NZ567201A - Diflufenican-containing oil suspension concentrates - Google Patents

Abstract

The disclosure relates to an oil suspension concentrate containing diflufenican, to salts of certain multivalent cations and to formulations embodied in the form of oil suspension concentrates comprising (a) diflufenican as the sole herbicidally active ingredient, (b) one or several solvents of hydrocarbon and vegetable oil groups, (c) one or several non-surfactant salts of polyvalent (multivalent) cations, wherein the product of solubility of said salts in water is greater than that of calcium sulphate, (d) one or more surfactants and (e) one or more thickeners. Particularly suitable non-surfactant salts of multivalent cations are calcium acetate, calcium formate, calcium propionate, calcium fluoride, calcium chloride, calcium nitrate, calcium nitrite, calcium hydrogencarbonate, calcium carbonate, magnesium acetate, magnesium formate, magnesium propionate, magnesium fluoride, magnesium chloride, magnesium nitrate, magnesium nitrite, magnesium hydrogencarbonate and magnesium carbonate. The oil suspension concentrate disclosed herein is suitable for plant protection.

Description

New Zealand Paient Spedficaiion for Paient Number 567201 1 PCT /E P2006/009261 Description Diflufenican-containing oil suspension concentrates The present invention relates to the field of plant protection formulations. The invention relates in particular to formulations in the form of oil suspension concentrates comprising the herbicidal active substance diflufenican.

Herbicidal active substances are not generally used in their pure form. Depending on 10 the field of use and the type of use, and on physical, chemical and biological parameters, the active substances are used in a mixture with standard auxiliaries and additives as active substance formulation. The combinations with additional active substances for broadening the spectrum of activity and/or for protecting crop plants (e.g., by safeners, antidotes) are also known.

Formulations of herbicidal active substances should generally exhibit high chemical and physical stability, should exhibit good applicability and user friendliness and should exhibit a broad biological action with high selectivity. The herbicidal active substance diflufenican is provided in several types of formulations exhibiting various 20 advantages and disadvantages according to intended purpose and conditions of use. Oil suspension concentrates comprising diflufenican and solvents from the group consisting of the hydrocarbons are known from WO 2005/011378. In practical application, however, it has been shown that these oil suspension concentrates, also known as OD formulations (oil dispersions), exhibit the disadvantage that, on diluting 25 with water, depending on the quality of the water, poorly redispersible precipitates frequently occur, which precipitates lead to blockages of the spray nozzles.

It is an object of the present invention to make available oil suspension concentrates for the active substance diflufenican which do not exhibit the abovementioned 30 disadvantages.

This object is achieved by diflufenican-comprising oil suspension concentrates to which certain salts are added.

WO 2007/042138 2 PCT/EP2006/009261 The present invention accordingly relates to oil suspension concentrates which comprise a) diflufenican, b) one or more solvents from the group consisting of hydrocarbons and 5 vegetable oils, c) one or more nonsurfactant salts of polyvalent cations, the solubility product of these salts in water being higher than that of calcium sulfate, d) one or more surfactants, e) one or more thickeners.

The dispersions according to the invention show outstanding storage stability and also, on diluting with soft water, do not tend to form poorly redispersible precipitates.

The term "oil suspension concentrate" is understood to mean, within the meaning of 15 the present invention, a suspension concentrate based on the solvents of component b) (hydrocarbons and/or vegetable oils). In this connection, one or more active substances are suspended in the solvents. Additional active substances may be dissolved therein.

The herbicidal active substance diflufenican a) is present in the oil suspension concentrate according to the invention in suspended form. This means that the main part (in % by weight) of diflufenican is present undissolved in finely divided form and a smaller part of diflufenican may be present dissolved. Preferably, diflufenican is suspended to more than 80% by weight, particularly preferably to more than 90% by 25 weight, in the solvents b), in each case based on the total amount of diflufenican in the oil suspension concentrate according to the invention.

The herbicidal active substance diflufenican present as component a) is known and commercially available (see, e.g., "The Pesticide Manual", 12th edition (2000), The 30 British Crop Protection Council, pages 296-297). Diflufenican is generally present in the oil suspension concentrate according to the invention in a proportion of 0.5 to 50% by weight, preferably 2.5 to 50% by weight, the indication "% by weight", here and in the whole of the description, unless otherwise defined, being in this connection based on the relative weight of the respective component based on the WO 2007/042138 3 PCT/EP2006/009261 total weight of the formulation.

In a preferred embodiment, these oil suspension concentrates comprise a) 0.5 to 50% of diflufenican, b) 5 to 80% of one or more solvents, c) 0.1 to 15% of one or more nonsurfactant salts of polyvalent cations, d) 1 to 50% of one or more surfactants, e) 0.1 to 5% of one or more thickeners, f) 0 to 25% of additional auxiliaries and additives.

