IL181558A - Liquid plant protection formulations comprising diflufenican - Google Patents

Abstract

The invention relates to liquid plant protection formulations comprising a) 0.1 to 8 % diflufenican in dissolved form, b) 1 to 80 % of a solvent, with both polar and non-polar groups, or a mixture of such solvents, c) 1 to 30 % of a detergent or detergent mixture, d) 0 to 70 % of one or more further agrochemical agents, e) 0 to 50 % of a non-polar solvent, f) 0 to 15 % of a dipolar solvent and g) 0 to 20 % of one or more adjuncts. Said plant protection formulations are suitable for the prevention of pests.

Description

558 f7'Ji I 453541 I IN LIQUID PLANT PROTECTION FORMULATIONS COMPRISING DIFLUFENICAN l p3oi £) Pearl Cohen Zedek Latzer P-9594-1L 181558/2 Description The present invention relates to the field of plant protection formulations. In particular, it relates to liquid formulations in which the active substance diflufenican is present in dissolved form.

Liquid formulations of agrochemical active substances are known to a person skilled in the art. In addition, liquid formulations, e.g. as aqueous suspension concentrate (SC) or emulsifiable concentrate (EC), trade name, e.g., First®, are well known for the herbicide diflufenican.

However, the known diflufenican-comprising liquid EC formulations have the disadvantage that they are not always stable on storage. Thus, for example, the active substance in the spray slurry may crystallize out and thereby cause the nozzles to become blocked. An additional disadvantage of these known formulations is that they comprise the toxicologically questionable solvent N-methylpyrrolidinone. The use of N-methylpyrrolidinone as solvent in formulations of plant protection agents is no longer desirable.

WO 2001/01777 (counterpart of IL 146955) discloses a non-aqueous, emulsifiable concentrate (EC) formulation for herbicidal crop protection active compounds which consists essentially of: a) 25 to 150 g/L of at least one fluorinated herbicidal compound; b) 400 to 900 g/L of one or more herbicidal alkyl phenoxyalkanoates; c) 10 to 100 g/L of at least one non-ionic surfactant; d) 10 to 100 g/L of at least one benzene sulfonate; e) 50 to 600 g/L of one or more solvent selected from the group consisting of aliphatic or aromatic hydrocarbons, methylated plant oils and water-miscible polar aprotic organic solvents; and f) optionally, up to 5 g/L of at least one defoamer; and to the use of such an emulsifiable concentrate as a herbicide.

WO 1998/48624 discloses an effective emulsifiable concentrate for a low dosage fluorinated agricultural chemical, e.g. diflufenican, a herbicide, in 181558/1 1a optional admixture with a diluent active agricultural chemical, e.g. bromoxynil octanoate or isooctylmetachlorophenyl acetate herbicides.

The object of the present invention was to make available a liquid formulation comprising diflufenican which is stable on storage, which is friendly towards application and which comprises no N-methylpyrrolidinone.

This object was achieved by preparation of a liquid formulation of diflufenican which comprises specific carboxamides and solvents and in which diflufenican is present in dissolved form.

A subject matter of the present invention is liquid plant protection formulations comprising a) 0.1 to 8% of diflufenican in dissolved form, b) 1 to 80% of a solvent selected from the group of fatty acid dialkyl amides of the formula (I), (I) in which R is (C6-C32)-alkyl, (C6-C32)-alkenyl or (C6-C32)-alkynyl each substituted by k radicals from the group consisting of hydroxyl and CO2-(C C4)-alkyl; k is 0, 1 , 2 or 3; R2 is hydrogen or (CrC20)-alkyl, (C2-C2o)-alkenyl or (C2-C20)-alkynyl each substituted by k radicals from the group consisting of hydroxyl and C02- (C C4)-alkyl; R3 is hydrogen or (Ci-C2o)-alkyl, (C2-C20)-alkenyl or (C2-C20)-alkynyl each 1 b substituted by k radicals from the group consisting of hydroxyl and C02- (C C4)-alkyl; or NR2R3 is a 3- to 8-membered ring which can be saturated, unsaturated or heteroaromatic, which comprises up to three additional heteroatoms from the group consisting of oxygen, sulfur and nitrogen, c) 1 to 30% of a surfactant or surfactant mixture, d) 0 to 70% of one or more additional agrochemical active substances, 2 e) 0 to 50% of a nonpolar solvent, f) 0 to 15% of a dipolar solvent, and g) 0 to 20% of one or more additional auxiliaries.

The term "a solvent from group b) having both polar and nonpolar groups" is understood to mean fatty acid dialkylamides of the formula (I) and esters of the formula (II).

R2 R1-CO-N R6-(CO),-(OA)-R5 R (I) GO R1 is (C6-C32)-alkyl, (C6-C32)-alkenyl or (C6-C32)-alkynyl each substituted by k radicals from the group consisting of hydroxyl and C02-(CrC4)-alkyl; R2 is hydrogen or (C C2o)-alkyl, (C2-C-2o)-alkenyl or (C2-C2o)-alkynyl each substituted by k radicals from the group consisting of hydroxyl and C02-(CrC4)-alkyl; R3 is hydrogen or (CrC2o)-alkyl, (C2-C2o)-alkenyl or (C2-C2o)-alkynyl each substituted by k radicals from the group consisting of hydroxyl and C02-(C C4)-alkyl; or NR2R3 is a 3- to 8-membered ring which can be saturated, unsaturated or heteroaromatic, which comprises up to three additional heteroatoms from the group consisting of oxygen, sulfur and nitrogen and which is substituted by p radicals from the group consisting of (C C4)-alkyl, (Ci-C4)-alkoxy, halogen, hydroxyl, cyano and nitro; OA is ethyleneoxy, propyleneoxy or butyleneoxy units; k is 0, 1 , 2 or 3; m is 0, 1 , 2, 3, 4, 5, 6, 7, 8, 9 or 10; is and R5 is (Ce-Ce)-alkyl; R6 is hydrogen or (Ci-C4)-alkyl; I is 0 or 1 ; or R5 is hydrogen or (d-G -alkyl; R6 is (Ce-Ce)-alkyl; I is O or 1.

