3 + D-2, A-5K + B-1 + C-1 + D-2, A-5K + B-1 + C-2 + D-2, A-5K + B-1 + C-3 + D -2, A-5 + B-1 + C-1 + D-1 + E-1, A-5 + B-1 + C-2 + D-1 + E-1, A-5 + B-1 + C-3 + D-1 + E-1, A-5Na + B-1 + C-1 + D-1 + E-1, A-5Na + B-1 + C- 2 + D-1 + E-1, A-5Na + B-1 + C-3 + D-1 + E-1, A-5K + B-1 + C-1 + D-1 + E-1, A-5K + B-1 + C-2 + D-1 + E-1, A-5K + B-1 + C-3 + D-1 + E-1, A-5 + B-1 + C- 1 + D-2 + E-1, A-5 + B-1 + C-2 + D-2 + E-1, A-5 + B-1 + C-3 + D-2 + E-1, A-5Na + B-1 + C-1 + D-2 + E-1, A-5Na + B-1 + C-2 + D-2 + E-1, A-5Na + B-1 + C- 3 + D-2 + E-1, A-5K + B-1 + C-1 + D-2 + E-1, A-5K + B-1 + C-2 + D-2 + E-1, A-5K + B-1 + C-3 + D-2 + E-1, A-5 + B-1 + C-1 + D-1 + E-2, A-5 + B-1 + C- 2 + D-1 + E-2, A-5 + B-1 + C-3 + D-1 + E-2, A-5Na + B-1 + C-1 + D-1 + E-2, A-5Na + B-1 + C-2 + D-1 + E-2, A-5Na + B-1 + C-3 + D-1 + E-2, A-5K + B-1 + C- 1 + D-1 + E-2, A-5K + B-1 + C-2 + D-1 + E-2, A-5K + B-1 + C-3 + D-1 + E-2, A-5 + B-1 + C-1 + D-2 + E-2, A-5 + B-1 + C-2 + D-2 + E-2, A-5 + B-1 + C- 3 + D-2 + E-2, A-5Na + B-1 + C-1 + D-2 + E-2, A-5Na + B-1 + C-2 + D-2 + E-2, A-5Na + B-1 + C-3 + D-2 + E-2, A-5K + B-1 + C-1 + D-2 + E-2, A-5K + B-1 + C- 2 + D-2 + E-2, A-5K + B-1 + C-3 + D-2 + E-2, A-5 + B-1 + C-1 + D-1 + E-3, A-5 + B-1 + C-2 + D-1 + E-3, A- 5 + B-1 + C-3 + D-1 + E-3, A-5Na + B-1 + C-1 + D-1 + E-3, A-5Na + B-1 + C-2 + D-1 + E-3, A-5Na + B-1 + C-3 + D-1 + E-3, A-5K + B-1 + C-1 + D-1 + E-3, A- 5K + B-1 + C-2 + D-1 + E-3, A-5K + B-1 + C-3 + D-1 + E-3, A-5 + B-1 + C-1 + D-2 + E-3, A-5 + B-1 + C-2 + D-2 + E-3, A-5 + B-1 + C-3 + D-2 + E-3, A-5Na + B-1 + C-1 + D-2 + E-3, A-5Na + B-1 + C-2 + D-2 + E-3, A-5Na + B-1 + C- 3 + D-2 + E-3, A-5K + B-1 + C-1 + D-2 + E-3, A-5K + B-1 + C-2 + D-2 + E-3, A-5K + B-1 + C-3 + D-2 + E-3, A-5 + B-1 + C-1 + D-1 + E-1 + E-2, A-5 + B- 1 + C-2 + D-1 + E-1 + E-2, A-5 + B-1 + C-3 + D-1 + E-1 + E-2, A-5Na + B-1 + C-1 + D-1 + E-1 + E-2, A-5Na + B-1 + C-2 + D-1 + E-1 + E-2, A-5Na + B-1 + C-3 + D-1 + E-1 + E-2, A-5K + B-1 + C-1 + D-1 + E-1 + E-2, A-5K + B-1 + C-2 + D-1 + E-1 + E-2, A-5K + B-1 + C-3 + D-1 + E-1 + E-2, A-5 + B-1 + C-1 + D-2 + E-1 + E-2, A-5 + B-1 + C-2 + D-2 + E-1 + E-2, A-5 + B-1 + C-3 + D-2 + E-1 + E-2, A-5Na + B-1 + C-1 + D-2 + E-1 + E-2, A-5Na + B-1 + C-2 + D-2 + E-1 + E-2, A-5Na + B-1 + C-3 + D-2 + E-1 + E-2, A-5K + B-1 + C-1 + D-2 + E-1 + E-2, A-5K + B-1 + C-2 + D-2 + E-1 + E-2, A-5K + B-1 + C-3 + D-2 + E-1 + E-2, A-5 + B-1 + C-1 + D-1 + E-1 + E-3, A-5 + B-1 + C-2 + D-1 + E-1 + E-3, A-5 + B-1 + C-3 + D-1 + E-1 + E-3, A-5Na + B-1 + C-1 + D-1 + E-1 + E-3, A-5Na + B-1 + C-2 + D-1 + E-1 + E-3, A-5Na + B-1 + C-3 + D-1 + E-1 + E-3, A-5K + B-1 + C-1 + D-1 + E-1 + E-3, A-5K + B-1 + C-2 + D-1 + E-1 + E-3, A-5K + B-1 + C-3 + D-1 + E-1 + E-3, A-5 + B-1 + C-1 + D-2 + E-1 + E-3, A-5 + B-1 + C-2 + D-2 + E-1 + E-3, A-5 + B-1 + C-3 + D-2 + E- 1 + E-3, A-5Na + B-1 + C-1 + D-2 + E-1 + E-3, A-5Na + B-1 + C-2 + D-2 + E-1 + E-3, A-5Na + B-1 + C-3 + D-2 + E-1 + E-3, A-5K + B-1 + C-1 + D-2 + E-1 + E-3, A-5K + B-1 + C-2 + D-2 + E-1 + E-3, A-5K + B-1 + C-3 + D-2 + E-1 + E-3, A-5 + B-1 + C-1 + D-1 + E-1 + E-2 + E-3, A-5 + B-1 + C-2 + D- 1 + E-1 + E-2 + E-3, A-5 + B-1 + C-3 + D-1 + E-1 + E-2 + E-3, A-5Na + B-1 + C-1 + D-1 + E-1 + E-2 + E-3, A-5Na + B-1 + C-2 + D-1 + E-1 + E-2 + E-3, A- 5Na + B-1 + C-3 + D-1 + E-1 + E-2 + E-3, A-5K + B-1 + C-1 + D-1 + E-1 + E-2 + E-3, A-5K + B-1 + C-2 + D-1 + E-1 + E-2 + E-3, A-5K + B-1 + C-3 + D-1 + E-1 + E- 2 + E-3, A-5 + B-1 + C-1 + D-2 + E-1 + E-2 + E-3, A-5 + B-1 + C-2 + D-2 + E-1 + E-2 + E-3, A-5 + B-1 + C-3 + D-2 + E-1 + E-2 + E-3, A-5Na + B-1 + C- 1 + D-2 + E-1 + E-2 + E-3, A-5Na + B-1 + C-2 + D-2 + E-1 + E-2 + E-3, A-5Na + B-1 + C-3 + D-2 + E-1 + E-2 + E-3, A-5K + B-1 + C-1 + D-2 + E-1 + E-2 + E- 3, A-5K + B-1 + C-2 + D-2 + E-1 + E-2 + E-3, and A-5K + B-1 + C-3 + D-2 + E-1 + E-2 + E-3. The bromoxynil can be used in each case in the form of the potassium salt or the heptanoate or octanoate. The liquid formulations according to the invention can be prepared by customary known processes, for example by mixing the various components with the aid of agitators, shakers, mills or mixers (static). In this context, heating of the mixtures is advantageous for a short time, in order to achieve total dissolution of all the components involved. The liquid formulations according to the invention show a significantly improved application behavior, which becomes noticeable in sieving residues and respectively obstructions of sieves and nozzles that have