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WO2011138701A1 - Dispersion à effet pesticide comprenant une phase dispersée nanostructurée - Google Patents

Dispersion à effet pesticide comprenant une phase dispersée nanostructurée Download PDF

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Publication number
WO2011138701A1
WO2011138701A1 PCT/IB2011/051745 IB2011051745W WO2011138701A1 WO 2011138701 A1 WO2011138701 A1 WO 2011138701A1 IB 2011051745 W IB2011051745 W IB 2011051745W WO 2011138701 A1 WO2011138701 A1 WO 2011138701A1
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WO
WIPO (PCT)
Prior art keywords
dispersion
dispersed phase
plants
dispersion according
pesticide
Prior art date
Application number
PCT/IB2011/051745
Other languages
English (en)
Inventor
Otto Glatter
Sandra Engelskirchen
Tatjana Levy
Helmut Auweter
Rainer Berghaus
Siegfried Strathmann
Original Assignee
Basf Se
Basf (China) Company Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Se, Basf (China) Company Limited filed Critical Basf Se
Priority to EP11777340.8A priority Critical patent/EP2566322A4/fr
Priority to JP2013508587A priority patent/JP2013525475A/ja
Priority to KR1020127031815A priority patent/KR20130100065A/ko
Priority to CN2011800277413A priority patent/CN102933075A/zh
Priority to BR112012028273A priority patent/BR112012028273A2/pt
Publication of WO2011138701A1 publication Critical patent/WO2011138701A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof

Definitions

  • Pesticidal dispersion comprising nanostructured dispersed phase
  • the present invention relates to a dispersion containing an aqueous continuous phase and a dispersed phase, wherein the dispersed phase exhibits a nano-sized self- assembled structurization and wherein the dispersed phase contains a pesticide with a water solubility at 25 °C of up to 10 g/l and a melting point of below 100 °C.
  • the present invention further relates to a method for preparing said dispersion comprising a step of contacting the components, and to a method for controlling phytopathogenic fungi and/or undesired plant growth and/or undesired attack by insects or mites and/or for regulating the growth of plants, where said dispersion is allowed to act on the particular pests, their habitat or the plants to be protected from the particular pest, the soil and/or on undesired plants and/or the useful plants and/or their habitat. Combinations of preferred embodiments with other preferred embodiments are within the scope of the present invention.
  • a dispersion containing an aqueous continuous phase and a dispersed phase, wherein the dispersed phase exhibits a nano-sized self-assembled structurization are well known: Yaghmur and Glatter ("Characterization and potential applications of nanostructured aqueous dispersion", Adv. Colloid Interface Sci. 2009, 147-148, 333-342) review in detail recent advances in characerization and utilization of the aforementioned dispersions.
  • Kaasgard and Drummond Ordered 2-D and 3-D nanostructred amphiphile self- assembly materials stable in excess solvent", Phys. Chem. Chemm. Phys. 2006, 8, 4957-4975) review the structures and amphiphils for the preparation of the aforementioned dispersions.
  • WO 2007/060177 discloses an oil-in-water emulsion wherein the oil droplets of a diameter in the range of 5 nm to hundreds of micrometers exhibit a nano-sized self- assembled structurization with hydrophilic domains having a diameter size in the range of 0.5 to 200 nm, due to the presence of a lipophilic additive and the oil-in-water emulsion contains an active element being present in the range comprised between 0.00001 and 79 % based on the total composition.
  • Said active element may be for example chemicals for agrochemical applications.
  • WO 2007/060171 discloses the use of a lipidic phase comprising an oil and a lipophilic additive (LPA), wherein the LPA content in the lipidic phase is comprised between 0.25 wt% and 84 wt%, for preparing an oil-in-water emulsion wherein the mixing of the lipidic phase and the aqueous phase containing an emulsifier is made by using a manual operation or a low energy device.
  • LPA lipophilic additive
  • EP 1 597 973 and EP 1 598 060 disclose an oil-in-water emulsion wherein the oil droplets of a diameter in the range of 5 nm to hundreds of micrometers exhibit a nano-sized structurisation with hydrophilic domains with a diameter size in the range of 0.5 to 50 nm and being formed by a lipophilic additive.
  • Object of the present invention was to find an aqueous based formulation of pesticides which overcomes the drawbacks of the state of the art. Another object was to find a formulation comprising a low amount of organic solvent, allowing a high loading with pesticide, being stable on storage or on dilution with water.
  • the object was solved by a dispersion containing an aqueous continuous phase and a dispersed phase, wherein the dispersed phase exhibits a nano-sized self-assembled structurization and wherein the dispersed phase contains a pesticide with a water solu- bility at 25 °C of up to 10 g/l and a melting point of below 100 °C.
  • the dispersed phase exhibiting the nano-sized self-assembled structurization may be determined by known methods, e.g. small angle X-ray scattering (SAXS), cryo- transmission electron microscopy (Cryo-TEM) and 13 C-NMR.
  • SAXS small angle X-ray scattering
  • Crystal-TEM cryo- transmission electron microscopy
  • 13 C-NMR 13 C-NMR
  • the nano-sized self-assembled structurization has a signal in SAXS. It is well known, that the shape of the signal, its intensity and the pattern of shapes depends on the nano-sized structurization.
  • Typical structurization types such as "emulsified L2-phase”, “micellar cubosomes”, “hexosomes”, “cubosomes”
  • SAXS signals are for example reviewed by Yaghmur and Glatter, Adv. Colloid Interface Sci. 2009, 147-148, 333-342 (especially Fig. 4, 6, 9).
  • the dispersed phase usually comprises water, pesticide, amphiphile and optionally adjuvant.
  • the dispersed phase preferably consists of water, pesticide, amphiphile and optionally adjuvant.
  • the dispersed phase contains less than 15 wt%, preferably less than 5 wt%, more preferably less than 1 wt%, and especially less than 0.1 wt% of an oil.
  • oil relates to mineral oils, hydrocarbons (e.g. aliphatic, alicyclic, aromatic hydrocar- bons), fatty acids, vegetable oils, fats, waxes, essential oils, flvouring oils.
  • the term oil relates to mineral oils and hydrocarbons.
  • the dispersed phase contains less than 15 wt%, preferably less than 5 wt%, more preferably less than 1 wt%, and especially less than 0.1 wt% of an oil-soluble solvent.
  • the oil-soluble solvent may dissolve the pesticide in an amount of at least 50 g/l at 20 °C.
  • the oil-soluble solvent is usually soluble in toluene of at least 50 g/l at 20 °C.
  • oil-soluble solvent relates to solvents, which have a solubility in water of less than 10 g/l, preferably less than 1 g/l and especially less than 0,1 g/l.
