EP1667519A1

EP1667519A1 - Surfactant/solvent mixtures

Info

Publication number: EP1667519A1
Application number: EP04764713A
Authority: EP
Inventors: Gerhard Frisch; Gerhard Schnabel; Andreas Röchling
Original assignee: Bayer CropScience AG
Current assignee: Bayer CropScience AG
Priority date: 2003-09-19
Filing date: 2004-09-02
Publication date: 2006-06-14
Also published as: ZA200602099B; DE10343390A1; CA2539497A1; AR045668A1; IL174239A0; WO2005036962A1; KR20060092217A; CN1863456A; ECSP066430A; MXPA06003059A; EA200600559A1; AU2004281507A1; JP2007505844A; AP2006003587A0; BRPI0414524A; US20050064004A1

Abstract

The invention relates to surfactant/solvent mixtures, containing a) one or several solvents of formula R-CO-NR<1>R<2>, wherein R = H, methyl, ethyl or propyl, wherein <) if R = H or methyl, R<l> and R<2> are the same or different tertiary butyl, (C5-C12)alkyl or (C1-C12)hydroxyalkyl, and ?) if R = ethyl or propyl, R<l> and R<2> are the same or different (C1-C12)alkyl or (C1-C12)hydroxyalkyl, and b) one or several surfactants. The inventive surfactant /solvent mixture is suitable for the production of active ingredient formulations.

Description

description

Surfactant / solvent mixtures

The present invention relates to combinations of surfactants and solvents (surfactant / solvent mixtures). The surfactant / solvent mixtures can be used to produce formulations of one or more active ingredients, in particular agrochemical active ingredients.

Solvents are known which can also be used in the field of crop protection products, for example aromatic solvents such as the Solvesso ^® series from Exxon, or aliphatic solvents such as BP-n-paraffin, ketones such as isophorone, cyclohexanone and acetophenone, or sulfosuccinates such as Triton ^® GR 7 ME from Dow Chem. Also known are crop protection formulations which contain dimethylformamide, dimethylacetamide or N-methylpyrrolidone (US 6420361, JP 2001 302422 A, WO 9951099).

The object of the present invention was a

To provide surfactant / solvent mixture which is suitable for the preparation of stable active ingredient formulations.

Surprisingly, it was found that this object can be achieved by surfactant / solvent mixtures with special carboxamides.

The present invention thus relates to a surfactant / solvent mixture containing

a) one or more solvents of the formula (I): R-CO-NR ¹ R ² (I)

.worin R = H, methyl, ethyl or propyl, where α) when R = H or methyl, R ¹ and R ^{2 are} identical or different tert.-butyl, (C ₅ - Cι ₂ ) alkyl or (Cι-Cι ₂ ) are hydroxyalkyl, preferably tert-butyl, C ₅ - or C ₆ -alkyl, and ß) when R = ethyl or propyl, R ¹ and R ^{2 are the} same or different (d-Cι ₂ ) alkyl or (Cι-C ₁₂ ) hydroxyalkyl, preferably (Cι-C ₆ ) alkyl, and b) one or more surfactants.

5 The alkyl radicals and hydroxyalkyl radicals R, R ¹ and R ² in formula (I) can be straight-chain or branched. Examples of alkyl radicals R are methyl, ethyl and propyl such as n-propyl or iso-propyl. Examples of alkyl radicals R ¹ and R ² are methyl, ethyl, propyl such as n-propyl or isopropyl, butyl such as n-butyl, or branched butyl such as sec-0 butyl, isobutyl or tert-butyl, pentyl such as n Pentyl or branched pentyl such as isopentyl or neopentyl, hexyl such as n-hexyl or branched hexyl, heptyl such as n-heptyl or branched heptyl, octyl such as n-octyl or branched octyl, nonyl such as n-nonyl or branched nonyl, decyl such as n Decyl or branched decyl, undecyl such as n-undecyl or branched undecyl, dodecyl such as n-dodecyl or branched 5 dodecyl. In a preferred embodiment, alkyl radicals R ¹ and R ^{2 are the} same.

Solvents a) contained in the surfactant / solvent mixtures according to the invention are e.g. N, N-di-tert-butylformamide, N, N-dipentylformamide, N, N- dihexylformamide, N, N-diheptylformamide, N, N-dioctylformamide, N, N-

.0 dinonylformamide, N, N-didecylformamide, N, N-diundecylformamide, N, N-didodecylformamide, N, N-di-hydroxymethylformamide, N, N-di-tert-butylacetamide, N, N-dipentylacetamide, NN-dihexylacetamide , N, N-diheptylacetamide, N, N- dioctylacetamide, N, N-dinonylacetamide, N, N-didecylacetamide, N, N-diundecylacetamide, N, N-didodecylacetamide, N, N-di-hydroxymethylacetamide, N, N-

