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
  • 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
  • A01N25/30—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 characterised by the surfactants
• • 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
  • A01N25/02—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 containing liquids as carriers, diluents or solvents
• • 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
  • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
  • A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
• • 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<
  • A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof

Definitions

• the present invention relates to an aqueous composition
• an aqueous composition comprising a) a suspended pesticide which is at most 10 g / l soluble in water at 20 0 C, b) a salt, and c) a protective colloid which is a C3-C32-alkylcarbonyl - and / or C3-C32-alkylcarbamoyl substituted polysaccharide.
• Another object is a process for preparing the composition by contacting a) the pesticide, b) a salt, and c) the protective colloid.
• an article is a use of salt for slowing particle growth in an aqueous composition containing the suspended pesticide, and the protective colloid. Combinations of preferred features with other preferred features are encompassed by the present invention.
• WO 2003/031043 discloses dispersions comprising a continuous aqueous phase which contains an electrolyte in a concentration of 0.1 to 1 mol / l and as surfactant a hydrophobically modified polymeric saccharide based on fructan-type or starch-type saccharides and substituted with hydrophobic moieties such as alkylcarbamoyl radicals or alkylcarbonyl radicals.
• the dispersions can be prepared for the field of pesticides.
• a principal problem in the formulation and application of pesticides in an aqueous environment is usually their low water solubility, which is often less than 10 g / L and especially less than 1 g / L at 20 ° C.
• Aqueous compositions of these pesticides are therefore heterogeneous systems wherein the active ingredient is present as a dispersed phase in a continuous aqueous phase.
• pesticide formulations usually contain surface-active substances such as emulsifiers and / or dispersants. These cause on the one hand a reduction in the surface tension of the aqueous phase and also stabilize the pesticide particles by electrostatic and / or steric interactions.
• aqueous pesticide formulations are often unstable and tend to deposit the active ingredient, for example by sedimentation. These problems are particularly pronounced if the formulation is stored for a long time at elevated temperature and / or at strongly changing temperatures or even near freezing. This problem is particularly pronounced when the active ingredient tends to crystallization, z.
• drugs that have a finite solubility in the aqueous phase and / or the surfactant.
• Another problem with the formulation of pesticides with finite or extremely low water solubility is that when diluting the active ingredients to the desired application concentration, deposition such as sedimentation or creaming of the pesticide may occur. This not only results in a loss of efficiency, but in the case of spray mixtures there is also the risk of blockage for filter and nozzle systems.
• the object of the present invention was to formulate sparingly water-soluble pesticides which are solid at room temperature in aqueous systems.
• the formulation should not crystallize on prolonged storage and not sediment.
• Another object was to provide a suspension of poorly water-soluble pesticides whose particle size does not increase or only slightly increases during storage.
• the formulation should be stabilized with the aid of an environmentally friendly surface-active compound, so that no damage to the plants is to be expected when applying the pesticides.
• an aqueous composition comprising a) a suspended pesticide which is at most 10 g / l soluble in water at 20 ° C., b) a salt, and c) a protective colloid which is a C 3-32 -alkylcarbonyl and / or C3-C32 alkylcarbamoyl substituted polysaccharide.
• pesticide denotes at least one active substance selected from the group of fungicides, insecticides, nematicides, herbicides, safeners and / or growth regulators.
• Preferred pesticides are fungicides, insecticides and herbicides, especially fungicides.
• mixtures of pesticides of two or more of the above classes may be used.
• One skilled in the art will be familiar with such pesticides as described, for example, in Pesticide Manual, 14th Ed. (2006), The British Crop Protection Council, London.
• Suitable insecticides are insecticides of the carbamate class, organophosphates, organochlorine insecticides, phenylpyrazoles, pyrethroids, neonicotinoids, spinosines, avermectins, milbemycins, juvenile hormone analogs, alkylhalides, organotin compounds, nereistoxin analogues, benzoylureas, diacylhydrazines, METI acaricides, and insecticides such as chloropicrin, pymetrozin, flonicamide, clofentezine, hexythiazox, etoxazole, diafenthiuron, propargite, tetradifon, chlorfenapyr, DNOC, buprofezin, cyromazine, amitraz, hydramethylnone, acequinocyl, fluacrypyrim, rotenone, or their derivatives.