Preference is given to the fatty acid dialkylamides of the formula (I), in which R1 is (C6-C2o)-alkyl, (C6-C20)-alkenyl or (C6-C2o)-alkynyl; R2 is hydrogen, (C C6)-alkyl, CH2CH2OH or (C C4)-alkyl mono-substituted by the radical C02R7; R3 is hydrogen, (C C6)-alkyl, CH2CH2OH or (d-C4)-alkyl mono-substituted by the radical C02R7; R7 is (Ci-C6)-alkyl, and m is 0, 1 , 2, 3, or 4.

Particular preference is given to the fatty acid dialkylamides of the formula (I), in which R1 is octyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, octenyl, decenyl, dodecenyl, tridecenyl, tetradecenyl, hexadecenyl or octadecenyl; 4 R2 is hydrogen, methyl, ethyl or CH2CH2OH; R3 is hydrogen, methyl, ethyl or CH2CH2OH.

In addition, the plant protection formulations according to the invention can also still comprise at least one additional agrochemical active substance from the group consisting of herbicides, fungicides, insecticides, safeners, acaricides, molluscicides, rodenticides, adjuvants and fertilizers, preferably herbicides.

In formulae (I) and (II), alkyl radicals with more than two carbon atoms can be straight-chain or branched. Alkyl radicals are, e.g., methyl, ethyl, n-propyl or isopropyl, n-butyl, isobutyl, t-butyl or 2-butyl, pentyls, such as n-pentyl or branched pentyl, such as isopentyl or neopentyl, hexyls, such as n-hexyl, isohexyl and 1 ,3-dimethylbutyl, heptyls, such as n-heptyl or branched heptyl, octyls, such as n-octyl or branched octyl, such as 2-ethylhexyl, nonyls, such as n-nonyl or branched nonyl, decyls, such as n-decyl or branched decyl, undecyls, such as n-undecyl or branched undecyl, or dodecyls, such as n-dodecyl or branched dodecyl. Halogen is fluorine, chlorine, bromine or iodine.

If a group is polysubstituted by radicals, this is to be understood as meaning that this group is substituted by one or more of the radicals mentioned which are identical or different.

In a preferred embodiment, the alkyl radicals are straight-chain.

The 3- to 8-membered ring formed by NR2R3 is, for example, aziridine, pyrrolidine, isoxazolidine, isoxazoline, thiazoline, thiazolidine, pyrazolidine, morpholine, piperidine, piperazine, azepane, pyrrole, pyrazole, imidazole, oxazole, thiazole, isoxazole, isothiazole, ,2,3-triazole, 1 ,2,4-triazole, 1 ,2,3-oxadiazole, 1 ,2,4-oxadiazole, 1 ,2,5-oxadiazole, 1 ,3,4-oxadiazole, 1 ,2,3-thiadiazole,' 1 ,2,4-thiadiazole, ,2,5-thiadiazole, 1 ,3,4-thiadiazole, tetrazole, pyridazine, pyrazine, 1 ,2,4-triazine or 1 ,3,5-triazinyl.

Examples of solvents of group b) are Genagen 4166®, Agsolex 8® and 2-ethylhexyl acetate.

Suitable surfactants of group c) are, in this connection, polymeric and nonpolymeric surfactants. The surfactants can be nonionic, anionic, cationic or zwitterionic in nature. The surfactants can, e.g., act as emulsifiers or dispersants or can also show wetting1 properties (wetting agents).

For example, nonaromatic-based or heteroaromatic-based surfactants, e.g. those based on heterocyclic compounds, olefins, aliphatic compounds or cycloaliphatic compounds, for example surface-active pyridine, pyrimidine, triazine, pyrrole, pyrrolidine, furan, thiophene, benzoxazole, benzothiazole and triazole compounds substituted with one or more alkyl groups and subsequently derivatized, e.g. alkoxylated, and/or aromatic-based surfactants, e.g. benzenes of phenols substituted with one or more alkyl groups and subsequently derivatized, are in the formulations according to the invention comprising surfactants from group c). The surfactants c) are generally soluble in the solvent phase and are suitable for emulsifying this, together with active substances dissolved therein, on diluting with water (for the spray mixture). The formulations according to the invention can, e.g., comprise nonaromatic or aromatic surfactants or mixtures of nonaromatic and aromatic surfactants.

Examples of surfactants from group c) are listed below, in which EO is ethyleneoxy units, PO is propyleneoxy units and BO is butyleneoxy units: c1 ) Cio-C24-Alcohols, which can be alkoxylated, e.g., with 1 -60 alkylene oxide units, preferably 1-60 EO and/or 1 -30 PO and/or 1-15 BO, in any sequence. The terminal hydroxyl groups of these compounds can be end group closed by an alkyl, cycloalkyl or acyl radical with 1 - 24 carbon atoms. Examples of such compounds are: Genapol®C, L, O, T, UD, UDD, X products from Clariant, Plurafac® and Lutensol®A, AT, ON, TO products from BASF, Marlipal®24 and Ο13 products from Condea, Dehypon® products from Henkel, Ethylan® products from Akzo-Nobel, such as Ethylan CD 120. c2) Anionic derivatives of the products described under c1 ) in the form of ether carboxylates, sulfonates, sulfates and phosphates and the inorganic (e.g., alkali metal and alkaline earth metal) and organic (e.g., amine- or alkanolamine-based) salts thereof, such as Genapol®LRO, Sandopan® products, Hostaphat Hordaphos® 6 products from Clariant.

Copolymers consisting of EO, PO and/or BO units, such as, for example, block copolymers, such as the Pluronic® products from BASF and the Synperonic® products from Uniquema, with a molecular weight of 400 to 108.

Alkylene oxide adducts of Ci-Cg-alcohols, such as Atlox®5000 from Uniquema or Hoe®S3510 from Clariant. c3) 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, thistle oil, walnut oil, peanut oil, olive oil or castor oil, in particular rapeseed oil, the term "vegetable oils" also being understood as meaning the transesterification products thereof, e.g. alkyl esters, such as rapeseed oil methyl ester or rapeseed oil ethyl ester, for example the Emulsogen® products from Clariant, salts of aliphatic, cycloaliphatic and olefinic carboxylic acids and polycarboxylic acids, and -sulfofatty acid esters, as available from Henkel. c4) Fatty acid amide alkoxylates, such as the Comperlan® products from Henkel or the Amam® products from Rhodia.

Alkyleneoxy adducts of alkynediols, such as the Surfynol® products from Air Products. Sugar derivatives, such as amino- and amidosugars from Clariant, glucitols from Clariant, alkylpolyglycosides in the form of the APG® products from Henkel or such as sorbitan esters in the form of the Span® or Tween® products from Uniquema or cyclodextrin esters or ethers from Wacker. c5) 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.

