EP1523236A1 - Solid adjuvants - Google Patents

Abstract

The invention relates to a solid adjuvant containing a) one or several surfactants of formula Ar-O-(CHR1-CHR2-O-)y-R3 (I), in which Ar represents aryl that is substituted with two or more (C1-C30)alkyl radicals, R1 represents H or (C1-C6)alkyl, R2 represents H or (C1-C6)alkyl; R3 represents H, an unsubstituted or substituted (C1-C30) hydrocarbon radical, a sulphonate radical, phosphonate radical, or acyl radical, and y represents a whole number between 1 and 100, and b) one or several fillers. The inventive adjuvant is particularly suitable in the area of plant protection.

Description

Fixed adjuvants

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

The technology to combine agrochemical agents and adjuvants (enhancers that are not themselves biologically active) - e.g. by mixing in the spray tank - finds a broad, practical meaning and is described intensively in the specialist literature. In the vast majority of the described cases, these are liquid adjuvants (see, for example, CLFoy, DW Pritchard (Ed.), "Pesticide Formulation and Adjuvant Technology", CRC Press, Ine, 1996, Boca Raton, Florida, USA). ,

It is known that the addition of adjuvants to a large number of agrochemical active ingredients can increase the control of undesired plant growth. Adjuvants in the form of a solid formulation are described in the literature (e.g. EP 955 810 A1, EP 955 809 A1, EP 968649 A1). However, such adjuvants have so far not been of economic relevance because they are expensive, physically not sufficiently stable in storage or not sufficiently user-friendly, e.g. insufficient disintegration in the spray liquor or large volume / weight ratio per area.

The object of the present invention was therefore to provide new adjuvants which have advantageous properties, in particular in combination with agrochemical active compounds, such as herbicides.

Surprisingly, it has now been found that this task is due to the special

Adjuvants of the present invention is solved.

The present invention thus relates to a solid adjuvant containing

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 two or more, preferably 2 to 10, (C

C ₃ o) alkyl radicals is substituted, R ^{1 is} H or (CC ₆ ) alkyl, R ² H or (dC ₆ ) is alkyl, R ³ H is an unsubstituted or substituted C ₁ -C ₃ o -hydrocarbon radical, preferably (CC ₃₀ ) Alkyl, (C ₂ -C ₃₀ ) alkenyl, (C ₂ -C ₃₀ ) alkynyl, a sulfonate residue, a phosphonate residue or an acyl residue, and y is an integer from 1 to 1000, and

b) one or more fillers.

In the surfactants of the formula (I), for y> 1, the y units (CHR ¹ -CHR ² -O) can be the same (for example ethylene oxide homopolymer units, propylene oxide 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, for example from "Presentation about selected Product Groups, Clariant GmbH, Surfactants Division, p.39, September 1997" 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).

^ Cy ArOH

(! ^■ ) (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) after standard reactions with R ³ = H. For example, surfactants of formula (I) with R ³ = (substituted) hydrocarbon radical such as alkyl, alkenyl or alkynyl by alkylation, alkenylation or alkynylation, for example using alkyl halides, alkenyl halides or alkynyl halides with 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 the formula (I ¹ ) can be prepared by known methods, for example from the corresponding alkenes, and are commercially available, for example 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 phenol, with alcohols, olefins or alkyl halides under catalytic 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 (-CC ₁₀ ) alkyl radicals. Ar is preferably tri (C ₁ -C ₆ ) alkylphenyl, particularly preferably tri-butylphenyl such as tri-2,4,6-sec-butylphenyl. R ¹ and R ² are preferably H or methyl, particularly preferably H. R ³ is preferably H, (-C ₂₂ ) alkyl, (C ₂ -C ₂₂ ) alkenyl, (C ₂ -C ₂ 2) alkynyl, an acyl radical such as CO- (CC ₃₀ ) alkyl, CO- (C ₂ -C ₃₀ ) alkenyl, CO- (C ₂ -C ₃₀ ) alkynyl, CO- (CC ₃₀ ) alkoxy, CO- (C ₂ -C ₃₀ ) alkenyloxy, CO- (C ₂ -C ₃₀ ) alkynyloxy or COH, or a sulfonate residue such as SO ₃ M where M is 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, e.g. a primary, secondary, tertiary or quaternary ammonium ion such as

NH ₃ CH ₃ , NH ₂ (CH ₃ ) _2l NH (C ₂ H ₅ ) ₃ or N (CH ₃ ) ₄ , or a phosphonate residue such as (O) P (OR ^' ) (OR ^" ), where R ^' , R ^" independently of one another H or a cation are like 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 ₅ ) ₂ , NH (C ₂ H ₃ ) ₃ or N (CH ₃ ) ₄ , and R ^' , R ^"can also be Ar-0- (CHR ¹ CHR ² ) _y , where Ar, R ¹ , R ² and y are as defined in formula (I).

R ³ = H, (CC ₆ ) alkyl or S0 ₃ M, where M is a cation, is particularly preferred.

