EP1926379A2 - Novel sulfonamide-containing solid formulations - Google Patents

Abstract

The invention relates to solid, water-dispersible formulations which comprise one or more herbicidal substances from the group of sulfonamides and the salts thereof, one or more safeners, one or more solvents, one or more excipients, selected from excipients having low and/or high absorbency, one or more conventional adjuvants and additives, selected from the group including emulsifiers, antifoaming agents, cross-linking agents, and dispersants. The ratio of safeners to solvents is chosen to be specific, and the ratio of the two components combined to the used excipients having high absorbency is chosen to be specific. The inventive formulations are suitable for use in plant protection.

Description

description

New sulfonamide-containing solid formulations

The present invention relates to the field of crop protection formulations. In particular, the invention relates to solid herbicidal formulations which contain herbicidal active compounds from the group of sulfonamides and their salts, in particular phenylsulfonamides, such as phenylsulfonylaminocarbonyltriazolinones or phenylsulfonylureas, heteroarylsulfonamides and other sulfonamides and salts thereof.

Active ingredients for crop protection are generally not used in their pure form. Depending on the field of application and the type of application, as well as on physical, chemical and biological parameters of the active ingredient is used in admixture with conventional auxiliaries and additives as active ingredient formulation. But the drug formulation of combinations with other agents to extend the spectrum of action and / or protection of crops (eg by safener, antidote) is an important field of formulation technology, as here active ingredients with sometimes quite different physical, chemical and biological parameters adequately in common must be formulated.

Thus, formulations of active ingredients, alone or in combinations of several active ingredients, for plant protection generally should have a high chemical and physical stability, good applicability and user-friendliness and a broad biological activity with high selectivity with regard to the active ingredients used, in addition to a technically good Formulability in the manufacturing process.

Solid formulations of active ingredients from the group of sulfonylureas are known per se, for example from WO-A-97/10714. However, so far with regard to sufficiently sufficient applicability no satisfactory active ingredient-containing solid formulations of combinations of the sulfonamides with other active ingredients, such as low-melting safeners before. In this context, the poor dispersibility of the solid formulation thus composed is usually observed in the preparation of aqueous spray mixtures, with the consequence of, for example, nozzle clogging and loss of effect after application.

In addition, herbicidal active substances from the group of sulfonamides generally have a high degree of chemical reactivity and are prone to chemical degradation, e.g. by hydrolysis, which must be critically assessed in terms of a sufficient storage stability in the formulations.

Stabilization of sulfonylureas contained in solid formulations is e.g. in JP-A-62-084004 by adding calcium carbonate and Na tripolyphosphate as stabilizers. In addition, however, the formulations themselves, due to the auxiliaries and additives contained therein, influence the stability of the active ingredients: WO-A-98/34482 describes test results with the phenylsulfonylureas tritosulfuron and metsulfuron, after which additives (adjuvants) from the group of fatty alcohol ethoxylates and ethoxylated fatty amines cause a lower storage stability as adjuvants from the group of sodium salts of aliphatic sulfonic acids, such as sodium alkanesulfonates and Na-alpha Olefιnsulfonate. EP-A-764404 describes a stabilization of the heteroarylsulfonylurea flazasulfuron by using Na-dioctylsulfosuccinate.

Corresponding stability studies with drugs from the group Phenylsulfonylaminocarbonyltriazolinone alone and in mixtures with other drugs from the group of sulfonamides, however, are not known. Likewise, there are no results from investigations of combinations of these active ingredients with other low-melting agents, such as safeners. The object of the present invention was to provide an improved pesticide-containing solid formulation which is composed of combinations of active substances from the group of sulfonamides and active ingredients from the group of safeners and which has good applicability with unchanged high biological effectiveness and crop plant tolerance the active ingredients. In addition, a high physical and chemical storage stability of these drug combinations in the formulation should be made possible, in addition to good formulability in the production process of the formulation and later ease of use.

This object is achieved by the solid, water-dispersible formulation of the present invention.

The present invention thus relates to a solid, water-dispersible formulation comprising:

(A) one or more active substances from the group of sulfonamides and their salts, with at least one active compound selected from the group Phenylsulfonylaminocarbonyltriazolinone;

(b) one or more safeners;

(c) one or more solvents,

(d) one or more support materials selected from one or more of the groups:

(d-1) low absorbency carriers, (d-2) high absorbency carriers;

(e) one or more common excipients and additives selected from one or more of the groups

(e-1) emulsifiers, (e-2) antifoaming agents, (e-3) wetting agents, (e-4) dispersants; in which Component (b) for component (c) is in the following ratio: (b): (c) generally 0.3 to 2.0: 1, preferably 0.4 to 1.5: 1, particularly preferably 0.5 to 1, 0: 1; and at the same time the sum of the components (b) and (c) to the component (d-2) in the following ratio: [(b) + (c)]: (d-2) in general 1, 7 to 3.9: 1, preferably 1.85 to 3.5: 1, more preferably 2.0 to 3.0: 1.

In addition, the solid, water-dispersible formulation according to the invention may optionally still contain as further components:

(f) one or more agrochemical agents other than components (a) and (b).

(g) one or more of the components (e) other customary auxiliaries and additives.

Preferred sulfonamides (component a) are phenylsulfonamides, such as phenylsulfonylaminocarbonyltriazolinones or phenylsulfonylureas, heteroarylsulfonamides and other sulfonamides, such as amidosulfuron, and salts thereof. Preferred phenylsulfonamides are compounds from the group of the phenylsulfonylaminocarbonyltriazolinones or the phenylsulfonylureas. The term phenylsulfonylureas also includes those sulfonylureas in which the phenyl group is bonded to the sulfone group (SO ₂ ) via a spacer such as CH ₂ , O or NH. examples for

Phenylsulfonylaminocarbonyltriazolinones are flucarbazones, propoxycarbazones or methyl 4 - [(4,5-dihydro-3-methoxy-4-methyl-5-oxo-1H-1,2,4-triazol-1-yl) carboxamidosulfonyl] -5- metylthiophene-3-carboxylate (eg known from WO-A-03/026427, Example I-2) and / or salts thereof. The sulfonamides are commercially available and / or can be prepared by known processes as described e.g. are described in EP-A-7687, EP-A-30138, US 5,057,144 and US 5,534,486.

Suitable phenylsulfonamides are, for example, phenylsulfonamides of the general formula (I) and / or salts thereof,

R ^α - (A) _m -SO ₂ -NR ^β -CO- (NR ^γ ) _n -R ^δ (I) wherein

R ^{α is} a phenyl radical which is unsubstituted or substituted, and wherein the

Phenyl radical including substituents 6-30 C-atoms, preferably 6-20 C-

Atoms, ^{Rβ is} a hydrogen atom or a hydrocarbon radical which is unsubstituted or substituted and, including substituents 1-10 C-atoms, for example unsubstituted or substituted C ₁ -C ₆ -alkyl, preferably one

Hydrogen atom or methyl, R ^{γ is} a hydrogen atom or a hydrocarbon radical which is unsubstituted or substituted and having 1-10 substituents C atoms, for example unsubstituted or substituted C-ι-C- _6- alkyl, preferably a

Is hydrogen atom or methyl, A is CH ₂ , O or NH, preferably O, m is zero or 1, n is zero or 1, preferably 1, and R ^{δ is} a heterocyclic radical such as a pyrimidinyl radical, a triazinyl radical or

Triazolinone is.

Preferred phenylsulfonamides are phenylsulfonylureas, for example phenylsulfonylureas of the general formula (II) and / or salts thereof,

R ^α - (A) _m -SO ₂ -NR ^β -CO-NR ^γ - R ^δ (II) wherein R ^{α is} a phenyl radical which is unsubstituted or substituted, and wherein the

Phenyl radical including substituents 6-30 C-atoms, preferably 6-20 C-

Atoms, ^{Rβ is} a hydrogen atom or a hydrocarbon radical which is unsubstituted or substituted and having 1-10 substituents C atoms, for example unsubstituted or substituted Ci-Ce-alkyl, preferably one

Hydrogen atom or methyl, R ^γ is a hydrogen atom or a hydrocarbon radical which is unsubstituted or substituted and including substituents has 1-10 carbon atoms includes, for example, unsubstituted or substituted C ₁ -C ₆ -alkyl, preferably a

Is hydrogen or methyl, A is CH ₂ , O or NH, preferably O, m is zero or 1, and R ^{δ is} a heterocyclic radical such as a pyrimidinyl radical or a triazinyl radical.

Preference is given to phenylsulfonylureas of the formula (III) and / or salts thereof,

wherein

R ^{4 is} C ₁ -C ₄ -alkoxy, preferably C ₂ -C ₄ -alkoxy, or CO-R ^a , where R ^a is OH, C ₁ -C ₄ -alkoxy or NR ^b R ^c , wherein R ^b and R ^c independently of one another are identical or different and are H or C ₁ -C ₄ -alkyl,

R ^{5 is} halogen, preferably iodine, or (A) _n -NR ^d R ^e , wherein n is zero or 1, A is a group CR'R ", wherein R 'and R" independently of one another are the same or different H or CrC ₄ -alkyl, R ^d is H or C 1 -C ₄ -alkyl and R ^{e is} an acyl radical such as formyl or C 1 -C ₄ -alkyl-sulfonyl, and R ^{5 is} the case where R ⁴ is C 1 -C ₄ Alkoxy, preferably C ₂ -C ₄ -alkoxy, may also be H,

R ^{6 is} H or C _r C ₄ alkyl, m is zero or 1,

X and Y are independently the same or different halogen or NR'R ", wherein R 'and R" are the same or different H or -C ₄ alkyl, or -C ₆ - alkyl, C ₁ -C ₆ -alkoxy, C _r C ₆ alkylthio, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ - alkynyl, C ₃ -C ₃ -C ₆ -alkyl are kynyloxy ₆ alkenyloxy or C, each of the eight last-mentioned unsubstituted radicals or ₄ -alkyl substituted by one or more radicals from the group halogen, C ₁ -C ₄ -alkoxy and C ₁ -C alkylthio, preferably C-ι-C ₄ alkyl or C ₁ -C ₄ -alkoxy, and Z is CH or N.

Particular preference is given to phenylsulfonylureas of the general formula (III) and / or salts thereof in which a) R ⁴ is CO- (C 1 -C ₄ -alkoxy), R ⁵ is halogen, preferably iodine, or R ⁵ is CH ₂ - NHR ⁶ is wherein R ^{e is} an acyl radical, preferably C 1 -C ₄ alkyl-sulfonyl, and m is zero, b) R ⁴ is CO-N (C 1 -C ₄ -alkyl) ₂ , R ⁵ is NHR ^e , where R ^{e is} an acyl radical, preferably formyl, and m is zero, or c) R ⁴ is C ₂ -C ₄ -alkoxy, R ⁵ is H and m is 1.

Typical phenylsulfonylureas include the following compounds and their salts, such as the sodium salts: bensulfuron-methyl, chlorimuron-ethyl, chlorosulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron-methyl, ethoxysulfuron and its sodium salt, metsulfuron-methyl, oxasulfuron, primisulfuron-methyl, Prosulfuron, sulfometuron-methyl, triasulfuron, tribenuron-methyl, triflusulfuron-methyl, tritosulfuron, lodosulfuron-methyl and its sodium salt (WO-A-92/13845), mesosulfuron-methyl and its sodium salt (Agrow No. 347, March 3, 2000 , Page 22 (PJB Publications Ltd. 2000)) and foramsulfuron and its sodium salt (Agrow No. 338, October 15, 1999, page 26 (PJB Publications Ltd. 1999)).

Particularly preferred phenylsulfonamides are: iodosulfuron-methyl and its sodium salt, mesosulfuron-methyl and its sodium salt, foramsulfuron and its sodium salt, flucarbazone and its sodium salt, propoxycarbazones and its sodium salt, methyl 4 - [(4,5-dihydro-3-methoxy- 4-methyl-5-oxo-1H-1, 2,4-triazole-1-ylcarboxamidosulfonyp-δ-methylthiophene-S-carboxylate and its sodium salt, and ethoxysulfuron and its sodium salt, metsulfuron-methyl and its sodium salt, tribenuron-methyl and its sodium salt, chlorosulfuron and its sodium salt. The active ingredients listed above are known, for example, from "The Pesticide Manual", 12th edition, The British Crop Protection Council (2000), or the references listed after the individual active ingredients.

Suitable heteroarylsulfonamides are, for example, compounds from the group of heteroarylsulfonylaminocarbonyltriazolinones or heteroarylsulfonylureas, preferably from the group of heteroarylsulfonylureas. Under the term

Heteroarylsulfonylureas are also understood to mean those sulfonylureas in which the heteroaryl group is bonded to the sulfone group (SO ₂ ) via a spacer such as CH ₂ , O or NH.

Suitable heteroarylsulfonamides are, for example, sulfonamides of the general formula (IV) and / or their salts,

R ^{α '} - (A') m ^' -SO ₂ -NR ^β' -CO- (NR ^γ ') n' - R ^δ> (IV) wherein R ° "is a heteroaryl radical which is unsubstituted or substituted, and wherein of the

Heteroaryl radical including substituents 1-30 C atoms, preferably 1-20 C

Atoms, ^{Rβ <is} a hydrogen atom or a hydrocarbon radical which is unsubstituted or substituted and having 1-10 carbon atoms including substituents, for example unsubstituted or substituted C 1 -C ₆ -alkyl, preferably one

Is hydrogen atom or methyl, R ^γ 'is a hydrogen atom or a hydrocarbon radical which is unsubstituted or substituted and including substituents has 1-10 carbon atoms includes, for example unsubstituted or substituted d-Ce-alkyl, preferably a

Is hydrogen or methyl, A 'is CH ₂ , O or NH, preferably O, m is zero or 1, n' is zero or 1, preferably 1, and R ^{δ <is} a heterocyclic radical such as a pyrimidinyl radical, a triazinyl radical or a triazolinone radical.

Preferred heteroarylsulfonamides are heteroarylsulfonylureas, for example sulfonylureas of the general formula (V) and / or salts thereof,

R ^{α '} - (AV-SO ₂ -NR ^β' -CO-NR ^γ> -R ^{δ '} (V) wherein R ⁰ "is a heteroaryl radical which is unsubstituted or substituted, and wherein the

Heteroaryl radical including substituents 1-30 C atoms, preferably 1-20 C

Atoms, ^Rβ 'is a hydrogen atom or a hydrocarbon radical which is unsubstituted or substituted and, including substituents 1-10 C-atoms, for example unsubstituted or substituted C ₁ -C ₆ -alkyl, preferably one

Is hydrogen atom or methyl, R ^{γ <is} a hydrogen atom or a hydrocarbon radical which is unsubstituted or substituted and has 1-10 C atoms inclusive of substituents, for example unsubstituted or substituted C 1 -C 6 -alkyl, preferably one

Is hydrogen or methyl, A 'is CH ₂ , O or NH, preferably O, m is zero or 1, and R ^{δ <is} a heterocyclic radical such as a pyrimidinyl radical or a triazinyl radical.