In a particularly preferred embodiment, these oil suspension concentrates comprise a) 2.5 to 50% of diflufenican, b) 5 to 80% of one or more solvents, c) 0.1 to 15% of one or more nonsurfactant salts of polyvalent cations, 15 d) 1 to 50% of one or more surfactants, e) 0.1 to 5% of one or more thickeners, f) 0 to 25% of additional auxiliaries and additives, g) 0 to 50% of one or more additional agrochemical active substances other than a).

In a very particularly preferred embodiment, these oil suspension concentrates comprise a) 5 to 35% of diflufenican, b) 5 to 80% of one or more solvents, c) 0.5 to 15% of one or more nonsurfactant salts of polyvalent cations, d) 5 to 50% of one or more surfactants, e) 0.1 to 5% of one or more thickeners, f) 0 to 25% of additional auxiliaries and additives, g) 0 to 50% of one or more additional agrochemical active substances other than 30 a).

All % indications are percentages by weight.

The term "polyvalent cations" is to be understood as meaning cations carrying more 4 than one charge. Suitable cations are those of the metals of the second main group and subgroup and those of the third main group of the Periodic Table of the Elements. Particularly suitable are those of the alkaline earth metals, such as magnesium and calcium, in particular calcium.

One or more hydrocarbons or one or more vegetable oils are present as component b) (see, e.g., Rompp Lexikon Chemie [Chemical Dictionary], 10th edition, volume 3, page 2202 (1997), Georg Thieme Verlag, Stuttgart/New York), preferably those which are liquid under standard conditions. The hydrocarbons can be acyclic (aliphatic) hydrocarbons or cyclic hydrocarbons, e.g. aromatic or alicyclic (cycloaliphatic) hydrocarbons.

Examples of hydrocarbons b) are: 1) aromatic hydrocarbons, e.g., • monoalkyl- or polyalkyl-substituted (e.g., substituted one, two or three times by (CrC-io)alkyl groups) aromatic compounds, e.g. benzenes, such as toluene, xylenes, mesitylene, ethylbenzene, or • hydrocarbons with condensed aromatic ring systems, such as naphthalenes, e.g. 1-methylnaphthalene, 2-methylnaphthalene or dimethylnaphthalene, or other condensed aromatic hydrocarbons, such as indane ortetralin, 2) cycloaliphatic hydrocarbons, e.g., saturated or unsaturated, optionally monoalkyl- or polyalkyl-substituted (e.g., substituted one, two or three times by (CrCio)alkyl groups) cycloaliphatic compounds, such as cycloalkanes, cycloalkenes or cycloalkynes, e.g. cyclohexane or methylcyclopentane, 3) aliphatic hydrocarbons, e.g., linear or branched, saturated or unsaturated aliphatic compounds, preferably C5-C16 -aliphatic compounds, e.g. alkanes, alkenes or alkynes, such as pentane, hexane, octane, 2-methylbutane or 2,2,4-trimethylpentane.

Mixtures of one or more aromatic hydrocarbons and/or of one or more cycloaliphatic hydrocarbons and/or of one or more aliphatic hydrocarbons can also be present as component b). Examples are mixtures of several aliphatic hydrocarbons, e.g. commercially available solvents of the Exxsol®D series, Isopar® series or bayol® series, e.g. Bayol®82 (ExxonMobil Chemicals), or of the Isane®IP series or Hydroseal®G series (TotalFinaElf), or mixtures of aromatic and aliphatic hydrocarbons, e.g. commercially available solvents of the Solvesso® series, e.g. Solvesso®100, Solvesso®150 or Solvesso®200 (ExxonMobil Chemicals), of the 5 Solvarex®/Solvaro® series (TotalFinaElf) or of the Caromax® series, e.g. Caromax®28 (Petrochem Cariess).

Of the hydrocarbons, aliphatic hydrocarbons are preferred, in particular saturated aliphatic hydrocarbons, such as C5-Ci6-alkanes, e.g. from the Bayol® series.

Suitable vegetable oils are generally known and commercially available. The term "vegetable oils" is to be understood as meaning, within the meaning of the present invention, e.g., oils from oleaginous plant species, such as soybean oil, rapeseed oil, corn oil, sunflower oil, cottonseed oil, linseed oil, coconut oil, palm oil, thistle oil, 15 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.

Examples of vegetable oils are Ci0-C22-fatty acid esters of glycerol or glycol with Cio-C22-fatty acids, or Ci-C2o-alkyl Cio-C22-fatty acid esters, such as those which can be obtained, e.g., by transesterification of the abovementioned glycerol or glycol r Cio-C22-fatty acid esters with Ci-C2o-alcohols (e.g., methanol, ethanol, propanol or butanol). The transesterification can be carried out according to known methods, 25 such as those which are described, e.g., in Rompp Chemie Lexikon [Chemical Dictionary], 9th edition, volume 2, page 1343, Thieme Verlag, Stuttgart.

