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WO2016016042A1 - Agrochemical suspoemulsion comprising hydrophobic modified silica particles - Google Patents

Agrochemical suspoemulsion comprising hydrophobic modified silica particles Download PDF

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Publication number
WO2016016042A1
WO2016016042A1 PCT/EP2015/066608 EP2015066608W WO2016016042A1 WO 2016016042 A1 WO2016016042 A1 WO 2016016042A1 EP 2015066608 W EP2015066608 W EP 2015066608W WO 2016016042 A1 WO2016016042 A1 WO 2016016042A1
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WO
WIPO (PCT)
Prior art keywords
suspoemulsion
water
pesticide
silica particles
suspoemulsion according
Prior art date
Application number
PCT/EP2015/066608
Other languages
French (fr)
Inventor
Helmut Auweter
Wen Xu
Megan RUMLEY
Original Assignee
Basf Se
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 filed Critical Basf Se
Publication of WO2016016042A1 publication Critical patent/WO2016016042A1/en

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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
    • 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
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof

Definitions

  • Agrochemical suspoemulsion comprising hydrophobic modified silica particles
  • the present invention relates to an aqueous suspoemulsion comprising a first pesticide which is dissolved in a water-immiscible solvent, a second pesticide which is suspended in a continuous aqueous phase, and hydrophobic modified silica particles. Furthermore, the invention relates to a process for the preparation of said suspoemulsion by contacting water, the first pesticide, the second pesticide, the water-immiscible solvent, and the silica particles.
  • suspoemulsion is allowed to act on the respective pests, their environment or the crop plants to be protected from the respective pest, on the soil and/or on undesired plants and/or on the crop plants and/or on their environment; and seed containing said suspoemulsion.
  • the present invention compris- es combinations of preferred features with other preferred features.
  • Agrochemical suspoemulsions are also known as "SE" type agroformulations.
  • Object of the present invention was to further improve agrochemical suspoemulsion formula- tions, for example with regard to their storage stability, their rain fastness, and their biological activity.
  • aqueous suspoemulsion comprising a first pesticide which is dissolved in a water-immiscible solvent, a second pesticide which is suspended in a continuous aqueous phase, and hydrophobic modified silica particles.
  • a suspoemulsion is typically a conventional type of formulation in the field of the agrochemical formulations.
  • SE formulations of pesticides the suspoemulsion is preformed in the commercial product and is conventionally diluted with a carrier, such as water, when making up the spray mixture.
  • the suspoemulsion usually comprises a continuous aqueous phase, a dispersed oil phase, and a suspended solid phase.
  • the oil phase usually forms droplets within the aqueous phase.
  • the oil phase usually comprises the water-immiscible solvent.
  • the oil phase usually comprises the first pesticide, which is dissolved in the water-immiscible solvent.
  • the solid phase usually forms solid particles within the aqueous phase.
  • the solid phase usually comprises the second pesticide, which is suspended in a continuous aqueous phase.
  • the first pesticide is dissolved in the water-immiscible solvent.
  • the first pesticide is present at least in the dispersed oil phase of the suspoemulsion.
  • the second pesticide is suspended in the continuous aqueous phase.
  • the second pesticide is present at least in the solid phase of the suspoemulsion.
  • the suspoemulsion may comprise at least one further pesticide in addition to the first and the second pesticide.
  • the further pesticide may be present in the oil phase and/or in the aqueous phase.
  • the mean droplet size of the oil phase droplets is usually in the range of from 0.1 to 20 ⁇ , in particular of from 0.3 to 10 ⁇ and specifically of from 0.5 to 4.0 ⁇ .
  • the mean droplet size can be determined by particle-size measurement by means of laser diffraction, for example using a Malvern Mastersizer 2000.
  • the second pesticide may be present in the form of crystalline or amorphous particles which are solid at 20°C.
  • the second pesticide usually is present in form of solid particles.
  • the second pesticide has a usually particle size distribution with an x50 value of from 0.1 to 10 ⁇ , preferably 0.2 ⁇ to 5 ⁇ and especially preferably 0.5 ⁇ to 2 ⁇ .
  • the particle size distribution can be determined by laser light diffraction of an aqueous suspension comprising the particles.
  • the sample preparation for example the dilution to the measuring concentration, will, in this measuring method, depend on the fineness and concentration of the active substances in the suspension sample and on the apparatus used (for example Malvern Mastersizer), inter alia.
  • the procedure should be developed for the system in question and is known to a person skilled in the art.
  • the suspoemulsion is an aqueous suspoemulsion, which means for example that the suspoemulsion comprises water.
  • the suspoemulsion can comprise at least 5% by weight, preferably at least 10% by weight and especially preferably at least 15% by weight of water based on the total weight of the suspoemulsion.
  • the suspoemulsion can comprise from 20 to 85% by weight, preferably from 30 to 75% by weight and especially preferably from 35 to 70% by weight of water, based on the total weight of the suspoemulsion.
  • the suspoemulsion comprises a water-immiscible solvent.
  • the water-immiscible solvent may be soluble in water at 20 °C up to 50 g/l, preferably up to 20 g/l, and in particular up to 5 g/l.
  • hydrocarbon solvent such as an aliphatic, cyclic and aromatic hydrocarbons (e. g. toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, mineral oil fractions of medium to high boiling point (such as kerosene, diesel oil, coal tar oils)); - benzyl acetate;
  • an aliphatic, cyclic and aromatic hydrocarbons e. g. toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, mineral oil fractions of medium to high boiling point (such as kerosene, diesel oil, coal tar oils)
  • - benzyl acetate such as kerosene, diesel oil, coal tar oils
  • a vegetable oil such as corn oil, rapeseed oil
  • a fatty acid ester such as Ci-Cio-alkylester of a Cio-C22-fatty acid
  • methyl- or ethyl esters of vegetable oils such as rapeseed oil methyl ester or corn oil methyl ester.
  • solvents are aromatic hydrocarbons.
  • Suitable water-immiscible solvent are aromatic hydrocarbons.
  • Aromatic hydrocarbons are compounds which consist of carbon and hydrogen and which comprise aromatic groups. Preferred are aromatic hydrocarbons or their mixtures with an initial boiling point of at least 160°C, preferably at least 180°C.
  • aromatic hydrocarbons examples include benzene, toluene, o-, m- or p- xylene, naphthalene, biphenyl, o- or m-terphenyl, aromatic hydrocarbons which are mono- or polysubstituted by Ci-C2o-alkyl, such as ethylbenzene, dodecylbenzene, tetradecylbenzene, hexadecylbenzene, methylnaphthalene, diisopropylnaphthalene, hexylnaphthalene or decylnaphthalene.
  • Others which are suitable are aromatic hydrocarbon mixtures with an initial boiling point of at least 160°C.
  • Preferred aromatic hydrocarbons are aromatic hydrocarbon mix- tures with an initial boiling point of at least 160°C, preferably at least 180°C. Mixtures of the above aromatic hydrocarbons are also possible.
  • the suspoemulsion comprises from 5 to 60% by weight, preferably from 15 to 55% by weight, especially preferably from 20 to 45% by weight of the water-immiscible solvent, in each case based on the total weight of the suspoemulsion.
  • the suspoemulsion may comprise in addition to the water-immiscible solvent also a water- soluble solvent.
  • the water-soluble solvent may be soluble in water at 20 °C more than 50 g/l, preferably more than 100 g/l.
  • the suspoemulsion comprises less than 10 % by weight, preferably less than 3 % by weight, especially preferably less than 1 % by weight of the water- soluble solvent, in each case based on the total weight of the suspoemulsion.
  • the suspoemulsion is essentially free of a water-soluble solvent.
  • pesticide refers to at least one active substance selected from the group of the fungi- cides, insecticides, nematicides, herbicides, safeners, biopesticides and/or growth regulators.
  • Preferred pesticides are fungicides, insecticides, herbicides and growth regulators.
  • Especially preferred pesticides are insecticides.
  • Mixtures of pesticides of two or more of the abovemen- tioned classes may also be used. The skilled worker is familiar with such pesticides, which can be found, for example, in the Pesticide Manual, 16th Ed. (2013), The British Crop Protection Council, London.
  • Suitable insecticides are insecticides from the class of the carbamates, organ- ophosphates, organochlorine insecticides, phenylpyrazoles, pyrethroids, neonicotinoids, spi- nosins, avermectins, milbemycins, juvenile hormone analogs, alkyl halides, organotin compounds nereistoxin analogs, benzoylureas, diacylhydrazines, METI acarizides, and insecticides such as chloropicrin, pymetrozin, flonicamid, clofentezin, hexythiazox, etoxazole, diafenthiuron, propargite, tetradifon, chlorofenapyr, DNOC, buprofezine, cyromazine, amitraz, hydramethyl- non, acequinocyl, fluacrypyrim, rotenone, or their derivatives.