Values from 15 to 100 are preferred for y, values from 30 to 80 are particularly preferred.

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 30 to 80, for example surfactants from the Sapogenat ^® T series from Clariant, such as Sapogenat ^® T 180, Sapogenat ^® T 300 and Sapogenat ^® T 500. Preferred surfactants Formula (I) are solid under normal conditions (room temperature, normal pressure).

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. If not specifically stated, these radicals generally have 1 to 30 carbon atoms, the lower carbon skeletons, for example having 1 to 6 carbon atoms or, in the case of unsaturated groups, having 2 to 6 carbon atoms, being 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; Aikenyl and alkynyl radicals have the meaning of the possible unsaturated radicals corresponding to the alkyl radicals; Aikenyl 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.

Aikenyl 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₎ alkenyloxy, etc., and (C ₃ -C) alkynyloxy etc.

A hydrocarbon residue means a straight chain, branched or cyclic and saturated or unsaturated aliphatic or aromatic hydrocarbon residue, e.g. Alkyl, aikenyl, 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, aikenyl 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 heteroatoms. The heterocyclic radical can be, for example, a heteroaromatic radical or ring (heteroaryl), such as 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 a partially or fully hydrogenated radical such as oxiranyl, oxetanyl , Pyrrolidyl, piperidyl, piperazinyl, dioxolanyl, morpholinyl, tetra hydrofuryl. Possible substituents for a substituted heterocyclic radical are the substituents mentioned below, and additionally oxo. The oxo group can also occur on the hetero ring atoms, which can exist in different oxidation states, for example in the case of N and S.

Halogen means, for example, fluorine, chlorine, bromine or iodine. Haloalkyl, aikenyl and alkynyl are partially or completely substituted alkyl, aikenyl 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 radicals, such as substituted hydrocarbon radicals, for example substituted alkyl, aikenyl, 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 as well as unsaturated aliphatic radicals, such as aikenyl, alkynyl, alkenyloxy, alkynyloxy, etc., corresponding to the saturated hydrocarbon-containing radicals mentioned. In the case of radicals with carbon atoms, those with 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms, are preferred. Substituents from the group halogen, for example fluorine and chlorine, (C ₁ -C ₄ ) alkyl, preferably methyl or ethyl, (CrC ₄ ) haloalkyl, preferably trifluoromethyl, are generally preferred, (-C-C ₄ ) alkoxy, preferably methoxy or ethoxy, (-C-C 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, (CtC ₄ ) alkyl, (CrC ₄ ) alkoxy, (C 1 -C ₄ ) haloalkyl , (-C-C ₄ ) haloalkoxy and nitro is substituted, for example o-, m- and p-tolyl, dimethylphenyls, 2-, 3- and 4-chlorophenyl, 2-, 3- and 4-trifluoro- and trichlorophenyl, 2,4-, 3,5-, 2,5- and 2,3-dichlorophenyl, o-, m- and p-methoxyphenyl or 2,4,6-tributylphenyl such as 2,4,6-tri-sec-butylphenyl ,

An acyl residue means the residue of an organic acid which formally arises from the removal of an OH group from the organic acid, 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 S0 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 can be substituted, for example as indicated above for phenyl, or alkyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, alkylsulfonyl, alkylsulfinyl, N-alkyl-1-iminoalkyl and others Remains of organic acids.

Formula (I) and the other formulas in this specification also include all stereoisomers and mixtures thereof. Such compounds contain a or several 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 fillers b) contained in the adjuvants according to the invention are solids. These are generally known, e.g. from: W. van Falkenburg (ed.), Pesticide Formulations, Marcel Dekker, Inc., New York, 1973; or from: Degussa No. 1 series, Synthetic Silicas for Plant Protection and Pesticides, March 1989. They are also commercially available.

Preferred fillers b) are e.g. inorganic or organic carriers such as polymeric carbohydrates or silicates. Polymeric carbohydrates are e.g. Cellulose and its derivatives such as Tylose®, Tylopur®, Methylan® and Finnix®, or starch and its derivatives such as Maizena® and Mondamin®. Silicates can be of natural or synthetic origin. Natural silicates are e.g. Kaolin, bentonite, talc, pyrophyllite or diatomaceous earth. Synthetic silicates are e.g. fumed silica or precipitated silica, e.g. Sipernat® (e.g. Sipernat® 50 S or Sipemat® 500 LS), Dessalon®, Aerosil®, Silkasil® or Ketiensil®. In the context of the present invention, the term silicates also includes silicates such as earth metal and alkaline earth metal silicates, e.g. Aluminum silicates or magnesium silicates.

The adjuvants according to the invention are solid under normal conditions (normal pressure, room temperature). Adjuvants according to the invention can be present, for example, in the form of granules, powders or dusts. They generally contain 10-80% by weight, preferably 25-75% by weight, particularly preferably 40-70% by weight, of one or more surfactants of the formula (I) and 90-20% by weight, preferably 75-25% by weight, particularly preferably 60-30% by weight, of fillers b). In In individual cases, these salary limits can also be exceeded or fallen short of. Preferred adjuvants according to the invention contain the surfactants of the formula (I) in excess over the fillers b).