! 5 dimethylpropionic acid amide, N, N-diethylpropionic acid amide, N, N-dipropylpropionic acid amide such as N, N-di-n-propylpropionic acid amide or N, N-diisopropylpropionic acid amide, N, N-dibutylpropionic acid amide such as N, N-di-n-butylpropionic acid amide Di-sec.-butylpropionic acid amide, N, N-diisobutylpropionic acid amide or N, N-di-tert.-butylpropionic acid amide, N, N-

: 0 dipentylpropionic acid amide, N, N-dihexylpropionic acid amide, N, N-diheptylpropionic acid amide, N, N-dioctylpropionic acid amide, N, N-dinonylpropionic acid amide, N, N-didecylpropionic acid amide, N, N- Diundecylpropionic acid amide, N, N-didodecylpropionic acid amide, N, N-dimethyl-n-butyric acid amide, N, N-diethyl-n-butyric acid amide, N, N-dipropyl-n-butyric acid amide such as NN-di-n-propyl-n-butyric acid amide or N, N-diisopropyl-n-butyric acid amide, N, N-dibutyl-n-butyric acid amide such as N, N-di-n-butyl-n-butyric acid amide, N, N-di-sec.butyl-n-butyric acid amide, N, N-diisobutyl-n-butyric acid amide, NN-di-tert.butyl-n-butyric acid amide, N, N-dipentyl-n-butyric acid amide, N, N-dihexyl-n-butyric acid amide, N, N-diheptyl-n-butyric acid amide, N, N-dioctyl-n-butyric acid amide, N, N-dinonyl-n-butyric acid amide, N, N-didecyl-n-butyric acid amide, N, N-diundecyl-n-butyric acid amide, N, N-didodecyl-n-butyric acid amide, N, N-dipentylisobutyric acid amide, N, N-dihexylisobutyric acid amide, N, N-diheptylisobutyric acid amide, N, N-dioctylisobutyric acid amide, N, N-dinonylisobutyric acid amide, N, N-didecylisobutyric acid amide, N, N-diidobutameamide, N, N-di-di-amide, N-pentylhexylformamide, N, N-pentylhexylacetamide, N, N -Pentylhexylpropionic acid amide, N, N-pentylhexyl-n-butyric acid amide, N, N-pentylhexylisobutyric acid amide, N, N-methylethylpropionic acid amide, N, N-methyl-n-propylpropionic acid amide, N, N-methylisopropylpropionic acid amide, N, N-methylpropionic acid n, N, N-methyl propionic acid , NN-methylethyl-n-butyric acid amide, N, N-methyl-n-butyric acid amide, N, N-methylisopropyl-n-butyric acid amide, N, N-methyl-n-butyl-n-butyric acid amide, N, N-methylethylisobutyric acid amide, N , N-methyl-n-propylisobutyric acid amide, N, N-methylisopropylisobutyric acid amide, N, N, -Methyl-n-butylisobutyric acid amide.

Preferred solvents of the formula (I) are those in which R = ethyl or propyl, such as n-propyl or isopropyl, and R ¹ and R ^{2 are} identical or different, preferably identical, (are C 1 -C 6 -alkyl, for example methyl, ethyl, propyl such as n-propyl or iso-propyl, butyl such as n-butyl, or branched butyl such as sec-butyl, iso-butyl or tert-butyl, pentyl such as n-pentyl or branched pentyl such as isopentyl or neopentyl, hexyl such as n-hexyl or branched hexyl.

Surfactants b) contained in the surfactant / solvent mixtures according to the invention are, for example, surfactants on a non-aromatic basis, for example on a heterocycle, olefin, aliphate or cycloaliphate basis, for example surface-active with or several aikyl groups substituted and subsequently derivatized, for example alkoxylated, sulfated, sulfonated or phosphated pyridine, pyrimidine, triazine, pyrol, pyrolidine, furan, thiophene, benzoxazole, benzothiazole and triazole compounds, and / or surfactants on aromatic Basis, for example substituted with one or more aikyl groups and subsequently derivatized, for example alkoxylated, sulfated, sulfonated or phosphated benzenes or phenols. The surfactants b) are generally soluble in the solvent phase and are suitable for emulsifying them - together with active ingredients dissolved therein - when diluted with water (for spray liquor). The surfactant / solvent mixtures according to the invention can contain, for example, non-aromatic or aromatic surfactants or mixtures of non-aromatic and aromatic surfactants.