Alkylene oxide adducts based on polyols, such as the Polyglykol® products from Clariant.

Surface-active polyglycerides and the derivatives thereof from Clariant. c6) Sulfosuccinates, alkanesulfonates, paraffinsulfonates and olefinsulfonates, such as Netzer lS®, 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. 7 c7) Sulfosuccinamates, such as the Aerosol® products from Cytec or the Empimin® products from Albright and Wilson. c8) Alkylene oxide adducts of fatty amines, quaternary ammonium compounds with 8 to 22 carbon atoms (C8-C22), such as, e.g., the Genamin®C, L, O, T products from Clariant. c9) 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. c10) Surface-active compounds based on silicones or silanes, such as the Tegopren® products from Goldschmidt and the SE® products from Wacker, and also the Bevaloid®, Rhodorsil® and Silcolapse® products from Rhodia (Dow Corning, Reliance, GE, Bayer). c1 1 ) Per- or polyfluorinated suface-active compounds, such as the Fluowet® products from Clariant, the Bayowet® products from Bayer, the Zonyl® products from DuPont and products of this type from Daikin and Asahi Glass. c12) Surface-active sulfonamides, e.g. from Bayer. c13) Surface-active polyacryiic and polymethacrylic denvatives, such as the Sokalan® products from BASF. c14) Surface-active polyamides, such as modified gelatin or derivatized polyaspartic acid from Bayer and the derivatives thereof. c15) Surface-active polyvinyl compounds, such as modified polyvinylpyrrolidone, such as the Luviskol® products from BASF and the Agrimer® products from ISP, or derivatized polyvinyl acetates, such as the Mowilith® products from Clariant, or polyvinyl butyrates, such as the Lutonal® products from BASF, the Vinnapas® and the Pioloform® products from Wacker, or modified polyvinyl alcohols, such as the Mowiol® products from Clariant. c16) Surface-active polymers based on maleic anhydride and/or reaction products of maleic anhydride, and also copolymers comprising maleic anhydride and/or reaction products of maleic anhydride, such as the Agrimer® VEMA products from ISP. c17) Surface-active derivatives of montan, polyethylene and polypropylene waxes, such as the Hoechst® waxes or the Licowet® products from Clariant. c18) Surface-active phosphonates and phosphinates, such as Fluowet® PL from Clariant. c19) Poly- or perhalogenated surfactants, such as, for example, 8 Emulsogen 1557 from Clariant. c20) Phenols, which may be alkoxylated, for example phenyl (C C4)alkyl ethers or (poly)alkoxylated phenols [= phenol (poly)alkylene glycol ethers], for example with 1 to 50 alkyleneoxy units in the (poly)alkyleneoxy part, the alkylene part preferably exhibiting 1 to 4 carbon atoms each time, preferably phenol reacted with 3 to 10 mol of alkylene oxide, (poly)alkylphenols or (poly)alkylphenol alkoxylates [= polyalkylphenol (poly)alkylene glycol ethers], for example with 1 to 12 carbon atoms per alkyl radical and 1 to 150 alkyleneoxy units in the polyalkyleneoxy part, preferably tri(n-butyl)phenol or triisobutylphenol reacted with 1 to 50 mol of ethylene oxide, polyarylphenols or polyarylphenol alkoxylates [= polyarylphenol (poly)alkylene glycol ethers], for example tristyrylphenol polyalkylene glycol ethers with 1 to 150 alkyleneoxy units in the polyalkyleneoxy part, preferably tristyrylphenol reacted with 1 to 50 mol of ethylene oxide. c21 ) Compounds which are formally the reaction products of the molecules described under c20) with sulfuric acid or phosphoric acid and the salts thereof neutralized with suitable bases, for example the acidic phosphoric ester of triethoxylated phenol, the acidic phosphoric ester of a nonylphenol reacted with 9 mol of ethylene oxide and the phosphoric ester, neutralized with triethanolamine, of the reaction product of 20 mol of ethylene oxide and 1 mol of tristyrylphenol. c22) Benzenesulfonates, such as alkyl- or arylbenzenesulfonates, e.g. (poly)alkyl- and (poly)arylbenzenesulfonates which are acidic and 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 the oil- soluble salts thereof, such as, for example, the calcium salt or the isopropylammonium salt of dodecylbenzenesulfonic acid.

Ethyleneoxy, propyleneoxy and butyleneoxy units, in particular ethyleneoxy units, are preferred for the alkyleneoxy units.

Examples of surfactants from the group of the nonaromatic-based surfactants are the surfactants of the abovementioned groups c1 ) to c19), preferably of the groups c1 ), c2), c6) and c8). 9 Examples of surfactants from the group of the aromatic-based surfactants are the surfactants of the abovementioned groups c20) to c22), preferably phenol reacted with 4 to 10 mol of ethylene oxide, available commercially, for example, in the form of the Agrisol® products (Akcros), triisobutylphenol reacted with 4 to 50 mol of ethylene oxide, available commercially, for example, in the form of the Sapogenat® T products (Clariant), nonylphenol reacted with 4 to 50 mol of ethylene oxide, available commercially, for example, in the form of the Arkopal® products (Clariant), tristyrylphenol reacted with 4 to 150 mol of ethylene oxide, for example from the Soprophor® series, such as Soprophor® FL, Soprophor® 3D33, Soprophor® BSU, Soprophor® 4D-384, Soprophor® CY/8 (Rhodia), and acidic (linear) dodecylbenzenesulfonate, available commercially, for example, in the form of the Marlon® products (Huls).

Preferred surfactants c) are, e.g., alkoxylated Ci0-C24-alcohols (c1 ) and the anionic derivatives thereof (c2), such as sulfates, sulfonates and phosphates, alkoxylated vegetable oils (c3), alkoxylated phenols (c20) and the reaction products thereof with sulfuric acid or phosphoric acid (c21 ), and alkylbenzenesulfonates (c22).