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 is intended to enable the intended handling of an agent.

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, Na ₂ SO, MgCl (0-50% by weight), (oligo-; poly -) - phosphates; Carbonates such as potassium carbonate;

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

• defoamers such as Fluowet ^® PP (0-2% by weight);

Disintegrant or disintegrant such as, for example, effervescent powder (citric acid / NaHCO ₃ ) (0-20% by weight), microcrystalline cellulose, polyvinylpyrrolidone;

• "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 stated 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 can be prepared by known methods (cf. Hans Mollet, Arnold Grubenmann, Formuliertechnik; Wiley-VCH, Weinheim, 2000; pp. 183 ff and references given there). The adjuvants can be present, for example, in the form of granules, powders or dusts. Granules can be obtained, for example, by melt extrusion and subsequent granulation. Powder or dusts can be obtained by pre-crushing strand pellets to the desired particle size, for example using an air jet mill.

The adjuvants according to the invention can be combined together with one or more agrochemical active ingredients to form agrochemicals, e.g. in the form of co-formulations or 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 different from 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 and S- (N-aryl-N-alkylcarbamoylmethyl) dithiophosphoric acid ester.

The ALS inhibitors are, in particular, imidazolinones, pyrimidinyloxy-pyridinecarboxylic acid derivatives, pyrimidyloxy-benzoic 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 where the radicals, including substituents, contain 1-30 carbon 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, including substituents, 1-10 carbon atoms, for example unsubstituted or substituted CC ₆ alkyl, preferably a hydrogen atom or methyl,

R ^{γ is} a hydrogen atom or a hydrocarbon radical which is unsubstituted or substituted and has substituents including 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} CrC 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 , in which R ^b and R ^{c are,} independently of one another, the same or different H or C 1 -C 4 alkyl,

R 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 C 1 -C ₄ -alkyl, R ^d is H or CC ₄ -alkyl and R ^{e is} an acyl radical such as formyl or CrC-alkyl Is sulfonyl, and R ⁵ in the event that R ⁴ is Cr

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

R ^(is H or CC ₄ alkyl, m is zero or 1, preferably zero,

X and Y are independently the same or different CrC- ₆ alkyl, CrCβ-alkoxy or -C-C ₆ alkylthio, each of the three radicals mentioned unsubstituted or by one or more radicals from the group halogen, -CC ₄ alkoxy and C- _t -C- ₄ alkylthio is substituted, or C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₆ alkenyloxy or C ₃ -C ₆ -Alkynyloxy, preferably CrC ₄ alkyl or -CC ₄ 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 ⁴ is CO- (CrC ₄ alkoxy) and R ⁵ is halogen, preferably iodine, or R ⁵ is CH ₂ -NHR ^e , where R ^{e is} an acyl radical, preferably C 1 -C 8 -alkyl- Is sulfonyl, or b) R ⁴ is CO-N (C ₁ -C ₄ -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 are always to be understood 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, for example 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 (alkylsulfonyl) 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 suitable sulfonylureas are A1) Phenyl- and benzylsulfonylureas and related compounds, e.g.

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

(Chlorsulfuron),

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-methoxycarbonylphenylsulfonyl) -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 ff.),

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

wherein

E CH or N, preferably CH,

R ²⁰ iodine or NR ²⁵ R ²⁶ ,

R ^{21 is} hydrogen, halogen, cyano, (CrC ₃ ) -alkyl, (-C-C ₃ ) - haloalkyl, (dC ^ -haloalkoxy, (CC ₃ ) -alkylthio, (dC ₃ ) -alkoxy- (CrC ₃ ) -alkyl, (-C-C ₃ ) -alkoxy-carbonyl, mono- or Di - ((-CC ₃ ) -alkyl) amino, (dC 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, (dC ₃ ) alkyl, (CC ₃ ) alkenyl, (dC ₃ ) - alkynyl or together - (CH ₂ ) ₄ -, - (CH ₂ ) s- 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, (CrC ₂₎ alkyl, (CrC ₂₎ alkoxy, (Cι-C ₂₎ -haloalkyl, in particular _CF3, (CrC ₂₎ -haloalkoxy, preferably _OCHF2 or OCH ₂ CF _3,

R 24 (Cι-C ₂₎ alkyl, (CrC ₂₎ -Halogenaikoxy, preferably OCHF _2, or (Cι-C ₂₎ - alkoxy,

_R 25 (CrC ₄ ) alkyl, _R 26 (CC ₄ ) alkyl sulfonyl 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-methylsulfonyl-N-methyl-aminopyridin-2-yl) sulfonylurea, or their salts;

A6) Alkoxyphenoxysulfonyl ureas, 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, N0 ₂ , CF ₃ , CN, (-C-C ₄ ) alkyl, (-C-C ₄ ) alkoxy, (CC ₄ ) alkylthio or (Cι-C ₃ ) alkoxy) carbonyl, preferably in 6-position on the phenyl ring, n 0, 1, 2 or 3, preferably 0 or 1,

