EP1523235A1 - Liquid adjuvants - Google Patents

Abstract

The invention relates to a liquid adjuvant containing a) at least one surfactant of formula (I), Ar-O-(CHR<1>-CHR<2>-O-)Y R<3>, wherein Ar represents Aryl which is substituted by at least two (C1-C3o)alkyl radicals, R<1> represents H or (C1-C6)alkyl, R<2 >represents H or (C1-C6) alkyl, R<3> represents H, an unsubstituted or substituted (C1-C3o) hydrocarbon radical, a sulfonate radical, a phosphonate radical or an acyl radical, and y represents a whole number from 1 to 100; and b) at least one fatty acid ester. Said adjuvant is especially suitable in the field of plant protection.

Description

Liquid adjuvants

The present invention relates to new liquid adjuvants, especially those which are advantageously useful in the field of crop protection, e.g. in combination with agrochemical agents.

Agrochemical active substances, in particular agrochemical active substances, which are applied post-emergence and are absorbed into the plants via the leaf, e.g. Post-emergence herbicides are often mixed with so-called adjuvants, e.g. to increase the biological effect of the agrochemical active substances. Adjuvants are understood to mean biological enhancers that are not themselves biologically active.

This technology has a broad practical meaning and is described intensively in the specialist literature (see, for example, CLFoy, DW Pritchard (Ed.), "Pesticide Formulation and Adjuvant Technology", CRC Press, Ine, 1996, Boca Raton, Florida, USA ; CL Foy (Ed.), "Adjuvants for Agrochemicals, CRC Press, Ine, 1992, Boca Raton, Florida, USA). For example, it is known to mix sulfonylureas with adjuvants based on vegetable oils, which are also commercially available (WO 01/30155).

The object was to provide new adjuvants which have advantageous properties, in particular in combination with agrochemical active ingredients, such as herbicides.

Surprisingly, it has now been found that this object is achieved by the special adjuvants of the present invention.

The present invention thus relates to a liquid adjuvant comprising a) one or more surfactants of the formula (I),

Ar-O- (CHR ¹ -CHR ² -O-) _y -R ³ (I) wherein

Ar is aryl which is substituted by at least two, preferably 2 to 10, (C-i-

C ₃₀ ) alkyl radicals is substituted, R ^{1 is} H or (C ¹ -C ₆ ) alkyl, R ² H or (C ₁ -C ₆ ) alkyl,

R ³ H, an unsubstituted or substituted (-C-C ₃₀ )

Hydrocarbon residue, preferably (CrC ₃₀ ) alkyl, (C ₂ -C ₃ o) alkenyl or (C ₂ -C ₃ o) alkynyl, a sulfonate residue, a phosphonate residue, an acyl residue, and y is an integer from 1 to 100, preferably 1 to 20 means and

b) one or more fatty acid esters.

In the surfactants of formula (I) for y> 1 the y units (CHR ¹ -CHR ² -O) can be the same (e.g. ethylene oxide homopolymer units, propylene oxide units).

Homopolymer units or butylene oxide homopolymer units) or different from one another (for example ethylene oxide / propylene oxide copolymer units or ethylene oxide / butylene oxide copolymer units). Surfactants of the formula (I) are generally known and are also commercially available, for example from the Sapogenat® T series from Clariant AG. In addition, surfactants of the formula (I) can be prepared by known reactions, for example surfactants of the formula (I) with R ³ = H by reacting commercially available epoxides, for example the formula (I '), with hydroxylaromatics, for example the formula (I " ), under catalytic conditions (e.g. NaOH and / or NaAcetat; temperature approx. 100 - 200 ° C; overpressure of approx. 2 - 10 bar).

- ° - ArOH

^ ^ R ²

(! ') (I ")

The radicals R ¹ and R ² in formula (I ') and the radical Ar in formula (I ") are defined as in formula (I). Surfactants of the formula (I) with R ³ ≠ H can be obtained from surfactants of the formula ( I) by standard reactions with R ³ = H. For example, surfactants of the formula (I) can be obtained with R ³ = (substituted) hydrocarbon radical such as alkyl, alkenyl or alkynyl by alkylation, alkenylation or alkynylation, for example with Alkyl halides, alkenyl halides or alkynyl halides under basic catalysis; with R ³ = sulfonate residue by sulfation followed by neutralization; with R ³ = phosphonate residue by phosphating; with R ³ = acyl residue by acylation.

These reactions are well known to those skilled in the art and are e.g. described in "Surfactants in Consumer Products" (J. Falbe, Springer Verlag Heidelberg, 1987, and literature cited therein) or J. March, Advanced Organic Chemistry, 4th Edition, John Wiley & Sons, New York, 1992.

The epoxides of formula (I ') can be prepared by known methods, e.g. from the corresponding alkenes and are commercially available, e.g. Ethylene oxide or propylene oxide.

The compounds of the formula (I ") are commercially available and described in the literature, and they can also be prepared by standard reactions which are known to the person skilled in the art. For example, hydroxyaromatics, such as, for example, phenol, with alcohols, olefins or alkyl halides under catalytic ones Conditions (protonic acids such as sulfuric or phosphoric acid or Lewis acids such as aluminum chloride or boron trifluoride diethyl ether) to the compounds of formula (I ") are implemented. A broad overview offers e.g. "Methods of Organic Chemistry" (Houben-Weyl) 4th edition, 1976, Vol 6/1 c, p. 925 ff; (ISBN 3- 13-204204-8).

Preferred surfactants of the formula (I) are those in which Ar in formula (I) is a naphthyl or phenyl radical which bears 3 to 7, preferably 3 to 5 (C 1 -C 6) alkyl radicals. Ar is preferably a phenyl radical which bears 3 to 5 (C 1 -C 10) alkyl radicals such as tri (C ₁ -C ₆ ) alkylphenyl, particularly preferably tri-butylphenyl such as tri-2,4,6-sec. butyl-phenyl.

R ¹ and R ² are preferably H or methyl, particularly preferably H. R ³ is preferably H, (CC ₂₂ ) alkyl, (C ₂ -C ₂₂ ) alkenyl, (C ₂ -C ₂₂ ) alkynyl, an acyl radical such as CO- (-C-C ₃₀ ) alkyl, CO- (C ₂ -C ₃₀ ) alkenyl, CO- (C ₂ -C ₃₀ ) alkynyl, CO- (CrC ₃ o) alkoxy, CO- (C ₂ -C ₃₀ ) alkenyloxy, CO- (C ₂ -C ₃₀ ) alkynyloxy or COH, or a Sulfonate radical such as SO ₃ X, where X is H or a cation such as an inorganic cation, for example an alkali metal or alkaline earth metal cation such as Na, K or Mg or an organic cation, for example a primary, secondary, tertiary or quaternary ammonium ion such as NH ₃ CH ₃ , NH ₂ (CH ₃ ) ₂ , NH (C ₂ Hs) ₃ or N (CH ₃ ), or a phosphonate residue such as (O) P (OR) (OR ^" ), where R ^' , R ^" independently of one another are H or a cation are like an inorganic cation, e.g. an alkali metal or alkaline earth metal cation like Na, K or Mg or an organic cation e.g. a primary, secondary, tertiary or quaternary ammonium ion like NH ₃ CH ₃ , NH ₂ (CH ₅ ) ₂ , NH ( C ₂ H ₃ ) ₃ or N (CH ₃ ) ₄ , and R ^' , R ^"can also be Ar-O- (CHR ¹ CHR ² ) _y , wherein Ar, R ¹ , R ² and y are as defined in formula (I). R ³ = H, (-CC) alkyl or S0 ₃ M, where M is a cation, is particularly preferred.

Values from 2 to 20 are preferred for y, particularly preferred are values from 2 to 14, very particularly preferably from 2 to 9.

Surfactants of the formula (I) are very particularly preferred in which Ar is tri (-C ₆ ) alkylphenyl, particularly preferably tri-butylphenyl such as tri-2,4,6-sec-butylphenyl, R ¹ = R ² = R ³ = H and y is an integer from 2 to 14, e.g. surfactants from the Sapogant® T series from Clariant, e.g. Sapogenat® T 040, Sapogenat® T 060, Sapogenat® T 070, Sapogenat® T 080, Sapogenat® T 090, Sapogenat® T 100, Sapogenat® T 110 and Sapogenat® T 130. Mixtures of two or more different surfactants of the formula (I), for example of two or more different surfactants, are also preferred as component a) the Sapogenat® T series.

In formula (I) and all other formulas in this description, carbon-containing radicals such as alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino and alkylthio and the corresponding unsaturated and / or substituted radicals in the carbon skeleton can each be straight-chain or branched. Unless specifically stated, these radicals generally have 1 to 30 carbon atoms, the lower carbon skeletons, for example with 1 to 6 carbon atoms or, in the case of unsaturated groups, with 2 to 6 carbon atoms, are preferred. Alkyl radicals, also in the composite meanings such as alkoxy, haloalkyl, etc., mean, for example, methyl, ethyl, n- or i-propyl, n-, i-, t- or sec-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 means, 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-in-1-yl, but-3-in-1-yl, 1-methyl-but-3-in-1-yl.

Alkenyl in the form (C ₃ -C ₄ ) alkenyl, (C ₃ -C ₅ ) alkenyl, (C ₃ -C ₆ ) alkenyl, (C ₃ -C ₈ ) alkenyl or (C ₃ -Cι ₂ ) alkenyl preferably an alkenyl radical having 3 to 4, 3 to 5, 3 to 6, 3 to 8 or 3 to 12 carbon atoms, in which the double bond is not due to the carbon atom which is associated with the rest of the molecular part of the compound of the formula ( I) is connected ("yl" position). The same applies to (C ₃ -C ₄₎ alkynyl etc., (C ₃ - C ₄₎ AIkenyloxy etc. and (C ₃ -C ₄₎ alkynyloxy etc.

A hydrocarbon residue means a straight-chain, branched or cyclic and saturated or unsaturated aliphatic or aromatic

Hydrocarbon residue, 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; A hydrocarbon radical is particularly preferably alkyl, alkenyl or alkynyl having up to 12 carbon 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 with 3 to 7 ring atoms or a heteroaromatic radical with 5 or 6 ring atoms and contains 1, 2 or 3

Hetero atoms. The heterocyclic residue can e.g. be a heteroaromatic residue or ring (heteroaryl), e.g. a mono-, bi- or polycyclic aromatic system in which at least 1 ring contains one or more heteroatoms, for example pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, thienyl, thiazolyl, oxazolyl, furyl, pyrrolyl, pyrazolyl and imidazolyl, or is one partially or fully hydrogenated radical such as oxiranyl, oxetanyl, pyrrolidyl, piperidyl, piperazinyl, dioxolanyl, morpholinyl, tetrahydrofuryl. Possible substituents for a substituted heterocyclic radical are the substituents mentioned below, and additionally oxo. The oxo group can also be attached to the hetero ring atoms, which can exist in different oxidation states, e.g. at N and S, occur.

Halogen means, for example, fluorine, chlorine, bromine or iodine. Haloalkyl, -alkenyl and -alkynyl are partially or completely substituted alkyl, alkenyl or alkynyl, for example CF ₃ , CHF ₂ , CH ₂ F, CF, by halogen, preferably by fluorine, chlorine and / or bromine, in particular by fluorine or chlorine ₃ CF ₂ , CH ₂ FCHCI, CCI ₃ , CHCI ₂ , CH ₂ CH ₂ CI; 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 CI; the same applies to haloalkenyl and other halogen-substituted radicals.

Substituted residues such as substituted hydrocarbon residues e.g. substituted

Alkyl, alkenyl, alkynyl, aryl, phenyl and benzyl, or substituted heterocyclyl or heteroaryl, mean, for example, a substituted radical derived from the unsubstituted basic body, the substituents being, for example, one or more, preferably 1, 2 or 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 the saturated hydrocarbon-containing radicals corresponding to unsaturated aliphatic radicals such as alkenyl, alkynyl, alkenyloxy, alkynyloxy etc. In the case of radicals with carbon atoms, those with 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms, are preferred. Preferred are generally substituents from the group halogen, for example fluorine and chlorine, (C 1 -C ₄ ) alkyl, preferably methyl or ethyl, (C 1 -C) haloalkyl, preferably trifluoromethyl, (CrC) alkoxy, preferably methoxy or ethoxy , (CrC ₄ ) haloalkoxy, nitro and cyano. The substituents methyl, methoxy and chlorine are particularly preferred.

Optionally substituted phenyl is preferably phenyl which is unsubstituted or one or more times, preferably up to three times, by identical or different radicals from the group halogen, (C 1 -C ₄ ) alkyl, (C 1 -C ₄ ) alkoxy, (C- ι-C ₄ ) haloalkyl, (CtC ₄ ) haloalkoxy and nitro is substituted, 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, 2,4,6-tributylphenyl such as 2,4,6-tri -sec-butylphenyl.

An acyl residue means the residue of an organic acid that is formally represented by

Elimination of an OH group from the organic acid results, e.g. the rest of a carboxylic acid and residues derived therefrom, such as thiocarboxylic acid, optionally N-substituted iminocarboxylic acids or the residues of carbonic acid monoesters, optionally N-substituted carbamic acids, sulfonic acids, sulfinic acids, phosphonic acids, phosphinic acids.

