WO2013017388A1 - Porous starch granulate containing an anionic or cationic pesticide and a cationic or anionic matrix - Google Patents

Porous starch granulate containing an anionic or cationic pesticide and a cationic or anionic matrix Download PDF

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Publication number
WO2013017388A1
WO2013017388A1 PCT/EP2012/063634 EP2012063634W WO2013017388A1 WO 2013017388 A1 WO2013017388 A1 WO 2013017388A1 EP 2012063634 W EP2012063634 W EP 2012063634W WO 2013017388 A1 WO2013017388 A1 WO 2013017388A1
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Prior art keywords
anionic
cationic
starch granules
pesticide
matrix
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PCT/EP2012/063634
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German (de)
French (fr)
Inventor
Ralph Rieger
Harald Keller
Robert Reinhard
Tina SCHRÖDER-GRIMONPONT
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Basf Se
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Publication of WO2013017388A1 publication Critical patent/WO2013017388A1/en

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    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles

Definitions

  • Porous starch granules containing an anionic or cationic pesticide and a cationic or anionic matrix The present invention relates to a porous, partially hydrolyzed starch granules containing an anionic or cationic pesticide and a cationic or anionic matrix, wherein the pesticide and the matrix are oppositely charged.
  • Further objects are a process for producing the starch granules by bringing a porous, partially hydrolyzed starch granules with a salt matrix containing the anionic or cationic pesticide and the cationic or anionic matrix in contact with each other; and methods for controlling phytopathogenic fungi and / or undesired plant growth and / or unwanted insect or mite infestation and / or for regulating the growth of plants, wherein the composition of the respective pests, their habitat or the plants to be protected from the respective pest , the soil and / or on unwanted plants and / or the crops and / or their habitat act. Combinations of preferred features with other preferred features are encompassed by the present invention.
  • US 2007/0160637 discloses a composition comprising a partially hydrolyzed porous granular starch in which a pesticide is absorbed and a binder or filler.
  • WO 1995/19376 discloses a porous starch granule which is combined with a binder and which can act as a carrier for insecticides or herbicides.
  • WO 1989/04842 discloses a partially hydrolyzed starch matrix containing a releasable absorptive such as insecticides or herbicides.
  • a disadvantage of the known starch granules is that they allow only a very rapid release of active ingredients.
  • the object of the present invention was to provide a composition comprising pesticide which overcomes these disadvantages.
  • the object has been achieved by a porous, partially hydrolyzed starch granules containing an anionic or cationic pesticide and a cationic or anionic matrix, wherein the pesticide and the matrix are oppositely charged.
  • the invention relates to porous, partially hydrolyzed starch granules containing an anionic pesticide and a cationic matrix. In another In preferred form, the invention relates to porous, partially hydrolyzed starch granules containing a cationic pesticide and an anionic matrix.
  • Porous, partially hydrolyzed starch granules are well known, for example from WO 1989/04842.
  • the starch granules may be prepared by treating starch granules in an aqueous medium (e.g., in aqueous suspension), with a glucoamylase, alpha-amylase, or mixtures thereof.
  • the temperature will usually be below the gel point of the starch.
  • Suitable alpha-amylases or glucoamylases are those of Rhizopus niveus, Aspergillus niger, Rhizopus oryzae, Bacillus subtilis.
  • the starch granules are used without further work-up, for example in an aqueous medium.
  • the starch granules are isolated in powder form, for example by drying. Suitable drying methods are freeze drying, spray drying, belt drying or drum drying. Suitable starch granules are based, for example, on corn starch, wheat, tapioca, potato. Preferred starch granules are based on corn starch.
  • the pore volume of the porous starch granules may range from 0.05 to 1 ml / g, preferably from 0.2 to 0.8 ml / g, more preferably from 0.35 to 0.65 ml / g.
  • the pore volume can be determined by the absorption of hexadecane compared to the hexadecane absorption of a non-porous starch granule.
  • the starch granules usually have a particle size of 1 to 300 ⁇ , preferably from 5 to 100 ⁇ , particularly preferably from 8 to 30 ⁇ .
  • the particle size can be measured by means of laser diffraction.
  • the matrix can be in the form of a continuous or discontinuous matrix.
  • the matrix mostly has ionic interactions with the pesticide. The ionic interactions can lead to reduced migration of the pesticide in the matrix.
  • the matrix can form salts with the pesticide.
  • the anionic matrix usually comprises at least one anionic compound.
  • the anionic matrix may contain at least 70% by weight, preferably at least 85% by weight and in particular at least 95% by weight of anionic compounds.
  • the anionic matrix preferably comprises an inorganic acid, an organic acid, and / or a polymeric acid, organic acid, in particular aliphatic C 2-30 carboxylic acids, and especially oxalic acid being preferred.
  • the inorganic, organic and / or polymeric acids may comprise one or more acid groups (eg carboxylic acid groups).
  • Suitable inorganic acids are sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, metaphosphoric acid, and boric acid, with phosphonic acid and phosphorous acid being preferred.
  • Suitable organic acids are aliphatic C 2-30 carboxylic acids (such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, citric acid, malic acid, tartaric acid) or aromatic C 7-30 carboxylic acids (such as terephthalic acid, phthalic acid, isophthalic acid).
  • Preferred organic acids are aliphatic C 2-20 carboxylic acids, more preferably C 2-8 aliphatic carboxylic acids such as oxalic acid.
  • the anionic matrix comprises a C2-3o-dicarboxylic acid.
  • the anionic matrix comprises organic acids having at least two deprotonation steps and a pKa value for the first deprotonation step of less than 2.5.
  • Suitable polymeric acids are organic polymeric acids, such as polymers obtainable from ethylenically unsaturated anionic monomers (for example, from mono- ethylenically unsaturated C3-5-carboxylic acids, such as acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid, sulfonic acids, such as vinylsulfonic acid , Styrenesulfonic acid and acrylamidomethylpropanesulfonic acid; and phosphonic acids, such as vinylphosphonic acid, and / or in each case the alkali metal, alkaline earth metal and / or ammonium salts of these acids), preferably poly (meth) acrylic acid.
  • anionic monomers for example, from mono- ethylenically unsaturated C3-5-carboxylic acids, such as acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid
  • acidic biopolymers such as alginic acid, gum arabic, nucleic acids, pectins, proteins, and chemically modified biopolymers, such as ionic or ionizable polysaccharides, eg. Carboxymethylcellulose, chitosan, chitosan sulfate, and lignosulfonate.
  • anionic resins such as phenolsulfonic acid resins, or sulfonated melamine-formaldehyde resin.
  • the cationic matrix usually comprises at least one cationic compound.
  • the cationic matrix may contain at least 70% by weight, preferably at least 85% by weight and in particular at least 95% by weight of cationic compounds.
  • the cationic matrix preferably comprises an amine, in particular an alkylamine or an amine-containing polymer. Most preferably, the cationic matrix comprises a C8-3o primary alkylamine, such as octadecylamine.
  • the alkylamine or the amine-containing polymer preferably has a melting point of at least 30 ° C., particularly preferably of at least 40 ° C., and in particular of at least 50 ° C.
  • Suitable amines are aliphatic or aromatic amines which optionally carry further functional groups, such as hydroxyl or ether groups.
  • Suitable alkylamines are amines which contain a linear, branched and / or cyclic alkyl group.
  • the alkylamines may optionally carry further functional groups, such as hydroxy or ether groups.
  • Preferred alkylamines are linear or branched, primary alkylamines having 4-36 C atoms, preferably 10-24, and particularly preferably 14-22 C atoms.
  • Examples of these primary alkylamines are octadecylamine, laurylamine, olamine, palmitylamine, of which octadecylamine is especially preferred.
  • Further preferred alkylamines are linear or branched, secondary alkylamines having 2-24 C atoms, preferably 4-22, particularly preferably 6-18 C atoms. Examples of these secondary alkylamines are dioctylamine, di (ethylhexyl) amine. Further preferred alkylamines are linear or branched, tertiary alkylamines having 3-24 C atoms, preferably 6-22, particularly preferably 8-18 C atoms. Examples of these tertiary alkylamines are tributylamine.
  • alkylamines are linear or branched, quaternary alkylamines having 2-24 C atoms, preferably 4-22, particularly preferably 6-18 C atoms.
  • Suitable amine-containing polymers based on, for example, vinylimidazole units, vinylamine units, ethyleneimine units, dialkylaminoalkyl (meth) acrylates, dialkylaminoalkyl (meth) acrylamide, vinylpyridine units, preferably on ethyleneimine units.
  • Examples are polyethylenimine, polyvinylpyridine and copolymers of hydrophobic monomers with vinylpyridine, polyvinylimidazole and copolymers of hydrophobic monomers with vinylimidazole, poly-2- (N-dimethylamino) ethyl (meth) acrylate and copolymers of hydrophobic monomers with poly-2- ( N-dimethylamino) ethyl (meth) acrylate, poly-2- ⁇ - Morpholinoethyl (meth) acrylate and copolymers of hydrophobic monomers with poly-2-N-morpholinoethyl (meth) acrylate.
  • pesticide denotes at least one active ingredient selected from the group of fungicides, insecticides, nematicides, herbicides, safeners and / or growth regulators.
  • Preferred pesticides are fungicides, insecticides and herbicides, especially fungicides and herbicides. Also, 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 analogs, benzoylureas, diacylhydrazines, METI acaricides, and insecticides such as chloro-picrine, pymetrozine, flonicamide, clofentezine, hexythiazox, etoxazole, diafenthiuron, propargit, tetradifon, chlorfenapyr, DNOC, buprofezin, cyromazine, amitraz, hydramethylnon, acequinocyl, fluacrypyrim, rotenone, or derivatives thereof.
  • Suitable fungicides are fungicides of the classes dinitroanilines, allylamines, anilinopyrimidines, antibiotics, aromatic hydrocarbons, benzenesulfonamides, benzimidazoles, benzisothiazoles, benzophenones, benzothiadiazoles, benzotriazines, benzylcarbamates, carbamates, carboxamides, carboxamides, chloronitriles, cyanoacetamide oximes, cyanoimidazoles, cyclopropanecarboxamides, dicarboximides , Dihydrodioxazines, dinitrophenylcrotonates, dithiocarbamates, dithiolanes, ethylphosphonates, ethylaminothiazolecarboxamides, guanidines, hydroxy (2-amino) pyrimidines, hydroxyanilides, imidazoles, imidazolinones, inorganics
  • Suitable herbicides are herbicides of the classes of 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, phthala
  • Suitable cationic pesticides comprise at least one amino group.
  • Preferred cationic pesticides are cationic fungicides, such as bupirimate, dimethirimol, ethirimol, cyprodinil, mepanipyrim, pyrimethanil, propamarocarb, prothiocarb, fuberidazole, carbendazim, diflumetorim, ametoctradine, iminoctadine, dodemorph, tridemorph, fenpropimoph, aldimorph, fenpropidin, piperanil, spiroxamine, prochloraz, pefurazoate, triflumizole, imazalil, pyrifenox. Particularly preferred is fenpropimorph.
  • Suitable anionic pesticides include at least one carboxyl, thiocarboxyl, sulfonyl, sulfinyl, thiosulfonyl or phosphoric acid group, with the carboxyl group being preferred.
  • carboxyl group is preferred.
  • One skilled in the art can easily select such anionic pesticides from the above list of pesticides.
  • anionic pesticides are anionic herbicides such as 2,4,5-T, 2,4-D, 2,4-DB, acifluorfen-sodium, amidosulfuron, aminopyralid, amitrole, asulam, azimsulfuron, benazolin, bensulfuron-methyl, bentazone, bispyribac-sodium, bromoxynil, butroxydim, chloramben, chlorimuron-ethyl, chlorosulfuron, cinosulfuron, clopyralid, cloransulam-methyl, cyclosulfamuron, cycloxy-dim, dalapon, dicamba, dichlorprop, dichlorprop-P, diclofop, diclosulam, diflufenzopyr, dinoseb, DNOC, endothal, ethametsulfuron-methyl, ethoxysulfuron, fenoprop, fenopurobutoty
  • the starch granules may include, in addition to the anionic or cationic pesticide, other pesticides, especially neutral pesticides (ie pesticides which are not anionic or cationic pesticides).
  • the molar ratio of ionic charges from pesticide to matrix may range from 5: 1 to 1: 3, with the range from 3: 1 to 1: 2, especially the range from 1, 5: 1 to 1: 1, 3, and in particular the range of 1, 1: 1 to 1: 1, 1 is preferred.