The vegetable oils can be present in the oil suspension concentrates according to the invention, e.g., in the form of commercially available vegetable oils, in particular 30 rapeseed oils, such as rapeseed oil methyl ester, e.g. Phytorob®B (Novance, France), Edenor® MESU and Agnique®ME series (Cognis, Germany), Radia® series (ICI), Prilube® series (Petrofina), or biodiesel or in the form of commercially available formulation additives comprising vegetable oils, in particular those based on rapeseed oils, such as rapeseed oil methyl ester, e.g. Hasten® (Victorian Chemical WO 2007/042138 6 PCT/EP2006/009261 Company, Australia, hereinafter referred to as Hasten, main constituent: rapeseed oil ethyl ester), Actirob®B (Novance, France, hereinafter referred to as ActirobB, main constituent: rapeseed oil methyl ester), Rako-Binol® (Bayer AG, Germany, hereinafter referred to as Rako-Binol, main constituent: rapeseed oil), Renol® 5 (Stefes, Germany, hereinafter referred to as Renol, vegetable oil constituent: rapeseed oil methyl ester) or Stefes Mero® (Stefes, Germany, hereinafter referred to as Mero, main constituent: rapeseed oil methyl ester).

Of the vegetable oils, rapeseed oil methyl ester is preferred. 1° Examples of synthetic fatty acid esters are, e.g., those derived from fatty acids having an odd number of carbon atoms, such as Cn-C2i-fatty acid esters.

Suitable nonsurfactant salts c) of polyvalent cations having a higher solubility product in water than that of calcium sulfate are, for example, the alkylcarboxylates, fluorides, chlorides, nitrates, nitrites, hydrogencarbonates or carbonates of calcium and magnesium. Particularly suitable are calcium acetate, calcium formate, calcium propionate, calcium fluoride, calcium chloride, calcium nitrate, calcium nitrite, calcium hydrogencarbonate, calcium carbonate, magnesium acetate, magnesium formate, magnesium propionate, magnesium fluoride, magnesium chloride, magnesium nitrate, magnesium nitrite, magnesium hydrogencarbonate and magnesium carbonate. Very particularly suitable are calcium acetate, calcium formate, calcium propionate and calcium chloride.

Suitable surfactants d) are, for example, nonaromatic-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, sulfated, sulfonated or phosphated, and/or aromatic-based surfactants, e.g. benzenes or phenols substituted with one or more alkyl groups and subsequently derivatized, e.g. alkoxylated, sulfated, sulfonated or phosphated. The surfactants d) are generally soluble in the solvent phase and are suitable for emulsifying or dispersing this, together with active substances dissolved therein, on 7 PCT/E P2006/009261 diluting with water (for the spray mixture). Mixtures of nonaromatic and aromatic surfactants are also suitable.

Examples of surfactants d) are listed below, in which EO is ethylene oxide units, PO 5 is propylene oxide units and BO is butylene oxide units: d1) C-io-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 10 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 013 products from Condea, Dehypon® products from Henkel, Ethylan® products from Akzo-Nobel, such as Ethylan CD 120. d2) Anionic derivatives of the products described under b1) 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® products from Clariant. 20 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 CrCg-alcohols, such as Atlox®5000 from Uniquema or Hoe®S3510 from Clariant. d3) 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 30 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 a-sulfofatty acid esters, as available from Henkel.

WO 2007/042138 8 PCT/EP2006/009261 d4) 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. d5) 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. d6) Alkanesulfonates, paraffinsulfonates and olefinsulfonates, such as Netzer IS®, Hoe®S1728, Hostapur®OS, Hostapur®SAS from Clariant. d7) 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. d8) 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. d9) 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). d10) 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. d11) Surface-active sulfonamides, e.g. from Bayer. d12) Surface-active polyacrylic and polymethacrylic derivatives, such as the Sokalan® products from BASF. d13) Surface-active polyamides, such as modified gelatin or derivatized polyaspartic acid from Bayer and the derivatives thereof. d14) Surface-active polyvinyl compounds, such as modified polyvinylpyrrolidone, WO 2007/042138 9 PCT/EP2006/009261 such as the Luviskol® products from BASF and the Agrimer® products from ISP, or derivatized po!y(vinyl acetate)s, such as the Mowilith® products from Clariant, or polyvinyl butyrate)s, such as the Lutonal® products from BASF, the Vinnapas® and the Pioloform® products from Wacker, or modified polyvinyl alcohol)s, such as the Mowiol® products from Clariant. d15) 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. d16) Surface-active derivatives of montan, polyethylene and polypropylene waxes, such as the Hoechst® waxes or the Licowet® products from Clariant. d17) Surface-active phosphonates and phosphinates, such as Fluowet® PL from Clariant. d18) Poly- or perhalogenated surfactants, such as, for example, Emulsogen® 1557 from Clariant. d19) Phenols, which may be alkoxylated, for example phenyl (C-i-C^alkyl ethers or (poly)alkoxylated phenols [= phenol (poly)alkylene glycol ethers], for example with 1 to 50 alkyieneoxy 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 alkyieneoxy 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 alkyieneoxy units in the polyalkyleneoxy part, preferably tristyrylphenol reacted with 1 to 50 mol of ethylene oxide. d20) Compounds which are formally the reaction products of the molecules described under b20) 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. d21) 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 5 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 alkyieneoxy units.

