WO2012028583A1 - Formulations contenant de la deltaméthrine - Google Patents

Formulations contenant de la deltaméthrine Download PDF

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Publication number
WO2012028583A1
WO2012028583A1 PCT/EP2011/064826 EP2011064826W WO2012028583A1 WO 2012028583 A1 WO2012028583 A1 WO 2012028583A1 EP 2011064826 W EP2011064826 W EP 2011064826W WO 2012028583 A1 WO2012028583 A1 WO 2012028583A1
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spp
microcapsules
deltamethrin
formulation
composition according
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PCT/EP2011/064826
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German (de)
English (en)
Inventor
Karl-Josef Haack
Heike Hungenberg
Andreas Stork
Elias Tapia Ramos
Kai Wirtz
Manuel Guillaumont
Ralf Hambrock
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Bayer Cropscience Ag
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Publication of WO2012028583A1 publication Critical patent/WO2012028583A1/fr

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof

Definitions

  • Deltamethrin is a synthetic pyrethroid used for pest control for decades.
  • Typical commercially available products are formulations as emulsifiable concentrate (EC) with a deltamethrin concentration of 10 to 180 g / L, as an aqueous emulsion (EW) with a deltamethrin concentration of 10 to 50 g / L, aqueous suspension concentrates (SC) with a Deltamethrin concentration of 10 to 250 g / L, suspensions in oil (OD) with a deltamethrin concentration of 7.5 to 40 g / L or water-dispersible granules (WG) with a deltamethrin concentration of, for example, 25 percent by mass.
  • EW aqueous emulsion
  • SC aqueous suspension concentrates
  • WG water-dispersible granules
  • the aforementioned products are usually diluted in water for application to plants, livestock or object surfaces, and the resulting emulsions or dispersions are then sprayed, for example, or the respective objects are immersed in or coated with the emulsions or dispersions.
  • aqueous emulsions resulting from formulations of the EC or EW type after dilution with water show an excellent immediate effect after application, i. Onset of action within a few minutes or hours, while corresponding aqueous suspensions have a slower onset of action.
  • EW formulations for pyrethroids are described in the prior art.
  • WO-A-1990/009103 discloses the combination of an ether phosphate and a film-forming component for stabilizing a pyrethroids-containing emulsion in water.
  • EP-A-1339281 discloses in detail formulations of EW formulations for deltamethrin.
  • Formulations in which a pyrethroid is present as a microencapsulated suspension (CS) are also already known from the prior art, ie CS formulations are described in WO-A-1997/044125, WO-A-2000/013503 and WO-A -2000 / 013504 generally claimed with pyrethroids as an agrochemical active ingredient, but not demonstrated for deltamethrin as an example.
  • CS microencapsulated suspension
  • deltamethrin-containing microcapsules is therefore generally in that one emulsifies a solution of a water-immiscible solvent containing the pyrethroid and di- or polyisocyanates in water and then (optionally with the addition of a di - or polyamine) by a polymerization reaction at the phase interface with a polyurea coating.
  • a water-immiscible solvent containing the pyrethroid and di- or polyisocyanates in water and then (optionally with the addition of a di - or polyamine) by a polymerization reaction at the phase interface with a polyurea coating.
  • WO-A-2009/000545 provides a summary of how the rate of release of drugs from formulations containing drug in microcapsules and a solvent (but not the drug itself) in an aqueous emulsion surrounding the microcapsules can be modulated.
  • WO-A-2009/000545 also mentions deltamethrin as a possible active ingredient in the microcapsules.
  • Formulations in which the agrochemical active ingredient is present exclusively as an emulsion or exclusively as a microencapsulated suspension are mixtures of EW and CS formulations, so-called ZW formulations (according to the nomenclature in the Catalog of Pesticide Formulation Types and International Coding System, Technical Monograph no. 2, 5th Edition, March 2002, CropLife International, Brussels), known in principle.
  • ZW formulations of pyrethroids are disclosed, for example, in EP-A-238184, although not exemplified for deltamethrin.
  • WO-A-1997/006688 discloses ZW formulations for transfluthrin.
  • WO-A-1997/006688 does not disclose which effect such a ZW formulation has on its stability, the acute (oral) mammalian toxicity or the knock-down effect, ie the lethal effect against harmful organisms within a few hours, and how they can be optimized. From the fact that ZW formulations exist for transfluthrin, one skilled in the art can not conclude that a ZW formulation of deltamethrin even has superior properties over corresponding EC, EW or CS formulations of deltamethrin.