• Suitable fungicides are fungicides of the classes dinitroanilines, allylamines, anilinopyrimidines, antibiotics, aromatic hydrocarbons, benzenesulfonamides, benzimidazoles, benzisothiazoles, benzophenones, benzothiadiazoles, benzotriazines, benzylcarbamates, carbamates, carboxamides, carboxylic acid amides, chloronitriles, cyanoacetamide oximes, cyanoimidazoles, cyclopropanecarboxamides, dicarboximides, dihydrodioxazines , Dinitrophenyl crotonates, dithiocarbamates, dithiolanes, ethyl phosphonates, ethylaminothiazolecarboxamides, gua nidines, hydroxy- (2-amino) -pymimetimidines, hydroxyanilides, imidazoles,
• Suitable herbicides are herbicides of the classes of the acetamides, amides, aryloxyphenoxypropionates, benzamides, benzofuran, benzoic acids, benzothiadiazinones, bipyridylium, carbamates, chloroacetamides, chlorocarboxylic acids, cyclohexanediones, dinitroanilines, dinitrophenol, diphenyl ethers, glycines, imidazolinones, isoxazoles, isoxazolidinones , Nitriles, N-phenylphthalimides, oxadiazoles, oxazolidinediones, oxyacetamides, phenoxycarboxylic acids, phenylcarbamates, phenylpyrazoles, phenylpyrazolines, phenylpyridazines, phosphinic acids, phosphoroamidates, phosphorodithioates, phthalamates
• the pesticide contains an insecticide, preferably the pesticide is at least one insecticide.
• the pesticide contains a fungicide, preferably the pesticide consists of at least one fungicide.
• Preferred fungicides are pyraclostrobin and prochloraz, especially pyraclostrobin.
• the pesticide contains a herbicide, preferably the pesticide consists of at least one herbicide.
• the pesticide contains a growth regulator, preferably the pesticide consists of at least one growth regulator.
• the pesticides contain at least two, preferably two or three, in particular two different pesticides.
• the pesticide is soluble in water at 20 0 C at most about 10 g / l, preferably at most 2 g / l and particularly preferably at most 0.5 g / l.
• pyraclostrobin is water soluble at 1.9 mg / l and prochloraz at 34 mg / l.
• the pesticide usually has a melting point of about 30 0 C, preferably about 40 0 C and especially above 45 0 C.
• pyraclostrobin has a melting point of 64 0 C and 47 0 C.
• the composition according to the invention usually comprises 0.1 to 70% by weight of pesticide, preferably 1 to 50% by weight, in particular 3 to 30% by weight, based on the composition.
• the pesticide is in suspended form in the composition, ie in the form of crystalline or amorphous particles which are solid at 20 ° C.
• the pesticide is in the form of amorphous particles.
• the viscosity of the pesticide particles is at least 1,000 mPas, preferably at least 5,000 mPas, and most preferably at least 10,000 mPas.
• the suspended pesticide usually has a particle size distribution with an Xso value of 0.1 to 10 .mu.m, preferably from 0.2 .mu.m to 5 .mu.m and particularly preferably from 0.5 .mu.m to 2 .mu.m.
• the particle size distribution can be determined by laser light diffraction of an aqueous suspension comprising the particles.
• Sample preparation for example dilution to measurement concentration, depends among other things on the fineness and concentration of the active ingredients in the suspension sample and on the measuring instrument used (eg Malvern Mastersizer). The procedure must be worked out for the respective system and is known to the person skilled in the art.
• Salts usually include an anion and a cation.
• Suitable salts are, for example, metal salts, ammonium salts, amine salts, quaternary ammonium salts and mixtures thereof, in particular metal salts and ammonium salts, especially metal salts and especially alkali metal salts.
• the cations include metal ions of monovalent, divalent, trivalent or tetravalent metals and ions comprising a nitrogen atom.
• Typical metal cations include ions of lithium, sodium, potassium, magnesium, calcium, barium, chromium, manganese, iron, cobalt, nickel, copper, zinc and aluminum.
• Typical cations containing a nitrogen atom include ammonium ions, ions of salts of primary, secondary and tertiary amines such as monoalkylamines, dialkylamines, trialkylamines and benzyldialkylamines, quaternary ammonium ions and organic nitrogen base ions such as morpholine, piperazine and heterocyclic compounds , such as pyridine.
• Preferred cations include ions of sodium, potassium, magnesium, calcium, iron, copper, zinc, aluminum and ammonium ions, more preferably sodium and potassium, especially potassium.