Examples of surfactants from the group of the nonaromatic-based surfactants are the surfactants of the abovementioned groups d1) to d18), preferably of the groups 15 d1), d2), d6) and d7).

Examples of surfactants from the group of the aromatic-based surfactants are the surfactants of the abovementioned groups d19)to d21), preferably phenol reacted with 4 to 10 mol of ethylene oxide, available commercially, for 20 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 (Hiils).

Preferred surfactants d) are, e.g., alkoxylated Cio-C24-alcohols (d1) and the anionic derivatives thereof (d2), such as sulfates, sulfonates and phosphates, alkoxylated vegetable oils (d3), alkoxylated phenols (d19) and the reaction products thereof with sulfuric acid or phosphoric acid (d20), and alkylbenzenesulfonates (d21). 11 The standard thickeners e) and also auxiliaries and additives f) present in the oil suspension concentrates according to the invention are known to a person skilled in the art and are, for example, described in standard works: McCutcheon's 5 "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. Verlagsgesellschaft, Stuttgart, 1976; Winnacker-Kuchler, "Chemische Technologie", volume 7, C. Hauser-Verlag, Munich, 4th edition, 1986; 10 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.

Suitable thickeners are, for example: 1) modified natural silicates, such as chemically modified bentonites, hectorites, attapulgites, montmorillonites, smectites or other silicate minerals, such as Bentone® (Elementis), Attagel® (Engelhard), Agsorb® (Oil-Dri Corporation) or Hectorite® (Akzo Nobel), preferably Bentone®, 2) synthetic silicates, such as silicates of the Sipernat®, Aerosil® or Durosil® series (Degussa), of the CAB-O-SIL® series (Cabot) or of the Van Gel series (R.T. Vanderbilt), 3) thickeners based on synthetic polymers, such as thickeners of the Thixin® or Thixatrol® series (Elementis), and also Rhodopol® (Rhodia) and Kelzan® S 25 (Kelco Corp.).

Examples of standard auxiliaries and additives f) which may also be present in the dispersions according to the invention are: thixotropic agents, wetting agents, antidrift agents, deposit builders, penetration agents, preservatives and antifreeze 30 agents, antioxidants, fillers, carriers, dyes, fragrances, antifoaming agents, fertilizers, adjuvants, evaporation inhibitors and agents which influence the pH and the viscosity.

Suitable antifreeze agents are those from the group of the ureas, diols and polyols, WO 2007/042138 12 PCT/EP2006/009261 such as ethylene glycol and propylene glycol. Suitable antifoaming agents are those based on silicones. Suitable structure-imparting substances are those from the group of the xanthans. Suitable preservatives, dyes and aromatic principles are known to a person skilled in the art.

The dispersions according to the invention can also comprise additional agrochemical active substances g), such as herbicides, fungicides, insecticides and safeners. These active substances are known to a person skilled in the art, for example from "The Pesticide Manual", 13th edition (2003), The British Crop 10 Protection Council. Preference is given to herbicides from the series of the sulfonylureas, such as iodosulfuron-methyl (A1) and the sodium salt thereof (A2), mesosulfuron-methyl (A3) and the sodium salt thereof (A4), foramsulfuron (A5) and the sodium salt thereof (A6), flucarbazone (A7) and the sodium salt thereof (A8), propoxycarbazone (A9) and the sodium salt thereof (A10), ethoxysulfuron (A11) and 15 the sodium salt thereof (A12), amidosulfuron (A13) and the sodium salt thereof (A14), and safeners, such as mefenpyr-diethyl (S1), N-({4-[(cyclopropy!amino)carbonyl]phenyl}sulfonyl)-2-methoxybenzamide (S2), isoxadifen-ethyl (S3) and cloquintocet-mexyl (S4).

N-({4-[(Cyclopropylamino)carbonyl]phenyl}sulfonyl)-2-methoxybenzamide (S2) is 20 known, for example, from WO 99/16744.

Mention may be made, as particularly preferred examples, of oil suspension concentrates according to the invention which comprise the components mentioned below, without the invention being limited thereby. In this connection, Bayol is a 25 solvent from the Bayol® series, preferably Bayol®82 or Bayol®85. DFF is diflufenican. RME is rapeseed oil methyl ester.