  • WO-A-2009/000545 also describes pyrethroids such as deltamethrin-containing mixtures of CS formulations with EW formulations, but the EW formulation portion contains no agrochemical active ingredient. Such mixtures may be referred to as "pseudo-ZW formulations" to distinguish them from the actual ZW formulations. To distinguish formulations containing agrochemical active substance in both EW and CS.
  • the procedure is generally to first prepare separately a CS and an EW formulation and then mix the CS formulation with the EW formulation and optionally diluted with water or other additives to the desired target concentration ,
  • a modified ZW formulation by mixing a CS formulation with an EC formulation and optionally diluting to the desired target concentration with water or other additives. It is also conceivable that you submit water or other additives and then mixes the CS formulation and a EC or EW formulation.
  • CS formulations are microencapsulated suspensions in water
  • EC formulations are water-emulsifiable concentrates (ie containing water at most in traces, ie ⁇ 1% by weight) and in EW formulations aqueous emulsions in which the aqueous phase is the continuous phase. It should be noted in these preparation paths that, during the mixing processes, the energy input must be controlled, for example by stirring or by mixing, in such a way that the microcapsules are not destroyed.
  • an (exclusive) CS formulation has a generally slower onset of action than the EW formulation and, in the special case in which the release of the active ingredient from the capsules is very easy, shows a maximum equally rapid onset of action as an EW formulation
  • ZW formulation is intended to include the mixed formulation of microcapsules (eg from a CS formulation) and an aqueous emulsion in which the aqueous phase is the continuous phase (EW formulation), both the microcapsules and the aqueous Emulsion (EW formulation) containing deltamethrin. Not included, however, are the so-called pseudo-ZW formulations in which the aqueous emulsion contains no active ingredient.
  • mixed formulation of microcapsules and an aqueous emulsion is intended, on the one hand, to mean a formulation in which the microcapsules are suspended in the continuous aqueous phase of the emulsion.
  • the term mixed formulation of microcapsules (eg from the CS formulation) and an aqueous emulsion should also include the combination formulation of the microcapsules (eg in the form of a CS formulation) and the aqueous emulsion (so-called "kit of parts") in which the microcapsules and the aqueous emulsion (eg EW formulation) are present side by side in a combination preparation intended for the preparation of a ZW formulation
  • the compositions according to the invention are mixed formulations within the meaning of this definition.
  • the object of the present invention is to provide ZW formulations for deltamethrin, which in comparison to the EC, EW or CS formulation underlying the ZW formulation and also in comparison with established deltamethrin commercial products (such as Decis®) have improved properties in terms of stability, pest control and / or acute oral toxicity in mammals.
  • deltamethrin should fulfill the following tasks: They should contain at least 10 g / l deltamethrin and should be stable, ie their physico-chemical properties should be maintained both at a storage temperature of 54 ° C for 8 weeks and at a multiple temperature change storage of -15 ° C / + 30 ° C / -. 15 ° C for one week and for storage at 24 ° C, 10 ° C, 5 ° C, 0 ° C, -5 ° C and -10 ° C for several weeks only slightly change.
  • the invention relates to a composition
  • a composition comprising a) an aqueous emulsion comprising a continuous aqueous phase and a disperse organic phase, wherein the organic phase contains at least one organic solvent and deltamethrin and wherein the concentration of deltamethrin at least 2 g / L, based on the volume of aqueous emulsion, and b) microcapsules, the microcapsules consisting of a capsule shell and a capsule filling, wherein the capsule shell of polyurea and / or polyurethane is constructed and obtained by reaction of an isocyanate with one or more isocyanate-reactive compound, and wherein the capsule filling contains deltamethrin and at least one organic solvent, wherein the concentration of deltamethrin in the microcapsules is at least 5 g / kg, based on the mass of the microcapsules.
  • the microcapsules b) consist of a capsule shell and a capsule filling, wherein the capsule shell is made of polyurea and / or polyurethane and is obtained by reaction of an isocyanate with one or more isocyanate-reactive compound, and wherein the capsule filling contains deltamethrin and an organic solvent from the group of aromatic hydrocarbons, wherein the concentration of deltamethrin in the microcapsules above 12 g per 100 g of solvent, preferably above 13.5 g per 100 g of solvent and most preferably between 15 and 25 g per 100 g of solvent.
