EP1282355A2 - Combinaisons de produits phytosanitaires avec des polymeres cationiques - Google Patents

Combinaisons de produits phytosanitaires avec des polymeres cationiques

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Publication number
EP1282355A2
EP1282355A2 EP01945089A EP01945089A EP1282355A2 EP 1282355 A2 EP1282355 A2 EP 1282355A2 EP 01945089 A EP01945089 A EP 01945089A EP 01945089 A EP01945089 A EP 01945089A EP 1282355 A2 EP1282355 A2 EP 1282355A2
Authority
EP
European Patent Office
Prior art keywords
alkyl
polymer
group
combination according
combination
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP01945089A
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German (de)
English (en)
Inventor
Gerhard Frisch
Julio Martinez De Una
Udo Bickers
Erwin Hacker
Hans Philipp Huff
Gerhard Schnabel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer CropScience AG
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Bayer CropScience AG
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Filing date
Publication date
Application filed by Bayer CropScience AG filed Critical Bayer CropScience AG
Publication of EP1282355A2 publication Critical patent/EP1282355A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02—Amines; Quaternary ammonium compounds
    • A01N33/12—Quaternary ammonium compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/32—Ingredients for reducing the noxious effect of the active substances to organisms other than pests, e.g. toxicity reducing compositions, self-destructing compositions
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
    • A01N37/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system having at least one carboxylic group or a thio analogue, or a derivative thereof, and one oxygen or sulfur atom attached to the same aromatic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof

Definitions

  • the present invention relates to combinations of crop protection active ingredients with such polymeric cationic auxiliaries which enable controlled release (“controUed release") of an active ingredient.
  • the combinations are able to increase culture selectivities and reduce antagonisms and give particularly good results with herbicides, in particular with mixtures of herbicides with growth regulators and safeners.
  • split application or an overdose of the antagonized active ingredient was recommended in the case of an antagonistic reduction.
  • a split application can often also be used, alternatively there is the possibility of underdosing.
  • all of these approaches are unattractive and uneconomical for various reasons.
  • the active substance formulation must be applied at least twice; that is time and labor intensive. If an active ingredient is overdosed, additional costs are incurred. In the event of an underdosage, there is a risk of reduced yield due to insufficient control of harmful organisms.
  • US 5,428,000 discloses active ingredient compositions which have a herbicide for broad-leaved weeds and a herbicide for narrow-leaved weeds.
  • the herbicide for narrow-leaf weeds is charge-neutral
  • the herbicide for broad-leaf weeds is anionic in nature and is present in combination with a hydrophilic polymer, which is a copolymer formed from an ammonium-containing compound and a non-ammonium-containing compound.
  • the ammonium-containing compound is generally derived from aromatic and non-aromatic nitrogen heterocycles, ammonium derivatives of acrylic acid and benzylammonium compounds.
  • the polymers are therefore exclusively polymers which do not contain the quaternary nitrogen atom in the main polymer chain.
  • the hydrophilic polymers used are exclusively copolymers of the type shown above. Sethoxydim, alloxidim, fluazifop, quizalofop or fenoxaprop are used as herbicides for narrow-leaf weeds, for broad-leaf weeds the use of bentazone, imazaquin, acifluorfen, fomesafen, chlorimuron, imazethapyr, thifensulfuron and 2,4-D is described.
  • This object is achieved by a combination of at least one anionic agrochemical active ingredient, in particular a herbicide, with a cationic polymer with the formation of electrostatic interaction between these components for the controlled release of active ingredient, characterized in that this polymer is wholly or at least partially composed of monomers with cationic Groups are built up, which in particular have quaternary nitrogen atoms, the proportion of monomer units, which have no cationic groups, in particular no quaternary nitrogen atoms, is at most 90% by weight, preferably at most 50% by weight, and the molecular weight M N of the polymers at values ⁇ 10,000 is in the case that the quaternary nitrogen atoms are arranged exclusively outside the main chain of the polymer.
  • Another object of the present invention is the application of the combination according to the invention for controlling unwanted harmful organisms, in particular undesired grasses and weeds.
  • polymer in the present invention encompasses both oligomers and polymers of the corresponding monomers, ie molecules with a low degree of polymerization as well as those with a high degree of polymerization.
  • the molecular weights M N of the compounds which can be used as polymers according to the invention are at least 500.
  • the agrochemical active ingredient enters into an attractive, reversible intermolecular interaction with the polymer in whole or in part. These interactions are electrostatic interactions.