  • Suitable fungicides are fungicides from the classes of dinitroanilines, allylamines, anilinopyrimidines, antibiotics, aromatic hydrocarbons, benzenesulfonamides, benzimidazoles, benzisothiazoles, benzophenones, benzothi- adiazoles, benzotriazines, benzyl carbamates, carbamates, carboxamides, carboxylic acid dia- mides, chloronitriles cyanoacetamide oximes, cyanoimidazoles, cyclopropanecarboxamides, dicarboximides, dihydrodioxazines, dinitrophenyl crotonates, dithiocarbamates, dithiolanes, ethylphosphonates, ethylaminothiazolecarboxamides, guanidines, hydroxy-(2- amino)pyrimidines, hydroxyanilides, imidazoles, imidazolinone
  • Suitable herbicides are herbicides from the classes of the acetamides, amides, aryloxyphenoxypropionates, benzamides, benzofuran, benzoic acids, benzothiadiazinones, bipyridylium, carbamates, chloroacetamides, chlorocarboxylic acids, cy- clohexanediones, dinitroanilines, dinitrophenol, diphenyl ether, glycines, imidazolinones, isoxa- zoles, isoxazolidinones, nitriles, N-phenylphthalimides, oxadiazoles, oxazolidinediones, oxya- cetamides, phenoxycarboxylic acids, phenylcarbamates, phenylpyrazoles, phenylpyrazolines, phenylpyridazines, phosphinic acids, phosphoroamidates, phosphorodi
  • the first pesticide may comprise at least one water-insoluble pesticide.
  • the second pesticide may comprise at least one water-insoluble pesticide.
  • Water-insoluble pesticides may have a solubility in water of up to 10 g/l, preferably up to 1 g/l, and in particular up to 0.5 g/l, at 20 °C.
  • the first pesticide may be soluble in the water-immiscible solvent (e.g. toluene), e.g. in an amount of at least 5 g/l, preferably at least 20 g/l and in particular at least 40 g/l, at 20 °C.
  • the first pesticide may be solid or liquid at 20 °C.
  • the second pesticide may have a melting point of at least 40 °C, preferably at least 50 °C, and in particular at least 70 °C.
  • the suspoemulsion comprises from 0.1 to 35% by weight, preferably from 0.5 to 20% by weight, especially preferably from 1 to 10% by weight of the first pesticide, in each case based on the total weight of the suspoemulsion.
  • the suspoemulsion comprises from 0.1 to 35% by weight, preferably from 0.5 to 25% by weight, especially preferably from 2 to 15% by weight of the second pesticide, in each case based on the total weight of the suspoemulsion.
  • the suspoemulsion comprises from 0.1 to 35% by weight, preferably from 0.5 to 25% by weight, especially preferably from 3 to 15% by weight of the sum of all pesticides (e.g. the sum of the first pesticide, the second pesticide and the further pesticide), in each case based on the total weight of the suspoemulsion.
  • the silica particles are hydrophobic modified.
  • silica is hydrophilic due to silanol (Si- OH) groups on the surface of the particles. These silanol groups may be chemically reacted with various reagents to render the silica hydrophobic.
  • the silica particles may be based on fumed or precipitated silica, where fumed silica is preferred.
  • the silica particles are preferably hydrophobic modified by treatment with a silanes, a siloxane, or a mixture thereof, whereas silanes or a mixture thereof are preferred.
  • silanes or siloxanes are dimethyldichlorosilane, octamethylcyclotetrasiloxane, polydimethylsiloxane, oc- tylsilane, hexamethyldisiloxane, methacrylsilane.
  • silanes or siloxanes are 2-acetoxyethyltrichlorosilane, 2-acetoxyethyltriethox- ysilane, 2-acetoxyethyltrimethoxysilane, acetoxymethyltriethoxysilane, acetoxymethyltrimethox- ysilane, 3-acetoxypropyltrimethoxysilane, 3-acetoxypropylmethyldichlorosilane, 4-aminobutyltri- ethoxysilane, m-N-(2-aminoethyl)aminomethylphenethyltrimethoxysilane, p-N-(2-aminoethyl)- aminomethylphenethyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrihydroxy
  • the silica particles may have a specific surface area (BET; Brunauer, Emmet and Teller) from 20 to 600 m 2 /g, preferably from 100 to 300 m 2 /g, and in particular from 150 to 250 m 2 /g.
  • BET Brunauer, Emmet and Teller
  • the specific surface area may be determined according to DIN ISO 9277.
  • the silica particles may have a carbon content from 0.1 to 12 wt%, preferably from 0.4 to 6.0 wt%, and in particular from 0.6 to 2.5 wt%.
  • the carbon content may be determined according to DIN ISO 3262-20 chapter eight.
  • the primary particle diameter of the silica particles is in general in the range from
  • the primary particle diameter is preferably determined via transmission electron microscopy (TEM).
  • a plurality of smaller particles having a primary particle
  • agglomerate may agglomerate to form a larger particle (having a secondary particle
  • the secondary particle diameter can therefore often also be designated as agglomerate size.
  • the agglomerate particle diameter of the silica particles is in general in the range from 0.1 to 500 ⁇ , preferably from 0.3 to 10 ⁇ , in particular from 1 to 20 ⁇ .
  • the agglomerate particle diameter usually designates the mean particle diameter which is determined according to the volume fraction from the particle size distribution. Said particle size distributions can be meas- ured by light scattering (for example on a Zetasizer Nano S apparatus from Malvern Instruments).
  • hydrophobic modified silica particles also known as “hydrophobic silica” are commercially available from various companies.
  • the suspoemulsion may comprise 0.1 to 20 wt%, preferably 0.2 to 10 wt% and in particular 0.4 to 5 wt% of the silica particles.
  • the suspoemulsion comprises usually a water-soluble nonionic emulsifier.
  • Water-soluble nonionic emulsifiers may be selected from alkoxylates or mixtures thereof, preferably from alkoxylate block polmyers or compounds such as alcohols, alkylphenols, amines, amides, ar- ylphenols, fatty acids or fatty acid esters which have been alkoxylated with 10 to 50 equivalents, where ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide.
  • the water-soluble nonionic emulsifier contains C2-C3-polyalkoxylat.es of C10-C22- hydroxy fatty acid triglycerides, C2-C3-polyalkoxylat.es of Cio-C22-fatty acid mono- or diglycer- ides, or mixtures thereof, and where the average degree of alkoxylation (preferably of ethoxyla- tion) of the Cio-C22-hydroxy fatty acid triglycerides or Cio-C22-fatty acid mono- or diglycerides is usually from 10 to 150, preferably from 15 to 100, in particular from 20 to 70 and specifically from 30 to 65.
  • the water-soluble nonionic emulsifier contains alkoxylate block polymers (e.g. block polymers of the A-B or A-B-A type, where the A-B-A type is preferred) comprising blocks of polyethylene oxide and polypropylene oxide.
  • alkoxylate block polymers comprise usually at least 30 wt%, preferably at least 40 wt% of polymerized ethylene oxide.
  • the alkoxylate block polymers is preferably a block polymers A-B-A type comprising blocks of polyethylene oxide (block "A") and polypropylene oxide (block "B”).
  • the molecular weight of the alkoxylate block polmyer may be from 1000 to 30000 Da, preferably from 2000 to 15000 Da.
  • the water-soluble nonionic emulsifier contains polyethoxylates of C12-C22- hydroxyfatty acid triglycerides, polyethoxylates of Ci2-C22-fatty acid mono- or diclycerides, alkoxylate block polymers, or mixtures thereof, and where the average degree of alkoxylation (preferably of ethoxylation) of the Ci2-C22-hydroxyfatty acid triglycerides or Ci2-C22-fatty acid mono- or diclycerides is usually from 10 to 150, preferably from 15 to 100, in particular from 20 to 70 and specifically from 30 to 65.
  • the water-soluble nonionic emulsifier contains polyethoxylates of C12-C22- hydroxyfatty acid triglycerides, alkoxylate block polymers, or mixtures thereof, and specifically polyethoxylates of castor oil, and where the average degree of of ethoxylation of the C12-C22- hydroxyfatty acid triglycerides (e.g. castor oil) is usually from 10 to 150, preferably from 15 to 100, in particular from 20 to 70 and specifically from 30 to 65.
  • the water-soluble nonionic emulsifier may have each an HLB value of at least 10, preferably of at least 12, and in particular of at least 13.5.
  • the water-soluble nonionic emulsifier may have an HLB value of up to 20, preferably of up to 19, and in particular of up to 18. The HLB value may be determined according to the method of Griffin.
  • the water-soluble nonionic emulsifier has each usually a solubility in water of at least 5 g/l, preferably at least 20 g/l, and in particular at least 100 g/l, as may determined at 25 °C.
  • the water-soluble nonionic emulsifier is usually present in the aqueous phase of the suspoemulsion.
  • the water-soluble nonionic emulsifier is present in dissolved form the aqueous phase of the suspoemulsion.
  • the suspoemulsion comprises from 0.1 to 15% by weight, preferably from 0.2 to 8 % by weight, especially preferably from 0.5 to 5% by weight of the sum of all water-soluble nonionic emulsifier, in each case based on the total weight of the suspoemulsion.