An acyl radical is preferably formyl or aliphatic acyl from the group CO-R ^x , CS-R ^X , CO-OR ^x , CS-OR ^x , CS-SR ^X , SOR ^γ or SO ₂ R ^γ , where R ^x and R ^γ each represents a C ₁ -C ₃ -hydrocarbon radical which is unsubstituted or substituted, or aminocarbonyl or aminosulfonyl, the latter two radicals being unsubstituted, N-monosubstituted or N, N-disubstituted. Acyl means, for example, formyl, haloalkylcarbonyl, alkylcarbonyl such as (-CC) alkylcarbonyl, phenylcarbonyl, where the phenyl ring may be substituted, for example as indicated above for phenyl, or alkyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, alkylsulfonyl, alkylsulfinyl, N-alkyl-1-iminoalkyl and other residues of organic acids.

Formula (I) and the other formulas in this description also encompass all stereoisomers and mixtures thereof. Such compounds contain one or more asymmetric carbon atoms or double bonds, which are not specified separately in the general formula. The possible stereoisomers defined by their specific spatial form, such as enantiomers, diastereomers, Z and E isomers, are all encompassed by the respective formulas and can be obtained from mixtures of the stereoisomers by customary methods or else by stereoselective reactions in combination with the use of stereochemically pure ones Starting materials are produced.

The fatty acid ester present in the novel adjuvants may be, for example of natural origin, for example, be natural oils such as animal oils or vegetable oils, or synthetic origin, for example Edenor ^® series, for example Edenor ^® MEPa or Edenor ^® MESU or AGNIQUE ^® ME series or AGNIQUE ^® AE Series (Cognis), SALIM ^® ME series (Salim), Radia ^® series eg Radia ^® 30167 (Fina Chemicals),

Priolube ^® series, e.g. Priolube ^® 1530 (Unichema), STEPAN ^® C series (Stepan) or WITCONOL ^® 23 series (Witco). The fatty acid esters are preferably esters of C ₁₀ -C ₂₂ , preferably Ci ₂ -C ₂ o fatty acids. The Cιo-C ₂₂ fatty acid esters are, for example, esters of unsaturated or saturated Cιo-C ₂₂ fatty acids, in particular with an even number of carbon atoms, for example erucic acid, lauric acid, palmitic acid and in particular C-ts fatty acids such as stearic acid, oleic acid, linoleic acid or linolenic acid.

Examples of fatty acid esters such as -C ₀ -C ₂₂ fatty acid esters are glycerol and glycol esters of fatty acids such as Cιo-C ₂₂ fatty acids or their transesterification products, for example alkyl fatty acid esters such as CrC ₂ o-alkyl-Cιo-C ₂₂ fatty acid esters , such as by transesterification of the aforementioned glycerol or glycol fatty acid esters such as Cιo-C- ₂₂ fatty acid esters with CrC ₂ o-alcohols (e.g. methanol, Ethanol, propanol or butanol) can be obtained. The transesterification can be carried out by known methods, as described, for example, in the Römpp Chemie Lexikon, 9th edition, volume 2, page 1343, Thieme Verlag Stuttgart.

Preferred alkyl fatty acid esters such as C ₁ -C 20 -alkyl-C ₂₂ -C 8 fatty acid esters are methyl esters, ethyl esters, propyl esters, butyl esters, 2-ethyl hexyl esters and dodecyl esters. Preferred glycol and glycerol fatty acid esters such as Cιo-C ₂₂ fatty acid esters are the uniform or mixed glycol esters and glycerol esters of Cι ₀ -C ₂₂ fatty acids, in particular those fatty acids with an even number of carbon atoms, for example erucic acid, lauric acid, palmitic acid and in particular Ci ₈ fatty acids such as stearic acid, oleic acid, linoleic acid or linolenic acid.

Animal oils b) contained in the adjuvants according to the invention are generally known and commercially available. The term animal oils in the sense of the present invention includes e.g. Oils of animal origin are understood as walnut oil, cod liver oil, musk oil or mink oil.

Vegetable oils b) contained in the adjuvants according to the invention are generally known and commercially available. Under the term vegetable oils in the sense of the present invention, e.g. Oils from oil-bearing plant species such as soybean oil, rapeseed oil, corn oil, sunflower oil, cottonseed oil, linseed oil, coconut oil, palm oil, safflower oil, walnut oil, peanut oil, olive oil or castor oil, in particular rapeseed oil, whereby the vegetable oils are also understood to mean their transesterification products, e.g. Alkyl esters such as rapeseed oil methyl ester or rapeseed oil ethyl ester.

The vegetable oils are preferably esters of C1 ₀ -C22, preferably Ci2-C ₂₀ fatty acids. The Cιo-C- ₂₂ fatty acid esters are, for example, esters of unsaturated or saturated Cι ₀ -C ₂₂ fatty acids, in particular with an even number of carbon atoms, for example erucic acid, lauric acid, palmitic acid and in particular C-is fatty acids such as stearic acid, oleic acid, linoleic acid or linolenic acid. Examples of vegetable oils are Cιo-C ₂₂ fatty acid esters of glycerol or glycol with the Cιo-C ₂₂ fatty acids, or CrC ₂ o-alkyl-Cι ₀ -C ₂₂ fatty acid esters, such as by transesterification of the aforementioned glycerol - Or glycol-Cιo-C ₂₂ fatty acid esters with CrC- ₂₀ alcohols (for example methanol, ethanol, propanol or butanol) can be obtained. The transesterification can be carried out according to known methods, as described, for example, in the Römpp Chemie Lexikon, 9th edition, volume 2, page 1343, Thieme Verlag Stuttgart.

The vegetable oils can be used in the adjuvants according to the invention, for example in the form of commercially available vegetable oils, in particular rapeseed oils such as rapeseed oil methyl ester, for example Phytorob®B (Novance, France, hereinafter referred to as Phytorob B), Edenor® MESU (Cognis, Germany, hereinafter referred to as Edenor) and Agnique® ME - Series (Cognis, Germany, hereinafter referred to as Agnique), Priolube ^® series (Unichema, hereinafter referred to as Priolube) or biodiesel or in the form of commercially available vegetable oil-containing formulation additives, in particular those based on rapeseed oils such as rapeseed oil methyl ester, for example Hasten® (Victorian Chemical Company, Australia, hereinafter referred to as Hasten, main constituent: rapeseed oil methyl ester), Actirob®B (Novance, France, hereinafter referred to as ActirobB, main constituent: rapeseed oil methyl ester), Rako-Binol® (Bayer AG, Germany, hereinafter referred to as Rako-Binol, main constituent: rapeseed oil), Renol ® (Stefes, Germany, hereinafter called Renol, vegetable oil component: Rapeseed oil methyl ester) or Stefes Mero® (Stefes, Germany, hereinafter referred to as Mero, main component: rapeseed oil methyl ester).

Examples of synthetic fatty acid esters are, for example, those derived from fatty acids with an odd number of carbon atoms, such as Cn-C ₂ ι fatty acid esters.

The adjuvants according to the invention are liquid under normal conditions (normal pressure, room temperature). They generally contain between 1 and 50% by weight, preferably between 2 and 30% by weight, particularly preferably between 2 and 20% by weight, of one or more surfactants of the formula (I), and between 99 and 50 % By weight, preferably between 98 and 70% by weight, particularly preferred between 98 and 80% by weight of one or more fatty acid esters b) such as vegetable oils. In individual cases, these salary limits can also be exceeded or fallen short of. Preferred adjuvants according to the invention contain the fatty acid esters b) such as vegetable oils in excess over the surfactants of the formula (I).

In addition, the adjuvants according to the invention can contain typical auxiliaries such as additives and formulation auxiliaries. The term auxiliary substances is understood to mean substances which are largely chemically and biologically inert and whose use enables an agent to be handled as intended.

Examples of auxiliary substances are

Wetting agents such as Genapol ^® LRO (0-20% by weight), dispersing agents such as Tamol ^® (0-15% by weight) or other surfactants (nonionic, cationic, anionic, polymeric surfactants) (0-30% by weight) );

• Inorganic salts such as NaCl, MgCl ₂ (0-50% by weight), (oligo-; poly -) - phosphates;

• fertilizers such as ammonium sulfate, ammonium nitrate, urea, phosphorus and potassium-containing components, optionally further trace elements (0-60% by weight);

• Defoamers, eg based on silicone such as SE2 ^® (Wacker Chemie) or Silolapse ^® 5020 (Rhodia) (0-2% by weight);

Binders such as suitable natural or synthetic substances such as polyamino acids, polyvinyl alcohols, polyvinyl pyrrolidone, polyacrylic acid derivatives (0-15% by weight); or

• Solvents such as water or organic solvents (0-15% by weight).

The amounts given for the auxiliaries (% by weight) are ranges which are to be regarded as typical, but which can also be exceeded or fallen short of in individual cases.

The adjuvants according to the invention are prepared by customary processes, for example mixing by dissolving or emulsifying the individual components, preferably at room temperature. If other auxiliaries are included, these are also preferably entered at room temperature. The order of addition of the individual components is generally arbitrary.

The adjuvants according to the invention can be combined with one or more agrochemical active ingredients c) to give agrochemical compositions, e.g. in the form of co-formulations or tank mixes, preferably in tank mixes. Such agrochemicals are also new and the subject of the present invention.

As agrochemical active ingredients, e.g. Herbicides, insecticides, fungicides, safeners and growth regulators. Herbicides, e.g. leaf-active herbicides such as ALS inhibitors (for example sulfonamides such as flucarbazone, propoxycarbazone or amicarbazone or sulfonylureas such as mesosulfuron, ethoxysulfuron, iodosulfuron, amidosulfuron, foramsulfuron), diflufenican, bromoxynil-containing phen, or loxynylapoxy-containing products, such as deroxoxylilyloxypoxides from deroxoxyliloxane-containing products, such as deroxoxyliloxane-containing products, such as deroxoxyliloxane-containing products from the class , Beet herbicides such as desmedipham, phenmedipham, ethofumesate or metamitron, glyphosate or glufosinate or also active substances from the class of the HPPD inhibitors (for example isoxaflutole, sulcotrione, mesotrione)

Herbicides contained in the agrochemical compositions according to the invention are, for example, ALS inhibitors (acetolactate synthetase inhibitors) or herbicides other than ALS inhibitors, such as herbicides from the group of carbamates, thiocarbamates, haloacetanilides, substituted phenoxy, naphthoxy and phenoxyphenoxycarboxylic acid derivatives and also Heteroaryloxyphenoxyalkanecarboxylic acid derivatives, such as quinolyloxy, quinoxalyloxy, pyridyloxy, benzoxazolyloxy and benzothiazolyloxyphenoxyalkane carboxylic acid esters, cyclohexanedione derivatives, phosphorus-containing herbicides, for example of the glufosinate type or of the glyphosate type (N) -Aryl-N-alkylcarbamoylmethyl) - dithiophosphoric acid ester. The ALS inhibitors are, in particular, imidazolinones, pyrimidinyloxy-pyridinecarboxylic acid derivatives, pyrimidyloxybenzoic acid derivatives, triazolo-pyrimidine-sulfonamide derivatives and sulfonamides, preferably from the group of sulfonylureas, particularly preferably those with the general formula ( II) and / or their salts,

R ^α -SO ₂ -NR ^ß -CO- (NR ^γ ) _x - R ^δ (II) where

R ^{α is} a hydrocarbon radical, preferably an aryl radical, such as phenyl, which is unsubstituted or substituted, or a heterocyclic radical, preferably a heteroaryl radical, such as pyridyl, which is unsubstituted or substituted, and the radicals including substituents have 1-30 C atoms, preferably 1 Have -20 C atoms, or R ^{a is} an electron-withdrawing group such as a sulfonamide radical,

R ^{ß is} a hydrogen atom or a hydrocarbon radical which is unsubstituted or substituted and has substituents including 1-10 C atoms, for example unsubstituted.es or substituted C ₁ -C ₆ alkyl, preferably a hydrogen atom or methyl, R ^γ a hydrogen atom or a Is 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 a hydrogen atom or methyl, x is zero or 1, and R ^{δ is} a heterocyclic radical ,

Particularly preferred ALS inhibitors are sulfonylureas of the formula (III) and / or their salts, wherein R ^{4 is} C ₁ -C ₄ alkoxy, preferably C ₂ -C ₄ alkoxy, or CO-R ^a , where R ^{a is the} same

Is OH, C 1 -C ₄ -alkoxy or NR ^b R ^c , where R ^b and R ^{c are,} independently of one another, the same or different H or C 1 -C ₄ alkyl,

R ^{1 is} halogen or (A) _n -NR ^d R ^e , where n is zero or 1, A is a group

CR'R "is in which R 'and R" are, independently of one another, the same or different H or CC 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 _{4 is} alkyl sulfonyl, and R ⁵ in the event that R ⁴ is Ci

C ₄ alkoxy, preferably C ₂ -C ₄ alkoxy, can also be H,

R ^{f is} H or C 1 -C ₄ alkyl, m is zero or 1, preferably zero,

X and Y are, independently of one another, identical or different, CrCβ-alkyl, Ci-C-β-alkoxy or Cι-C ₆ alkylthio, where each of the three radicals mentioned is unsubstituted or by one or more radicals from the group halogen, CrC -alkoxy and -C-C ₄ alkylthio is substituted, or C ₃ -C ₆ -cycloalkyl, C ₂ -C ₆ -alkenyl, C ₂ -C ₆ -alkynyl, Ca-Cβ-alkenyloxy or C ₃ -C ₆ -alkynyloxy are preferred CC ₄ alkyl or CrC ^ alkoxy, and

Z is CH or N.