Particularly preferred are heteroarylsulfonamides of the following formula (VI),

R-SO ₂ - NH-CO- (NFOn ^{- Rδ <} (VI)

wherein

R ⁰ "is a substituted heteroaryl radical, such as substituted pyridyl, thienyl,

Pyrazolyl or imidazolyl, R ^γ 'H, (Ci-C ₃ ) alkyl, optionally substituted with halogen (F, C, Br, I) or

(Halo) alkoxy (C ₁ -C ₃ ), preferably H or methyl, for n 'is 1, R ^{δl is} a pyrimidinyl radical or a triazinyl radical, preferably

and for n 'is zero, R ^{δl is} a triazolinone ^radical , preferably

R ^{7 is} (Ci-C-ιo) alkyl which is optionally substituted by halogen (F, Cl, Br, I) or (CrC ₃ ) halo AIkVl,

R ⁸ (C ₁ -C 10) alkyl which is optionally substituted by halogen (F, Cl, Br, I) or (C ₁ -C ₃ ) haloalkyl,

X and Y independently of one another are identical or different halogen or NR'R ", in which R 'and R" are, identically or differently, H or C ₁ -C ₄ -alkyl, or C ₁ -C -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -alkylthio , C ₃ -C ₆ -cycloalkyl, C ₂ -C ₆ -alkenyl, C-2-C ₆ -alkynyl, C ₃ -CO-AI kenyloxy or C ₃ -Cβ-alkynyloxy, each of the eight latter radicals unsubstituted or by one or more radicals from the group halogen, -C ₄ -alkoxy and CrC ₄ - substituted alkylthio, C _r C preferably ₄ alkyl or -C ₄ alkoxy.

Particularly preferably, R ° "is the same

in which

R ⁹ (C ₁ -C ₆ ) AlKyl, (C ₁ -C ₆ ) alkoxy, (C ₂ -C ₆ ) alkenyloxy, (C ₂ -C ₆ ) alkynyloxy,

(CrC ₆₎ alkylsulfonyl, (C _{r C6)} alkylcarbonyl, (CrC ₆₎ alkoxycarbonyl, (C ₂ -C ₆₎ alkenyloxycarbonyl, (C ₂ -C ₆₎ alkynyloxycarbonyl, CONR ¹ R ", (CrC ₆₎ halo-alkyl , (C ₁ -C ₆₎ Haio -alkoxy, (C ₂ -C ₆₎ halo-alkenyloxy, (C ₂ -C ₆₎ alkynyloxy halo, (CrC ₆₎ halo alkylsulfonyl, (CrC ^ alkylcarbonyl halo, ( CrC ₆ ) halo-alkoxycarbonyl, (C ₂ -C ₆ ) halo-alkenyloxycarbonyl, (C ₂ -C ₆ ) haloalkynyloxycarbonyl,

R ¹⁰ is H, (C _r C ₃₎ alkyl, (C ₁ -C ₃₎ -alkoxy, (C _r C ₃₎ halo alkyl, (C ₁ -C ₃₎ -alkoxy or Haio

Halogen (F, Cl, Br, I),

I zero or 1,

R ¹¹ (C _r C ₆ ) alkyl, (C _r C ₆ ) alkoxy, (C ₂ -C ₆ ) alkenyloxy, (C ₂ -C ₆ ) alkynyloxy,

(Ci-C ₆ ) alkylsulfonyl, (CrC ₆ ) alkylcarbonyl, (C _r C ₆ ) alkoxycarbonyl, (C ₂ -C ₆ ) alkenyloxycarbonyl, (C ₂ -C ₆ ) alkynyloxycarbonyl, (CrCe) haloalkyl, (C ₁ -C ₆₎ Haio -alkoxy, (C ₂ -C ₆₎ halo-alkenyloxy, (C ₂ -C ₆₎ alkynyloxy halo, (C ₁ - C ₆₎ halo alkylsulfonyl, (CrCβJHalo alkylcarbonyl, (CrC ₆₎ Halo-alkoxycarbonyl, (C ₂ -C ₆ ) halo-alkenyloxycarbonyl, (C ₂ -C ₆ ) haloalkynyloxycarbonyl, CONR ¹ R ",

R ^{12 is} halogen (F, Cl, Br, I), (C _r C ₆ ) alkyl, (C ₁ -C ₆ ) alkoxy, (C ₁ -C ₆ ) alkylsulfonyl,

(CrC ₆₎ alkoxycarbonyl, (C ₂ -C ₆₎ alkenyloxycarbonyl, (C ₂ - C ₆₎ alkynyloxycarbonyl, (C _{r C6)} alkyl-halo, (C ₁ -C ₆₎ Haio -alkoxy, (C ₁ - C ₆ ) haloalkylsulfonyl, (C ₁ -C ₆ -alkoxycarbonyl, (C ₂ -C ₆ ) halo-alkenyloxycarbonyl, (C ₂ -C ₆ ) haloalkynyloxycarbonyl, R ¹³ (CrC ₆ ) alkoxycarbonyl, (C ₂ -C ₆ ) alkenyloxycarbonyl, (C ₂ -

C ₆₎ alkynyloxycarbonyl, (CrC ₆₎ alkyl, (CrC ₆₎ -alkoxy ₁ (Ci-C ₆₎ alkylsulfonyl, (CrCβJHalo alkoxycarbonyl, (C ₂ -C ₆₎ halo alkenyloxycarbonyl, (C ₂ - C ₆₎ halo alkynyloxycarbonyl, (C _r C ₆₎ halo-alkyl, (CrC ₆₎ Haio -alkoxy, (C _r Cβ) Halo-alkylsulfonyl, halo (F, Cl, Br, I), CONR ¹ R ", or R ¹³ is a heterocyclic ring which may be saturated, unsaturated or aromatic and preferably contains 4-6 ring atoms and one or more heteroatoms from the group N, O, S, and optionally by one or more substituents, preferably from the group (C-ι-C - ₃ ) alkyl, (Ci-Cs) Al koxy, (Ci-C3) halo-alkyl, (Ci-C ₃ ) halo-alkoxy or halogen may be substituted, particularly preferably

R ¹⁴ H, halogen (F, C, Br, I), (C _r C ₆ ) alkyl, (C _r C ₆ ) haloalkyl,

R ¹⁵ H, (C _r C ₆ ) alkyl, (C ₁ -C ₆ ) haloalkyl,

R ^{16 is} (C _r C ₆ ) alkyl, (C _r C ₆ ) alkoxy, (C ₂ -C ₆ ) alkenyloxy, (C ₂ -C ₆ ) alkynyloxy, (Cr

C ₆₎ alkylsulfonyl, (CrC ₆₎ alkylcarbonyl, (C _{r C6)} alkoxycarbonyl, (C ₂ - C ₆₎ alkenyloxycarbonyl, (C ₂ -C ₆₎ alkynyloxycarbonyl, (CiC ₆₎ halo-alkyl, (Cr C ₆₎ Haio -alkoxy, (C ₂ -C ₆₎ halo-alkenyloxy, (C ₂ -C ₆₎ alkynyloxy halo, (d- C ₆₎ halo alkylsulfonyl, (CrCeJHalo alkylcarbonyl, (CrC ₆₎ halo- alkoxycarbonyl, ( C ₂ -C ₆₎ halo alkenyloxycarbonyl, (C ₂ -C ₆₎ alkynyloxycarbonyl halo-, CONR'R ", in particular SO ₂ is ethyl, and

R 'and R "independently of one another are H, (C _r C ₆ ) alkyl, (C _r C ₆ ) haloalkyl, (C ₂ -C ₆ ) alkenyl, (C ₂ -C ₆ ) haloalkenyl, (C ₂ -C ₆ ) Alkynyl, (C ₂ -C ₆ ) haloalkynyl, or NR'R "forms a heterocyclic ring which may be saturated, unsaturated or aromatic and preferably contains 4-6 ring atoms and one or more heteroatoms from the group N, O, S. ₍₃ CrC) -alkoxy, be substituted Haio -alkoxy or halo (C ₁ -C ₃ C), and optionally alkyl substituted by one or more substituents, preferably from the group (Cr C ₃₎ (C _r C ₃₎ halo-alkyl, can. Particularly preferred heteroarylsulfonylureas are, for example, nicosulfuron and its salts, such as the sodium salt, rimsulfuron and its salts, such as the sodium salt, thifensulfuron-methyl and its salts, such as the sodium salt, pyrazosulfuron-ethyl and its salts, such as the sodium salt, flupyrsulfuron-methyl and its salts, such as the sodium salt , Sulfosulfuron and its salts such as the sodium salt, trifloxysulfuron and its salts such as the sodium salt, azimsulfuron and its salts such as the sodium salt, flazasulfuron and its salts such as the sodium salt and flucetosulfuron (1- [3 - [[[[(4,6-dimethoxy -2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] -2-pyridinyl] -2-fluoropropyl methoxyacetate) and its salts such as the sodium salt.

The active ingredients listed above are e.g. known from "The Pesticide Manual", 12th edition, The British Crop Protection Council (2000), or the references listed after the individual active ingredients.

For the purposes of the present invention, the sulfonamides (component a) present in the solid, water-dispersible formulations according to the invention are always understood to mean all forms of use such as acids, esters, salts and isomers, such as stereoisomers and optical isomers. Thus, besides the neutral compounds, their salts with inorganic and / or organic counterions are always to be understood. For example, sulfonamides can form salts in which the hydrogen of the -SO ₂ -NH group is replaced by a cation suitable for agriculture. These salts are, for example, metal salts, in particular alkali metal salts or alkaline earth metal salts, in particular sodium and potassium salts, or else ammonium salts or salts with organic amines. Likewise, salt formation can take place by addition of an acid to basic groups, such as, for example, amino and alkylamino. Suitable acids for this purpose are strong inorganic and organic acids, for example HCl, HBr, H ₂ SO ₄ or HNO ₃ . Preferred esters are the alkyl esters, especially the CiC-io-alkyl esters such as methyl esters. Insofar as the term acyl radical is used in the abovementioned description, this means the radical of an organic acid which is formed formally by elimination of an OH group from the organic acid, for example the radical of a carboxylic acid and radicals derived therefrom, such as the thiocarboxylic acid, optionally N -substituted iminocarboxylic acids or the radicals of carbonic acid monoesters, optionally N-substituted carbamic acids, sulfonic acids, sulfinic acids, phosphonic acids, phosphinic acids. An acyl radical is preferably formyl or acyl from the group CO-R ^Z, CS-R ^Z, CO-OR ^2, CS-OR ^2, CS-SR ^2, SOR ² or SO ₂ R ^2, wherein R ² are each a C ₁ -C ₁₀ - hydrocarbon radical such as C ₁ -C ₁₀ -alkyl or C ₆ -C ₁₀ -alkyl which is unsubstituted or substituted, for example by one or more substituents from the group halogen such as F, Cl, Br, I, alkoxy, Haloalkoxy, hydroxy, amino, nitro, cyano or alkylthio, or R ² means aminocarbonyl or aminosulfonyl, where the latter two radicals are unsubstituted, N-monosubstituted or N, N-disubstituted, for example by substituents from the group alkyl or aryl. Acyl is for example formyl, haloalkylcarbonyl, alkylcarbonyl such as _(Ci-C4) Al kylcarbonyl, phenylcarbonyl, where the phenyl ring may be substituted, or alkyloxycarbonyl, such as (C ₁ -C ₄₎ alkyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, alkylsulfonyl, such as (C ₁ -C ₄₎ alkylsulfonyl, alkylsulfinyl, such as C ₁ - C ₄ (alkylsulfinyl), N-alkyl-1-iminoalkyl, such as N- (C ₁ -C ₄₎ -1-imino- (C ₁ -C ₄₎ alkyl and other residues of organic acids.

A hydrocarbon radical means a straight, branched or cyclic and saturated or unsaturated aliphatic or aromatic hydrocarbon radical, e.g. Alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl or aryl. A hydrocarbon radical preferably has 1 to 40 C atoms, preferably 1 to 30 C atoms; particularly preferably a hydrocarbon radical is alkyl, alkenyl or alkynyl having up to 12 C atoms or cycloalkyl having 3, 4, 5, 6 or 7 ring atoms or phenyl.

Aryl means a mono-, bi- or polycyclic aromatic system, for example phenyl, naphthyl, tetrahydronaphthyl, indenyl, indanyl, pentalenyl, fluorenyl and the like, preferably phenyl. A heterocyclic radical or ring (heterocyclyl) can be saturated, unsaturated or heteroaromatic and unsubstituted or substituted; it preferably contains one or more heteroatoms in the ring, preferably from the group N, O and S; it is preferably an aliphatic heterocyclyl radical having 3 to 7 ring atoms or a heteroaromatic radical having 5 or 6 ring atoms and contains 1, 2 or 3 heteroatoms. The heterocyclic radical may be, for example, a heteroaromatic radical or ring (heteroaryl), for example a mono-, bi- or polycyclic aromatic system in which at least one ring contains one or more heteroatoms, for example pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, Thienyl, thiazolyl, oxazolyl, furyl, pyrrolyl, pyrazolyl and imidazolyl, or is a partially or fully hydrogenated radical such as oxiranyl, oxetanyl, pyrrolidyl, piperidyl, piperazinyl, triazolyl, dioxolanyl, morpholinyl, tetrahydrofuryl. Preference is given to pyrimidinyl and triazinyl. Suitable substituents for a substituted heterocyclic radical are the substituents mentioned below in question, in addition also oxo. The oxo group may also occur on the hetero ring atoms, which may exist in different oxidation states, eg at N and S. Substituted radicals, such as substituted hydrocarbon radicals, for example substituted alkyl, alkenyl, alkynyl, aryl, phenyl and benzyl, or substituted heterocyclyl or heteroaryl, represent, for example, a substituted radical derived from the unsubstituted radical, where the substituents are, for example, one or more, preferably 1, 2 or 3 3 radicals from the group halogen, alkoxy, haloalkoxy, alkylthio, hydroxy, amino, nitro, carboxy, cyano, azido, alkoxycarbonyl, alkylcarbonyl, formyl, carbamoyl, mono- and dialkylaminocarbonyl, substituted amino, such as acylamino, mono- and dialkylamino, and Alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl and, in the case of cyclic radicals, also alkyl and haloalkyl and said saturated hydrocarbon-containing radicals corresponding unsaturated aliphatic radicals, such as alkenyl, alkynyl, alkenyloxy, alkynyloxy, etc. For radicals with C atoms, those having 1 to 4 C atoms, in particular 1 or 2 C atoms, are preferred. As a rule, preference is given to substituents from the group halogen, for example fluorine and chlorine, preferably methyl or ethyl, (C 1 -C ₄ ) haloalkyl, preferably trifluoromethyl, (C 1 -C ₄ ) alkoxy, preferably methoxy or ethoxy, (C 1 -C ₄ ) haloalkoxy, nitro and cyano. Particularly preferred are the substituents methyl, methoxy and Chlorine.

Optionally substituted phenyl is preferably phenyl which is unsubstituted or mono- or polysubstituted, preferably up to trisubstituted, by identical or different radicals, preferably from the group comprising halogen, (C ₁ -C ₄₎ -alkyl, (CrC ₄₎ -alkoxy, (CrC ₄₎ Haloalkyl, (C 1 -C ₄ ) haloalkoxy and nitro, for example o-, m- and p-tolyl, dimethylphenyl, 2-, 3- and 4-chlorophenyl, 2-, 3- and 4-trifluoro and trichlorophenyl, 2 , 4-, 3,5-, 2,5- and 2,3-dichlorophenyl, o-, m- and p-methoxyphenyl.