  • Suitable oil- soluble solvents are organic solvents such as mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives.
  • the hydrodynamic radius (RH) of the dispersed phase is usually in a range from 10 nm to 2,0 ⁇ , preferably in a range from 20 to 1000 nm, more preferably from 50 to 800 nm, as determined by dynamic light scattering.
  • the aqueous continuous phase comprises typically water and stabilizing surfactant.
  • further components may be present, such a thickener, further pesticides, an anti-freezing agent, water-soluble adjuvants or other common auxiliaries.
  • Amphiphiles which are suitable for use in the dispersed phase, which exhibits a nano- sized self-assembled structurization, are well known. Suitable amphiphiles are listed by Kaasgard and Drummond (Phys. Chem. Chem. Phys. 2006, 8, 4957-4975) on page 4961 -4972 under the headings ethylene oxide amphiphiles, monoacylglacerols, glycol- ipids, phosphatidylethanolamine amphiphiles and urea amphiphiles, or by WO
  • the amphiphile have a solubility in water at 20 °C of up to 10 wt%, preferably of up to 3 wt%, more preferably of up to 1 wt% and especially of up to 0.1 wt%.
  • amphiphile are amphiphilic lipids, polyethylene oxide amphiphiles, and/or urea-based amphiphiles. More preferred amphiphiles are amphiphilic lipids. Mixtures of different amphiphiles are also suitable.
  • amphiphile lipids examples are:
  • glycerides e. g. monoglycerides, diglycerides, and triglycerides
  • oils and PEG e. g. ethoxylated castor oil (e. g. Cre- mophor EL (BASF))
  • ethoxylated hydrogenated castor oil e. g. Cremophor® RH-40 (BASF)
  • ethoxylated corn oil e. g. Labrafil® M 2125 CS (Gattefosse)
  • - fatty alcohols e. g. phytantriol (3,7,1 1 ,15- tetramethyl-1 , 2,3-hexadecantriol)
  • - ether lipids e. g. monooleyl glyceryl ether
  • - natural and synthetic phospholipids e. g. egg lecithin, soya lecithin, hydrogenated lecithin, phosphatidyl choline, phosphatidyl ethanolamine, phosphatidyl serine, phosphatidyl glycerol, phosphatidic acid
  • lysophospholipids e. g. lyso-lecithin, lyso-phosphatidyl choline, lyso-oleyl phos- phatidyl choline
  • lyso-lecithin e. g. lyso-phosphatidyl choline, lyso-oleyl phos- phatidyl choline
  • sterols and sterol derivatives e. g. cholesterol, sitosterol, lanesterol and their esters, especially with PEG or fatty acids
  • - galactolipids e. g. digalactosyl diacylglycerol, monogalactosyl diacylglycerol
  • - sphingolipids e. g. sphingomyelin
  • ethoxylated surfactants such as PEG-fatty acid mono-and diesters (e. g. of the Crodet (Croda), Cithrol® (Croda), Nikkol® (Nikko), Myrj (ICI) series, Solutol® HS 15 (BASF)),
  • PEG-fatty acid mono-and diesters e. g. of the Crodet (Croda), Cithrol® (Croda), Nikkol® (Nikko), Myrj (ICI) series, Solutol® HS 15 (BASF)
  • PEG glycerol fatty acid esters e. g. Tagat® L and O (Goldschmidt), Glycerox® L series (Croda), Capmul® EMG (Abitec)
  • Tagat® L and O Goldschmidt
  • Glycerox® L series Croda
  • Capmul® EMG Abitec
  • transesterification products of oils and PEG e. g. of the Labrafil® (Gattefosse), Cremophor® (BASF) Crovol® (Croda) and Nikko HCO (Nikko) series
  • Labrafil® Gattefosse
  • Cremophor® BASF
  • Crovol® Crovol®
  • Nikko HCO Nikko HCO
  • PEG alkyl esters e. g. of the Brij® (ICI) and Volpo (Croda) series
  • PEG alkyl phenol surfactants e. g. of the Triton X and N series (Rohm & Haas); polyglycerised fatty acids (e. g. Nikkol® Decaglyn (Nikko), PluroIX Oleique (Gatte- fosse)),
  • propylene glycol fatty acid esters e. g. Capryl® 90 (Gattefosse), Lutrol OP2000 (BASF), Captez (Abitec) ),
  • glycerol/propylene glycol fatty acid esters e. g. Arlacel® 186 (ICI)
  • sorbitan fatty acid esters e. g. of the Span® (ICI) and Crill® (Croda) series
  • - sugar esters e. g. of the SUCRO ESTER® (Gattefosse) and Crodesta (Croda) series
  • polyoxyethylene-polyoxypropylene block copolymers (so-called poloxamers, e. g. of the Pluronic® (BASF), Synperonic (ICI) and LutrolO (BASF) series),
  • urea-based amphiphiles are Cs to C22 alkylurea, e.g. dodecylurea, octa- decylurea, oleylurea,oleylbiuret, phytanylurea, hexafarnesylurea.
  • amphiphiles are glycerol and diglycerol monooleate and monoli- noleate, glyceoldioleate (GDO), dioleyl phosphatidyl ethanolamine (DOPE), dioleyl phosphatidylcholine (DOPC) and phytantriol, and mixtures of these with up to 50% fatty acids, in particular oleic acid and linoleic acid, polysorbate 80 (Tween 80), polyethylene glycol 660 12-hydroxysterate (Solutol® HS 15), or lysophospholipids, especially lyso- oleyl phosphatidylcholine (LOPC).
  • Especiylly preferred amphiphiles are glycerol mono- linoleate (also known as 1 -monolinolein) and phytantriol.
  • amphiphile will contain components in the form of extracted and purified natural products and will thus contain a mixture of related compounds.
  • Soy bean phosphatidyl choline for example is a mixture of compounds having around 60-75% C18:2 acyl groups, around 12-16% C16:0 and the balance others.
  • commercial glycerol monooleate (GMO) or commercial glycerol monolinoleate is typically at least 90% monoglyceride but contains small amounts of diglyceride and free fatty acid.
  • GMO glycerol monooleate
  • the acyl groups of GMO are usually over 60-90% C18:1 , 5-10% saturated and the remainder largely higher unsaturated acyl groups.
  • the acyl groups of 1 - monolinolein are usually over 60-90% C18:2, 5-10% saturated and the remainder largely higher unsaturated acyl groups. As indicated above, this is largely monoglyceride with an oleoyl or linolein acyl chain but contains certain amounts of other compounds. These are included in the term GMO or monolinoleate as used herein.