Examples of surfactants b) are listed below, in which EO = ethylene oxide units, PO = propylene oxide units and BO = butylene oxide units: b1) C ₁ -C ₂ -alcohols which can be alkoxylated, for example with 1-60 alkylene oxide units, preferably 1-60 EO and / or 1-30 PO and / or 1-15 BO in any order. The terminal hydroxyl groups of these compounds can be closed by an alkyl, cycloalkyl or acyl radical with 1-24 carbon atom end groups. Examples of such compounds are: GenapofC-.L-.OJ-.UD-.UDD-.X products from Clariant, Plurafäc ^® - and Lutensol ^® A, AT, ON, TO products from BASF, Marlipal ^® 24 and 013 products from Condea, Dehypon ^® products from Henkel, Ethylan ^® products from Akzo Nobel such as Ethylan CD 120. b2) Anionic derivatives of the products described under b1) in the form of ether carboxylates, sulfonates, sulfates and phosphates and their inorganic (e.g. alkali and alkaline earth) and organic salts (e.g. based on amine or alkanolamine) such as Genapol ^® LRO, Sandopan ^® products, Hostaphat / Hordaphos ^® products from Clariant. Copolymers consisting of EO, PO and / or BO units such as block copolymers such as the Pluronic ^® products from BASF and Synperonic ^® products from Uniquema with a molecular weight of 400 to 10 ⁸ . Alkylene oxide adducts of Ci - C ₉ alcohols such as Atlox ^® 5000 from Uniquema or Hoe ^® -S3510 from Clariant. b3) Fatty acid and triglyceride alkoxylates such as the Serdox ^® NOG products from Condea or alkoxylated vegetable oils 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, especially under rapeseed oil, among which the vegetable oils also include their transesterification products are understood, for example, alkyl esters such as Rapsölmethylester or rapeseed, for example, Emulsogen ^® products from Clariant, salts of aliphatic, cycloaliphatic and olefinic carboxylic acids and polycarboxylic acids, and alpha sulfo fatty acid as available from Henkel. b4) Fatty acid amide alkoxylates such as the Comperlan ^® products from Henkel or the Amam ^® products from Rhodia. Alkylene oxide adducts of alkynediols such as the Surfynol ^® products from Air Products. Sugar derivatives such as amino and amido sugar from Clariant.Glucitole from Clariant, alkylpolyglycosides in the form of APG ^® products from Henkel or such as sorbitan esters in the form of Span ^® or Tween ^® products from Uniquema or cyclodextrin esters or ethers from Wacker. b5) Surface-active cellulose and algin, pectin and guar derivatives such as the Tylose ^® products from Clariant, the Manutex ^® products from Kelco and guar derivatives from Cesalpina. Polyol-based alkylene oxide adducts such as Polyglykol ^® products from Clariant. Surface-active polyglycerides and their derivatives from Clariant. b6) Sulfosuccinates, alkanesulfonates, paraffin and olefin sulfonates such as Netzer IS ^® , Hoe ^® S1728, Hostapur ^® OS, Hostapur ^® SAS from Clariant, Triton ^® GR7ME and GR5 from Union Carbide, Empimin ^® products from Albright and Wilson, Marlon ^® - PS65 from Condea. b7) Sulfosuccinamates such as the Aerosol ^® products from Cytec or the Empimin ^® products from Albright and Wilson. b8) alkylene oxide adducts of fatty amines, quaternary ammonium compounds with 8 to 22 carbon atoms (C ₈ -C ₂₂₎ such as Genamin ^® C, L, 0, T products from Clariant. b9) Surface-active, zwitterionic compounds such as taurides, betaines and sulfobetaines in the form of Tegotain ^® products from Goldschmidt, Hostapon ^® T and Arkopon ^® T products from Clariant. b10) Surface-active compounds based on silicone or silane, such as the Tegopren ^® products from Goldschmidt and the SE ^® products from Wacker, and the Bevaloid ^® -. Rhodorsil ^® - and Silcolapse ^® products from Rhodia (Dow Corning, Reliance, GE, Bayer). b11) Per- or polyfluorinated surface-active compounds such as Fluowet ^® products from Clariant, the Bayowet ^® products from Bayer, the Zonyl ^® products from DuPont and products of this type from Daikin and Asahi Glass. b12) surface-active sulfonamides, for example from Bayer. b13) Surface-active polyacrylic and polymethacrylic derivatives such as the Sokalan ^® products from BASF. b14) Surface-active polyamides such as modified gelatin or derivatized polyaspartic acid from Bayer and their derivatives. b15) Surfactant polyvinyl compounds such as modified polyvinyl pyrollidone such as the Luviskol ^® products from BASF and the Agrimer ^® products from ISP or the derivatized polyvinyl acetates such as the Mowilith ^® products from Clariant or the butyrates such as the Lutonal ^® products from BASF Vinnapas ^® - and the Pioloform ^® products from Wacker or modified polyvinyl alcohols such as the Mowiol ^® products from Clariant. b16) Surface-active polymers based on maleic anhydride and / or reaction products of maleic anhydride, and maleic anhydride and / or reaction products of maleic anhydride-containing copolymers such as the Agrimer® VEMA ^® products from ISP. b17) Surface-active derivatives of montan, polyethylene and polypropylene waxes such as the Hoechst ^® waxes or the Licowet ^® products from Clariant. b18) Surface-active phosphonates and phosphinates such as Fluowet ^® PL from Clariant. b19) Poly- or perhalogenated surfactants such as Emulsogen ^® 1557 from Clariant. b20) phenols, which can be alkoxylated, for example phenyl (CrC ₄ ) alkyl ether or (poly) alkoxylated phenols [= phenol (poly) alkylene glycol ether], for example with 1 to 50 alkyleneoxy units in the (poly) alkyleneoxy part, where the alkylene part preferably each has 1 to 4 carbon atoms, preferably phenol reacted with 3 to 10 mol of alkylene oxide, (poly) alkylphenols or (poly) alkylphenol alkoxylates [= polyalkylphenol (poly) alkylene glycol ether], for example with 1 to 12 carbon atoms per Alkyl radical and 1 to 150 alkyleneoxy units in the polyalkyleneoxy part, preferably tri-n-butylphenol or triisobutylphenol reacted with 1 to 50 mol of ethylene oxide, polyarylphenols or polyarylphenol alkoxylates [= polyarylphenol (poly) alkylene glycol ether], for example tristyrylphenol polyalkylene glycoloxy units with 1 to 150 alkylene Polyalkyleneoxy part, preferably tristyrylphenol reacted with 1 to 50 mol of ethylene oxide. b21) Compounds which formally represent the reaction products of the molecules described under b20) with sulfuric acid or phosphoric acid and their salts neutralized with suitable bases, for example the acidic phosphoric acid ester of triple ethoxylated phenol, the acidic phosphoric acid ester of a nonylphenol reacted with 9 mol of ethylene oxide and that with triethanolamine neutralized phosphoric acid esters of the reaction product of 20 mol ethylene oxide and 1 mol tristyrylphenol. b22) benzenesulfonates such as alkyl or arylbenzenesulfonates, for example acidic (poly) alkyl and (poly) arylbenzenesulfonates neutralized with suitable bases, for example having 1 to 12 carbon atoms per alkyl radical or having up to 3 styrene units in the polyaryl radical, preferably (Linear) dodecylbenzenesulfonic acid and its oil-soluble salts such as the calcium salt or the isopropylammonium salt of dodecylbenzenesulfonic acid. In the alkyleneoxy units, ethyleneoxy, propyleneoxy and butyleneoxy units, in particular ethyleneoxy units, are preferred.