been markedly reduced. The amount consumed of the formulations according to the invention per hectare fluctuates in general between 0.5 and 5 liters, preferably between 1.0 and 4.0 liters. For the application, the formulations according to the invention can be diluted in a conventional manner, for example to give suspensions, emulsions, suspoemulsione or solutions, preferably emulsions, for example by water. It may be advantageous to add other agrochemical active substances (eg binders in the form of corresponding formulations) and / or additives and additives customary for the application, eg self-emulsifying oils as vegetable oils or paraffin oils and / or fertilizing agents. Therefore, they are also the object of the present invention are the herbicidal agents prepared in such a manner. Usually the ratio of the formulation according to the invention to water is from 1: 500 to 1: 50. For the broth for projecting, they are usually used from 50 to 500 liters, preferably from 75 to 350 liters of water. In some cases it is also possible to pass below and respectively above the indicated limit values. The formulations are also suitable for an aircraft application. For this, the formulations according to the invention are spread either undiluted, or diluted with water or organic solvents. The volume of additional support liquid fluctuates in this case as a rule from 0.5 to 50 liters per hectare. Therefore, such herbicidal agents are also subject to the present invention, based on liquid formulations according to the invention. The formulations and herbicidal compositions according to the invention have excellent herbicidal activity against a broad spectrum of harmful mono- and di-plants. economically important cotyledons. Perennial weeds that are hard to combat are also perfectly covered, sprouting from rhizomes, roots root balls or other permanent organs. In such a case, as a general rule it is not important that the substances are spread according to pre-planting procedures, before the outbreak or after the outbreak. In particular, mention should be made, by way of example, of representatives of the mono- and di-cotyledonous weed flora, which can be repressed by means of the compounds according to the invention, without this limitation having to be limited to certain species. On the side of monocotyledonous weed species they are perfectly encompassed, for example, Apera spica venti, Avena spp., Alopecurus spp., Brachiaria spp., Digitaria spp., Lolium spp., Echinochloa spp., Panicum spp., Phalaris spp. ., Poa spp., Setaria spp., As well as Bromus spp. such as Bromus catharticus, Bromus secalinus, Bromus erectus, Bromus tectorum and Bromus japonicus, and Cyperus species of the annuals, and perennial species include Agropyron, Cynodon, Imperata as well as Sorghum and also persistent species of Cyperus In the case of dicotyledonous weed species, the spectrum of effects extends to species such as, for example, Abutilon spp., Amaranthus spp., Chenopodium spp., Chrysanthemum spp., Galium spp. such as Galium aparine, Ipomoea spp., Kochia spp., Lamium spp., Matrica spp., Pharbitis spp., Polygonum spp., Sida spp., Sinapis spp., Solanum spp., Stellaria spp., Veronica spp. and Viola spp., Xanthium spp., on the side of the annuals, as well as Convolvulus, Cirsium, Rumex and Artemisia in the case of perennial weeds. Harmful plants that occur in rice under specific cultivation conditions, such as, for example, Echinochloa, Sagittaria, Alisma, Cyperus, Eleocharis, Scirpus and Cyperus, are also suppressed by the agents according to the invention. If the herbicidal agents according to the invention are applied before germination on the surface of the soil, either the sprouting of the weed seedlings is completely prevented, or the weeds grow until the stage of cotyledons is reached, but then they stop growing and they finally die completely after three to four weeks have elapsed. In the case of the application of the herbicidal compositions according to the invention on the green parts of the plants according to the post-emergence method, a drastic growth arrest also appears very quickly after the treatment, and the weed plants remain in the plant. stage of growth that existed at the time of application or die completely after a certain period of time, so that in this way competition for weeds that are harmful to the cultivated plants is eliminated very early and persistently.