  • the suspoemulsion may comprise further nonionic emulsifiers beside the water-soluble nonionic emulsifier.
  • the further nonionic emulsifiers are usually different from the water-soluble nonionic emulsifiers.
  • the further nonionic emulsifier is usually water-insoluble.
  • the further nonionic emulsifier has usually a solubility in water of below 5 g/l, below 20 g/l, orbelow 100 g/l, as may determined at 25 °C.
  • the further nonionic emulsifier may have an HLB value of below 10, below 12, or below 13.5.
  • the suspoemulsion comprises from 0.1 to 20% by weight in each case based on the total weight of the suspoemulsion.
  • the suspoemulsion comprises from 0.1 to 25 by weight of the first pesticide (e.g. solubility in water of up to 10 g/l), from 0.1 to 30 by weight of the second pesticide (e.g. solubility in water of up to 10 g/l), 10 to 50% by weight of the water-immiscible solvent (e.g. aromatic hydrocarbons), 0.1 to 10% by weight of the silica particles, and optionally 0.1 to 10% by weight of the water-soluble nonionic emulsifier, where the sum of these components is from 25 to 75 wt%, in each case based on the total weight of the suspoemulsion.
  • the first pesticide e.g. solubility in water of up to 10 g/l
  • the second pesticide e.g. solubility in water of up to 10 g/l
  • the water-immiscible solvent e.g. aromatic hydrocarbons
  • the silica particles e.g. aromatic hydrocarbons
  • the suspoemulsion comprises from 0.5 to 15 by weight of the first pesticide (e.g. solubility in water of up to 5 g/l), from 1 to 20 by weight of the second pesticide (e.g. solubility in water of up to 5 g/l), 15 to 45% by weight of the water-immiscible solvent (e.g. aromatic hydrocarbons), 0.2 to 7% by weight of the silica particles, and optionally 0.2 to 7% by weight of the water-soluble nonionic emulsifier, where the sum of these components is from 30 to 70 wt%, in each case based on the total weight of the suspoemulsion.
  • the first pesticide e.g. solubility in water of up to 5 g/l
  • the second pesticide e.g. solubility in water of up to 5 g/l
  • the water-immiscible solvent e.g. aromatic hydrocarbons
  • the silica particles e.g. aromatic hydrocarbons
  • the suspoemulsion comprises from 1 to 10 by weight of the first pesticide (e.g. solubility in water of up to 1 g/l), from 3 to 15 by weight of the second pesticide (e.g. solubility in water of up to 1 g/l), 20 to 40% by weight of the water-immiscible solvent (e.g. aromatic hydrocarbons), 0.4 to 5% by weight of the silica particles, and optionally 0.5 to 5% by weight of the water-soluble nonionic emulsifier, where the sum of these components is from 35 to 65 wt%, in each case based on the total weight of the suspoemulsion.
  • the first pesticide e.g. solubility in water of up to 1 g/l
  • the second pesticide e.g. solubility in water of up to 1 g/l
  • the water-immiscible solvent e.g. aromatic hydrocarbons
  • the silica particles e.g. aromatic hydrocarbons
  • the suspoemulsion may comprise auxiliaries for agrochemical formulations.
  • auxiliaries for agrochemical formulations.
  • suitable auxiliaries are surfactants, dispersants, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.
  • Suitable surfactants are surface-active compounds, such as anionic, cationic, and amphoteric surfactants, polyelectrolytes, and mixtures thereof.
  • Such surfactants can be used as dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant.
  • surfactants are listed in McCutcheon's, Vol.1 : Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
  • Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof.
  • sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of con- densed 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 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 polyelectrolytes are poly- acids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or polyethyleneamines.
  • Suitable adjuvants are compounds, which have a negligible or even no pesticidal activity themselves, and which improve the biological performance of the compound I on the target.
  • examples are surfactants, mineral or vegetable oils, and other auxilaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.
  • Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates.
  • Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones.
  • Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
  • Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
  • Suitable colorants are pigments of low water solubility and water- soluble dyes.
  • examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanofer- rate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).
  • Suitable tackifiers or binders are polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols, pol- yacrylates, biological or synthetic waxes, and cellulose ethers.
  • the suspoemulsion may be employed for the purposes of treatment of plant propagation materials, particularly seeds.
  • the compositions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations. Application can be carried out before or during sowing.
  • Meth- ods for applying or treating the suspoemulsion on to plant propagation material, especially seeds include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material.
  • the suspoemulsion is applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.
  • the amounts of active substances 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.
  • amounts of active substance 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 active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.
  • oils, wetters, adjuvants, fertilizer, or micronutrients, and other pesticides may be added to the suspoe- mulsion as premix or, if appropriate not until immediately prior to use (tank mix).
  • pesticides e.g. herbicides, insecticides, fungicides, growth regulators, safeners
  • These agents can be admixed with the compositions according to the invention in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1.
  • the user applies the suspoemulsion or the tank mix prepared from the suspoemulsion usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system.
  • the suspoemulsion is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical compo- sition according to the invention is thus obtained.
  • 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.
  • the present inventnion further relates to a method of preparing the suspoemulsion by contact- ing water, the pesticide, the water-immiscible solvent, the water-soluble nonionic emulsifier and the silica particles, and optionally the auxiliaries.
  • the contacting may be achieved in a known manner, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
  • the contacting is achieved by mixing (eg in a high shear mixer) at ambient temperatures (eg 10 to 40 °C).
  • the present inventnion further relates to a method of controlling phytopathogenic fungi and/or undesired plant growth and/or unde-sired insect or mite attack and/or for regulating the growth of plants, wherein the suspoemulsion is allowed to act on the respective pests, their environ- ment or the crop plants to be protected from the respective pest, on the soil and/or on undesired plants and/or on the crop plants and/or on their environment.
  • suitable crop plants are cereals, for example wheat, rye, barley, triticale, oats or rice; beet, for example sugar or fodder beet; pome fruit, stone fruit and soft fruit, for example apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, currants or gooseberries; legumes, for example beans, lentils, peas, lucerne or soybeans; oil crops, for example oilseed rape, mustard, olives, sunflowers, coconut, cacao, castor beans, oil palm, peanuts or soybeans; cucurbits, for example pumpkins/squash, cucumbers or melons; fiber crops, for example cotton, flax, hemp or jute; citrus fruit, for example oranges, lemons, grapefruit or tange- rines; vegetable plants, for example spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, pumpkin/squash or capsicums; plants of the laurel family, for example avocados, cinnamon or camphor;
  • crop plants also includes those plants which have been modified by breeding, muta- genesis or recombinant methods, including the biotechnological agricultural products which are on the market or in the process of being developed.
  • Genetically modified plants are plants whose genetic material has been modified in a manner which does not occur under natural conditions by hybridizing, mutations or natural recombination (i.e. recombination of the genetic material).
  • one or more genes will, as a rule, be integrated into the genetic material of the plant in order to improve the plant's properties.
  • Such recombinant modifications also comprise posttranslational modifications of proteins, oligo- or polypeptides, for example by means of gly- cosylation or binding polymers such as, for example, prenylated, acetylated or farnesylated residues or PEG residues.
  • the present inventnion further relates to seed containing the suspoemulsion.
  • the advantages of the suspoemulsion according to the invention are high storage stability, even at varying or low temperatures. In particular, no phase separation is observed during storage.
  • the droplet size in the suspoemulsion is small and/or stable.
  • suspoemulsion is small and/or stable. Moreover, the suspoemulsion according to the invention permits, if required, the addition of large amounts of fat-soluble or water-soluble adjuvants in the oil phase or the aqueous phase. The good storage stability is retained even when such substances are added. Another advantage is the high rainfastness of the suspoemulsion on the crops; a reduced toxicity; a reduced amount of emulsifiers and/or surfactants; a reduced spray drift, e.g. for ground or aerial spray application.
  • Silica Particles Silica particles, hydrophobic modified with hexadecyltrimethoxysilan, specific surface area (BET) about 175 to 205 m 2 /g, carbon content about 1.0 to about 1 .7 wt%, primary particle diameter about 10-15 nm.
  • BET specific surface area
  • Hydrocarbon A Aromatic hydrocarbon solvent, initial boiling point about 230 °C, aromatic content at least 99 vol%, flash point 100-1 10 °C.
  • Auxiliary A Oleyl alcohol, ethoxylated with 3 units of ehtylene oxide, HLB 6-7, water-insoluble.
  • Auxiliary B Ethylene oxide / propylene oxide / ethylene oxide triblock polymer (about 50 wt%
  • Emulsifier A Castor oil, ethoxylated with 50-60 units of ethylene oxide, HLB 14-15, melting point 30-35 °C, soluble in cold water.
  • Wetting Agent Water-soluable naphthalene sulfonate condensate.
  • Biocide Aqueous mix of 2-methyl-4-isothiazolin-3-one and 1 ,2-benzisothiazolin -3-one.
  • Antifoamer Silicon defoamer.