DFF + Bayol®82 + RME + A1 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A2 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A3 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A4 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A5 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A6 + calcium formate + Bentone 34; 13 DFF + Bayol®82 + RME + A7 + calcium formate + Bentone 34; DFF + Bayo!®82 + RME + A8 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A9 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A10 + calcium formate + Bentone 34; 5 DFF + Bayol®82 + RME + A11 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A12 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A13 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A14 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A1 + S1 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A1 + S2 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A1 + S3 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A1 + S4 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A2 + S1 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A2 + S2 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A2 + S3 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A2 + S4 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A3 + S1 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A3 + S2 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A3 + S3 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A3 + S4 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A4 + S1 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A4 + S2 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A4 + S3 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A4 + S4 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A5 + S1 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A5 + S2 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A5 + S3 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A5 + S4 + calcium formate + Bentone 34; 14 DFF + Bayol®82 + RME + A6 + S1 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A6 + S2 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A6 + S3 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A6 + S4 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A7 + S1 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A7 + S2 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A7 + S3 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A7 + S4 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A8 + S1 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A8 + S2 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A8 + S3 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A8 + S4 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A9 + S1 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A9 + S2 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A9 + S3 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A9 + S4 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A10 + S1 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A10 + S2 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A10 + S3 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A10 + S4 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A11 + S1 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A11 + S2 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A11 + S3 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A11 + S4 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A12 + S1 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A12 + S2 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A12 + S3 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A12 + S4 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A13 + S1 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A13 + S2 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A13 + S3 + calcium formate + Bentone 34; 5 DFF + Bayol®82 + RME + A13 + S4 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A14 + S1 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A14 + S2 + calcium formate + Bentone 34; DFF + Bayol®82 + RME + A14 + S3 + calcium formate + Bentone 34; 10 DFF + Bayol®82 + RME + A14 + S4 + Calcium formate + Bentone 34.

The oil suspension concentrates according to the invention can be prepared by known processes, e.g. by mixing the components. Thus, e.g., the component b) can be introduced and the additional components a), d), c), e), f) and/org) can be added. 15 Before addition of the other components, the component b) can optionally also be mixed with a thickener. The oil suspension obtained can subsequently, optionally after premilling, be subjected to fine milling.

Standard mixing devices, which are optionally temperature-controlled, can be used 20 for the preparation of the mixtures. High pressure homogenizers or mills operating according to the rotor-stator principle, e.g., can be used for the premilling, such as Ultra-Turrax homogenizers, e.g. from IKA, or toothed colloid mills, e.g. from Puck. Bead mills operating batchwise, e.g. from Drais, or bead mills operating continuously, e.g. from Bachofen, e.g., can be used for the fine milling. The 25 preparation process can be adjusted according to the properties of the components used and also processing and safety requirements and for reasons of costs, and may optionally dispense with premilling or even with fine milling.

The components a) to g) used for the preparation may comprise water as a minor 30 constituent, which water is reencountered in the oil suspension concentrates according to the invention. The oil suspension concentrates according to the invention may accordingly comprise small amounts of water, generally from 0 to 5% by weight. 16 For use, the oil suspension concentrates according to the invention can optionally be diluted in the usual way, e.g. using water, e.g. to give emulsions, suspensions, suspoemulsions or dispersions. It can be advantageous to add, to spray mixtures obtained, additional agrochemical active substances (e.g., tank mix partners in the 5 form of appropriate formulations) and/or auxiliaries and additives standard for application, e.g. self-emulsifying oils, such as vegetable oils or paraffin oils, and/or fertilizers. Accordingly, another subject matter of the present invention is such liquid herbicidal compositions which can be obtained by diluting the oil suspension concentrates according to the invention.

The herbicidal compositions according to the invention (subsequently always also comprising the oil suspension concentrates 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 15 sprout from rhizomes, root stocks 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.

Specifically, mention may be made, by way of example, of some representatives of the mono- and dicotyledonous weed flora which can be controlled by the herbicidal 20 compositions according to the invention, without the designation resulting in a limitation to certain species.

In the case of the monocotyledonous weed species, Apera spica venti, Avena spp., Alopecurus spp., Brachiaria spp., Digitaria spp., Lolium spp., Echinochloa spp., 25 Panicum spp., Phalaris spp., Poa spp., Setaria spp. and also Bromus spp., such as Bromus catharticus, Bromus secalinus, Bromus erectus, Bromus tectorum and Bromus japonicus, and Cyperus species from the group of the annuals and, in the case of the perennial species, Agropyron, Cynodon, Imperata and also Sorghum and even perennial Cyperus species, e.g., are successfully included.

With dicotyledonous weed species, the spectrum of activity applies to species such as, e.g., Abutilon spp., Amaranthus spp., Chenopodium spp., Chrysanthemum spp., Galium spp., such as Galium aparine, Ipomoea spp., Kochia spp., Lamium spp., Matricaria spp., Pharbitis spp., Polygonum spp., Sida spp., Sinapis spp., Solanum 17 spp., Stellaria spp., Veronica spp. and Viola spp., Xanthium spp., in the case of the annuals, and Convolvulus, Cirsium, Rumex and Artemisia with the perennial weeds.