Examples of surfactants from the group of non-aromatic surfactants are the surfactants from the groups b1) to b19) mentioned above, preferably from the groups b1), b2), b6) and b8).

Examples of surfactants from the group of aromatic-based surfactants are the surfactants of the abovementioned groups b20) -B22), preferably with 4 to 10 moles of ethylene oxide, unreacted phenol, commercially available for example in the form of AgrisoI ^® products (Akcros), with 4 to 50 moles of ethylene oxide triisobutylphenol reacted, commercially available for example in the form of the Sapogenat ^® T-products (Clariant), tristyrylphenol reacted with 4 to 50 mol of ethylene oxide, commercially available for example in the form of the Arkopal ^® products (Clariant), with 4 to 150 mol of ethylene oxide reacted tristyrylphenol, such as ^® from the Soprophor series as Soprophor ^® FL, Soprophor ^® 3D33, Soprophor ^® BSU, Soprophor ^® 4D-384, Soprophor ^® CY / 8 (Rhodia), and acid (linear) dodecylbenzenesulfonate, available commercially, for example in the form of the Marlon ^® products (Hüls) available.

Preferred surfactants (b) are, for example, alkoxylated C 10 -C ₂₄ alcohols (b1) and their anionic derivatives (b2) such as sulfates, sulfonates and phosphates, alkoxylated vegetable oils (b3), alkoxylated phenols (b20) and their reaction products with sulfuric acid or Phosphoric acid (b21) and alkylbenzenesulfonates (b22).

The weight ratio of solvent a) to surfactant b) is generally in the range from 10,000: 1 to 1:99, preferably from 1000: 1 to 10:90, particularly preferably the solvent a) is in excess compared to the surfactant b), for example in a weight ratio of 100: 1 to 2: 1. The surfactant / solvent mixtures according to the invention are suitable, for example, for the preparation of active ingredient formulations such as emulsions and suspensions and their concentrates or granules such as water-emulsifiable granules, in particular of liquid active ingredient formulations such as oil suspensions, oil suspension concentrates, suspoemulsions, suspoemulsion concentrates, emulsions, for example on W / O- or O / W base, emulsion concentrates, microemulsions, microemulsion concentrates, and (aqueous) spray liquors obtainable therefrom.

The invention thus also relates to active substance formulations, in particular agrochemical active substance formulations, such as liquid agrochemical, e.g. Herbicidal, insecticidal or fungicidal active ingredient formulations comprising (1) one or more active ingredients, in particular agrochemical, e.g. herbicidal, insecticidal or fungicidal active ingredients, (2) the surfactant / solvent mixture according to the invention,

(3) optionally further organic solvents and

(4) if appropriate, customary auxiliaries and additives, such as thickeners and thixotropic agents, wetting agents, anti-drift agents, adhesives, penetrants, preservatives and antifreeze agents, antioxidants, fillers, carriers, dyes, fragrances, defoamers, fertilizers, evaporation inhibitors, and agents influencing the pH and viscosity, and

(5) optionally water.

The surfactant / solvent mixtures according to the invention can be used to prepare stable active ingredient formulations, in particular active ingredients which are poorly soluble in water, e.g. those with a solubility of less than 5 g of active ingredient / l of water. These agents can e.g. Dyes, agrochemical active substances, adhesives, explosives, pharmaceutical or veterinary active substances, cleaners, fragrances or proteins, agrochemical active substances are preferred.