R ^{29 is} hydrogen, (CC ₄ ) -alkyl or (C ₃ -C ₄ ) -alkenyl,

R ³⁰ , R ³¹ independently of one another halogen, (dC ₂ ) -alkyl, (dC ₂ ) -alkoxy, (dC ₂ ) - haloalkyl, (dC ₂ ) -haloalkoxy or (Cι-C ₂ ) -alkoxy- (dC ₂ ) alkyl, preferably OCH ₃ or CH ₃ , 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 substances include the compounds listed below: amidosulfuron, azimsulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, flupyrsulfuron, methyl-sulfonon-methyluron-methyl-sodium-methyl- Metsulfuron-Methyl, Nicosulfuron, Oxasulfuron, Primisulfuron-Methyl, Prosulfuron, Pyrazosulfuron-Ethyl, Rimsulfuron, Sulfometuron-Methyl, Sulfosulfuron, Thifensulfuron-Methyl, Triasulfuron, Tribenuron-Methyl, Triflusulfuroniums-Methyl, Iodine-Sulfuron-Methyl, Iodine 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-imidazolin-2-methyl) -yl) -4-methylbenzoic acid (imazamethabenz),

5-ethyl-2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) pyridine-3-carboxylic acid (imazethapyr),

2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) -quinoline-3-carboxylic acid (imazaquin), 2- (4-isopropyl-4-methyl-5-oxo-2- imidazolin-2-yl) pyridine-3-carboxylic acid (imazapyr), 5-methyl-2- (4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) pyridine-3-carboxylic acid ( imazethamethapyr);

C) triazolopyrimidine sulfonamide derivatives, e.g. N- (2,6-difluorophenyl) -7-methyl-1, 2,4-triazolo [1,5-c] pyrimidine-2-sulfonamide (flumetsulam),

N- (2,6-dichloro-3-methylphenyl) -5,7-dimethoxy-1, 2,4-triazolo [1,5-c] pyrimidine-2-sulfonamide,

N- (2,6-difluorophenyl) -7-fluoro-5-methoxy-1,2,4-triazolo [1,5-c] pyrimidine-2-sulfonamide, N- (2,6-dichloro-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-Dimethoxypyrimidin-2-yl) -oxypyridine-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, for example methyl 2- (4- (2,4-dichlorophenoxy) phenoxy) propionate (diclofop-methyl), 2- (4- (4-bromo-2-chlorophenoxy) phenoxy ) methyl propionate (DE-A 26 01 548), 2- (4- (4-bromo-2-fluorophenoxy) phenoxy) methyl propionate (US-A 4,808,750), 2- (4- (2-chloro-4-trifluoromethylphenoxy) phenoxy ) methyl propionate (DE-A 24 33 067), 2- (4- (2-Fluoro-4-trifluoromethylphenoxy) phenoxy) propionic acid methyl ester (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-en-oate,

Methyl 2- (4- (4-trifluoromethylphenoxy) phenoxy) propionate (DE-A 24 33 067);

E2) "Mononuclear" heteroaryloxyphenoxy alkane carboxylic acid derivatives, e.g. 2- (4- (3,5-dichloropyridyl-2-oxy) phenoxy) propionic acid ethyl ester (EP-A 0 002 925), 2- (4- (3,5-dichloropyridyl-2-oxy) phenoxy) propionic acid propyl ester (EP- A 0 003 114),

Methyl 2- (4- (3-chloro-5-trifluoromethyl-2-pyridyloxy) phenoxy) propionate (EP-A 0 003 890),

Ethyl 2- (4- (3-chloro-5-trifluoromethyl-2-pyridyloxy) phenoxy) propionate (EP-A 0 003 890),

Propargic acid 2- (4- (5-chloro-3-fluoro-2-pyridyloxy) phenoxy) propionate (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),

Methyl 2- (4- (6-fluoro-2-quinoxalyloxy) phenoxy) propionate (see J. Pest. Sci. 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-diethyl-chloroacetanilide (alachlor), N- (3-methoxyprop-2-yl) -2-methyl-6-ethyl-chloroacetanilide (metolachlor), N- (3-methyl-1, 2 , 4-oxadiazol-5-yl-methyl) -chloroacetic acid-2,6-dimethylanilide, N- (2,6-dimethylphenyl) -N- (1-pyrazolylmethyl) -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) cyciohex-2-enone (cycloxydim),

2- (1-Ethoxyiminopropyl) -5- (2,4,6-trimethylphenyl) -3-hydroxy-cyclohex-2-en-1-one

(Tralkoxydim);

I) benzoylcyclohexanediones, e.g.