Harmful plants occurring under the specific cultivation conditions in rice, such as, 5 e.g., Echinochloa, Sagittaria, Alisma, Eleocharis, Scirpus and Cyperus, are likewise combated in an outstanding fashion by the compositions according to the invention.

If the herbicidal compositions according to the invention are applied to the soil surface before germination, then either the emergence of the weed seedlings is 10 completely prevented or the weeds grow until they have reached the cotyledon stage but then their growth ceases and finally, after 3 to 4 weeks have elapsed, they completely die.

On application of the herbicidal compositions according to the invention to the green 15 parts of the plants in the postemergence method, a drastic halt in growth likewise occurs very quickly after the treatment and the weed plants stay in the growth stage present at the time of application or completely die after a certain time, so that in this way competition by weeds, which is harmful for the crop plants, is eliminated very early and with lasting effect.

The herbicidal compositions according to the invention are distinguished by a rapidly commencing and longlasting herbicidal action. The resistance to rain of the active substances in the herbicidal compositions according to the invention is generally good. A particular advantage is crucially that the dosages of herbicidal compounds 25 which are used in the herbicidal compositions and which are effective can be adjusted to such a low value that their soil action is optimally low. Accordingly, not only is their use finally possible in sensitive crops but groundwater contamination is virtually avoided. A substantial reduction in the amount of the active substances which has to be expended is made possible by the active substance combination 30 according to the invention.

The properties and advantages mentioned are of use in the practical combating of weeds in order to keep agricultural crops free from undesirable competing plants and accordingly to safeguard and/or to increase the yields in terms of quality and 18 quantity. The technical standard is, with regard to the properties described, clearly exceeded by these new compositions.

Although the herbicidal compositions according to the invention exhibit an 5 outstanding herbicidal activity with regard to mono- and dicotyledonous weeds, crop plants of economically important crops, e.g. dicotyledonous crops, such as soya, cotton, rape, sugar beet, or gramineous crops, such as wheat, barley, rye, oats, millet, rice or corn, are only insignificantly damaged or completely undamaged. The present compounds, for these reasons, are very well suited to the selective 10 combating of undesirable plant growth in agriculturally useful plants or in ornamental plants.

In addition, the herbicidal compositions according to the invention exhibit outstanding growth-regulatory properties in crop plants. They intervene in a regulatory manner in 15 the plants' metabolism and can accordingly be used for the selective influencing of plant contents and for making it easier to harvest, such as, e.g., by controlling desiccation and stunted growth. Furthermore, they are also suitable for the general control and inhibition of undesirable vegetative growth, without in this connection killing the plants. Inhibition of vegetative growth plays a major role in many mono-20 and dicotyledonous crops since lodging can be reduced or completely prevented through this.

Because of their herbicidal and plant-growth-regulatory properties, the herbicidal compositions according to the invention can also be used for combating harmful 25 plants in crops of known genetically modified plants or genetically modified plants still to be developed. The transgenic plants are generally distinguished by particular advantageous properties, for example by resistance to certain pesticides, mainly certain herbicides, resistance to plant diseases or causative agents of plant diseases, such as certain insects or microorganisms, such as fungi, bacteria or 30 viruses. Other particular properties relate, e.g., to the harvested crops with regard to amount, quality, storability, composition and special ingredients. Thus, transgenic plants with increased starch content or modified quality of the starch or those with a different fatty acid composition of the harvested crops are known. 19 Preference is given to the use of the compositions according to the invention in economically important transgenic crops of useful and ornamental plants, e.g. of gramineous crops, such as wheat, barley, rye, oats, millet, rice and corn, or also crops of sugar beet, cotton, soya, rape, potato, tomato, peas and other kinds of 5 vegetable. Preferably, the compositions according to the invention can be used as herbicides in crops of useful plants which are resistant to the phytotoxic effects of the herbicides or which have been made resistant by genetic engineering.

When the herbicidal compositions according to the invention are used in transgenic 10 crops, effects often occur, in addition to the effects with regard to harmful plants to be observed in other crops, which are specific for the application in the respective transgenic crop, for example a modified or specially broadened weed spectrum which can be combated, modified amounts to be expended which can be used for the application, preferably good ability to be combined with the herbicides to which 15 the transgenic crop is resistant, and influencing of growth and yield of the transgenic crop plants.

Another subject matter of the present invention is furthermore a process for the combating of undesirable plant growth (e.g., harmful plants, such as 20 monocotyledonous or dicotyledonous weeds or undesirable crop plants), preferably in plant crops such as cereals (e.g., wheat, barley, rye, oats, rice, corn, millet), sugar beet, sugar cane, rape, cotton and soya, particularly preferably in monocotyledonous crops, such as cereals, e.g. wheat, barley, rye, oats, hybrids thereof, such as triticale, rice, corn and millet, one or more herbicidal compositions according to the 25 invention being applied to the plants (e.g., harmful plants), plant parts, the seed (e.g., plant seeds) or the area on which the plants are growing (e.g., the area under cultivation).