Examples of agrochemical active substances (1) are herbicides, insecticides, fungicides (preferably those which are not azole compounds), safeners and Growth regulators into consideration. Herbicides are preferred, for example leaf-active herbicides such as ALS inhibitors (for example sulfonamides such as flucarbazones, propoxycarbazones or amicarbazones or sulfonylureas such as mesosulfuron, iodosulfuron, amidosulfuron, foramsulfuron), diflufenican, bromoxynil-containing or loxynyloxy-containing products of the p-ethyl, sugar beet herbicides such as desmedipham, phenmedipham, ethofumesate or metamitron, or also active ingredients from the class of the HPPD inhibitors (for example isoxaflutole, sulcotrione, mesotrione).

If the active ingredients contain one or more asymmetric carbon atoms or double bonds, which are not specified separately, all isomers are included. The possible stereoisomers defined by their specific spatial form, such as enantiomers, diastereoisomers, Z and E isomers, are all included and can be obtained from mixtures of the stereoisomers by customary methods or can also be prepared by stereoselective reactions in combination with the use of stereochemically pure starting materials. The stereoisomers mentioned in pure form and also their mixtures can thus be used according to the invention.

In the context of the present invention, the active ingredients contained as a component in the active ingredient formulations according to the invention always include not only the neutral compounds but also their salts with inorganic and / or organic counterions. For example, sulfonylureas can form salts, for example, 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, especially alkali metal salts or alkaline earth metal salts, especially 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 S0 ₄ or HN0 ₃ . 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 (N) -Aryl-N-alkylcarbamoyΙmethyl) - 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 the sulfonylureas.

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 (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 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-Ethoxycarbonylphenylsulfonyl) -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 5 (triasulfuron), 1- (2-methoxycarbonylphenylsulfonyl) -3- (4,6-dimethylpyrimidin-2- yl) urea (sulfometuron-methyl), 1- (2-methoxycarbonylphenylsulfonyl) -3- (4-methoxy-6-methyl-1, 3,5-triazin-2-yl) -3-methylurea (tribenuron-methyl), 0 1 - (2-Methoxycarbonylbenzylsulfonyl) -3- (4,6-dimethoxypyrimidin-2-yl) urea (bensulfuron-methyl), 1- (2-methoxycarbonylphenylsulfonyl) -3- (4,6-bis- (difluoromethoxy) pyrimidine -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- 5 [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-iodo-p henylsulfonyl) urea (iodosulfuron-methyl and its salts such as the sodium salt, WO 0 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-methanesulfon-amido-5 methyl-benzoate (mesosulfuron-methyl and its salts such as the sodium salt, WO 95/10507), N, N-dimethyl-2- [3- (4,6-dimethoxypyrimidine-2 -yl) ureidosulfonyl] -4-formylamino-benzamide (foramsulfuron and its salts such as the sodium salt, WO 95/01344); A2) thienylsulfonylureas, for example d 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), and trifloxysulfuron and its sodium salt;

A6) Alkoxyphenoxysulfonylureas, e.g. are described in EP-A 0 342 569, preferably 3- (4,6-dimethoxypyrimidin-2-yl) -1- (2-ethoxyphenoxy) sulfonylurea (ethoxysulfuron) or its 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 following Compounds listed and their salts: amidosulfuron, azimsulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorosulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, flupyrsulfuron-methyl-sodium, halosulfuron-methyl-halosulfuron-methyl-halosulfuron-methyl-halosulfuron-methyl Oxasulfuron, primisulfuron-methyl, prosulfuron, pyrazosulfuron-ethyl, rimsulfuron, sulfometuron-methyl, sulfosulfuron, thifensulfuron-methyl, triasulfuron, tribenuron-methyl, triflusulfuron-methyl, trifloxysulfuron and its sodium salt (92) and iodide sodium salt (92) ), 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 e.g. known 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, for example 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-triazoIo [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-triazoIo [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 agents contained in the herbicidal compositions according to the invention which are different from ALS inhibitors are, for example, herbicides from the group of the carbamates, thiocarbamates, haloacetanilides, substituted phenoxy, naphthoxy and phenoxyphenoxycarboxylic acid derivatives and also heteroaryloxyphenoxyalkane carboxylic acid derivatives, such as quinolyloxy. , Quinoxalyloxy, pyridyloxy, benzoxazolyloxy and benzothiazolyloxyphenoxyalkane carboxylic acid esters, cyclohexanedione derivatives, and S- (N-aryl-N-alkylcarbamoylmethyl) dithiophosphoric acid esters. Phenoxycarboxylic acid, phenoxyphenoxy and heteroaryloxyphenoxycarboxylic acid esters and salts and herbicides such as bentazone, cyanazine, atrazine, dicamba or hydroxybenzonitriles such as bromoxynil and loxynil and their esters 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),