2- (2-chloro-4-methylsulfonylbenzoyl) cyclohexane-1,3-dione (SC-0051, EP-A

0 137 963), 2- (2-nitrobenzoyl) -4,4-dimethyl-cyclohexane-1,3-dione (EP-A 0 274 634),

2- (2-nitro-4-methylsulfonylbenzoyl) -4,4-dimethylcyclohexan-1, 3-dione (WO 91/13548,

Mesotrione); J) S- (N-aryl-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)

R *

wherein

R x ^λ (CC ₄ ) alkyl or (-C-C ₄ ) haloalkyl; R ^γ (CrC ₄ ) alkyl, (C ₃ -C ₆ ) cycloalkyl or (C ₃ -C ₆ ) cycloalkyl (dC 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 Pesticide Manual", 12th edition, 2000, The British Crop Protection Council, "Agricultural Chemicals Book II - Herbicides -", by WT Thompson, Thompson Publications, Fresno CA, USA 1990 and "Farm Chemicals Handbook '90", Meister Publishing Company, Willoughby OH, USA, 1990. In a preferred embodiment, the agrochemical compositions according to the invention contain one or more active substances from the group diflufenican, fenoxaprop-P-ethyl, metamitron, ethofumesate, phenmedipham, desmedipham or the above-mentioned group L) of the phosphorus-containing herbicides, for example glufosinate-ammonium or glyphosate.

The agrochemical compositions according to the invention can contain, in addition to the adjuvants according to the invention and one or more agrochemical active ingredients, further 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. Due to the improved control of the harmful plants by the agrochemical agents according to the invention, it becomes possible to reduce the application rate and / or to increase the 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 fillers b) and agrochemical active ingredients c). It should especially be emphasized that even in combinations with application rates or weight ratios of a): b): c) in which one Synergism cannot always be demonstrated easily - for example because the individual compounds are usually used in combination in very different application rates or because the control of the harmful plants is already very good due to the individual compounds - the agrochemical compositions of the invention generally have a synergistic effect is inherent. The agrochemical compositions according to the invention are prepared by customary processes, for example mixing by grinding, dissolving or dispersing the individual components, preferably at room temperature. An extrusion such as a melt extrusion can then take place, for example. 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. in the tank mixing process together 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 according to the invention are obtained through a suitable choice of the auxiliaries or manufacturing processes, which show a very good disintegration in the spray tank and which can also be used economically.

The adjuvants according to the invention can be produced in various ways, for example as granules, powders or dusts. Possible formulation options are, for example: wettable powder (WP), water-soluble powder (SP), water-dispersible granules (WG), water-soluble granules (SG) and melt granules. Granules such as melt granules are preferred. The agrochemical compositions according to the invention and the agrochemical active ingredients c) can be formulated in different ways, depending on which biological and / or chemical-physical parameters are specified. Possible formulation options are, for example: wettable powder (WP), water-soluble powder (SP), water-soluble concentrates (SL), emulsifiable concentrates (EC), microemulsions (ME), emulsions (EW), such as oil-in-water and water in-oil emulsions, sprayable solutions, suspension concentrates (SC), suspoemulsion concentrates (SE), oil or water-based dispersions, oil-miscible solutions, capsule suspensions (CS), dusts (DP), mordants, granules for spreading and soil application, granules (GR) in the form of micro, spray, elevator and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV formulations, microcapsules and waxes. 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 Edition 1986, Wade van Valkenburg, "Pesticide 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.

Formulation aids 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 E., Darland Books, Caldwell N.J .; H. V. Olphen, "Introduction to Clay Colloid Chemistry"; 2nd Ed., J. Wiley & Sons, N.Y. Marsden, Solvents Guide, 2nd Ed., Interscience, N.Y. 1950; McCutcheon's, "Detergents and Emulsifiers Annual," MC Publ. Corp, Ridegewood N.J .; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y. 1964; Schönfeldt, "Interface-active ethylene oxide adducts", Wiss. Publishing company, 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 ingredients, such as herbicides, fungicides, insecticides, as well Manufacture safeners, fertilizers and / or growth regulators, for example in the form of a ready-to-use formulation or as a tank mix.

Spray powders (wettable powders) are preparations which are uniformly dispersible in water and which, in addition to components a), b) and c), optionally diluents or inert substances and other ionic or nonionic surfactants (wetting agents, dispersing agents), e.g. contain polyethylated alkylphenols, polyethoxylated fatty alcohols or fatty amines, alkanesulfonates or alkylbenzenesulfonates, ligninsulfonic acid sodium, 2,2'-dinaphthylmethane-6,6'-disulfonic acid sodium, dibutylnaphthalenesulfonic acid sodium or also oleoylmethyltauric acid sodium. To produce the wettable powders, components a) and b) are finely ground, for example in conventional apparatus such as hammer mills, blower mills and air jet mills, and mixed at the same time or subsequently with the formulation auxiliaries.

Dusts are obtained by grinding components a) and c) with finely divided solid substances such as fillers b).