Cycloalkyl means a carbocyclic, saturated ring system preferably having 3-6 C-atoms, eg cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. The carbon-containing radicals such as alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino and alkylthio and the corresponding unsaturated and / or substituted radicals in the carbon skeleton in each case be straight-chain or branched. Unless specifically stated, in these radicals, the lower carbon skeletons, for example having 1 to 6 carbon atoms or in unsaturated groups having 2 to 6 carbon atoms, are preferred. Alkyl radicals, including in the composite meanings such as alkoxy, haloalkyl, etc., mean, for example, methyl, ethyl, n- or i-propyl, n-, i-, t- or 2-butyl, pentyls, hexyls, such as n-hexyl, i -Hexyl and 1, 3-dimethylbutyl, heptyls such as n-heptyl, 1-methylhexyl and 1, 4-dimethylpentyl; Alkenyl and alkynyl radicals have the meaning of the possible unsaturated radicals corresponding to the alkyl radicals; Alkenyl is, for example, allyl, 1-methylprop-2-en-1-yl, 2-methyl-prop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl , 1-methyl-but-3-en-1-yl and 1-methyl-but-2-en-1-yl; Alkynyl means, for example, propargyl, but-2-yn-1-yl, but-3-yn-1-yl, 1-methylbut-3-yn-1-yl. Halogen is, for example, fluorine, chlorine, bromine or iodine. Haloalkyl, -alkenyl and -alkynyl by halogen, preferably by fluorine, chlorine and / or bromine, in particular by fluorine or chlorine, partially or completely substituted alkyl, alkenyl or alkynyl, for example CF ₃ , CHF ₂ , CH ₂ F, CF ₃ CF ₂ , CH ₂ FCHCl, CCI ₃ , CHCl ₂ , CH ₂ CH ₂ Cl; Haloalkoxy is, for example, OCF ₃ , OCHF ₂ , OCH ₂ F, CF ₃ CF ₂ O, OCH ₂ CF ₃ and OCH ₂ CH ₂ Cl; the same applies to haloalkenyl and other halogen-substituted radicals. Very particularly preferred of the active compounds from the group of sulfonamides and their salts (component a) are propoxycarbazones and their sodium salt (propoxycarbazone-methyl-sodium), methyl-4 - [(4,5-dihydro-3-methoxy-4-methyl -5- oxo-1H-1 ^^ -triazol-i-y-carboxamido-sulfonyl-δ-metylthiophene-S-carboxylate and its sodium salt, amidosulfuron and its sodium salt (amidosulfuron-methyl-sodium), iodosulfuron-methyl and its sodium salt (iodosulfuronyl) methylsodium), foramsulfuron and its sodium salt, thifensulfuron-methyl and its sodium salt, and mesosulfuron-methyl and its sodium salt.

The active compounds from the group of sulfonamides and their salts (component a) are in the formulations of the invention generally in amounts of 0.1 to 80 wt .-%, preferably 1-75 wt .-%, particularly preferably 3-50 wt. %, very particularly preferably 5-25% by weight, in this case the term "% by weight" (weight percent) here and in the entire description, unless otherwise defined, refers to the relative weight of the respective component the total weight of the formulation.

The active ingredients which may be present as component (b) and designated by the term "safener" are compounds which are suitable for reducing phytotoxic effects of crop protection active ingredients such as herbicides on crop plants.

The safeners (component b) are preferably selected from the group consisting of: a) compounds of the formulas (S-II) to (S-IV),

(S-II) (S-III) (S-IV) where the symbols and indices have the following meanings: n 'is a natural number from 0 to 5, preferably 0 to 3; T is a (C or C ^ -alkanediyl chain which is [C _{r 3)} alkoxy (C] carbonyl unsubstituted or substituted with one or two (CrC ₄₎ alkyl or;

W is an unsubstituted or substituted divalent heterocyclic radical from the group of unsaturated or unsaturated five-membered ring heterocycles having 1 to 3 hetero ring N or O atoms, at least one N atom and at most one O atom in the ring, preferably a radical from the group (W 1) to (W4),

m 'is 0 or 1;

R ¹⁷ , R ¹⁹ are the same or different halogen,

(C _r C ₄ ) alkyl, (C ₁ -C ₄ ) alkoxy, nitro or (C _r C ₄ ) haloalkyl;

R ¹⁸ , R ²⁰ are identical or different OR ²⁴ , SR ²⁴ or NR ²⁴ R ²⁵ or a saturated or unsaturated 3- to 7-membered heterocycle having at least one N atom and up to 3 heteroatoms, preferably from the group O and S. , which is connected via the N-atom with the carbonyl group in (S-II) or (S-III) and unsubstituted or by radicals from the group (C-ι-C ₄ ) alkyl, (Ci-C ₄ ) alkoxy or optionally substituted phenyl, preferably a radical of the formula OR ²⁴ , NHR ²⁵ or N (CHs) ₂ , in particular of the formula OR ²⁴ ;

R ²⁴ is hydrogen or an unsubstituted or substituted aliphatic hydrocarbon radical, preferably having a total of 1 to 18 C atoms; R ²⁵ is hydrogen, (C ₁ -C ₆ ) alkyl, (C ₁ -C ₆ ) Al koxy or substituted or unsubstituted phenyl;

R ^x is H ₁ (C ₁ -C ₈ ) alkyl, C _r C ₈ (haloalkyl), (C ₁ -C 4) alkoxy (C ₁ -C ₈ ) alkyl, cyano or COOR ²⁶ , wherein R ^{26 is} hydrogen, (C _r C ₈₎ alkyl, (C _r C ₈₎ haloalkyl, (C ₁ -C ₄₎ AIkOXy- (Ci-C ₄₎ alkyl, (C _{r C6)} hydroxyalkyl, _(C3-Ci2) -cycloalkyl or tri- ( CrC ₄ ) -alkyl-silyl;

R ²⁷ , R ²⁸ , R ²⁹ are identical or different hydrogen, (C 1 -C ₈ ) alkyl,

(Ci-C ₈₎ haloalkyl, (C ₃ -C ₂₎ cycloalkyl or substituted or unsubstituted phenyl;

R ²¹ is (C _{r C4)} alkyl, (Ci-C ₄₎ HaIOaIkVl ₁ (C ₂ -C ₄₎ alkenyl, (C ₂ -C ₄₎ haloalkenyl, (C ₃ -C ₇₎ cycloalkyl, preferably dichloromethyl;

R ²² , R ²³ is identical or different hydrogen, (C _r C ₄ ) alkyl, (C ₂ -C ₄ ) alkenyl,

(C ₂ -C ₄₎ alkynyl, (CrC ₄₎ haloalkyl, (C ₂ -C ₄₎ haloalkenyl, (CrC ₄₎ alkylcarbamoyl (CrC ₄₎ alkyl, (C ₂ -C ₄₎ Alkenylcarbamoyl- (C _r C ₄ alkyl), (CrC ₄₎ alkoxy (CrC ₄₎ alkyl, dioxolanyl (CrC ₄₎ alkyl, thiazolyl, furyl, furylalkyl, thienyl, piperidyl, substituted or unsubstituted phenyl, or R ²² and R ²³ together form a substituted or unsubstituted heterocyclic ring, preferably an oxazolidine, thiazolidine, piperidine, morpholine, hexahydropyrimidine or benzoxazine ring; preferably safeners of the following subgroups of compounds of the formulas (S-II) to (S-IV):

Compounds of the type of the dichlorophenylpyrazoline-3-carboxylic acid (ie of the formula (S-II) in which W = (W1) and (R ¹⁷ V = 2,4-Cl ₂ ), preferably compounds such as 1- (2,4-Cl ₂ ) Dichlorophenyl) -5- (ethoxycarbonyl) -5-methyl-2-pyrazoline-3-carboxylic acid ethyl ester (11-1, mefenpyr-diethyl), mefenpyr-dimethyl and mefenpyr (HO), and related compounds as described in WO-A -91 / 07874 are described;

Derivatives of dichlorophenylpyrazolecarboxylic acid (ie of formula (S-II) wherein W = (W ₂ ) and (R ¹⁷ ) n = 2,4-Cl ₂ ), preferably compounds such as 1- (2,4-dichlorophenyl) - Ethyl 5-methyl-pyrazole-3-carboxylate (II-2), 1- (2,4-dichloro-phenyl) -5-isopropyl-pyrazole-3-carboxylate (II-3), 1- (2,4-dichlorophenyl) - 5- (1, 1-dimethyl-ethyl) -pyrazole-3-carboxylic acid ethyl ester (II-4), 1- (2,4-dichlorophenyl) -5-phenyl-pyrazole-3-carboxylic acid ethyl ester (11-5) and related compounds as described in EP-A-0333131 and EP-A-0269806;

Compounds of the triazolecarboxylic acid type (ie of the formula (S-Il) where W = (W3) and (R ¹⁷ J _n ¹ = 2,4-Cl _2), preferably compounds such as ethyl Fenchlorazol-, ie 1- (2 , 4-dichlorophenyl) -5-trichloromethyl- (1 H) -1, 2,4-triazole-3-carboxylic acid ethyl ester (II-6), and related compounds (see EP-A-0174562 and EP-A-0346620);

Compounds of the 5-benzyl or 5-phenyl-2-isoxazoline-3-carboxylic acid type or of the 5,5-diphenyl-2-isoxazoline-3-carboxylic acid, such as isoxadifen (11-12), (wherein W = (W4) preferably, compounds such as ethyl 5- (2,4-dichlorobenzyl) -2-isoxazoline-3-carboxylate (II-7) or 5-phenyl-2-isoxazoline-3-carboxylate (MS) and related compounds as described in U.S. Pat WO-A-91/08202 or the ethyl 5,5-diphenyl-2-isoxazolinecarboxylate (II-9, isoxadifen-ethyl) or n-propyl ester (11-10) or 5- (4-fluorophenyl ) -5-phenyl-2-isoxazoline-3-carboxylic acid ethyl ester (11-11), as described in WO-A-95/07897.

Compounds of the 8-quinolinoxyacetic acid type, for example those of the formula (S-III) in which (R ¹⁹ ) _n '= 5-Cl, R ²⁰ = OR ²⁴ and T = CH ₂ , preferably

Compounds (5-chloro-8-quinolinoxy) acetic acid (1-methylhexyl) ester (111-1, cloquintocet-mexyl), (5-chloro-8-quinolinoxy) acetic acid (1, 3-dimethyl-but-1 -yl) ester (III-2), (5-chloro-8-quinolinoxy) acetic acid 4-allyl oxy-butyl ester (III-3), (5-chloro-8-quinolinoxy) acetic acid 1-allyloxy prop-2-yl-ester (III-4), (5-chloro-8-quinolinoxy) acetic acid ethyl ester (III-5), (5-chloro-8-quinolinoxy) acetic acid methyl ester (III-6), (5-chloro-8- quinolinoxy) allyl acetate (III-7), (5-chloro-8-quinolinoxy) acetic acid 2- (2-propylidene-iminoxy) -1-ethyl ester (III-8), (5-chloro-8-quinolinoxy) acetic acid 2-oxo-prop-1-yl-ester (III-9), (5-chloro-8-quinolinoxy) acetic acid (III-10) and its salts as described, for example, in WO-A-02/34048 and related Compounds as described in EP-A-0860750, EP-A-0094349 and EP-A-0191736 or EP-A-0492366. - Compounds of the type of (5-chloro-8-quinolinoxy) -malonic acid, ie of the formula (S-III), wherein (R ¹⁹ ) _n ^< = 5-Cl ₁ R ²⁰ = OR ²⁴ , T = -CH (COO -Alkyl) - is, preferably the

Compounds (5-chloro-8-quinolinoxy) -malonic acid diethyl ester (111-11), (5-chloro-8-quinolinoxy) -malonic acid diallyl ester, (5-chloro-8-quinolinoxy) -malonic acid methyl ethyl ester and related compounds as described in EP-A-0582198.

- Dichloroacetamide type compounds, i. of the formula (S-IV), preferably: N, N-diallyl-2,2-dichloroacetamide (dichloromide (IV-1), from US 4,137,070), 4-dichloroacetyl-3,4-dihydro-3-methyl-2H- 1, 4-benzoxazine (IV-2, Benoxacor, from EP 0149974), N1, N2-diallyl-N2-dichloroacetylglycine amide (DKA-24 (IV-3), from HU 2143821), 4-dichloroacetyl-1-oxa-4 α-spiro [4,5] decane (AD-67), 2,2-dichloro-N- (1, 3-dioxolan-2-ylmethyl) -N- (2-propenyl) acetamide (PPG-1292), 3-dichloroacetyl-2,2,5-trimethyloxazolidine (R-29148, IV-4), 3-dichloroacetyl-2,2-dimethyl-5-phenyloxazolidine, 3-dichloroacetyl-2,2-dimethyl-5- (2-methyl) thienyl) oxazolidine, 3-dichloroacetyl-5- (2-furanyl) -2,2-dimethyloxazolidine (furilazole (IV-5), MON

13900), 1-dichloroacetyl-hexahydro-3,3,8a-trimethylpyrrolo [1,2-a] pyrimidin-6 (2H) -one (dicyclonone, BAS 145138),

b) one or more compounds from group:

1,8-naphthalic anhydride, methyl-diphenylmethoxyacetate, 1- (2-chlorobenzyl) -3- (1-methyl-1-phenylethyl) -urea (cumyluron), O, O-diethyl S-2-ethylthioethyl phosphorodithioate (disulfonyl), 4 -chlorophenyl-methylcarbamate (Mephenate), O ₁ O- diethyl-O-phenylphosphorotioat (Dietholate), 4-carboxy-3,4-dihydro-2H-1 - benzopyran-4-acetic acid (CL-304415, CAS Regno: 31541 -57-8), cyanomethoxyimino (phenyl) acetonitrile (Cyometrinil), 1, 3-dioxolan-2-ylmethoxyimino (phenyl) acetonitrile (oxabetrinil), 4'-chloro-2,2,2-trifluoroacetophenone O-1, 3 dioxolan-2-ylmethyloxime (Fluxofenim), 4,6-dichloro-2-phenylpyrimidine (fenclorim), benzyl 2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate (flurazole), 2-dichloromethyl- 2-methyl-1,3-dioxolane (MG-191), N- (4-methylphenyl) -N '- (1-methyl-1-phenylethyl) urea (Dymron), (2,4-dichlorophenoxy) acetic acid (2 , 4-D), (4-chlorophenoxy) acetic acid, (R, S) -2- (4-chloro-o-tolyloxy) propionic acid (mecoprop), 4- (2,4-dichlorophenoxy) butyric acid (2,4- DB), (4-chloro-o-tolyloxy) acetic acid acid (MCPA), 4- (4-chloro-o-tolyloxy) butyric acid, 4- (4-chlorophenoxy) butyric acid, 3,6-dichloro-2-methoxybenzoic acid (Dicamba), 1- (ethoxycarbonyl) ethyl 3,6-dichloro-2-methoxybenzoate (lactidichloro ) and their salts and esters, preferably (d-Cβ);

c) N-acylsulfonamides of the formula (S-V) and their salts,

wherein

R ^{30 is} hydrogen, a hydrocarbon radical, a hydrocarbonoxy radical, a hydrocarbylthio radical or a heterocyclyl radical which is preferably bonded via a carbon atom, where each of the last-mentioned 4 radicals is unsubstituted or substituted by one or more identical or different radicals from the group halogen, cyano, nitro , Amino, hydroxy, carboxy, formyl, carbonamide, sulfonamide and radicals of the formula -Z ^a -R ^{a is} substituted, wherein each hydrocarbon moiety preferably 1 to 20 carbon atoms and a C-containing radical R ³⁰ including substituents preferably 1 to 30 Having C atoms;

R ^{31 is} hydrogen or (C 1 -C ₄ ) -alkyl, preferably hydrogen, or

R ³⁰ and R ³¹ together with the group of the formula -CO-N- denote the radical of a 3- to 8-membered saturated or unsaturated ring;

R 32 is identical or different and is halogen, cyano, nitro, amino, hydroxyl, carboxy, formyl, CONH ₂ , SO ₂ NH ₂ or a radical of the formula -Z ^b -R ^b ; i33 is hydrogen or (C 1 -C ₄ ) -alkyl, preferably H;