Methyl 2- (4- (4-bromo-2-chlorophenoxy) phenoxy) propionate (DE-A 26 01 548), methyl 2- (4- (4-bromo-2-fluorophenoxy) phenoxy) propionate (US-A 4,808,750),

Methyl 2- (4- (2-chloro-4-trifluoromethylphenoxy) phenoxy) propionate (DE-A

24 33 067),

2- (4- (2-Fluoro-4-trifluoromethylphenoxy) phenoxy) propionic acid methyl ester (US-A

4,808,750), 2- (4- (2,4-dichlorobenzyl) phenoxy) propionic acid methyl ester (DE-A 24 17487),

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. 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" heteroarγloxyphenoxy-alkane carboxylic acid derivatives, for example 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);

E4) Phenoxycarboxylic acid derivatives such as

2,4-D, 2,4-DP, 2,4-DB, CMPP and MCPA and their esters and salts;

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) cyclohex-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-dimethylcyclohexane-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-Aryl-N-alkyl-carbamoylmethyl) dithiophosphonic acid esters such as S- [N- (4-chlorophenyl) -N-isopropyl-carbamoylmethyl] -0,0-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-8/15537, 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 (I)

H wherein R> x ^λ (-CC ₄ ) alkyl or (dC ₄ ) haloalkyl;

R ^γ (-C-C ₄ ) alkyl, (C ₃ -C ₆ ) cycloalkyl or (C ₃ -C ₆ ) cycloalkyl (C ₁ -C ₄ ) alkyl and A -CH ₂ -, -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -, -O-, -CH _2- CH ₂ -0-, -CH ₂ -CH ₂ -CH ₂ -0-, particularly preferably those of the formula 11 -17

The herbicides of groups B to K are, for example, from the respective publications mentioned above and from "The Pesticide 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.

Examples of the agrochemical active ingredients contained in the active ingredient formulations according to the invention are:

Acetochlor, aclonifen, alachlor, amidochlor, amidosulfuron, bensulfuron-methyl, bitertanol, bromoxynil octanoate, butachlor, chlormequat chloride, chlorosulfuron, Cinosulfuron, clodinafop-propargyl, cypermethrin, 2,4-D-ester, 2,4-DB-ester, 2,4-DP-ester, CMPP-ester, MCPA-ester, deltamethrin, desmedipham, diciofop-methyl, diflufenican, ethofumesate, Fenxoapropethyl, fipronil, Fluoroglykofen, foramsulfuron, imazapyr, imazosulfuron, iodosulfuron-methyl, imidacloprid, ioxynil octanoate, isoxaflutole, lactofen, mesosulfuron-methyl, metolachlor, metsulfuron-methyl, metamitron, nicosulfuron, oxyfluorfen, pendimethalin, phenmedipham, primisulfuron-methyl, Propaquizafop, pyrazosulfuron-methyl, rimsulfuron, tebuconazole, triflusulfuron-methyl, trifloxystrobin, trifluralin, iodosulfuron, prochloraz, amitraz, oxazinone, oxadiargyl, metamitron, mefenpyr-diethyl, phenmedip and ismed, diemedip, isdiamine, phenmedipham isd, desiphene, phenmedipham, desifen, desp.

Other organic solvents (3) optionally present in the active substance formulations according to the invention are, for example, nonpolar solvents, polar protic or aprotic dipolar solvents and mixtures thereof. Examples of other organic solvents in the context of the invention are aliphatic or aromatic hydrocarbons, such as mineral oils, paraffins or toluene, xylenes and naphthalene derivatives, in particular 1-methylnaphthalene, 2-methylnaphthalene, C ₆ -C ₆ -aromatic mixtures such as the Solvesso ^® series ( ESSO) with the types Solvesso ^® 100 (bp. 162-177 ° C), Solvesso ^® 150 (bp. 187-207 ° C) and Solvesso ^® 200 (bp. 219-282 ° C) and 6-20C-Aliphaten, which can be linear or cyclic, such as the products of the Shellsol ^® series, types T and K or BP-n paraffins, halogenated aliphatic or aromatic hydrocarbons such as methylene chloride or chlorobenzene, mono- and / or polybasic esters such as triacetin ( Acetic acid triglyceride), butyrolactone, propylene carbonate, triethyl citrate and phthalic acid (Cι- C ₂₂ ) alkyl esters, especially phthalic acid (C -C ₈ ) alkyl esters, ethers such as diethyl ether, tetrahydrofuran (THF), dioxane, alkylene glycol monoalkyl ether and dialkyl ether such as propylene glycol monomethyl ether, especially Dowanol ^® PM (propylene glycol monomethyl ether), Propylene glycol monoethyl ether, ethylene glycol monomethyl ether or monoethyl ether, diglyme and tetraglyme, ketones, for example water-miscible ketones such as acetone, or water-immiscible ketones such as cyclohexanone or isophorone, 5-nitriles such as acetonitrile, propionitrile, butyronitrile and sulfonyl oxides and sulfonitrile and sulfonitrile (DMSO) and sulfolane as well as oils of natural origin, for example vegetable oils such as corn oil and rapeseed oil and their transesterification products such as rapeseed oil methyl ester. Preferred other organic solvents for the purposes of the present invention are, in particular, aromatic solvents such as the Solvesso ^® series from Exxon and water-miscible ketones such as acetone.