The plant crops can also be modified by genetic engineering or obtained by mutation 30 selection and are preferably tolerant to acetolactate synthase (ALS) inhibitors.

The oil suspension concentrates of the present invention exhibit an outstanding chemical stability during preparation and storage and are in particular also suitable for combinations of active substances with different physicochemical properties. In addition, the oil suspension concentrates exhibit outstanding physical stability, good applicability and user friendliness, and high biological effectiveness and selectivity.

The following comparative example is intended to illustrate the invention without 5 having a limiting nature.

Explanation: Bentone® 34 = Modified sheet silicate, Elementis Edenor® MESU = Rapeseed oil methyl ester, Cognis Emulsogen® EL-400 = Polyethoxylated castor oil with 40 ethylene oxide units, Clariant Triton® GR-7M E = Di(2-ethylhexyl) sulfosuccinate, sodium salt, in aromatic solvent, Dow Chemicals Bayol® 82 = Paraffin oil (Exxon) Genapol® X060 methyl ether = Isotridecyl alcohol with 6 ethylene oxide units, end- closed with methyl (Clariant) Exemplary embodiment 1 according to the invention: a) 14.85% Diflufenican b) 6.00% Edenor ME SU b) 0.20% Propylene carbonate b) 33.50% Bayol 82 c) 3.50% Calcium formate d) 19.80% Genapol X 060 (methyl ether) d) .00% Triton GR-7M E d) .00% Emulsogen EL 400 e) 2.00% Bentone 34 f) 0.15% Sodium carbonate 33.5 g of Bayol® 82 were introduced into a vessel and 2.0 g of Bentone® 34 were added. After mixing with an Ultra-Turrax®, 0.2 g of propylene carbonate was added and brought to the gelled state using the Ultra-Turrax® at high shear forces. 6 g of Edenor® MESU were then added and again incorporated using high shear forces. Subsequently, 15 g of Triton® GR7ME and 5 g of Emulsogen® EL400 were added 21 and again incorporated using the Ultra-Turrax®. 19.8 g of Genapol® X 060 methyl ether, 0.15 g of sodium carbonate, 3.5 g of calcium formate and then premilled diflufenican were subsequently added portionwise while mixing with the Ultra-Turrax® until completely incorporated. An oil suspension concentrate was obtained 5 and was subsequently run through a Dynomill® mill with a rotational speed of ca. 3000 rpm and an outlet temperature of 25-30°C. After milling, the oil suspension concentrate was subsequently stirred for 20 minutes and then filled to containers.

Comparative example 2 (without calcium formate): a) 14.85% Diflufenican b) 6.00% Edenor ME SU b) 0.20% Propylene carbonate b) 37.00% Bayol 82 d) 19.80% Genapol X 060 (methyl ether) d) .00% Triton GR-7M E d) .00% Emulsogen EL 400 e) 2.00% Bentone 34 f) 0.15% Sodium carbonate The oil suspension concentrate prepared for comparison purposes was prepared analogously to example 1 but 37.0 g of Bayol 82 and no calcium formate were used.

Application test: Redispersibility Water with a defined water hardness (20 and 100 ppm; prepared from CIPAC 25 standard water D (342 ppm) by diluting with deionized water) and the oil suspension concentrate 1 according to the invention or the comparative example 2 are used to prepare, at ambient temperature, 250 ml each of a 0.34% or 1.22% mixture in a 250 ml graduated measuring cylinder.

The mixtures are mixed thoroughly by 30 manual inversions (1 inversion = rotation 30 by 180° and back). The mixtures are subsequently left standing for 24 h. 30 inversions are now again carried out and, after 30 min, the mixtures are rated for sediment formation: in the case of the oil suspension concentrate 1 according to the invention, no settling (sediment formation) is observed, i.e. the oil suspension concentrate 1 according to the invention form is completely redispersible. On the

Claims (26)

WO 2007/042138 22 PCT/EP2006/009261 other hand, in the case of comparative example 2, significant sediment formation occurs, i.e. comparative example 2 is not completely redispersible. Formulation according to example Concentration Water hardness Result 1 0.34 % 20 redispersible 2 0.34 % 20 not redispersible 1 0.34 % 100 redispersible 2 0.34 % 100 not redispersible 1 1.22 % 20 redispersible 2 1.22 % 20 not redispersible 1 1.22 % 100 redispersible 2 1.22% 100 not redispersible Received at IPONZ on 20-Apr-2011 23 What is claimed is:

1. An oil suspension concentrate which comprises: a) diflufenican as the sole herbicidally active ingredient, b) one or more solvents from the group consisting of hydrocarbons and vegetable oils, 5 c) one or more nonsurfactant salts of polyvalent cations, the solubility product of these salts in water being higher than that of calcium sulfate, d) one or more surfactants, and e) one or more thickeners. 10

2. An oil suspension concentrate as claimed in claim 1, which comprises, as component b), one or more solvents from the group consisting of acyclic hydrocarbons, cyclic hydrocarbons and vegetable oils.