R 34 is identical or different and is halogen, cyano, nitro, amino, hydroxyl, carboxy, CHO, CONH ₂ , SO ₂ NH ₂ or a radical of the formula -Z ^c -R ^c ; R ^{a is} a hydrocarbon radical or a heterocyclyl radical, where each of the latter two radicals is unsubstituted or substituted by one or more identical or different radicals from the group halogen, cyano, nitro, amino, hydroxyl, mono- and di- [(C 1 -C ₄ ) -alkyl] -amino, or an alkyl radical in which several, preferably 2 or 3, non-adjacent CH ₂ groups are each replaced by an oxygen atom;

R ^b , R ^c, identically or differently, are a hydrocarbon radical or a

Heterocyclylrest, wherein each of the last two radicals unsubstituted or by one or more identical or different radicals selected from the group halogen, cyano, nitro, amino, hydroxy, phosphoryl, halogeno (C 1 -C-O-alkoxy, mono- and di- [(Ci C ₄ ) -alkyl] -amino, or an alkyl radical in which several, preferably 2 or 3, non-adjacent CH ₂ groups are each replaced by an oxygen atom;

Z ^{a is} a divalent group of the formula -O-, -S-, -CO-, -CS-, -CO-O-, -CO-S-,

-O-CO-, -S-CO-, -SO-, -SO ₂ -, -NR * -, -CO-NR ^* -, -NR ^* -CO-, -SO ₂ -NR ^* - or - NR * -SO ₂ -, where the bond of the respective divalent group indicated on the right is the bond to the radical R ^a and where the R * in the last-mentioned 5 radicals are each independently H, (C 1 -C ₄ ) -alkyl or halo (C 1 -C ₄ ) - alkyl;

Z ^b , Z ^c independently of one another a direct bond or a divalent group of the formula -O-, -S-, -CO-, -CS-, -CO-O-, -CO-S-, -O-CO-, -S-CO-, -SO-, -SO ₂ -, -NR * -, -SO ₂ -NR * -, -NR * -SO ₂ -, -CO-NR * - or -NR * -CO-, where the bond of the respective divalent group indicated on the right is the bond to the radical R ^b or R ^c and wherein the R * in the last-mentioned 5 radicals are each independently H, (C 1 -C ₄ ) -alkyl or halo- (C 1 -C ₄ ) -alkyl mean; n is an integer from 0 to 4, preferably 0, 1 or 2, in particular O or 1, and m is an integer from 0 to 5, preferably 0, 1, 2 or 3, in particular 0, 1 or 2; mean; preferably safeners of compounds of formula (SV) wherein

R ³⁰ = H ₃ CO-CH ₂ -, R ³¹ = R ³³ = H, R ³⁴ = 2-Ome is (V-1), R ³⁰ = H ₃ CO-CH ₂ -, R ³¹ = R ³³ = H, R ³⁴ = 2-Ome-5-CI is (V-2),

R ³⁰ = cyclopropyl, R ³¹ = R ³³ = H, R ³⁴ = 2-Ome is (V-3),

R ³⁰ = cyclopropyl, R ³¹ = R ³³ = H, R ³⁴ = 2-Ome-5-CI is (V-4),

R ³⁰ = cyclopropyl, R ³¹ = R ³³ = H, R ³⁴ = 2-Me is (V-5),

R ³⁰ = tert. Butyl, ^R31 = ^R33 = H, ^R34 = 2-Ome is (V-6).

d) Acylsulfamoylbenzoesäureamide of the general formula (S-Vl), optionally in salt form,

wherein

X ^{3 is} CH or N;

R ^{35 is} hydrogen, heterocyclyl or a hydrocarbon radical, where the latter two radicals are optionally substituted by one or more, identical or different radicals from the group halogen, cyano, nitro, amino, hydroxy, carboxy, CHO, CONH ₂ , SO ₂ NH ₂ and Z ^a -R ^{a are} substituted;

R ³⁶ is hydrogen, hydroxy, (dC ₆₎ alkyl, (C ₂ -C ₆₎ -alkenyl, _(C2 -Ce) -Al kinyl, (C ₁ -C ₆₎ - alkoxy, (C ₂ -C ₆₎ alkenyloxy, wherein the five last-mentioned radicals optionally substituted by one or more identical or different radicals from the group halogen, hydroxy, (CICO-alkyl, (CrC ₄₎ -alkoxy and (C ₁ -C ₄₎ - substituted alkylthio, or

R ³⁵ and R ³⁶ together with the nitrogen atom carrying them have a 3- to 8-membered saturated or unsaturated ring;

R ^{37 is} halogen, cyano, nitro, amino, hydroxy, carboxy, CHO, CONH ₂ , SO ₂ NH ₂ or Z ^b -R ^b ;

R ³⁸ is hydrogen, (C _{r C4)} alkyl, (C ₂ -C ₄₎ -alkenyl or (C ₂ -C ₄₎ alkynyl;

R ^{39 is} halogen, cyano, nitro, amino, hydroxy, carboxy, phosphoryl, CHO, CONH ₂ , SO ₂ NH ₂ or Z ^c -R ^c ;

R ^{a is} a (C ₂ -C ₂ 0) -alkyl radical whose carbon chain is mono- or polysubstituted Oxygen atoms is interrupted, heterocyclyl or a hydrocarbon radical, where the last two radicals optionally substituted by one or more identical or different radicals from the group halogen, cyano, nitro, amino, hydroxyl, mono- and di - [(C-ι-C ₄ ) alkyl] amino;

R ^b, R ^{c are} identical or different and are a (C ₂ -C ₂ o) -alkyl radical whose carbon chain one or more times interrupted by oxygen atoms, is heterocyclyl or a hydrocarbon radical, where the last two radicals, the same or optionally substituted by one or more different Radicals from the group halogen, cyano, nitro, amino, hydroxy, phosphoryl, (CrC ₄ ) - haloalkoxy, mono- and di - [(C 1 -C ₄ ) -alkyl] -amino are substituted;

Z ^{a is} a divalent unit selected from O, S, CO, CS, C (O) O, C (O) S, SO, SO ₂ , NR ^d , C (O) NR ^d or SO ₂ NR ^d ;

Z ^b , Z ^{c are,} identically or differently, a direct bond or a divalent unit from the group O, S, CO, CS, C (O) O ₁ C (O) S, SO, SO ₂ , NR ^d , SO ₂ NR ^d or C (O) NR ^d ;

R ^{d is} hydrogen, (C _r C ₄ ) alkyl or (dC ₄ ) haloalkyl; n is an integer from 0 to 4, and in the case that X is CH, an integer from 0 to 5, and in the case where X is N, an integer from 0 to 4; preferably safeners of compounds of the formula (S-VI), in which

X ³ is CH;

R ³⁵ is hydrogen, (C _{r C6)} alkyl, (C ₃ -C ₆₎ -cycloalkyl, (C ₂ -C ₆₎ alkenyl, (C ₅ -C ₆₎ - cycloalkenyl, phenyl or 3- to 6 hetero-cyclic heterocyclyl having up to three heteroatoms from the group consisting of nitrogen, oxygen and sulfur, wherein the six last-mentioned radicals are optionally substituted by one or more identical or different substituents selected from the group consisting of halogen, (C ₁ -C ₆ ) -alkoxy, (C _r C ₆₎ -haloalkoxy, (C _r C ₂₎ alkylsulfinyl, _(Ci-C2) alkylsulfonyl, (C ₃ -C ₆₎ -cycloalkyl, (dC ₄₎ alkoxycarbonyl, (C _r C ₄₎ -alkylcarbonyl and phenyl and in the case of cyclic radicals also (C 1 -C ₄ ) -alkyl and (C 1 -C ₄ ) -haloalkyl are substituted; R ^{36 is} hydrogen, (C _r C ₆ ) -alkyl, (C ₂ -C ₆ ) -alkenyl, (C ₂ -C ₆ ) -alkynyl, where the last three radicals mentioned are optionally substituted by one or more, identical or different substituents from the group halogen, hydroxy, (C ₁ -C ₄₎ - alkyl, (C ₁ -C ₄ ^ -alkoxy and (CrC ₄₎ -alkylthio;

R ³⁷ is halogen, (C _{r C4)} -haloalkyl, (C _r C ₄₎ -haloalkoxy, nitro, (CrC ₄₎ alkyl, (C ₁ -C ₄₎ - alkoxy, (CrC ₄₎ alkylsulfonyl, (CrC ₄ ) alkoxycarbonyl or (C ₁ -C ₄ ) alkylcarbonyl;

R ^{38 is} hydrogen;

R ³⁹ is halogen, nitro, (Ci-C ₄₎ alkyl, (C ₁ -C ₄₎ -haloalkyl, (CrC ₄₎ -haloalkoxy, (C ₃ -C ₆₎ -

Cycloalkyl, phenyl, (CrC ₄₎ -alkoxy, cyano, (Ci-C ₄₎ alkylthio, (C ₁ -C ₄₎ - alkylsulfinyl, (CrC ₄₎ alkylsulfonyl, (C _{r C4)} -alkoxycarbonyl or (C ₁ -C ₄ ) - alkylcarbonyl; n is 0, 1 or 2 and m is 1 or 2.

In particular, compounds of the acylsulfamoylbenzoic acid amide type represented by the following formula (S-VII), e.g. are known from WO-A-99/16744,

wherein R ²¹ = cyclopropyl and R ²² = H (S3-1 =

4-cyclopropylaminocarbonyl-N- (2-methoxybenzoyl) benzenesulfonamide,

Cyprosulfamide)

R ²¹ = cyclopropyl and R ²² = 5-CI is (S3-2), R ²¹ = ethyl and R ²² = H is (S3-3), R ²¹ = iso-propyl and R ²² = 5-CI (S3-4) and R ²¹ = ISSO-propyl and R ²² = H (S3-5 =

4-ISSO-propylaminocarbonyl-N- (2-methoxybenzoyl) benzenesulfonamide); e) compounds of the type of the N-acylsulfamoylphenylureas of the formula (S-VIII) ₁ which are known, for example, from EP-A-365484,

wherein

A for a rest of the group

R ^α and R ^ß independently hydrogen, Ci-Cβ alkyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ alkynyl,

or by C ₁ -C ₄ -alkoxy or

substituted C ₁ -C ₄ -alkoxy, or

R ^α and R ^ß together are a C ₄ -C ₆ alkylene or by oxygen, sulfur, SO, SO _2, NH or -N (C _r C ₄ alkyl) - interrupted C ₄ -C ₆ - alkylene bridge,

R ^{γ is} hydrogen or C 1 -C ₄ -alkyl,

R ^a and R ^b independently of one another represent hydrogen, halogen, cyano, nitro,

Trifluoromethyl, C ₁ -C ₄ -AIk ^, C _r C ₄ alkoxy, -C ₄ alkylthio, C _r C ₄ alkylsulfinyl, C _r C ₄ alkylsulfonyl, -COOR ^J , -CONR ^k R ^m , -COR ", -SO ₂ NR ^k R ^m or -OSO ₂ -C ₁ - C ₄ alkyl, or R ^a and R ^b together for a C ₃ -C ₄ alkylene bridge which may be substituted by halogen or CrC ₄ alkyl or C ₃ -C ₄ - Alkenylenbrϋcke, which may be substituted by halogen or -C ₄ alkyl, or a C ₄ -alkadienylene bridge, which may be substituted by halogen or C 1 -C ₄ -alkyl, and

R ⁹ and R ^h independently of one another are hydrogen, halogen, C 1 -C ₄ -alkyl, trifluoromethyl, methoxy, methylthio or -COOR ^j , where

R ^{c is} hydrogen, halogen, ^C 1 -C ₄ -alkyl or methoxy,

R ^d is hydrogen, halogen, nitro, -C ₄ alkyl, Ci-C ₄ alkoxy, -C ₄ alkylthio, C ₁ - C ₄ alkylsulfinyl, C _r C ₄ alkylsulfonyl, -COOR ^j or -CONR ^k R ^m,

R ^e is hydrogen, halogen, CrC ^d ₄ alkyl, -COOR ^j, trifluoromethyl or methoxy, or R and R ^e together represent a C ₃ -C ₄ alkylene bridge,

R ^{f is} hydrogen, halogen or C 1 -C ₄ -alkyl,

R ^x and R ^γ independently represent hydrogen, halogen, Ci-C ₄ alkyl, C ₁ -C ₄ - alkoxy, C _r C ₄ alkylthio, -COOR ^4, trifluoromethyl, nitro or cyano,

R ^j , R ^k and R ^m independently of one another denote hydrogen or C ₁ -C ₄ -alkyl,

R ^k and R ^m together represent a C-rCβ-alkylene bridge or a C ₄ -C ₆ -alkylene bridge interrupted by oxygen, NH or -N (C ₁ -C ₄ -alkyl) -, and

R ^{n is} C 1 -C ₄ alkyl, phenyl or phenyl substituted by halogen, C 1 -C ₄ alkyl, methoxy, nitro or trifluoromethyl; preferably safeners of the formula (S-VIII)

1- [4- (N-2-methoxybenzoylsulfamoyl) phenyl] -3-methylurea, 1- [4- (N-2-methoxybenzoylsulfamoyl) phenyl] -3,3-dimethylurea, 1- [4- (N-4, 5-dimethylbenzoylsulfamoyl) phenyl] -3-methylurea, 1- [4- (N-naphthoylsulfamoyl) phenyl] -3,3-dimethylurea, including stereoisomers and those commonly used in agriculture

Salts.

Unless otherwise defined in detail, the following definitions generally apply to the radicals in the formulas (S-II) to (S-VIII). The radicals alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino and alkylthio and the corresponding unsaturated and / or substituted radicals can each be straight-chain or branched in the carbon skeleton. Alkyl radicals, even in the composite meanings such as alkoxy, haloalkyl, etc., preferably have 1 to 4 carbon atoms and, for example, methyl, ethyl, n- or i-propyl, n-, i-, t- or 2-butyl. Alkenyl and alkynyl radicals have the meaning of the possible unsaturated radicals corresponding to the alkyl radicals; Alkenyl is for example AlII, 1-methylprop-2-en-1-yl, 2-methyl-prop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl , 1-methyl-but-3-en-1-yl and 1-methyl-but-2-en-1-yl. Alkynyl means, for example, propargyl, but-2-yn-1-yl, but-3-yn-1-yl, 1-methylbut-3-yn-1-yl. "(C 1 -C ₄ ) -alkyl" is the short notation for alkyl having 1 to 4 carbon atoms; the same applies to other general remainder definitions with bracketed ranges for the possible number of C atoms.

Cycloalkyl is preferably a cyclic alkyl radical having 3 to 8, preferably 3 to 7, particularly preferably 3 to 6, C atoms, for example cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Cycloalkenyl and cycloalkynyl refer to corresponding unsaturated compounds.

Halogen is fluorine, chlorine, bromine or iodine. Haloalkyl, haloalkenyl and haloalkynyl by halogen, preferably by fluorine, chlorine and / or bromine, in particular by fluorine or chlorine, partially or completely substituted alkyl, alkenyl or alkynyl, for example CF ₃ , CHF ₂ , CH ₂ F, CF ₂ CF ₃ , CH ₂ CHFCl, CCI ₃ , CHCl ₂ , CH ₂ CH ₂ Cl. Haloalkoxy is eg OCF ₃ , OCHF ₂ , OCH ₂ F, OCF ₂ CF ₃ , OCH ₂ CF ₃ and OCH ₂ CH ₂ Cl. The same applies to other halogen-substituted radicals. A hydrocarbon radical can be an aromatic or an aliphatic hydrocarbon radical, where an aliphatic hydrocarbon radical is generally a straight-chain or branched saturated or unsaturated hydrocarbon radical, preferably having 1 to 18, particularly preferably 1 to 12, carbon atoms, for example alkyl, alkenyl or alkynyl.