Possible additional agrochemical active substances for the formulations according to the invention are, for example, known active substances, such as herbicides, insecticides or fungicides, such as are described in, e.g., Weed Research, 26, 441-445 (1986), or "The Pesticide Manual", 12th edition, The British Crop Protection Council, 2000, and the literature cited therein, e.g. in mixed formulations or as tank mix components. Mention may be made, as herbicides known from the literature which can be present in the herbicidal compositions according to the invention, of the following active substances, for example. The compounds are described either with the "common name" according to the International Organization for Standardization (ISO) or with the chemical name, if appropriate together with a standard code number, and always comprise all application forms, such as acids, salts, esters and isomers, such as stereoisomers and optical isomers: acetochlor; acifluorfen; aclonifen; AKH 7088, i.e. [[[1-[5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrophenyl]-2-methoxyethylidene]amino]oxy]-acetic acid and -acetic acid methyl ester; alachlor; alloxydim; ametryn; amidosulfuron; amitrole; AMS, i.e. ammonium sulfamate; aniiofos; asulam; atrazine; azafenidin (DPX-R6447); azimsulfuron (DPX-A8947); aziprotryn; barban; BAS 516 H, i.e. 5-fluoro-2-phenyl-4H-3,1-benzoxazin-4-one; benazolin; benfluralin; benfuresate; bensulfuron-methyl; bensulide; bentazon; benzofluor; benzoylprop-ethyl; benzthiazuron; bialaphos, bifenox; bispyribac-sodium (KIH-2023), bromacil; bromobutide; bromofenoxim; bromoxynil, in particular bromoxynil octanoate and bromoxynil heptanoate; butachlor; butamifos; butenachlor; buthidazole; butralin; butroxydim (ICI-0500); butylate; cafenstrole (CH-900); carbetamide; carfentrazone; CDAA, i.e. 2-chloro-N,N-di(2-propenyl)acet-amide; CDEC, i.e. diethyldithiocarbamic acid 2-chloroallyl ester; chlomethoxyfen; chloramben; cloransulam-methyl (XDE-565); chlorazifop-butyl; chlorbromuron; chlorbufam; chlorfenac; chlorflurenol-methyl; chloridazon; chlorimuron-ethyl; chlornitrofen; chlorotoluron; chloroxuron; chlorpropham; chlorthal-dimentyl; chlorthiamid; cinidon-ethyl, cinmethylin; cinosulfuron; clethodim; clodinafop and the ester derivatives thereof (e.g., clodinafop-propargyl); clomazone; clomeprop; cloproxydim; clopyralid; cumyluron (JC 940); cyanazine; cycloate; cyclosulfamuron (AC 014); cycloxydim; cycluron; cyhalofop and the ester derivatives thereof (e.g., butyl ester, DEH-112); cyperquat; cyprazine; cyprazole; 2,4-D; 2,4-DB; dalapon; desmedipham; desmetryn; di-allate; dicamba; dichlobenil; dichlorprop; diclofop and the esters thereof, such as diclofop-methyl; diclosulam (XDE-564); diethatyl; difenoxuron; difenzoquat; diflufenzopyr-sodium (SAN-835H); dimefuron; dimethachlor; dimethametryn; dimethenamid (SAN-582H); dimidazon; 5-(4,6-dimethylpyrimidin-2-ylcarbamoylsulfamoyl)-1-(2-pyridyl)pyrazole-4-carboxylic acid methyl ester (NC-330); triaziflam (IDH-1105); cinosulfon; dimethipin; dinitramine; dinoseb; dinoterb; diphenamid; dipropetryn; diquat; dithiopyr; diuron; DNOC; eglinazine-ethyl; EL 177, i.e. 5-cyano-1-(1 ,1-dimethylethyl)-N-methyl-1 H-pyrazole-4-carboxamide; endothal; indanofan (MK-243); EPTC; esprocarb; ethalfluralin; ethametsulfuron-methyl; ethidimuron; ethiozin; ethofumesate; F5231 , i.e. N-[2-chloro-4-fluoro-5-[4-(3-fluoropropyl)-4,5-dihydro-5-oxo-1 H-tetrazol-1-yl]phenyl]ethanesulfonamide; ethoxyfen and the esters thereof (e.g., ethyl ester, HN-252); ethoxysulfuron (from EP 342 569); etobenzanid (HW 52); 3-(4-ethoxy-6-ethyl-1 ,3,5-triazin-2-yl)-1 -(2,3-dihydro-1 ,1-dioxo-2-methylbenzo[b]thiophen-7-sulfonyl)urea (EP-A 079 683); 3-(4-ethyl-6-methoxy- ,3,5-triazin-2-yl)-1-(2,3-dihydro-1 ,1-dioxo-2-methylbenzo[b]thiophen-7-sulfonyl)urea (EP-A 079 683); fenoprop; 11 clomazone; fenoxaprop and fenoxaprop-P and the esters thereof, e.g. fenoxaprop-P-ethyl and fenoxaprop-ethyl; butroxydim; fenuron; flamprop- methyl; flazasulfuron; flufenacet (BAY-FOE-5043); fluazifop and fluazifop-P and the esters thereof, e.g. fluazifop-butyl and fluazifop-P-butyl; florasulam (DE-570); fluchloralin; flumetsulam; fluometuron; flumiclorac and the esters thereof (e.g., pentyl ester, S-2303 ); flumioxazin (S-482); flumipropyn; flupoxam (KNW-739); fluorodifen; fluoroglycofen-ethyl; flupropacil (UBIC- 4243); flupyrsulfuron-methyl-sodium (DPX-KE459); fluridone; flurochloridone; fluroxypyr; flurtamone; fluthiacet-methyl (KIH-9201 ), fomesafen; fosamine; furyloxyfen; glufosinate; glyphosate; halosafen; halosulfuron and the esters thereof (e.g., methyl ester, NC-319); haloxyfop and the esters thereof; haloxyfop-P (= R-haloxyfop) and the esters thereof; hexazinone; imazamethabenz-methyl; imazamox (AC-299263); imazapyr; imazaquin and salts, such as the ammonium salt; imazapic; imazethapyr; imazosulfuron; iodosulfuron-methyl-sodium (methyl 4-iodo-2-[3-(4-methoxy- 6-methyl-1 ,3,5-triazin-2-yl)ureidosulfonyl]benzoate, sodium salt, WO 92/13845); ioxynil; isocarbamid; isopropalin; isoproturon; isouron; isoxaben; isoxapyrifop; karbutilate; lactofen; lenacil; linuron; MCPA, and derivatives derived therefrom; MCPB; mecoprop; mefenacet; mefluidide; metamitron; metazachlor; methabenzthiazuron; metam; methazole; methoxyphenone; methyldymron; metobenzuron, mesosulfuron-methyl (WO 95/10507); metobromuron; metolachlor; S-metolachlor; metosulam (XRD 511 ); metoxuron; metribuzin; maleic hydrazide; molinate; monalide; monocarbamide; dihydrogensulfate; monolinuron; monuron; MT 128, i.e. 6-chloro-N-(3-chloro-2-propenyl)-5-methyl-N-phenyl-3-pyridazinamine; MT 5950, i.e. N-[3-chloro-4-(1-methylethyl)phenyl]-2-methylpentanamide; foramsulfuron (WO 95/01344); naproanilide; napropamide; naptalam; NC 310, i.e. 4-(2,4-dichlorobenzoyl)-1-methyl-5-benzyloxypyrazole; neburon; nicofulsuron; nipyraclofen; nitralin; nitrofen; nitrofluorfen; norflurazon; orbencarb; oryzalin; oxadiargyl (RP-020630); oxadiazon; oxaziclomefone (MY-100); oxyfluorfen; oxasulfuron (CGA-277476); paraquat; pebulate; pendimethalin; pentoxazone (KPP-314); perfluidone; phenisopham; phenmedipham; picloram; piperophos; pyributicarb; pirifenop-butyl; pretilachlor; primisulfuron-methyl; procyazine; prodiamine; profluralin; proglinazine-ethyl; prometon; prometryn; propachlor; propanil; propaquizafop and the esters thereof; propazine; propham; propisochlor; propoxycarbazone-sodium; propyzamide; prosulfalin; prosulfocarb; prosulfuron (CGA-152005); prynachlor; pyraflufen-ethyl (ET-751 ); 12 choridazone; pyrazosulfuron-ethyl; pyrazoxyfen; pyribenzoxim, pyridate; pyriminobac-methyl (KIH-6127); pyrithiobac (KIH-2031 ); pyroxofop and the esters thereof (e.g., propargyl ester); quinclorac; quinmerac; quizalofop, quizalofop and quizalofop-P and the ester derivatives thereof, e.g. quizalofop-ethyl, quizalofop-P-tefuryl and -ethyl; rimsulfuron (DPX-E 9636); S 275, i.e. 2-[4-chloro-2-fluoro-5-(2-propynyloxy)phenyl]-4,5,6,7-tetrahydro-2H-indazole; secbumeton; sethoxydim; siduron; simazine; simetryn; SN 106279, i.e. 2-[[7-[2-chloro-4-(trifluoromethyl)phenoxy]-2-naphthyl]oxy]-propanoic acid and methyl ester; flazasulfuron (FMC-97285, F-6285); sulfazuron; sulfometuron-methyl; glyphosate-trimesium (ICI-A0224); sulfosulfuron (MON-37500); TCA; tebutam (GCP-5544); tebuthiuron; tepraloxydim (BAS-620H); terbacil; terbucarb; terbuchlor; terbumeton; terbuthylazine; terbutryn; TFH 450, i.e. N,N-diethyl-3-[(2-ethyl-6-methylphenyl)sulfonyl]-1 H-1 ,2,4-triazole-1 -carboxamide; thenylchlor (NSK-850); thiazafluron; thiazopyr (Mon- 3200); thidiazimin (SN-124085); thiobencarb; tiocarbazil; tralkoxydim; tri-allate; triasulfuron; triazofenamide; triclopyr; tridiphane; trietazine; trifluralin; triflusulfuron and ester (e.g., methyl ester, DPX-66037); trimeturon; tsitodef; vernolate; WL 110547, i.e. 5-phenoxy-1-[3-(trifluoromethyl)phenyl]-1 H-tetrazole; UBH-509; D-489; LS 82-556; KPP-300; KPP-421 ; MT-146, NC-324; butenachlor (KH-218); KPX-N8189; haloxyfop-etotyl (DOWCO-535); DK-8910; flumioxazin (V-53482); PP-600; MBH-001 , amicarbazone; aminopyralid; beflubutamid; benzobicyclon; benzofenap; benzfendizone; butafenacil; chlorfenprop; cloprop; daimuron; dichlorprop-P; dimepiperate; dimethenamid-P; fentrazamide; flamprop-M; fluazolate; flucarbazone; flucetosulfuron; foramsulfuron; indanofan; isoxachlortole; isoxaflutole; MCPA-thioethyl; mecoprop-P; mesosulfuron; mesotrione; metamifop; penoxsulam; pethoxamid; picolinafen; profluazol; profoxydim; propoxycarbazone; pyraclonil; pyrazolynate; pyridafol; pyriftalid; sulcotrione; thidiazuron; trifloxysulfuron; tritosulfuron.