Preferred sulfonylureas of the general formula (III) and / or their salts are those in which

m is zero, and

a) R is CO- (CrC ₄ -alkoxy) and R ⁵ is halogen, preferably iodine, or R ⁵ is CH ₂ -NHR ⁶ , wherein R ^{e is} an acyl radical, preferably C 1 -C ₄ -alkyl sulfonyl , or b) R ⁴ is CO-N (dC-alkyl) ₂ and R ⁵ is NHR ^e , where R ^{e is} an acyl radical, preferably formyl.

In the context of the present invention, the active ingredients from the group of ALS inhibitors, such as sulfonylureas, contained as a component in the herbicidal compositions according to the invention always include, in addition to the neutral compounds, their salts with inorganic and / or organic counterions. For example, sulfonylureas 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 also ammonium salts or salts with organic amines. Salt formation can also take place by addition of an acid to basic groups, such as amino and alkylamino. Suitable acids for this are strong inorganic and organic acids, for example HCl, HBr, H ₂ SO or HNO ₃ .

Preferred ALS inhibitors come from the series of sulfonylureas, e.g. Pyrimidine or triazinylaminocarbonyl- [benzene, pyridine, pyrazole, thiophene and (alkylsulfonyl) alkylamino -] sulfamides. Preferred substituents on the pyrimidine ring or triazine ring are alkoxy, alkyl, haloalkoxy, haloalkyl, halogen or

Dimethylamino, where all substituents can be combined independently of one another. Preferred substituents in the benzene, pyridine, pyrazole, thiophene or (AΙkylsulfonyl) alkylamino part are alkyl, alkoxy, halogen such as F, Cl, Br or J, amino, alkylamino, dialkylamino, acylamino such as formylamino, nitro, alkoxycarbonyl , Aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkoxyaminocarbonyl, haloalkoxy, haloalkyl, alkylcarbonyl, alkoxyalkyl, alkylsulfonylaminoalkyl, (alkanesulfonyl) alkylamino. Examples of such suitable sulfonylureas are

A1) phenyl- and benzylsulfonylureas and related compounds, for example 1- (2-chlorophenylsulfonyl) -3- (4-methoxy-6-methyl-1, 3,5-triazin-2-yl) urea (chlorosulfuron), 1- (2-EthoxycarbonylphenylsuIfonyl) -3- (4-chloro-6-methoxypyrimidine-2-yl) urea

(Chlorimuron-ethyl),

1- (2-methoxyphenylsulfonyl) -3- (4-methoxy-6-methyl-1, 3,5-triazin-2-yl) urea

(Metsulfuron-methyl), 1 - (2-chloroethoxyphenylsulfonyl) -3- (4-methoxy-6-methyl-1, 3,5-triazin-2-yl) urea

(Triasulfuron),

1- (2-Methoxycarbonylphenylsulfonyl) -3- (4,6-dimethylpyrimidin-2-yl) urea

(Sulfumeturon-methyl),

1- (2-methoxycarbonylphenylsulfonyl) -3- (4-methoxy-6-methyl-1, 3,5-triazin-2-yl) -3-methylurea (tribenuron-methyl),

1- (2-Methoxycarbonylbenzylsulfonyl) -3- (4,6-dimethoxypyrimidin-2-yl) urea

(Bensulfuron-methyl),

1- (2-methoxycarbonylphenylsulfonyI) -3- (4,6-bis- (difluoromethoxy) pyrimidin-2-yl) urea, (primisulfuron-methyl), 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 0 796 83),

3- (4-Ethoxy-6-ethyl-1,3,5-triazin-2-yl) -1- (2,3-dihydro-1,1-dioxo-2-methylbenzo [b] thiophene-7- sulfonyl) urea (EP-A 0 079 683),

3- (4-methoxy-6-methyl-1, 3,5-triazin-2-yl) -1- (2-methoxycarbonyl-5-iodophenylsulfonyl) urea (iodosulfuron-methyl and its salts like that Sodium salt, WO

92/13845)

DPX-66037, triflusulfuron-methyl (see Brighton Crop Prot. Conf. - Weeds - 1995, p.

853),

CGA-277476, (see Brighton Crop Prot. Conf. - Weeds - 1995, p. 79), methyl-2- [3- (4,6-dimethoxypyrimidin-2-yl) ureidosulfonyl] -4-methanesulfonamido methyl benzoate (mesosulfuron methyl and its salts such as the sodium salt, WO

95/10507)

N, N-dimethyl-2- [3- (4,6-dimethoxypyrimidin-2-yl) ureidosulfonyl] -4-formylamino-benzamide (foramsulfuron and its salts such as the sodium salt, WO 95/01344);

A2) Thienylsulfonylureas, e.g. 1- (2-methoxycarbonylthiophene-3-yl) -3- (4-methoxy-6-methyl-1, 3,5-triazin-2-yl) urea (thifensulfuron-methyl);

A3) pyrazolylsulfonylureas, e.g. 1 - (4-ethoxycarbonyl-1-methylpyrazol-5-yl-sulfonyl) -3- (4,6-dimethoxypyrimidin-2-yl) urea (pyrazosulfuron-methyl);

Methyl 3-chloro-5- (4,6-dimethoxypyrimidin-2-ylcarbamoylsulfamoyl) -1-methyl-pyrazole-4-carboxylate (EP-A 0 282 613);

5- (4,6-Dimethylpyrimidin-2-yl-carbamoylsulfamoyl) -1- (2-pyridyl) -pyrazole-4-carboxylic acid methyl ester (NC-330, see Brighton Crop Prot. Conference 'Weeds' 1991, vol. 1, p. 45 f.), DPX-A8947, Azimsulfuron, (see Brighton Crop Prot. Conf. 'Weeds' 1995, p. 65);

A4) sulfone diamide derivatives, e.g. 3- (4,6-Dimethoxypyrimidin-2-yl) -1 - (N-methyl-N-methylsulfonylaminosulfonyl) urea (amidosulfuron) and its structural analogues (EP-A 0 131 258 and Z. Pfl. Krankh. Pfl. Schutz , Special Issue XII, 489-497 (1990));

A5) pyridylsulfonylureas, e.g. 1- (3-N, N-dimethylaminocarbonylpyridin-2-ylsulfonyl) -3- (4,6-dimethoxypyrimidin-2-yl) urea (nicosulfuron),

1- (3-Ethylsulfonylpyridin-2-ylsulfonyl) -3 - (- (4,6-dimethoxypyrimidin-2-yl) urea

(Rimsulfuron),

2- [3- (4,6-Dimethoxypyrimidin-2-yl) ureidosulfonyl] -6-trifluoromethyl-3-pyridinecarboxylic acid methyl ester, sodium salt (DPX-KE 459, flupyrsulfuron, see Brighton Crop

Prot. Conf. Weeds, 1995, p. 49),

Pyridylsulfonylureas, as described, for example, in DE-A 40 00 503 and DE-A 40 30 577, preferably those of the formula

worm

E CH or N, preferably CH, R ²⁰ iodine or NR ²⁵ R ²⁶ ,

R ^{21 is} hydrogen, halogen, cyano, (-C-C ₃ ) -alkyl, (Cι-C ₃ ) -alkoxy, (C1-C3) - haloalkyl, (Cι-C ₃ ) -haloalkoxy, (Cι-C ₃ ) - Alkylthio, (-C-C ₃ ) -alkoxy- (-C-C ₃ ) -alkyl, (Cι-C ₃ ) -alkoxy-carbonyl, mono- or di - ((C ₁ -C ₃ ) -alkyl) -amino, (CrC ₃ ) -alkylsulfinyl or -sulfonyl, SO ₂ -NR ^x R ^y or CO-NR ^x R ^y , in particular hydrogen,

R ^x , R ^y independently of one another hydrogen, (CC ₃ ) alkyl, (-C-C ₃ ) alkenyl, (C-1-C3) - alkynyl or together - (CH ₂ ) ₄ -, - (CH ₂ ) ₅ - or - (CH ₂ ) ₂ -O- (CH ₂ ) ₂ -, n is 0.1, 2 or 3, preferably 0 or 1,

R ^{22 is} hydrogen or CH ₃ , R ^{23 is} halogen, (-CC ₂ ) alkyl, (CC ₂ ) -alkoxy, (-C-C ₂ ) -haloalkyl, in particular CF ₃ , (-C-C ₂ ) -haloalkoxy, preferably OCHF ₂ or OCH ₂ CF ₃ ,

R ²⁴ (-C 1 -C ₂ ) alkyl, (-C 1 -C ₂ ) haloalkoxy, preferably OCHF ₂ , or (C 1 -C ₂ ) alkoxy,

R ²⁵ (dC ₄ ) alkyl, R ²⁶ (dC ₄ ) alkylsulfonyl or

R ²⁵ and R ²⁶ together represent a chain of the formula - (CH ₂ ) ₃ SO ₂ - or - (CH ₂ ) ₄ SO ₂ -, e.g. 3- (4,6-dimethoxypyrimiden-2-yl) -1 - (3rd -N-methyIsuϊfonyl-N-methyl-aminopyridin-2-yl) sulfonylurea, or their salts;

A6) Alkoxyphenoxysulfonylureas, as described for example in EP-A 0 342 569, preferably those of the formula wherein

E CH or N, preferably CH,

R ²⁷ ethoxy, propoxy or isopropoxy, R ²⁸ halogen, NO ₂ , CF ₃ , CN, (C ₁ -C ₄ ) alkyl, (Cι-C ₄ ) alkoxy, (CC ₄ ) alkylthio or (Cι-C ₃ ) -alkoxy) -carbonyl, preferably in the 6-position on the phenyl ring, n 0, 1, 2 or 3, preferably 0 or 1,

R ²⁹ is hydrogen, (C-ι-C ₄₎ -alkyl or (C ₃ -C ₄₎ alkenyl,

R ³⁰ , R ³¹ independently of one another halogen, (C 1 -C ₂ ) -alkyl, (CrC ₂ ) -alkoxy, (Ci-C ₂ ) -haloalkyl, (dC ₂ ) -haloalkoxy or (Cι-C ₂ ) - Alkoxy- (C ₁ -C ₂ ) -alkyl, preferably OCH ₃ or CH ₃ , mean, for example 3- (4.6 ~ dimethoxypyrimidin-2-yl) -1- (2-ethoxyphenoxy) sulfonylurea, or their salts;

A7) imidazolylsulfonylureas, e.g. MON 37500, Sulfosulfuron (see Brighton Crop Prot. Conf. 'Weeds', 1995, p: 57), and other related sulfonylurea derivatives and mixtures thereof.

Typical representatives of these active ingredients include the compounds listed below: amidosulfuron, azimsulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorosulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron-methyl, ethoxysulfuron and its sodium salt, flazasulfuron, methyl-flurosulfuron, flupyrsulfuron , Imazosulfuron, metsulfuron-methyl, nicosulfuron, oxasulfuron, primisulfuron-methyl, prosulfuron, pyrazosulfuron-ethyl, rimsulfuron, sulfometuron-methyl, sulfosulfuron, thifensulfuron-methyl, triasulfuron, tribenuron-sulfuron-methyl, trifuronium-methyl-trifuronium-sulfonon WO 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)). The active ingredients listed above are known, for example, from "The Pesticide Manual", 12th edition (2000), The British Crop Protection Council or the literature references listed according to the individual active ingredients.

Other suitable ALS inhibitors are e.g.

B) Imidazolinones, e.g. Methyl 2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -5-methylbenzoate and 2- (4-isopropyl-4-methyl-5-oxo-2-oxo-2-imidazolin-2) yl) -4-methylbenzoic

(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);

C) triazolopyrimidine sulfonamide derivatives, e.g. N- (2,6-difluorophenyI) -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-3-methylphenyl ) -7-chloro-5-methoxy-1, 2,4-triazolo [1, 5-c] pyrimidine-2-sulfonamide,

N- (2-chloro-6-methoxycarbonyl) -5,7-dimethyl-1, 2,4-triazolo [1,5-c] pyrimidine-2-sulfonamide (EP-A 0 343 752, US-A 4,988,812) ;

D) pyrimidinyloxy-pyridinecarboxylic acid or pyrimidinyloxybenzoic acid

Derivatives, e.g. 3- (4,6-dimethoxypyrimidin-2-yl) -oxypyridine-2-carboxylic acid benzyl ester (EP-A 0 249 707),

3- (4,6-Dimethoxypyhmidin-2-yl) -oxypyridin-2-carboxylic acid methyl ester (EP-A 0 249 707), 2,6-bis [(4,6-dimethoxypyrimidin-2-yl) -oxy] -benzoic acid (EP-A 0 321 846),

2,6-bis [(4,6-dimethoxypyrimidin-2-yl) -oxy] -benzoic acid 1- (ethoxycarbonyl-oxyethyl) ester (EP-A 0472 113).