Granules can be, for example, granules for spreading and soil application, granules (GR) in the form of micro, spray, elevator and adsorption granules or water-dispersible granules (WG). They can be produced, for example, by spraying the active ingredient onto adsorbable, granulated inert material or by applying active ingredient concentrates by means of adhesives, for example polyvinyl alcohol, polyacrylic acid sodium or mineral oils, to the surface of carriers such as sand, kaolinite or granulated inert material. Suitable active ingredients can also be granulated in the manner customary for the production of fertilizer granules, if desired in a mixture of fertilizers. For example, the agrochemical active ingredients can be ground, for example, with the surfactants of the formula (I) and the fillers b) and, if appropriate, other auxiliaries, subjected to melt extrusion and then granulated to the desired particle size. Water-dispersible granules are generally prepared using the usual methods such as spray drying, fluidized bed Granulation, plate granulation, mixing with high-speed mixers and extrusion made without solid inert material. For the production of plate, fluidized bed, extruder and spray granules, see, for example, the process in "Spray-Drying Handbook" 3rd ed. 1979, G. Goodwin Ltd., London; JE Browning, "Agglomeration", Chemical and Engineering 1967, pages 147 ff. "Perry's Chemical Enigeer's Handbook", 5th Ed., McGraw-Hill, New York 1973, pp. 8-57.

Emulsifiable concentrates are obtained by dissolving the surfactant a) 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 which can be used are: alkylarylsulfonic acid calcium salts such as Ca-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 e.g. Sorbitan fatty acid esters or polyoxethylene sorbitan esters such as e.g. Polyoxyethylene.

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.

For further details on the formulation of crop protection agents, see, for example, GC Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961, pages 81-96 and JD Freyer, SA 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. happen by application to the harmful organisms or the places where they occur, e.g. B. by spraying. The agrochemical active ingredients c) to be used according to the invention are generally applied together with the surfactants a) and fillers b) or in succession, preferably in the form of a spray mixture which comprises the surfactants a), the fillers b) and the agrochemical active ingredients c) Contains amounts and, where appropriate, other conventional auxiliaries. The spray liquor is preferably based on water and / or an oil, e.g. a vegetable oil or a high-boiling hydrocarbon such as kerosene or paraffin. The agrochemical compositions according to the invention can e.g. can be implemented as a tank mix 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.

The spray liquor is preferably produced on the basis of water. The weight ratio of surfactant (I): agrochemical active ingredient can vary within wide ranges. As a rule, it is in the range from 5000: 1 to 1: 1000, preferably 2000: 1 to 1:50, particularly preferably 1000: 1 to 1: 2. The application rates of the surfactant of the formula (I) are generally between 10 and 5000 g / ha, preferably between 50 and 2000 g / ha. In individual cases, however, the specified limits can also be exceeded or fallen short of.

The concentration of the surfactants of the formula (I) in the spray mixture is generally between 0.001 and 4% by weight, preferably 0.01 and 2% by weight. The concentration of fillers is generally between 0.001 and 4% by weight, preferably 0.01 and 2% by weight.

In principle, the preparation processes mentioned for the adjuvants according to the invention also allow the incorporation of agrochemical active substances, so that agrochemical agents, e.g. are available in the form of granules, powders or dusts which, in addition to the adjuvant according to the invention, also contain one or more agrochemical active ingredients.

The agrochemical active ingredients which can be formulated together with the surfactants of the formula (I) are preferably compounds with a Melting point greater than 80 ° C. In individual cases, the melting point of the agrochemical active ingredients can also be below 80 ° C.

The weight ratio between the surfactants of the formula (I) and the agrochemical active ingredients generally fluctuates between 5000: 1 - 1: 1000, and in individual cases can exceed or fall short of or exceed the stated limits. In a very particularly preferred embodiment, the weight ratio is in the range from 10: 1 to 1: 2, in particular 5: 1 to 1: 1.5. These described solid products such as granules, powders or dusts containing adjuvants according to the invention and agrochemical active substances are also the subject of the present invention.

The agrochemical compositions according to the invention are preferably herbicidal compositions which 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 captured by the active ingredients. The funds can e.g. are applied in the pre-sowing, pre-emergence or post-emergence process. Some representatives of the monocotyledonous and dicotyledonous weed flora can be mentioned in detail, which can be controlled by the compounds according to the invention without the name being intended to restrict them to certain species.

On the side of the monocotyledon weed species, for example, Apera spica venti, Avena spp., Alopecurus spp., Brachiaria spp., Digitaria spp., Lolium spp., Echinochloa spp., Panicum spp., Phalaris spp., Poa spp., Setaria spp , 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. In the case of dicotyledonous 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 parts of the plant 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 completely after a certain time, so that one for harmful crop competition 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. By the invention Combination of active ingredients enables a significant reduction in the amount of active ingredients 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, some of the agents according to the invention have excellent growth-regulating properties in the 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, for example 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 crop losses during storage.

Because of their herbicidal and plant growth regulatory properties, the agents according to the invention for controlling harmful plants can be used in genetically modified crops or crop plants obtained by mutation selection. These crop plants are generally distinguished by special advantageous properties, such as resistance to herbicidal compositions or resistance to plant diseases or pathogens causing 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. For example, Transgenic plants with increased starch content or changed starch quality or those 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 crop 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. applied the acreage.