In addition to the active substances mentioned, derivatives derived therefrom, such as, e.g., salts or esters, are also to be regarded as possible components of the formulation according to the invention.

Preferred active substances additionally present in the formulation according to the invention are herbicides, in particular bromoxynil and the derivatives thereof, such as, e.g., bromoxynil octanoate ester, ioxynil and derivatives, such as, e.g. ioxynil octanoate ester, MCPA and the derivatives thereof, such as, e.g., MCPA 2-ethylhexyl ester, or mecoprop-P and the 13 prosulfalin; prosulfocarb; prosulfuron (CGA-152005); prynachlor; pyraflufen-ethyl (ET-751 ), chloridazon; pyrazosulfuron-ethyl; pyrazoxyfen; pyribenzoxim, pyridate; pyriminobac-methyl (KIH-6127), pyrithiobac (KIH-2031 ); pyroxofop und dessen Ester (z.B. Propargylester); quinclorac; quinmerac; quizalofop, quizalofop und quizalofop-P und deren Esterderivate z.B. quizalofop-ethyl; quizalofop-P-tefuryl und -ethyl; rimsulfuron (DPX-E 9636); S 275, d.h. 2-[4-Chlor-2-fluor-5-(2-propynyloxy)-phenyl]-4,5,6,7-tetrahydro-2H-indazol; secbumeton; sethoxydim; siduron; simazine; simetryn; SN 106279, d.h. 2-[[7-[2-Chlor-4-(trifluor-methyl)-phenoxy]-2-naphthalenyl]-oxy]-propansaure und -methylester; flazasulfuron (FMC-97285, F-6285); sulfazuron; sulfometuron-methyl; glyphosate-trimesium (ICI-A0224); sulfosulfuron (MON-37500), TCA; tebutam (GCP-5544); tebuthiuron; tepraloxydim (BAS-620H), terbacil; terbucarb; terbuchlor; terbumeton; terbuthylazine; terbutryn; TFH 450, d.h. N,N-Diethyl-3-[(2-ethyl-6-methylphenyl)-sulfonyl]-1 H-1 ,2,4-triazol-1-carboxamid; thenylchlor (NSK-850); thiazafluron; thiazopyr (Mon-13200); thidiazimin (SN-124085); thiobencarb; tiocarbazil; tralkoxydim; tri-allate; triasulfuron; triazofenamide; triclopyr; tridiphane; trietazine; trifluralin; triflusulfuron und Ester (z.B. Methylester, DPX-66037); trimeturon; tsitodef; vernolate; WL 110547, d.h. 5-Phenoxy-1-[3-(trifluormethyl)-phenyl]-1 H-tetrazol; UBH-509; D-489; LS 82-556; KPP-300; KPP-421 , MT-146, NC-324; butenachlor (KH-218); DPX-N8189; haloxyfop-etotyl (DOWCO-535); DK-8910; flumioxazin (V-53482); PP-600; MBH-001 , amicarbazone, aminopyralid, beflubutamid, benzobicyclon, benzofenap, benzfendizone, butafenacil, chlorfenprop, cloprop, daimuron, dichlorprop-P, dimepipeate, dimethenamid-P, fentrazamide, flamprop-M, fluazolate, flucarbazone, flucetosulfuron, foramsulfuron, indanofan, isoxachlortole, isoxaflutole, MCPA-thioethyl, mecoprop-P, mesosulfuron, mesotrione, metamifop, penoxsulam, pethoxamid, picolinafen, profluazol, profoxydim, propoxycarbazone, pyraclonil, pyrazolynate, pyridafol, pyriftalid, sulcotrione, thidiazuron, trifloxysulfuron, tritosulfuron.

Neben den genannten Wirkstoffen sind auch davon abgeleitete Derivate wie z.B. Salze oder Ester, als mogliche Komponenten der erfindungsgema^en Formulierung anzusehen. 14 Preferred embodiments are characterized as follows: a) 0.1 to 8% of diflufenican in dissolved form, b) 1 to 80% of a solvent having both polar and nonpolar groups, or a mixture of such solvents, c) 1 to 30% of a surfactant or surfactant mixture, d) 0 to 50% of one or more additional agrochemical active substances, e) 0 to 50% of a nonpolar solvent, f) 0 to 15% of a dipolar solvent, and g) 0 to 20% of one or more additional auxiliaries.

Particularly preferred embodiments are characterized as follows: a) 0.5 to 3.5% of diflufenican, b) 10 to 35% of a solvent having both polar and nonpolar groups, or a mixture of such solvents, c) 1 to 30% of a surfactant or surfactant mixture, d) 15 to 45% of one or more additional agrochemical active substances, e) 20 to 50% of a nonpolar solvent, f) 0 to 15% of a dipolar solvent, g) 0 to 20% of one or more additional auxiliaries, and h) the plant protection formulations according to the invention exist as oil dispersions (OD), microemulsions (ME), microemulsion concentrates (MC), suspoemulsions (SE), oil-in-water emulsions (EW) or emulsifiable concentrates (EC).

Very particularly preferred embodiments are characterized as follows: a) 0.5 to 2% of diflufenican, b) 10 to 35% of a solvent having both polar and nonpolar groups, or a mixture of such solvents, c) 1 to 30% of a surfactant or surfactant mixture, d) 15 to 45% of one or more additional agrochemical active substances, e) 20 to 50% of a nonpolar aromatic solvent, f) 0 to 15% of a dipolar solvent, g) 0 to 20% of one or more additional auxiliaries, h) the plant protection formulations according to the invention exist as an MC or EC formulation, in particular as an EC formulation, and i) the formulation is used on cereals (e.g., wheat, barley) for the control of undesirable plant growth.

An additional very particularly preferred embodiment is characterized in that it is defined as above but comprises no additional agrochemical active substance.

The abovementioned different types of formulations, microemulsions, microemulsion concentrates, oil dispersions, suspoemulsions, oil-in-water emulsions and emulsifiable concentrates, are fully known to a person skilled in the art and can be prepared by known processes. Their preparation procedure is, for example, described in: Winnacker-Kuchler, "Chemische Technologie" [Chemical Technology], Volume 7, C. Hauser Verlag, Munich, 4th edition, 1986; Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, N.Y., 1973; K. Martens, "Spray Drying Handbook", 3rd Ed., 1979, G. Goodwin Ltd., London.

The formulation auxiliaries which may be necessary, such as inert materials, surfactants, solvents and additional additives, are likewise known and are, for example, described in: Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell N.J.; H.v. Olphen, "Introduction to Clay Colloid Chemistry", 2nd Ed., J. Wiley & Sons, N.Y.; C. Marsden, "Solvents Guide", 2nd Ed., Interscience, N.Y., 1963; McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood, N.J.; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y., 1964; Schonfeldt, "Grenzflachenaktive Athylenoxidaddukte" [Surface-active ethylene oxide adducts], Wiss. Verlagsgesell., Stuttgart, 1976; Winnacker-Kuchler, "Chemische Technologie" [Chemical Technology], Volume 7, C. Hauser Verlag, Munich, 4th edition, 1986.

Emulsifiable concentrates (EC) are prepared, e.g., by dissolution of the active substance, e.g. of the herbicidal active substance and/or of the safener, in an organic solvent, such as butanol, cyclohexanone, dimethylformamide, xylene or also high boiling point hydocarbons, such as aromatic hydrocarbons or saturated or unsaturated aliphatic or alicyclic hydrocarbons, or mixtures of the organic solvents, with the addition of one or more surfactants of ionic and/or nonionic type (emulsifiers). Use may be 16 made, as emulsifiers, for example, of (C6-Ci8)-alkylarylsulfonic acid calcium salts, such as calcium dodecylbenzenesulfonate, or nonionic emulsifiers, such as fatty acid poiyglycol esters, (C2-Ci8)-alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide/ethylene oxide condensation products, alkyl polyethers, sorbitan esters, such as sorbitan fatty acid esters, or polyoxyethylene sorbitan esters, such as polyoxyethylene sorbitan fatty acid esters. Oil-base suspension concentrates can, for example, be prepared by wet milling using commercial bead mills and optionally adding surfactants, such as, e.g., those already cited with the other formulation types.