  • the pesticidal suspoemulsions were produced by the following procedure:
  • Chlorphenapyr Chlorphenapyr, the Wetting Agent, the Stabilizer and the Defoamer were added to water under agitation.
  • Example 3 Stability
  • the storage stability of the suspoemulsions A and B of Examples 1 and 2 was tested each with a sample at 54 °C for four weeks, with another sample in a daily cycling temperature from - 10 °C to +30 °C for four weeks, with another sample at 21 °C for four weeks and yet with another sample at -10 °C for four weeks.
  • suspoemulsion stability was determined by visual observation of the samples. No noticeable phase separation or increase in droplet size occurred for suspoemulsion A, while suspoemulsion B was unstable at storage temperatures of 21 and 54 °C as well as under cycling conditions.
  • a Pyraclostrobin and Metconazole suspoemulsion C with a composition according to Table 2 was prepared by the procedure described in example 1.
  • suspoemulsion C from Example 4 was tested with a sample at 54 °C for two weeks, with another sample in a daily cycling temperature from -10 °C to +10 °C for two weeks, with another sample at 21 °C for two weeks and yet with another sample at -10 °C for two weeks.
  • suspoemulsion stability was determined by visual observation of the samples. No noticea- ble phase separation occurred for suspoemulsion C.
  • the oil droplet size was measured before and after storage by a Malvern ® Mastersizer 2000. No droplet size increase was observed for suspoemulsion C.

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Abstract

The present invention relates to an aqueous suspoemulsion comprising a first pesticide which is dissolved in a water-immiscible solvent, a second pesticide which is suspended in a continuous aqueous phase, and hydrophobic modified silica particles. Furthermore, the invention relates to a process for the preparation of said suspoemulsion by contacting water, the first pesticide, the second pesticide, the water-immiscible solvent, and the silica particles. Further subject matter are a method of controlling phytopathogenic fungi and/or undesired plant growth and/or undesired insect or mite attack and/or for regulating the growth of plants, wherein the suspoemulsion is allowed to act on the respective pests, their environment or the crop plants to be protected from the respective pest, on the soil and/or on undesired plants and/or on the crop plants and/or on their environment; and seed containing said suspoemulsion.

Description

Agrochemical suspoemulsion comprising hydrophobic modified silica particles
Description The present invention relates to an aqueous suspoemulsion comprising a first pesticide which is dissolved in a water-immiscible solvent, a second pesticide which is suspended in a continuous aqueous phase, and hydrophobic modified silica particles. Furthermore, the invention relates to a process for the preparation of said suspoemulsion by contacting water, the first pesticide, the second pesticide, the water-immiscible solvent, and the silica particles. Further subject matter are a method of controlling phytopathogenic fungi and/or undesired plant growth and/or undesired insect or mite attack and/or for regulating the growth of plants, wherein the suspoemulsion is allowed to act on the respective pests, their environment or the crop plants to be protected from the respective pest, on the soil and/or on undesired plants and/or on the crop plants and/or on their environment; and seed containing said suspoemulsion. The present invention compris- es combinations of preferred features with other preferred features.
Agrochemical suspoemulsions are also known as "SE" type agroformulations.
Object of the present invention was to further improve agrochemical suspoemulsion formula- tions, for example with regard to their storage stability, their rain fastness, and their biological activity.
The object was achieved by an aqueous suspoemulsion comprising a first pesticide which is dissolved in a water-immiscible solvent, a second pesticide which is suspended in a continuous aqueous phase, and hydrophobic modified silica particles.
A suspoemulsion (SE) is typically a conventional type of formulation in the field of the agrochemical formulations. In SE formulations of pesticides, the suspoemulsion is preformed in the commercial product and is conventionally diluted with a carrier, such as water, when making up the spray mixture.
The suspoemulsion usually comprises a continuous aqueous phase, a dispersed oil phase, and a suspended solid phase. The oil phase usually forms droplets within the aqueous phase. The oil phase usually comprises the water-immiscible solvent. The oil phase usually comprises the first pesticide, which is dissolved in the water-immiscible solvent. The solid phase usually forms solid particles within the aqueous phase. The solid phase usually comprises the second pesticide, which is suspended in a continuous aqueous phase.
The first pesticide is dissolved in the water-immiscible solvent. Preferably, the first pesticide is present at least in the dispersed oil phase of the suspoemulsion. The second pesticide is suspended in the continuous aqueous phase. Preferably, the second pesticide is present at least in the solid phase of the suspoemulsion. The suspoemulsion may comprise at least one further pesticide in addition to the first and the second pesticide. The further pesticide may be present in the oil phase and/or in the aqueous phase. The mean droplet size of the oil phase droplets is usually in the range of from 0.1 to 20 μηη, in particular of from 0.3 to 10 μηη and specifically of from 0.5 to 4.0 μηη. The mean droplet size can be determined by particle-size measurement by means of laser diffraction, for example using a Malvern Mastersizer 2000. The second pesticide may be present in the form of crystalline or amorphous particles which are solid at 20°C. The second pesticide usually is present in form of solid particles. The second pesticide has a usually particle size distribution with an x50 value of from 0.1 to 10 μηη, preferably 0.2 μηη to 5 μηη and especially preferably 0.5 μηη to 2 μηη. The particle size distribution can be determined by laser light diffraction of an aqueous suspension comprising the particles. The sample preparation, for example the dilution to the measuring concentration, will, in this measuring method, depend on the fineness and concentration of the active substances in the suspension sample and on the apparatus used (for example Malvern Mastersizer), inter alia. The procedure should be developed for the system in question and is known to a person skilled in the art.
The suspoemulsion is an aqueous suspoemulsion, which means for example that the suspoemulsion comprises water. The suspoemulsion can comprise at least 5% by weight, preferably at least 10% by weight and especially preferably at least 15% by weight of water based on the total weight of the suspoemulsion. The suspoemulsion can comprise from 20 to 85% by weight, preferably from 30 to 75% by weight and especially preferably from 35 to 70% by weight of water, based on the total weight of the suspoemulsion.
The suspoemulsion comprises a water-immiscible solvent. The water-immiscible solvent may be soluble in water at 20 °C up to 50 g/l, preferably up to 20 g/l, and in particular up to 5 g/l.
Suitable examples for water-immiscible solvents are
a hydrocarbon solvent such a an aliphatic, cyclic and aromatic hydrocarbons (e. g. toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, mineral oil fractions of medium to high boiling point (such as kerosene, diesel oil, coal tar oils)); - benzyl acetate;
a vegetable oil such as corn oil, rapeseed oil;
a fatty acid ester such as Ci-Cio-alkylester of a Cio-C22-fatty acid; or
methyl- or ethyl esters of vegetable oils such as rapeseed oil methyl ester or corn oil methyl ester.
Mixtures of aforementioned solvents are also possible. Preferred solvents are aromatic hydrocarbons. Suitable water-immiscible solvent are aromatic hydrocarbons. Aromatic hydrocarbons are compounds which consist of carbon and hydrogen and which comprise aromatic groups. Preferred are aromatic hydrocarbons or their mixtures with an initial boiling point of at least 160°C, preferably at least 180°C. Examples of aromatic hydrocarbons are benzene, toluene, o-, m- or p- xylene, naphthalene, biphenyl, o- or m-terphenyl, aromatic hydrocarbons which are mono- or polysubstituted by Ci-C2o-alkyl, such as ethylbenzene, dodecylbenzene, tetradecylbenzene, hexadecylbenzene, methylnaphthalene, diisopropylnaphthalene, hexylnaphthalene or decylnaphthalene. Others which are suitable are aromatic hydrocarbon mixtures with an initial boiling point of at least 160°C. Preferred aromatic hydrocarbons are aromatic hydrocarbon mix- tures with an initial boiling point of at least 160°C, preferably at least 180°C. Mixtures of the above aromatic hydrocarbons are also possible.
Usually, the suspoemulsion comprises from 5 to 60% by weight, preferably from 15 to 55% by weight, especially preferably from 20 to 45% by weight of the water-immiscible solvent, in each case based on the total weight of the suspoemulsion.
The suspoemulsion may comprise in addition to the water-immiscible solvent also a water- soluble solvent. The water-soluble solvent may be soluble in water at 20 °C more than 50 g/l, preferably more than 100 g/l. Usually, the suspoemulsion comprises less than 10 % by weight, preferably less than 3 % by weight, especially preferably less than 1 % by weight of the water- soluble solvent, in each case based on the total weight of the suspoemulsion. In one form the suspoemulsion is essentially free of a water-soluble solvent.