The herbicidal compositions according to the invention are distinguished by a herbicidal effect that starts quickly and lasts a long time. The resistance to rain of the active substances in the combinations according to the invention is generally favorable. Of special importance is the fact that the dosages of herbicidal compounds, which are used in the herbicidal compositions according to the invention and are effective, can be adjusted so that their effect on the soil is optimally low. Therefore, its use is not only possible for the first time in sensitive crops, but also virtually avoids contamination of groundwater. By means of the combination according to the invention of active substances, a considerable reduction of the necessary amount to be consumed of the active substances is possible. The mentioned properties and advantages are useful in the practical repression of weeds, in order to keep agricultural crops free from unwanted competitive plants, and thereby ensure and / or increase yields qualitatively and quantitatively. The technical pattern is clearly overcome by these new agents in regard to the properties described. Even when the herbicidal agents have an excellent herbicidal activity against mono- and di-cotyledonous weeds, the cultivated plants of economically important crops, eg of crops of dicotyledonous plants, such as those of soybean, cotton, rapeseed, sugar beets , or grass crops such as wheat, barley, rye, oats, millet, rice or corn, are damaged only insignificantly or even not damaged at all. The herbicidal agents according to the invention are suitable for these reasons very well for the selective control of unwanted vegetation of plants in useful agricultural plantations or in ornamental plantations. In addition, the herbicidal compositions according to the invention have outstanding growth regulating properties in the case of cultivated plants. They intervene in the plant metabolism in the sense of regulating it, and therefore can be used for the deliberate influence on the constituent substances of the plants and for the facilitation of the crops, such as, for example, by provocation of a desiccation and a stifling of growth. In addition, they are also suitable for the general control and inhibition of undesired vegetative growth, without annihilating the plants in such a case. An inhibition of vegetative growth plays a large role in many crops of mono- and di-cotyledonous plants, since with it it can be reduced or totally prevented from falling. By virtue of their herbicidal and plant growth regulating properties, the herbicidal agents according to the invention can also be used for the control of harmful plants in genetically modified plant crops, known or still to be developed. Transgenic plants are generally distinguished by special advantageous properties, for example by resistance to certain pesticides, especially against certain herbicides, resistances against plant diseases or pathogens of plant diseases, such as certain insects or microorganisms such as fungi, bacteria or viruses. Other special properties concern, for example, the harvested material in terms of quantity, quality, storage capacity, composition and special constituents. Thus, transgenic plants with an increased content of starch or a modified quality of the starch, or those having a different fatty acid composition of the harvested material are known. Preference is given to the application of the herbicidal compositions according to the invention in economically important transgenic crops of useful and ornamental plants, for example of grass crops such as wheat, barley, rye, oats, millet, rice and corn or also beet crops. sugar, cotton, soy, rapeseed, potato, tomato, peas and other species of legumes. Preferably, the herbicidal agents according to the invention can be used in crops of useful plants, which are resistant or made resistant by genetic technology to the phytotoxic effects of the herbicides. In the case of the use of the herbicidal agents according to the invention in transgenic crops, together with the effects against harmful plants, which can be observed in other crops, effects that are specific for the application in the respective transgenic crop often appear, example a specially modified or expanded spectrum of weeds, which can be repress, modified consumed quantities, which can be used for the application, preferably a good aptitude for the combination with the other herbicidal active substances, against which the transgenic crop is resistant, as well as an influence on the vegetation and the yield of plants cultivated transgenic. The object of the present invention is, therefore, also a method for the control of unwanted vegetation of plants, preferably in crops of plants such as cereals (eg wheat, rye, barley, oats, rice, corn, millet), sugar beet, sugar cane, rapeseed, cotton and soya, particularly preferably in crops of monocotyledonous plants such as cereals, eg wheat, barley, rye, oats, crosses thereof such as triticales, rice, corn and millet, applying one or more herbicidal agents according to the invention on the harmful plants, the parts of the plants, the seeds of plants or the surface on which the plants grow, eg the cultivated area. The plant cultures can also be modified by genetic technology or have been obtained by mutation selection and are preferably tolerant to acetolactate synthetase (ALS) inhibitors. Emulsifiable concentrates are prepared, for example, by dissolving the active substance A) or active substances A) and E) in one or more solvents D) with the addition of a dialkyl sulfosuccinate B) and a surfactant C) as eventually other substances adjuvants and additives F).