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 combating undesirable plant growth, for example in plantation crops, on roadsides, squares, industrial plants or railway plants. 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, and 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 separately 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 filler b ) applied, e.g. in the pre-emergence, post-emergence or in the pre-and post-emergence, preferably in the 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 at rates of from 0.1 to 2,000 g of active substance / ha, preferably from 0.5 to 1,000 g of active substance / ha. Also particularly preferred is the application of the active ingredients in the form of a co-formulation or in the form of tank mixtures, the individual components, e.g. in the form of formulations, mixed together in the tank with water and the spray mixture obtained is 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, can these are considered 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) pyrazole-3-carboxylic acid ethyl ester (compound S1-4), 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-isoxazoine-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), (5-chloro-8-quinolinoxy) -acetic acid-2-oxo-prop-1-ethyl ester (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 known as safeners, for example for rice, such as fenclorim (= 4,6-dichloro-2-phenylpyrimidine, Pesticide Manual, 11th edition, 1997, pp. 511-512), dimepiperate (= piperidine-1-thiocarboxylic acid) -S-1-methyl-1-phenylethyl ester, Pesticide Manual, 11th edition, 1997, pp. 404-405), Daimuron (= 1 - (1-methyl-1-phenylethyl) -3-p-tolyl-urstoff, Pesticide 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-methoxybenzophenone, 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 combinations which can be used in low doses without a safener little broad impact led to inadequate 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 includes both the treatment of the acreage before sowing and the treatment of the sown but not yet overgrown acreage. 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 1 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 fillers b) 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.

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.

In a preferred embodiment, for example, various herbicidal active compounds of the formula (III) and / or their salts can be combined with one another, for example 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 have high physical stability and a high surfactant load and are also ecologically advantageous. They are also suitable for the production of agrochemicals that have a high biological effectiveness, a high active ingredient load and an excellent tank mix quality.

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

Examples

Preparation of the adjuvants

example 1

A mixture of 50 g Sapogenat ^® T500, 20 g Sipernat ^® 50S, 10 g Atlox ^® Metasperse 150S, 5 g Morwet ^® EFW, 10 g ammonium sulfate, 5 g effervescent powder (citric acid / sodium hydrogen carbonate) is mixed in a kneader (LUK 025TV from Werner and Pfleiderer) mixed thoroughly at temperatures of 80-100 ° C (duration: 40 min.). The mixture is then transferred to a benchtop pelletizer (Benchtop KAR-75) and to extrusion granules transferred. The dispersibility as well as the suspendability of the samples thus obtained indicated very good quality according to CIPAC measurement methods, even after the samples had been stored after 2 weeks at 54 ° C.

The adjuvants listed in Table 1 below (Examples 2-5) were obtained in an analogous manner in the form of granules (data in% by weight):

Table 1 :

Adjuvant 2 3 4 5

Sapogenat ^® T500 52.91 52.91 50.76 41, 69

Sipernat ^® 50S 17.99 17.99 21, 32 17.20

Tamol ^® PP 5.29 - - ~

Genapol ^® LRO (paste, 69%) 7.94 7.94 7.61 8.60

Kaolin 1777 15.87 - - -

Atlox ^® Metasperse 150S - 5.29 5.08 -

Steamic ^® OOS - 15.87 - -

Morwet ^® EFW - - - 5.06

Ammonium sulfate - - 15.23 27.40

Fluowet ^® PP __ - __ 0.05

Example 6

31 g lumpy Sapogenat ^® T500 were ground on an IKA laboratory mill to a grain size of approx. 200μ, and in a kitchen mixer with 21.05 g glufosinate ammonium, 16.75 g Sipernat ^® 350 (highly disperse silica), 3.04 g Atlox ^® Metasperse 150S, 5.10g Genapol ^® LRO (paste, 69%), 0.06g Fluowet ^® PP, 20g ammonium sulfate and 3g Agrimer ^® XLF intimately mixed.

This premix was metered by means of a vibrating trough into a melt extrusion apparatus from Thermo-Prism (type twin-screw extruder Eurolab 16mm) and through a multi-hole nozzle with 0.7mm holes extruded. The operating temperature was 25 ° C in the feed area, 65 ° C in the entire mixing and kneading zone, and 60 ° C directly in front of the nozzle. The extrudate solidified within a few seconds after leaving the extruder and was broken into pieces approximately 3 mm long. The dispersibility of the extrudate was measured under conditions according to CIPAC MT174 and was 70% by weight. This method is described in: CIPAC Handbook, Collaborative International Pesticides Analytical Council Ltd 1995: Physico-chemical Methods for Technical and Formulated Pesticides, Vol. F, page 435.

Example 7

Example 6 was repeated with the only difference that glyphosate was used as the active ingredient instead of glufosinate ammonium. The dispersibility of the extrudate was 76% by weight.