  • microcapsules c) are a preferred embodiment of the microcapsules b).
  • the invention further relates to an aqueous suspension of the microcapsules c) (so-called CS formulation), which consist of a capsule shell and a capsule filling, wherein the capsule shell of polyurea and / or polyurethane is constructed and by reaction of an isocyanate with one or more isocyanate-reactive Compound, and wherein the capsule filling contains deltamethrin and an organic solvent from the group of aromatic hydrocarbons, wherein the concentration of deltamethrin in the microcapsules above 12 g per 100 g of solvent, preferably above 13.5 g per 100 g of solvent and more particularly preferably between 15 and 25 g per 100 g of solvent.
  • CS formulation aqueous suspension of the microcapsules c)
  • the deltamethrin concentration is well above the thermodynamic solubility of the deltamethrin in the aromatic hydrocarbons (e.g., at 20 ° C). From comparable supersaturated solutions of the same temperature (e.g., 20 ° C) in which aromatic hydrocarbons constitute the continuous phase, deltamethrin crystallizes within a few minutes. Apparently, at a given temperature, it is possible to keep deltamethrin in solution in significantly higher concentrations in the encapsulated droplets of aromatic hydrocarbons than in the equal but unencapsulated volume of aromatic hydrocarbons. This means that more concentrated solutions of deltamethrin can be provided and has z. B. the advantage that for a given deltamethrin application rate less solvent must be applied.
  • the microcapsules c) contained in the aqueous suspension are a preferred embodiment of the microcapsules b) and are preferably used in the composition according to the invention (containing the aqueous emulsion and microcapsules).
  • the aqueous suspension of the microcapsules c) is preferably used for the production of the composition according to the invention (containing the aqueous emulsion and microcapsules), but can also be used as the sole formulation-likewise preferred.
  • the determination of the concentration of deltemethrin in the microcapsules b) and the microcapsules c) is preferably carried out as explained in the examples.
  • the aqueous emulsion a) and the microcapsules b) are preferably mixed and the microcapsules b) are suspended in the aqueous phase of the aqueous emulsion a).
  • the microcapsules c) are preferably used as microcapsules b).
  • the microcapsules are preferably present in the aqueous carrier medium present in the CS formulation (generally consisting of water and optionally adjuncts).
  • the invention thus also relates to a composition ("kit of parts") containing at least two containers, wherein
  • AI a first container containing the aqueous emulsion a), and Bl) a second container containing the microcapsules b), wherein the microcapsules b) are present as granules or are preferably suspended in an aqueous carrier medium.
  • composition according to the invention may also contain other auxiliaries, such as, for example, pH adjusters, biocides, defoamers, antifreeze agents, spreading agents, rainproofing agents, retention promoters, penetration promoters and the like.
  • auxiliaries such as, for example, pH adjusters, biocides, defoamers, antifreeze agents, spreading agents, rainproofing agents, retention promoters, penetration promoters and the like.
  • the deltamethrin-containing aqueous emulsion mentioned under a) contains, in addition to water, at least one organic solvent and deltmethrin, preferably one or more emulsifiers. If necessary, additional aids such as biocides, defoamers, antifreeze, spreading agents, rainfastness improvers, retention promoters, penetration promoters, etc. are also available.
  • additional aids such as biocides, defoamers, antifreeze, spreading agents, rainfastness improvers, retention promoters, penetration promoters, etc. are also available.
  • the solvents mentioned are from the group of aromatic hydrocarbons, carboxylic acid esters, dicarboxylic acid esters, ethers, carboxylic acid amides, dicarboxylic acid diamides, dicarboxylic acid ester amides, glycols, ketones, mineral oils and vegetable oils.
  • Preferred solvents are selected from the group of aromatic hydrocarbons, carboxylic acid esters, dicarboxylic acid esters, aromatic ethers, ketones, mineral oils and vegetable oils, most preferably from the group of aromatic hydrocarbons
  • Solvesso 100 (Solvesso 100 is a mixture of aromatic C8-C10 hydrocarbons)
  • Solvesso 150 Solvesso 150 is a mixture of aromatic C10-C13 hydrocarbons
  • Solvesso 150 ND Solvesso 150 ND is a mixture of aromatic C10-C13 hydrocarbons that are preferred Depleted of naphthalene
  • Solvesso 200 Solvesso 200 is a mixture of C10-C14 aromatic hydrocarbons
  • Solvesso 200 ND (Solvesso 200 ND is a mixture of C10-C14 aromatic hydrocarbons preferentially depleted in naphthalene)
  • BVA XK3 (BVA XK3 is a mixture of diisopropylbipheny
  • the emulsifiers mentioned for component a) are selected from the group of nonionic or ionic emulsifiers optionally with the addition of film-forming polymers.