EXAMPLES OF MODALITY The concepts used in the following Examples mean: Emulsogen® EL 400 = Ethoxylated castor oil with 40 units of ethyleneoxy Genapol® X-060 = nonionic surfactant that is based on an isotridecanol-polyglycol ether ethoxylate Genapol® X-150 = nonionic surfactant that is based on an isotridecanol-polyglycol ether ethoxylate Preparation of emulsifiable concentrates The preparation mode described below refers to the recipes of the following Examples 1 to 4: Component A) and component B) are mixed by stirring in a container with stirring system to give a dispersion and then heat at 80 ° C. After component A) has been dissolved, add the components D), C) and E) are stirred.

EXAMPLE 1 A) 3.50 g of the potassium salt of pyrasulfotol (A-5K) B) 30.00 g of bis- (2-ethyl-hexyl) sulfosuccinate sodium as a 64% solution in Solvesso® 100 (B-1), C ) 9.50 g of Emulsogen® EL 400 (C-1), D) 57.00 g of Solvesso® 200 ND (D-2).

EXAMPLE 2 A) 3.50 g of the potassium salt of pyrasulfotol (A-5K) B) 30.00 g of bis- (2-ethyl-hexyl) sulfosuccinate sodium as a 64% solution in Solvesso® 100 (B-1), C) 7.50 g of Emulsogen® EL 400 (C-1), C) 7.50 g of Genapol® X-150 (C-3), D) 42.00 g of Solvesso® 200 ND (D-2), E) 2.70 g of mefenpyr-diethyl (E-1), E) 6.80 g of fenoxaprop-P-ethyl (E-2).