• the anions include hydroxyl anions and anions derived from both inorganic acids and organic acids such as hydrogen halides including hydrofluoric acid, hydrochloric acid, hydrobromic acid and hydroiodic acid, sulfuric acid, phosphoric acid, carbonic acid, formic acid, acetic acid and lactic acid.
• Preferred anions are chloride, sulfate, hydrogen sulfate, phosphate, hydrogen phosphate, dihydrogen phosphate, carbonate, bicarbonate, formate and acetate, particularly preferably chloride, sulfate, hydrogen sulfate, phosphate, hydrogen phosphate, dihydrogen phosphate, in particular hydrogen phosphate.
• Preferred salts are sodium chloride, lithium chloride, ammonium formate, ammonium chloride, lithium formate, dipotassium hydrogen phosphate, potassium dihydrochloride, genphosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, particularly preferably dipotassium hydrogen phosphate (DKHP).
• DKHP dipotassium hydrogen phosphate
• the composition according to the invention usually contains at least 10% by weight of salt, preferably at least 15% by weight, more preferably at least 20% by weight and in particular at least 25% by weight, based on the composition.
• the upper limit of the salt content is determined by the solubility of the salt in the composition.
• the composition according to the invention usually contains at most as much salt as is maximally soluble in the composition.
• the composition contains at most 60% by weight of salt, more preferably at most 50% by weight, particularly preferably at most 40% by weight.
• the salt is usually present in dissolved form in the composition.
• a suitable protective colloid which is a polysaccharide substituted with C3-C32-alkylcarbonyl and / or C3-C32-alkylcarbamoyl groups, is usually based on homodisperse or polydisperse, linear or branched polysaccharides. Suitable polysaccharides are fructans, modified starches and starch hydrolysates. Preferred polysaccharides are inulin and starch hydrolysates.
• the protective colloid is preferably a polysaccharide which is substituted by C ⁇ -Cis-alkylcarbonyl and / or C ⁇ -Cis-alkylcarbamoyl groups.
• fructans examples include inulin, oligofructose, fructooligosaccharide, partially hydrolyzed inulin, levan and partially hydrolyzed levan, preferably inulin and partially hydrolyzed inulin.
• Inulin is a fructan composed of molecules consisting mainly of fructosyl units bound together by ß (2-1) -fructosyl-fructosyl bonds and possibly having a terminal glucosyl unit. It is synthesized by various plants as reserve carbohydrate and certain bacteria and can also be obtained synthetically by an enzymatic process from sugars containing fructose units, such as sucrose.
• Well-suited inulin is polydisperse, linear inulin or slightly branched inulin of plant origin having a degree of polymerization (DP) in the range of three to about 100. Inulin usually has a branching below 20%, preferably below 10%. Particularly well-suited inulin is chicory inulin with a DP in the range of three to about 70 and an average DP of 10. Even more suitable is chicory inulin, which has been treated to remove most of the monomeric and dimeric saccharide by-products, and the optionally also treated to remove inulin molecules having a lower DP, usually a DP of three to nine. These grades of chicory inulin can be obtained from chicory roots by conventional extraction, purification and fractionation techniques.
• DP degree of polymerization
• suitable fructans contain partially hydrolyzed inulin and inulin molecules with a DP in the range of three to about nine, namely oligofructose and fructo-oligosaccharides (ie oligofructose molecules with an additional terminal glucosyl unit).
• oligofructose and fructo-oligosaccharides ie oligofructose molecules with an additional terminal glucosyl unit.
• suitable products are obtained by partial, enzymatic hydrolysis of chicory inulin.
• Suitable fructans are levan and partially hydrolyzed levan, molecules consisting mainly of fructosyl units linked together by ⁇ (2-6) fructosyl-fructosyl bonds and possibly having a terminal glucosyl moiety.
• glucosyl units are usually linked by ⁇ -1,4-glucosyl-glucosyl bonds forming linear molecules called amylose, or by ⁇ -1,4 and ⁇ -1,6-glucosyl-glucosyl bonds, the branched molecules Called amylopectin.
• the bonds between the glucosyl units in starch can be chemically cleaved. This phenomenon is used industrially to prepare modified starches and starch hydrolysates by heat treatment of starch frequently in the presence of a catalyst, by acid hydrolysis, by enzymatic hydrolysis or by shear or by combinations of such treatments.