  • the agrochemical active ingredient can be an active ingredient that has partial selectivity. Alternatively, an active substance which has an antagonistic effect in an intended mixture of active substances can also be brought into interaction with the polymer. Two or more active ingredients in one active ingredient can also be incorporated into such an interaction.
  • the polymers used according to the invention can also be surface-active substances. Due to their physicochemical properties, they can be dispersed, emulsified or dissolved in water or organic solvents. The polymers can preferably be dissolved, the preferred solvents being polar protic and polar aprotic organic solvents and water. It is most preferred if the polymers dissolve in water.
  • Polymers suitable for the combinations according to the invention preferably have the property of penetrating the harmful organism only slowly or not at all, which generally occurs, for example, via the leaf or the root.
  • the absorption or penetration rate of the polymers used according to the invention is between ⁇ 0.01% and 80%, preferably well below 50% in 24 hours.
  • the polymers used according to the invention have suitable stable cationic groups, which are preferably selected from the group of the so-called onium functions.
  • Suitable onium groups include phosphonium, ammonium and sulfonium groups.
  • Ammonium functions are preferred according to the invention. These have nitrogen atoms with a positive charge, generally quaternary nitrogen atoms. These are understood to mean nitrogen atoms with a total of four valence bonds to the connected atoms, for example four single bonds, but also two single and one double bond.
  • the average molecular weight MN as is also to be understood as such above, of the polymers used according to the invention is about> 500, preferably about 1,000 to 1,000,000.
  • These polymers can be homopolymers or copolymers and are prepared in conventional polymerization reactions, for example polyadditions, polycondensation, radical and ionic polymerizations and metal complex-catalyzed polymerizations.
  • Modified natural polymers for example oligo- and polypeptides and oligo- and polysaccharides, are also suitable.
  • the quaternary cationic nitrogen atom in the polymers containing ammonium groups which are preferably used according to the invention can be located outside the main polymer chain, ie outside the chain which forms the backbone of the molecule.
  • An example of a preferred polymer of this type are polymers which have monomer units of the formula (I) below.
  • R and R 2 are independently selected from the group consisting of hydrogen, linear and branched d-C ⁇ -alkyl radicals, linear and branched Ci-Cs-alkylol radicals, cyclopentyl and cyclohexyl radicals.
  • Another preferred polymer of this type contains monomer units shown in the following formula (II).
  • n is an integer from 1-10, preferably 2-5, and the substituents R 1 to R 3 are independently selected from the group consisting of hydrogen, linear and branched Ci-C ⁇ -alkyl groups, linear and branched d-Cs alkylol groups, cyclopentyl and cyclohexyl groups.
  • the quaternary cationic nitrogen atom can also be attached in the main chain of the polymer.
  • Such polymers are preferred in the context of the present invention.
  • Main chains are, for example, those of the following formula (III)
  • n is an integer from 3 to 50, preferably an average of 6,
  • n is an integer from 10 to 200, preferably 100 on average.
  • Mirapol ® for example as Mirapol WT ® (Formula III) and Mirapol AD-1 (Formula IV).
  • X is an anion of an acid of inorganic or organic origin, and examples thereof include carboxylates, e.g. acetate, sulfate, carbonate, sulfonate and halide.
  • carboxylates e.g. acetate, sulfate, carbonate, sulfonate and halide.
  • suitable polymers having cationic nitrogen atoms are known to a person skilled in the art. Generally, commercially available products will be used.
  • Copolymers of monomers containing quaternary nitrogen atoms with monomers containing no quaternary nitrogen atoms can also be used as polymers.
  • the proportion of monomers which do not contain quaternary nitrogen atoms is at most 90% by weight, preferably at most 50% by weight, of the polymer.
  • the molecular weight MN of this polymer is ⁇ 10,000.
  • the polymer in which the cationic nitrogen atoms are located exclusively outside the main polymer chain, it is preferred if the polymer consists exclusively of monomers which have quaternary nitrogen atoms, for example exclusively of monomer units of the formula (I) or those of the formula (II) or copolymers thereof.
  • Agrochemical active substances suitable for the present invention have functional groups which are negatively charged or carry a negative partial charge and can be converted into anionic functions.
  • the active ingredients can already be present as anions before formulation. However, it is also possible for these active substances to be converted into anions only during the formulation or preparation of the so-called tank mixture, for example by abstraction of an acidic hydrogen atom during these processes.