  • GMO or monolinoleate as used herein.
  • Commercial preparations of GMO include GMOrphic-80 and Myverol 18-99 (available from Eastman Kodak), Rylo MG 19 and Dimodan DGMO (available from Danisco).
  • Suitable stabilizing surfactants include anionic, cationic, nonionic and amphoteric surfactants, block polymers and polyelectrolytes. Further on, polysaccharide (e.g. starch, starch derivatives, celloluse derivatives, xanthan gum, gelatin) may be used as stabiliz- ing surfactants.
  • Preferred stabilizing surfactans are nonionic surfactants (preferably alkoxylates, such as comb polymers) and/or block polymers. Mixtures of aforementioned stabilizing surfactants are also suitable.
  • stabilizing surfactants have an HLB of at least 12, preferably at least 14.
  • the solubility in water at 20 °C of the stabilizing surfactant is usually at least 5 wt%, preferably at least 10 wt%, more preferably at least 20 wt%, and especially at least 30 wt%.
  • Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates or carboxylates.
  • sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, sulfonates of fatty acids and oils, sul- fonates of ethoxylated alkylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates.
  • Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters.
  • Examples of phosphates are phosphate esters.
  • Examples of carboxylates are alkyl carboxylates and carboxylated alcohol or alkylphenol ethoxylates.
  • Suitable nonionic surfactants are alkoxylates, N-alkylated fatty acid amides, amine oxides, esters or sugar-based surfactants.
  • alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated.
  • Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, 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 alkylpolygluco- sides.
  • Further alkoxylates are comb polymers comprising polyethylene glycol, such as comb polymers comprising polyethylene glycol (meth)acrylate.
  • Preferred comb polymers are those made of methacrylic acid, methyl methacrylate and methoxy polyethylene glycol methacrylate (e.g. Atlox® 4913, commercially available Croda).
  • Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long- chain primary amines.
  • Suitable amphoteric surfactants are alkylbetains and imidazolines.
  • Suitable block polymers are block polymers of the 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.
  • Further suitable block copolymers are poloxamers, which comprise at least one block of polyoxyethylene and at least one block of polyoxypropylene. Examples are poloxamer 407 (e. g. Pluronic F127, BASF), poloxamer 188 (e. g. PluronicE F68, BASF), poloxamer 124 (PluronicX L44, BASF), and polysorbates 20, 60 and/or 80 (referred to herein a P20, P60 & P80 respectively e. g. Tween® 80, ICI).
  • Preferred block polymers are those comprising blocks of polyethylene oxide and polypropylene oxide, such as poloxamer 407.
  • Suitable polyelectrolytes are polyacids or polybases.
  • Examples of polyacids are alkali salts of polyacrylic acid.
  • Examples of polybases are polyvinylamines or polyethyl- eneamines.
  • the term pesticide refers to at least one active substance selected from the group of the fungicides, insecticides, nematicides, herbicides, safeners and/or growth regulators.
  • Preferred pesticides are fungicides, insecticides, herbicides and growth regula- tors. Mixtures of pesticides of two or more of the abovementioned classes may also be used. The skilled worker is familiar with such pesticides, which can be found, for example, in the Pesticide Manual, 14th Ed.
  • Suitable insecticides are insecticides from the class of the carbamates, organo- phosphates, organochlorine insecticides, phenylpyrazoles, pyrethroids, neonicotinoids, spinosins, avermectins, milbemycins, juvenile hormone analogs, alkyl halides, organo- tin compounds nereistoxin analogs, benzoylureas, diacylhydrazines, and METI acari- zides.
  • Suitable fungicides are fungicides from the classes of dinitroanilines, allylamines, anilinopyrimidines, antibiotics, aromatic hydrocarbons, benzenesulfonamides, benzimi- dazoles, benzisothiazoles, benzophenones, benzothiadiazoles, benzotriazines, benzyl carbamates, carbamates, carboxamides, carboxylic acid diamides, chloronitriles cyanoacetamide oximes, cyanoimidazoles, cyclopropanecarboxamides, dicarbox- imides, dihydrodioxazines, dinitrophenyl crotonates, dithiocarbamates, dithiolanes, eth- ylphosphonates, ethylaminothiazolecarboxamides, guanidines, hydroxy-(2- amino)pyrimidines, hydroxyanilides, imidazoles, imidazolinone
  • N-phenylcarbamates oxazolidinediones, oximinoacetates, oximinoacetamides, pepti- dylpyrimidine nucleosides, phenylacetamides, phenylamides, phenylpyrroles, pheny- lureas, phosphonates, phosphorothiolates, phthalamic acids, phthalimides, piperazi- nes, piperidines, propionamides, pyridazinones, pyridines, pyridinylmethylbenzamides, pyrimidinamines, pyrimidines, pyrimidinonehydrazones, pyrroloquinolinones, quinazoli- nones, quinolines, quinones, sulfamides, sulfamoyltriazoles, thiazolecarboxamides, thiocarbamates, thiophanates, thiophenecarboxamides, tolu
  • Suitable herbicides are herbicides from the classes of the acetamides, amides, aryloxyphenoxypropionat.es, benzamides, benzofuran, benzoic acids, benzothiadiazinones, bipyridylium, carbamates, chloroacetamides, chlorocar- boxylic acids, cyclohexanediones, dinitroanilines, dinitrophenol, diphenyl ether, glycines, imidazolinones, isoxazoles, isoxazolidinones, nitriles, N-phenylphthalimides, oxadiazoles, oxazolidinediones, oxyacetamides, phenoxycarboxylic acids, phenylcar- bamates, phenylpyrazoles, phenylpyrazolines, phenylpyridazines, phosphinic acids, phosphoroamidates, phosphorodithioates,