• Starch hydrolysates usually refer to polydisperse mixtures composed of D-glucose, oligomeric (DP two to ten) and / or polymeric (DP> ten) D-glucosyl chain molecules. Starch hydrolysates are usually defined by their D.E. value (dextrose equivalents). Starch hydrolysates may range from a product consisting essentially of glucose via products with a D.E., greater than 20 (often referred to as glucose syrups), to a D.E. of 20 or less (often referred to as maltodextrins). Well suited are starch hydrolysates having a D.E. in the range of two to 47. They can be obtained by conventional methods from various sources of starch, such as corn, potato, tapioca, rice, sorghum and wheat.
• the polysaccharides are substituted by C3-C32-alkylcarbonyl and / or C3-C32-alkylcarbamoyl groups, preferably by at least two of these groups.
• the polysaccharides are preferably substituted by C ⁇ -Cis-alkylcarbonyl or C ⁇ -Cis-alkylcarbamoyl groups.
• the chemical structures of the alkylcarbonyl group (1) and the alkylcarbamoyl group (2) are as follows, where " * " represents the bond to a former OH group of the polysaccharide:
• Alkyl " ⁇ * N (1) ( 2 )
• Alkyl here means a linear or branched, saturated or unsaturated aliphatic radical having from 3 to 32, preferably from 4 to 20, particularly preferably 6 to 14 and especially 8 to 12 carbon atoms.
• alkyl is a saturated, linear aliphatic radical.
• the substituted polysaccharide usually has two, three or four hydroxyl groups per saccharide unit, whose hydrogen atom may be substituted by a C3-C32-alkylcarbonyl and / or C3-C32-alkylcarbamoyl group.
• the number of substituted groups per unit is often referred to as the average degree of substitution (DS).
• the DS of the substituted polysaccharide is usually in the range of 0.01 to 0.5, preferably 0.02 to 0.4, more preferably 0.05 to 0.35, and most preferably 0.1 to 0.3.
• the protective colloid which is a polysaccharide substituted by C3-C32-alkylcarbonyl and / or C3-C32-alkylcarbamoyl groups, usually has a molecular weight of at least 1000 g / mol, preferably at least 4000 g / mol.
• the water solubility of the protective colloid is usually below 10% by weight, preferably below 5% by weight and more preferably below 1% by weight, in each case at 20 ° C.
• the polysaccharide substituted with C3-C32 alkylcarbonyl and / or C3-C32 alkylcarbamoyl groups can be prepared by conventional methods.
• C 3 -C 32 alkylcarbonyl groups can be linked to the polysaccharide by reaction of the
• composition according to the invention usually contains from 0.001 to 20% by weight, preferably from 0.01 to 8% by weight, particularly preferably from 0.01 to 5% by weight, of protective colloid c), based on the total amount of the composition.
• the composition according to the invention usually contains formulation auxiliaries, wherein the choice of the auxiliaries usually depends on the specific application form or the pesticide.
• suitable auxiliaries are solvents, solid carriers, surface-active substances (such as surfactants, solubilizers, further protective colloids, wetting agents and adhesives), organic and inorganic thickeners, Bactericides, antifreeze, defoamers, if necessary dyes and adhesives (eg for seed treatment).
• surfactants are the alkali, alkaline earth, ammonium salts of aromatic sulfonic acids, eg. B. of lignin (Borresperse ® grades, Borregaard, Norway), phenol, naphthalene (Morwet ® types, Akzo Nobel, USA) and dibutyl (nekal ® types, BASF, Germany), and of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, as well as salts of sulfated hexa-, hepta- and octadecanols and of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulf
• Suitable surfactants are, in particular, anionic, cationic, nonionic and amphoteric surfactants, block polymers and polyelectrolytes.
• Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates or carboxylates.
• sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefinsulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of condensed naphthalene, sulfonates of dodecyl and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates.
• Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters.
• Examples of phosphates are phosphate esters.
• Examples of carboxylates are alkyl carboxylates and carboxylated alcohol or alkylphenol ethoxylates.
• Suitable nonionic surfactants are alkoxylates, N-alkylated fatty acid amides, amine oxides, esters or sugar-based surfactants.
• alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated.
• ethylene oxide and / or propylene oxide can be used, preferably ethylene oxide.
• N-alkylated fatty acid amides are fatty acid glucamides or fatty acid alkanolamides.
• esters are fatty acid esters, glycerol esters or monoglycerides.
• sugar-based Surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkyl polyglucosides.
• Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds having one or two hydrophobic groups, or salts of long-chain primary amines.