Preferably, aliphatic hydrocarbon radical alkyl, alkenyl or alkynyl having up to 12 carbon atoms; the same applies to an aliphatic hydrocarbon radical in a Kohlenwasserstoffoxyrest. Aryl is generally a mono-, bi- or polycyclic aromatic system with preferably 6-20 C-atoms, preferably 6 to 14 C-atoms, more preferably 6 to 10 C-atoms, eg phenyl, naphthyl, tetrahydronaphthyl, indenyl, indanyl, pentalenyl and fluorenyl, more preferably phenyl.

Heterocyclic ring, heterocyclic radical or heterocyclyl means a mono-, bi- or polycyclic ring system which is saturated, unsaturated and / or aromatic and contains one or more, preferably 1 to 4, heteroatoms, preferably from the group N, S and O. ,

Preferred are saturated heterocycles having 3 to 7 ring atoms and one or two heteroatoms from the group N, O and S, wherein the chalcogens are not adjacent. Particularly preferred are monocyclic rings having 3 to 7 ring atoms and a heteroatom from the group N, O and S, and morpholine, dioxolane, piperazine, imidazoline and oxazolidine. Very particularly preferred saturated heterocycles are oxirane, pyrrolidone, morpholine and tetrahydrofuran. Also preferred are partially unsaturated heterocycles having 5 to 7 ring atoms and one or two heteroatoms from the group N, O and S. Particularly preferred are partially unsaturated heterocycles having 5 to 6 ring atoms and one heteroatom from the group N, O and S. Very particular preferred partially unsaturated heterocycles are pyrazoline, imidazoline and isoxazoline. Also preferred is heteroaryl, for example mono- or bicyclic aromatic heterocycles having 5 to 6 ring atoms containing one to four heteroatoms from the group N, O, S, wherein the chalcogens are not adjacent. Particularly preferred are monocyclic aromatic heterocycles having 5 to 6 ring atoms which contain a heteroatom from the group, N, O and S, and pyrimidine, pyrazine, pyridazine, oxazole, thiazole, thiadiazole, oxadiazole, pyrazole, triazole and isoxazole. Very particular preference is given to pyrazole, thiazole, triazole and furan. Substituted radicals, such as substituted hydrocarbon radicals, for example substituted alkyl, alkenyl, alkynyl, aryl, such as phenyl and arylalkyl, such as benzyl, or substituted heterocyclyl, represent a substituted radical derived from the unsubstituted radical, where the substituents are preferably one or more, preferably 1, 2 or 3 , in the case of Cl and F also up to the maximum possible number, substituents from the group halogen, alkoxy, haloalkoxy, alkylthio, hydroxy, amino, nitro, carboxy, cyano, azido, alkoxycarbonyl, alkylcarbonyl, Formyl, carbamoyl, mono- and dialkylaminocarbonyl, substituted amino such as acylamino, mono- and dialkylamino and alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl and, in the case of cyclic radicals, also alkyl and haloalkyl and the said saturated hydrocarbon-containing substituents corresponding unsaturated aliphatic substituents, preferably alkenyl , Alkynyl, alkenyloxy, alkynyloxy. For radicals with C atoms, those having 1 to 4 C atoms, in particular 1 or 2 C atoms, are preferred. As a rule, preferred substituents are selected from the group halogen, for example fluorine or chlorine, (Ci-C ₄₎ alkyl, preferably methyl or ethyl, (CrC ^ haloalkyl, preferably trifluoromethyl, (CrC ₄₎ -alkoxy, preferably methoxy or ethoxy, (CrC ₄ ) Haloalkyl, nitro and cyano, particular preference being given to the substituents methyl, methoxy and chlorine.

Mono- or disubstituted amino means a chemically stable radical from the group of substituted amino radicals which are N-substituted by, for example, one or two identical or different radicals from the group consisting of alkyl, alkoxy, acyl and aryl; preferably monoalkylamino, dialkylamino, acylamino, arylamino, N-alkyl-N-arylamino and N-heterocycles. In this case, alkyl radicals having 1 to 4 carbon atoms are preferred. Aryl is preferably phenyl. Substituted aryl is preferably substituted phenyl. For acyl, the definition given below applies, preferably (C 1 -C ₄ ) alkanoyl. The same applies to substituted hydroxylamino or hydrazino.

Optionally substituted phenyl is preferably phenyl which is unsubstituted or mono- or polysubstituted, preferably up to three times, in halogens such as Cl and F also up to five times, by identical or different radicals from the group halogen, (C _r C ₄ ) alkyl, ( C _r C ₄ ) alkoxy, (CrC ₄ ) haloalkyl, (CrC ₄ ) haloalkoxy and nitro, for example o-, m- and p-tolyl, dimethylphenyls, 2-, 3- and 4-chlorophenyl, 2-, 3 and 4-trifluoro and trichlorophenyl, 2,4-, 3,5-, 2,5- and 2,3-dichlorophenyl, o-, m- and p-methoxyphenyl.

An acyl radical means the radical of an organic acid having preferably up to 6 C atoms, for example the radical of a carboxylic acid and radicals derived therefrom, such as the thiocarboxylic acid, optionally N-substituted iminocarboxylic acids, or the radical of carbonic acid monoesters, optionally N-substituted Carbamic acids, sulfonic acids, sulfinic acids, phosphonic acids, phosphinic acids. Acyl is, for example, formyl, alkylcarbonyl, such as (C 1 -C ₄ -alkyl) carbonyl, phenylcarbonyl, where the phenyl ring may be substituted, for example as indicated above for phenyl, or alkyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, alkylsulfonyl, alkylsulfinyl or N-alkyl- 1-iminoalkyl.

Also encompassed by the formulas (S-II) to (S-VIII) are all stereoisomers which have the same topological linkage of the atoms, and mixtures thereof. Such compounds contain one or more asymmetric C atoms or double bonds, which are not specified separately in the general formulas. The possible defined by their specific spatial form possible stereoisomers, such as enantiomers, diastereomers, Z and E isomers can be obtained by conventional methods from mixtures of stereoisomers or prepared by stereoselective reactions in combination with the use of stereochemically pure starting materials.

The compounds of the formula (S-II) are described, for example, in EP-A-0333131 (ZA-89/1960), EP-A-0269806 (US 4,891,057), EP-A-0346620 (AU-A-89/34951 ), EP-A-0174562, EP-A-0346620 (WO-A-91/08202), WO-A-91/07874 or WO-A-95/07897 (ZA 94/7120) and the literature cited therein or can be prepared by or analogously to the processes described therein. The compounds of the formula (S-III) are known from EP-A-0086750, EP-A-094349 (US 4,902,340), EP-A-0191736 (US 4,881,966) and EP-A-0492366 and literature cited therein or US Pat can be prepared according to or analogously to the methods described therein. Some compounds are further described in EP-A-0582198 and WO-A-02/34048. The compounds of formula (S-IV) are known from numerous patent applications, for example US 4,021,224 and US 4,021,229. Compounds of subgroup b) are further from CN-A-87/102789, EP-A-365484 and from "The Pesticide Manual", 11th to 13th edition, British Crop Protection Council and the Royal Society of Chemistry (1997), known. The compounds of subgroup c) are described in WO-A-97/45016, those of subgroup d) in WO-A-99/16744 (in particular in EP-A-365484). The cited documents contain detailed information on preparation processes and starting materials and name preferred Links. These documents are expressly referred to, they are by quotation as part of this description.

Safener (component b) are those having melting points of <(less than or equal to) 150 ° C, particularly preferably <100 ⁰ C, most preferably <75 ⁰ C. In addition, are safeners (component b) is preferably suitable for use in cereals , such as wheat, barley, rye, oats, millet, rice, corn.

Particular preference is given as safeners (component b), which may optionally be present in the formulations according to the invention, inter alia: 4-dichloroacetyl-1-oxa-4-aza-spiro [4.5] -decane (AD-67), 1 Dichloroacetyl-hexahydro-3,3,8a-trimethylpyrrolo [1,2-a] pyrimidine-6 (2H) -one (dicyclonone, BAS-145138), 4-dichloroacetyl-3,4-dihydro-3-methyl- 2H-1,4-benzoxazine (Benoxacor), 5-chloro-quinolin-8-oxy-acetic acid (1-methyl-hexyl ester) (cloquintocet-mexyl), α- (cyanomethoxyimino) -phenylacetonitrile (cyometrinil), 2,2 Dichloro-N- (2-oxo-2- (2-propenylamino) -ethyl) -N- (2-propenyl) -acetamide (DKA-24), 2,2-dichloro-N, N-di-2- propenyl-acetamide (dichloromide), N- (4-methyl-phenyl) -N '- (1-methyl-1-phenyl-ethyl) -urea (dymron), 4,6-dichloro-2-phenyl-pyrimidine (fenclorim ), 1- (2,4-dichlorophenyl) -5-trichloromethyl-1 H-1, 2,4-triazole-3-carboxylic acid ethyl ester (Fenchlorazolethyl), 2-chloro-4-trifluoromethyl-thiazole 5-carboxylic acid phenylmethyl ester (flurazole), 4-chloro-N- (1, 3-dioxolan-2-y 1-methoxy) -α-trifluoro-acetophenone oxime (Fluxofenim), 3-dichloroacetyl-5- (2-furanyl) -2,2-dimethyl-oxazolidine (furilazole, MON-13900), ethyl 4,5-dihydro-5 , 5-diphenyl-3-isoxazolecarboxylate (isoxadifen-ethyl), diethyl-1 - (2,4-dichlorophenyl) -4,5-dihydro-5-methyl-1H-pyrazole-3,5-dicarboxylate (mefenpyr-diethyl ), 2-dichloromethyl-2-methyl-1,3-dioxolane (MG-191), 1,8-naphthalic anhydride, α- (1,3-dioxolan-2-ylmethoximino) -phenylacetonitrile (oxabetrinil), 2, 2-dichloro-N- (1,3-dioxolan-2-ylmethyl) -N- (2-propenyl) -acetamide (PPG-1292), 3-dichloroacetyl-2,2-dimethyl-oxazolidine (R-28725 ), 3-dichloroacetyl-2,2,5-trimethyl-oxazolidine (R-29,148), 1- (2-chloro-phenyl) -5-phenyl-1-H-pyrazole-3-carboxylic acid methyl ester, 4-cyclopropylaminocarbonyl N- (2-methoxybenzoyl) benzenesulfonamide (Cyprosulfamide), 4-iso-propylaminocarbonyl-N- (2- methoxybenzoyl) benzenesulfonamide and N- (2-methoxybenzoyl) -4 - [(methylaminocarbonyl) amino] benzenesulfonamide.

Very particular preference is given to mefenpyr-diethyl, isoxadifen-ethyl, 4-cyclopropylaminocarbonyl-N- (2-methoxybenzoyl) benzenesulfonamide (cyprosulfamide), 4-iso-propylaminocarbonyl-N- (2-methoxybenzoyl) benzenesulfonamide, in particular particularly preferred is mefenpyr-diethyl ,

The proportion of safeners (component b) contained in the formulations according to the invention may be from 0.01 to 50% by weight, preferably from 0.5 to 25% by weight, more preferably from 2 to 20% by weight, completely particularly preferably 5 to 17 wt .-% amount.

Suitable solvents (component c) for the formulations according to the invention can be selected from the group of aromatic and aliphatic hydrocarbons, esters and amides of organic and inorganic acids, aromatic, aliphatic and cycloaliphatic ketones and alcohols.

Typical representatives of suitable solvents include © Solvesso types (aromatic hydrocarbon), © Essobayol (aliphatic hydrocarbon), ®Exxate (esters of organic acids), © Hallcomide (organic acid amides, acetone phenone (aromatic ketone), methyl isobutyl ketone (aliphatic ketone), ®Anone (cyclohexanone: cycloaliphatic ketone).

Preferred are solvents from the group of aromatic and aliphatic hydrocarbons, such as © Solvesso types (aromatic hydrocarbons), more preferably aromatic hydrocarbons, such as © Solvesso 200 ND (alkylated naphthalene). The proportion of the solvents (component c) in the formulations according to the invention may be from 0.01 to 50% by weight, preferably from 0.5 to 25% by weight, particularly preferably from 2 to 20% by weight, very particularly preferably from 5 to 17 Wt .-% amount.

The formulations according to the invention use one or more carrier materials (component d) selected from one or more of the groups: low absorbency excipients (component d-1) and high absorbency excipients (component d-2).

The proportion of the support materials (component d) in the formulations according to the invention can be 0.1-90% by weight, preferably 10-80% by weight, particularly preferably 15-50% by weight, very particularly preferably 25-45% by weight. -%.

The low absorbency excipients (component d-1) in the formulations of the present invention can be taken from a group containing minerals, carbonates, sulfates and phosphates of alkaline earth and earth metals such as calcium carbonate, polymeric carbohydrates, scaffold silicates such as low absorbency precipitated silicas, and natural framework silicates such as kaolin. In addition, they are characterized by a capacity of less than 200 g of dibutyl phthalate per 100 g of carrier material.

Typical representatives of suitable carriers (component d-1) include © Agsorb LVM-GA (attapulgite), © Harborlite 300 (perlite), © Collys HV (modified starch), © Omya chalk (calcium carbonate), © Extrusil (precipitated silica) , © Kaolin Tea 1 (kaolin, aluminum hydrosilicate), © Steamic 00S (talc, magnesium silicate). Preference is given here to natural framework silicates and calcium carbonate types such as © Omya chalk (calcium carbonate), © Kaolin Ted (kaolin) and © Harborlite 300 (perlite), particularly preferably natural framework silicates such as © Kaolin Tea 1 (kaolin, aluminum hydrosilicate) and © Harborlite 300 (perlite). The proportion of the carriers with low absorbency (component d-1) in the formulations according to the invention may be from 0.5 to 85% by weight, preferably from 7 to 70% by weight, particularly preferably from 15 to 35% by weight.

Suitable excipients with high absorbency (component d-2) in the formulations according to the invention are characterized by a receptivity of at least 200 g of dibutyl phthalate per 100 g of carrier material and can be selected from this group.

Typical representatives of suitable excipients (component d-2) include © Calflo E (calcium silicate) and © Sipernat grades (synthetic high-absorbency synthetic precipitated silica).

Preference is given to calcium silicate, such as © Calflo E, and precipitated silica, such as © Sipernat 5OS.

The proportion of high-absorbency carriers (component d-2) in the formulations according to the invention may be from 0.1 to 90% by weight, preferably from 0.3 to 20% by weight, particularly preferably from 1 to 17% by weight, completely particularly preferably 3 to 13 wt .-% amount.

In a particular embodiment of the invention, the carrier materials (component d) consist of a mixture of at least one carrier with low absorbency (component d-1) and at least one carrier with high absorbency (component d-2).

The formulations according to the invention use one or more customary auxiliaries and additives (component e) selected from one or more of the groups: emulsifiers (component e-1), antifoam agents (component e-2), wetting agents (component e-3) and dispersants (Component e-4).

The classification of component (e) in emulsifiers, wetting agents and dispersants is not a limitation of use, since it is known that, for example Dispersants may also have 'wetting' properties and, for example, wetting agents may also have a dispersing effect.

Suitable customary auxiliaries and additives (component e) can be selected from one or more of the groups of the ionic, neutral and / or zwitterionic surfactants, as well as from the groups of the neutral to (weakly) alkaline surfactants (pH 6 -14).

Suitable emulsifiers (component e-1) may be of anionic and / or nonionic nature and are selected from the group comprising: salts of alkylated aromatic sulfonic acids, optionally alkylated copolymers of alkylene oxides, such as ethylene oxide and propylene oxide (EO / PO), ethoxylated castor oil, fatty acylated sorbitan ethoxylate, mono- and diglycerides of fatty acids and their salts, fatty acids and their salts, reaction products of optionally aliphatically or aromatically substituted phenols with alkylene oxides, and optionally partial esters of these surfactants with organic acids such as acetic or citric acid, or inorganic acids such as sulfur - or phosphoric acid.