  • the pesticide has a water solubility at 25 °C of up to 10 g/l, preferably of up to 1 g/l, more preferably of up to 0,2 g/l and especially of up to 0,05 g/l.
  • the pesticide has a melting point of below 100 °C, preferably below 90 °C, more preferably below 80 °C, especially below 70 °C. and most preferred below 60 °C.
  • Adjuvants are a well known class of compounds, which increase the efficacy of a pesticide. Examples may be found in WO 2004/017734, page 2, line 13 to page 3, line 27. Suitable adjuvants are organic modified polysiloxanes such as Break Thru S 240 ® ; al- cohol alkoxylates such as Atplus 245 ® , Atplus MBA 1303 ® , Plurafac LF 300 ® and Lu- tensol ON 30 ® ; EO/PO block polymers, e. g.
  • Pluronic RPE 2035 ® and Genapol B ® alcohol ethoxylates such as Lutensol XP 80 ® ; and dioctyl sulfosuccinate sodium such as Leophen RA ® .
  • the solubility in water at 20 °C of the adjuvant is usually up to 50 g/l, preferably up to 5 g/l, more preferably up to 0,5 g/l.
  • the dispersion according to the invention may also comprise auxiliaries which are customary in agrochemical compositions.
  • these auxiliaries are present in the continuous phase of the dispersion.
  • the auxiliaries used depend on the particular application form and active substance, respectively. Examples for suitable auxiliaries are solvents, solid carriers, dispersants or emulsifiers (such as further solubilizers, protective colloids, surfactants and adhesion agents), organic and anorganic thickeners, bactericides, anti-freezing agents, anti-foaming agents, if appropriate colorants and tackifiers or binders (e. g. for seed treatment formulations).
  • Such auxiliaries may be present either in the aqueous continuous phase of the dispersed phase or in both phases, de- pending on the solubility of the auxiliaries.
  • Suitable solvents are water, organic solvents such as mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e. g.
  • Preferred solvent are water, and water comprising up to 30 wt% (preferably up to 10 wt%, more preferably up to 2 wt%, in each case based on the total amount of the solvent) of the aforementeioned organic solvent. Most preferred solvent is water.
  • Suitable surfactants are alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, such as ligninsoulfonic acid (Borresperse ® types, Borregard, Norway) phenolsulfonic acid, naphthalenesulfonic acid (Morwet ® types, Akzo Nobel, U.S.A.), dibutylnaphthalene- sulfonic acid (Nekal ® types, BASF, Germany), and fatty acids, alkylsulfonates, alkyl- arylsulfonates, alkyl sulfates, laurylether sulfates, fatty alcohol sulfates, and sulfated hexa-, hepta- and octadecanolates, sulfated fatty alcohol glycol ethers, further
  • methylcellulose g. methylcellulose
  • hydrophobically modified starches polyvinyl alcohols (Mowiol ® types, Clariant, Switzerland), polycarboxylates (Sokolan ® types, BASF, Germany), polyalkoxylates, polyvinyl- amines (Lupasol ® types, BASF, Germany), polyvinylpyrrolidone and the copolymers therof.
  • thickeners i. e. compounds that impart a modified flowability to compositions, i. e. high viscosity under static conditions and low viscosity during agitation
  • thickeners are polysaccharides and organic and anorganic clays such as Xanthan gum (Kelzan ® , CP Kelco, U.S.A.), methyl cellulose, Rhodopol ® 23 (Rhodia, France), Veegum ® (R.T. Van- derbilt, U.S.A.) or Attaclay ® (Engelhard Corp., NJ, USA).
  • Bactericides may be added for preservation and stabilization of the composition.
  • suitable bactericides are those based on dichlorophene and benzylalcohol hemi formal (Proxel ® from ICI or Acticide ® RS from Thor Chemie and Kathon ® MK from Rohm & Haas) and isothiazolinone derivatives such as alkylisothiazolinones and ben- ziothiazolinones (Acticide ® MBS from Thor Chemie).
  • suitable anti- freezing agents are ethylene glycol, propylene glycol, urea and glycerol.
  • anti-foaming agents are silicone emulsions (such as e. g.
  • Silikon ® SRE Wacker, Germany or Rhodorsil ® , Rhodia, France
  • long chain alcohols fatty acids, salts of fatty ac- ids, fluoroorganic compounds and mixtures thereof.
  • tackifiers or binders are polyvinylpyrrolidone, polyvinylacetates, polyvinyl alcohols and cellulose ethers (Ty- lose ® , Shin-Etsu, Japan).
  • the dispersion may comprises up to 70 wt% water, based on the weight of the disper- sion.
  • the dispersion comprises at least 10 wt% water, preferably at least 20 wt%, more preferably at least 30 wt%, and especially at least 40 wt%, based on the total weight of the dispersion.
  • the continuous phase comprises usually from 10 to 99.9 wt% water, preferably from 20 to 99.5 wt%, more preferably from 30 to 99.5 wt%, based on the weight of the continuous phase.
  • the dispersion comprises usually at least 5 wt% pesticide, preferably at least 10 wt%, more preferably at least 15 wt% and most preferably at least 20 wt%, based on the weight of the dispersion.
  • the dispersed phase comprises usually at least 25 wt% pesticide, preferably at least 40 wt%, more preferably at least 60 wt% and most preferably at least 70 wt%, based on the weight of the dispersed phase.
  • the dispersion comprises from 1 to 50 wt% amphiphile, preferably from 3 to 40 wt%, more preferably from 5 to 30 wt%, based on the total weight of the dispersion.