• Suitable amphoteric surfactants are alkyl betaines and imidazolines.
• Suitable block polymers are block polymers of the AB or ABA type comprising blocks of polyethylene oxide and polypropylene oxide or of the ABC type comprising alkanol, polyethylene oxide and polypropylene oxide.
• Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali metal salts of polyacrylic acid. Examples of polybases are polyvinylamines or polyethylene amines.
• composition according to the invention may comprise from 0.1 to 40% by weight, preferably from 1 to 30 and in particular from 2 to 20% by weight, of total amount of surface-active substances and surfactants, based on the total amount of the composition.
• the protective colloid which is a polysaccharide substituted with C3-C32 alkylcarbonyl and / or C3-C32 alkylcarbamoyl groups, is not included in this total amount.
• adjuvants examples include organically modified polysiloxanes such as BreakThruS 240 ®; Alcohol alkoxylates such as Atplus ® 245 ® Atplus MBA 1303 ®, Plurafac LF and Lutensol ® ON; EO-PO block polymers, eg. B. Pluronic RPE 2035 ® and Genapol B ®; Alcohol ethoxylates, eg. B. Lutensol ® XP 80; and sodium dioctylsulfosuccinate, e.g. B. Leophen ® RA.
• organically modified polysiloxanes such as BreakThruS 240 ®
• Alcohol alkoxylates such as Atplus ® 245 ® Atplus MBA 1303 ®, Plurafac LF and Lutensol ® ON
• EO-PO block polymers eg. B. Pluronic RPE 2035 ® and Genapol B ®
• Alcohol ethoxylates e
• thickeners ie, compounds that give the composition a modified flow properties, ie high viscosity at rest and low viscosity in motion
• thickeners are polysaccharides and organic and inorganic sheet minerals, such as xanthan gum (Kelzan ®, CP Kelco), Rhodopol ® 23 (Rhodia) or Veegum ® (RT Vanderbilt) or attaclay ® (Engelhard Corp.).
• Bactericides may be added to stabilize the composition.
• bactericides are those based on dichlorophen and benzyl alcohol formal (Proxel ®. Fa. ICI or Acetide ® RS from Thor Chemie and Kathon ® MK from. Rohm & Haas), and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones (Acetide ® MBS from Thor Chemie).
• Suitable antifreeze agents are ethylene glycol, propylene glycol, urea and glycerin.
• defoamers are silicone emulsions (such as, for example, silicone ® SRE, Wacker, Germany or Rhodorsil ®, Rhodia, France), long chain alcohols, fatty acids, salts of fatty acids, organofluorine compounds and mixtures thereof.
• colorants are both water-insoluble pigments and water-soluble dyes. Examples which may be mentioned under the names Rhodamine B, CI Pigment Red 112 and CI Solvent Red 1, Pigment Blue 15: 4, Pig- blue 15: 3, Pigment blue 15: 2, Pigment blue 15: 1, Pigment blue 80, Pigment yellow low 1, Pigment yellow 13, Pigment red 48: 2, Pigment red 48: 1, Pigment red 57: 1, Pigment red 53, Pigment orange 43, Pigment orange 34, Pigment orange 5, Pigment green 36, Pigment green 7, Pigment white 6, Pigment brown 25, Basic violet 10, Basic violet 49, Acid red 51, Acid red 52, Acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108 known dyes and pigments.
• adhesives examples include polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and CEI luloseether (Tylose ®, Shin-Etsu, Japan).
• composition of the invention is usually diluted before use to produce the so-called tank mix. Dilution is made of medium to high boiling point mineral oil fractions such as kerosene or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strong polar solvents, e.g. Dimethylsulfoxide, N-methylpyrrolidone or water into consideration.
• mineral oil fractions such as kerosene or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Toluene, xylene, paraffin, tetrahydr
• the diluted composition is usually applied by spraying or atomizing.
• wetting agents, adjuvants, herbicides, bactericides, fungicides can be added immediately before use (tank mix). These agents can be added to the compositions according to the invention in a weight ratio of 1: 100 to 100: 1, preferably 1:10 to 10: 1.
• the pesticide concentration in the tank mix can be varied in larger areas. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%.
• the application rates in the application in crop protection, depending on the nature of the desired effect between 0.01 and 2.0 kg of active ingredient per ha.