Typical representatives of suitable emulsifiers are inter alia © phenylsulfonate CA (calcium dodecylbenzenesulfonate), © soprophor types (optionally esterified derivatives of tristyrylphenol ethoxylates), © emulsan 3510 (alkylated EO / PO copolymer), © Emulsogen EL 400 (ethoxylated castor oil) , © Tween types (fatty acylated sorbitan ethoxylates), © Calsogen AR 100 (Ca dodecylbenzenesulfonate). Preference is given to combinations of salts of alkylated aromatic sulfonic acids, such as © phenylsulfonate Ca and / or Calsogen AR 100, with alkylated copolymers of ethylene oxide and propylene oxide, such as © Emulsogen 3510. Particularly preferred are combinations of salts of dodecylbenzenesulfonic acid, such as © Calsogen AR 100 with alkylated copolymer of ethylene and propylene oxide, such as © Emulsogen 3510. The proportion of emulsifiers (component e-1) in the formulations according to the invention may be from 0.001 to 25% by weight, preferably from 0.005 to 10% by weight, particularly preferably from 0.05 to 6% by weight, very particularly preferably from 0.5 - 3.5 wt .-% amount.

Suitable antifoams (component e-2) can be selected from the group of the esters of phosphoric acid with lower alcohols, C6-C10 alcohols, silicone surfactants (suspoemulsions of hydrophobicized silica particles in aqueous emulsion concentrates based on liquid silicone surfactants), such as polydimethylsiloxane, and their absorbates on solid carrier material.

Typical representatives of suitable antifoam agents include © Rhodorsil 432 (silicone surfactant), butyl phosphate, iso-butyl phosphate, n-octanol, © Wacker ASP15 (polydimethylsiloxane, supported on solid support), ® antifoam agent SE 2 (polydimethylsiloxane).

Preference is given to suspoemulsions of hydrophobized silica particles in aqueous emulsion concentrates based on liquid silicone surfactants, such as © antifoam agent SE (polydimethylsiloxane), and solid antifoams, such as © Wacker ASP 15 (polydimethylsiloxane).

The proportion of antifoams (component e-2) in the formulations according to the invention can be from 0.1 to 10% by weight, preferably from 0.3 to 5% by weight, particularly preferably from 0.5 to 3% by weight.

Suitable wetting agents (component e-3) may be solid surfactants, anionic and / or zwitterionic surfactants, sulfonates (sulfosuccinates), sulfates, phosphonates, phosphates and carboxylates, but also alkaline surfactants (for example © Synperonic T types). They can be selected from the group of solid, ie, at room temperature, non-liquid wetting agents, for example of waxy, amorphous or crystalline nature, preferably from the group of the reaction products of alkylene oxides with Alkylenpolyaminen, naphthalenesulfonic acids and the group of sulfosuccinic acid derivatives and the salts of these groups , the on the one hand mono- and di-esters of sulfosuccinic acid and their salts (sulfosuccinates) may contain and on the other hand may contain alkylated naphthalenesulfonic acids and their salts.

Typical representatives of suitable wetting agents include inter alia © Synperonic T-types (block polymers of propylene oxide and ethylene oxide on ethylenediamine), © Aerosol OTB (dioctylsulfosuccinate), © Morwet EFW (alkylated naphthalenesulfonates), © Nekal BX (alkylated naphthalenesulfonates), © Galoryl MT 804 ( alkylated naphthalenesulfonates).

Preference is given here to block polymers of propylene oxide and ethylene oxide to ethylenediamine (© Synperonic T 905), the salts of the alkylated naphthalenesulfonic acids and the salts of dioctylsulfosuccinic acid, particularly preferably the sodium salts of alkylated naphthalenesulfonates, such as, for example, © Morwet EFW, and the sodium salts of dioctylsulfosuccinic acid, e.g. © Aerosol OTB, and block polymer of propylene oxide and ethylene oxide on ethylenediamine, e.g. © Synperonic T 905.

The proportion of wetting agents (component e-3) in the formulations according to the invention can be from 0.1 to 50% by weight, preferably from 0.25 to 30% by weight, particularly preferably from 0.5 to 30% by weight.

Suitable dispersants (component e-4) can be selected from the group consisting of ethoxylated triarylphenols whose optionally partial esters with phosphoric acid, ligninsulfonic acids, condensation products of aromatic, optionally polynuclear, sulfonic acids (naphthalenesulfonic acid) with formaldehyde, polymers of optionally alkylated acrylic acids (example of alkaline dispersants), Condensation products of optionally polynuclear phenols with formaldehyde and Na sulfite, sulfonic acids of polynuclear aromatics, and the alkali, Erdkali- and ammonium salts these substances. Typical representatives of suitable dispersants include © soprophor BSU (phosphated triarylphenol ethoxylate), © Borresperse NA (lignosulfonate), © Rapidaminreserve D (condensation product phenol with Na sulfite and formaldehyde), © Galoryl DT brands (condensation product of aromatic sulfonic acids with formaldehyde), © Morwet D425 (condensation product of naphthalenesulfonic acid and formaldehyde).

Preference is given to condensation products of aromatic sulfonic acids with formaldehyde and salts thereof, particularly preferred are the sodium salts of naphthalenesulfonic acids with formaldehyde, © such as galoryl DT505 and © Morwet D425 (both condensation products of naphthalenesulfonic acid and formaldehyde).

The proportion of dispersants (component e-4) may be 1 to 50% by weight, preferably 5 to 30% by weight, particularly preferably 10 to 20% by weight.

As optional agrochemical active ingredients (component f), various agrochemical active substances such as herbicides, fungicides, insecticides, plant growth regulators and the like can be contained, for example, of components (a) and (b).

Suitable active ingredients other than components (a) and (b) are preferably herbicidal active ingredients. These include herbicides from the group of carbamates, thiocarbamates, haloacetanilides, substituted phenoxy, naphthoxy and Phenoxyphenoxycarbonsäure derivatives and Heteroaryloxy- phenoxyalkancarbonsäure derivatives, such as quinolyloxy, quinoxalyl-oxy, pyridyloxy, Benzoxazolyloxy- and Benzthiazolyloxyphenoxyalkan-carboxylic acid ester , Cyclohexanedione derivatives, phosphorus-containing herbicides, eg glufosinate type or glyphosate type; and S- (N-aryl-N-alkylcarbamoylmethyl) dithiophosphoric acid ester. Especially for example:

A) Herbicides of the phenoxyphenoxy and heteroaryloxyphenoxycarboxylic acid type, such as A1) phenoxyphenoxy- and benzyloxyphenoxy-carboxylic acid derivatives, for example methyl 2- (4- (2,4-dichlorophenoxy) -phenoxy) -propionate (diclofop-methyl), 2- (4- (4-bromo-2-chlorophenoxy) -phenoxy methyl propionate (DE-A-2601548), methyl 2- (4- (4-bromo-2-fluorophenoxy) phenoxy) propionate (US Pat. No. 4,808,750), methyl 2- (4- (2-chloro-4-trifluoromethylphenoxy) phenoxy) propionate ( DE-A-2433067), methyl 2- (4- (2-fluoro-4-trifluoromethylphenoxy) phenoxy) propionate (US Pat. No. 4,808,750), methyl 2- (4- (2,4-dichlorobenzyl) phenoxy) propionate (DE-A-2417487 ), 4- (4- (4-trifluoromethylphenoxy) phenoxy) pent-2-enoic acid ethyl ester, 2- (4- (4-trifluoromethylphenoxy) phenoxy) propionic acid methyl ester (DE-A-2433067); A2) "mononuclear" heteroaryloxyphenoxyalkanecarboxylic acid derivatives, for example ethyl 2- (4- (3,5-dichloropyridyl-2-oxy) phenoxy) propionate (EP-A-0002925), 2- (4- (3,5-dichloropyridyl -2-oxy) phenoxy) propionic acid propargyl ester (EP-A-0003114), methyl 2- (4- (3-chloro-5-trifluoromethyl-2-pyridyloxy) phenoxy) propionate (EP-A-0003890), 2- (4-8) Ethyl 4- (3-chloro-5-trifluoromethyl-2-pyridyloxy) phenoxy) propionate (EP-A-0003890), 2- (4- (5-chloro-3-fluoro-2-pyridyloxy) phenoxy) propionic acid propargyl ester (EP- A-0191736), butyl 2- (4- (5-trifluoromethyl-2-pyridyloxy) phenoxy) propionate (fluazifop-butyl);

A3) "binuclear" heteroaryloxyphenoxy-alkanecarboxylic acid derivatives, e.g. Methyl 2- (4- (6-chloro-2-quinoxalyloxy) phenoxy) propionate and ethyl ester (quizalofopmethyl and quizalofopethyl), 2- (4- (6-fluoro-2-quinoxalyloxy) phenoxy) propionic acid methyl ester (see J. Pest. Vol. 10, 61 (1985)), 2- (4- (6-chloro-2-quinoxalyloxy) phenoxy) propionic acid 2-isopropylideneaminooxyethyl ester (propaquizafop), 2- (4- (6-chlorobenzoxazole-2 ethyl (phenoxy) phenoxy) propionate (fenoxaprop-ethyl) and its D (+) isomer (fenoxaprop-P-ethyl, EX) and ethyl 2- (4- (6-chlorobenzothiazol-2-yloxy) phenoxy) propionate (DE-) A-2640730), 2- (4- (6-chloroquinoxalloxy) phenoxy) propionic acid tetrahydro-2-furylmethyl ester (EP-A-0323727);

A4) phenoxycarboxylic acid derivatives such as 2,4-D, 2,4-DP, 2,4-DB, CMPP and MCPA and their esters and salts; B) Chloroacetanilides, for example N-methoxymethyl ^. Δ-diethyl-chloroacetanilide (alachlor), N- (3-methoxyprop-2-yl) -2-methyl-6-ethyl-chloroacetanilide (metolachlor), N- (3-methyl - 1,2,4-oxadiazol-5-ylmethyl) -chloroacetic acid-2,6-dimethylanilide, N- (2,6-dimethylphenyl) -N- (1-pyrazolylmethyl) -chloroacetic acid amide (metazachlor);

C) thiocarbamates, e.g. S-ethyl-N, N-dipropylthiocarbamate (EPTC), S-ethyl-N, N-diisobutylthiocarbamate (butylate);

D) cyclohexanedione oximes, e.g. 3- (1-Allyloxyiminobutyl) -4-hydroxy-6,6-dimethyl-2-oxocyclohex-3-encarboxylic acid methyl ester, (alloxydim), 2- (1-ethoxyiminobutyl) -5- (2-ethylthiopropyl) -3- hydroxycyclohex-2-en-1 -one (sethoxydim), 2- (1-ethoxyiminobutyl) -5- (2-phenylthiopropyl) -3-hydroxy-cyclohex-2-en-1-one (cloproxydime), 2- (1- (3-chloroallyloxy) iminobutyl) -5- (2-ethylthiopropyl) -3-hydroxycyclohex-2-en-1-one, 2- (1- (3-chloroallyloxy) iminopropyl) -5- (2 ethylthiopropyl) -3-hydroxycyclohex-2-en-1-one (clethodim), 2- (1-ethoxyiminobutyl) -3-hydroxy-5- (thian-3-yl) -cyclohex-2-enone (cycloxydim ), 2- (1-ethoxyiminopropyl) -5- (2,4,6-trimethylphenyl) -3-hydroxycyclohex-2-en-1-one (tralkoxydim);

E) benzoylcyclohexanediones, e.g. 2- (2-chloro-4-methylsulfonylbenzoyl) cyclohexane-1,3-dione (SC-0051, EP-A-0137963), 2- (2-nitrobenzoyl) -4,4-dimethylcyclohexane-1,3 -dione (EP-A-0274634), 2- (2-nitro-4-methylsulfonylbenzoyl) -4,4-dimethylcyclohexane-1,3-dione (WO-A-91/13548, Mesotrione);

F) S- (N-aryl-N-alkyl-carbamoylmethyl) -dithiophosphonic acid esters, such as S- [N- (4-chlorophenyl) -N-isopropyl-carbamoylmethyl] -O, O-dimethyl-dithiophosphate (anilophos).

G) Alkylazines, for example 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 and also 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 R ^{x is} (C _r C ₄ ) alkyl or (C _r C ₄ ) haloalkyl; R ^{γ is} (C ₁ -C ₄ ) -alkyl, (C ₃ -C ₆ ) -cycloalkyl or (C ₃ -C ₆ ) -cycloalkyl- (C ₁ -C ₄ ) -alkyl and A is -CH ₂ -, -CH ₂ -CH ₂ -, CH ₂ -CH ₂ -CH ₂ -, -O-, -CH ₂ -CH ₂ -O-, -CH ₂ -CH ₂ -CH ₂ -O- mean, particularly preferably those of the formula G1-G7

H) phosphorus-containing herbicides, e.g. glufosinate type such as glufosinate in the strict sense, d. H. D, L-2-amino-4- [hydroxy (methyl) phosphinyl] butanoic acid, glufosinate monoammonium salt, L-glufosinate, L- or (2S) -2-amino-4- [hydroxy (methyl) phosphinyl] butanoic acid , L-glufosinate monoammonium salt or bialaphos (or bilanafos), ie L-2-amino-4- [hydroxy (methyl) phosphinyl] -butanoyl-L-alanyl-L-alanine, especially its sodium salt, or glyphosate-type such as glyphosate, i. N- (phosphonomethyl) glycine, glyphosate monoisopropylammonium salt, glyphosate sodium salt, or sulfosates, d. H. N- (phosphonomethyl) glycine trimesium salt = N- (phosphonomethyl) -glycine trimethylsulfoxonium salt.

Mention should also be made here of imidazolinones, pyrimidinyloxypyridinecarboxylic acid derivatives, pyrimidyloxybenzoic acid derivatives, triazolopyrimidine-sulfonamide derivatives with typical representatives, such as, for example, Diflufenican, Bromoxynilhaltige or loxynilhaltige products, herbicides from the class of oxyacetamides such as flufenacet, herbicides from the class of aryloxy phenoxypropionates such as fenoxaprop-p-ethyl, beet herbicides such as Desmedipham, Phenmedipham, ethofumesate or Metamitron, or also active ingredients from the class of HPPD Inhibitors (eg isoxaflutole, sulcotrione, mesotrione). Especially for example:

I) imidazolinones, eg 2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -5- methyl benzoate and 2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -4-methylbenzoic acid (imazamethabenz), 5-ethyl-2- (4-isopropyl-4-methyl) 5-oxo-2-imidazolin-2-yl) -pyridine-3-carboxylic acid (imazethapyr), 2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -quinoline-3- carboxylic acid (imazaquin), 2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -pyridine-3-carboxylic acid (imazapyr), 5-methyl-2- (4-isopropyl-4 - methyl-5-oxo-2-imidazolin-2-yl) -pyridine-3-carboxylic acid (imazethamethapyr);

J) Triazolopyrimidine sulfonamide derivatives, e.g. N- (2,6-Difluorophenyl) -7-methyl-1,2,4-triazolo [1,5-c] pyrimidine-2-sulfonamide (flumetsulam), N- (2,6-dichloro-3-methylphenyl) -5,7-dimethoxy-1,2,4-triazolo [1,5-c] pyrimidine-2-sulfonamide, N- (2,6-difluorophenyl) -7-fluoro-5-methoxy-1, 2,4 -triazolo [1,5-c] pyrimidine-2-sulfonamide, N- (2,6-dichloro-S-methylphenyl-y-chloro-δ -nethoxy-1-triazolol-.s-clpyrimidine-sulfonamide, N - (2-chloro-6-methoxycarbonyl) -5,7-dimethyl-1,2,4-triazolo [1,5-c] pyrimidine-2-sulfonamide (EP-A-0343752, US 4,988,812);

K) pyrimidinyloxy-pyridinecarboxylic acid or pyrimidinyloxybenzoic acid derivatives, e.g. 3- (4,6-dimethoxypyrimidin-2-yl) -oxy-pyridine-2-carboxylic acid benzyl ester (EP-A-0249707), 3- (4,6-dimethoxypyrimidin-2-yl) -oxy-pyridine-2 -carboxylic acid methyl ester (EP-A-0249707), 2,6-bis [(4,6-dimethoxypyrimidin-2-yl) oxy] benzoic acid (EP-A-0321846), 2,6-bis [(4,6 -dimethoxypyrimidin-2-yl) oxy] benzoic acid 1 - (ethoxycarbonyl-oxyethyl) ester (EP-A-0472113).