The herbicidal active ingredients contained in the herbicidal compositions according to the invention which are different from ALS inhibitors are, for example: Herbicides from the group of carbamates, thiocarbamates, haloacetanilides, substituted phenoxy, naphthoxy and phenoxyphenoxycarboxylic acid derivatives as well as heteroaryloxyphenoxyalkane carboxylic acid derivatives, such as quinolyloxy, quinoxalyloxy, pyridyloxy, benzoxazolyloxyphenyl, phenoxyalkiono, phenoxyalkiono, phenoxyalkiono and phenoxyalkionoxybenzoxybenzoxybenzoxybenzoxy benzyl azobenzyl benzyl , Phosphorus-containing herbicides, for example of the glufosinate type or of the glyphosate type, and S- (N-aryl-N-alkylcarbamoylmethyl) dithiophosphoric acid ester. Phenoxyphenoxy and heteroaryloxyphenoxy carboxylic acid esters and salts and herbicides such as bentazone, cyanazine, atrazine, dicamba or hydroxybenzonitriles such as bromoxynil and loxynil and other leaf herbicides are preferred.

Suitable herbicidal active substances which differ from ALS inhibitors and which may be present as a component in the agrochemical compositions according to the invention are, for example:

E) Herbicides of the phenoxyphenoxy and

Heteroaryloxyphenoxycarboxylic acid derivatives, such as

E1) Phenoxyphenoxy and benzyloxyphenoxy carboxylic acid derivatives, e.g. 2- (4-

(2,4-dichlorophenoxy) phenoxy) propionic acid methyl ester (diclofop-methyl), 2- (4- (4-bromo-2-chlorophenoxy) phenoxy) propionic acid methyl ester (DE-A 26 01 548),

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 24 33 067),

Methyl 2- (4- (2-fluoro-4-trifluoromethylphenoxy) phenoxy) propionate (US-A 4,808,750), methyl 2- (4- (2,4-dichlorobenzyl) phenoxy) propionate (DE-A 24 17 487), 4- (4- (4-trifluoromethylphenoxy) phenoxy) pent-2-ene acid ethyl ester, methyl 2- (4- (4-trifluoromethylphenoxy) phenoxy) propionate (DE-A 24 33 067);

E2) "Mononuclear" heteroaryloxyphenoxy alkane carboxylic acid derivatives, e.g. Ethyl 2- (4- (3,5-dichloropyridyl-2-oxy) phenoxy) propionate (EP-A 0 002 925),

2- (4- (3,5-dichloropyridyl-2-oxy) phenoxy) propionsäurepropargylester

(EP-A 0 003 114),

2- (4- (3-chloro-5-trifluoromethyl-2-pyridyloxy) phenoxy) propionic acid methylester

(EP-A 0 003 890), 2- (4- (3-chloro-5-trifluoromethyl-2-pyridyloxy) phenoxy) propionic acid ethyl ester

(EP-A 0 003 890),

2- (4- (5-chloro-3-fluoro-2-pyridyloxy) phenoxy) propionsäurepropargylester

(EP-A 0 191 736),

2- (4- (5-trifluoromethyl-2-pyridyloxy) phenoxy) propionic acid butyl ester (fluazifop-butyl);

E3) "dinuclear" heteroaryloxyphenoxy alkane carboxylic acid derivatives, e.g.

2- (4- (6-chloro-2-quinoxalyloxy) phenoxy) propionic acid methyl ester and ethyl ester

(Quizalofopmethyl and Quizalofopethyl), 2- (4- (6-fluoro-2-quinoxalyloxy) phenoxy) propionic acid methyl ester (see J. Pest. Be. Vol.

10, 61 (1985)),

2- (4- (6-chloro-2-quinoxalyloxy) phenoxy) propionic acid 2-isopropylideneaminooxy ethyl ester (propaquizafop),

2- (4- (6-Chlorobenzoxazol-2-yl-oxy) phenoxy) propionic acid ethyl ester (fenoxaprop-ethyl), its D (+) isomer (fenoxaprop-P-ethyl) and 2- (4- (6-chlorobenzthiazol-2 yloxy) phenoxy) propionic acid ethyl ester (DE-A 26 40 730), 2- (4- (6-chloroquinoxalyloxy) phenoxy) propionic acid tetrahydro-2-furylmethyl ester (EP-A 0 323 727);

F) chloroacetanilides, e.g. N-methoxymethyl-2,6-diethylchloroacetanilide (alachlor),

N- (3-methoxyprop-2-yl) -2-methyl-6-ethyl-chloroacetanilide (metolachlor), N- (3-methyl-1, 2,4-oxadiazol-5-yI-methyl) -chloroacetic acid-2 , 6-dimethylanilide, N- (2,6-dimethylphenyl) -N- (1-pyrazolyImethyl) chloroacetic acid amide (metazachlor);

G) thiocarbamates, e.g.

S-ethyl-N, N-dipropylthiocarbamate (EPTC), S-ethyl-N, N-diisobutylthiocarbamate (butylates);

H) 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-hydroxy-cyclohex-2-en-1-one

(Sethoxydim),

2- (1-ethoxyiminobutyl) -5- (2-phenylthiopropyl) -3-hydroxy-cyclohex-2-en-1-one (cloproxydim),

2- (1- (3-chloroallyloxy) iminobutyl) -5- (2-ethylthiopropyl) -3-hydroxy-cyclohex-2-en-1-one,

2- (1- (3-chloroallyloxy) iminopropyl) -5- (2-ethylthiopropyl) -3-hydroxy-cyclohex-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-hydroxy-cyclohex-2-en-1-on

(Tralkoxydim);

I) benzoylcyclohexanediones, e.g.

2- (2-chloro-4-methylsulfonylbenzoyl) cyclohexane-1,3-dione (SC-0051, EP-A-O 137 963, Suleotrione), 2- (2-nitrobenzoyl) -4,4-dimethyl-cyclohexane 1,3-dione (EP-A 0 274 634), 2- (2-nitro-4-methylsulfonylbenzoyl) -4,4-dimethylcyclohexane-1,3-dione (WO 91/13548, mesotrione); J) S- (N-AryI-N-alkyl-carbamoylmethyl) dithiophosphonic acid esters, such as S- [N- (4-

Chlorophenyl) -N-isopropyl-carbamoylmethyl] -O, O-dimethyl dithiophosphate

(Anilophos).

K) alkyl azines, e.g. 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 (E)

wherein

R (C _r C ₄ ) alkyl or (-C-C ₄ ) haloalkyl; R ^γ (C ₁ -C ₄ ) alkyl, (C ₃ -C ₆ ) cycloalkyl or (C ₃ -C ₆ ) cycloalkyl (CC ₄ ) alkyl and A -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-, particularly preferably those of the formula E IE VII

L) Phosphorus-containing herbicides, e.g. of the glufosinate type such as glufosinate in the narrower 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 of the glyphosate type such as glyphosate, i.e. H. N- (phosphonomethyl) glycine, glyphosate monoisopropylammonium salt, glyphosate sodium salt, or sulfosate, i.e. H. N- (phosphonomethyl) glycine trimesium salt = N- (phosphonomethyl) glycine trimethylsulfoxonium salt.

The herbicides of groups B to L are, for example, from the publications mentioned above and from "The Pestieide Manual", 12th edition, 2000, The British Crop Protection Council, "Agricultural Chemicals Book II - Herbicides -", by W.T. Thompson, Thompson Publications, Fresno CA, USA 1990 and "Farm Chemicals Handbook '90", Meister Publishing Company, Willoughby OH, USA, 1990.

Particularly preferred herbicides are, for example, mesosulfuron and its salts and esters such as mesosulfuron-methyl and mesosulfuron-methyl-sodium (C1) (e.g. Atlantis®, Archipel®), iodosulfuron and its salts and esters such as iodosulfuron-methyl and iodosulfuron-methyl-sodium ( C2) (e.g. Hussar®, Hussar® OF, Sekkator®, Chekker®), foramsulfuron and its salts such as foramsulfuron sodium (C3) (e.g. MaisTer®, Option®, Option® S), amidosulfuron and its salts such as amidosulfuron sodium (C4) (e.g. Gratil®), one or more sugar beet herbicides from the group Phenmedipham, Desmedipham, Ethofumesate, Metamitron (C5) (e.g. Betanal® Quattro, Betanal® Crop, Betanal® Expert), Isoproturon (C6), Diflufenican (C7), loxynil and its esters such as loxyniloctanoate (C8), bromoxynil and its esters such as bromoxynil octanoate (C9) (e.g. Quartz®, Tolkan®flo, First®, Azur®), fenoxaprop-p-ethyl (C10), diclofop-methyl (C11), ethoxysulfuron and its salts such as ethoxysulfuron sodium (C12) , The designations C1-C12 include all herbicides listed before the respective designation, preferably the explicitly mentioned herbicides. For example, the designation C1 includes mesosulfuron and all salts and esters, preferably mesosulfuron-methyl and mesosulfuron-methyl-sodium, and the designation C5 includes phenmedipham, desmedipham, ethofumesate and metamitron and their combinations.

In addition to the adjuvants according to the invention and one or more agrochemicals, the agrochemical compositions according to the invention can

Active ingredients contain other components, e.g. Formulation aids such as anti-drift agents, substances to influence moisture (humectants), fertilizers such as ammonium sulfate, urea or multi-component fertilizers e.g. based on phosphorus, potassium and nitrogen, such as P, K, N fertilizers, or commercially available surfactants other than formula (I), such as nonionic, cationic, anionic, betaine or polymeric surfactants, stabilizers such as pH stabilizers, bioeides, UV stabilizers, Defoamers, synthetic or natural polymers, solvents, e.g. polar solvents such as water or alcohols or non-polar solvents such as saturated or unsaturated aliphatic solvents which can be branched or unbranched, or aromatic solvents such as Solvesso® 100, Solvesso® 150 or Solvesso® 200 or xylene. These agrochemicals and their use are also new and the subject of this invention.

The agrochemical compositions according to the invention show excellent agrochemical activity against harmful organisms such as harmful plants. Because of the improved control of the harmful plants by the agrochemical compositions according to the invention, it becomes possible to reduce the application rate and / or the Increase safety margin. Both make economic and ecological sense.

In a preferred embodiment, agrochemical compositions according to the invention are characterized in that they have a synergistically effective content of a combination of the surfactants a) with fatty acid esters b) such as vegetable oils and agrochemical active ingredients c). Above all, it should be emphasized that even in combinations with application rates or weight ratios of a): b): c) in which a synergism cannot always be demonstrated in every case - for example because the individual compounds are usually used in combination in very different application rates or also because the control of the harmful plants is already very good through the individual compounds - the agrochemical compositions of the invention are generally inherent in a synergistic effect.

The agrochemical compositions according to the invention can be prepared by customary processes, e.g. Mixing by grinding, dissolving or dispersing the individual components, preferably at room temperature. If further auxiliaries are contained, these are also preferably entered at room temperature. The order in which the individual components are added generally does not play a decisive role.

Components a), b) and c) of the agrochemical compositions according to the invention can be contained together in a finished formulation which can then be prepared in a conventional manner, e.g. can be applied in the form of a spray mixture or they can be formulated separately and e.g. together in the tank mixing process or separately, e.g. can be applied in succession. If the components are formulated separately, components a), b) and c) e.g. can be formulated individually or the components a) and b), a) and c) or b) and c) can be formulated together and the respective third-party component is formulated separately.

The adjuvants and agrochemical compositions according to the invention and their Components can be formulated in various ways, depending on which biological and / or chemical-physical parameters are specified. Possible formulation options include, in particular, liquid formulations, for example: water-soluble concentrates, microemulsions (ME), emulsifiable concentrates (EC), emulsions (EW), such as oil-in-water and

Water-in-oil emulsions, sprayable solutions, suspension concentrates (SC), suspoemulsion concentrates (SE), dispersions based on oil or water, oil-miscible solutions, capsule suspensions (CS) and ULV formulations. If the agrochemical active ingredients c) are formulated separately, they can also be present as a solid formulation, for example as a dusting agent (DP), pickling agent,

Granules for litter and soil application, granules (GR) in the form of micro, spray, elevator and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG), microcapsules, waxes, wettable powders (WP) and water-soluble powders ( SP).

The manufacturing processes or formulation types are known in principle and are described, for example, in Winnacker-Küchler, "Chemical Technology", volume 7, C. Hauser Verlag Munich, 4th ed. 1986, Wade van Valkenburg, "Pestieide Formulations", Marcel Dekker, NY , 1973; K. Martens, "Spray Drying" Handbook, ^3rd Ed. 1979, G. Goodwin Ltd. London; H. Mollet, A. Grubenmann, "Formulation Technology", Wiley-VCH, Weinheim 2000.