  • the invention further relates to a process for the preparation of starch granules according to the invention by bringing a porous, partially hydrolyzed starch granules with a salt matrix containing the anionic or cationic pesticide and the cationic or anionic matrix in contact with each other.
  • the salt matrix contains the anionic or cationic pesticide and the cationic or anionic matrix, with the pesticide and matrix being oppositely charged.
  • the salt matrix also contains a liquid.
  • the salt matrix may contain from 1 to 90% by weight, preferably from 5 to 70% by weight, and in particular from 15 to 50% by weight, of anionic or cationic pesticide.
  • the starch granules are usually dispersed in a liquid.
  • Preferred liquid is water or an organic solvent which is at least 5% by weight soluble in water at 20 ° C.
  • the person skilled in the art depends on the solubility of the pesticide.
  • pesticides like Dicamba-Na, Dicamba-IPA, Imazapyr-Na
  • water is suitable.
  • Dicamba-H i.e., free acid
  • fenpropimorph organic solvents are suitable.
  • Preferred organic solvents are acetone, methyl ethyl ketone, methanol, ethanol, propanol, isopropanol, 1-butanol, isobutanol, THF. Particularly preferred are acetone, ethanol and isobutanol.
  • the temperature in the production process with aqueous pesticide solutions is usually from 10 to 80.degree. C., preferably from 15.degree. C. to 60.degree.
  • the temperature during filling with organic pesticide solutions is usually at least 10 ° C.
  • the temperature can rise to the boiling point of the organic solvent, preferably up to a maximum of 5 ° below the boiling point.
  • In order to bring the components into contact usually a period of 1 min to 24 h, preferably 0.5 h to 3 h. During this time, the components can be mixed.
  • the order of bringing the components into contact is arbitrary.
  • the organic solvent used can be removed, for example under vacuum.
  • the ratio of starch granules to pesticide may range from 1.2 to 5, preferably from 1.4 to 4.
  • the starch granules of the invention may also be contained in an agrochemical composition.
  • the composition may contain formulation auxiliaries, wherein the choice of the auxiliaries usually depends on the specific application form or the active substance.
  • suitable formulation auxiliaries are additional solvents, surfactants and other surface-active substances (such as solubilizers, protective colloids, wetting agents and adhesives), adjuvants, organic and inorganic thickeners, bactericides, antifreeze agents, defoamers, dyes and adhesives (for example for seed treatment).
  • Suitable agrochemical compositions are water-soluble concentrates (SL, LS), redispersible concentrates (TLC), emulsifiable concentrates (EC), emulsions (EW, EO, ES, ME), suspensions (SC, OD, FS), suspoemulsions (SE) , and powders and granules (WP, WG).
  • Additional solvents include organic solvents such as medium to high boiling point mineral oil fractions such as kerosene and diesel oil, as well as coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Paraffins, tetrahydronaphthalene, alkylated naphthalenes and derivatives thereof, alkylated benzenes and their derivatives, alcohols such as ethanol, propanol, butanol, benzyl alcohol and cyclohexanol, glycols, ketones such as cyclohexanone, gamma-butyrolactone, dimethyl fatty acid amides, fatty acids and fatty acid esters and highly polar Solvent, eg Amines such as N-methylpyrrolidone, into consideration.
  • solvent mixtures can also be used.
  • Surfactants can be used individually or in a mixture.
  • Surfactants are compounds that reduce the surface tension of water.
  • Suitable surfactants are anionic, cationic, nonionic and amphoteric surfactants, block polymers and polyelectrolytes.
  • Suitable anionic surfactants are alkali metal, alkaline earth metal or ammonium salts of sulfonates, sulfates, phosphates or carboxylates.
  • sulfonates are alkyla- rylsulfonates, diphenylsulfonates, alpha-olefinsulfonates, lignosulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of ethoxylated arylphenols, sulfonates of condensed naphthalene, sulfonates of dodecyl and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates ,
  • sulfates are sulfates of fatty acid and
  • phosphates are phosphate esters.
  • carboxylates are alkylcarboxylates and carboxylated alcohol or alkylphenol ethoxylates.
  • Preferred anionic surfactants are sulfonates of ethoxylated arylphenols, in particular phosphated or sulfated di- and / or Tristyrylphenylalkoxylate, as described for example in WO 2007/1 10355, page 3, line 30 to page 5, line 11.
  • 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 imidazoline.
  • Suitable block polymers are block polymers of A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide or of the A-B-C 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 polyethyleneamines.
  • composition of the invention may comprise any amount of surfactant. It can comprise from 0.1 to 40% by weight, preferably from 1 to 30% by weight and in particular from 2 to 20% by weight, of the total amount of surfactants, based on the total amount of the composition.
  • 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 ®; alcoholic Lethoxylates, z. 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 ®
  • alcoholic Lethoxylates z.
  • 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.
  • adhesives are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and cellulose ethers (Tylose ®, Shin-Etsu, Japan).
  • the agrochemical composition is usually diluted before use to produce the so-called tank mix.
  • mineral oil fractions of medium to high boiling point such as kerosene or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, eg toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, Propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone or water into consideration.
  • 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 may be mixed into the agrochemical compositions 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 a method for controlling phytopathogenic fungi and / or undesired plant growth and / or undesired insect or mite infestation and / or for regulating the growth of plants, wherein the starch granule (as in an agrochemical composition) affecting the particular pests, their habitat or the plants to be protected from the respective pest, the soil and / or undesirable plants and / or the crops and / or their habitat.
  • Advantages of the invention are that a slow release of the pesticide is possible, that controllable release of the pesticide is possible, that only a lesser loss of volatile pesticides takes place (eg a reduction in the evaporation rate, such as fenpropimorph), that the pesticide is resistant to chemical degradation is protected and that hydrophobic pesticides are more dispersible in aqueous formulations.
  • the preparation of the porous starch particles was carried out from corn starch having an average particle size of 14 ⁇ m as described in WO89 / 04842.
  • the preparation of a fine powder was carried out by freeze-drying.
  • the pore volume of the starch particles was calculated as follows:
  • Pore volume [(weight (weight) - weight (porous)) / density (strength)] x
  • the density of the starch was 1, 464 g / ml.
  • Example 1 Dicamba Na starch particles (not according to the invention)
  • porous starch particles 300 g were added to 399 g of aqueous solution of Dicamba isopropylammonium salt having a solids content of 50.1 wt.% And mixed with a mechanical stirrer at 20 ° C for 20h. Subsequently, the mixture was dried in a drying oven at 40 ° C and 100 mbar. This gave 513.3 g of colorless powder with a residual moisture content of 2.8%.
  • Example 3 Dicamba-H starch particles (not according to the invention)
  • Example 5 Dicamba H and Dicamba (Cationic Matrix) starch particles
  • Step A 10.0 g dicamba (free acid) and 1 1.33 g octadecylamine were mixed and heated to 120 ° C until a clear solution was obtained. After cooling to 20 ° C gave a waxy solid which has a melting point of 58 ° C.
  • Step B) 3.5 g of porous starch particles (pore volume 0.48 ml / g) and 1, 5 g of the product of step A and 3.33 g of iso-butanol were heated to 50 ° C and stirred for 1 h at this temperature. Subsequently, the iso-butanol was removed on a rotary evaporator at 60 ° C at a pressure of 8 mbar. This gives 4.78 g of powdery solid.
  • Example 6 Dicamba-H and Dicamba-H (Cationic Matrix) Thickness Particles Step A) 10.0 g of dicamba (free acid) and 9.26 g of octadecylamine were mixed and heated to 120 ° C until a clear solution resulted. After cooling to 20 ° C to give a waxy solid.
  • Step B) 3.5 g of porous starch particles (pore volume 0.48 ml / g) and 1, 5 g of the product of step A and 3.33 g of iso-butanol were heated to 50 ° C and stirred for 1 h at this temperature. Subsequently, the iso-butanol was removed on a rotary evaporator at 60 ° C at a pressure of 8 mbar. This gives 4.78 g of powdery solid.
  • Example 7 Starch particles with Dicamba-H and octadecylamine (cationic matrix) Step A) 10.0 g of dicamba (free acid) and 5.67 g of octadecylamine were mixed and heated to 120 ° C until a clear solution was formed. After cooling to 20 ° C gave a highly viscous liquid. Step B) 3.5 g of porous starch particles (pore volume 0.48 ml / g), 1, 5 g of the product of step A and 3.33 g of iso-butanol were heated to 50 ° C and stirred for 1 h at this temperature. Subsequently, the isobutanol was removed on a rotary evaporator at 60 ° C. at a pressure of 8 mbar. This gives 4.78 g of powdery solid.
  • the bottle was removed from the roller mixer and the sample allowed to sediment for 10 minutes. With a syringe 0.2 ml of the supernatant solution were removed and the pesticide content determined by HPLC.
  • Pesticide release was compared to a reference sample.
  • the reference sample was prepared under the same conditions and contained the same pesticide, but no retarding matrix.
  • the pesticide release of the reference sample was normalized to 100%.
  • the pesticide release of the matrix samples was reported relative to the reference sample (Table 1). By the starch granules according to the invention, the release could be slowed down.
  • Example 9 Starch particles with fenpropimorph and oxalic acid (anionic matrix) 1.0 g of fenpropimorph were dissolved in 3.3 g of acetone and admixed with 4 g of porous starch particles (pore volume 0.53 ml / g) and stirred at 20 ° C. for 1 h. Then, the acetone was removed at a pressure of 600 mbar and a bath temperature of 40 ° C on a rotary evaporator. To the residue was added a solution of 0.42 g of oxalic acid in 3.6 g of water. The residue was stirred at 20 ° C for 15 min.
  • Example 10 Starch particles with fenpropimorph and oxalic acid (anionic matrix) 1.0 g of fenpropimorph were dissolved in 3.3 g of acetone and admixed with 4 g of porous starch particles (pore volume 0.53 ml / g) and stirred at 20 ° C. for 1 h. Then, the acetone was removed at a pressure of 600 mbar and a bath temperature of 40 ° C on a rotary evaporator.
  • Example 1 1-Starch particles with fenpropimorph and oxalic acid (anionic matrix) 1.0 g of fenpropimorph were dissolved in 3.3 g of acetone and mixed with 4 g of porous starch particles (pore volume 0.53 ml / g) and stirred at 20 ° C. for 1 h , Then the acetone was removed at a pressure of 600 mbar and a bath temperature of 40 ° C on a rotary evaporator. To the residue was added a solution of 0.14 g of oxalic acid in 3.6 g of water. The residue was stirred at 20 ° C for 15 min. Subsequently, the water was removed at 40 ° C on a rotary evaporator. 4.85 g of colorless powder were obtained.
  • Example 12 Fenpropimorph starch particles (not according to the invention)
  • fenpropimorph 1.0 g of fenpropimorph were dissolved in 3.3 g of acetone and admixed with 4 g of porous starch particles (pore volume 0.53 ml / g) and stirred at 20 ° C. for 1 h. Then, the acetone was removed at a pressure of 600 mbar and a bath temperature of 40 ° C on a rotary evaporator.

Abstract

The invention relates to a porous, partially hydrolyzed starch granulate containing an anionic or cationic pesticide and a cationic or anionic matrix, wherein the pesticide and the matrix carry opposite charges. The invention further relates to a method for producing the starch granulate by contacting a porous, partially hydrolyzed starch granulate with a salt matrix containing the anionic or cationic pesticide and the cationic or anionic matrix, and to a method for controlling phytopathogenic fungi and/or undesired plant growth and/or undesired insects or mite infestation and/or for regulating the growth of plants, wherein the composition is allowed to act on the respective pests, on the habitat thereof or on the plants to be protected from the respective pests, on the soil and/or on undesired plants and/or on useful plants and/or on the habitat thereof.