  • exemplary of emulsifiers are copolymers of ethylene oxide and propylene oxide, ethers and / or esters of copolymers of ethylene oxide and propylene oxide, ethoxylated tristyrylphenols, ethoxylated tributylphenols, ethoxylated tri (methylstyryl)] phenols, ethoxylated fatty acid esters, ethoxylated fatty acids, ethoxylated alcohols, ethoxylated fats, propoxylated and ethoxylated amines , Alkyl sulfates and their salts, alkyl phenyl sulfates and their salts, alkyl phosphates and their salts, alkylphenyl phosphates and their salts,
  • film-forming polymers are polyvinyl acetate, polyvinyl pyrrolidone, polyvinyl ethers, polyacrylates, polymethacrylates and their copolymers.
  • Preferred emulsifiers are ethoxylated tristyrylphenols, ethoxylated tributylphenols, ethoxylated tri (methylstyryl)] phenols, ethoxylated fatty acid esters, ethoxylated fatty acids, ethoxylated fatty alcohols, (optionally alkylated) copolymers of propylene oxide and ethylene oxide, ethoxylated fats, alkyl sulfates and their salts, alkylphenyl sulfates and their salts, Alkyl phosphates and their salts, alkylphenyl phosphates and their salts, sulfated or phosphated ethoxylated tristyrylphenols and their salts
  • emulsifiers are ethoxylated tristyrylphenols, ethoxylated tributylphenols, ethoxylated tri (methylstyryl)] phenols, sulfated or phosphated ethoxylated fatty acid alcohols and salts thereof, optionally with addition of polyvinylpyrrolidone as the film-forming component.
  • the size of the droplets of the dispersed organic phase of the aqueous emulsion a) is determined by laser diffraction [method according to CIPAC MT 187 described in CIPAC Handbook Volume K, Analysis of Technical and Formulated Pesticides, W. Dobrat, and A. Martijn, eds. (2003 ), ISBN 0 902951 15 7, page 153 ff .; Measuring device: Malvern Mastersizer S with dispersion unit QS, measuring medium water, 2000 measuring operations] and is typically between 0.2 ⁇ m and 20 ⁇ m.
  • the capsule filling of the microcapsules mentioned under b), which are preferably suspended in the aqueous phase of the aqueous emulsion a), contains a solution of deltamethrin in an organic solvent and optionally adjuvants such as dispersants, biocides, defoamers, spreading agents, rainfastness improvers, retention promoters, Penetration promoter etc.
  • solvents contained in the capsule filling are those from the group of aromatic hydrocarbons, carboxylic acid esters, dicarboxylic acid esters, ethers, carboxylic acid amides, dicarboxylic acid diamides, glycols, ketones, mineral oils and vegetable oils, preferably from the group of aromatic hydrocarbons, carboxylic acid esters, dicarboxylic acid esters, aromatic Ethers, carboxylic acid amides, ketones, mineral oils and vegetable oils, particularly preferably from the group of aromatic hydrocarbons [eg Solvesso 100, Solvesso 150, Solvesso 200, Solvesso 200 ND, BVA XK3], carboxylic acid amides [e.g.
  • Octanoic acid or decanoic acid dimethylamide and mixtures thereof] acetophenone, cyclohexanone, benzoic acid esters, ethylhexyl lactate, phthalic acid esters, fatty acid esters, phenetole and very particularly preferably from the group Solvesso 100, Solvesso 150, Solvesso 150 ND, Solvesso 200, Solvesso 200 ND, phenetole, octanoic acid dimethylamide, Decanklaklad, cyclohexanone and rapeseed methyl ester.
  • the capsule filling consists of a solution of deltamethrin in an organic solvent and one or more of said auxiliaries.