The formulation auxiliaries such as inert materials, surfactants, solvents and other additives are also known and are described, for example, in: Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell N.J., H.v. Olphen, "Introduction to Clay Colloid Chemistry"; 2nd Ed., J. Wiley & Sons, N.Y .; C. Marsden, "Solvent Guide"; 2nd Ed., Interscience, N.Y. 1963; McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood N.J .; Sisley and Wood, "Encyclopedia of

Surface Active Agents ", Chem. Publ. Co. Inc., NY 1964; Schönfeldt," Interface-active ethylene oxide adducts ", Wiss. Verlagsgesellschaft., Stuttgart 1976; Winnacker-Küchler, "Chemical Technology", Volume 7, C. Hauser Verlag Munich, 4th ed. 1986.

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

Spray powders (wettable powders) are preparations which are uniformly dispersible in water and, if appropriate, in addition to components a), b) and / or c)

Diluents or inert substances and other ionic and / or non-ionic surfactants (wetting agents, dispersing agents) eg polyoxyethylated alkylphenols, polyoxethylated fatty alcohols, polyoxethylated fatty amines, fatty alcohol polyglycol ether sulfates, alkane sulfonates, alkylbenzenesulfonates, lignin sulfonic acid sodium, 2,2 ^, -dinaphthalene'6'-methane'-6'-naphtha Contain sodium, dibutylnaphthalene-sulfonic acid sodium or oleoylmethyl tauric acid sodium. To produce the wettable powders, components a) and / or b) and / or c) are finely ground, for example in conventional apparatus such as hammer mills, fan mills and air jet mills, and mixed simultaneously or subsequently with the formulation auxiliaries.

Emulsifiable concentrates are obtained by dissolving the surfactant a) and / or fatty acid ester b) such as vegetable oil and / or agrochemical active ingredient c) in an organic solvent e.g. Butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons or mixtures of organic solvents with the addition of one or more surfactants of ionic and / or nonionic type (emulsifiers). Examples of emulsifiers that can be used are: alkylarylsulfonic acid calcium salts such as calcium dodecylbenzenesulfonate or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers,

Propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters such as sorbitan fatty acid esters or polyoxethylene sorbitan esters such as Polyoxyethylene.

Dusts are obtained by grinding the surfactant a) and / or vegetable oil b) and / or agrochemical active ingredient c) with finely divided solid substances, e.g. Talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.

Suspension concentrates can be water or oil based. You can, for example, by wet grinding using commercially available bead mills and optionally adding other surfactants, such as those e.g. already listed above for the other types of formulation.

Emulsions, e.g. Oil-in-water emulsions (EW) can be used, for example, with stirrers, colloid mills and / or static mixers using aqueous organic solvents and optionally other surfactants, such as those e.g. already listed above for the other types of formulation.

Granules can either be produced by spraying the surfactant a) and / or fatty acid ester b) such as vegetable oil and / or agrochemical active ingredient c) onto adsorbable, granulated inert material or by applying active ingredient concentrates by means of adhesives, e.g. Polyvinyl alcohol, sodium polyacrylic acid or mineral oils, on the surface of carriers such as sand, kaolinite or granulated inert material. Suitable surfactants a) and / or fatty acid esters b) such as vegetable oils and / or agrochemical active ingredients c) can also be granulated in the manner customary for the production of fertilizer granules - if desired in a mixture with fertilizers.

Water-dispersible granules are generally produced using the customary methods, such as spray drying, fluidized bed granulation, plate granulation, mixing with high-speed mixers and extrusion without solid inert material. For the production of plate, fluidized bed, extruder and spray granules see e.g. Procedure in "Spray-Drying Handbook" 3rd ed. 1979, G. Goodwin Ltd., London; JE Browning, "Agglomeration", Chemical and Engineering 1967, pages 147 ff; "Perry's Chemical Engineer's Handbook," 5th Ed., McGraw-Hill, New York 1973, pp. 8-57.

For more details on the formulation of crop protection products see e.g. G.C. Klingman, "Weed Control as a Science," John Wiley and Sons, Inc., New York, 1961, pp. 81-96, and J.D. Freyer, S.A. Evans, "Weed Control Handbook," 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pages 101-103.

In addition, the active ingredient formulations mentioned may contain the customary auxiliaries such as adhesives, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreezes and solvents, fillers, carriers and dyes, defoamers, evaporation inhibitors and the pH and viscosity influencing agents.

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

The use of the agrochemical compositions according to the invention can e.g. done by application to the harmful organisms or the places where they occur, e.g. by spraying. The agrochemical active ingredients c) to be used according to the invention are generally used together with the surfactants a) and

Fatty acid esters b) such as vegetable oils or applied in succession, preferably in the form of a spray mixture which contains the surfactants a), the fatty acid esters b) such as vegetable oils and the agrochemical active ingredients c) in effective amounts and, if appropriate, other customary auxiliaries. The spray liquor is preferably produced on the basis of water and / or an oil, for example a vegetable oil or a high-boiling hydrocarbon such as kerosene or paraffin. there The agrochemical compositions according to the invention can be implemented, for example, as a tank mixture or via a co-formulation.

The agrochemical formulations generally contain 0.1 to 99 percent by weight, in particular 2 to 95% by weight, of agrochemical active ingredients, the following concentrations being customary, depending on the type of formulation: The active ingredient concentration in wettable powders is generally about 10 to 90% by weight. -%, the rest of 100 wt .-% consists of conventional formulation components. In the case of emulsifiable concentrates, the active substance concentration can be about 1 to 90% by weight, preferably 5 to 80% by weight. Dust-like formulations contain 1 to 30% by weight of active ingredient, preferably mostly 5 to 20% by weight of active ingredient, sprayable solutions contain about 0.05 to 80, preferably 2 to 50% by weight of active ingredient. In the case of water-dispersible granules, the active ingredient content depends in part on whether the active compound is in liquid or solid form and which granulating aids, fillers, etc. are used. The active ingredient content of the water-dispersible granules is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight. In individual cases the stated weight percentages can also be exceeded or fallen short of.

When applied, the weight ratio of agrochemical active ingredient c): adjuvant according to the invention is generally in the range from 1: 10,000 to 100: 1, preferably 1: 1000 to 10: 1, particularly preferably 1: 100 to 1: 1, depending on the effectiveness of the respective agrochemical active ingredient.

When applied, the concentration of agrochemical active ingredient c) is generally 10 ^"6 to 10% by weight, preferably 10 ^{" 5} to 4% by weight, particularly preferably 10 ^"4 to 0.1% by weight, in the applied agent, for example the spray liquor, at an application rate of 1 to 5000 l / ha, preferably 50 to 1000 l / ha. The concentration of adjuvant according to the invention is generally 0.001 to 10% by weight, preferably 0.005 to 5% by weight. %, particularly preferably 0.05 to 3% by weight in the applied agent, for example the spray liquor, at an application rate of 1 to 5,000 l / ha, preferably 50 to 1,000 l / ha. In addition to components a), b) and c), the agrochemical compositions according to the invention preferably also contain water and, if appropriate, organic solvents and are formulated in the form of an aqueous concentrated dispersion or emulsion or as a tank mix in the form of a dilute dispersion, emulsion or solution with a degree of dilution of up to to that of the ready-to-use spray liquor. Particularly preferred is an agrochemical agent produced as a tank mix, which for use contains the preferred amounts of surfactant a), fatty acid ester b) such as vegetable oil and agrochemical active ingredient c).

For use, concentrated formulations present in commercially available form are optionally diluted in customary form, wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules, e.g. by means of water. Dust-like preparations, spray and absorption granules, sprayable solutions and spray mixtures prepared as a tank mix are usually no longer diluted with other inert substances before use. It may be advantageous to add further amounts of surfactants a), fatty acid esters b) such as vegetable oil and / or other customary auxiliaries, in particular self-emulsifying oils or paraffin oils, to the spray liquors.

The application rate of the agrochemical active ingredients c) varies with the external conditions, such as temperature, humidity and the type of herbicide used. It can fluctuate within wide limits, e.g. between 0.001 and 10 kg / ha or more of active substance, preferably between 0.005 and 5 kg / ha.

The agrochemical compositions according to the invention are preferably herbicidal compositions. These have excellent herbicidal activity against a broad spectrum of economically important mono- and dicotyledonous harmful plants. Perennial weeds that are difficult to control and that sprout from rhizomes, rhizomes or other permanent organs are also well recorded. The funds can be applied, for example, by pre-sowing, pre-emergence or post-emergence. Some representatives of the monocotyledonous and dicotyledonous weed flora are examples called, which can be controlled by the herbicidal compositions according to the invention, without any limitation to certain species being made by the naming.

On the side of the monocot weed species, 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. and Bromus spp. such as Bromus catharticus, Bromus secalinus, Bromus erectus, Bromus tectorum and Bromus japonicus and Cyperus species from the annual group and on the part of the perennial species Agropyron, Cynodon, Imperata as well as Sorghum and also persistent Cyperus species.

With dicotyledon weed species, the spectrum of activity extends to species such as Abutilon spp., Amaranthus spp., Chenopodium spp., Chrysanthemum spp., Galium spp. such as Galium aparine, Ipomoea spp., Kochia spp., Lamium spp., Matricaria spp., Pharbitis spp., Polygonum spp., Sida spp., Sinapis spp., Solanum spp., Stellaria spp., Veronica spp. and Viola spp., Xanthium spp., on the annual side, and convolvulus, cirsium, rumex and artemisia in the perennial weeds.

Harmful plants occurring in rice under the specific crop conditions, e.g. Echinochloa, Sagittaria, Alisma, Eleocharis, Scirpus and Cyperus are also superbly combated by the agents according to the invention.

If the herbicidal compositions according to the invention are applied to the surface of the earth before germination, either weed seedlings are prevented completely or the weeds grow to the cotyledon stage, but then stop growing and finally die completely after three to four weeks.

When the herbicidal compositions according to the invention are applied to the green plant parts in the post-emergence process, there is also a drastic growth stop very quickly after the treatment and the weed plants remain in the growth stage present at the time of application or die from a certain time, so that weed competition harmful to crops is eliminated very early and sustainably.

The herbicidal compositions according to the invention are notable for a rapid onset and long-lasting herbicidal action. The rain resistance of the active ingredients in the combinations according to the invention is generally favorable. A particular advantage is the fact that the effective dosages of herbicidal compounds used in the herbicidal compositions can be set so low that their soil action is optimally low. This makes their use not only possible in sensitive crops, but groundwater contamination is practically avoided. The combination of active substances according to the invention enables a considerable reduction in the amount of active substances required.

When adjuvants according to the invention are used together with agrochemical active substances, in particular herbicides, in a preferred embodiment, superadditive (= synergistic) effects occur. The effect in the combinations is stronger than the expected sum of the effects of the individual components used. The synergistic effects allow a reduction in the application rate, the control of a broad spectrum of weeds and weeds, a faster use of the herbicidal action, a longer lasting effect, better control of the harmful plants with only one or a few applications and an expansion of the possible application period. In part, the use of the agents also reduces the amount of harmful ingredients, such as nitrogen or oleic acid, and their entry into the soil.

The properties and advantages mentioned are useful in practical weed control in order to keep agricultural crops free of undesired competing plants and thus to ensure and / or increase the yields qualitatively and quantitatively. These new means significantly exceed the technical standard in terms of the properties described. Although the herbicidal compositions according to the invention have excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, crop plants of economically important crops, for example dicotyledonous crops such as soybean, cotton, rape, sugar beet, or Gramineae crops such as wheat, barley, rye, oats, millet, rice, are grown or maize, only slightly or not at all damaged. For these reasons, the present compounds are very suitable for the selective control of undesired plant growth in agricultural crops or in ornamental crops.

In addition, the herbicidal compositions according to the invention have excellent growth-regulating properties in crop plants. They intervene regulating the plant's own metabolism and can thus be used to influence plant constituents in a targeted manner and to facilitate harvesting, e.g. by triggering desiccation and stunted growth. Furthermore, they are also suitable for general control and inhibition of undesirable vegetative growth without killing the plants. Inhibiting vegetative growth plays a major role in many monocotyledonous and dicotyledonous crops, as this can reduce or completely prevent storage.

Because of their herbicidal and plant growth regulatory properties, the herbicidal compositions according to the invention can also be used to control harmful plants in crops of known or still to be developed genetically modified plants. The transgenic plants are generally distinguished by special advantageous properties, for example 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 concern e.g. B. the crop in terms of quantity, quality, shelf life, composition and special ingredients. Transgenic plants with an increased starch content or altered starch quality or with a different fatty acid composition of the crop are known. Preferred is the use of the agents according to the invention in economically important transgenic crops of useful and ornamental plants, for. B. Gramineae crops such as wheat, barley, rye, oats, millet, rice and maize or crops of sugar beet, cotton, soybeans, rapeseed, potatoes, tomatoes, peas and other vegetables. The agents according to the invention can preferably be used as herbicides in crops which are resistant to the phytotoxic effects of the herbicides or have been made resistant to genetic engineering.

When the herbicidal compositions according to the invention are used in transgenic crops, in addition to the effects on harmful plants which can be observed in other crops, there are often effects which are specific to the application in the respective transgenic crop, for example a changed or specially expanded weed spectrum which can be controlled, changed

Application rates that can be used for the application, preferably good combinability with the herbicides to which the transgenic culture is resistant, and influencing the growth and yield of the transgenic crop plants.