The term pesticide refers to at least one active substance selected from the group of the fungi- cides, insecticides, nematicides, herbicides, safeners, biopesticides and/or growth regulators. Preferred pesticides are fungicides, insecticides, herbicides and growth regulators. Especially preferred pesticides are insecticides. Mixtures of pesticides of two or more of the abovemen- tioned classes may also be used. The skilled worker is familiar with such pesticides, which can be found, for example, in the Pesticide Manual, 16th Ed. (2013), The British Crop Protection Council, London. Suitable insecticides are insecticides from the class of the carbamates, organ- ophosphates, organochlorine insecticides, phenylpyrazoles, pyrethroids, neonicotinoids, spi- nosins, avermectins, milbemycins, juvenile hormone analogs, alkyl halides, organotin compounds nereistoxin analogs, benzoylureas, diacylhydrazines, METI acarizides, and insecticides such as chloropicrin, pymetrozin, flonicamid, clofentezin, hexythiazox, etoxazole, diafenthiuron, propargite, tetradifon, chlorofenapyr, DNOC, buprofezine, cyromazine, amitraz, hydramethyl- non, acequinocyl, fluacrypyrim, rotenone, or their derivatives. Suitable fungicides are fungicides from the classes of dinitroanilines, allylamines, anilinopyrimidines, antibiotics, aromatic hydrocarbons, benzenesulfonamides, benzimidazoles, benzisothiazoles, benzophenones, benzothi- adiazoles, benzotriazines, benzyl carbamates, carbamates, carboxamides, carboxylic acid dia- mides, chloronitriles cyanoacetamide oximes, cyanoimidazoles, cyclopropanecarboxamides, dicarboximides, dihydrodioxazines, dinitrophenyl crotonates, dithiocarbamates, dithiolanes, ethylphosphonates, ethylaminothiazolecarboxamides, guanidines, hydroxy-(2- amino)pyrimidines, hydroxyanilides, imidazoles, imidazolinones, inorganic substances, isoben- zofuranones, methoxyacrylates, methoxycarbamates, morpholines, N-phenylcarbamates, oxa- zolidinediones, oximinoacetates, oximinoacetamides, peptidylpyrimidine nucleosides, phenyla- cetamides, phenylamides, phenylpyrroles, phenylureas, phosphonates, phosphorothiolates, phthalamic acids, phthalimides, piperazines, piperidines, propionamides, pyridazinones, pyri- dines, pyridinylmethylbenzamides, pyrimidinamines, pyrimidines, pyrimidinonehydrazones, pyr- roloquinolinones, quinazolinones, quinolines, quinones, sulfamides, sulfamoyltriazoles, thia- zolecarboxamides, thiocarbamates, thiophanates, thiophenecarboxamides, toluamides, tri- phenyltin compounds, triazines, triazoles. Suitable herbicides are herbicides from the classes of the acetamides, amides, aryloxyphenoxypropionates, benzamides, benzofuran, benzoic acids, benzothiadiazinones, bipyridylium, carbamates, chloroacetamides, chlorocarboxylic acids, cy- clohexanediones, dinitroanilines, dinitrophenol, diphenyl ether, glycines, imidazolinones, isoxa- zoles, isoxazolidinones, nitriles, N-phenylphthalimides, oxadiazoles, oxazolidinediones, oxya- cetamides, phenoxycarboxylic acids, phenylcarbamates, phenylpyrazoles, phenylpyrazolines, phenylpyridazines, phosphinic acids, phosphoroamidates, phosphorodithioates, phthalamates, pyrazoles, pyridazinones, pyridines, pyridinecarboxylic acids, pyridinecarboxamides, pyrim- idinediones, pyrimidinyl(thio)benzoates, quinolinecarboxylic acids, semicarbazones, sulfonyla- minocarbonyltriazolinones, sulfonylureas, tetrazolinones, thiadiazoles, thiocarbamates, triazines, triazinones, triazoles, triazolinones, tnazolocarboxamides, triazolopyrimidines, triketones, uracils, ureas.
The first pesticide may comprise at least one water-insoluble pesticide. The second pesticide may comprise at least one water-insoluble pesticide. Water-insoluble pesticides may have a solubility in water of up to 10 g/l, preferably up to 1 g/l, and in particular up to 0.5 g/l, at 20 °C. The first pesticide may be soluble in the water-immiscible solvent (e.g. toluene), e.g. in an amount of at least 5 g/l, preferably at least 20 g/l and in particular at least 40 g/l, at 20 °C.
The first pesticide may be solid or liquid at 20 °C. The second pesticide may have a melting point of at least 40 °C, preferably at least 50 °C, and in particular at least 70 °C.
Usually, the suspoemulsion comprises from 0.1 to 35% by weight, preferably from 0.5 to 20% by weight, especially preferably from 1 to 10% by weight of the first pesticide, in each case based on the total weight of the suspoemulsion.
Usually, the suspoemulsion comprises from 0.1 to 35% by weight, preferably from 0.5 to 25% by weight, especially preferably from 2 to 15% by weight of the second pesticide, in each case based on the total weight of the suspoemulsion.
Usually, the suspoemulsion comprises from 0.1 to 35% by weight, preferably from 0.5 to 25% by weight, especially preferably from 3 to 15% by weight of the sum of all pesticides (e.g. the sum of the first pesticide, the second pesticide and the further pesticide), in each case based on the total weight of the suspoemulsion.
The silica particles are hydrophobic modified. In general silica is hydrophilic due to silanol (Si- OH) groups on the surface of the particles. These silanol groups may be chemically reacted with various reagents to render the silica hydrophobic. The silica particles may be based on fumed or precipitated silica, where fumed silica is preferred.
The silica particles are preferably hydrophobic modified by treatment with a silanes, a siloxane, or a mixture thereof, whereas silanes or a mixture thereof are preferred. Examples for silanes or siloxanes are dimethyldichlorosilane, octamethylcyclotetrasiloxane, polydimethylsiloxane, oc- tylsilane, hexamethyldisiloxane, methacrylsilane.
Examples of silanes or siloxanes are 2-acetoxyethyltrichlorosilane, 2-acetoxyethyltriethox- ysilane, 2-acetoxyethyltrimethoxysilane, acetoxymethyltriethoxysilane, acetoxymethyltrimethox- ysilane, 3-acetoxypropyltrimethoxysilane, 3-acetoxypropylmethyldichlorosilane, 4-aminobutyltri- ethoxysilane, m-N-(2-aminoethyl)aminomethylphenethyltrimethoxysilane, p-N-(2-aminoethyl)- aminomethylphenethyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrihydroxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(6-aminohexyl)-3-aminopropyltriethox- ysilane, N-(6-aminohexyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrihydroxysilane, 3- aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-benzoylpropyltrimethoxysilane, benzyldimethylchlorosilane, benzyltrichlorosilane, benzyltriethoxysilane, benzyltrimethoxysilane, [1 ,3-bis(glycidyloxy)propy]ltetramethyldisiloxane, N,N-bis(2-hydroxyethyl)-3-aminopropyltrieth- oxysilane, o-bromophenyltrimethoxysilane, m-bromophenyltrimethoxysilane, p-bromophenyltri- methoxysilane, 3-bromopropyltrichlorosilane, 3-bromopropyltrimethoxysilane, 1 1 -bro- moundecyltrimethoxysilane, 1 1 -bromoundecyltrichlorosilane, tert-butyldiphenylmethoxysilane, tert-butyldiphenylchlorosilane, n-butyltrichlorosilane, tert-butyltrichlorosilane, n-butyltrimethox- ysilane, tert-butyltrimethoxysilane, methyl 3-trichlorosilylpropionate, trihydroxysilylacetic acid sodium salt, 4-chlorobutyldimethylchlorosilane, 2-chloroethyldichloromethylsilane, 2-chloro- ethylmethyldimethoxysilane, 2-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, chloromethyldimethylethoxysilane, chloromethyldimethylisopropoxysilane, chloromethyldime- thylchlorosilane, chloromethylmethyldiethoxysilane, chloromethylmethyldiisopropoxysilane, p- chloromethylphenyltrichlorosilane, p-chloromethylphenyltrimethoxysilane, chloromethyltri- chlorosilane, chloromethyltriethoxysilane, chloromethyltrimethoxysilane, o-chlorophenyltri- chlorosilane, m-chlorophenyltrichlorosilane, p-chlorophenyltrichlorosilane, o-chlorophenyltrieth- oxysilane, m-chlorophenyltriethoxysilane, p-chlorophenyltriethoxysilane, 3-chloropropyl- dimethylchlorosilane, chloropropyldimethylmethoxysilane, 3-chloropropylmethyldichlorosilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrichlorosilane, 3-chloropropyltriethoxy- silane, 3-chloropropyltrimethoxysilane, 2-[4-chlorosulfonylphenyl]ethyltrichlorosilane, 2-[4- chlorosulfonylphenyl]ethyltrimethoxysilane, 3-cyanobutyldimethylchlorosilane,