  • Suitable anionic active ingredients for use in the combinations according to the invention are preferably the agrochemical active ingredients belonging to the group which include herbicides, fungicides, insecticides, growth regulators, safeners, molluscicides, acaricides and nematicides.
  • Herbicides particularly acetolactate synthase (ALS) inhibitors such as sulfonylureas and their salts, hydroxybenzonitriles such as bromoxynil and loxynil and their salts, bentazone, so-called aryloxyalkylcarboxylic acid and their derivatives such as esters or salts, are particularly suitable for combination with the cationic polymers used according to the invention and esters such as MCPA, 2,4-D, CMPP, 2,4-DP, 2,4-DB, so-called (hetero) aryloxy-aryloxyalkylcarboxylic acids and their salts and esters, such as, for example, fenoxaprop-p-ethyl, or their salts and esters, dichlofop-methyl, clodinafop-propargyl, fluazifop, HPPDO inhibitors or their salts such as, for example, mesotrione, sulcotrione; tri
  • M® is a suitable cation, preferably an ammonium ion containing an alkali metal or an optionally organic substituent, most preferably a Na, K, ammonium, tetralkylammonium, tetraalkylolammonium or mono-, di-, trialkylammonium ion,
  • R ' is hydrogen or a (-CC) -alkyl radical, preferably hydrogen or methyl
  • R is a radical which is selected from the group consisting of the compounds corresponding to the formulas (Va) to (Vf)
  • R 1 is selected from the group consisting of
  • Halogen preferably Cl or F
  • R 2 , R 3 , R 4 independently of one another H, CH 3 , -OH, -OtCrC-io-alkyl), -NH (C 1 -C ⁇ o-alkyl), -N (C ⁇ -C ⁇ 0 -alkyl) 2l NHCHO, -NHCO 2 (-CC 10 alkyl), -CH2NHSO2CH3, halogen, preferably F, Cl, Br or I, Het for a radical of the formula (Vg)
  • R 5 , R 6 independently of one another are halogen, preferably F or Cl, -O (-CC 4 -
  • Z represents N or a CH group.
  • the corresponding derivatives known to the person skilled in the art as suitable for use such as acids, esters or salts of the active substances, can of course also be used in all of the above-mentioned agrochemical active substances.
  • the combinations according to the invention allow a reduction in the phytotoxic potential of active substances and a suppression of the antagonization of other active substances in mixtures with these.
  • Active ingredients to be combined according to the invention can therefore be used together with other active ingredients or as the only active ingredient, optionally together with the usual additives and adjuvants. Examples of preferred combinations according to the invention are described below. In all of these combinations, the use of the active ingredients described above as particularly or most suitable is of course also preferred, even if this is not specifically mentioned.
  • the combinations according to the invention are produced by the customary processes known to a person skilled in the art. These are, for example, stirring, dissolving and / or grinding the components.
  • agrochemical active substances combined with the polymer used according to the invention can be formulated with other active substances, optionally also combined with polymers according to the present invention, to give mixtures which give advantageous results.
  • a preferred embodiment of the present invention is represented by combinations in which an agrochemical active substance, such as a herbicide, is wholly or partially combined with a cationic polymer according to the invention and additionally contains at least one further agrochemical active substance, such as a herbicide or safener.
  • herbicides are formulated with safeners and / or growth regulators in combination with the polymers used according to the invention, at least one of the agrochemical active compounds being wholly or partly combined with these polymers according to the invention.
  • Another preferred embodiment of the combination according to the invention consists of mixtures of one or more graminicides with one or more herbicides, which preferably act against dicotyledon weeds, at least one of the agrochemical active compounds being wholly or partly combined according to the invention.
  • one or more graminicides are mixed with a safener, at least one of the agrochemical active compounds having been wholly or partly combined according to the invention.
  • one or more herbicides with a very fast mechanism of action with one or more herbicides with a relatively slow mechanism of action, at least one of the agrochemical active compounds having been wholly or partly combined according to the invention.
  • acetolactate synthase inhibitors in particular sulfonylureas, according to the invention in whole or in part to increase the culture selectivity.
  • the weight ratio between polymer and anionic active substance or active substances is from 0.001: 1 to 1: 0.001, preferably 0.01: 1 up to 1: 0.01, most preferably 0.1: 1 to 1: 0.1.
  • adjuvants or adjuvant mixtures for example oils, solvents, surfactants or surfactant mixtures, is advantageous.