Description

Poröses Stärkegranulat enthaltend ein anionisches oder kationisches Pestizid und ein kationische oder anionische Matrix Gegenstand der vorliegenden Erfindung ist ein poröses, teilhydrolysiertes Stärkegranulat enthaltend ein anionisches oder kationisches Pestizid und eine kationische oder anionische Matrix, wobei das Pestizid und die Matrix entgegengesetzt geladen sind. Weitere Gegenstände sind ein Verfahren zur Herstellung des Stärkegranulats indem man ein poröses, teilhydrolysiertes Stärkegranulat mit einer Salzmatrix enthaltend das anionische oder kationische Pestizid und die kationische oder anionische Matrix miteinander in Kontakt bringt; und Verfahren zur Bekämpfung von phytopathogenen Pilzen und/oder unerwünschtem Pflanzenwuchs und/oder unerwünschtem Insekten- oder Milbenbefall und/oder zur Regulation des Wachstums von Pflanzen, wobei man die Zusammensetzung auf die jeweiligen Schädlinge, deren Lebensraum oder die vor dem jeweiligen Schädling zu schützenden Pflanzen, den Boden und/oder auf unerwünschte Pflanzen und/oder die Nutzpflanzen und/oder deren Lebensraum einwirken lässt. Kombinationen bevorzugter Merkmale mit anderen bevorzugten Merkmalen werden von der vorliegenden Erfindung umfasst. US 2007/0160637 offenbart eine Zusammensetzung enthaltend ein teilhydrolysiertes, poröses Stärkegranulat, in dem ein Pestizid absorbiert ist, und ein Bindemittel oder Füllstoff.  Porous starch granules containing an anionic or cationic pesticide and a cationic or anionic matrix The present invention relates to a porous, partially hydrolyzed starch granules containing an anionic or cationic pesticide and a cationic or anionic matrix, wherein the pesticide and the matrix are oppositely charged. Further objects are a process for producing the starch granules by bringing a porous, partially hydrolyzed starch granules with a salt matrix containing the anionic or cationic pesticide and the cationic or anionic matrix in contact with each other; and methods for controlling phytopathogenic fungi and / or undesired plant growth and / or unwanted insect or mite infestation and / or for regulating the growth of plants, wherein the composition of the respective pests, their habitat or the plants to be protected from the respective pest , the soil and / or on unwanted plants and / or the crops and / or their habitat act. Combinations of preferred features with other preferred features are encompassed by the present invention. US 2007/0160637 discloses a composition comprising a partially hydrolyzed porous granular starch in which a pesticide is absorbed and a binder or filler.
WO 1995/19376 offenbart ein poröses Stärkegranulat, das mit einem Bindemittel ver- bunden ist, und das als Träger für Insektizide oder Herbizide wirken kann. WO 1995/19376 discloses a porous starch granule which is combined with a binder and which can act as a carrier for insecticides or herbicides.
WO 1989/04842 offenbart eine teilhydrolysierte Stärkematrix, die ein freisetzbares Ab- sorbat wie Insektizide oder Herbizide enthält. Nachteilig an den bekannten Stärkegranulaten ist, dass sie nur eine sehr schnelle Freisetzung von Wirkstoffen ermöglichen. WO 1989/04842 discloses a partially hydrolyzed starch matrix containing a releasable absorptive such as insecticides or herbicides. A disadvantage of the known starch granules is that they allow only a very rapid release of active ingredients.
Aufgabe der vorliegenden Erfindung war eine Zusammensetzung umfassend Pestizid bereitzustellen, welche diese Nachteile überwindet. The object of the present invention was to provide a composition comprising pesticide which overcomes these disadvantages.
Die Aufgabe wurde gelöst durch ein poröses, teilhydrolysiertes Stärkegranulat enthaltend ein anionisches oder kationisches Pestizid und eine kationische oder anionische Matrix, wobei das Pestizid und die Matrix entgegengesetzt geladen sind. The object has been achieved by a porous, partially hydrolyzed starch granules containing an anionic or cationic pesticide and a cationic or anionic matrix, wherein the pesticide and the matrix are oppositely charged.
In einer bevorzugten Form betrifft die Erfindung poröses, teilhydrolysiertes Stärkegranulat enthaltend ein anionisches Pestizid und eine kationische Matrix. In einer weiteren bevorzugten Form betrifft die Erfindung poröses, teilhydrolysiertes Stärkegranulat enthaltend ein kationisches Pestizid und eine anionsche Matrix. In a preferred form, the invention relates to porous, partially hydrolyzed starch granules containing an anionic pesticide and a cationic matrix. In another In preferred form, the invention relates to porous, partially hydrolyzed starch granules containing a cationic pesticide and an anionic matrix.
Poröses, teilhydrolysiertes Stärkegranulat ist allgemein bekannt, beispielsweise aus WO 1989/04842. Das Stärkegranulat kann hergestellt werden durch Behandlung von Stärkegranulat in einem wässrigem Medium (z.B. in wässriger Suspension), mit einer Glucoamylase, alpha-Amylase oder deren Mischungen. Die Temperatur wird meist unter dem Gelpunkt der Stärke sein. Geeignete alpha-Amylasen oder Glucoamylasen sind solche aus Rhizopus niveus, Aspergillus niger, Rhizopus oryzae, Bacillus subtilis. Porous, partially hydrolyzed starch granules are well known, for example from WO 1989/04842. The starch granules may be prepared by treating starch granules in an aqueous medium (e.g., in aqueous suspension), with a glucoamylase, alpha-amylase, or mixtures thereof. The temperature will usually be below the gel point of the starch. Suitable alpha-amylases or glucoamylases are those of Rhizopus niveus, Aspergillus niger, Rhizopus oryzae, Bacillus subtilis.
In einer bevorzugten Form wird das Stärkegranulat ohne weitere Aufarbeitung verwendet, beispielsweise in wässrigem Medium. In a preferred form, the starch granules are used without further work-up, for example in an aqueous medium.
In einer weiteren bevorzugten Form wird das Stärkegranulat in Pulverform isoliert, beispielsweise durch Trocknung. Geeignete Trocknungsmethoden sind Gefriertrocknung, Sprühtrocknung, Bandtrocknung oder Walzentrocknung. Geeignetes Stärkegranulat basiert beispielsweise auf Stärke aus Mais, Weizen, Tapio- ca, Kartoffel. Bevorzugtes Stärkegranulat basiert auf Stärke aus Mais. In a further preferred form, the starch granules are isolated in powder form, for example by drying. Suitable drying methods are freeze drying, spray drying, belt drying or drum drying. Suitable starch granules are based, for example, on corn starch, wheat, tapioca, potato. Preferred starch granules are based on corn starch.
Das Porenvolumen des porösen Stärkegranulats kann im Bereich von 0,05 bis 1 ml/g, bevorzugt von 0,2 bis 0,8 ml/g, besonders bevorzugt von 0,35 bis 0,65 ml/g liegen. Das Porenvolumen kann bestimmt werden durch die Absorption von Hexadecan im Vergleich zu der Hexadecanabsorption eines nicht porösen Stärkegranulates. The pore volume of the porous starch granules may range from 0.05 to 1 ml / g, preferably from 0.2 to 0.8 ml / g, more preferably from 0.35 to 0.65 ml / g. The pore volume can be determined by the absorption of hexadecane compared to the hexadecane absorption of a non-porous starch granule.
Das Stärkegranulat hat üblicherweise eine Teilchengröße von 1 bis 300 μηη, bevorzugt von 5 bis 100 μηη, besonders bevorzugt von 8 bis 30 μηη. Die Teilchengröße kann mit- tels Laserbeugung gemessen werden. The starch granules usually have a particle size of 1 to 300 μηη, preferably from 5 to 100 μηη, particularly preferably from 8 to 30 μηη. The particle size can be measured by means of laser diffraction.
Die Matrix kann als kontinuierliche oder diskontinuierliche Matrix vorliegen. Die Matrix hat meist ionische Wechselwirkungen mit dem Pestizid. Die ionischen Wechselwirkungen können zu einer verringerten Migration des Pestizides in der Matrix führen. Die Matrix kann Salze bilden mit dem Pestizid. The matrix can be in the form of a continuous or discontinuous matrix. The matrix mostly has ionic interactions with the pesticide. The ionic interactions can lead to reduced migration of the pesticide in the matrix. The matrix can form salts with the pesticide.
Die anionische Matrix umfasst üblicherweise mindestens eine anionsche Verbindung. Die anionische Matrix kann mindestens 70 Gew%, bevorzugt mindestens 85 Gew.-% und insbesondere mindestens 95 Gew.% anionische Verbindungen enthalten. Bevor- zugt umfasst die anionische Matrix eine anorganische Säure, eine organische Säure, und/oder eine polymere Säure, wobei organische Säure, insbesondere aliphatische C2- 30 Carbonsäuren, und speziell Oxalsäure bevorzugt sind. Die anorganischen, organischen und/oder polymeren Säuren könne eine oder mehrere Säuregruppen (z.B. Car- bonsäuregruppen) umfassen. The anionic matrix usually comprises at least one anionic compound. The anionic matrix may contain at least 70% by weight, preferably at least 85% by weight and in particular at least 95% by weight of anionic compounds. Before- The anionic matrix preferably comprises an inorganic acid, an organic acid, and / or a polymeric acid, organic acid, in particular aliphatic C 2-30 carboxylic acids, and especially oxalic acid being preferred. The inorganic, organic and / or polymeric acids may comprise one or more acid groups (eg carboxylic acid groups).
Geeignete anorganische Säuren sind Schwefelsäure, schweflige Säure, Phosphorsäure, Phosphorige Säure, Phosphonsäure, Phosphinsäure, Metaphosphorsäure, und Borsäure, wobei Phosphonsäure und Phosphorige Säure bevorzugt sind. Suitable inorganic acids are sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, metaphosphoric acid, and boric acid, with phosphonic acid and phosphorous acid being preferred.
Geeignete organische Säuren sind aliphatische C2-30 Carbonsäuren (wie Oxalsäure, Malonsäure, Bernsteinsäure, Glutarsäure, Adipinsäure, Maleinsäure, Fumarsäure, Zitronensäure, Äpfelsäure, Weinsäure) oder aromatische C7-30 Carbonsäuren (wie Terephtalsäure, Phthalsäure, Isophthalsäure). Bevorzugte organische Säuren sind aliphatische C2-20 Carbonsäuren, besonders bevorzugt aliphatische C2-8 Carbonsäuren, wie Oxalsäure. Suitable organic acids are aliphatic C 2-30 carboxylic acids (such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, citric acid, malic acid, tartaric acid) or aromatic C 7-30 carboxylic acids (such as terephthalic acid, phthalic acid, isophthalic acid). Preferred organic acids are aliphatic C 2-20 carboxylic acids, more preferably C 2-8 aliphatic carboxylic acids such as oxalic acid.
Bevorzugt umfasst die anionische Matrix eine C2-3o-Dicarbonsäure. In einer weiteren Form umfasst die anionische Matrix organische Säuren, die mindestens zwei Deprotonierungsstufen haben, und mit einem pKs-Wert für die erste Depro- tonierungsstufe von kleiner 2,5. Preferably, the anionic matrix comprises a C2-3o-dicarboxylic acid. In another form, the anionic matrix comprises organic acids having at least two deprotonation steps and a pKa value for the first deprotonation step of less than 2.5.
Geeignete polymere Säuren sind organische polymere Säuren, wie aus ethylenisch ungesättigten anionischen Monomeren erhältliche Polymere (z.B. aus mono- ethylenisch ungesättigte C3-5-Carbonsauren wie Acrylsäure, Methacrylsäure, Ethacryl- säure, Crotonsäure, Maleinsäure, Fumarsäure und Itaconsäure; Sulfonsäuren wie Vi- nylsulfonsäure, Styrolsulfonsäure und Acrylamidomethylpropansulfonsäure; und Phos- phonsäuren wie Vinylphosphonsäure; und/oder jeweils die Alkalimetall-, Erdalkalime- tall-und/oder Ammoniumsalze dieser Säuren), bevorzugt Poly(meth)acrylsäure. Weiterhin geeignet sind saure Biopolymere, wie Alginsäure, Gummi arabicum, Nucleinsäu- ren, Pektine, Proteine, sowie chemisch modifizierte Biopolymere, wie ionische oder ionisierbare Polysaccharide, z. B. Carboxymethylcellulose, Chitosan, Chitosansulfat, und Ligninsulfonat. Weiterhin geeignet sind anionische Harze, wie Phenolsulfonsäu- reharze, oder sulfoniertes Melamin-Formaldehydharz. Suitable polymeric acids are organic polymeric acids, such as polymers obtainable from ethylenically unsaturated anionic monomers (for example, from mono- ethylenically unsaturated C3-5-carboxylic acids, such as acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid, sulfonic acids, such as vinylsulfonic acid , Styrenesulfonic acid and acrylamidomethylpropanesulfonic acid; and phosphonic acids, such as vinylphosphonic acid, and / or in each case the alkali metal, alkaline earth metal and / or ammonium salts of these acids), preferably poly (meth) acrylic acid. Also suitable are acidic biopolymers, such as alginic acid, gum arabic, nucleic acids, pectins, proteins, and chemically modified biopolymers, such as ionic or ionizable polysaccharides, eg. Carboxymethylcellulose, chitosan, chitosan sulfate, and lignosulfonate. Also suitable are anionic resins, such as phenolsulfonic acid resins, or sulfonated melamine-formaldehyde resin.