3-cyanobutylmethyldichlorosilane, 3-cyanobutyltrichlorosilane, 2-cyanoethylmethyl- dichlorosilane, 2-cyanoethyltrichlorosilane, 2-cyanoethyltriethoxysilane, 2-cyanoethyl- trimethoxysilane, 3-cyanopropyldimethylchlorosilane, 3-cyanopropylmethyldichlorosilane, 3- cyanopropylmethyldimethoxysilane, 3-cyanopropyltrichlorosilane, 3-cyanopropyltriethoxysilane, 3-cyanopropyltrimethoxysilane, 1 1 -cyanoundecyltrichlorosilane, 1 1 -cyanoundecyl- trimethoxysilane, cyclohexyldimethylchlorosilane, cyclohexylmethyldichlorosilane, cyclohexyl- methyldimethoxysilane, (cyclohexylmethyl)trichlorosilane, cyclohexyltrichlorosilane, cyclohex- yltrimethoxysilane, cyclopentyltrichlorosilane, cyclopentyltrimethoxysilane, n-decyldi- methylchlorosilane, n-decylmethyldichlorosilane, n-decyltrichlorosilane, n-decyltriethoxysilane, di-n-butyldichlorosilane, di-n-butyldimethoxysilane, (dichloromethyl)methyldichlorosilane, 1 ,3-dichlorotetramethyldisiloxane, Ν,Ν-diethylaminomethyltriethoxysilane, diethyldichlorosilane, diethyldiethoxysilane, 2-(diethylphosphoryl)ethyltriethoxysilane, dimethyldihydroxysilane, di-n- hexyldichlorosilane, diisopropyldichlorosilane, diisopropyldimethoxysilane, 3-N,N-dimethyl- aminopropyltrimethoxysilane, dimethyldichlorosilane, dimethyldiethoxysilane, dimethyl- dimethoxysilane, 1 ,3-dimethyltetramethoxydisiloxane, 3-(2,4-dinitrophenylamino)propyl- triethoxysilane, di-n-octyldichlorosilane, diphenyldichlorosilane, diphenyldiethoxysilane, diphe- nyldimethoxysilane, diphenyldifluorosilane, diphenylmethylchlorosilane, diphenylmethyl- ethoxysilane, diphenyldihydroxysilane, docosylmethyldichlorosilane, docosyltrichlorosilane, do- decyldimethylchlorosilane, dodecylmethyldichlorosilane, dodecylmethyldiethoxysilane, dodecyl- trichlorosilane, dodecyltriethoxysilane, 3-N-ethylaminoisobutylmethyldiethoxysilane, 3-N- ethylaminoisobutyltrimethoxysilane, ethyldimethylchlorosilane, ethylmethyldichlorosilane, m- ethylphenethyltrimethoxysilane, ethyltriacetoxysilane, ethyltrichlorosilane, ethyltriethoxysilane, ethyltrimethoxysilane, 3-glycidyloxypropyldimethylethoxysilane, 3-glycidyloxy- propylmethyldiethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropyltri- ethoxysilane, 3-glycidyloxypropyltrimethoxysilane, n-heptylmethyldichlorosilane, n-heptyltri- chlorosilane, n-hexadecyltrichlorosilane, n-hexadecyltriethoxysilane, n-hexadecyltrimethox- ysilane, n-hexylmethyldichlorosilane, n-hexyltrichlorosilane, n-hexyltriethoxysilane, hydroxyme- thyltriethoxysilane, 3-iodopropyltrimethoxysilane, isobutyldimethylchlorosilane, isobutylmethyl- dimethoxysilane, isobutyltrichlorosilane, isobutyltriethoxysilane, isobutyltrimethoxysilane, 3-isocyanatopropyldimethylchlorosilane, 3-isocyanatopropyltriethoxysilane, 3-isocya- natopropyltrimethoxysilane, isooctyltrichlorosilane, isooctyltrimethoxysilane, isopropyldime- thylchlorosilane, isopropylmethyldichlorosilane, 3-mercaptopropylmethyldimethoxysilane,
3-mercaptopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-(p-methoxyphenyl)propyl- methyldichlorosilane, 3-(p-methoxyphenyl)propyltrichlorosilane, 2-[methoxy(polyethyleneoxy)]- propyltrimethoxysilane, 3-methoxypropyltrimethoxysilane, 3-(N-methylamino)propyl- methyldimethoxysilane, 3-(N-methylamino)propyltrimethoxysilane, methyltribromosilane, methyl- trichlorosilane, methyltriethoxysilane, methyltrimethoxysilane, methyltrifluorosilane, methyltri-n- propoxysilane, tris(methoxyethoxy)methylsilane, n-octadecyldimethylchlorosilane, n-octadecyl- dimethylmethoxysilane, n-octadecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride, n- octadecylmethoxydichlorosilane, n-octadecylmethyldichlorosilane, n-octadecylmethyl- diethoxysilane, n-octadecylmethyldimethoxysilane, n-octadecyltrichlorosilane, n-octadecyl- triethoxysilane, n-octadecyltrimethoxysilane, S-(octanoyl)mercaptopropyltriethoxysilane, n- octyldimethylchlorosilane, n-octyldimethylmethoxysilane, n-octyltrichlorosilane, n-octyltri- ethoxysilane, n-octyltrimethoxysilane, n-pentyltrichlorosilane, n-pentyltriethoxysilane, 2- phenylethyltrichlorosilane, 2-phenylethyltrimethoxysilane, 3-phenoxypropyltrichlorosilane, 3-(N-phenylamino)propyltriethoxysilane, 3-(N-phenylamino)propyltrimethoxysilane, phenylme- thyldichlorosilane, phenylmethyldiethoxysilane, phenylmethyldimethoxysilane, phenyltri- chlorosilane, phenyltriethoxysilane, phenyltrifluorosilane, phenyltrimethoxysilane, n- propyldimethylchlorosilane, n-propylmethyldichlorosilane, n-propyltrichlorosilane, n- propyltriethoxysilane, n-propyltrimethoxysilane, 1 ,3-diethoxy-1 ,1 ,3,3-tetramethyldisiloxane, tet- ra-n-propoxysilane, 3-thiocyanatopropyltriethoxysilane, p-tolyltrichlorosilane, p- tolyltrimethoxysilane, triacontyldimethylchlorosilane, triacontyltrichlorosilane, tri-tert- butoxyhydroxysilane, 3-(2-sulfolanyloxyethoxy)propyltriethoxysilane, 3-(tert-butyloxy- carbonylamino)propyltriethoxysilane, 3-(ethyloxycarbonylamino)propyltriethoxysilane,
3-[(2-hydroxypolyethyleneoxy)carbonylamino]propyltriethoxysilane, 3-(triethoxysilylpropyl)— dihy- dro-3,5-furandione, (3,3,3-trifluoropropyl)trimethoxysilane, 3-(hydroxysulfonyl)- propyltrihydroxysilane, 3-(methylphosphonyl)propyltrihydroxysilane, triisopropylsilane, N-[(5- trimethoxysilyl)-2-aza-1 -oxypentyl]caprolactam, (3-trimethoxysilylpropyl)diethylene- triaminetriacetic acid trisodium salt, N-trimethoxysilylpropyl-N,N,N-trimethylammonium chloride, trimethylchlorosilane, trimethylbromosilane, trimethylethoxysilane, trimethylfluorosilane, trime- thyliodosilane, trimethylmethoxysilane, trimethyl-n-propoxysilane, triphenylchlorosilane, tri- phenylethoxysilane, triphenylhydroxysilane, 3-ureidopropyltriethoxysilane, 3- ureidopropyltrimethoxysilane, 1 ,1 ,1 ,3,3,3-hexamethyldisilazane, 1 ,3-di-n-butyl-1 ,1 ,3,3-tetra- methyldisilazane. It will be appreciated that it is also possible in accordance with the invention to use mixtures of silane compounds.
The silica particles may have a specific surface area (BET; Brunauer, Emmet and Teller) from 20 to 600 m2/g, preferably from 100 to 300 m2/g, and in particular from 150 to 250 m2/g. The specific surface area may be determined according to DIN ISO 9277.
The silica particles may have a carbon content from 0.1 to 12 wt%, preferably from 0.4 to 6.0 wt%, and in particular from 0.6 to 2.5 wt%. The carbon content may be determined according to DIN ISO 3262-20 chapter eight. The primary particle diameter of the silica particles is in general in the range from
0.1 to 1000 nm, preferably from 1 to 100 nm, in particular from 3 to 30 nm. The primary particle diameter is preferably determined via transmission electron microscopy (TEM).
In general, a distinction is made in the case of particles between the primary and the secondary particle diameter. A plurality of smaller particles (having a primary particle
diameter) may agglomerate to form a larger particle (having a secondary particle
diameter). The secondary particle diameter can therefore often also be designated as agglomerate size. The agglomerate particle diameter of the silica particles is in general in the range from 0.1 to 500 μηη, preferably from 0.3 to 10 μηη, in particular from 1 to 20 μηη. The agglomerate particle diameter usually designates the mean particle diameter which is determined according to the volume fraction from the particle size distribution. Said particle size distributions can be meas- ured by light scattering (for example on a Zetasizer Nano S apparatus from Malvern Instruments).
The hydrophobic modified silica particles (also known as "hydrophobic silica") are commercially available from various companies.