  • adjuvants are to be understood as meaning additives to active substance / polymer combinations which are not themselves active, but which strengthen the properties of the active substance.
  • Nonionic surfactants are suitable, for example those of the general formula RO (CH 2 CH 2 ⁇ ) n H, in which R is a (C- ⁇ o-C22) fatty alcohol, tristyrylphenol, tributylphenol, (C ⁇ -Ci 4 ) alkylphenol -, tridecyl alcohol, glyceride or castor oil-derived radical and n is an integer from 1 to 500, preferably from 3 to 200.
  • Block copolymers can be used based on ethylene oxide, propylene oxide and / or butylene oxide, for example, the compounds sold under the names Pluronics ® or Tetronics® ® by BASF AG.
  • Anionic or betaine surfactants can also be used.
  • anionic surfactants include Ca-dodecylbenzyl sulfonate, succinates, phosphated, sulfated and sulfonated nonionic surfactants, such as those of the type mentioned above, and sorbitates, these anionic compounds being neutralized with alkali, alkaline earth or ammonium ions.
  • Such surfactants are available under the name Genapol ® LRO (Clariant GmbH).
  • Betainic surfactants are available from Goldschmidt AG under the name Tegotain ® .
  • cationic surfactants for example those based on quaternary ammonium, phosphonium and tertiary sulfonium salts, for example Atlas ® G3634 A from Uniquema.
  • the amount of surfactant is from 10 to 2,000 g / ha, preferably from 50 to 2,000 g / ha.
  • nitrogen additions such as urea, ammonium nitrate, ammonium sulfate, ammonium hydrogen sulfate or mixtures thereof is often advantageous.
  • Polymers containing monomers of the formulas (I) - (IV) can be used together with acetolacetate synthase (ALS) inhibitors, preferably sulfonylureas of the formula (V), in order to increase the compatibility with crops, such as in crops of maize, wheat, barley, rice , Soy, sugar beet or cotton.
  • ALS acetolacetate synthase
  • the compatibility of the type iodosulfuron Mirapol ® can be at an expenditure of 1 to 10 g / ha by combination with polymers of Rhodia GmbH in a weight ratio of preferably from 0.1: 1 to 1: 0.1 in crops such as corn or wheat significantly increase.
  • a possible antagonistic effect of anionic agrochemical active substances in particular herbicides which act against weeds, such as, for example, sulfonylureas or their salts, hydroxybenzonitriles such as bromoxynil and their salts, loxynil and their salts, aryloxyalkylcarboxylic acids and their salts or bentazone on graminicides, for example fenoxaprop-p -ethyl, can be reduced or avoided by using polymers with cationic functional groups.
  • the simultaneous application leads from Fenoxyprop-p-ethyl (30-90 g / ha), bromoxynil-potassium (150-600 g / ha) and a polyanion, for example, Mirapol ® (50 to 5000 g / ha, preferably 50-2000 g / ha) for a significantly better grass control than a corresponding application without a polymer.
  • a polyanion for example, Mirapol ® (50 to 5000 g / ha, preferably 50-2000 g / ha) for a significantly better grass control than a corresponding application without a polymer.
  • Other substances that may optionally be present are safeners, other herbicides, Adjuvants such as Genapol ® LRO or fertilizers such as ammonium sulfate, ammonium hydrogen sulfate, urea or ammonium nitrate.
  • ALS inhibitors in particular sulfonylureas and their salts (for example iodosulfuron, metsulfuron or rimsulfuron) can be used with known polymers from the Mirapol ® series from Rhodia GmbH or the Genamin ® series from Clariant GmbH. Further substances which may optionally be present are safeners, other herbicides, adjuvants such as Genapol ® LRO or fertilizers such as ammonium sulfate, ammonium hydrogen sulfate, urea or ammonium nitrate.
  • ALS inhibitors in particular sulfonylureas and their salts (for example iodosulfuron, metsulfuron, rimsulfuron) for application with known polymers, for example the Mirapol ® series from Rhodia GmbH or the Genamin ® series from Clariant GmbH or comparable polymers and mixed with graminicides, for example fenoxaprop-p-ethyl.
  • known polymers for example the Mirapol ® series from Rhodia GmbH or the Genamin ® series from Clariant GmbH or comparable polymers and mixed with graminicides, for example fenoxaprop-p-ethyl.