Example 8

900g Sapogenat ^® T500 was melted in a steam-heated 5L Lödige mixer. 269.6 g of Sipernat ^® 50S were added and the mixture was homogenized until a free-flowing absorbate was present. The heating was then switched off and 618.4 g of diflufenican (premilled to a particle size of 5 μm) were mixed in. Then 130 g of Genapol ^® X-150, 80 g of Atlox Metasperse ^® 150S and 2 g of Fluowet ^® PP were added and homogenized. This mixture was melt extruded as indicated in Example 6. The dispersibility of the extrudate was 69% by weight

Example 9

180.95g piece Sapogenat ^® T500 were ground in an IKA laboratory mill to a grain size of 200μ, and in a kitchen mixer with 187.5g Metamitron and an absorbent of 78.1g Genapol ^® LRO (paste, 69%) on 78.1g Sipernat ^® 50S, 18.35g Atlox ^® Metasperse ^® 150S, 5g Disintex ^® 200 and 0.35g Fluowet ^® PP intimately mixed. This mixture was melt extruded as indicated in Example 6. The dispersibility of the extrudate was 71% by weight.

Explanation:

Sapogenat ^® T500 2,4,6-tri-sec-butylphenyl polyethoxylate (Clariant) Sipernat ^® 50S, 350 highly dispersed precipitated silica (Degussa) Tamol ^® PP phenolsulfonic acid-formaldehyde polycondensate Na salt (BASF)

Genapol ^® LRO (paste, 69%) lauryl ethoxyl ether sulfate (Clariant) Genapol ^® X-150 isotridecyl alcohol ethoxylate (Clariant) Kaolin ^® 1777 clay (Ziegler, Wunsiedel) Atlox Metasperse ^® 150S styrene-acrylic acid copolymer (Uniquema) Steamic ^® OOS aluminum hydrosilicate (Tale de Luzenac) Morwet ^® EFW alkylnaphthalenesulfonic acid derivative (Akzo Nobel) Fluowet ^® PP perfluoroalkylphosphonic acid (Clariant) Agrimer ^® XLF cross-linked polyvinylpyrolidone (ISP) Disintex ^® 200 cross-linked polyvinylpyrolidone (ISP)

Claims

claims:

1. Solid adjuvant containing

a) one or more surfactants of the formula (I), Ar-O- (CHR ¹ -CHR ² -0-) _y -R ³ (I) in which

Ar is aryl which is substituted by two or more (-CC ₃₀ ) alkyl radicals, R ¹ H or (dC ₆ ) alkyl, R ² H or (dC ₆ ) alkyl, R ³ H, an unsubstituted or substituted ( Cι-C ₃ o)

Hydrocarbon residue, a sulfonate residue, a phosphonate residue or a

Is acyl and y is an integer from 1 to 100, and

b) one or more fillers.

2. A solid adjuvant according to claim 1, wherein in formula (I) y is an integer from 15 to 100.

3. A solid adjuvant according to claim 1 or 2, wherein

Ar is a naphthyl or phenyl radical which bears 3 to 7 (-CC ₂ o) alkyl radicals, is RH or methyl,

R ^{2 is} H or methyl,

R ^{3 is} H, (-CC ₃₀ ) alkyl, (C ₂ -C ₃₀ ) alkenyl, (C ₂ -C ₃₀ ) alkynyl, a sulfate residue, a phosphate residue or an acyl residue, and y is an integer from 15 to 100 ,

4. Solid adjuvant according to one or more of claims 1-3, wherein the filler b) is an inorganic or organic carrier.

5. Solid adjuvant according to one or more of claims 1-4, additionally containing one or more auxiliaries customary in crop protection.

6. A method of making a solid adjuvant according to one or more of claims 1-5, wherein the components are mixed together.

7. Use of a solid adjuvant according to one or more of claims 1-5, for the preparation of an agrochemical agent.

8. Containing agrochemical

α) one or more solid adjuvants according to one or more of the

Claims 1-5, and ß) one or more agrochemical active substances.

9. The agrochemical composition according to claim 8, wherein the agrochemical active ingredient is a herbicide.

10. Agrochemical composition according to claim 8 or 9, wherein the agrochemical active ingredients are selected from the group diflufenican, fenoxaprop-P-ethyl, metamitron, ethofumesate, phenmedipham, desmedipham or the phosphorus-containing herbicides.

11. Agrochemical composition according to one or more of claims 8-10, additionally containing one or more further components from the group of agrochemical active substances and the auxiliaries customary in crop protection.

12. A method for controlling harmful organisms, wherein the components of the agrochemical agent, defined according to one or more of the claims 8 - 11, to which harmful organisms or the places where they occur are applied together or separately.

13. A method for controlling harmful plants, wherein the components of the herbicidal composition, defined according to one or more of claims 9 to 11, are applied together or separately to the plants, parts of plants, plant seeds or the area on which the plants grow.

14. The method according to claim 13 for the selective control of harmful plants in plant crops.

15. Use of the agrochemical composition defined according to one or more of claims 8 to 11 for controlling harmful organisms.

16. Use of the herbicidal composition defined for one or more of claims 9 to 11 for combating harmful plants.

17. A method for producing an agrochemical agent, defined according to one or more of claims 8 to 11, wherein the components are mixed together.