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

For further details with regard to the formulating of plant protection compositions, see, e.g., G.C. Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961 , pages 81 -96, and J.D. Freyer and S.A. Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pages 101 -103.

The formulations according to the invention show, in comparison with commercial products, a significantly improved application behavior which makes itself felt in markedly reduced sieve residues or sieve or nozzle blockages.

The amount of the formulations according to the invention expended per hectare generally varies between 0.5 and 5 liters, preferably between 1 .0 and 4.0 liters.

For application, the formulations according to the invention can optionally be diluted, e.g. using water, in the usual way, e.g., to give suspensions, emulsions, suspoemulsions or solutions, preferably emulsions. It can be advantageous for the spray mixtures obtained to be treated with additional agrochemical active substances (e.g., tank mix components in the form of appropriate formulations) and/or, for application, with standard auxiliaries and additives, e.g. self-emulsifying oils, such as vegetable oils or liquid paraffins, and/or fertilizers. Another subject matter of the present invention 17 is accordingly the herbicidal compositions prepared in such a way.

The ratio of formulation according to the invention to water is usually from 1 :500 to 1 :50. The spray mixture per ha is usually from 50 to 500 liters, preferably from 75 to 350 liters of water. In some cases, it is possible to even fall short of or exceed the limiting values given here.

The formulations are also suitable for application by aircraft. For this, formulations according to the invention are applied either undiluted, diluted with water or diluted with organic solvents. In this connection, the volume of additional carrier liquid generally varies from 0.5 to 50 liters per hectare.

Use is made, as tank mix components, for example, of isoproturon-based formulations, and also in particular graminicides, products for post-emergence application, e.g. aryloxyphenoxyacetic acid derivatives, such as fenoxaprop-P-ethyl, diclofop-methyl or clodinafop-propargyl, or also sulfonylureas, such as, e.g., mesosulfuron- or iodosulfuron-based products. The spray mixtures resulting therefrom are novel herbicidal compositions which are likewise a subject matter of this invention.

These herbicidal compositions according to the invention exhibit an outstanding herbicidal activity against a broad spectrum of economically important harmful monocotyledonous and dicotyledonous plants. Even perennial weeds which sprout from rhizomes, rootstocks or other perennial organs and which are difficult to combat are successfully included. In this connection, the compositions can be applied, e.g., in the presowing, preemergence or postemergence method.

The plant protection formulations according to the invention are suitable, depending on the type of the additional agrochemical active substance d), for the combating of undesirable plants, insects, spider mites, snails and slugs, and other harmful organisms, in particular of undesirable plants. An additional subject matter of the present invention is accordingly a process for the combating of harmful organisms, in which an effective amount of a plant protection formulation according to the invention is applied to the harmful organisms or the places where they occur. An additional subject matter of the present invention is accordingly also the use of liquid plant protection formulations for the combating of harmful organisms, in particular of undesirable plants. 18 Formulation examples To prepare the examples mentioned in table 1 , the solvent (the solvents) is/are first placed in the vessel. Diflufenican and the additional formulation constituents are subsequently added with stirring. The sequence of the addition of the additional components is generally unimportant.

Example 8 is an example not according to the invention prepared for comparative purposes.

Table 1 (Particulars follow in % by weight) The commercial products used here in the examples are products with the following composition: First®: Emulsifiable concentrate with a density of 1 .105 g/ml comprising diflufenican, bromoxynil octanoate, ioxynil octanoate, N-methylpyrrolidone, Solvesso 150 and nonylphenol ethoxylate. 19 Genagen® 4166: Fatty acid dialkylamides of the formula (I), in which R2 and R3 are each methyl and R1 is Cs- and C 0-alkyl.

Agsolex® 8: N-Octyl-2-pyrrolidinone.

Soprophor® BSU: 2,4,6-Tristyrylphenol ethoxylate with 16 ethyleneoxy units.

Sapogenate® T080: 2,4,6-Tri(sec-butyl)phenol ethoxylate with 8 ethyleneoxy units.

Emulsogen® EL360: Ethoxylated castor oil with 36 ethyleneoxy units.

Solvesso® 200 ND: Mixture of aromatic compounds.

Application examples Example according to the invention: A spray mixture is prepared from 2 ml of example 9 according to the invention from table 1 and 250 m! of water. After stirring at 10°C for 2 hours, the spray mixture is filtered through a sieve (mesh size 0.15 mm). No residues are observed.

Comparative example: A spray mixture is prepared from 1 ml of the commercially available formulation First® and 251 ml of water. After stirring at 10°C for 2 hours, the spray mixture is filtered through a sieve (mesh size 0.15 mm). After drying, significant amounts of diflufenican are found on the sieve.

Biological example Example 9 according to the invention of table 1 (1.5 liters/ha) is applied in comparison with the commercial product Firs® (0.75 liters/ha) in the combating of weeds in wheat. The assessment is subsequently carried out at different points in time. In this connection, it turns out that formulation 9 according to the invention from table 1 makes possible, with comparable selectivity, improved weed control than the commercial product First®; in particular, Galium, which is difficult to combat, is better controlled. 181558/2 Biological examples The harmful effect on the plants is evaluated optically on a scale from 0 to 100% in comparison with control plants: 0% = no visible effect in comparison with the untreated plants, 100% = treated plants die Herbicidal effect in postemergence Seeds of monocotyledonous and dicotyledonous weeds and of crop plants are planted in sandy loam in plastic pots, covered with earth and placed in a greenhouse under good growing conditions. Three weeks after sowing, the test plants are treated at the 3-4 leaf stage. The individual active substances according to the invention formulated as emulsion concentrates are sprayed in different dosages, individually or as mixtures, onto the green parts of the plants with an amount of water expended of 300 l/ha (converted). After the test plants have stood in the greenhouse under optimum growing conditions for 3 weeks, the effect of the preparations is rated optically in comparison with untreated controls. As the examples show, the combinations of sulfonylureas and safeners according to the invention are able to combat, with lasting effect, a broad spectrum of weeds, damage to crop plants being substantially reduced in comparison with the application of the individual sulfonylureas without safeners.

Material described in the specification, which is not within the ambit of the claims is not covered by the claimed invention. The scope of protection is as defined in the claims, and as stipulated in the Patent Law (5727-1967).