Die kationische Matrix umfasst üblicherweise mindestens eine kationische Verbindung. Die kationische Matrix kann mindestens 70 Gew%, bevorzugt mindestens 85 Gew.-% und insbesondere mindestens 95 Gew.% kationische Verbindungen enthalten. Bevor- zugt umfasst die kationische Matrix ein Amin, insbesondere ein Alkylamin oder ein A- min-haltiges Polymer. Besonders bevorzugt umfasst die kationische Matrix ein primäres C8-3o-Alkylamin, wie Octadecylamin. Bevorzugt hat das Alkylamin oder das Amin-haltige Polymer eine Schmelzpunkt von mindestens 30 °C, besonders bevorzugt von mindestens 40 °C, und insbesondere von mindestens 50 °C. The cationic matrix usually comprises at least one cationic compound. The cationic matrix may contain at least 70% by weight, preferably at least 85% by weight and in particular at least 95% by weight of cationic compounds. Before- The cationic matrix preferably comprises an amine, in particular an alkylamine or an amine-containing polymer. Most preferably, the cationic matrix comprises a C8-3o primary alkylamine, such as octadecylamine. The alkylamine or the amine-containing polymer preferably has a melting point of at least 30 ° C., particularly preferably of at least 40 ° C., and in particular of at least 50 ° C.
Geeignete Amine sind aliphatische oder aromatische Amine, die optional weitere funk- tionelle Gruppen tragen, wie Hydroxy- oder Ether-gruppen. Suitable amines are aliphatic or aromatic amines which optionally carry further functional groups, such as hydroxyl or ether groups.
Geeignete Alkylamine sind Amine, die eine lineare, verzweigte und/oder cyclische Al- kylgruppe enthalten. Die Alkylamine können optional weitere funktionelle Gruppen tragen, wie Hydroxy- oder Ether-gruppen. Suitable alkylamines are amines which contain a linear, branched and / or cyclic alkyl group. The alkylamines may optionally carry further functional groups, such as hydroxy or ether groups.
Bevorzugte Alkylamine sind lineare oder verzweigte, primäre Alkylamine mit 4-36 C Atomen, bevorzugt 10-24, und besonders bevorzugt 14-22 C Atomen. Beispiele für diese primäre Alkylamine sind Octadecylamin, Laurylamin, Ölamin, Palmitylamin, wovon Octadecylamin speziell bevorzugt ist. Preferred alkylamines are linear or branched, primary alkylamines having 4-36 C atoms, preferably 10-24, and particularly preferably 14-22 C atoms. Examples of these primary alkylamines are octadecylamine, laurylamine, olamine, palmitylamine, of which octadecylamine is especially preferred.
Weiterhin bevorzugte Alkylamine sind lineare oder verzweigte, sekundäre Alkylamine mit 2-24 C Atomen, bevorzugt 4-22, besonders bevorzugt 6-18 C Atomen. Beispiele für diese sekundären Alkylamine sind Dioctylamin, Di(ethylhexyl)amin. Weiterhin bevorzugte Alkylamine sind lineare oder verzweigte, tertiäre Alkylamine mit 3-24 C Atomen, bevorzugt 6-22, besonders bevorzugt 8-18 C Atomen. Beispiele für diese tertiären Alkylamine sind Tributylamin. Further preferred alkylamines are linear or branched, secondary alkylamines having 2-24 C atoms, preferably 4-22, particularly preferably 6-18 C atoms. Examples of these secondary alkylamines are dioctylamine, di (ethylhexyl) amine. Further preferred alkylamines are linear or branched, tertiary alkylamines having 3-24 C atoms, preferably 6-22, particularly preferably 8-18 C atoms. Examples of these tertiary alkylamines are tributylamine.
Weiterhin bevorzugte Alkylamine sind lineare oder verzweigte, quarternäre Alkylamine mit 2-24 C Atomen, bevorzugt 4-22, besonders bevorzugt 6-18 C Atomen. Further preferred alkylamines are linear or branched, quaternary alkylamines having 2-24 C atoms, preferably 4-22, particularly preferably 6-18 C atoms.
Geeignete Amin-haltige Polymere basierend auf z.B. Vinylimidazoleinheiten, Vinyla- mineinheiten, Ethylenimineinheiten, Dialkylaminoalkyl(meth)acrylaten, Dialkylaminoal- kyl(meth)acrylamid, Vinylpyridineinheiten, bevorzugt auf Ethylenimineinheiten. Beispie- le sind Polyethylenimin, Polyvinylpyridin und Copolymere von hydrophoben Monomeren mit Vinylpyridin, Polyvinylimidazol und Copolymere von hydrophoben Monomeren mit Vinylimidazol, Poly-2-(N-Dimethylamino)ethyl-(meth)acrylat und Copolymere von hydrophoben Monomeren mit Poly-2-(N-Dimethylamino)ethyl-(meth)acrylat, Poly-2-Ν- Morpholinoethyl-(meth)acrylat und Copolymere von hydrophoben Monomeren mit Poly- 2-N-Morpholinoethyl-(meth)acrylat. Suitable amine-containing polymers based on, for example, vinylimidazole units, vinylamine units, ethyleneimine units, dialkylaminoalkyl (meth) acrylates, dialkylaminoalkyl (meth) acrylamide, vinylpyridine units, preferably on ethyleneimine units. Examples are polyethylenimine, polyvinylpyridine and copolymers of hydrophobic monomers with vinylpyridine, polyvinylimidazole and copolymers of hydrophobic monomers with vinylimidazole, poly-2- (N-dimethylamino) ethyl (meth) acrylate and copolymers of hydrophobic monomers with poly-2- ( N-dimethylamino) ethyl (meth) acrylate, poly-2-Ν- Morpholinoethyl (meth) acrylate and copolymers of hydrophobic monomers with poly-2-N-morpholinoethyl (meth) acrylate.
Der Begriff Pestizid bezeichnet mindestens einen Wirkstoff ausgewählt aus der Gruppe der Fungizide, Insektizide, Nematizide, Herbizide, Safener und/oder Wachstumsregulatoren. Bevorzugte Pestizide sind Fungizide, Insektizide und Herbizide, insbesondere Fungizide und Herbizide. Auch Mischungen von Pestiziden aus zwei oder mehr der vorgenannten Klassen können verwendet werden. Der Fachmann ist vertraut mit solchen Pestiziden, die beispielsweise in Pesticide Manual, 14th Ed. (2006), The British Crop Protection Council, London, gefunden werden können. Geeignete Insektizide sind Insektizide der Klasse der Carbamate, Organophophate, Organochlor-Insektizide, Phenylpyrazole, Pyrethroide, Neonicotinoide, Spinosine, Avermectine, Milbemycine, Juvenil Hormon Analoga, Alkylhalide, Organozinn-Verbindungen, Nereistoxin-Analoga, Benzoylharnstoffe, Diacylhydrazine, METI Akarizide, sowie Insektizide wie Chloro- picrin, Pymetrozin, Flonicamid, Clofentezin, Hexythiazox, Etoxazol, Diafenthiuron, Pro- pargit, Tetradifon, Chlorfenapyr, DNOC, Buprofezin, Cyromazin, Amitraz, Hydrame- thylnon, Acequinocyl, Fluacrypyrim, Rotenon, oder deren Derivate. Geeignete Fungizide sind Fungizide der Klassen Dinitroaniline, Allylamine, Anilinopyrimidine, Antibiotica, aromatische Kohlenwasserstoffe, Benzenesulfonamide, Benzimidazole, Benzisothiazo- le, Benzophenone, Benzothiadiazole, Benzotriazine, Benzylcarbamate, Carbamates, Carboxamide, Carbonsäureamide, Chloronitrile, Cyanoacetamideoxime, Cyanoimida- zole, Cyclopropanecarboxamide, Dicarboximide, Dihydrodioxazine, Dinitrophenylcroto- nate, Dithiocarbamate, Dithiolane, Ethylphosphonate, Ethylaminothiazolcarboxamide, Guanidines, Hydroxy-(2-amino-)pyrimidine, Hydroxyanilides, Imidazole, Imidazolinone, Anorganika, Isobenzofuranone, Methoxyacrylate, Methoxycarbamates, Morpholines, N- Phenylcarbamate, Oxazolidinedione, Oximinoacetate, Oximinoacetamide, Peptidylpy- rimidinnucleoside, Phenylacetamide, Phenylamide, Phenylpyrrole, Phenylharnstoffe, Phosphonate, Phosphorothiolate, Phthalamsäuren, Phthalimide, Piperazine, Piperidi- ne, Propionamide, Pyridazinone, Pyridine, Pyridinylmethylbenzamide, Pyrimidinamine, Pyrimidine, Pyrimidinonehydrazone, Pyrroloquinolinone, Quinazolinone, Chinoline, Chinone, Sulfamide, Sulfamoyltriazole, Thiazolecarboxamide, Thiocarbamate, Thi- ophanate, Thiophenecarboxamide, Toluamide, Triphenylzinn Verbindungen, Triazine, Triazole. Geeignete Herbizide sind Herbizide der Klassen der Acetamide, Amide, Ary- loxyphenoxypropionate, Benzamide, Benzofuran, Benzoesäuren, Benzothiadiazinone, Bipyridylium, Carbamate, Chloroacetamide, Chlorcarbonsäuren, Cyclohexanedione, Dinitroaniline, Dinitrophenol, Diphenylether, Glycine, Imidazolinone, Isoxazole, Iso- xazolidinone, Nitrile, N-phenylphthalimide, Oxadiazole, Oxazolidinedione, Oxyacetami- de, Phenoxycarbonsäuren, Phenylcarbamate, Phenylpyrazole, Phenylpyrazoline, Phe- nylpyridazine, Phosphinsäuren, Phosphoroamidate, Phosphorodithioate, Phthalamate, Pyrazole, Pyridazinone, Pyridine, Pyridincarbonsäuren, Pyridinecarboxamide, Pyrimi- dindione, Pyrimidinyl(thio)benzoate, Chinolincarbonsäuren, Semicarbazone, Sul- fonylaminocarbonyltriazolinone, Sulfonylharnstoffe, Tetrazolinone, Thiadiazole, Thio- carbamate, Triazine, Triazinone, Triazole, Triazolinone, Triazolocarboxamide, Triazo- lopyrimidine, Triketone, Uracile, Harnstoffe. The term pesticide denotes at least one active ingredient selected from the group of fungicides, insecticides, nematicides, herbicides, safeners and / or growth regulators. Preferred pesticides are fungicides, insecticides and herbicides, especially fungicides and herbicides. Also, 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 analogs, benzoylureas, diacylhydrazines, METI acaricides, and insecticides such as chloro-picrine, pymetrozine, flonicamide, clofentezine, hexythiazox, etoxazole, diafenthiuron, propargit, tetradifon, chlorfenapyr, DNOC, buprofezin, cyromazine, amitraz, hydramethylnon, acequinocyl, fluacrypyrim, rotenone, or derivatives thereof. Suitable fungicides are fungicides of the classes dinitroanilines, allylamines, anilinopyrimidines, antibiotics, aromatic hydrocarbons, benzenesulfonamides, benzimidazoles, benzisothiazoles, benzophenones, benzothiadiazoles, benzotriazines, benzylcarbamates, carbamates, carboxamides, carboxamides, chloronitriles, cyanoacetamide oximes, cyanoimidazoles, cyclopropanecarboxamides, dicarboximides , Dihydrodioxazines, dinitrophenylcrotonates, dithiocarbamates, dithiolanes, ethylphosphonates, ethylaminothiazolecarboxamides, guanidines, hydroxy (2-amino) pyrimidines, hydroxyanilides, imidazoles, imidazolinones, inorganics, isobenzofuranones, methoxyacrylates, methoxycarbamates, morpholines, N-phenylcarbamates, oxazolidinediones, oximinoacetates , Oximinoacetamides, peptidyl-pyrimidine nucleosides, phenylacetamides, phenylamides, phenylpyrroles, phenylureas, phosphonates, phosphorothiolates, phthalamic acids, phthalimides, piperazines, piperidines, propionamides, pyridazinones, pyridines, pyridinylmethylbenzamides, Py rimidinamines, pyrimidines, pyrimidinonehydrazones, pyrroloquinolinones, quinazolinones, quinolines, quinones, sulphamides, sulphamoyltriazoles, thiazolecarboxamides, thiocarbamates, thiopanates, thiophenecarboxamides, toluamides, triphenyltin compounds, triazines, triazoles. Suitable herbicides are herbicides of the classes of 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, Pyrazoles, pyridazinones, pyridines, pyridinecarboxylic acids, pyridinecarboxamides, pyrimidinedione, pyrimidinyl (thio) benzoates, quinolinecarboxylic acids, semicarbazones, sulfonylaminocarbonyltriazolinones, sulfonylureas, tetrazolinones, thiadiazoles, thiocarbamates, triazines, triazinones, triazoles, triazolinones, triazolocarboxamides, triazolones lopyrimidines, triketones, uracils, ureas.