The present invention furthermore also relates to a process for controlling unwanted vegetation, preferably in crops such as cereals (for example wheat, barley, rye, oats, rice, corn, millet), sugar beet, sugar cane, rape, cotton and soybeans, particularly preferably in monocotyledon crops such as cereals, e.g. Wheat, barley, rye, oats, crosses thereof such as triticale, rice, corn and millet, one or more herbicidal compositions according to the invention being applied to the harmful plants, parts of plants, plant seeds or the area on which the plants grow, e.g. the acreage, applied.

The plant cultures can also be genetically modified or obtained by mutation selection and are preferably tolerant of acetolactate synthase (ALS) inhibitors. The invention also relates to the use of the herbicidal compositions according to the invention for controlling harmful plants, preferably in plant crops.

The herbicidal compositions according to the invention can also be used non-selectively for controlling unwanted vegetation, e.g. in plantation crops, on roadsides, squares, industrial plants or railway systems.

The agrochemical compositions according to the invention, in particular herbicidal compositions, can be present both as mixed formulations, if appropriate with further agrochemical active ingredients, auxiliaries such as additives and / or formulation auxiliaries, which are then diluted with water in the customary manner, or as so-called tank mixtures by diluting them together formulated or partially separately formulated components with water.

Because of the relatively low application rate of the herbicidal compositions according to the invention, their tolerance is generally very good. In particular, the combinations according to the invention achieve a reduction in the absolute application rate compared to the single application of a herbicidal active ingredient. The invention therefore also relates to a process for controlling harmful plants, preferably for selectively controlling harmful plants in plant crops, characterized in that a herbicidally effective amount of the herbicides c) mentioned is used in combination with at least one of the surfactants a) and at least one fatty acid ester b ) applied like vegetable oil, e.g. pre-emergence, post-emergence or pre- and post-emergence, preferably pre-emergence, together or in succession, on the plants, parts of plants, plant seeds or the area on which the plants grow, e.g. the acreage.

In a preferred process variant, the herbicides c) are applied in amounts of 0.005 (preferably 0.1) to 5,000 g of active substance / ha, particularly preferably from 0.5 to 1,000 g of active substance / ha. It is also particularly preferred to apply the active ingredients in the form of a co-formulation or in the form of tank mixtures, the individual components, for example in the form of formulations, being mixed together with water in the tank and the spray liquor obtained being applied.

Since the crop plant tolerance of the combinations according to the invention is extremely good with very high control of the harmful plants at the same time, these can be regarded as selective. In a preferred modification of the process, herbicidal compositions with the active compound combinations according to the invention are therefore used for the selective control of undesired plants.

In order to further increase the tolerance and / or selectivity of the herbicidal compositions according to the invention, if desired, it can be advantageous to use them together in a mixture or in succession - separately in succession together with safeners or antidotes.

Compounds suitable as safeners or antidots for the herbicidal compositions according to the invention are, for. B. from EP-A-333 131 (ZA-89/1960), EP-A-269 806 (US-A-4,891, 057), EP-A-346 620 (AU-A-89/34951) and the international patent applications PCT / EP 90/01966 (WO-91108202) and PCT / EP 90102020 (WO-911078474) and the literature cited therein are known or can be prepared by the processes described therein. Other suitable safeners are known from EP-A-94 349 (US-A-4,902,304), EP-A-191 736 (US-A-4,881, 966) and EP-A-0 492 366 and the literature cited therein.

In a preferred embodiment, the herbicidal compositions of the present invention therefore contain an additional content of one or more compounds which act as safeners or antidotes. Particularly preferred antidotes or safeners or groups of compounds which are suitable as safeners or antidots for the herbicidal compositions of the invention described above include:

a) Compounds of the dichlorophenylpyrazoline-3-carboxylic acid type, preferably compounds such as 1- (2,4-dichlorophenyl) -5- (ethoxycarbonyl) -5-methyl-2-pyrazoline-3-carboxylic acid ethyl ester (compound S1 -1, mefenpyr- diethyl) and related compounds as described in international application WO 91/07874 (PCT / EP 90102020); b) Derivatives of dichlorophenylpyrazole carboxylic acid, preferably compounds such as ethyl 1- (2,4-dichlorophenyl) -5-methyl-pyrazole-3-carboxylate (compound S1-2), 1- (2,4-dichlorophenyl) -5-isopropyl-pyrazole -3-carboxylic acid ethyl ester (compound S1 -3), 1- (2,4-dichlorophenyl) -5- (1, 1-dimethyl-ethyl) pyrazoI-3-carboxylic acid ethyl ester (compound S 1-4), 1- (2, 4-dichlorophenyl) -5-phenylpyrazole-3-carboxylic acid ethyl ester (compound S1-5) and related compounds as described in EP-A-0 333 131 and EP-A-0 269 806; c) Compounds of the triazole carboxylic acid type, preferably compounds such as 1- (2,4-dichlorophenyl) -5-trichloromethyl- (1 H) -1, 2,4-triazole-3-carboxylic acid ethyl ester (compound S1-6, fenchlorazole) and related compounds (see EP-A-0 174 562 and EP-A-0 346 620); d) compounds of the dichlorobenzyl-2-isoxazoline-3-carboxylic acid type, compounds of the 5-benzyl or 5-phenyl-2-isoxazoline-3-carboxylic acid type, preferably compounds such as

Ethyl 5- (2,4-dichlorobenzyl) -2-isoxazoline-3-carboxylate (compound S1 -7) or ethyl 5-phenyl-2-isoxazoline-3-carboxylate (compound S1-8) and related compounds as described in the international patent application WO 91/08202 (PCT / EP 90/01966) are described; e) Compounds of the 8-quinolineoxyacetic acid type, preferably

Compounds such as (5-chloro-8-quinolinoxy) acetic acid (1-methyl-hex-1-yl) ester (S2-1; cloquintocet-mexyl), (5-Chloro-8-quinolinoxy) acetic acid (1,3-dimethyl-but-1-yl) ester (S2-2), (5-chloro-8-quinolinoxy) acetic acid-4-allyl-oxy -butyl ester (S2-3), (5-chloro-8-quinolinoxy) -acetic acid-1-allyl-oxy-prop-2-yl ester (S2-4), (5-chloro-8-quinolinoxy) -acetic acid ethyl ester (S2 -5), (5-chloro-8-quinolinoxy) -acetic acid methyl ester (S2-6),

(5-chloro-8-quinolinoxy) -acetic acid allyl ester (S2-7), (5-chloro-8-quinolinoxy) -acetic acid-2- (2-propylidene-iminoxy) -1-ethyl ester (S2-8), (5th Chloro-8-quinolinoxy) 2-oxo-prop-1-ethyl acetate (S2-9) and related compounds as described in EP-A-0 086 750, EP-A-0 094 349 and EP-A- 0 191 736 or EP-A-0 492 366; f) Compounds of the (5-chloro-8-quinolinoxy) malonic acid type, preferably compounds such as (5-chloro-8-quinolinoxy) malonic acid diethyl ester, (5-chloro-8-quinolinoxy) malonic acid diallyl ester, (5-chloro 8-quinolinoxy) methyl malonate and related compounds as described and proposed in German patent application EP-A-0 582 198; g) active compounds of the phenoxyacetic or propionic acid derivative type or aromatic carboxylic acids, such as. B. 2,4-dichlorophenoxyacetic acid (ester) (2,4-D), 4-chloro-2-methyl-phenoxypropionic acid (mecoprop), MCPA or 3,6-dichloro-2-methoxy-benzoic acid (ester) ( dicamba). h) Compounds of the 5,5-diphenyl-2-isoxazoline-3-carboxylic acid type, preferably 5,5-diphenyl-2-isoxazoline-3-carboxylic acid ethyl ester (S3-1, isoxadifen-ethyl). i) compounds which, as safeners, e.g. known for rice are fenclorim (= 4,6-dichloro-2-phenylpyrimidine, Pestieide Manual, 11th edition, 1997, p.

511-512), dimepiperate (= piperidine-1-thiocarboxylic acid-S-1-methyl-1-phenylethyl ester, Pestieide Manual, 11th edition, 1997, pp. 404-405), daimuron (= 1 - (1-methyl- 1-phenylethyl) -3-p-tolylurea, Pestieide Manual, 11th edition, 1997, p. 330), cumyluron (= 3- (2-chlorophenylmethyl) -1 - (1-methyl-1-phenyl-ethyl ) - urea, JP-A-60/087254), methoxyphenone (=

3,3'-dimethyl-4-methoxy-benzophenone, COD (= 1-bromo-4- (chloromethylsulfonyl) benzene, CAS Reg. No. 54091-06-4). The compounds mentioned are also at least partially described in EP-A-0 640 587, to which reference is hereby made for the purposes of disclosure.

j) Another important group of compounds suitable as safeners and antidotes is known from WO 95/07897.

The safeners (antidotes) from groups a) to j) above reduce or prevent phytotoxic effects which can occur when the herbicidal compositions according to the invention are used in crops without impairing the effectiveness of the herbicides against harmful plants. As a result, the field of use of the herbicidal compositions according to the invention can be expanded considerably and, in particular, the use of safeners enables the use of herbicidal compositions which have hitherto been able to be used only to a limited extent or with insufficient success, ie H. of combinations which, without safeners in low doses with little breadth effect, did not lead to adequate control of the harmful plants.

The components a), b) and c) of the herbicidal compositions according to the invention and the safeners mentioned can be applied together (for example as a finished formulation or in the tank-mixing method) or in succession in any order. The weight ratio of safener: herbicide (compound (s) of the formula (I) and / or their salts) can vary within wide limits and is preferably in the range from 1: 100 to 100: 1, in particular from 1: 100 to 50: 1. The optimum amounts of herbicide (s) and safener (s) in each case are usually dependent on the type of herbicidal composition and / or on the safener used and on the type of crop to be treated.

Depending on their properties, the safeners can be used for the pretreatment of the seed of the crop (dressing of the seeds) or introduced into the seed furrows before sowing or used together with the herbicide mixture before or after emergence of the plants. Pre-emergence treatment closes both the treatment of the cultivated area before sowing and the treatment of the sown but not yet overgrown cultivated areas. Co-application with the herbicide mixture is preferred. Tank mixes or ready-to-use formulations can be used for this.

Depending on the indication and the herbicide used, the application rates of the safeners can vary within wide limits and are generally in the range from 0.001 to 5 kg, preferably 0.005 to 0.2 kg, of active compound per hectare.

The herbicidal compositions according to the invention can be applied in a customary manner, for example using water as a vehicle in spray liquor amounts of about 5 to 4000 liters / ha. Use of the agents in the so-called low-volume and ultra-low-volume process (ULV) is just as possible as their application in the form of granules and microgranules.

A preferred use relates to the use of herbicidal compositions which have components a), b) and c) in a synergistically effective amount.

The invention also includes mixtures of one or more surfactants a), with one or more fatty acid esters b) such as vegetable oils and one or more herbicides c). In addition, one, two or more agrochemical active ingredients (e.g. insecticides, fungicides, safeners) which are different from the herbicides c) can additionally be present in the herbicidal compositions of the invention to round off the properties, usually in minor amounts.