  • the dispersed phase comprises usually from 1 to 80 wt% amphiphile, preferably from 5 to 70 wt%, more preferably from 10 to 60 wt%, based on the weight of the dispersed phase.
  • the dispersion comprises from 0.1 to 20 wt% stabilizing surfactant, preferably from 0.5 to 12 wt%, more preferably from 2 to 8 wt%, based on the total weight of the dispersion.
  • the continuous phase comprises usually from 0.5 to 30 wt% stabilizing surfactant, preferably from 3 to 20 wt%, more preferably from 7 to 15 wt%, based on the weight of the continuous phase.
  • the dispersion comprises up to 50 wt% adjuvant, preferably from 3 to 30 wt%, more preferably from 7 to 25 wt%, based on the total weight of the dispersion.
  • the dispersion may comprises up to 10 wt% thickener, preferably 0.01 to 3 wt%, more preferably 0.1 to 1 wt%, based on the weight of the dispersion.
  • the present invention further relates to a method for preparing the dispersion according to the invention comprising a step of contacting the components. Suitable methods are:
  • a multistep premixing method including the formation of a dry lipid/stabilizer film and the application of mechanical stirring during the hydration of the dry film.
  • the method for preparing the dispersion according to the invention comprising a step of contacting the components under application of high-energy input, preferably in a shearing process.
  • the method comprises a first step of preparing the continuous aqueous phase and the dispersed phase separately. In a second step, both phases are contacted under application of high-energy input.
  • the present invention also relates to a method for controlling phytopathogenic fungi and/or undesired plant growth and/or undesired attack by insects or mites and/or for regulating the growth of plants, where the dispersion according to the invention is allowed to act on the particular pests, their habitat or the plants to be protected from the particular pest, the soil and/or on undesired plants and/or the useful plants and/or their habitat.
  • the dispersion may be used as such or solvents, such as water may be added prior to application to arrive at a concentration of pesticide, which is suitable for the desired amount of pesticide to be applied.
  • the method according to the invention are particularly important for various cultivated plants, such as cereals, e. g. wheat, rye, barley, triticale, oats or rice; beet, e. g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e. g.
  • cereals e. g. wheat, rye, barley, triticale, oats or rice
  • beet e. g. sugar beet or fodder beet
  • fruits such as pomes, stone fruits or soft fruits, e. g.
  • plant propagation material is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants, including seedlings and young plants, which are to be transplanted after germi- nation or after emergence from soil. These young plants may also be protected before transplantation by a total or partial treatment by immersion or pouring.
  • cultivadas plants is to be understood as including plants which have been modified by breeding, mutagenesis or genetic engineering including but not limiting to agricultural biotech products on the market or in development.
  • Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination.
  • one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant.
  • Such genetic modifications also include but are not lim- ited to targeted post-translational modification of protein(s), oligo- or polypeptides e. g.
  • the amounts of pesticide applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, in particular from 0.1 to 0.75 kg per ha.
  • treatment of plant propagation materials such as seeds, e. g.
  • amounts of pesticide are of from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant propagation material (preferably seed) are generally required.
  • the amount of pesticide applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are, e. g., 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.
  • the user applies the dispersion according to the invention usually from a predosage device, a knapsack sprayer, a spray tank or a spray plane.
  • the dispersion is made up with water and/or buffer to the desired application concentration, it being possible, if appropriate, to add further auxiliaries, and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained.
  • 50 to 500 liters of the ready-to-use spray liquor are applied per hectare of agricultural useful area, preferably 100 to 400 liters.
  • the dispersion may comprise various polar or unpolar pes- ticides and even additional adjuvants.
  • the dispersion is thermodynamically stable, which allows long storage time, even under changing temperatures.
  • the pesticide has a high bioavailability.
  • the dispersion may be distributed in concentration and diluted with water to prepare a ready to use tank mix. Such a dilution is possible with various amount of water without adverse effect on the inner structure of the dispersion.
  • the viscosity (important for spray applications) may be adjusted by adding various amounts of water, again without adverse effect on the dispersion.
  • Stabilizer A ⁇ - ⁇ -Hydroxy terminated triblock polymer (EO/PO/EO), water soluble, average mol weight 12000 to 14000.
  • Stabilizer B Aqueuous composition containing 33 wt% comb polymer made of metha- crylic acid, methyl methacrylate and methoxy polyethylene glycol methacrylate.
  • Monoglyceride A monoglyceride comprising about 65 % of monolinolein.
  • Adjuvant A Hydrophobic fatty alcohol ethoxylate alkoxylate, liquid at room temperature, dynamic viscosity at 25 °C 70-80 mPas.