Geeignete kationische Pestizide umfassen mindestens eine Amino-Gruppe. Der Fachmann kann solche kationischen Pestizide aus oben stehender Liste von Pestiziden einfach auswählen. Bevorzugte kationische Pestizide sind kationische Fungizide, wie bupirimate, dimethirimol, ethirimol, Cyprodinil, mepanipyrim, pyrimethanil, Propa- mocarb, prothiocarb, fuberidazole, carbendazim, diflumetorim, ametoctradin, iminocta- dine, dodemorph, tridemorph, fenpropimoph, aldimorph, fenpropidin, piperanil, spiro- xamine, prochloraz, pefurazoate, triflumizole, imazalil, pyrifenox. Besonders bevorzugt ist Fenpropimorph. Suitable cationic pesticides comprise at least one amino group. One skilled in the art can easily select such cationic pesticides from the above list of pesticides. Preferred cationic pesticides are cationic fungicides, such as bupirimate, dimethirimol, ethirimol, cyprodinil, mepanipyrim, pyrimethanil, propamarocarb, prothiocarb, fuberidazole, carbendazim, diflumetorim, ametoctradine, iminoctadine, dodemorph, tridemorph, fenpropimoph, aldimorph, fenpropidin, piperanil, spiroxamine, prochloraz, pefurazoate, triflumizole, imazalil, pyrifenox. Particularly preferred is fenpropimorph.
Geeignete anionische Pestizide umfassen mindestens eine Carboxyl-, Thiocarboxyl-, Sulfonyl-, Sulfinyl-, Thiosulfonyl- oder Phosphorsäure-Gruppe, wobei die Car- boxylgruppe bevorzugt ist. Der Fachmann kann solche anionischen Pestizide aus oben stehender Liste von Pestiziden einfach auswählen. Bevorzugte anionische Pestizide sind anionische Herbizide, wie 2,4,5-T, 2,4-D, 2,4-DB, acifluorfen-sodium, amidosulfu- ron, aminopyralid, amitrole, asulam, azimsulfuron, benazolin, bensulfuron-methyl, bentazone, bispyribac-sodium, bromoxynil, butroxydim, chloramben, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, clopyralid, cloransulam-methyl, cyclosulfamuron, cycloxy- dim, dalapon, dicamba, dichlorprop, dichlorprop-P, diclofop, diclosulam, diflufenzopyr, dinoseb, DNOC, endothal, ethametsulfuron-methyl, ethoxysulfuron, fenoprop, fenop- rop-butotyl, flamprop, flazasulfuron, florasulam, fluazifop, fluazifop-P, flucarbazone- sodium, flucetosulfuron, flumetsulam, flupyrsulfuron-methyl-sodium, fomesafen, fora- msulfuron, glufosinate, glyphosate, halosulfuron-methyl, haloxyfop, haloxyfop-P, ima- zamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, iodosulfuron- methyl-sodium, ioxynil, MCPA, MCPB, mecoprop, mecoprop-P, mefluidide, mesosulfu- ron-methyl, mesotrione, metosulam, metsulfuron-methyl, naptalam, nicosulfuron, nonanoic acid, oxasulfuron, penoxsulam, pentachlorophenol, picloram, primisulfuron- methyl, profoxydim, propoxycarbazone-sodium, prosulfuron, pyrasulfotole, pyrazosulfu- ron-ethyl, pyrithiobac-sodium, pyroxsulam, quinclorac, quinmerac, quizalofop-P-tefuryl, rimsulfuron, saflufenacil, sulcotrione, sulfentrazone, sulfometuron-methyl, sulfosulfuron, tembotrione, tepraloxydim, thifensulfuron-methyl, topramezone, tralkoxydim, triasulfu- ron, tribenuron-methyl, triclopyr, trifloxysulfuron-sodium, triflusulfuron-methyl, Tritosul- furon. Besonders bevorzugt ist Dicamba. Das Stärkegranulat kann neben dem anionischen oder kationischen Pestizid auch weitere Pestizide umfassen, insbesondere neutrale Pestizide (d.h. Pestizide, die keine anionische oder kationische Pestizide sind). Das Molverhältnis der ionischen Ladungen von Pestizid zu Matrix kann im Bereich von 5:1 bis 1 :3 liegen, wobei der Bereich von 3:1 bis 1 :2, besonders der Bereich von 1 ,5:1 bis 1 :1 ,3, und insbesondere der Bereich von 1 ,1 :1 bis 1 :1 ,1 bevorzugt ist. Suitable anionic pesticides include at least one carboxyl, thiocarboxyl, sulfonyl, sulfinyl, thiosulfonyl or phosphoric acid group, with the carboxyl group being preferred. One skilled in the art can easily select such anionic pesticides from the above list of pesticides. Preferred anionic pesticides are anionic herbicides such as 2,4,5-T, 2,4-D, 2,4-DB, acifluorfen-sodium, amidosulfuron, aminopyralid, amitrole, asulam, azimsulfuron, benazolin, bensulfuron-methyl, bentazone, bispyribac-sodium, bromoxynil, butroxydim, chloramben, chlorimuron-ethyl, chlorosulfuron, cinosulfuron, clopyralid, cloransulam-methyl, cyclosulfamuron, cycloxy-dim, dalapon, dicamba, dichlorprop, dichlorprop-P, diclofop, diclosulam, diflufenzopyr, dinoseb, DNOC, endothal, ethametsulfuron-methyl, ethoxysulfuron, fenoprop, fenopurobutotyl, flamprop, flazasulfuron, florasulam, fluazifop, fluazifop-P, flucarbazone-sodium, flucetosulfuron, flumetsulam, flupyrsulfuron-methyl-sodium, fomesafen, foramsulfuron, glufosinate, glyphosate, halosulfuron-methyl, haloxyfop, haloxyfop-P, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, iodosulfuron-methyl-sodium, ioxynil, MCPA, MCPB, mecoprop, mecoprop-P, mefluidide, mesosulphur ron-methyl, mesotrione, metosulam, me tsulfuron-methyl, naptalam, nicosulfuron, nonanoic acid, oxasulfuron, penoxsulam, pentachlorophenol, picloram, primisulfuron-methyl, profoxydim, propoxycarbazone-sodium, prosulfuron, pyrasulfotole, pyrazosulfuron-ethyl, pyrithiobac-sodium, pyroxsulam, quinclorac, quinmerac, quizalofop P-tefuryl, rimsulfuron, saflufenacil, sulcotrione, sulfentrazone, sulfometuron-methyl, sulfosulfuron, tembotrione, tepraloxydim, thifensulfuron-methyl, topramezone, tralkoxydim, triasulfuron, tribenuron-methyl, triclopyr, trifloxysulfuron-sodium, triflusulfuron-methyl, tritosul - furon. Particularly preferred is Dicamba. The starch granules may include, in addition to the anionic or cationic pesticide, other pesticides, especially neutral pesticides (ie pesticides which are not anionic or cationic pesticides). The molar ratio of ionic charges from pesticide to matrix may range from 5: 1 to 1: 3, with the range from 3: 1 to 1: 2, especially the range from 1, 5: 1 to 1: 1, 3, and in particular the range of 1, 1: 1 to 1: 1, 1 is preferred.
Die Erfindung betrifft weiterhin ein Verfahren zur Herstellung des erfindungsgemäßen Stärkegranulats indem man ein poröses, teilhydrolysiertes Stärkegranulat mit einer Salzmatrix enthaltend das anionische oder kationische Pestizid und die kationische oder anionische Matrix miteinander in Kontakt bringt. The invention further relates to a process for the preparation of starch granules according to the invention by bringing a porous, partially hydrolyzed starch granules with a salt matrix containing the anionic or cationic pesticide and the cationic or anionic matrix in contact with each other.
Die Salzmatrix enthält das anionische oder kationische Pestizid und die kationische oder anionische Matrix, wobei das Pestizid und die Matrix entgegengesetzt geladen sind. Bevorzugt enthält die Salzmatrix auch eine Flüssigkeit. Die Salzmatrix kann 1 bis 90 Gew.%, bevorzugt 5 bis 70 Gew.%, und insbesondere 15 bis 50 Gew.% von anionischem oder kationischem Pestizid enthalten. Bei dem Herstellverfahren ist das Stärkegranulat üblicherweise in einer Flüssigkeit dis- pergiert. The salt matrix contains the anionic or cationic pesticide and the cationic or anionic matrix, with the pesticide and matrix being oppositely charged. Preferably, the salt matrix also contains a liquid. The salt matrix may contain from 1 to 90% by weight, preferably from 5 to 70% by weight, and in particular from 15 to 50% by weight, of anionic or cationic pesticide. In the production process, the starch granules are usually dispersed in a liquid.
Bevorzugte Flüssigkeit ist Wasser oder ein organisches Lösungsmittel ist, welches bei 20 °C zu mindestens 5 Gew.% in Wasser löslich ist. Der Fachmann richtet sich dabei nach der Löslichkeit des Petizides. Für Pestizide wie Dicamba-Na, Dicamba-IPA, Ima- zapyr-Na ist Wasser geeignet. Für Pestizide wie Dicamba-H (d.h. freie Säure) und Fenpropimorph sind organische Lösemittel geeignet.  Preferred liquid is water or an organic solvent which is at least 5% by weight soluble in water at 20 ° C. The person skilled in the art depends on the solubility of the pesticide. For pesticides like Dicamba-Na, Dicamba-IPA, Imazapyr-Na, water is suitable. For pesticides such as Dicamba-H (i.e., free acid) and fenpropimorph, organic solvents are suitable.
Bevorzugte organische Lösungsmittel sind Aceton, Methylethylketon, Methanol, Ethanol, Propanol, iso-Propanol, 1 -Butanol, iso-Butanol, THF. Besonders bevorzugt sind Aceton, Ethanol und iso-Butanol. Preferred organic solvents are acetone, methyl ethyl ketone, methanol, ethanol, propanol, isopropanol, 1-butanol, isobutanol, THF. Particularly preferred are acetone, ethanol and isobutanol.
Die Temperatur beim Herstellverfahren mit wässrigen Pestizidlosungen liegt meist bei 10 bis 80°C, bevorzugt bei 15°C bis 60°C. Die Temperatur beim Befüllen mit organischen Pestizidlosungen liegt meist bei mindestens 10°C. Die Temperatur kann bis zum Siedepunkt des organischen Lösungsmittels steigen, bevorzugt bis maximal 5° unterhalb des Siedepunktes. Um die Komponenten in Kontakt zu bringen, reicht meist eine Zeitdauer von 1 min bis 24 h, bevorzugt on 0,5 h bis 3 h. Während dieser Zeit können die Komponenten vermischt werden. Die Reihenfolge des in Kontakt bringens der Komponenten ist beliebig. Zur Aufarbeitung kann das eingesetzte organische Lösungsmittel entfernt werden, beispielsweise unter Vakuum. The temperature in the production process with aqueous pesticide solutions is usually from 10 to 80.degree. C., preferably from 15.degree. C. to 60.degree. The temperature during filling with organic pesticide solutions is usually at least 10 ° C. The temperature can rise to the boiling point of the organic solvent, preferably up to a maximum of 5 ° below the boiling point. In order to bring the components into contact, usually a period of 1 min to 24 h, preferably 0.5 h to 3 h. During this time, the components can be mixed. The order of bringing the components into contact is arbitrary. For workup, the organic solvent used can be removed, for example under vacuum.