Claims (15)

1. 21 181558/2 A liquid plant protection formulation, which comprises a) 0.1 to 8% of diflufenican in dissolved form, b) 1 to 80% of a solvent selected from the group of fatty acid dialkyl amides of the formula (I), (I) in which R1 is (C6-C32)-alkyl, (C6-C32)-alkenyl or (C6-C32)-alkynyl each substituted by k radicals from the group consisting of hydroxyl and C02-(Ci-C4)-alkyl; k is 0, 1 , 2 or 3; R2 is hydrogen or (C C2o)-alkyl, (C2-C2o)-alkenyl or (C2-C20)-alkynyl each substituted by k radicals from the group consisting of hydroxyl and C02- (C C4)-alkyl; R3 is hydrogen or (CrC2o)-alkyl, (C2-C20)-alkenyl or (C2-C20)-alkynyl each substituted by k radicals from the group consisting of hydroxyl and C02- (C C4)-alkyl; or NR2R3 is a 3- to 8-membered ring which can be saturated, unsaturated or heteroaromatic, which comprises up to three additional heteroatoms from the group consisting of oxygen, sulfur and nitrogen, c) 1 to 30% of a surfactant or surfactant mixture, d) 0 to 70% of one or more additional agrochemical active substances, e) 0 to 50% of a nonpolar solvent, f) 0 to 15% of a dipolar solvent, and g) 0 to 20% of one or more additional auxiliaries. 181558/3 22

2. The liquid plant protection formulation as claimed in claim 1 , wherein R1 is (C6-C2o)-alkyl, (C6-C20)-alkenyl or (C6-C2o)-alkynyl; R2 is hydrogen, (C C6)-alkyl, CH2CH2OH or (C C4)-alkyl monosubstituted by the radical C02R7; R3 is hydrogen, (C C6)-alkyl, CH2CH2OH or (C C4)-alkyl monosubstituted by the radical C02R7; R7 is (CrC6)-alkyl.

3. The liquid plant protection formulation as claimed in claim 1 or 2, wherein R1 is octyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, octenyl, decenyl, dodecenyl, tridecenyl, tetradecenyl, hexadecenyl or octadecenyl; R2 is hydrogen, methyl, ethyl or CH2CH2OH; R3 is hydrogen, methyl, ethyl or CH2CH2OH.

4. The liquid plant protection formulation as claimed in any one of claims 1 to 3, wherein the 3- to 8-membered ring formed by NR2R3 is aziridine, pyrrolidine, isoxazolidine, isoxazoline, thiazoline, thiazolidine, pyrazolidine, morpholine, piperidine, piperazine, azepane, pyrrole, pyrazole, imidazole, oxazole, thiazole, isoxazole, isothiazole, 1 ,2,3-triazole, 1 ,2,4-triazole, 1 ,2,3-oxadiazole, 1 ,2,4-oxadiazole, 1 ,2,5-oxadiazole, 1 ,3,4-oxadiazole, 1 ,2,3-thiadiazole, 1 ,2,4-thiadiazole, 1 ,2,5-thiadiazole, 1 ,3,4-thiadiazole, tetrazole, pyridazine, pyrazine, 1 ,2,4-triazine or 1 ,3,5-triazinyl.

5. The liquid plant protection formulation as claimed in any one of claims 1 to 4, wherein the surfactants c) come from the group of the alkoxylated Cio-C24-alcohols and the anionic derivatives thereof, alkoxylated vegetable oils, alkoxylated phenols and the reaction products thereof with sulfuric acid or phosphoric acid, and also alkylbenzenesulfonates. 181558/3 23

6. The liquid plant protection formulation as claimed in any one of claims 1 to 5, which comprises a) 0.1 to 8% of diflufenican in dissolved form, b) 1 to 80% of a solvent having both polar and nonpolar groups, or a mixture of such solvents, c) 1 to 30% of a surfactant or surfactant mixture, d) 0 to 50% of one or more additional agrochemical active substances, e) 0 to 50% of a nonpolar solvent, f) 0 to 15% of a dipolar solvent, g) 0 to 20% of one or more additional auxiliaries.

7. The liquid plant protection formulation as claimed in any one of claims 1 to 6, which comprises a) 0.5 to 3.5% of diflufenican, b) 10 to 35% of a solvent having both polar and nonpolar groups, or a mixture of such solvents, c) 1 to 30% of a surfactant or surfactant mixture, d) 15 to 45% of one or more additional agrochemical active substances, e) 20 to 50% of a nonpolar solvent, f) 0 to 15% of a dipolar solvent, g) 0 to 20% of one or more additional auxiliaries, and which, additionally, h) exists as oil dispersions (OD), microemulsions (ME), microemulsion concentrates (MC), suspoemulsions (SE), oil-in-water emulsions (EW) or emulsifiable concentrates (EC).

8. The liquid plant protection formulation as claimed in any one of claims 1 to 7, which comprises a) 0.5 to 2% of diflufenican, b) 10 to 35% of a solvent having both polar and nonpolar groups, or a mixture of such solvents, c) 1 to 30% of a surfactant or surfactant mixture, d) 15 to 45% of one or more additional agrochemical active substances, e) 20 to 50% of a nonpolar aromatic solvent, f) 0 to 15% of a dipolar solvent, g) 0 to 20% of one or more additional auxiliaries, and which, additionally, 181558/3 24 h) exists as an MC or EC formulation, in particular as an EC formulation, and i) is used on cereals (e.g., wheat, barley) for the control of undesirable plant growth.

9. The liquid plant protection formulation as claimed in any one of claims 1 to 8, which comprises one or more additional agrochemical active substances from the group consisting of herbicides, fungicides, insecticides, safeners, acaricides, molluscicides, rodenticides, adjuvants and fertilizers.

10. The liquid plant protection formulation as claimed in any one of claims 1 to 9, which comprises one or more additional herbicidal active substances.

11. The liquid plant protection formulation as claimed in any one of claims 1 to 10, which comprises one or more active substances from the group consisting of bromoxynil, ioxynil, MCPA and mecoprop-P, and in each case the derivatives thereof.

12. A process for the combating of harmful organisms, in which an effective amount of a liquid plant protection formulation as claimed in one or more of claims 1 to 11 is applied to the harmful organisms or the places where they occur.

13. The process as claimed in claim 12 for the combating of undesirable plants.

14. The liquid plant protection formulation as claimed in any one of claims 1 to 11 for use in combating of harmful organisms.

15. The liquid plant protection formulation as claimed in claim 14 for the combating of undesirable plants. For the Applicant, P-9594-IL