The suspoemulsion may comprise 0.1 to 20 wt%, preferably 0.2 to 10 wt% and in particular 0.4 to 5 wt% of the silica particles. The suspoemulsion comprises usually a water-soluble nonionic emulsifier. Water-soluble nonionic emulsifiers may be selected from alkoxylates or mixtures thereof, preferably from alkoxylate block polmyers or compounds such as alcohols, alkylphenols, amines, amides, ar- ylphenols, fatty acids or fatty acid esters which have been alkoxylated with 10 to 50 equivalents, where ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide.
In a form the water-soluble nonionic emulsifier contains C2-C3-polyalkoxylat.es of C10-C22- hydroxy fatty acid triglycerides, C2-C3-polyalkoxylat.es of Cio-C22-fatty acid mono- or diglycer- ides, or mixtures thereof, and where the average degree of alkoxylation (preferably of ethoxyla- tion) of the Cio-C22-hydroxy fatty acid triglycerides or Cio-C22-fatty acid mono- or diglycerides is usually from 10 to 150, preferably from 15 to 100, in particular from 20 to 70 and specifically from 30 to 65.
In another form the water-soluble nonionic emulsifier contains alkoxylate block polymers (e.g. block polymers of the A-B or A-B-A type, where the A-B-A type is preferred) comprising blocks of polyethylene oxide and polypropylene oxide. The alkoxylate block polymers comprise usually at least 30 wt%, preferably at least 40 wt% of polymerized ethylene oxide. The alkoxylate block polymers is preferably a block polymers A-B-A type comprising blocks of polyethylene oxide (block "A") and polypropylene oxide (block "B"). The molecular weight of the alkoxylate block polmyer may be from 1000 to 30000 Da, preferably from 2000 to 15000 Da.
In a preferred form the water-soluble nonionic emulsifier contains polyethoxylates of C12-C22- hydroxyfatty acid triglycerides, polyethoxylates of Ci2-C22-fatty acid mono- or diclycerides, alkoxylate block polymers, or mixtures thereof, and where the average degree of alkoxylation (preferably of ethoxylation) of the Ci2-C22-hydroxyfatty acid triglycerides or Ci2-C22-fatty acid mono- or diclycerides is usually from 10 to 150, preferably from 15 to 100, in particular from 20 to 70 and specifically from 30 to 65.
In a preferred form the water-soluble nonionic emulsifier contains polyethoxylates of C12-C22- hydroxyfatty acid triglycerides, alkoxylate block polymers, or mixtures thereof, and specifically polyethoxylates of castor oil, and where the average degree of of ethoxylation of the C12-C22- hydroxyfatty acid triglycerides (e.g. castor oil) is usually from 10 to 150, preferably from 15 to 100, in particular from 20 to 70 and specifically from 30 to 65. The water-soluble nonionic emulsifier may have each an HLB value of at least 10, preferably of at least 12, and in particular of at least 13.5. The water-soluble nonionic emulsifier may have an HLB value of up to 20, preferably of up to 19, and in particular of up to 18. The HLB value may be determined according to the method of Griffin.
The water-soluble nonionic emulsifier has each usually a solubility in water of at least 5 g/l, preferably at least 20 g/l, and in particular at least 100 g/l, as may determined at 25 °C. The water-soluble nonionic emulsifier is usually present in the aqueous phase of the suspoemulsion. Preferably, the water-soluble nonionic emulsifier is present in dissolved form the aqueous phase of the suspoemulsion.
Usually, the suspoemulsion comprises from 0.1 to 15% by weight, preferably from 0.2 to 8 % by weight, especially preferably from 0.5 to 5% by weight of the sum of all water-soluble nonionic emulsifier, in each case based on the total weight of the suspoemulsion.
The suspoemulsion may comprise further nonionic emulsifiers beside the water-soluble nonionic emulsifier. The further nonionic emulsifiers are usually different from the water-soluble nonionic emulsifiers. The further nonionic emulsifier is usually water-insoluble. The further nonionic emulsifier has usually a solubility in water of below 5 g/l, below 20 g/l, orbelow 100 g/l, as may determined at 25 °C. The further nonionic emulsifier may have an HLB value of below 10, below 12, or below 13.5. Usually, the suspoemulsion comprises from 0.1 to 20% by weight in each case based on the total weight of the suspoemulsion.
In another form the suspoemulsion comprises from 0.1 to 25 by weight of the first pesticide (e.g. solubility in water of up to 10 g/l), from 0.1 to 30 by weight of the second pesticide (e.g. solubility in water of up to 10 g/l), 10 to 50% by weight of the water-immiscible solvent (e.g. aromatic hydrocarbons), 0.1 to 10% by weight of the silica particles, and optionally 0.1 to 10% by weight of the water-soluble nonionic emulsifier, where the sum of these components is from 25 to 75 wt%, in each case based on the total weight of the suspoemulsion.
In another form the suspoemulsion comprises from 0.5 to 15 by weight of the first pesticide (e.g. solubility in water of up to 5 g/l), from 1 to 20 by weight of the second pesticide (e.g. solubility in water of up to 5 g/l), 15 to 45% by weight of the water-immiscible solvent (e.g. aromatic hydrocarbons), 0.2 to 7% by weight of the silica particles, and optionally 0.2 to 7% by weight of the water-soluble nonionic emulsifier, where the sum of these components is from 30 to 70 wt%, in each case based on the total weight of the suspoemulsion. In another form the suspoemulsion comprises from 1 to 10 by weight of the first pesticide (e.g. solubility in water of up to 1 g/l), from 3 to 15 by weight of the second pesticide (e.g. solubility in water of up to 1 g/l), 20 to 40% by weight of the water-immiscible solvent (e.g. aromatic hydrocarbons), 0.4 to 5% by weight of the silica particles, and optionally 0.5 to 5% by weight of the water-soluble nonionic emulsifier, where the sum of these components is from 35 to 65 wt%, in each case based on the total weight of the suspoemulsion.
The suspoemulsion may comprise auxiliaries for agrochemical formulations. Examples for suit- able auxiliaries are surfactants, dispersants, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders. Suitable surfactants are surface-active compounds, such as anionic, cationic, and amphoteric surfactants, polyelectrolytes, and mixtures thereof. Such surfactants can be used as dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol.1 : Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of con- densed 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 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 polyelectrolytes are poly- acids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or polyethyleneamines.
Suitable adjuvants are compounds, which have a negligible or even no pesticidal activity themselves, and which improve the biological performance of the compound I on the target. Examples are surfactants, mineral or vegetable oils, and other auxilaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.
Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates. Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones.
Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin. Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
Suitable colorants (e.g. in red, blue, or green) are pigments of low water solubility and water- soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanofer- rate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).
Suitable tackifiers or binders are polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols, pol- yacrylates, biological or synthetic waxes, and cellulose ethers.
The suspoemulsion may be employed for the purposes of treatment of plant propagation materials, particularly seeds. The compositions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations. Application can be carried out before or during sowing. Meth- ods for applying or treating the suspoemulsion on to plant propagation material, especially seeds include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material. Preferably, the suspoemulsion is applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.
When employed in plant protection, the amounts of active substances 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. In treatment of plant propagation materials such as seeds, e. g. by dusting, coating or drenching seed, amounts of active substance 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. When used in the protection of materials or stored products, the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.
Various types of oils, wetters, adjuvants, fertilizer, or micronutrients, and other pesticides (e.g. herbicides, insecticides, fungicides, growth regulators, safeners) may be added to the suspoe- mulsion as premix or, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the compositions according to the invention in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1.
The user applies the suspoemulsion or the tank mix prepared from the suspoemulsion usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the suspoemulsion is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical compo- sition according to the invention is thus obtained. Usually, 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.
The present inventnion further relates to a method of preparing the suspoemulsion by contact- ing water, the pesticide, the water-immiscible solvent, the water-soluble nonionic emulsifier and the silica particles, and optionally the auxiliaries. The contacting may be achieved in a known manner, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005. Usually, the contacting is achieved by mixing (eg in a high shear mixer) at ambient temperatures (eg 10 to 40 °C).
The present inventnion further relates to a method of controlling phytopathogenic fungi and/or undesired plant growth and/or unde-sired insect or mite attack and/or for regulating the growth of plants, wherein the suspoemulsion is allowed to act on the respective pests, their environ- ment or the crop plants to be protected from the respective pest, on the soil and/or on undesired plants and/or on the crop plants and/or on their environment.
Examples of suitable crop plants are cereals, for example wheat, rye, barley, triticale, oats or rice; beet, for example sugar or fodder beet; pome fruit, stone fruit and soft fruit, for example apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, currants or gooseberries; legumes, for example beans, lentils, peas, lucerne or soybeans; oil crops, for example oilseed rape, mustard, olives, sunflowers, coconut, cacao, castor beans, oil palm, peanuts or soybeans; cucurbits, for example pumpkins/squash, cucumbers or melons; fiber crops, for example cotton, flax, hemp or jute; citrus fruit, for example oranges, lemons, grapefruit or tange- rines; vegetable plants, for example spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, pumpkin/squash or capsicums; plants of the laurel family, for example avocados, cinnamon or camphor; energy crops and industrial feedstock crops, for example maize, soybeans, wheat, oilseed rape, sugar cane or oil palm; maize; tobacco; nuts; coffee; tea; bananas; wine (dessert grapes and grapes for vinification); hops; grass, for example turf; sweetleaf (Stevia rebaudania); rubber plants and forest plants, for example flowers, shrubs, deciduous trees and coniferous trees, and propagation material, for example seeds, and harvested produce of these plants.