The herbicides of groups A to K are known, for example, from the publications cited above and from "The Pesticide Manual", 12th edition (2000) and 13th edition (2003), The British Crop Protection Council, "Agricultural Chemicals Book II - Herbicides - ", by WT. Thompson, Thompson Publications, Fresno CA, USA 1990, and "Farm Chemicals Handbook '90", Meister Publishing Company, Willoughby OH, USA 1990.

As optional contained of the components (a) and (c) agrochemical active ingredients (component f) are for the formulations according to the invention, for example, the following known active ingredients in Question, as described in eg Weed Research 26, 441-445 (1986), or "The Pesticide Manual", 12th edition (2000) and 13th edition (2003), The British Crop Protection Council, and cited there literature , eg in mixture formulations or as a tank mixing partner. The compounds are designated either by the "common name" according to the International Organization for Standardization (ISO) or by the chemical name, if appropriate together with a customary code number, and always include all forms of use, such as acids, salts, esters and isomers, such as stereoisomers and optical Isomers: acetochlor; acifluorfen; aclonifen; AKH 7088, ie methyl [[[1- [5- [2-chloro-4- (trifluoromethyl) phenoxy] -2-nitrophenyl] -2-methoxyethylidene] amino] oxyacetate and acetic acid; alachlor; alloxydim; ametryn; amitrol; AMS, ie ammonium sulfamate; anilofos; asulam; atrazine; azafenidines (DPX-R6447), aziprotryn; barban; BAS 516H, ie 5-fluoro-2-phenyl-4H-3,1-benzoxazin-4-one; benazolin; benfluralin; benfuresate; bensulide; bentazone; benzofluor; benzoylprop-ethyl; benzthiazuron; bialaphos; bifenox; bispyribac sodium (KIH-2023), bromacil; bromobutide; bromofenoxim; bromoxynil, in particular bromoxyniloctanoate and bromoxynilheptanoate; butachlor; butamifos; butenachlor; buthidazole; butraline; butroxydim (ICI-0500), butylate; cafenstrole (CH-900); carbetamide; cafentrazone; CDAA, ie 2-chloro-N, N-di-2-propenylacetamide; CDEC, ie diethyldithiocarbamic acid 2-chloroallyl ester; chlomethoxyfen; chloramben; cloransulam-methyl (XDE-565), chloroazifop-butyl, chlorobromuron; chlorbufam; chlorfenac; chlorflurenol-methyl; chloridazon; chlornitrofen; chlorotoluron; chloroxuron; chlorpropham; chlorthal-dimethyl; chlorthiamid; cinidon-ethyl, cinmethylin; clethodim; clodinafop and its ester derivatives (eg clodinafoppropargyl); clomazone; clomeprop; cloproxydim; clopyralid; cumyluron (JC 940); cyanazine; cycloate; cycloxydim; cycluron; cyhalofop and its ester derivatives (eg, butyl ester, DEH-112); cyperquat; cyprazine; cyprazole; 2,4-D; 2,4-DB; dalapon; desmedipham; Desmetryn; di-allate; dicamba; dichlobenil; dichloroprop; diclofop and its esters such as diclofop-methyl; diclosulam (XDE-564), diethatyl; difenoxuron; difenzoquat; diflufenican; diflufenzopyr sodium (SAN-835H), dimefuron; dimethachlor; dimethametryn; dimethenamid (SAN-582H); dimidazone, 5- (4,6-dimethylpyrimidin-2-yl-carbamoylsulfamoyl) -1- (2-pyridyl) -pyrazole-4- carboxylic acid methyl ester (NC-330); triaziflam (IDH-1105), cinosulfone; dimethipine, dinitramine; dinoseb; dinoterb; diphenamid; dipropetryn; diquat; dithiopyr; diuron; DNOC; eglinazine-ethyl; EL 177, ie 5-cyano-1- (1, 1-dimethylethyl) -N-methyl-1H-pyrazole-4-carboxamide; endothal; indanofan (MK-243), EPTC; esprocarb; ethalfluralin; Ethidimuron; ethiozin; ethofumesate; F5231, ie N- [2-chloro-4-fluoro-5- [4- (3-fluoropropyl) -4,5-dihydro-5-oxo-1H-tetrazol-1-yl] -phenyl] -ethanesulfonamide; ethoxyfen and its esters (eg ethyl ester, HN-252); etobenzanide (HW 52); 3- (4-Ethoxy-θ-ethyl-1-5,5-triazine-1-O-1-5-dihydro-1-dioxo-1-methylbenzotebthiophene-7-sulfonyl) urea (EP-A-079683) ; 3- (4-Ethyl-6-methoxy-1,3,5-triazin-2-yl) -1- (2,3-dihydro-1, 1-dioxo-2-methylbenzo [b] thiophene-7-sulfonyl ) urea (EP-A-079683); fenoprop; clomazone, fenoxaprop and fenoxaprop-P and their esters, eg fenoxaprop-P-ethyl and fenoxaprop-ethyl; butroxydimfenuron; flamprop-methyl; flufenacet (BAY-FOE-5043), fluazifop and fluazifop-P and their esters, eg fluazifop-butyl and fluazifop-P-butyl, florasulam (DE-570); fluchloralin; flumetsulam; fluometuron; flumiclorac and its esters (eg, pentyl ester, S-23031); flumioxazine (S-482); flumipropyn; flupoxam (KNW-739); fluorodifen; fluoroglycofen-ethyl; flupropacil (UBIC-4243); fluridone; flurochloridone; fluroxypyr; flurtamone; fluthiacetemethyl (KIH-9201), fomesafen; fosamine; furyloxyfen; glufosinate; glyphosate; halo safen; haloxyfop and its esters; haloxyfop-P (= R-haloxyfop) and its esters; hexazinone; imazamethabenz-methyl; imazamox (AC-299263), imazapyr; imazaquin and salts such as the ammonium salt; imazapic; imazethapyr; ioxynil; isocarbamid; isopropalin; isoproturon; isouron; isoxaben; isoxapyrifop; karbutilate; lactofen; lenacil; linuron; MCPA; MCPB; mecoprop; mefenacet; mefluidide; metamitron; metazachlor; methabenzthiazuron; metam; methazole; methoxyphenone; methyldymron; metobenzuron, metobromuron; metolachlor; S-metolachlor, metosulam (XRD 511); metoxuron; metribuzin; maleic hydrazides; molinate; monalide; monocarbamide dihydrogen sulfates; monolinuron; monuron; MT 128, ie 6-chloro-N- (3-chloro-2-propenyl) -5-methyl-N-phenyl-3-pyridazineamine; MT 5950, ie N- [3-chloro-4- (1-methylethyl) phenyl] -2-methylpentanamide; naproanilide; napropamide; naptalam; NC 310, ie 4- (2,4-dichlorobenzoyl) -1-methyl-5-benzyloxypyrazole; neburon; nipyraclophen; nitralin; nitrofen; nitrofluorfen; norflurazon; orbencarb; oryzalin; oxadiargyl (RP-020630); oxadiazon; oxaziclomefones (MY-100), oxyfluorfen; paraquat; pebulate; pendimethalin; pentoxazone (KPP-314), perfluidone; phenisopham; phenmedipham; picloram; piperophos; pyributicarb; pirifenop-butyl; pretilachlor; procyazine; prodi amines; profluralin; proglinazine-ethyl; prometon; prometryne; propachlor; propanil; propaquizafop and its esters; propazine; propham; propisochlor; Propyzamide; prosulfalin; prosulfocarb; prynachlor; pyraflufen-ethyl (ET-751), chloridazon; pyrazoxyfen; pyribenzoxime, pyridates; pyriminobac-methyl (KIH-6127), pyrithiobac (KIH-2031); pyroxofop and its esters (eg propargyl esters); quinclorac; quinmerac; quizalofop, quizalofop and quizalofop-P and their ester derivatives eg quizalofop-ethyl; quizalofop-P-tefuryl and -ethyl; S 275, ie 2- [4-chloro-2-fluoro-5- (2-propynyloxy) -phenyl] -4,5,6,7-tetrahydro-2H-indazole; secbumeton; sethoxydim; siduron; simazine; simetryn; SN 106279, ie 2 - [[7- [2-chloro-4- (trifluoromethyl) phenoxy] -2-naphthalenyl] oxy] propanoic acid and methyl ester; sulfazuron; glyphosate trimesium (ICI-A0224); TCA; tebutam (GCP-5544); tebuthiuron; tepral oxydim (BAS-620H), terbacil; terbucarb; terbuchlor; terbumeton; Terbuthylazine; terbutryn; TFH 450, ie N, N-diethyl-3 - [(2-ethyl-6-methylphenyl) sulfonyl] -1H-1, 2,4-triazole-1-carboxamide; thenylchlor (NSK-850); thiazafluron; thiazopyr (Mon-13200); thidiazimin (SN-124085); thiobencarb; tiocarbazil; tralkoxydim; tri-allate; triazofenamide; triclopyr; tridiphane; trietazine; trifluralin; trimeturon; tsitodef; vernolate; WL 110547, ie 5-phenoxy-1- [3- (trifluoromethyl) phenyl] -1H-tetrazole; UBH-509; D-489; LS 82-556; KPP-300; KPP-421, MT-146, NC-324; butenachlor (KH-218); DPX-N8189; haloxyfop-etotyl (DOWCO-535); DK-8910; flumioxazine (V-53482); PP-600; MBH-001, amicarbazone, aminopyralid, beflubutamide, benzobicyclone, benzofenap, benzfendizone, butafenacil, chlorfenprop, cloprop, daimuron, dichlorprop-P, dimepipeate, dimethenamid-P, fentrazamide, flamprop-M, fluazolate, indanofan, isoxachlortole, isoxaflutole, MCPA thioethyl, mecoprop-P, mesotrione, metamifop, penoxsulam, pethoxamide, picolinafen, profluazole, profoxydim, pyraclonil, pyrazolynate, pyridafol, pyriftalid, sulcotrione, thidiazuron.

The proportion of agrochemically active compounds (component f) which are different from components (a) and (b) and which may be present in the compounds according to the invention Formulations may contain from 0.05 to 70 wt .-%, preferably 0.1 to 20 wt .-%, particularly preferably 0.3 to 10 wt .-%, most preferably 0.5 to 5 wt. %.

As optional further customary auxiliaries and additives (component g) it is possible for example for component (e) to contain various auxiliaries and additives selected from the group consisting of disintegrating agents, binders (adhesion promoters), pH adjusting agents and the like.

Suitable disintegrating agents can be selected from the group of modified carbohydrates, such as microcrystalline cellulose, and cross-linked

Polyvinylpyrrolidones.

Typical representatives of suitable disintegrating agents include © Avicel PH

101 (microcrystalline cellulose), © Agrimer XLF (cross-linked polyvinylpyrrolidone),

© Disintex 200 (cross-linked polyvinylpyrrolidone).

Preference is given to cross-linked polyvinylpyrrolidones, such as © Agrimer XLF.

The proportion of disintegrating agents which may be present in the inventive

Formulations may be 0.1 to 50 wt .-%, preferably 0.5 to 25

Wt .-%, particularly preferably 1 - 10 wt .-% amount.

Suitable binders (adhesion promoters) can be selected from the group consisting of polyvinylpyrrolidone (PVP), polyvinyl alcohol, co-polymer of PVP and dimethylaminoethyl methacrylate, butylated PVP, co-polymer of vinyl chloride and vinyl acetate, Na salt of the co-polymer of propensulfonic acid and partially hydrolyzed vinyl acetate , Sodium caseinate, phenolic resins, modified cellulose types.

Typical representatives of suitable binders include © Luviskol (polyvinylpyrrolidone), © Mowiol (polyvinyl alcohol), © Tylose (modified cellulose). Preferred are polyvinylpyrrolidone types, particularly preferred are low molecular weight types such as © Luviskol K30. The proportion of binders which may optionally be present in the formulations according to the invention may be 0.5 to 20% by weight, preferably 1 to 10% by weight, more preferably 3 to 8% by weight.

Suitable pH adjusting agents may be selected from the group of hydroxides and carbonates of alkali and alkaline earth metals. Typical representatives of suitable pH adjusting agents include NaOH, KOH, Na ₂ CO ₃ and K ₂ CO ₃ . Preference is given to NaOH and Na ₂ CO.

The proportion of pH adjusting agents which may optionally be present in the formulations according to the invention may be 0.01-5% by weight, preferably 0.05-3% by weight, more preferably 0.1-2 Wt .-% amount.

A particularly preferred embodiment of the invention contains (by way of example trade products and their proportions) (a) phenylsulfonylaminocarbonyltriazolinones, such as 6.85% by weight of propoxycarbazone sodium, and

(A) another active ingredient from the group of sulfonamides and their salts, such as mesosulfuron-methyl with 4.5 wt .-%;

(b) a safener such as mefenpyr-diethyl at 9% by weight;

(c) a solvent such as © Solvesso 200ND at 15.25% by weight;

(d) several support materials selected from the groups:

(d-1) Low Absorbent Carrier, such as © Harborlite 300 at 5 wt% and © Kaolin 1777 at 18.99 wt%, and (d-2) High Absorbency Carrier, such as © Sipernat 5OS at 12% by weight;

(e) several common auxiliaries and additives selected from the groups: (e-1) emulsifiers, such as © Calsogen AR100 ND (anionic) at 2.63% by weight and © Emulsogen 3510 (nonionic) at 1.5 wt .-%,

(e-2) antifoaming agent, such as, for example, © antifoam agent SE 2 with 1% by weight, (e-3) wetting agents such as, for example, © Synperonic T / 905 with 6% by weight, (e-4) dispersants, such as © Morwet D425 at 10% by weight;

(g) a plurality of other excipients and additives other than component (c) selected from the groups:

Binder, such as © Luviskol K30 with 5 wt .-%, and means for adjusting the pH, such as Na-hydroxide (NaOH, 100%) with 0.38 wt .-%, and a residual moisture content with, for example 2 wt .-%, wherein the component (b) to the component (c) in the ratio 0.6 (b): 1 (c) and at the same time the sum of the components (b) and (c) to the component (d-2 ) in the

Ratio: 2 [(b) + (c)]: 1 (d-2).

The invention further relates to a herbicidal composition which can be prepared from the formulations according to the invention by dilution with liquids, preferably water.

For use, the formulations of the invention may optionally be prepared in the usual manner, e.g. into suspensions, emulsions, suspoemulsions or solutions, e.g. by means of water. It may be advantageous for the herbicidal compositions (spray liquors) thus obtained to contain further active ingredients, preferably agrochemical active compounds (for example as tank mix partners in the form of corresponding formulations) and / or for use customary auxiliaries and additives, e.g. Adjuvants, e.g. self-emulsifying oils such as vegetable oils or paraffin oils and / or fertilizers. The present invention therefore also relates to the herbicidal compositions prepared in such a way.