  • Adjuvant B Fatty alcohol ethoxylate alkoxylate, liquid at room temperature, cloud point according to EN 1890 (1 g in 100 g water) 28-30 °C, water solubility at least 10 wt% at room 20 °C.
  • the internally self-assembled dispersion was diluted with water as the dispersion according to the invention should be readily dilutable with water.
  • Dynamic light scattering was used to determine the hydrodynamic radius (RH) of the internally self-assembled particles.
  • SAXS Small angle X-ray scattering
  • the equipment comprised a SAXSess camera (Anton-Paar, Graz, Austria), connected to an Xray generator (Philips, PW 1730/10) operating at 40 kV and 50 mA with a sealed-tube Cu anode.
  • the 2D scattering pattern was recorded by a PI-SCX fused fiber optic taper CCD Camera from Princeton Instruments, a division of Roper Scien- tific, Inc.
  • the CCD detector featured a 2084x2084 array with 24x24 ⁇ pixel size (chip size: 50 ⁇ 50 mm) at a sample detector distance of 31 1 mm.
  • the CCD was operated at -30 °C with a 10 °C water-assisted cooling to reduce the thermally generated charge.
  • Cosmic ray correction and background subtraction were performed on the 2D image prior to further data processing. No sample background was subtracted.
  • the temperature of the capillary and the metallic sample holder was controlled by a Peltier element. The dispersions were exposed to three 10-min periods of X-rays for averaging.
  • the water-in-oil microemulsion shows a single broad correlation peak.
  • the pendant drop technique was used to determine the air-liquid surface tension ⁇ of the internally self-assembled dispersion.
  • the dispersion was prepared with CIPAC water D (342 ppm hardness) as described above.
  • the concentrated dispersion was diluted with CIPAC water D according to the following concentrations: 0.1wt% dispersion in CIPAC water D; 0.5wt%; 1.0wt%; 2.0wt% and 5.0wt%.
  • the instrument used was the OCA 10 from dataphysics. In the experiment a drop as large as possible was generated at the tip of a needle by ejecting a defined sample volume (typically 1 ⁇ ).
  • the shape of the drop was detected by a CCD camera as a function of time (1 picture per second) and analyzed using the Young-Laplace equation. The dynamic measurement was performed until the equilibrium value was reached.
  • Step B) Preparation of the aqueous phase:
  • a 15wt.% stock solution of Stabilizer A in water was produced to ensure that Stabilizer A was dissolved completely.
  • the stock solution was kept at 9°C until use.
  • 5,0 g of dispersed phase 0.05 g Stabilizer A were added, i.e. 3.33 g of stock solution.
  • the stock solution has to be diluted with 1 .67g of water to arrive at a total of 5,0 g of aqueous phase. After mixing the aqueous phase gently to avoid foam formation it was thermostated at the shearing temperature.
  • a total of 10g of raw dispersion was prepared as follows: The aqueous phase and the dispersed phase (both 5,0 g) were weighed into glass vessels sealed with a screw cap and thermostated separately at the shearing tempera- ture of 40°C. To prepare the raw-dispersion the dispersed phase was poured into the aqueous phase and dispersed with a heated spatula. The raw-dispersion was then sheared immediately.
  • the raw dispersion was immediately sheared mechanically through the shearing device based on Couette geometry.
  • the shear rate was kept constant at 15.000 s _1 , the shearing device was preheated to 40°C.
  • the raw dispersion was poured into the top opening of the shearing device and sheared as fast as possible through the narrow gap between the rotor and the stator.
  • the internally self-assembled dispersion was col- lected from the outlet at the bottom of the shear cell.
  • Examples 2-9 The total composition of examples 1 to 9 is given in Table 1 . All dispersions were prepared as in Example 1 in a total amount of 10,0 g.
  • the pesticide was fenpropimorph in examples 1 , 2, 6, 7 and 8, pyraclostrobin in ex- ample 3, and prochloraz in examples 4, 5 and 9.
  • the amphiphil was Monoglyceride in examples 1 -3, and 6, and phytantriol in examples 4, 5, and 7-9.
  • the stabilizing surfactant (“Stabilizer”) was Stabilizer A in examples 1 -5, 8 and 9, or Stabilizer B in examples 6 and 7.
  • prochloraz is an amorphous solid at room temperature.
  • 4,8 g prochloraz and 1 ,2 g phy- tantriol were weighed into a glass vessel and sealed. The mixture was thermostated well above the melting temperature of prochloraz (48°C) until prochloraz was molten. The mixture was homogenized on a rotating shaker several times.
  • methylcellulose (Methocel® A4C, 27.5-31 .5 methoxyl content, viscosity 12-18 cps as 2 wt% solution in water) was added prior to the preparation of the raw dispersion. To ensure complete dissolution of methylcellulose a stock-solution was prepared and stored at 9°C for 2 days. The stock solution was then added to the aqueous phase.
  • Table 1 Composition of examples 1 -9 (all amounts are given in gram)
  • Prochloraz samples were tested for their curative activity on netblotch in barley in greenhouse trials in concentrations of 2250, 563 and 141 ppm in comparison to an emulsion concentrate (EW) of prochloraz (450 g/l active, with 12-13 wt% o-sec- butylphenol and 4-4 wt% solvent naphtha, commercially available as Sportak® 45 EW from BASF SE), Without treatment the infection was in the range of 48 %. 7 days after treatment the infected area of barley leaves was assessed. The results are summarized in the table below.
  • EW emulsion concentrate