Das Mengenverhältnis von Stärkegranulat zu Pestizid kann im Bereich von 1 ,2 bis 5, bevorzugt von 1 ,4 bis 4 liegen. The ratio of starch granules to pesticide may range from 1.2 to 5, preferably from 1.4 to 4.
Das erfindungsgemäße Stärkegranulat kann auch in einer agrochemischen Zusammensetzung enthalten sein. Die Zusammensetzung kann Formulierungshilfsmittel enthalten, wobei sich die Wahl der Hilfsmittel üblicherweise nach der konkreten Anwendungsform bzw. dem Wirkstoff richtet. Beispiele für geeignete Formulierungshilfsmittel sind zusätzliche Lösungsmittel, Tenside und andere oberflächenaktive Stoffe (wie So- lubilisatoren, Schutzkolloide, Netzmittel und Haftmittel), Adjuvantien, organische und anorganische Verdicker, Bakterizide, Frostschutzmittel, Entschäumer, Farbstoffe und Kleber (z. B. für Saatgutbehandlung). Geeignete agrochemische Zusammensetzungen sind wasserlösliche Konzentrate (SL, LS), redispergierbare Konzentrate (DC), emul- gierbare Konzentrate (EC), Emulsionen (EW, EO, ES, ME), Suspensionen (SC, OD, FS), Suspoemulsionen (SE), und Pulver und Granulate (WP, WG). The starch granules of the invention may also be contained in an agrochemical composition. The composition may contain formulation auxiliaries, wherein the choice of the auxiliaries usually depends on the specific application form or the active substance. Examples of suitable formulation auxiliaries are additional solvents, surfactants and other surface-active substances (such as solubilizers, protective colloids, wetting agents and adhesives), adjuvants, organic and inorganic thickeners, bactericides, antifreeze agents, defoamers, dyes and adhesives (for example for seed treatment). , Suitable agrochemical compositions are water-soluble concentrates (SL, LS), redispersible concentrates (TLC), emulsifiable concentrates (EC), emulsions (EW, EO, ES, ME), suspensions (SC, OD, FS), suspoemulsions (SE) , and powders and granules (WP, WG).
Als zusätzliche Lösungsmittel kommen organische Lösungsmittel wie Mineralölfraktionen von mittlerem bis hohem Siedepunkt wie Kerosin und Dieselöl, ferner Kohlenteer- öle sowie Öle pflanzlichen oder tierischen Ursprungs, aliphatische, cyclische und aromatische Kohlenwasserstoffe, z.B. Paraffine, Tetrahydronaphthalin, alkylierte Naphtha- line und deren Derivate, alkylierte Benzole und deren Derivate, Alkohole wie Ethanol, Propanol, Butanol, Benzylalkohol und Cyclohexanol, Glykole, Ketone wie Cyclohexa- non, gamma-Butyrolacton, Dimethylfettsäureamide, Fettsäuren und Fettsäureester und stark polare Lösungsmittel, z.B. Amine wie N-Methylpyrrolidon, in Betracht. Grundsätzlich können auch Lösungsmittelgemische verwendet werden. Additional solvents include organic solvents such as medium to high boiling point mineral oil fractions such as kerosene and diesel oil, as well as coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Paraffins, tetrahydronaphthalene, alkylated naphthalenes and derivatives thereof, alkylated benzenes and their derivatives, alcohols such as ethanol, propanol, butanol, benzyl alcohol and cyclohexanol, glycols, ketones such as cyclohexanone, gamma-butyrolactone, dimethyl fatty acid amides, fatty acids and fatty acid esters and highly polar Solvent, eg Amines such as N-methylpyrrolidone, into consideration. In principle, solvent mixtures can also be used.
Tenside können einzeln oder in Mischung eingesetzt werden. Tenside sind Verbindungen, welche die Oberflächenspannung von Wasser verringern. Als Tenside kommen anionische, kationische, nicht-ionische und amphotere Tenside, Blockpolymere und Polyelektrolyte in Betracht. Surfactants can be used individually or in a mixture. Surfactants are compounds that reduce the surface tension of water. Suitable surfactants are anionic, cationic, nonionic and amphoteric surfactants, block polymers and polyelectrolytes.
Geeignete anionische Tenside sind Alkali-, Erdalkali- oder Ammoniumsalze von Sulfo- naten, Sulfaten, Phosphaten oder Carboxylaten. Beispiele für Sulfonate sind Alkyla- rylsulfonate, Diphenylsulfonate, alpha-Olefinsulfonate, Ligninsulfonate, Sulfonate von Fettsäuren und Ölen, Sulfonate von ethoxylierten Alkylphenolen, Sulfonate von ethoxy- lierten Arylphenolen, Sulfonate von kondensierten Naphtalinen, Sulfonate von Dodecyl und Tridecylbenzolen, Sulfonate von Naphthalinen und Alkylnaphthalinen, Sulfosucci- nate oder Sulfosuccinamate. Beispiele für Sulfate sind Sulfate von Fettsäure und Ölen, von ethoxylierten Alkylphenolen, von Alkoholen, von ethoxylierten Alkoholen, oder von Fettsäureestern. Beispiele für Phosphate sind Phosphatester. Beispiele für Carboxylate sind Alkylcarboxylate und carboxylierte Alkohol- oder Alkylphenolethoxylate. Bevorzugte anionische Tenside sind Sulfonate von ethoxylierten Arylphenolen, insbesondere phophatierte oder sulfatierte Di- und/oder Tristyrylphenylalkoxylate, wie sie beispielsweise in WO 2007/1 10355, Seite 3, Zeile 30 bis Seite 5, Zeile 1 1 beschrieben sind. Suitable anionic surfactants are alkali metal, alkaline earth metal or ammonium salts of sulfonates, sulfates, phosphates or carboxylates. Examples of sulfonates are alkyla- rylsulfonates, diphenylsulfonates, alpha-olefinsulfonates, lignosulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of ethoxylated arylphenols, sulfonates of condensed naphthalene, sulfonates of dodecyl and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates , Examples of sulfates are sulfates of fatty acid 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 alkylcarboxylates and carboxylated alcohol or alkylphenol ethoxylates. Preferred anionic surfactants are sulfonates of ethoxylated arylphenols, in particular phosphated or sulfated di- and / or Tristyrylphenylalkoxylate, as described for example in WO 2007/1 10355, page 3, line 30 to page 5, line 11.
Geeignete nicht-ionische Tenside sind Alkoxylate, N-alkylierte Fettsäureamide, Aminoxide, Ester oder Zucker-basierte Tenside. Beispiele für Alkoxylate sind Verbindun- gen, wie Alkohole, Alkylphenole, Amine, Amide, Arylphenole, Fettsäuren oder Fettsäureester, die alkoxyliert wurden. Zur Alkoxylierung kann Ethylenoxid und/oder Propy- lenoxid eingesetzt werden, bevorzugt Ethylenoxid. Beispiele für N-alkylierte Fettsäureamide sind Fettsäureglucamide oder Fettsäurealkanolamide. Beispiele für Ester sind Fettsäureester, Glycerinester oder Monoglyceride. Beispiele für Zucker-basierte Tenside sind Sorbitane, ethoxilierte Sorbitane, Saccharose- und Glucoseester oder Alkylpolyglucoside. Suitable nonionic surfactants are alkoxylates, N-alkylated fatty acid amides, amine oxides, esters or sugar-based surfactants. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated. For the alkoxylation, ethylene oxide and / or propylene oxide can be used, preferably ethylene oxide. Examples of N-alkylated fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkyl polyglucosides.
Geeignete kationische Tenside sind quarternäre Tenside, beispielsweise quartäre Ammonium-Verbindungen mit einer oder zwei hydrophoben Gruppen, oder Salze lang- kettiger primärer Amine. Geeignete amphothere Tenside sind Alkylbetaine und Imida- zoline. Geeignete Blockpolymere sind Blockpolymere vom A-B oder A-B-A Typ umfassend Blöcke aus Polyethylenoxid und Polypropylenoxid oder vom A-B-C Typ umfassend Alkanol, Polyethylenoxid und Polypropylenoxid. Geeignete Polyelektrolyte sind Polysäuren oder Polybasen. Beispiele für Polysäuren sind Alkalisalze von Polyacryl- säure. Beispiele für Polybasen sind Polyvinylamine oder Polyethylenamine. 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 imidazoline. Suitable block polymers are block polymers of A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide or of the A-B-C 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 polyethyleneamines.
Die erfindungsgemäße Zusammensetzung kann beliebige Mengen Tensid umfassen. Sie kann 0,1 bis 40 Gew.%, bevorzugt 1 bis 30 Gew.-% und insbesondere 2 bis 20 Gew.% Gesamtmenge von Tensiden umfassen, bezogen auf die Gesamtmenge der Zusammensetzung. The composition of the invention may comprise any amount of surfactant. It can comprise from 0.1 to 40% by weight, preferably from 1 to 30% by weight and in particular from 2 to 20% by weight, of the total amount of surfactants, based on the total amount of the composition.
Beispiele für Adjuvantien sind organisch modifizierte Polysiloxane, wie BreakThruS 240®; Alkoholalkoxylate, wie Atplus®245, Atplus®MBA 1303, Plurafac®LF und Lutensol® ON ; EO-PO-Blockpolymerisate, z. B. Pluronic® RPE 2035 und Genapol® B; Alkoho- lethoxylate, z. B. Lutensol® XP 80; und Natriumdioctylsulfosuccinat, z. B. Leophen® RA. Examples of adjuvants are 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 ®; alcoholic Lethoxylates, z. B. Lutensol ® XP 80; and sodium dioctylsulfosuccinate, e.g. B. Leophen ® RA.
Beispiele für Verdicker (d. h. Verbindungen, die der Zusammensetzung ein modifiziertes Fließverhalten verleihen, d. h. hohe Viskosität im Ruhezustand und niedrige Visko- sität im bewegten Zustand) sind Polysaccharide sowie organische und anorganische Schichtmineralien wie Xanthan Gum (Kelzan®, CP Kelco), Rhodopol® 23 (Rhodia) oder Veegum® (R.T. Vanderbilt) oder Attaclay® (Engelhard Corp.). Examples of thickeners (ie, compounds that give the composition a modified flow properties, ie high viscosity at rest and low viscosity in motion) 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.).
Bakterizide können zur Stabilisierung der Zusammensetzung zugesetzt werden. Bei- spiele für Bakterizide sind solche basierend auf Diclorophen und Benzylalkoholhemi- formal (Proxel® der Fa. ICI oder Acticide® RS der Fa. Thor Chemie und Kathon® MK der Fa. Rohm & Haas) sowie Isothiazolinonderivaten wie Alkylisothiazolinonen und Benzisothiazolinonen (Acticide® MBS der Fa. Thor Chemie). Beispiele für geeignete Frostschutzmittel sind Ethylenglycol, Propylenglycol, Harnstoff und Glycerin. Beispiele für Entschäumer sind Silikonemulsionen (wie z. B. Silikon® SRE, Wacker, Deutschland oder Rhodorsil®, Rhodia, Frankreich), langkettige Alkohole, Fettsäuren, Salze von Fettsäuren, fluororganische Verbindungen und deren Gemische. Beispiele für Kleber sind Polyvinylpyrrolidon, Polyvinylacetat, Polyvinylalkohol und Cel- luloseether (Tylose®, Shin-Etsu, Japan). Bactericides may be added to stabilize the composition. Examples of 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). Examples of suitable antifreeze agents are ethylene glycol, propylene glycol, urea and glycerin. Examples of 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. Examples of adhesives are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and cellulose ethers (Tylose ®, Shin-Etsu, Japan).