  • Examples of substances for constructing the capsule shells of the microcapsules mentioned under b) and c) are isomer mixtures of toluene diisocyanate, isomeric mixtures of methylenediphenyl diisocyanate, isomeric mixtures of methylenediphenyl polyisocyanate, hexamethylene diisocyanate, dimer or trimer of hexamethylene diisocyanate, 2H-l, 3,5-Oxadiazine-2,4,6- (3H, 5H) -trione-3,5-bis- (6-isocyanato-hex-1-yl), the 4,4'-methylenebis (cyclohexyisocyanate), the Isophorone diisocyanate, the naphthalene diisocyanate and the mixtures of the aforementioned compounds.
  • Isomer mixtures of toluene diisocyanate, isophorone diisocyanate and mixtures of methylene diphenyl diisocyanate and methylene diphenyl polyisocyanate are particularly preferred. Very particular preference is given to isophorone diisocyanate and mixtures of methylene diphenyl diisocyanate and methylene diphenyl polyisocyanate with a weight ratio of diisocyanate to polyisocyanate of 1: 1 (di / poly) to 1: 5 (di / poly).
  • water or di- or polyamine or di- or polyhydroxy or aminohydroxyl compounds or mixtures of the abovementioned substance classes are used.
  • examples are ethylenediamine, propylenediamine, butyldiamine, hexamethylenediamine, piperazine, phenylenediamine, isophoronediamine, diethylenetriamine, triethylenetetramine, glycol, ethoxylated glycols, propanediols, ethoxylated propanediols, glycerol, ethoxylated glycerol, diethanolamine, triethanolamine.
  • the compounds are preferably ethylenediamine, diethylenetriamine and diethanolamine. Particularly preferred is diethylenetriamine. At this point it should be noted that in a likewise particularly preferred variant, no amine or polyol component is added.
  • polyurea is formed via in situ hydrolyzed isocyanate.
  • the capsule shell consists entirely of polyurea and / or polyurethane, but may also contain, for example, fillers or other foreign substances. Particularly preferably, the capsule shell consists of 80 to 100 wt .-%, more preferably 90 to 100 wt .-% and most preferably 98 to 100 wt .-% of polyurea and / or polyurethane.
  • dispersants are copolymers of ethylene oxide and propylene oxide, ethers and / or esters of copolymers of ethylene oxide and propylene oxide, ethoxylated tristyrylphenols, ethoxylated tributylphenols, ethoxylated tri (methylstyryl)] phenols, ethoxylated fatty acid esters, ethoxylated fatty acids, ethoxylated alcohols, ethoxylated fats, propoxylated and ethoxylated amines, alkyl sulfates and their salts, alkylphenyl sulfates and their salts, alkyl phosphates and their salts, alkylphenyl phosphates and their salts, sulfated or phosphated ethoxylated tristyrylphenols and their salts,
  • Preferred emulsifiers are ethoxylated tristyrylphenols, ethoxylated tributylphenols, ethoxylated tri (methylstyryl)] phenols, ethoxylated fatty acid esters, ethoxylated fatty acid alcohols, (optionally alkylated) copolymers of propylene oxide and ethylene oxide, ethoxylated fats, alkyl sulfates and their salts, Alkylphenylsulfates and their salts, alkyl phosphates and their salts, alkylphenyl phosphates and their salts, sulfated or phosphated ethoxylated tristyrylphenols and their salts, sulfated or phosphated ethoxylated tributylphenols and their salts, sulfated or phosphated ethoxylated tri (methylstyryl)] phenols and their salts
  • the size of the microcapsules b) and c) is determined by laser diffraction [method according to CIPAC MT 187 described in CIPAC Handbook Volume K, Analysis of Technical and Formulated Pesticides, W. Dobrat and A. Martijn, Eds. (2003), ISBN 0902951 15 7, page 153 ff; Measuring device: Malvern Mastersizer S with dispersion unit QS, measuring medium water, 2000 measuring operations] and is typically between 1 D and 15 ⁇ .
  • compositions according to the invention are generally prepared by first preparing separately the microcapsules b) or a CS formulation of the microcapsules b) and the aqueous emulsion a) (EW formulation) and then the microcapsules or the CS formulation the microcapsules mixed with the EW formulation and optionally diluted with water or other additives to the desired target concentration.