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

Abstract

La présente invention concerne une dispersion contenant une phase aqueuse continue et une phase dispersée, cette dernière étant dotée d'une structure de taille nanométrique auto-assemblée et contenant un pesticide dont la solubilité dans l'eau à 25 °C peut atteindre 10 g/l et le point de fusion est inférieur à 100 °C. L'invention concerne également un procédé de préparation de ladite dispersion, ledit procédé comprenant une étape consistant à mettre les constituants en contact, ainsi qu'un procédé visant à empêcher la croissance des champignons phytopathogènes et/ou de plantes indésirables et/ou empêcher l'attaque d'insectes ou d'acariens et/ou réguler la croissance de plantes, ladite dispersion étant rendue capable d'agir sur les nuisibles ciblés, leur habitat ou les plantes à protéger desdits nuisibles, sur le sol et/ou sur les plantes indésirables et/ou utiles et/ou sur leur habitat.
PCT/IB2011/051745 2010-05-06 2011-04-21 Dispersion à effet pesticide comprenant une phase dispersée nanostructurée WO2011138701A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP11777340.8A EP2566322A4 (fr) 2010-05-06 2011-04-21 Dispersion à effet pesticide comprenant une phase dispersée nanostructurée
JP2013508587A JP2013525475A (ja) 2010-05-06 2011-04-21 ナノ構造化分散相を含む農薬分散剤
KR1020127031815A KR20130100065A (ko) 2010-05-06 2011-04-21 나노구조화 분산상을 포함하는 살충 분산액
CN2011800277413A CN102933075A (zh) 2010-05-06 2011-04-21 包含纳米结构化分散相的农药分散体
BR112012028273A BR112012028273A2 (pt) 2010-05-06 2011-04-21 dispersão que contêm uma fase contínua aquosa e uma fase dispersa, método para a preparação da dispersão e método para o controle de fungos fitopatogênicos

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP10162155 2010-05-06
EP10162155.5 2010-05-06

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WO2011138701A1 true WO2011138701A1 (fr) 2011-11-10

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KR (1) KR20130100065A (fr)
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CN104798772B (zh) * 2015-03-13 2017-05-24 中国农业科学院农业环境与可持续发展研究所 一种农药纳米固体分散体及其制备方法

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WO2003106168A1 (fr) * 2000-08-16 2003-12-24 Lyotropic Therapeutics, Inc. Particules enrobees, procedes d'utilisation et de fabrication associes
AU2004275594A1 (en) * 2003-09-30 2005-04-07 Solubest Ltd. Water soluble nanoparticles inclusion complexes
WO2005110370A1 (fr) * 2004-05-18 2005-11-24 Nestec S.A. Emulsion huile dans eau a administrer
WO2007060171A1 (fr) * 2005-11-22 2007-05-31 Nestec S.A. Phase lipidique facilement dispersible
WO2007060177A1 (fr) * 2005-11-22 2007-05-31 Nestec S.A. Emulsion d'huile dans l'eau et son utilisation dans l'administration d'une fonctionnalite

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US5612047A (en) * 1994-03-08 1997-03-18 Duffy; Eric P. Pesticidal microemulsion formulation
US6534078B1 (en) * 1999-10-18 2003-03-18 Natural Pest Fx, Inc. Micro-encapsulated pepper-mustard composition and methods of using the same
US9433207B2 (en) * 2004-10-09 2016-09-06 Enviroquest Research Limited Non-ionic surfactant aggregates
US20090306003A1 (en) * 2006-01-10 2009-12-10 Innovation Technologies, Llc Pesticide Delivery System
WO2007140510A1 (fr) * 2006-06-02 2007-12-13 Monash University Composition agrochimique comprenant des particules de cristaux liquides

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WO2003106168A1 (fr) * 2000-08-16 2003-12-24 Lyotropic Therapeutics, Inc. Particules enrobees, procedes d'utilisation et de fabrication associes
US20030232095A1 (en) * 2002-06-12 2003-12-18 Nutralease Ltd. Nano-sized self-assembled structured liquids
AU2004275594A1 (en) * 2003-09-30 2005-04-07 Solubest Ltd. Water soluble nanoparticles inclusion complexes
WO2005110370A1 (fr) * 2004-05-18 2005-11-24 Nestec S.A. Emulsion huile dans eau a administrer
WO2007060171A1 (fr) * 2005-11-22 2007-05-31 Nestec S.A. Phase lipidique facilement dispersible
WO2007060177A1 (fr) * 2005-11-22 2007-05-31 Nestec S.A. Emulsion d'huile dans l'eau et son utilisation dans l'administration d'une fonctionnalite

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JP2013525475A (ja) 2013-06-20
BR112012028273A2 (pt) 2015-09-15
EP2566322A1 (fr) 2013-03-13
EP2566322A4 (fr) 2013-12-11
KR20130100065A (ko) 2013-09-09
CN102933075A (zh) 2013-02-13

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