Die agrochemische Zusammensetzung wird meist vor der Anwendung verdünnt um den so genannten Tankmix herzustellen. Zur Verdünnung kommen Mineralölfraktionen von mittlerem bis hohem Siedepunkt, wie Kerosin oder Dieselöl, ferner Kohlenteeröle sowie Öle pflanzlichen oder tierischen Ursprungs, aliphatische, cyclische und aromatische Kohlenwasserstoffe, z.B. Toluol, Xylol, Paraffin, Tetrahydronaphthalin, alkylierte Naphthaline oder deren Derivate, Methanol, Ethanol, Propanol, Butanol, Cyclohexanol, Cyclohexanon, Isophoron, stark polare Lösungsmittel, z.B. Dimethylsulfoxid, N-Methyl- pyrrolidon oder Wasser in Betracht. Bevorzugt wird Wasser verwendet. Die verdünnte Zusammensetzung wird üblicherweise durch Versprühen oder Vernebeln angewendet. Zu dem Tankmix können Öle verschiedenen Typs, Netzmittel, Adjuvante, Herbizide, Bakterizide, Fungizide unmittelbar vor der Anwendung (Tankmix) zugesetzt werden. Diese Mittel können zu den agrochemischen Zusammensetzungen im Gewichtsverhältnis 1 :100 bis 100:1 , bevorzugt 1 :10 bis 10:1 zugemischt werden. Die Pestizidkon- zentration im Tankmix kann in größeren Bereichen variiert werden. Im Allgemeinen liegen sie zwischen 0,0001 und 10%, vorzugsweise zwischen 0,01 und 1 %. Die Aufwandmengen liegen bei der Anwendung im Pflanzenschutz je nach Art des gewünschten Effektes zwischen 0,01 und 2,0 kg Wirkstoff pro ha. Die vorliegende Erfindung betrifft auch ein Verfahren zur Bekämpfung von phytopatho- genen Pilzen und/oder unerwünschtem Pflanzenwuchs und/oder unerwünschtem Insekten- oder Mi Iben befall und/oder zur Regulation des Wachstums von Pflanzen, wobei man das Stärkegranualt (wie in einer agrochemischen Zusammensetzung) auf die jeweiligen Schädlinge, deren Lebensraum oder die vor dem jeweiligen Schädling zu schützenden Pflanzen, den Boden und/oder auf unerwünschte Pflanzen und/oder die Nutzpflanzen und/oder deren Lebensraum einwirken lässt. The agrochemical composition is usually diluted before use to produce the so-called tank mix. For dilution come mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, eg toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, Propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone or water into consideration. Preferably, water is used. The diluted composition is usually applied by spraying or atomizing. To the tank mix oils of various types, wetting agents, adjuvants, herbicides, bactericides, fungicides can be added immediately before use (tank mix). These agents may be mixed into the agrochemical compositions 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 a method for controlling phytopathogenic fungi and / or undesired plant growth and / or undesired insect or mite infestation and / or for regulating the growth of plants, wherein the starch granule (as in an agrochemical composition) affecting the particular pests, their habitat or the plants to be protected from the respective pest, the soil and / or undesirable plants and / or the crops and / or their habitat.
Vorteile der Erfindung sind, dass eine langsame Freisetzung des Pestizids möglich ist, dass eine kontrollierbare Freisetzung des Pestizids möglich ist, dass nur ein geringerer Verlust von flüchtigen Pestiziden stattfindet (z.B. eine Verringerung der Abdampfrate, wie von Fenpropimorph), dass das Pestizid gegen chemischen Abbau geschützt ist, und dass hydrophoben Pestiziden in wässrigen Formulierungnen besser dispergierbar sind. Advantages of the invention are that a slow release of the pesticide is possible, that controllable release of the pesticide is possible, that only a lesser loss of volatile pesticides takes place (eg a reduction in the evaporation rate, such as fenpropimorph), that the pesticide is resistant to chemical degradation is protected and that hydrophobic pesticides are more dispersible in aqueous formulations.
Beispiele Examples
Die Herstellung der porösen Stärkepartikel erfolgte aus Maisstärke mit einer mittleren Partikelgröße von 14 μηη wie beschrieben in WO89/04842. Die Herstellung eines feinen Pulvers erfolgte durch Gefriertrocknung.  The preparation of the porous starch particles was carried out from corn starch having an average particle size of 14 μm as described in WO89 / 04842. The preparation of a fine powder was carried out by freeze-drying.
Das Porenvolumen der Stärkepartikel wurde wie folgt berechnet: The pore volume of the starch particles was calculated as follows:
Porenvolumen = [(Einwaage (Stärke) - Auswaage (poröse Stärke)) / Dichte (Stärke)] x Pore volume = [(weight (weight) - weight (porous)) / density (strength)] x
Auswaage (poröse Stärke). Weighing (porous starch).
Dabei wurde für die Dichte der Stärke der Wert 1 ,464 g/ml verwendet. The density of the starch was 1, 464 g / ml.
Beispiel 1 - Stärkepartikel mit Dicamba-Na (nicht erfindungsgemäß) Example 1 - Dicamba Na starch particles (not according to the invention)
40 g Dicamba Natrium-Salz wurden mit 66,7 g Wasser gemischt. Dann wurden 100 g poröse Stärkepartikel (Porenvolumen 0,51 ml/g) zugegeben und mit einem mechanischen Rührer bei 20°C für 20h durchmischt. Anschließend wurde die Mischung in einem Trockenschrank bei 40°C und 100 mbar getrocknet. Man erhielt 143,7 g farbloses Pulver mit einer Restfeuchte von 3,2%. Beispiel 2 - Stärkepartikel mit Dicamba-IPA (nicht erfindungsgemäß) 40 g of Dicamba sodium salt was mixed with 66.7 g of water. Then, 100 g of porous starch particles (pore volume 0.51 ml / g) were added and mixed with a mechanical stirrer at 20 ° C for 20h. Subsequently, the mixture was dried in a drying oven at 40 ° C and 100 mbar. This gave 143.7 g of colorless powder with a residual moisture content of 3.2%. Example 2 - Dicamba-IPA starch particles (not according to the invention)
300 g poröse Stärkepartikel (Porenvolumen 0,52 ml/g) wurden in 399 g wässrige Lösung von Dicamba Isopropylammonium-Salz mit einem Feststoffgehalt von 50,1 Gew.% gegeben und mit einem mechanischen Rührer bei 20°C für 20h durchmischt. Anschließend wurde die Mischung in einem Trockenschrank bei 40°C und 100 mbar getrocknet. Man erhielt 513,3 g farbloses Pulver mit einer Restfeuchte von 2,8%. 300 g of porous starch particles (pore volume 0.52 ml / g) were added to 399 g of aqueous solution of Dicamba isopropylammonium salt having a solids content of 50.1 wt.% And mixed with a mechanical stirrer at 20 ° C for 20h. Subsequently, the mixture was dried in a drying oven at 40 ° C and 100 mbar. This gave 513.3 g of colorless powder with a residual moisture content of 2.8%.
Beispiel 3 - Stärkepartikel mit Dicamba-H (nicht erfindungsgemäß) Example 3 - Dicamba-H starch particles (not according to the invention)
134 g Dicamba (freie Säure) wurden in 400g Aceton gelöst. Dann wurden 200 g poröse Stärkepartikel (Porenvolumen 0,47 ml/g) zugegeben und 1 h bei 20°C gerührt. Anschließend wurde das Aceton bei 40°C am Rotationsverdampfer entfernt. Man erhielt 332 g farbloses Pulver. Beispiel 4 - Stärkepartikel mit Imazapyr-Na (nicht erfindungsgemäß) 134 g of dicamba (free acid) were dissolved in 400 g of acetone. Then, 200 g of porous starch particles (pore volume 0.47 ml / g) were added and stirred at 20 ° C for 1 h. Subsequently, the acetone was removed at 40 ° C on a rotary evaporator. 332 g of colorless powder were obtained. Example 4 - Starch particles with imazapyr-Na (not according to the invention)
200 g poröse Stärkepartikel (Porenvolumen 0,59 ml/g) wurden in 502g wässrige Lösung von  200 g of porous starch particles (pore volume 0.59 ml / g) were dissolved in 502 g of aqueous solution of
Imazapyr Na-Salz mit einem Feststoffgehalt von 21 ,5 Gew.% gegeben. Es wurde 20h bei 20°C durchmischt. Anschließend wurde das Wasser bei 40°C am Rotationsver- dampfer entfernt. Man erhielt 308 g farbloses Pulver.  Imazapyr Na salt with a solids content of 21, 5 wt.% Added. It was mixed for 20h at 20 ° C. Subsequently, the water was removed at 40 ° C. on a rotary evaporator. 308 g of colorless powder were obtained.
Beispiel 5 - Stärkepartikel mit Dicamba-H und Octadecylamin (kationische Matrix) Schritt A) 10,0 g Dicamba (freie Säure) und 1 1 ,33 g Octadecylamin wurden gemischt und auf 120°C erwärmt bis eine klare Lösung entstand. Nach dem Abkühlen auf 20°C erhielt man einen wachsartigen Feststoff, der einen Schmelzpunkt von 58°C hat. Example 5 - Dicamba H and Dicamba (Cationic Matrix) starch particles Step A) 10.0 g dicamba (free acid) and 1 1.33 g octadecylamine were mixed and heated to 120 ° C until a clear solution was obtained. After cooling to 20 ° C gave a waxy solid which has a melting point of 58 ° C.
Schritt B) 3,5 g poröse Stärkepartikel (Porenvolumen 0,48 ml/g) und 1 ,5 g des Produktes von Schritt A und 3,33 g iso-Butanol wurden auf 50°C erwärmt und 1 h bei dieser Temperatur gerührt. Anschließend wurde bei 60°C bei einem Druck von 8 mbar das iso-Butanol am Rotationsverdampfer entfernt. Man erhält 4,78 g pulverartigen Feststoff. Step B) 3.5 g of porous starch particles (pore volume 0.48 ml / g) and 1, 5 g of the product of step A and 3.33 g of iso-butanol were heated to 50 ° C and stirred for 1 h at this temperature. Subsequently, the iso-butanol was removed on a rotary evaporator at 60 ° C at a pressure of 8 mbar. This gives 4.78 g of powdery solid.
Beispiel 6 - Stärkepartikel mit Dicamba-H und Octadecylamin (kationische Matrix) Schritt A) 10,0 g Dicamba (freie Säure) und 9,26 g Octadecylamin wurden gemischt und auf 120°C erwärmt bis eine klare Lösung entstand. Nach dem Abkühlen auf 20°C erhielt man einen wachsartigen Feststoff. Example 6 - Dicamba-H and Dicamba-H (Cationic Matrix) Thickness Particles Step A) 10.0 g of dicamba (free acid) and 9.26 g of octadecylamine were mixed and heated to 120 ° C until a clear solution resulted. After cooling to 20 ° C to give a waxy solid.
Schritt B) 3,5 g poröse Stärkepartikel (Porenvolumen 0,48 ml/g) und 1 ,5 g des Produktes von Schritt A und 3,33 g iso-Butanol wurden auf 50°C erwärmt und 1 h bei dieser Temperatur gerührt. Anschließend wurde bei 60°C bei einem Druck von 8 mbar das iso-Butanol am Rotationsverdampfer entfernt. Man erhält 4,78g pulverartigen Feststoff. Step B) 3.5 g of porous starch particles (pore volume 0.48 ml / g) and 1, 5 g of the product of step A and 3.33 g of iso-butanol were heated to 50 ° C and stirred for 1 h at this temperature. Subsequently, the iso-butanol was removed on a rotary evaporator at 60 ° C at a pressure of 8 mbar. This gives 4.78 g of powdery solid.
Beispiel 7 - Stärkepartikel mit Dicamba-H und Octadecylamin (kationische Matrix) Schritt A) 10,0 g Dicamba (freie Säure) und 5,67 g Octadecylamin wurden gemischt und auf 120°C erwärmt bis eine klare Lösung entstand. Nach dem Abkühlen auf 20°C erhielt man eine hochviskose Flüssigkeit. Schritt B) 3,5 g poröse Stärkepartikel (Porenvolumen 0,48 ml/g), 1 ,5 g des Produktes von Schritt A und 3,33 g iso-Butanol wurden auf 50°C erwärmt und 1 h bei dieser Temperatur gerührt. Anschließend wurde bei 60°C bei einem Druck von 8 mbar das iso- Butanol am Rotationsverdampfer entfernt. Man erhält 4,78g pulverartigen Feststoff. Beispiel 8 - Freisetzungstest Example 7 - Starch particles with Dicamba-H and octadecylamine (cationic matrix) Step A) 10.0 g of dicamba (free acid) and 5.67 g of octadecylamine were mixed and heated to 120 ° C until a clear solution was formed. After cooling to 20 ° C gave a highly viscous liquid. Step B) 3.5 g of porous starch particles (pore volume 0.48 ml / g), 1, 5 g of the product of step A and 3.33 g of iso-butanol were heated to 50 ° C and stirred for 1 h at this temperature. Subsequently, the isobutanol was removed on a rotary evaporator at 60 ° C. at a pressure of 8 mbar. This gives 4.78 g of powdery solid. Example 8 - Release Test
0,1 g der fein pulverisierten Probe wurden in eine 100ml-Glasflasche eingewogen. 0.1 g of the finely powdered sample was weighed into a 100 ml glass bottle.