  • EW formulation aqueous emulsion a
  • a CS formulation of the microcapsules b) already containing water is mixed with an EC formulation and optionally diluted with water or other additives to the desired target concentration. It is also conceivable to submit water or other additives and then admix a CS formulation and an EC or EW formulation. If an EC formulation is used, it contains the same solvents and optionally auxiliaries as described above for the aqueous emulsion a). It should be noted in these preparation paths that, during the mixing processes, the energy input must be controlled, for example by stirring or by mixing, in such a way that the microcapsules are not destroyed.
  • the formulations according to the invention are preferably prepared by mixing a CS formulation and an EW formulation, if appropriate with the addition of water or other additives.
  • compositions according to the invention have an improved biological activity compared to the market standard Decis® EC 100.
  • the Decis® Expert EC 100 formulation was used in the examples diluted with water in the spray mixture and was therefore present in the examples as EW formulation without CS formulation content.
  • Examples AI, Bl, B2, Cl, Dl and D2 show that the ZW formulation shows an improved effect compared to the Decis® Expert EC 100 with the same application rate of deltamethrin.
  • the ZW formulations of deltamethrin according to the invention also have an improved biological duration activity in comparison to the components a) and b) on which the ZW formulation is based.
  • Example XI demonstrates that the ZW formulation with the same application rate of deltamethrin of 3.75 g deltamethrin / ha improved compared to the EW and the CS formulations effect (ZW: 40 - 50%, EW: 20%, CS: 0% effect) shows. While the "pure" CS - formulations after 3 days show no effect and apparently still no active ingredient released have the ZW formulations according to the invention clear effect, which are also significantly better than that of the EW formulations.
  • the combination of the CS formulation with the EW formulation in the ZW formulation causes, compared to the exclusive CS formulation, a significantly faster release of the active ingredient from the CS formulation portion after or during the application.
  • Such a finding is already described in principle in Examples 16A and 16B of WO-A-2009/000545 for "pseudo-ZW formulations" in which the EW content contains no active substance.
  • the EW formulation components of the ZW formulations according to the invention contain the agrochemical active ingredient deltamethrin
  • the effect of the ZW formulations according to the invention is 3 days This is true even though in both cases the application rate in g / ha or g / m2 is identical overall, ie the same amount of active substance per area has been applied, and thus, the total amount of deltamethrin in the EW formulation portion of the ZW formulation is lower than in the comparable EW exclusive formulation.
  • the ZW formulations of deltamethrin according to the invention have an improved acute (ie already detectable a few hours after application) biological activity in comparison to the components a) and b) on which the ZW formulation is based, even in the case in which component a) is an EW formulation.
  • component a) is an EW formulation.
  • YI demonstrates that the ZW formulation has an improved effect with respect to the EW and CS formulations at the same dose rate of deltamethrin of 7.5 g deltamethrin / hectare (ZW: 35-55%, EW: 25%, CS : ⁇ 25% effect) shows.
  • ZW 35-55%
  • EW 25%
  • CS CS : ⁇ 25% effect
  • the EW formulation in its acute (ie already detectable a few hours after application) effect.
  • the EW formulation is clearly superior to the CS formulation in terms of acute biological activity, which was to be expected.
  • the result thus shows that the acute effect of the ZW formulations, which is improved in comparison with the EW formulation, can be attributed to the combination according to the invention of the EW formulation and the CS formulation in the ZW formulation.
  • the inventive ZW formulations of deltamethrin thus show an improved effect both in comparison with the comparable exclusive CS formulation and in comparison with the comparable exclusive EW formulation.
  • the prepared ZW formulations but also the prepared CS formulations (ie, the aqueous suspensions of the microcapsules b) or c)) at 24, 10, 5, 0, -5, -10 ° C and at 54 ° C can be stored for weeks, ie stable for a long time (see Experimental Part III, Table 2).