  • safeners other herbicides
  • adjuvants such as Genapol ® LRO
  • fertilizers such as ammonium sulfate, ammonium hydrogen sulfate, urea or ammonium nitrate.
  • aryloxyalkyl carboxylic acids for example 2,4-D
  • the aryloxyalkyl carboxylic acids are combined for application with cationic polymers from the Mirapol ® series from Rhodia GmbH or the Genamin ® series from Clariant GmbH and then mixed with the graminicide, for example fenoxaprop-p-ethyl.
  • Further substances which may optionally be present are safeners, other herbicides, adjuvants such as Genapol ® LRO or fertilizers, such as ammonium sulfate, ammonium hydrogen sulfate, urea or ammonium nitrate.
  • Bromoxynil or loxynil or their salts can be combined for application with cationic polymers from the Mirapol ® series from Rhodia GmbH or the Genamin ® series from Clariant GmbH and with graminicides, for example fenoxaprop-p-ethyl, clodinafop-propargyl, clethodim or setoxidim Suppression of antagonistic interactions can be mixed.
  • Further substances which may optionally be present are safeners, other herbicides, adjuvants such as Genapol ® -LRO or fertilizers such as ammonium sulfate, ammonium hydrogen sulfate, urea or ammonium nitrate.
  • ALS inhibitors in particular sulfonylureas such as iodosulfuron, metsulfuron or rimsulfuron, with bromoxynil or its salts are combined for application with cationic polymers from the Mirapol series from Rhodia GmbH or the Genamin ® series from Clariant GmbH.
  • Mixtures of this combination with graminicides for example fenoxaprop-p-ethyl, clodinafop-propagyl or clethodim, are distinguished by a reduced antagonistic action.
  • ALS inhibitors in particular sulfonylureas such as, for example, iodosulfuron, metsulfuron or rimsulfuron, with so-called aryloxyalkylcarboxylic acids, for example 2,4-D, are for application with cationic polymers from the Mirapol ® series from Rhodia GmbH or the Genamin ® series from Clariant GmbH combined.
  • graminicides for example fenoxaprop-p-ethyl, diclofop-methyl, or clodinafop-propagyl are notable for a reduced antagonistic effect.
  • Further substances which may optionally be present are safeners, other herbicides, adjuvants such as Genapol ® LRO or fertilizers, such as ammonium sulfate, ammonium hydrogen sulfate, urea or ammonium nitrate.
  • the proportion of active ingredients in the different formulations can be varied within wide ranges.
  • the formulations contain about 0.01 to 95% by weight of active ingredients, about 90-10% by weight of liquid or solid carriers and optionally up to 50% by weight, preferably up to 30% by weight of surface-active substances, the Sum of these shares should result in 100%.
  • mixtures according to the invention with polymer, one or more active substances and the possible adjuvants and other auxiliaries can also be present as a separate tank mixture, in other formulations as well.
  • Formulation options include:
  • Spray powder (WP), water-soluble powder (SP), suspension concentrates (SC) based on oil or water, water-soluble concentrates (SL), emulsifiable concentrates (EC), micro and macro emulsions (EW / ME) such as oil-in-water and water-in-oil emulsions, sprayable solutions, suspension emulsions (SE), oil-miscible solutions, capsule suspensions (CS), dusts (DP), pickling agents, granules for spreading and soil application, granules (GR) in the form of micro , Spray, elevator and adsorption granules, water-dispersible granules (WDG), water-soluble granules (WSG), ULV formulations, microcapsules and waxes.
  • Formulation aids such as inert materials, antifreeze, thickeners, surfactants, solvents and other additives are also known and are described, for example, in: Watkins, “Handbook of Insecticide Dust Diluents and Carriers", 2 nd Ed., Darla ⁇ d Books, Caldwell NJ, HvOlphen, "Introduction to Clay Colloid Chemistry "; 2 nd Ed, J. Wiley & Sons, NY. . C. Marsden, “Solvents Guide”, 2nd Ed, Interscience, NY 1963; McCutcheon's
  • Wettable powders are uniformly dispersible in water and which, besides the combination of the invention as a diluent or inert substance, surfactants of ionic and / or nonionic type (wetting agents, dispersants), for example polyoxyethylated alkylphenols, polyoxyethylated fatty alcohols, polyoxyethylated fatty amines, fatty alcohol polyglycol ether, alkanesulfonates, alkylbenzenesulfonates, ligninsulfonate Sodium, 2,2'-dinaphthylmethane-6,6'-disulfonic acid sodium, dibutylnaphthalenesulfonic acid sodium or oleoylmethyl tauric acid sodium.