100 g vollentsalztes Wasser wurden zugegeben und die Flasche verschlossen. Auf einem Rollenmischer wird die Flasche mit 50 Umdrehungen/min 24 h durchmischt.100 g of deionized water was added and the bottle capped. On a roller mixer, the bottle is mixed with 50 revolutions / min for 24 h.
Man nahm die Flasche vom Rollenmischer herunter und ließ die Probe 10 min sedi- mentieren. Mit einer Spritze wurden 0,2 ml der überstehenden Lösung entnommen und der Pestizidgehalt mittels HPLC bestimmt. The bottle was removed from the roller mixer and the sample allowed to sediment for 10 minutes. With a syringe 0.2 ml of the supernatant solution were removed and the pesticide content determined by HPLC.
Die Pestizidfreisetzung wurde im Vergleich zu einer Referenzprobe durchgeführt. Die Referenzprobe wurde unter gleichen Bedingungen hergestellt und enthielt das gleiche Pestizid, jedoch keine retardierende Matrix. Die Pestizidfreisetzung der Referenzprobe wurde auf 100% normiert. Die Pestizidfreisetzungen der Proben mit Matrix wurden relativ zur Referenzprobe angegeben (Tabelle 1 ). Durch die erfindungsgemäßen Stärkegranulate konnte die Freisetzung verlangsamt werden.  Pesticide release was compared to a reference sample. The reference sample was prepared under the same conditions and contained the same pesticide, but no retarding matrix. The pesticide release of the reference sample was normalized to 100%. The pesticide release of the matrix samples was reported relative to the reference sample (Table 1). By the starch granules according to the invention, the release could be slowed down.
Tabelle 1 : Table 1 :
Figure imgf000014_0001
Figure imgf000014_0001
a) nicht erfindungsgemäß  a) not according to the invention
Beispiel 9 - Stärkepartikel mit Fenpropimorph und Oxalsäure (anionische Matrix) 1 ,0 g Fenpropimorph wurden in 3,3 g Aceton gelöst und mit 4 g poröse Stärkepartikel (Porenvolumen 0,53 ml/g) versetzt und 1 h bei 20°C gerührt. Dann wurde das Aceton bei einem Druck von 600 mbar und einer Badtemperatur von 40°C am Rotationsverampfer entfernt. Zu dem Rückstand wurde eine Lösung von 0,42 g Oxalsäure in 3,6 g Wasser gegeben. Der Rückstand wurde 15 min bei 20°C gerührt. Anschließend wurde das Wasser bei 40°C am Rotationsverdampfer entfernt. Man erhielt 5,61 g farbloses Pulver. Beispiel 10 - Stärkepartikel mit Fenpropimorph und Oxalsäure (anionische Matrix) 1 ,0 g Fenpropimorph wurden in 3,3 g Aceton gelöst und mit 4 g poröse Stärkepartikel (Porenvolumen 0,53 ml/g) versetzt und 1 h bei 20°C gerührt. Dann wurde das Aceton bei einem Druck von 600 mbar und einer Badtemperatur von 40°C am Rotationsverampfer entfernt. Zu dem Rückstand wurde eine Lösung von 0,21 g Oxalsäure in 3,6 g Wasser gegeben. Der Rückstand wurde 15 min bei 20°C gerührt. Anschließend wurde das Wasser bei 40°C am Rotationsverdampfer entfernt. Man erhielt 5,0 g farbloses Pulver. Example 9 - Starch particles with fenpropimorph and oxalic acid (anionic matrix) 1.0 g of fenpropimorph were dissolved in 3.3 g of acetone and admixed with 4 g of porous starch particles (pore volume 0.53 ml / g) and stirred at 20 ° C. for 1 h. Then, the acetone was removed at a pressure of 600 mbar and a bath temperature of 40 ° C on a rotary evaporator. To the residue was added a solution of 0.42 g of oxalic acid in 3.6 g of water. The residue was stirred at 20 ° C for 15 min. Subsequently, the water was removed at 40 ° C on a rotary evaporator. 5.61 g of colorless powder were obtained. Example 10 - Starch particles with fenpropimorph and oxalic acid (anionic matrix) 1.0 g of fenpropimorph were dissolved in 3.3 g of acetone and admixed with 4 g of porous starch particles (pore volume 0.53 ml / g) and stirred at 20 ° C. for 1 h. Then, the acetone was removed at a pressure of 600 mbar and a bath temperature of 40 ° C on a rotary evaporator. To the residue was added a solution of 0.21 g of oxalic acid in 3.6 g of water. The residue was stirred at 20 ° C for 15 min. Subsequently, the water was removed at 40 ° C on a rotary evaporator. 5.0 g of colorless powder were obtained.
Beispiel 1 1 - Stärkepartikel mit Fenpropimorph und Oxalsäure (anionische Matrix) 1 ,0 g Fenpropimorph wurden in 3,3 g Aceton gelöst und mit 4 g poröse Stärkepartikel (Porenvolumen 0,53 ml/g) versetzt und 1 h bei 20°C gerührt. Dann wurde das Aceton bei einem Druck von 600 mbar und einer Badtemperatur von 40°C am Rotations- verampfer entfernt. Zu dem Rückstand wurde eine Lösung von 0,14 g Oxalsäure in 3,6 g Wasser gegeben. Der Rückstand wurde 15 min bei 20°C gerührt. Anschließend wurde das Wasser bei 40°C am Rotationsverdampfer entfernt. Man erhielt 4,85 g farbloses Pulver. Beispiel 12 - Stärkepartikel mit Fenpropimorph (nicht erfindungsgemäß) Example 1 1-Starch particles with fenpropimorph and oxalic acid (anionic matrix) 1.0 g of fenpropimorph were dissolved in 3.3 g of acetone and mixed with 4 g of porous starch particles (pore volume 0.53 ml / g) and stirred at 20 ° C. for 1 h , Then the acetone was removed at a pressure of 600 mbar and a bath temperature of 40 ° C on a rotary evaporator. To the residue was added a solution of 0.14 g of oxalic acid in 3.6 g of water. The residue was stirred at 20 ° C for 15 min. Subsequently, the water was removed at 40 ° C on a rotary evaporator. 4.85 g of colorless powder were obtained. Example 12 - Fenpropimorph starch particles (not according to the invention)
1 ,0 g Fenpropimorph wurden in 3,3 g Aceton gelöst und mit 4 g poröse Stärkepartikel (Porenvolumen 0,53 ml/g) versetzt und 1 h bei 20°C gerührt. Dann wurde das Aceton bei einem Druck von 600 mbar und einer Badtemperatur von 40°C am Rotationsverampfer entfernt.  1.0 g of fenpropimorph were dissolved in 3.3 g of acetone and admixed with 4 g of porous starch particles (pore volume 0.53 ml / g) and stirred at 20 ° C. for 1 h. Then, the acetone was removed at a pressure of 600 mbar and a bath temperature of 40 ° C on a rotary evaporator.
Man erhielt 4,9 g farbloses Pulver. 4.9 g of colorless powder were obtained.

Claims

Ansprüche claims
1 . Poröses, teilhydrolysiertes Stärkegranulat enthaltend ein anionisches oder kationisches Pestizid und eine kationische oder anionische Matrix, wobei das Pestizid und die Matrix entgegengesetzt geladen sind. 1 . Porous, partially hydrolyzed starch granules containing an anionic or cationic pesticide and a cationic or anionic matrix, wherein the pesticide and the matrix are oppositely charged.
2. Stärkegranulat nach Anspruch 1 , wobei das Mengenverhältnis von Stärkegranulat zu Pestizid im Bereich von 1 ,2 bis 5 liegt. 2. starch granules according to claim 1, wherein the amount ratio of starch granules to pesticide in the range of 1, 2 to 5.
3. Stärkegranulat nach Anspruch 1 oder 2, wobei die anionische Matrix eine anorganische Säure, eine organische Säure, und/oder eine polymere Säure umfasst. 3. starch granules according to claim 1 or 2, wherein the anionic matrix comprises an inorganic acid, an organic acid, and / or a polymeric acid.
4. Stärkegranulat nach einem der Ansprüche 1 bis 3, wobei die anionische Matrix eine C2-3o-Dicarbonsäure umfasst. 4. starch granules according to any one of claims 1 to 3, wherein the anionic matrix comprises a C2-3o-dicarboxylic acid.
5. Stärkegranulat nach einem der Ansprüche 1 bis 4, wobei die kationische Matrix ein Alkylamin oder ein Amin-haltiges Polymer umfasst. Starch granules according to any one of claims 1 to 4, wherein the cationic matrix comprises an alkylamine or an amine-containing polymer.
Stärkegranulat nach einem der Ansprüche 1 bis 5, wobei die kationische Matrix ein primäres C8-3o-Alkylamin umfasst. Starch granules according to any one of claims 1 to 5, wherein the cationic matrix comprises a primary C 8 to C 30 alkylamine.
Stärkegranulat nach einem der Ansprüche 1 bis 6, wobei das kationische Pestizid mindestens eine Amino-Gruppe umfasst. Starch granules according to any one of claims 1 to 6, wherein the cationic pesticide comprises at least one amino group.
Stärkegranulat nach einem der Ansprüche 1 bis 7, wobei das kationische Pestizid Fenpropimorph umfasst. Starch granules according to any one of claims 1 to 7, wherein the cationic pesticide comprises fenpropimorph.
Stärkegranulat nach einem der Ansprüche 1 bis 8, wobei das anionische Pestizid mindestens eine Carboxyl-, Thiocarboxyl-, Sulfonyl-, Sulfinyl-, Thiosulfonyl- oder Phosphorsäure-Gruppe umfasst. Starch granules according to any one of claims 1 to 8, wherein the anionic pesticide comprises at least one carboxyl, thiocarboxyl, sulfonyl, sulfinyl, thiosulfonyl or phosphoric acid group.
10. Stärkegranulat nach einem der Ansprüche 1 bis 9, wobei das anionische Pestizid Dicamba umfasst. Starch granules according to any one of claims 1 to 9, wherein the anionic pesticide comprises dicamba.
1 1 . Stärkegranulat nach einem der Ansprüche 1 bis 10, wobei das Molverhältnis der ionischen Ladungen von Pestizid zu Matrix im Bereich von 5:1 bis 1 :3 liegt. 1 1. Starch granules according to any one of claims 1 to 10, wherein the molar ratio of ionic charges from pesticide to matrix ranges from 5: 1 to 1: 3.
12. Verfahren zur Herstellung des Stärkegranulats gemäß einem der Ansprüche 1 bis 1 1 indem man ein poröses, teilhydrolysiertes Stärkegranulat mit einer Salzmatrix enthaltend das anionische oder kationische Pestizid und die kationische oder anionische Matrix miteinander in Kontakt bringt. 12. A process for the preparation of the starch granules according to any one of claims 1 to 1 1 by passing a porous, partially hydrolyzed starch granules with a salt matrix containing the anionic or cationic pesticide and the cationic or anionic matrix is brought into contact with each other.
13. Verfahren nach Anspruch 12, wobei das Stärkegranulat in einer Flüssigkeit disper- giert ist. 13. The method of claim 12, wherein the starch granules are dispersed in a liquid.
14. Verfahren nach Anspruch 12 oder 13, wobei die Flüssigkeit Wasser oder ein organisches Lösungsmittel ist, welches bei 20 °C zu mindestens 5 Gew.% in Wasser löslich ist. 14. The method of claim 12 or 13, wherein the liquid is water or an organic solvent which is soluble at 20 ° C to at least 5 wt.% In water.
15. Verfahren zur Bekämpfung von phytopathogenen Pilzen und/oder unerwünschtem Pflanzenwuchs und/oder unerwünschtem Insekten- oder Milbenbefall und/oder zur Regulation des Wachstums von Pflanzen, wobei man das Stärkegranulat gemäß einem der Ansprüche 1 bis 1 1 auf die jeweiligen Schädlinge, deren Lebensraum oder die vor dem jeweiligen Schädling zu schützenden Pflanzen, den Boden und/oder auf unerwünschte Pflanzen und/oder die Nutzpflanzen und/oder deren Lebensraum einwirken lässt. 15. A method for controlling phytopathogenic fungi and / or undesired plant growth and / or undesired insect or mite infestation and / or for regulating the growth of plants, wherein the starch granules according to one of claims 1 to 1 1 to the respective pests whose habitat or the plants to be protected from the respective pest, the soil and / or undesirable plants and / or the crops and / or their habitat.
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