EXAMPLE 3 A) 3.50 g of the potassium salt of pyrasulfotol (A-5K) B) 30.00 g of bis- (2-ethyl-hexyl) sulfosuccinate sodium as a 64% solution in Solvesso® 100 (B-1), C) 7.30 g of Emulsogen® EL 400 (C-1), C) 11.50 g of Genapol® X-060 (C-2), D) 45.00 g of Solvesso® 200 ND (D-2), E) 2.70 g of mefenpyr-diethyl (E-1).

EXAMPLE 4 A) 3.50 g of the potassium salt of pyrasulfotol (A-5K) B) 30.00 g of bis- (2-ethyl-hexyl) sulfosuccinate sodium as a 64% solution in Solvesso® 100 (B-1), C ) 5.00 g of Emulsogen® EL 400 (C-1), C) 15.00 g of Genapol® X-150 (C-3), D) 37.00 g of Solvesso® 200 ND (D-2), E) 2.70 g of mefenpyr-diethyl (E-1), E) 6.80 g of fenoxaprop-P-ethyl (E-2).

The emulsifiable concentrates according to the invention, as well as obtained, are chemically stable and remain transparent and homogeneous also after prolonged storage and can be diluted with water to give homogeneous emulsions.

COMPARATIVE EXAMPLE For comparative purposes, they are mixed by shaking under the above-mentioned conditions A) 3.50 g of the potassium salt of pyrasulfotol (A-5K) C) 7.30 g of Emulsogen® EL 400 (C-1), C) 11.50 g of Genapol® X-060 (C-3), D) 75.00 g of Solvesso® 200 ND (D-2) and E) 2.70 g of mefenpyr-diethyl ether (E-1) but without component B). In contrast to the modality examples According to the invention, no transparent homogeneous solution is formed.

Claims (9)

NOVELTY OF THE INVENTION CLAIMS

1. - Liquid formulations containing A) one or more herbicidal active substances taken from the group of HPPD inhibitors, B) one or more surfactants taken from the group of dialkyl sulfosuccinates, C) one or more other surfactants of B), and D) one or more solvents, the molar ratio of the HPPD inhibitor being to the dialkyl sulfosuccinate less than or equal to 1 to 6.

2. The liquid formulations according to claim 1, further characterized in that they contain HPPD inhibitors of the formula (I), wherein R means cyclohexane-1,3-dion-2-yl, 5-hydro-1 H -pyrazol-4-yl or isoxazol-4-yl, these three rings being unsubstituted or substituted with one or two radicals taken between the group consisting of methyl, ethyl, propyl and cyclopropyl; R stands for methyl, methoxy, trifluoromethoxy, trifluoromethyl, methylsulfonyl, chlorine or bromine; R5 means hydrogen, methyl, methoxy, trifluoromethoxy, trifluoromethyl, chloro, bromo, 2,2,2-trifluoro-ethoxymethyl or 4,5- dihydro-isoxazol-3-yl; R6 is chlorine, bromine, trifluoromethoxy, trifluoromethyl or methylsulfonyl.

3. The liquid formulations according to claim 1 or 2, further characterized in that they contain A) from 0.1 to 50% of one or more inhibitors of HPPD, B) from 1 to 50% of one or more dialkyl sulfosuccinates, C) from 2 to 40% of one or several other surfactants, and D) from 5 to 80% of one or more solvents, E) from 0 to 25% of other additives and additives, and F) from 0 to 50 % of one or more other agrochemical active substances other than A).

4. Liquid formulations according to one or more of claims 1 to 3, further characterized in that they contain A) from 0.1 to 50% of one or more inhibitors of HPPD, B) from 1 to 50% of one or more dialkyl sulfosuccinates, C) from 2 to 40% of one or more other surfactants, D) from 5 to 80% of one or more solvents, E) from 0 to 20% of other additives and additives, and F) from 0 to 40% of one or several other agrochemical active substances different from A).

5. A process for the preparation of a liquid formulation according to one or more of claims 1 to 4, wherein the components are mixed.

6. The use of a liquid formulation according to one or more of claims 1 to 4, for the preparation of a herbicidal agent.

7. - A liquid herbicidal agent, obtainable by dilution of a liquid formulation according to one or more of claims 1 to 4.

8. The use of a liquid formulation according to one or more of claims 1 to 4 or of a herbicidal agent according to claim 7, for the control of unwanted vegetation of plants.

9. A method for the control of an unwanted plant vegetation, in which an effective amount of a liquid formulation according to one or more of claims 1 to 4 or of a herbicidal agent according to claim 7 is applied about the plants, the parts of the plants, the seed material or the surface on which the plants grow.