  • surfactants of ionic and / or nonionic type for example polyoxyethylated alkylphenols, polyoxyethylated fatty alcohols, polyoxyethylated fatty amines,
  • the active compounds are finely ground in conventional apparatus such as hammer mills, blower mills and air jet mills and mixed at the same time or subsequently with the formulation auxiliaries and the polymers used according to the invention.
  • Emulsifiable concentrates are obtained by dissolving the active ingredient in combination with polymer in an organic solvent, e.g. butanol, cyclohexanone, dimethylformamide, xylene or even higher-boiling aromatics or hydrocarbons or mixtures of the organic solvents with the addition of one or more ionic and / or nonionic surfactants (emulsifiers ) manufactured.
  • an organic solvent e.g. butanol, cyclohexanone, dimethylformamide, xylene or even higher-boiling aromatics or hydrocarbons or mixtures of the organic solvents with the addition of one or more ionic and / or nonionic surfactants (emulsifiers ) manufactured.
  • alkylarylsulfonic acid calcium salts such as Ca-dodecylbenzenesulfonate or nonionic emulsifiers such as alkylaryl polyglycol ethers which are different from para-alkylphenol ethoxylates, fatty acid polyglycol esters, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products,
  • Dusts are obtained by grinding the active ingredient in combination with polymers which can be used according to the invention with finely divided solid substances, e.g. Talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
  • polymers which can be used according to the invention with finely divided solid substances, e.g. Talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
  • Suspension concentrates can be based on water or oil. They can be prepared, for example, by wet grinding using commercially available bead mills and, if appropriate, addition of surfactants, as already mentioned above for the other types of formulation.
  • Emulsions e.g. Oil-in-water emulsions (EW) can be used, for example, with stirrers, colloid mills and / or static mixers using aqueous organic solvents and optionally surfactants, such as those e.g. already listed above for the other formulation types.
  • EW Oil-in-water emulsions
  • Granules can either be produced by spraying the active ingredient in combination with polymer usable according to the invention onto adsorbable, granulated inert material or by applying the combination by means of adhesives, for example sugars such as pentoses and hexoses or mineral oils, to the surface of carriers such as sand, kaolinites or granulated Inert material.
  • adhesives for example sugars such as pentoses and hexoses or mineral oils
  • Suitable active ingredients can also be granulated in combination with the polymer which can be used according to the invention in the manner customary for the production of fertilizer granules, if desired in mixtures with fertilizers.
  • Water-dispersible granules are generally produced using the customary methods, such as spray drying, fluidized bed granulation, plate granulation, mixing with high-speed mixers and extrusion without solid inert material.
  • formulations mentioned with the combinations according to the invention optionally contain the customary adhesives, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreeze and solvents, fillers, carriers and dyes, defoamers, evaporation inhibitors and the pH -Value and agents influencing viscosity.
  • mixtures with other pesticidally active substances such as herbicides, insecticides, fungicides, and also antidots or safeners, fertilizers and / or growth regulators can be prepared, e.g. in the form of a finished formulation or for use as tank mixes.
  • the combinations according to the invention have excellent effectiveness. In the case of combining herbicides with polymers to the Combinations according to the invention have excellent herbicidal activity against a broad spectrum of economically important mono- and dicotyledonous harmful plants. Perennial weeds that are difficult to control and that sprout from seeds or rhizomes, rhizomes or other permanent organs are also well captured by the active ingredient combinations. It does not matter whether combinations according to the invention are applied using the pre-sowing, pre-emergence or post-emergence method. The combinations according to the invention are preferably applied to above-ground parts of plants. The combinations according to the invention are also suitable for the dessication of crop plants such as potatoes, cotton and sunflower.
  • the combinations according to the invention can be used, for example, to control the following harmful plants:
  • the combinations according to the invention allow the control of otherwise resistant harmful plants in an excellent manner.
  • the combinations according to the invention can also be used to control harmful plants in crops of known or still to be developed genetically modified plants.
  • the transgenic plants are generally distinguished by special advantageous properties, for example resistance to certain pesticides, especially certain herbicides, resistance to plant diseases or pathogens of plant diseases such as certain insects or microorganisms such as fungi, bacteria or viruses.
  • Other special properties relate, for example, to the crop in terms of quantity, quality, storability, composition and special ingredients.