The conventional auxiliaries and additives (4) optionally present in the active substance formulations according to the invention are known in principle and are described, for example, in standard works: McCutcheon ^'s "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood NJ; Sisley and Wood, "Cyclopedia of Surface Active Agents", Chem. Publ.Co.Inc, NY 1964; Schönfeldt, "interfacial ethylene oxide adducts", Wiss. Verlagsgesellschaft, Stuttgart 1976; .0 Winnacker-Küchler, "Chemische Technologie", Volume 7, C.Hauser-Veriag, Munich, 4th edition 1986.

As usual auxiliaries and additives (4) in the active substance formulations according to the invention e.g. still included: thickeners and thixotropic agents, wetting agents, anti-drift agents, adhesives, penetrants, preservatives and antifreeze agents, antioxidants, fillers, carriers, dyes, fragrances, defoamers, fertilizers, evaporation inhibitors, and the pH Value and viscosity influencing agents.

i0 The active ingredient formulations according to the invention can be prepared by customary, already known processes, for example by mixing the various components with the aid of stirrers, shakers, mills or (static) mixers. In this case, it may be advantageous to briefly heat the mixtures in order to achieve complete dissolution of all the components involved.

The surfactant / solvent mixtures according to the invention make it possible to produce stable formulations with active ingredient loading and active ingredient composition which can be varied within wide limits. For example, the drug loading can e.g. vary between 0.1 and 60, preferably between 1 and 45 percent by weight. One, two or more active ingredients can be included.

With the aid of the surfactant / solvent mixtures according to the invention, active ingredient formulations, preferably liquid active ingredient formulations, in particular agrochemical such as herbicidal, insecticidal or fungicidal active ingredients, can be prepared, characterized by a content of

1) 0.1 to 60% by weight, preferably 15 to 35% by weight, of agrochemical active ingredients,

2) 1 to 99.9% by weight, preferably 10 to 70% by weight of the surfactant / solvent mixture according to the invention, preferably 0.9-99% by weight, preferably 35-99% by weight of the solvent of the Formula (I) are contained, 3) 0 to 80% by weight, preferably 0 to 30% by weight, of further organic solvents,

4) 0 to 20% by weight, preferably 0 to 10% by weight, of conventional auxiliaries and additives such as formulation auxiliaries and

5) 0 to 96% by weight, preferably 0 to 70% by weight, in particular 0 to 10% by weight of water, it being preferred if the solvent of the formula (I) is in excess compared to the optional organic solvent 3 ) is included.

Preferred agrochemical active ingredient formulations are: emulsion concentrates and microemulsion concentrates containing

1) 0.1 to 60% by weight of agrochemical active ingredients,

2) 10 to 99.9% by weight of the surfactant / solvent mixture according to the invention, preferably 0.9 to 99% by weight, preferably 35 to 99% by weight of the solvent of the formula (I) are present,

3) 0 to 35% by weight of further organic solvents and

4) 0 to 10% by weight of conventional auxiliaries and additives, such as formulation auxiliaries, it being preferred if the solvent of the formula (I) is present in excess compared to the optional organic solvent 3).

Emulsions and microemulsions containing 1) 0.1 to 60% by weight of agrochemical active ingredients, 2) 10 to 60% by weight of the surfactant / solvent mixture according to the invention, preferably 0.9-59% by weight, preferably 35-59 % By weight of the solvent of the formula (I) are present,

3) 0 to 35% by weight of further organic solvents,

4) 0 to 10% by weight of conventional auxiliaries and additives, such as formulation auxiliaries, and

5) 0.001 to 89% by weight of water, it being preferred if the solvent of the formula (I) is present in excess compared to the optional organic solvent 3).

Containing oil suspension concentrates and oil suspensions

1) 0.1 to 60% by weight of agrochemical active ingredients,

2) 10 to 99.9% by weight of the surfactant / solvent mixture according to the invention, preferably 0.9 to 99% by weight, preferably 35 to 99% by weight of the solvent of the formula (I) being contained, 3) 0 up to 35% by weight of further organic solvents, and

4) 0 to 10% by weight of conventional auxiliaries and additives, such as formulation auxiliaries, in particular 0.001 to 5% by weight of organic and / or inorganic thickeners, it being preferred if the solvent of the formula (I) is in excess over the optional organic solvent 3) is included. Suspoemulsion concentrates and Suspoemulsions containing

1) 10 to 40% by weight of agrochemical active ingredients,

2) 10 to 60% by weight of the surfactant / solvent mixture according to the invention, preferably 0.9-59% by weight, preferably 35-59% by weight of the solvent of the formula (I) being present,

3) 0 to 35% by weight of further organic solvents,

4) 0 to 10% by weight of customary auxiliaries and additives such as formulation auxiliaries, in particular 0.001 to 5% by weight of organic and / or inorganic thickeners, and 5) 0.001 to 80% by weight of water, it being preferred if the solvent of formula (I) is present in excess of the optional organic solvent 3).