Preferred examples of the herbicidal compositions according to the invention are combinations of surfactants from the Sapogenat ^® T series (for example Sapogenat ^® T020, Sapogenat ^® T040, Sapogenat ^® T060, Sapogenat ^® T080, Sapogenat ^® T100 or Sapogenat ^® T110) with vegetable oils, for example rapeseed oils such as Rapeseed oil methyl ester and herbicidal active ingredients c) such as the herbicides C1-C12, in particular the following combinations of surfactants from the Sapogenat ^® T series (hereinafter referred to as Sapogenat) with rapeseed oils such as rapeseed oil methyl ester and the herbicides C1 C12 called, without this should be limited to the explicitly mentioned combinations:

Sapogenat + Actirob B + C1, Sapogenat + Hasten + C1, Sapogenat + Mero + C1, Sapogenat + Rako-Binol + C1, Sapogenat + Phytorob B + C1, Sapogenat + Edenor

+ C1, sapogenate + agnique + C1;

Sapogenat + Actirob B + C2, Sapogenat + Hasten + C2, Sapogenat + Mero + C2,

Sapogenat + Rako-Binol + C2, Sapogenat + Phytorob B + C2, Sapogenat + Edenor

+ C2, sapogenate + agnique + C2; Sapogenat + Actirob B + C3, Sapogenat + Hasten + C3, Sapogenat + Mero + C3,

Sapogenat + Rako-Binol + C3, Sapogenat + Phytorob B + C3, Sapogenat + Edenor

+ C3, sapogenate + agnique + C3;

Sapogenat + Actirob B + C4, Sapogenat + Hasten + C4, Sapogenat + Mero + C4,

Sapogenat + Rako-Binol + C4, Sapogenat + Phytorob B + C4, Sapogenat + Edenor + C4, Sapogenat + Agnique + C4;

Sapogenat + Actirob B + C5, Sapogenat + Hasten + C5, Sapogenat + Mero + C5,

Sapogenat + Rako-Binol + C5, Sapogenat + Phytorob B + C5, Sapogenat + Edenor

+ C5, sapogenate + agnique + C5;

Sapogenat + Actirob B + C6, Sapogenat + Hasten + C6, Sapogenat + Mero + C6, Sapogenat + Rako-Binol + C6, Sapogenat + Phytorob B + C6, Sapogenat + Edenor

+ C6, sapogenate + agnique + C6;

Sapogenat + Actirob B + C7, Sapogenat + Hasten + C7, Sapogenat + Mero + C7,

Sapogenat + Rako-Binol + C7, Sapogenat + Phytorob B + C7, Sapogenat + Edenor

+ C7, sapogenate + agnique + C7; Sapogenat + Actirob B + C8, Sapogenat + Hasten + C8, Sapogenat + Mero + C8,

Sapogenat + Rako-Binol + C8, Sapogenat + Phytorob B + C8, Sapogenat + Edenor

+ C8, sapogenate + agnique + C8;

Sapogenat + Actirob B + C9, Sapogenat + Hasten + C9, Sapogenat + Mero + C9,

Sapogenat + Rako-Binol + C9, Sapogenat + Phytorob B + C9, Sapogenat + Edenor + C9, Sapogenat + Agnique + C9; Sapogenat + Actirob B + C10, Sapogenat + Hasten + C10, Sapogenat + Mero + C10, Sapogenat + Rako-Binol + C10, Sapogenat + Phytorob B + C10, Sapogenat + Edenor + C10, Sapogenat + Agnique + C10;

Sapogenat + Actirob B + C11, Sapogenat ^' + Hasten + C11, Sapogenat + Mero + C11, Sapogenat + Rako-Binol + C11, Sapogenat ^• + Phytorob B + C11, Sapogenat + Edenor + C11, Sapogenat + Agnique + C11;

Sapogenat + Actirob B + C12, Sapogenat + Hasten + C12, Sapogenat + Mero + C12, Sapogenat + Rako-Binol + C12, Sapogenat + Phytorob B + C12, Sapogenat + Edenor + C12, Sapogenat + Agnique + C12.

The mixtures described above can expediently be used together with one or more safeners. Examples of preferred safeners are 1- (2,4-dichlorophenyl) -5- (ethoxycarbonyl) -5-methyl-2-pyrazoline-3-carboxylic acid ethyl ester (S1-1, mefenpyr-diethyl), (5-chloro-8-quinolinoxy ) -acetic acid- (1-methyl-hex-1-yl) ester (S2-1, Cloquintocet-mexyl) and 5.5-

Diphenyl-2-isoxazoline-3-carboxylic acid ethyl ester (S3-1, isoxadifen-ethyl).

In the combinations listed, the use of a safener can offer advantages, since this can reduce possible damage to the crop which can arise from sulfonylurea derivatives or other herbicidally active compounds.

Furthermore, the safeners S1-1, S2-1 and S3-1 can advantageously be replaced by one or more compounds from the following group of safeners or used together with one or more of the following compounds:

Ethyl 1- (2,4-dichlorophenyl) -5-methyl-pyrazole-3-carboxylate (S1-2),

Ethyl 1- (2,4-dichlorophenyl) -5-isopropyl-pyrazole-3-carboxylate (S1-3),

Ethyl 1- (2,4-dichlorophenyl) -5- (1,1-dimethyl-ethyl) pyrazole-3-carboxylate (S1 -4),

Ethyl 1- (2,4-dichlorophenyl) -5-phenyl-pyrazole-3-carboxylate (S1-5), 1 - (2,4-dichlorophenyl) -5-trichloromethyl- (1 H) -1, 2,4-triazole-3-carboxylic acid ethyl ester (S1-6, fenchlorazole)

5- (2,4-dichlorobenzyl) -2-isoxazoline-3-carboxylic acid ethyl ester (S1-7), 5-phenyl-2-isoxazoline-3-carboxylic acid ethyl ester (S1 -8), 5-chloro-8-quinolinoxy) acetic acid - (1,3-dimethyl-but-1-yl) ester (S2-2), (5-chloro-8-quinolinoxy) -acetic acid-4-allyl-oxy-butyl ester (S2-3), (5- Chloro-S-quinolinoxy) -acetic acid-1-allyl-oxy-prop-2-yl ester (S2-4), (5-chloro-8-quinolinoxy) -acetic acid ethyl ester (S2-5), (5-chloro-8- quinolinoxy) -acetic acid methyl ester (S2-6), (5-chloro-8-quinolinoxy) -acetic acid allyl ester (S2-7), (5-chloro-8-quinolinoxy) -acetic acid-2- (2-propylidene-iminoxy) -1 ethyl ester (S2-8),

(5-chloro-8-quinolinoxy) -acetic acid-2-oxo-prop-1-yl ester (S2-9), (5-chloro-8-quinolinoxy) -malonic acid diethyl ester, (5-chloro-8-quinolinoxy) -malonic acid diallyester , (5-Chloro-8-quinolinoxy) -malonic acid methyl ester 2,4-dichlorophenoxyacetic acid (ester) (2,4-D), 4-chloro-2-methylphenoxy-propionester (Mecoprop), MCPA, 3,6-dichloro -2-methoxy-benzoic acid (ester) (dicamba).

Preferred mixtures are:

Sapogenat + Actirob B + S1-1 + C1, Sapogenat + Hasten + S1-1 + C1, Sapogenat +

Mero + S1-1 + C1, Sapogenat + Rako-Binol + S1-1 + C1, Sapogenat + Phytorob B + S1-1 + C1, Sapogenat + Edenor + S1-1 + C1, Sapogenat + Agnique + S1-1 + C1 ; Sapogenat + Actirob B + S1-1 + C2, Sapogenat + Hasten + S1-1 + C2, Sapogenat + Mero + S1-1 + C2, Sapogenat + Rako-Binol + S1-1 + C2, Sapogenat + Phytorob B + S1- 1 + C2, Sapogenat + Edenor + S1-1 + C2, Sapogenat + Agnique + S1-1 + C2; Sapogenat + Actirob B + S1-1 + C3, Sapogenat + Hasten + S1-1 + C3, Sapogenat + Mero + S1-1 + C3, Sapogenat + Rako-Binol + S1-1 + C3, Sapogenat + Phytorob B + S1- 1 + C3, sapogenate + Edenor + S1-1 + C3, sapogenate + agnique + S1-1 + C3; Sapogenat + Actirob B + S1-1 + C4, Sapogenat + Hasten + S1-1 + C4, Sapogenat + Mero + S1-1 + C4, Sapogenat + Rako-Binol + S1-1 + C4, Sapogenat + Phytorob B + S1- 1 + C4, Sapogenat + Edenor + S1-1 + C4, Sapogenat + Agnique + S1-1 + C4; Sapogenat + Actirob B + S1-1 + C5, Sapogenat + Hasten + S1-1 + C5, Sapogenat + Mero + S1-1 + C5, Sapogenat + Rako-Binol + S1-1 + C5, Sapogenat + Phytorob B + S1- 1 + C5, Sapogenat + Edenor + S1-1 + C5, Sapogenat + Agnique + S1-1 + C5; Sapogenat + Actirob B + S1-1 + C6, Sapogenat + Hasten + S1-1 + C6, Sapogenat + Mero + S1-1 + C6, Sapogenat + Rako-Binol + S1-1 + C6, Sapogenat + Phytorob B + S1- 1 + C6, Sapogenat + Edenor + S1-1 + C6, Sapogenat + Agnique + S1-1 + C6; Sapogenat + Actirob B + S1-1 + C7, Sapogenat + Hasten + S1-1 + C7, Sapogenat + Mero + S1-1 + C7, Sapogenat + Rako-Binol + S1-1 + C7. Sapogenat + phytorob B + S1-1 + C7, sapogenat + edenor + S1-1 + C7, sapogenat + agnique + S1-1 + C7; Sapogenat + Actirob B + S1-1 + C8, Sapogenat + Hasten + S1-1 + C8, Sapogenat + Mero + S1-1 + C8, Sapogenat + Rako-Binol + S1-1 + C8, Sapogenat + Phytorob B + S1- 1 + C8, Sapogenat + Edenor + S1-1 + C8, Sapogenat + Agnique + S1-1 + C8; Sapogenat + Actirob B + S1-1 + C9, Sapogenat + Hasten + S1-1 + C9, Sapogenat + Mero + S1-1 + C9, Sapogenat + Rako-Binol + S1-1 + C9, Sapogenat + Phytorob B + S1- 1 + C9, Sapogenat + Edenor + S1-1 + C9, Sapogenat + Agnique + S1-1 + C9; Sapogenat + Actirob B + S1-1 + C10, Sapogenat + Hasten + S1-1 + C10, Sapogenat + Mero + S1-1 + C7, Sapogenat + Rako-Binol + S1-1 + C10, Sapogenat + Phytorob B + S1- 1 + C10, Sapogenat + Edenor + S1-1 + C10, Sapogenat + Agnique + S1-1 + C10;

Sapogenat + Actirob B + S1-1 + C11, Sapogenat + Hasten + S1-1 + C11, Sapogenat + Mero + S1-1 + C11, Sapogenat + Rako-Binol + S1-1 + C11, Sapogenat + Phytorob B + S1- 1 + C11, Sapogenat + Edenor + S1-1 + C11, Sapogenat + Agnique + S1-1 + C11;

Sapogenat + Actirob B + S1-1 + C12, Sapogenat + Hasten + S1-1 + C12, Sapogenat + Mero + S1-1 + C12, Sapogenat + Rako-Binol + S1-1 + C12, Sapogenat + Phytorob B + S1- 1 + C12, Sapogenat + Edenor + S1-1 + C12, Sapogenat + Agnique + S1-1 + C12; Sapogenat + Actirob B + S2-1 + C1, Sapogenat + Hasten + S2-1 + C1, Sapogenat + Mero + S2-1 + C1, Sapogenat + Rako-Binol + S2-1 + C1, Sapogenat + Phytorob B + S2- 1 + C1, Sapogenat + Edenor + S2-1 + C1, Sapogenat + Agnique + S2-1 + C1; Sapogenat + Actirob B + S2-1 + C2, Sapogenat + Hasten + S2-1 + C2, Sapogenat + Mero + S2-1 + C2, Sapogenat + Rako-Binol + S2-1 + C2, Sapogenat + Phytorob B + S2- 1 + C2, Sapogenat + Edenor + S2-1 + 2, Sapogenat + Agnique + S2-1 + C2; Sapogenat + Actirob B + S2-1 + C3, Sapogenat + Hasten + S2-1 + C3, Sapogenat + Mero + S2-1 + C3, Sapogenat + Rako-Binol + S2-1 + C3, Sapogenat + Phytorob B + S2- 1 + C3, Sapogenat + Edenor + S2-1 + C3, Sapogenat + Agnique + S2-1 + C3; Sapogenat + Actirob B + S2-1 + C4, Sapogenat + Hasten + S2-1 + C4, Sapogenat + Mero + S2-1 + C4, Sapogenat + Rako-Binol + S2-1 + C4, Sapogenat + Phytorob B + S2- 1 + C4, Sapogenat + Edenor + S2-1 + C4, Sapogenat + Agnique + S2-1 + C4; Sapogenat + Actirob B + S2-1 + C5, Sapogenat + Hasten + S2-1 + C5, Sapogenat + Mero + S2-1 + C5, Sapogenat + Rako-Binol + S2-1 + C5, Sapogenat + Phytorob B + S2- 1 + C5, Sapogenat + Edenor + S2-1 + C5, Sapogenat + Agnique + S2-1 + C5; Sapogenat + Actirob B + S2-1 + C6, Sapogenat + Hasten + S2-1 + C6, Sapogenat + Mero + S2-1 + C6, Sapogenat + Rako-Binol + S2-1 + C6, Sapogenat + Phytorob B + S2- 1 + C6, Sapogenat + Edenor + S2-1 + C6, Sapogenat + Agnique + S2-1 + C6; Sapogenat + Actirob B + S2-1 + C7, Sapogenat + Hasten + S2-1 + C7, Sapogenat + Mero + S2-1 + C7, Sapogenat + Rako-Binol + S2-1 + C7, Sapogenat + Phytorob B + S2- 1 + C7, Sapogenat + Edenor + S2-1 + C7, Sapogenat + Agnique + S2-1 + C7; Sapogenat + Actirob B + S2-1 + C8, Sapogenat + Hasten + S2-1 + C8, Sapogenat + Mero + S2-1 + C8, Sapogenat + Rako-Binol + S2-1 + C8, Sapogenat + Phytorob B + S2- 1 + C8, Sapogenat + Edenor + S2-1 + C8, Sapogenat + Agnique + S2-1 + C8; Sapogenat + Actirob B + S2-1 + C9, Sapogenat + Hasten + S2-1 + C9, Sapogenat + Mero + S2-1 + C9, Sapogenat + Rako-Binol + S2-1 + C9, Sapogenat + Phytorob B + S2- 1 + C9, Sapogenat + Edenor + S2-1 + C9, Sapogenat + Agnique + S2-1 + C9; Sapogenat + Actirob B + S2-1 + C10, Sapogenat + Hasten + S2-1 + C10, Sapogenat + Mero + S2-1 + C10, Sapogenat + Rako-Binol + S2-1 + C10, Sapogenat + Phytorob B + S2- 1 + C10, Sapogenat + Edenor + S2-1 + C10, Sapogenat + Agnique + S2-1 + C10; Sapogenat + Actirob B + S2-1 + C11, Sapogenat + Hasten + S2-1 + C11, Sapogenat + Mero + S2-1 + C11, Sapogenat + Rako-Binol + S2-1 + C11, Sapogenat + Phytorob B + S2- 1 + C11, Sapogenat + Edenor + S2-1 + C11, Sapogenat + Agnique + S2-1 + C11; Sapogenat + Actirob B + S2-1 + C12, Sapogenat + Hasten + S2-1 + C12, Sapogenat + Mero + S2-1 + C12, Sapogenat + Rako-Binol + S2-1 + C12, Sapogenat + Phytorob B + S2- 1 + C12, Sapogenat + Edenor + S2-1 + C12, Sapogenat + Agnique + S2-1 + C12;