  • cereals such as wheat, barley, rye, oats, millet, rice, cassava and corn or also crops of sugar beet, cotton, soybeans, rapeseed, potatoes, tomatoes, peas and other vegetables.
  • the combinations according to the invention can preferably be used with herbicidal compositions, plant growth regulators and / or safeners in useful plant crops which are resistant to the phytotoxic effects of the herbicides or have been made genetically resistant.
  • new plants which have modified properties in comparison to previously occurring plants are, for example, classic breeding methods and the generation of mutants.
  • new plants with modified properties can be produced using genetic engineering processes (see, for example, EP-A-0 221 044, EP-A-0 131 624).
  • genetic engineering processes see, for example, EP-A-0 221 044, EP-A-0 131 624.
  • Several cases have been described, for example genetic modifications of crop plants for the purpose of modifying the starch synthesized in the plants (for example WO 92/11376, WO 92/14827, WO
  • Glufosinate see e.g. EP-A-0 242236, EP-A-0242 246) or glyphosate (WO
  • nucleic acid molecules can be introduced into plasmids which allow mutagenesis or a sequence change by recombination of DNA sequences.
  • base exchanges made, partial sequences removed or natural or synthetic sequences added.
  • adapters or linkers can be attached to the fragments.
  • the production of plant cells with a reduced activity of a gene product can be achieved, for example, by the expression of at least one corresponding antisense RNA, a sense RNA to achieve a cosuppression effect or the expression of at least one accordingly constructed ribozyme that specifically cleaves transcripts of the above gene product.
  • DNA molecules can be used that comprise the entire coding sequence of a gene product, including any flanking sequences that may be present, and on the other hand, DNA molecules that only comprise parts of the coding sequence, these parts having to be long enough to be able to encode Cells to cause an antisense effect. It is also possible to use DNA sequences which have a high degree of homology to the coding sequences of a gene product, but which are not completely identical.
  • the synthesized protein can be located in any compartment of the plant cell. However, in order to achieve localization in a certain compartment, e.g. the coding region is linked to DNA sequences which ensure localization in a specific compartment.
  • the transgenic plant cells can be regenerated into whole plants using known techniques.
  • the transgenic plants can in principle be plants of any plant species, i.e. both monocot and dicot plants.
  • the combinations according to the invention can preferably be used in transgenic crops which are resistant to herbicides from the group of the sulfonylureas, glufosinate-ammonium or glyphosate-isopropylammonium and analogous active compounds.
  • Iodosulfuron methyl sodium salt (5 g / ha) was applied in combination with Mirapol ® A15 (20 g / ha) on wheat and rice crops. Compared to the use of iodosulfuron methyl sodium salt (5 g / ha), an increased selectivity with lower phytotoxicity was found with a comparable herbicidal effect.
  • Iodosulfuron methyl sodium salt (5 g / ha) was combined with Mirapol ® A15 (10 g / ha) and applied with Genapol ® LRO (70%, 300 ml / ha) to wheat and rice crops. Compared to the use of iodosulfuron methyl sodium salt (5 g / ha) in a mixture with Genapol ® LRO (70%, 300 ml / ha), an improved selectivity with lower phytotoxicity and comparable herbicidal activity was observed.
  • Iodosulfuron methyl sodium salt (5 g / ha) was applied with Mirapol ® A15 (20 g / ha) rice cultures. Compared to the use of iodosulfuron methyl sodium salt (5 g / ha) in a mixture with Genapol ® LRO (70%, 300 ml / ha), an improved selectivity with lower phytotoxicity and comparable herbicidal activity was observed.
  • Iodosulfuron methyl sodium salt (5 g / ha) was combined with Mirapol ® A15 (50 g / ha) and applied with Genapol ® LRO (70%, 300 ml / ha) to wheat and rice crops.
  • Genapol ® LRO 70%, 300 ml / ha
  • Hussar ® OF (11 / ha) was combined with Mirapol ® A15 (50 g / ha) and applied to wheat and rice crops in a mixture with Genapol ® LRO (70%, 300 ml / ha). Compared to the use of Hussar ® OF in an amount of 1 l / ha in a mixture with Genapol ® LRO (70%, 300 ml / ha), an increased effect with greatly reduced phytotoxicity and better selectivity in stress was observed.