• the present invention also relates to the use of a composition according to the invention for controlling phytopathogenic fungi and / or undesired plant growth and / or undesired insect or mite infestation and / or for regulating the growth of plants, the composition being based on the respective pests whose Habitat or plants to be protected from the particular pest, soil and / or undesirable plants and / or crops and / or their habitat. Furthermore, the invention relates to the use of a composition according to the invention for controlling unwanted insect or mite infestation on plants and / or for controlling phytopathogenic fungi and / or for controlling undesired plant growth, treating crop seeds with the composition.
• the invention relates to seed which has been pickled with a composition according to the invention.
• the seed preferably contains the additive according to the invention.
• composition. This composition can be applied to the seed undiluted or, preferably, diluted.
• the corresponding composition can be diluted 2 to 10 times, so that 0.01 to 60% by weight, preferably 0.1 to 40% by weight of pesticide are present in the compositions to be used for the stain ,
• the application can be done before sowing.
• the treatment of plant propagation material in particular the treatment of seeds, is known to the person skilled in the art and is carried out by dusting, coating, pelleting, dipping or impregnating the plant propagation material, wherein the treatment is preferably carried out by pelleting, coating and dusting, so that z. B. premature germination of the seed is prevented.
• pesticide amounts of 1 to 1000 g / 100 kg, preferably 5 to 100 g / 100 kg of propagation material or seed are generally used.
• the invention also relates to a use of salt for slowing particle growth in an aqueous composition containing a suspended one
• a pesticide which is at most 10 g / l soluble in water at 20 ° C and a protective colloid which is a polysaccharide substituted with C3-C32 alkylcarbonyl and / or C3-C32 alkylcarbamoyl groups.
• the aqueous phase contains at least 10% by weight of salt, based on the composition.
• Preferred salts and preferred amounts of salts are as described above.
• Preferred protective colloids are as described above. Particle growth is usually slowed down compared to a salt-free composition.
• the invention also relates to a process for the preparation of a composition according to the invention comprising: a) a pesticide which is at most 10 g / l soluble in water at 20 ° C. b) a salt, and c) a protective colloid containing a C 3 C32 alkylcarbonyl and / or C3-C32 alkylcarbamoyl substituted polysaccharide is brought into contact with each other.
• the dispersed pesticide a) may be brought into contact with components b) and c) in an aqueous system, or it may be dispersed in an aqueous system after contacting components a), b) and c).
• Suitable processes are, for example, precipitation processes, evaporation processes, melt emulsification or milling processes, preferably precipitation processes and melt emulsification.
• the preparation process results in a composition according to the invention in which the pesticide is suspended. During melt emulsification, the pesticide may briefly be present as an emulsion of the molten pesticide, but the pesticide rapidly solidifies into suspended form upon cooling.
• the process according to the invention preferably comprises precipitation of the pesticide (precipitation process) or solidification of an emulsified melt of the pesticide (melt liquorization).
• the precipitation process usually includes the steps
• the process step can be carried out batchwise, for example in a stirred tank, or continuously.
• Continuous machines and apparatuses for emulsification are, for example, colloid mills, sprocket dispersing machines and other types of dynamic mixers, furthermore high-pressure homogenizers, pumps with downstream nozzles, valves, membranes or other narrow gap geometries, static mixers, in-line mixers according to the rotor-stator principle (Uitara-Turrax, Inline Dissolver), micromixing systems and ultrasonic emulsification systems.
• Sprocket dispersing machines or high-pressure homogenizers are preferably used.
• water-miscible organic solvent in this context means that the organic solvents at 20 0 C without phase separation at least 10 wt .-%, preferably 15 wt.%, Particularly preferably mixed to 20 wt .-% with water
• the solution may optionally comprise further formulation auxiliaries, for example dispersants
• Suitable solvents are C 1 -C 6 -alkyl alcohols such as methanol, ethanol, propanol, isopropanol, 1-butanol, 2-butanol, tert - Butanol, esters, ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, acetals, ethers, cyclic ethers such as tetrahydrofuran, aliphatic carboxylic acids such as formic acid, acetic acid, propionic acid, N-substituted or
• Preferred solvents are glycols, methanol, ethanol, isopropanol, dimethylformamide, N-methylpyrrolidone, methylene chloride, chloroform, 1, 2-dichloroethane, chlorobenzene, acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, tetrahydrofuran and mixtures of said solvents.
• Particularly preferred solvents are propylene glycol, methanol, ethanol, isopropanol, dimethylformamide and tetrahydrofuran, in particular propylene glycol.