Sapogenat + Actirob B + S3-1 + C1, Sapogenat + Hasten + S3-1 + C1, Sapogenat + Mero + S3-1 + C1, Sapogenat + Rako-Binol + S3-1 + C1, Sapogenat + Phytorob B + S3- 1 + C1, Sapogenat + Edenor + S3-1 + C1, Sapogenat + Agnique + S3-1 + C1; Sapogenat + Actirob B + S3-1 + C2, Sapogenat + Hasten + S3-1 + C2, Sapogenat + Mero + S3-1 + C2, Sapogenat + Rako-Binol + S3-1 + C2, Sapogenat + Phytorob B + S3- 1 + C2, Sapogenat + Edenor + S3-1 + C2, Sapogenat + Agnique + S3-1 + C2; Sapogenat + Actirob B + S3-1 + C3, Sapogenat + Hasten + S3-1 + C3, Sapogenat + Mero + S3-1 + C3, Sapogenat + Rako-Binol + S3-1 + C3, Sapogenat + Phytorob B + S3- 1 + C3, Sapogenat + Edenor + S3-1 + C3, Sapogenat + Agnique + S3-1 + C3; Sapogenat + Actirob B + S3-1 + C4, Sapogenat + Hasten + S3-1 + C4, Sapogenat + Mero + S3-1 + C4, Sapogenat + Rako-Binol + S3-1 + C4, Sapogenat + Phytorob B + S3- 1 + C4, Sapogenat + Edenor + S3-1 + C4, Sapogenat + Agnique + S3-1 + C4; Sapogenat + Actirob B + S3-1 + C5, Sapogenat + Hasten + S3-1 + C5, Sapogenat + Mero + S3-1 + C5, Sapogenat + Rako-Binol + S3-1 + C5, Sapogenat + Phytorob B + S3- 1 + C5, Sapogenat + Edenor + S3-1 + C5, Sapogenat + Agnique + S3-1 + C5; Sapogenat + Actirob B + S3-1 + C6, Sapogenat + Hasten + S3-1 + C6, Sapogenat + Mero + S3-1 + C6, Sapogenat + Rako-Binol + S3-1 + C6, Sapogenat + Phytorob B + S3- 1 + C6, Sapogenat + Edenor + S3-1 + C6, Sapogenat + Agnique + S3-1 + C6; Sapogenat + Actirob B + S3-1 + C7, Sapogenat + Hasten + S3-1 + C7, Sapogenat + Mero + S3-1 + C7, Sapogenat + Rako-Binol + S3-1 + C7, Sapogenat + Phytorob B + S3- 1 + C7, Sapogenat + Edenor + S3-1 + C7, Sapogenat + Agnique + S3-1 + C7; Sapogenat + Actirob B + S3-1 + C8, Sapogenat + Hasten + S3-1 + C8, Sapogenat + Mero + S3-1 + C8, Sapogenat + Rako-Binol + S3-1 + C8, Sapogenat + Phytorob B + S3- 1 + C8, Sapogenat + Edenor + S3-1 + C8, Sapogenat + Agnique + S3-1 + C8; Sapogenat + Actirob B + S3-1 + C9, Sapogenat + Hasten + S3-1 + C9, Sapogenat + Mero + S3-1 + C9 Sapogenat + Rako-Binol + S3-1 + C9, Sapogenat + Phytorob B + S3-1 + C9, Sapogenat + Edenor + S3-1 + C9, Sapogenat + Agnique + S3-1 + C9; Sapogenat + Actirob B + S3-1 + C10, Sapogenat + Hasten + S3-1 + C10, Sapogenat + Mero + S3-1 + C10, Sapogenat + Rako-Binol + S3-1 + C10, Sapogenat + Phytorob B + S3- 1 + C10, Sapogenat + Edenor + S3-1 + C10, Sapogenat + Agnique + S3-1 + C10;

Sapogenat + Actirob B + S3-1 + C11, Sapogenat + Hasten + S3-1 + C11, Sapogenat + Mero + S3-1 + C11, Sapogenat + Rako-Binol + S3-1 + C11, Sapogenat + Phytorob B + S3- 1 + C11, Sapogenat + Edenor + S3-1 + C11, Sapogenat + Agnique + S3-1 + C11; Sapogenat + Actirob B + S3-1 + C12, Sapogenat + Hasten + S3-1 + C12, Sapogenat + Mero + S3-1 + C12, Sapogenat + Rako-Binol + S3-1 + C12, Sapogenat + Phytorob B + S3- 1 + C12, Sapogenat + Edenor + S3-1 + C12, Sapogenat + Agnique + S3-1 + C12.

This results in numerous possibilities for combining several agrochemical active substances with one another and using them together to control harmful plants in plant crops without departing from the concept of the invention.

For example, in a preferred embodiment, e.g. various herbicidal active compounds of the formula (III) and / or their salts are combined with one another, e.g.

Mesosulfuron-methyl + iodosulfuron-methyl,

Mesosulfuron-methyl + iodosulfuron-methyl-sodium,

Mesosulfuron-methyl + foramsulfuron,

Mesosulfuron-methyl + foramsulfuron-sodium, mesosulfuron-methyl-sodium + iodosulfuron-methyl,

Mesosulfuron-methyl-sodium + iodosulfuron-methyl-sodium,

Mesosulfuron-methyl-sodium + foramsulfuron, Mesosulfuron-methyl-sodium + foramsulfuron-sodium, foramsulfuron + iodosulfuron-methyl, foramsulfuron + iodosulfuron-methyl-sodium, foramsulfuron-sodium + iodosulfuron-methyl, foramsulfuron-sodium + iodosulfuron-methyl-sodium.

The herbicidal active ingredients c) and their mixtures, e.g. the aforementioned active ingredient mixtures of active ingredients of the formula (III) and / or their salts can be combined with one or more safeners, in particular with the safeners mefenpyr-diethyl (S1-1), cloquintocet-mexyl (S2-1) and isoxadifen-ethyl (S3-1).

The adjuvants according to the invention can both enhance the biological effect of agrochemical active substances and, in combination with agrochemical active substances and water, form a pointed broth with high physical stability.

The adjuvants according to the invention show an advantageous physical application behavior. Adjuvant and agrochemical active ingredient remain evenly distributed in the spray tank during application, which enables even application to the crop or cultivated area. Mixtures formed in the spray tank, such as aqueous solutions, suspensions, emulsions or suspoemulsions, are stable, so that deposits such as irreversible creams, sedimentations, agglomerations do not occur. In addition, the adjuvants according to the invention can be handled economically and are ecologically and toxicologically harmless.

The agrochemical compositions according to the invention have an excellent biological action. These effects allow, among other things, a reduction of the application rate, the fight against a wider spectrum of

Harmful organisms, the closing of gaps in effectiveness, a faster and safer effect, a longer lasting effect, complete control of the Harmful organisms with only one or a few applications, and an extension of the application period.

The following exemplary embodiments explain the invention and have no limiting character.

Examples

A. Preparation of the adjuvants

example 1

950 g of rapeseed oil methyl ester were introduced and 50 g of Sapogenat® T 080 were added with stirring. 1000 g of the corresponding adjuvant according to the invention were obtained (Table 1, Example 1). Examples 2-15 were carried out analogously to example 1.

Table 1 shows adjuvants according to the invention, which were prepared by mixing the components. In Examples 12 and 13 there was another

Emulsifier (Atplus® 309F, sorbitan-based. Surfactant mixture) added.

Table 1: Adjuvants according to the invention

The adjuvants thus obtained are very inexpensive and powerful adjuvants.

B. Application examples

The adjuvants according to the invention were tested for their usability in an application test. For this purpose, a spray mixture consisting of water, agrochemical active ingredient and the adjuvants according to the invention listed in Table 1 was produced in a spray apparatus. The spray liquor was then sprayed under the following conditions: stationary field sprayer (Hardy, 400 liter tank); Pump capacity: 116 liters / min .: injector mixer with variable mixing intensity (15-50 liters / min); Water hardness: 18 German water hardness; Water temperature: 10 ° C; Dosage: 0.15 kg of MaisTerΘ granules (weight ratio foramsulfuron: iodosulfuron-methyl-sodium: isoxadifen-ethyl ^: 30: 1: 30); 2 liters of adjuvant; 75-100 liters of water; Nozzles: 80 015 XR; Stirring intensity: 30 liters / min; Stirring time: 20 min after filling the spray mixture into the syringe. After the spray liquor had been applied, the precipitates on the filters of the spray apparatus, such as suction filters (50 mesh), pressure filters (80 mesh) or nozzle filters (100 mesh), were determined by optical assessment, in order to assess the applicability of the adjuvants according to the invention. The pore size of the filter is given in mesh.

Table 2 shows the test results. The precipitation on the filters is given in% of the filter area. The results demonstrate the excellent applicability of the adjuvants according to the invention.

Table 2: Application tests

Claims

claims:

1. Containing liquid adjuvant

a) one or more surfactants of the formula (I),

Ar-O- (CHR ¹ -CHR ² -O-) _y -R ³ (I) wherein Ar is aryl which is substituted by at least two (-C-C ₃₀ ) alkyl radicals, R ¹ H or (dC ₆ ) alkyl .

R ^{2 is} H or (C ₁ -C ₆ ) alkyl, R ³ H is an unsubstituted or substituted (C-ι-C ₃ o) hydrocarbon radical, a sulfonate radical, a phosphonate radical or an acyl radical, and y is an integer from 1 to 100 means, and

b) one or more fatty acid esters.

2. A liquid adjuvant according to claim 1, wherein in formula (I) y is an integer from 1 to 20.

3. A liquid adjuvant according to claim 1 or 2, wherein in formula (I)

Ar is a naphthyl or phenyl radical which bears 3-7 (CrC, o) alkyl radicals, R ^{1 is} H or methyl, R ^{2 is} H or methyl,

R ³ H, (C ₁ -C ₃₀ ) alkyl, (C ₂ -C ₃₀ ) alkenyl, (C ₂ -C ₃₀ ) alkynyl, a sulfate residue

Is phosphate or an acyl group, and y is an integer from 1 to 20.

4. Liquid adjuvant according to one or more of claims 1-3, wherein the fatty acid ester b) is a natural oil or a synthetic oil.

5. Liquid adjuvant according to one or more of claims 1-4, wherein the fatty acid ester b) is a vegetable oil or an animal oil.

6. Liquid adjuvant according to one or more of claims 1-5, wherein the fatty acid ester b) is a rapeseed oil.

7. Liquid adjuvant according to one or more of claims 1-6, additionally containing one or more auxiliaries customary in crop protection.

8. A method for producing a liquid adjuvant according to one or more of claims 1-7, wherein the components are mixed together.

9. Use of a liquid adjuvant according to one or more of claims 1-7, for the preparation of an agrochemical agent.

10. Agrochemical agent containing α) one or more liquid adjuvants according to one or more of claims 1-7, and β) one or more agrochemical active ingredients.

11. The agrochemical composition according to claim 10, wherein the agrochemical active ingredient is a herbicide.

12. The agrochemical composition according to claim 10 or 11, wherein the agrochemical active ingredient is a sulfonylurea.

13. Agrochemical composition according to one or more of claims 10-12, additionally containing one or more further components from the group of agrochemical active substances and the auxiliaries customary in crop protection.

14. A method for controlling harmful organisms, in which the components of the agrochemical composition, as defined in one or more of claims 10-13, are applied to the harmful organisms or to the locations where they occur, together or separately.

15. A method for combating harmful plants, wherein the components of the herbicidal composition, defined according to one or more of claims 11 to 13, are applied jointly or separately to the plants, parts of plants, plant seeds or the area on which the plants grow.

16. The method according to claim 15 for the selective control of harmful plants in plant crops.

17. Use of the agrochemical agent defined according to one or more of claims 10 to 13 for controlling harmful organisms.

18. Use of the herbicidal composition defined according to one or more of claims 11 to 13 for controlling harmful plants.

19. A method for producing an agrochemical agent, defined according to one or more of claims 10 to 13, wherein the components are mixed together.