  • Titus ® (rimsulfuron, origin: Du Pont) (10 g / ha) was combined with Mirapol ® A15 (20 g / ha) and applied to maize crops in a mixture with Genapol ® LRO (70%, 300 ml / ha). Compared to the use of Titus ® in an amount of 10 g / ha in combination with Genapol ® LRO (70%, 300 ml / ha), a significantly reduced phytotoxicity was observed with the same effect.
  • Titus ® (rimsulfuron, origin: Du Pont) (10 g / ha) was combined with Genamin ® PDAC (50 g / ha) and applied to maize crops in a mixture with Genapol ® LRO (70%, 300 ml / ha). Compared to the use of Titus ® in an amount of 10 g / ha in combination with Genapol ® LRO (70%, 300 ml / ha), a significantly reduced phytotoxicity was observed with the same effect.

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  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Agronomy & Crop Science (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Toxicology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne la combinaison d'un principe actif agrochimique anionique avec un polymère cationique, avec production d'une interaction électrostatique pour le dégagement contrôlé de ce principe actif. Ce polymère comprend de préférence des azotes quaternaires cationiques. Les combinaisons selon l'invention ou les formulations agrochimiques contenant ces combinaisons servent à supprimer des interactions antagonistes entre différents principes actifs, ainsi qu'à augmenter la sélectivité de culture de principes actifs individuels.
EP01945089A 2000-05-11 2001-05-05 Combinaisons de produits phytosanitaires avec des polymeres cationiques Withdrawn EP1282355A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10022987A DE10022987A1 (de) 2000-05-11 2000-05-11 Kombinationen von Pflanzenschutzmitteln mit kationischen Polymeren
DE10022987 2000-05-11
PCT/EP2001/005096 WO2001084925A2 (fr) 2000-05-11 2001-05-05 Combinaisons de produits phytosanitaires avec des polymeres cationiques

Publications (1)

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EP1282355A2 true EP1282355A2 (fr) 2003-02-12

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EP (1) EP1282355A2 (fr)
JP (1) JP2003532649A (fr)
AR (1) AR028092A1 (fr)
AU (1) AU2001267409A1 (fr)
BR (1) BR0110708A (fr)
CA (1) CA2408397A1 (fr)
DE (1) DE10022987A1 (fr)
MX (1) MXPA02011046A (fr)
PL (1) PL365954A1 (fr)
WO (1) WO2001084925A2 (fr)

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JP2008527191A (ja) * 2005-01-05 2008-07-24 ダウ グローバル テクノロジーズ インコーポレイティド 紙及び板紙中の殺菌剤の効力の強化
AU2006302237C1 (en) * 2005-10-07 2012-11-08 The University Of Alabama Multi-functional ionic liquid compositions
US20080249136A1 (en) * 2005-10-25 2008-10-09 Ioana Annis Antimicrobial Composition and Method
WO2012006313A2 (fr) * 2010-07-06 2012-01-12 The Board Of Trustees Of The University Of Alabama Compositions herbicides et procédés d'utilisation
WO2013017388A1 (fr) * 2011-07-29 2013-02-07 Basf Se Granulat d'amidon poreux contenant un pesticide anionique ou cationique et une matrice cationique ou anionique
US20130084395A1 (en) * 2011-09-29 2013-04-04 Roshan V. Chapaneri Treatment of Plastic Surfaces After Etching in Nitric Acid Containing Media
EP3376946A1 (fr) * 2015-11-16 2018-09-26 Hill-Rom Services, Inc. Systèmes de détection d'incontinence pour lits d'hôpital

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US5428000A (en) * 1992-06-26 1995-06-27 Toho Chemical Industry Co., Ltd. Antagonism inhibitors for herbicides, herbicide compositions and herbicidal methods
DE19833066A1 (de) * 1998-07-22 2000-02-03 Elotex Ag Sempach Station Verfahren zur Herstellung wäßriger Dispersionen von (Co-)Polymerisaten, die danach erhältlichen Dispersionen, aus den Dispersionen erhältliche redispergierbare Pulver sowie deren Verwendung

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US20020019314A1 (en) 2002-02-14
CA2408397A1 (fr) 2002-11-06
DE10022987A1 (de) 2001-11-22
MXPA02011046A (es) 2004-08-19
AR028092A1 (es) 2003-04-23
BR0110708A (pt) 2003-01-28
JP2003532649A (ja) 2003-11-05
WO2001084925A2 (fr) 2001-11-15
WO2001084925A3 (fr) 2002-04-18
AU2001267409A1 (en) 2001-11-20
PL365954A1 (en) 2005-01-24

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