• the pesticide is in step 1) usually in a water-miscible organic solvent at temperatures greater than 30 0 C, preferably between 50 0 C and 240 ° C, in particular 100 0 C to 200 ° C, particularly preferably 140 ° C to 180 0 C, possibly under pressure, dissolved.
• step 2) The thus obtained molecular disperse solution is then added in step 2) directly with the optionally cooled aqueous molecular disperse or colloidally disperse solution containing salt b) and protective colloid c), wherein the solvent component from step 1) is transferred to the aqueous phase and the hydrophobic phase of the pesticide is formed as a disperse phase.
• a mixture temperature of about 35 ° C to 80 ° C is established.
• step c) optionally, the organic solvents used are removed and the resulting suspension of pesticide is concentrated by removing excess water to the desired level of pesticide.
• Melt emulsification usually involves solidification of an emulsified melt of the pesticide.
• a melt comprising the molten pesticide is emulsified in an aqueous solution and cooled below the solidification point.
• the melt may be emulsified in an aqueous solution by melting the pesticide and introducing this melt into the aqueous solution, preferably with the addition of energy.
• the melt can be emulsified in an aqueous solution by melting the pesticide directly in an aqueous solution while supplying energy.
• energy may be introduced by shaking, stirring, tubular mixing, injecting one liquid into another, oscillating and cavitating the mixture (eg, with ultrasound), emulsifying centrifuges, colloid mills, spreader dispersing machines, or high pressure homogenizers.
• the temperature difference between the melt and the aqueous phase is generally from 0 to 200 ° C.
• the melt is from 20 to 200 ° C. warmer than the aqueous phase.
• both the continuous phase comprising the aqueous solution and the disperse phase comprising the molten pesticide can be mixed with the auxiliaries necessary for the formulation and the subsequent application, such as surfactants.
• the continuous phase comprising the aqueous solution and the disperse phase comprising the molten pesticide are combined with each other and pre-emulsified coarsely dispersed, it is called a crude emulsion.
• the crude emulsion can then be treated in an emulsifying apparatus, wherein the disperse-phase droplets are finely comminuted (so-called fine emulsification).
• the process step of the fine emulsification can be carried out batchwise, for example in a stirred tank, or continuously. Continuous machinery and apparatus for emulsification are known in the art.
• Examples are colloid mills, sprocket dispersing machines and other types of dynamic mixers, furthermore high-pressure homogenizers, pumps with downstream nozzles, valves, membranes or other narrow gap geometries, static mixers, in-line mixers according to the rotor-stator principle (Ultra-Turrax, Inline Dissolver ), Micromixing systems and ultrasonic emulsification systems.
• Sprocket dispersing machines or high-pressure homogenizers are preferably used. After the fine emulsification, the fine emulsion may be cooled below the melting point or melting range of the pesticide.
• This step can be carried out by cooling with stirring (batch mode) or by passing the fine emulsion through a heat exchanger (continuous mode).
• the pesticide solidifies in the disperse phase in particulate, preferably in particulate amorphous form.
• the introduced in an aqueous solution melt at a cooling rate of at least 0.5 K / min is cooled by means of a controllable cooling apparatus.
• a controllable cooling apparatus comprises a tube which can be cooled and through which the substances to be cooled flow.
• the cooling rate can be regulated by the flow rate and / or the temperature of the cooled tube.
• the cooling is generally carried out to below the melting point of the crystalline form of the pesticide, preferably below 50 ° C., more preferably below 30 ° C.
• the melt emulsification generally leads to an aqueous suspension comprising at least 5% by weight, preferably at least 15% by weight and particularly preferably at least 20% by weight of particles which comprise the agrochemical active ingredients preferably in amorphous form, in each case based on the aqueous suspension.
• composition auxiliaries can be added to the melt, to the aqueous solution or to the aqueous suspension of the particles.
• Formulation aids are, for example, solvents, surfactants, inorganic emulsifiers (so-called ckering emulsifiers), anti-foaming agents, thickeners, antifreeze, and bactericides.
• intended formulations may additionally contain adhesives and optionally pigments.
• compositions in the form of suspension concentrates are stable and do not tend to crystallize.
• the particle size of the suspended pesticide does not rise during storage or only slightly.
• the Ostwaldreifung is largely suppressed by the present invention.
• the formulation aid used is based on polysaccharides, which are known to be well tolerated by the treated plants.