The herbicidal agent (spray mixture) per ha is usually 50 to 1500 liters, preferably 50 to 500 liters, more preferably 75 to 350 liters of water. In some cases, the limits given here can also be exceeded or exceeded. The formulations are also suitable for aircraft application. For this purpose, formulations according to the invention are either undiluted, diluted with water or applied with organic solvents. The volume of additional carrier liquid usually varies from 0.5 to 50 liters per hectare.

The application rate of the formulations according to the invention per hectare varies in general and depends on each individual active substance from the group of sulfonamides and their salts component (a) in the respective combinations. With regard to the total formulation according to the invention, it is generally from 5 g to 5 kg of solid, water-dispersible formulation per hectare, preferably from 25 g to 2.5 kg, particularly preferably from 25 g to 1.5 kg, very particularly preferably from 50 g to 1, 5 kg and more preferably 50 g to 500 g; and with regard to component (a) in general 0.5 g to 200 g of active ingredient per hectare, preferably 1, 0 g to 100 g, more preferably 1, 0 g to 75 g, in some cases, the limits specified here also under - or can be exceeded.

A particular embodiment of the invention relates to the use of the herbicidal compositions obtainable from the formulations according to the invention for controlling undesired plant growth (harmful plants), hereinafter referred to as "herbicidal agent", with simultaneous excellent crop plant compatibility, i. high selectivity.

The herbicidal compositions have an excellent herbicidal activity against a broad spectrum of economically important monocotyledonous and dicotyledonous harmful plants. Even hard-to-control perennial weeds that sprout from rhizomes, rhizomes or other permanent organs are well recorded. In this case, the herbicidal agents can be applied, for example, in the pre-seed, pre-emergence or post-emergence process. Specifically, by way of example, some representatives of the monocotyledonous and dicotyledonous weed flora may be mentioned, which can be controlled by the herbicidal agents, without any restriction being made to certain Species should be done.

On the side of the monocotyledonous weeds, e.g. 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. As Bromus catharticus, Bromus secalinus, Bromus erectus, Bromus tectorum and Bromus japonicus and Cyperusarten from the annuelle group and on the part of the perennial species Agropyron, Cynodon, Imperata and Sorghum and also perennial Cyperusarten well. In dicotyledonous weed species, the spectrum of activity extends to species such as e.g. Abutilon spp., Amaranthus spp., Chenopodium spp., Chrysanthemum spp., Galium spp. Galium aparine, Ipomoea spp., Kochia spp., Lamium spp., Matricaria spp., Pharitis spp., Polygonum spp., Sida spp., Sinapis spp., Solanum spp., Stellaria spp., Veronica spp. And Viola spp., Xanthium spp., On the annall side, as well as Convolvulus, Cirsium, Rumex, and Artemisia on perennial weeds.

Under the specific culture conditions occurring in rice harmful plants such. Echinochloa, Sagittaria, Alisma, Eleocharis, Scirpus and Cyperus are also excellently controlled by the herbicidal agents.

When the herbicidal agents are applied to the surface of the earth prior to germination, either weed seedling emergence is completely prevented or the weeds grow to the cotyledon stage, but then cease to grow and finally die completely after three to four weeks.

Upon application of the herbicidal agents to the green parts of the plants postemergence also occurs very quickly after treatment, a drastic halt in growth and the weed plants remain in the existing stage of application growth stage or die after a certain time completely off, so that in this way one for the Crops harmful weed competition is eliminated very early and sustainably. The herbicidal compositions are characterized by a rapidly onset and long-lasting herbicidal activity. The rainfastness of the active ingredients in the herbicidal compositions is generally favorable. A particular advantage is the fact that the effective and used in the herbicidal compositions dosages of herbicidal compounds can be set so low that their soil effect is optimally low. Thus, their use is not only possible in sensitive cultures, but groundwater contamination is virtually avoided. The combination of active substances according to the invention enables a considerable reduction in the required application rate of the active substances.

The said properties and advantages are useful in the practical weed control in order to keep agricultural crops free from undesired competing plants and thus to secure and / or increase the yields qualitatively and quantitatively. The technical standard is significantly exceeded by these new herbicidal compositions in terms of the properties described.

Although the herbicidal compositions have excellent herbicidal activity against mono- and dicotyledonous weeds, crops of economically important crops, e.g. dicotyledonous crops such as soybean, cotton, oilseed rape, sugarbeet or graminaceous crops such as wheat, barley, rye, oats, millet, rice or maize, only marginally or not at all damaged. For these reasons, the present herbicidal compositions are very well suited for the selective control of undesired plant growth in agricultural crops or in ornamental plantings.

In addition, the corresponding herbicidal compositions have excellent growth-regulatory properties in crop plants. They regulate the plant's own metabolism and can thus be used to specifically influence plant ingredients and facilitate harvesting, such as through Triggering of desiccation and stunting are used. Furthermore, they are also suitable for the general control and inhibition of unwanted vegetative growth, without killing the plants. Inhibition of vegetative growth plays an important role in many monocotyledonous and dicotyledonous cultures, as storage can be reduced or completely prevented.

Due to their herbicidal and plant growth regulatory properties, the herbicidal compositions can also be used for controlling harmful plants in crops of known or yet to be developed genetically modified plants. The transgenic plants are usually characterized by particular advantageous properties, for example by resistance to certain pesticides, especially certain herbicides, resistance to plant diseases or pathogens of plant diseases such as certain insects or microorganisms such as fungi, bacteria or viruses. Other special properties relate to z. B. the crop in terms of quantity, quality, shelf life, composition and special ingredients. Thus, transgenic plants with increased starch content or altered quality of the starch or those with other fatty acid composition of the crop are known.

Preferably, the application of the herbicidal agents in economically important transgenic crops of useful and ornamental plants, eg. B. Graminaceous crops such as wheat, barley, rye, oats, millet, rice and corn or even cultures of sugar beet, cotton, soybeans, rape, potato, tomato, pea and other vegetables. Preferably, the herbicidal agents can be used in crops that are resistant to the phytotoxic effects of the herbicides or have been made genetically resistant.

In the application of the herbicidal agents in transgenic crops, in addition to the effects observed in other crops on harmful plants, effects which are specific for the application in the respective transgenic crop often occur, for example a modified or specially extended weed spectrum which can be controlled Application rates for the application can be used, preferably good compatibility with the other herbicidal active ingredients to which the transgenic culture is resistant, and influencing the growth and yield of the transgenic crops.

The present invention therefore also provides a method for controlling undesired plant growth (harmful plants), preferably in crops such as cereals (eg wheat, barley, rye, oats, rice, corn, millet), sugarbeet, sugarcane, rapeseed, cotton and soybeans, particularly preferred in monocotyledonous crops such as cereals, eg Wheat, barley, rye, oats, crosses thereof, such as triticale, rice, maize and millet, characterized in that the herbicidal compositions according to the invention are grown on the harmful plants, plant parts, plant seeds or the area on which the plants grow, e.g. applied the acreage.

The plant cultures may also be genetically engineered or obtained by mutation selection and are preferably tolerant to acetolactate synthase (ALS) inhibitors.

The preparation process of the formulations according to the invention can be selected from a number of processes known per se which permit the preparation of solid formulations such as water-dispersible powders (WP), granules (WG) and compactates obtainable therefrom, such as Schulpen, tablets, etc. Preference is given from this to the methods of extrusion, pan and fluidized bed granulation, particularly preferably the fluidized bed granulation. All methods have in common that the individual components are brought together in the respective production-related quantitative ratios.

The formulations according to the invention show a significantly improved application behavior in comparison to commercially available products, which manifests itself in markedly reduced sieve residues or screen or nozzle clogging. In addition, the formulations according to the invention have excellent chemical stability during production and storage and are also particularly suitable for combinations of active compounds having different physicochemical properties. Likewise, the formulations according to the invention have excellent physical stability, good user-friendliness, and high biological effectiveness and selectivity.

In the formulations according to the invention, the pH, for example in 10% strength aqueous solution, is generally between 7 and 9.

Overall, the formulations of the invention show the desired long-term storage stability and are technically flawless.

Examples

The examples are intended to illustrate the invention and are not limited to the methods and compounds described in them.

Production method:

The safeners (component b) are applied with the solvents (component c) and optionally emulsifiers (component e-1) to the support material (component d-2), whereby a free-flowing absorbate is prepared. This then the remaining formulation components are mixed in the respective proportions. The resulting mixture is then finely ground by means of air jet mill, and then moistened with about 5% water. This moistened material is subjected to extrusion granulation by means of a hood extruder, for example a perforated hood with bores of 0.5 to 0.8 mm in width. The moist granules are then dried in air until they have a predetermined residual water content. The examples shown in Table 1 contain a residual water content of about <2 wt .-%. Description of the commercial products used in the text and examples:

Test method for determining the dispersibility of solid, water-dispersible formulations (WG):

The sample (about 1.5 g of WG) is placed in a graduated cylinder with 100 ml of CIPAC standard water D (= 342 ppm) from room temperature. The cylinder is closed and immediately rotated 180 degrees and back (within about 2 seconds). The completeness of the dispersion is checked visually. The procedure is repeated after about 4 seconds until no undispersed material remains. The maximum number of cylinder revolutions in this test method is 30. If no complete dispersion of the sample is completed within this number, the test is terminated and the dispersibility is negated (dispersibility: NO).

Note: Table 1 shows the composition of solid, water-dispersible formulations, Example 1 having a standard prior art composition while Example 2 shows the composition of the present invention.

The result from the test method for determining the dispersibility clearly shows that only the composition of the formulation according to the invention (Example 2) has sufficient dispersibility (dispersibility: YES).

Claims

claims

1. Solid, water-dispersible formulation comprising:

(a) one or more active substances from the group of sulfonamides and their salts, with at least one active substance from the group phenylsulfonylaminocarbonyltriazolinones,

(b) one or more safeners;

(c) one or more solvents,

(d) one or more support materials selected from one or more of the groups:

(d-1) low absorbency carriers, (d-2) high absorbency carriers;

(e) one or more common excipients and additives selected from one or more of the groups

(e-1) emulsifiers,

(e-2) antifoam,

(e-3) wetting agent,

(e-4) dispersants; wherein component (b) for component (c) is in the following ratio: (b): (c) generally 0.3 to 2.0: 1, preferably 0.4 to 1.5: 1, more preferably 0, 5 to 1, 0: 1; and at the same time the sum of the components (b) and (c) to the component (d-2) in the following ratio: [(b) + (c)]: (d-2) in general 1, 7 to 3.9: 1, preferably 1.85 to 3.5: 1, more preferably 2.0 to 3.0: 1.

2. Solid, water-dispersible formulation according to claim 1, wherein as component (a) are contained, at least two or more active substances from the group of sulfonamides and their salts.

3. Solid, water-dispersible formulation according to claim 1 or 2, wherein as component (a) are contained, herbicidal active compounds from the group of Phenylsulfonamide, such as Phenylsulfonylaminocarbonyltriazolinone or Phenylsulfonylureas, Heteroarylsulfonamide and other sulfonamides, and their salts.

4. Solid, water-dispersible formulation according to one or more of claims 1 to 3, wherein as component (a) are contained, active ingredients from the group propoxycarbazone and its sodium salt, methyl-4 - [(4,5-dihydro-3-methoxy- 4-methyl-5-oxo-1H-1, 2,4-triazol-1-yl) carboxamidosulfonyl] -5-methylthiophene-3-carboxylate and its sodium salt, amidosulfuron and its sodium salt, iodosulfuron-methyl and its sodium salt, foramsulfuron and its sodium salt, thifensulfuron-methyl and its sodium salt, mesosulfuron-methyl and its sodium salt.

5. Solid, water-dispersible formulation according to one or more of claims 1 to 4, wherein as component (b) are contained safeners from the group mefenpyr-diethyl, isoxadifen-ethyl, 4-cyclopropylaminocarbonyl-N- (2-methoxybenzoyl) benzenesulfonamide ( Cyprosulfamides), 4-iso-propylaminocarbonyl-N- (2-methoxybenzoyl) benzenesulfonamide.

6. Solid, water-dispersible formulation according to one or more of claims 1 to 5, wherein as component (c) are included, solvents from the group of aromatic and aliphatic hydrocarbons

7. Solid, water-dispersible formulation according to one or more of claims 1 to 6, wherein as component (d-1) are contained, carriers from the group of natural framework silicates.

8. Solid, water-dispersible formulation according to one or more of claims 1 to 7, wherein as component (d-2) are contained, excipients from the group of calcium silicates and precipitated silicas.

9. Solid, water-dispersible formulation according to one or more of claims 1 to 8, wherein as component (e-1) are contained, emulsifiers from the Group of combinations of salts of alkylated aromatic sulfonic acids with alkylated copolymers of ethylene and propylene oxide.

10. Solid, water-dispersible formulation according to one or more of claims 1 to 9, wherein as component (e-2) are, antifoams from the group of suspoemulsions of hydrophobicized silica particles in aqueous emulsion concentrates based on liquid silicone surfactants and solid antifoams.

11. Solid, water-dispersible formulation according to one or more of claims 1 to 10, wherein as component (e-3), wetting agents from the group of block polymers of propylene oxide and ethylene oxide to ethylenediamine, the salts of alkylated naphthalenesulfonic acids and the salts of Dioctylsulfobernsteinsäure ,

12. Solid, water-dispersible formulation according to one or more of claims 1 to 11, wherein as component (e-4) are included, dispersants from the group of the condensation products of aromatic sulfonic acids with formaldehyde and salts thereof.

13. Solid, water-dispersible formulation according to one or more of claims 1 to 12, additionally comprising as component (f) one or more herbicidal active compounds from the group of carbamates, thiocarbamates, haloacetanilides, substituted phenoxy, naphthoxy and Phenoxyphenoxycarbonsäure derivatives and heteroaryloxy phenoxyalkanecarboxylic acid derivatives, such as quinolyloxy, quinoxalyl-oxy, pyridyloxy, benzoxazolyloxy and benzthiazolyloxyphenoxyalkane-carboxylic acid esters, cyclohexanedione derivatives, phosphorus-containing glufosinate-type or glyphosate-type herbicides, and also S- (N-aryl) N-alkylcarbamoylmethyl) dithiophosphoric acid ester.

14. Solid, water-dispersible formulation according to one or more of claims 1 to 13, additionally comprising as component (g) one or more of the component (e) different excipients and additives from the group of disintegrating agents, such as crosslinked polyvinylpyrrolidones, binders (adhesion promoters ), such as polyvinylpyrrolidone types, and means for adjusting the pH, such as NaOH and Na ₂ CO.

15. A process for preparing a solid, water-dispersible formulation according to one or more of claims 1 to 14, wherein the individual components are brought together in the respective production-related quantitative ratios.

16. A method for controlling harmful plants, wherein an effective amount of a solid, water-dispersible formulation according to one or more of claims 1 to 14 is applied to the harmful plants, parts of the plants, plant seeds, the area on the plants grow.

17. Use of a solid, water-dispersible formulation according to one or more of claims 1 to 14, for controlling harmful plants.

18. Use of a solid, water-dispersible formulation according to one or more of claims 1 to 14, for the preparation of a herbicidal composition.

19. A herbicidal composition containing a solid, water-dispersible formulation according to one or more of claims 1 to 14.

20. A method of controlling harmful plants, wherein an effective amount of a herbicidal composition according to claim 19 is applied to the harmful plants, parts of the plants, plant seeds, the area on the plants grow.

21. Use of a herbicidal composition according to claim 19, for controlling harmful plants.