The term crop plants also includes those plants which have been modified by breeding, muta- genesis or recombinant methods, including the biotechnological agricultural products which are on the market or in the process of being developed. Genetically modified plants are plants whose genetic material has been modified in a manner which does not occur under natural conditions by hybridizing, mutations or natural recombination (i.e. recombination of the genetic material). Here, one or more genes will, as a rule, be integrated into the genetic material of the plant in order to improve the plant's properties. Such recombinant modifications also comprise posttranslational modifications of proteins, oligo- or polypeptides, for example by means of gly- cosylation or binding polymers such as, for example, prenylated, acetylated or farnesylated residues or PEG residues. The present inventnion further relates to seed containing the suspoemulsion.
The advantages of the suspoemulsion according to the invention are high storage stability, even at varying or low temperatures. In particular, no phase separation is observed during storage. The droplet size in the suspoemulsion is small and/or stable. The particle size in the
suspoemulsion is small and/or stable. Moreover, the suspoemulsion according to the invention permits, if required, the addition of large amounts of fat-soluble or water-soluble adjuvants in the oil phase or the aqueous phase. The good storage stability is retained even when such substances are added. Another advantage is the high rainfastness of the suspoemulsion on the crops; a reduced toxicity; a reduced amount of emulsifiers and/or surfactants; a reduced spray drift, e.g. for ground or aerial spray application.
The examples which follow illustrate the invention without imposing any limitation.
Examples
Silica Particles: Silica particles, hydrophobic modified with hexadecyltrimethoxysilan, specific surface area (BET) about 175 to 205 m2/g, carbon content about 1.0 to about 1 .7 wt%, primary particle diameter about 10-15 nm.
Hydrocarbon A: Aromatic hydrocarbon solvent, initial boiling point about 230 °C, aromatic content at least 99 vol%, flash point 100-1 10 °C.
Auxiliary A: Oleyl alcohol, ethoxylated with 3 units of ehtylene oxide, HLB 6-7, water-insoluble.
Auxiliary B: Ethylene oxide / propylene oxide / ethylene oxide triblock polymer (about 50 wt%
EO), HLB 17-18, water-soluble (>10% at 25 °C), molecular weight about 6000- 7000 Da.
Emulsifier A : Castor oil, ethoxylated with 50-60 units of ethylene oxide, HLB 14-15, melting point 30-35 °C, soluble in cold water.
Wetting Agent: Water-soluable naphthalene sulfonate condensate.
Biocide: Aqueous mix of 2-methyl-4-isothiazolin-3-one and 1 ,2-benzisothiazolin -3-one. Antifoamer: Silicon defoamer.
Example 1 - Preparation
An alpha-Cypermethrin and Chlorfenapyr suspoemulsion A with a composition according to Table 1 was prepared.
Table 1
Component Concentration [wt%]
Alpha-Cypermethrin 3.8
Chlorfenapyr 7.7
Emulsifier A 1 .0
Auxiliary A 1 .5
Hydrocarbon A 34
Wetting Agent 0.4
Propylene Glycol 6.0 Biocide 0.4
Antifoamer 0.2
Silica Particles 1 .5
Auxiliary B 0.2
Xanthan Gum 0.2
Water To 100%
The pesticidal suspoemulsions were produced by the following procedure:
I. Preparation of the oil-in-water emulsion
a) Alpha-Cypermethrin and the Auxiliary A were added to the Hydrocarbon A and stirred until they were dissolved (oil phase).
b) The Silica Particles, the Emulsifier A, propylene glycol, the Biocide and the Antifoamer were mixed with water to obtain uniformity (aqueous phase).
c) The oil phase was poured into the aqueous phase under agitation.
d) Homogenization was achieved my mixing with 2 minutes at 7000 rpm with a Silverson high shear mixer. Droplet size was assessed and shearing continued until the oil droplet size reached a value below 3 μηη.
II. Preparation of the suspension
e) Chlorphenapyr, the Wetting Agent, the Stabilizer and the Defoamer were added to water under agitation.
f) The above mixture was then wet milled using a bead mill to particle size around
2 μηη.
III. Preparation of the final suspoemulsion
g) Thickener and the above suspension were added to the above emulsion and mixed until uniformity was obtained.
Example 2 - Preparation (comparative)
The procedure of Example 1 was repeated to generate suspoemulsion B, wherein the Silica Particles were omitted. Example 3 - Stability
The storage stability of the suspoemulsions A and B of Examples 1 and 2 was tested each with a sample at 54 °C for four weeks, with another sample in a daily cycling temperature from - 10 °C to +30 °C for four weeks, with another sample at 21 °C for four weeks and yet with another sample at -10 °C for four weeks.
The suspoemulsion stability was determined by visual observation of the samples. No noticeable phase separation or increase in droplet size occurred for suspoemulsion A, while suspoemulsion B was unstable at storage temperatures of 21 and 54 °C as well as under cycling conditions.
The oil droplet size was measured before and after storage by a Malvern® Mastersizer 2000. No droplet size increase was observed for suspoemulsion A., while suspoemulsion B showed inreased droplet size. Example 4 - Preparation
A Pyraclostrobin and Metconazole suspoemulsion C with a composition according to Table 2 was prepared by the procedure described in example 1.
Table 2
Figure imgf000016_0001
Example 5 - Stability
The storage stability of suspoemulsion C from Example 4 was tested with a sample at 54 °C for two weeks, with another sample in a daily cycling temperature from -10 °C to +10 °C for two weeks, with another sample at 21 °C for two weeks and yet with another sample at -10 °C for two weeks.
The suspoemulsion stability was determined by visual observation of the samples. No noticea- ble phase separation occurred for suspoemulsion C.
The oil droplet size was measured before and after storage by a Malvern® Mastersizer 2000. No droplet size increase was observed for suspoemulsion C.

Claims

Claims
An aqueous suspoemulsion comprising a first pesticide which is dissolved in a water- immiscible solvent, a second pesticide which is suspended in a continuous aqueous phase, and hydrophobic modified silica particles.
The suspoemulsion according to claim 1 , where the suspoemulsion comprises from 0.1 to 10 wt% of the silica particles.
The suspoemulsion according to claim 1 or 2, where the silica particles have a specific surface area from 100 to 300 m2/g.
The suspoemulsion according to claims 1 to 3, where the silica particles have a primary particle diameter of about 1 to 50 nm.
The suspoemulsion according to claims 1 to 4, where the silica particles are hydrophobic modified by treatment with a silanes, a siloxane, or a mixture thereof.
The suspoemulsion according to claims 1 to 5, where the solvent is a hydrocarbon solvent, benzyl acetate, a vegetable oil, a fatty acid ester, a methyl- or ethyl esters of vegetable oils, or a mixture thereof.
The suspoemulsion according to claims 1 to 6, where the solvent is an aromatic hydrocarbon.
8. The suspoemulsion according to claims 1 to 7 comprising 30 to 75 wt% of water.
9. The suspoemulsion according to claims 1 to 8, where the suspoemulsion comprises from 15 to 55 wt% of the water-immiscible solvent.
10. The suspoemulsion according to claims 1 to 9, comprising a water-soluble nonionic emulsifier
1 1 . The suspoemulsion according to claims 1 to 10, where the water-soluble nonionic emulsifier has a solubility in water of at least 5 g/l at 25 °C.
12. The suspoemulsion according to claims 1 to 1 1 , where the water-soluble nonionic emulsifier has an HLB value of at least 10.
13. The suspoemulsion according to claims 1 to 12, where the water-soluble nonionic emulsifier comprises C2-C3-polyalkoxylates of Cio-C22-hydroxy fatty acid triglycerides, C2-C3- polyalkoxylates of Cio-C22-fatty acid mono- or diglycerides, alkoxylate block polymers, or mixtures thereof, and where the average degree of alkoxylation of the Cio-C22-hydroxy fatty acid triglycerides or Cio-C22-fatty acid mono- or diglycerides is from 10 to 150. A method of preparing the suspoemulsion according to any of claims 1 to 13, by contacting water, the first pesticide, the second pesticide, the water-immiscible solvent, the silica particles, and optionally the water-soluble nonionic emulsifier.
A method of controlling phytopathogenic fungi and/or undesired plant growth and/or undesired insect or mite attack and/or for regulating the growth of plants, wherein the suspoemulsion as defined in any of claims 1 to 13 is allowed to act on the respective pests, their environment or the crop plants to be protected from the respective pest, on the soil and/or on undesired plants and/or on the crop plants and/or on their environment.
PCT/EP2015/066608 2014-07-31 2015-07-21 Agrochemical suspoemulsion comprising hydrophobic modified silica particles WO2016016042A1 (en)

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