3. An oil suspension concentrate as claimed in claim 1 or 2, which comprises 15 a) 0.5 to 50% of diflufenican, b) 5 to 80% of one or more solvents, c) 0.1 to 15% of one or more nonsurfactant salts of polyvalent cations, d) 1 to 50% of one or more surfactants, e) 0.1 to 5% of one or more thickeners, 20 f) 0 to 25% of additional auxiliaries and additives.

4. An oil suspension concentrate as claimed in any one of claims 1 to 3, which comprises a) 2.5 to 50% of diflufenican, 25 b) 5 to 80% of one or more solvents, c) 0.1 to 15% of one or more nonsurfactant salts of polyvalent cations, d) 1 to 50% of one or more surfactants, e) 0.1 to 5% of one or more thickeners, and f) 0 to 25% of additional auxiliaries and additives. 30

5. An oil suspension concentrate as claimed in any one of claims 1 to 4, which comprises a) 5 to 35% of diflufenican, b) 5 to 80% of one or more solvents, 35 c) 0.5 to 15% of one or more nonsurfactant salts of polyvalent cations, d) 5 to 50% of one or more surfactants, e) 0.1 to 5% of one or more thickeners, Received at IPONZ on 20-Apr-2011 24 f) 0 to 25% of additional auxiliaries and additives.

6. An oil suspension concentrate as claimed in any one of claims 1 to 5, wherein the nonsurfactant salts of polyvalent cations are selected from the group consisting of 5 alkylcarboxylates, fluorides, chlorides, nitrates, nitrites, hydrogencarbonates or carbonates of calcium and magnesium.

7. An oil suspension concentrate as claimed in claim 6, wherein the nonsurfactant salts of polyvalent cations are selected from the group consisting of calcium acetate, calcium 10 formate, calcium propionate, calcium fluoride, calcium chloride, calcium nitrate, calcium nitrite, calcium hydrogencarbonate, calcium carbonate, magnesium acetate, magnesium formate, magnesium propionate, magnesium fluoride, magnesium chloride, magnesium nitrate, magnesium nitrite, magnesium hydrogencarbonate and magnesium carbonate. 15

8. An oil suspension concentrate as claimed in claim 7, wherein the nonsurfactant salts of polyvalent cations are selected from the group consisting of calcium acetate, calcium formate, calcium propionate and calcium chloride.

9. A process for the preparation of an oil suspension concentrate as claimed in any one 20 of claims 1 to 8, which comprises mixing and optionally milling the components.

10. A process for combating undesirable plant growth, which comprises applying an effective amount of an oil suspension concentrate as claimed in any one of claims 1 to 8 to the plants, parts of the plants, the seed or the area on which plants grow. 25

11. The use of an oil suspension concentrate as claimed in any one of claims 1 to 8 for combating undesirable plant growth.

12. The use of an oil suspension concentrate as claimed in any one of claims 1 to 8 for 30 preparing a herbicidal composition.

13. The use as claimed in claim 12, the herbicidal composition being a suspension, suspoemulsion or dispersion. 35 14. A liquid herbicidal composition, which can be obtained by diluting an oil suspension concentrate as claimed in any one of claims 1 to 8.

14. Received at IPONZ on 20-Apr-2011 25

15. A liquid herbicidal composition as claimed in claim 14, the herbicidal composition being an emulsion, suspension, suspoemulsion or dispersion.

16. A liquid herbicidal composition, which comprises 5 a) diflufenican as the sole herbicidally active ingredient, b) one or more solvents from the group consisting of hydrocarbons and vegetable oils, c) one or more nonsurfactant salts of polyvalent cations, the solubility product of these salts in water being higher than that of calcium sulfate, d) one or more surfactants, 10 e) one or more thickeners.

17. A liquid herbicidal composition as claimed in any one of claims 14 to 16, which additionally comprises water. 15

18. A process for combating undesirable plant growth, which comprises applying an effective amount of a herbicidal composition as claimed in any one of claims 14 to 17 to the plants, parts of the plants, the seed or the area on which plants grow.

19. The use of a herbicidal composition as claimed in any one of claims 14 to 17 for 20 combating undesirable plant growth.

20. An oil suspension concentrate according to claim 1, substantially as herein described or exemplified. 25

21. A process according to claim 9, substantially as herein described or exemplified.

22. A process according to claim 10, substantially as herein described or exemplified.

23. A use according to claim 11, substantially as herein described or exemplified. 30

24. A use according to claim 12, substantially as herein described or exemplified.

25. A liquid herbiical composition according to claim 14, substantially as herein described or exemplified. 35

26. A liquid herbiical composition according to claim 16, substantially as herein described or exemplified.