• DKHP is an advantageous salt due to its high water solubility, low toxicity and high reduction of the water solubility of organic substances.
• Inutec® SP1 A powdered lauryl carbamate-substituted chicory inulin prepared by reacting an isocyanate with inulin in the presence of a basic catalyst (commercially available from Beneo-Orafti, Ghent or NRC Nordmann, Rassmann) having a water solubility of ⁇ 1 wt. % at 20 ° C., an average molar mass> 4500 g / mol, a content of at least 95% by weight and a pH in water of 5.0-8.0 (as 5% by weight solution in water).
• a basic catalyst commercially available from Beneo-Orafti, Ghent or NRC Nordmann, Rassmann
• Example 1 Preparation of a pesticide suspension by melt emulsification 10% Pyraclostrobin 1% Inutec® SP 1
• the dipotassium hydrogen phosphate was dissolved in water at room temperature. Then the Inutec® SP 1 was added to the saline solution and thoroughly dispersed with an Ultraturrax T25. The saline and pyraclostrobin were heated separately from each other to about 80 to 85 ° C. The molten drug was added to the aqueous solution and coarsely predispersed using an Ultraturrax T25. The fine dispersion of the active ingredient in the aqueous solution was carried out with a high pressure homogenizer performed at 2000 bar dispersion pressure and a product temperature of 80 to 85 ° C. Finally, the sample was cooled rapidly to room temperature in ice-water.
• the characteristic parameters of the particle size distribution were determined directly after preparation ("start") and after 6 months of stable storage at room temperature (Table 1).
• Example 2 Preparation of a pesticide suspension by melt emulsification 25% Pyraclostrobin 2.5% lnutec® SP 1
• a dispersion was prepared as described in Example 1.
• the characteristic parameters of the particle size distribution were determined directly after preparation ("start") and 46 days of stable storage at room temperature (Table 2).
• a dispersion was prepared as described in Example 1.
• the characteristic parameters of the particle size distribution were obtained directly after production (“Start") and determined after 17 hours of quiet storage at room temperature (Table 3). Under the light microscope, clearly coarse crystals were visible after 17 h.
• a dispersion was prepared as described in Example 1.
• Time course of the particle growth Table 4 shows the time course of the particle growth, which was determined in each case on a sample from Example 1 and Comparative Example 1 and 2 as described above.
• Example 3 Preparation of a substituted Ci2-alkylcarbonyl starch hydrolyzate 480 ml N, N-dimethylacetamide was submitted, then 162.1 g (1, 0 mol) starch hydrolyzate while stirring and heated to 80 0 C so that a solution formed. at
• a saline solution was prepared consisting of 0.5 to 2 g of polysaccharide (Inutec® SP1 or acetylated starch of Example 3), 500 g of salt (DKHP or CaCl 2 ) and 1000 g of water.
• 16.0 g of pyraclostrobin and 144 g of propylene glycol were weighed into a 250 ml glass bottle and mixed with 100 ml glass beads (3 mm diameter). The mixture was suspended for 60 minutes with a shaker. The resulting, still coarse suspension was fed at a flow rate of 1 kg / h through a mixing nozzle of a release cell.
• propylene glycol was added at a temperature of 200 0 C with a pumping rate of 2 kg / h. In the dissolution cell, both streams were mixed turbulently and a solution of pyraclostrobin was produced.
• the resulting solution of pyraclostrobin was moved to a second mixing nozzle and mixed with the prepared salt solution at a pumping rate of 16 kg / h turbulent.
• the saline solution was cooled to 5 ° C before being run in a cryostat. In the mixture, a particle formation of pyraclostrobin takes place.
• the resulting amorphous precipitate of pyraclostrobin was discharged.
• An aqueous dispersion of 0.36% by weight of amorphous pyrablostrobin containing 10.0% by weight of the respective polysaccharide with respect to the amount of pyraclostrobin and 0.036% by weight, respectively, with respect to the total composition was obtained (see Table 5 for the respective composition).
• Particle sizes were determined by laser diffraction (Malvern Mastersizer S) and laser scattering (Brookhaven Instruments BI90) (Table 6).
• the batch was repeated without addition of salt or polysaccharide and analyzed.
• the experiment was repeated except that no polysaccharide was used, but 4 g of sodium dodecyl sulfate (SDS) was added to the mixture of pyracrocrobotine and propylene glycol.
• SDS sodium dodecyl sulfate

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