The above-mentioned agrochemical active substance formulations can additionally be diluted with water and, for example, form aqueous spray liquors which likewise represent active substance formulations in the sense of the present invention.

The surfactant / solvent mixture according to the invention is preferably suitable for producing stable agrochemical active substance formulations, in particular liquid agrochemical active substance formulations, including aqueous spray liquors. The formulations which can be prepared with the surfactant / solvent mixture according to the invention also have biologically advantageous results when used. An effective amount of the formulation is applied to the harmful organisms or the places where they occur, for example to the plant, parts of plants, plant seeds or the area on which the plants grow, for example the area under cultivation. In addition, the biological activity of the agrochemical active substances used can be increased, in particular in a synergistic manner, by using the surfactant / solvent mixture according to the invention. Examples

The formulations given in the table below were prepared as follows:

The solvents a) were placed in a flask. The surfactants b) and auxiliaries and active ingredients were then added in succession with stirring. The mixtures were then stirred at 50 ° C for one hour. The formulations obtained were then diluted with water to form a spray liquor and stored for one week to examine the stability. The formulations from Examples 1 and 2 were stable, while the formulations from Comparative Examples 1 and 2 were not stable. The proportions of the formulation constituents (in% by weight) are given in the table below.

Formulation ingredients Example 1 Example 2 Comparative Comparative Example 1 example 2- bromoxynil octanoate 18.22 18.22 18.22 18.22 loxynil octanoate 9.63 9.63 9.63 9.63 Diflufenican 3.71 3.71 3 71 3.71 3.17 3.17 3.17 AASCA ^® 60, 3.17

Antarox ^® 724P 4.52 4.52 4.52 4.52 N, N-dimethyl-propionic acid amide 40.39 N, N-dimethyl-isobutyric acid amide 40.39 N, N-dimethylformamide 40.39 N, N-dimethylacetamide 40, 39 Solvesso ^® 150 20.16 20.16 20.16 20.16

Explanations:

AASCA ^® 60 (Rhodia) = calcium dodecylbenzenesulfonate (60% in isobutanol)

Antarox ^® 724P (Rhodia) = ethylene oxide / propylene oxide (p-nonylphenol) copolymer with 18 EO / PO units Solvesso ^® 150 (Exxon) = aromatic mineral oil

Claims

claims

1. surfactant / solvent mixture containing a) one or more solvents of the formula (I): R-CO-NR ¹ R ² (I) .wherin R = H, methyl, ethyl or propyl, where α) when R = H or is methyl, R ¹ and R ^{2 are the} same or different tert-butyl, (C ₅ -C ₂ ) alkyl or (C 1 -C ₁₂ ) hydroxyalkyl, and ß) when R = ethyl or propyl, R and R ^{2 are the} same or different (Cr C ₁₂ ) alkyl or (CC ₁₂ ) hydroxyalkyl, and b) one or more surfactants.

2. surfactant / solvent mixture according to claim 1, containing as component a) one or more compounds of formula (I), wherein R = ethyl or propyl and

R ¹ and R ^{2 are the} same or different (-C-Ce) alkyl.

3. surfactant / solvent mixture according to claim 1 or 2, containing as component b) one or more compounds from the group alkoxylated C-io-C ₂ alcohols and their anionic derivatives, alkoxylated vegetable oils, alkoxylated phenols and their reaction products with sulfuric acid or phosphoric acid, and alkylbenzenesulfonates.

4. active ingredient formulation containing (1) one or more active ingredients,

(2) the surfactant / solvent mixture according to one or more of claims 1 to 3,

(3) optionally further organic solvents,

(4) optional auxiliaries and additives, and (5) optionally water.

5. Active ingredient formulation according to claim 4, containing one or more agrochemical active ingredients, preferably from the group of herbicides, insecticides or fungicides.

6. Active ingredient formulation according to claim 4 or 5, in liquid form.

7. Active ingredient formulation according to one or more of claims 4 to 6, in the form of an emulsion concentrate, microemulsion concentrate, oil suspension concentrate, suspoemulsion concentrate, emulsion, microemulsion, oil suspension, suspoemulsion, or a spray mixture.

8. A process for the preparation of an active substance formulation as defined in one or more of claims 4 to 7, the components being mixed with one another.

9. Use of the surfactant / solvent mixture according to one or more of claims 1 to 3 for the preparation of active substance formulations.

10. Use according to claim 9 for the preparation of emulsion concentrates, microemulsion concentrates, oil suspension concentrates,

Suspoemulsion concentrates, emulsions, microemulsions, oil suspensions, suspoemulsions or spray liquors.

11. A method for combating harmful organisms, wherein an effective amount of an agrochemical active ingredient formulation according to one or more of claims 4 to 7 is applied to the harmful organisms or to the locations where they occur.

12. Use of an agrochemical active ingredient formulation according to one or more of claims 4 to 7, for controlling harmful organisms.