  • the formulations according to the invention may contain, in addition to deltamethrin, further active compounds from the group of insecticides, acaricides, fungicides or herbicides. Suitable insecticides are listed below:
  • acetylcholinesterase (AChE) inhibitors such as carbamates, eg alanycarb, aldicarb, bendocarb, benfuracarb, butocarboxime, butoxycarboxime, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, Methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamates, trimethacarb, XMC and xylylcarb; or
  • AChE acetylcholinesterase
  • Organophosphates e.g. Acephates, azamethiphos, azinphos (-methyl, -ethyl), cadusafos, chloroethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos (-methyl), coumaphos, cyanophos, demeton-S-methyl, di-azinone, dichlorvos / DDVP, dicrotophos, dimethoates, dimethylvinphos , Disulfoton, EPN, Ethion, Ethoprophos, Famphur, Fenamiphos, Fenitrothion, Fenthion, Fosthiazate, Heptenophos, Isofenphos, Isopropyl O- (methoxyaminothio-phosphoryl) salicylate, Isoxathion, Malathion, Mecarbam, Methamidophos, Methidathione, Mevinphos, Monocrotophos, Naled ,
  • Organochlorines e.g. Chlordane and endosulfan (alpha); or
  • Fiproles phenylpyrazoles
  • Ethiprole e.g. Ethiprole
  • Fipronil e.g. Fipronil
  • Pyrafluprole e.g. Pyrafluprole
  • Pyriprole e.g. Ethiprole
  • Sodium channel modulators / voltage dependent sodium channel blockers such as
  • Pyrethroids e.g. Acrinathrin, allethrin (d-cis -trans, d-trans), bifenthrin, bioallethrin, bioallethrin-S-cyclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin (beta), cyhalothrin (gamma, lambda), cypermethrin (alpha, beta , theta, ceta-), cyphenothrin [(IR) trans isomers], dimefluthrin, empenthrin [(EZ) - (IR) isomers], esfenvalerates, etofenprox, fenpropathrin, fenvalerates, flucythrinates, flumethrin, fluvalinates (tau -), Halfenprox, Imiprothrin, Metofluthrin, Permethrin, Ph
  • nicotinergic acetylcholine receptor agonists such as Neonicotinoids, eg acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam; or
  • Allosteric acetylcholine receptor modulators such as spinosyns, e.g. Spinetoram and spinosad.
  • Avermectins / milbemycins e.g. Abamectin, Emamectin benzoate, Lepimectin and Milbemectin.
  • Juvenile hormone analogs e.g. Hydroprene, kinoprene, methoprene; or fenoxycarb; Pyriproxyfen.
  • agents with unknown or nonspecific modes of action such as fumigants, e.g. Methyl bromide and other alkyl halides; or
  • chloropicrin sulfuryl fluoride
  • Borax Tartar emetic.
  • mite growth inhibitors e.g. Clofentezine, diflovidazine, hexythiazox, etoxazole.
  • Microbial disruptors of the insect gut membrane such as Bacillus thuringiensis subspecies israelensis, Bacillus sphaericus, Bacillus thuringiensis subspecies aizawai, Bacillus thuringiensis subspecies kurstaki, Bacillus thuringiensis subspecies tenebrionis, and BT plant proteins, e.g. CrylAb, CrylAc, CrylFa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb, Cry34 / 35Abl.
  • inhibitors of oxidative phosphorylation such as diafenthiuron; or organotin compounds, eg azocyclotine, cyhexatin, fenbutatin oxide; or propargite; Tetradifon.
  • (12) Decoupling of oxidative phosphorylation by interruption of the H proton gradient, such as chlorfenapyr and DNOC.
  • Nicotinergic acetylcholine receptor antagonists such as Bensultap, Cartap (hydrochloride), thiocyclam, and thiosultap (-sodium).
  • inhibitors of chitin biosynthesis, type 0, such as benzoylureas, e.g. Bistrifluron, chlorofluorazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, novilflumuron, teflubenzuron and triflumuron.
  • inhibitors of chitin biosynthesis type 1, such as buprofezin.
  • Diacylhydrazines e.g. Chromafenozide, Halofenozide, Methoxyfenozide and Tebufenozide.
  • Octopaminergic agonists such as amitraz.
  • complex III electron transport inhibitors such as hydramethylnone; acequinocyl; Fluacrypyrim.
  • Complex I electron transport inhibitors for example from the group of the METI acaricides, e.g. Fenazaquin, Fenpyroximate, Pyrimidifen, Pyridaben, Tebufenpyrad, Tolfenpyrad; or
  • (23) inhibitors of acetyl-CoA carboxylase such as tetronic acid derivatives, e.g. Spirodiclofen and spiromesifen; or tetramic acid derivatives, e.g. Spirotetramat.
  • tetronic acid derivatives e.g. Spirodiclofen and spiromesifen
  • tetramic acid derivatives e.g. Spirotetramat.
  • complex IV electron transport inhibitors such as phosphines, eg, aluminum phosphide, calcium phosphide, phosphine, zinc phosphide; or cyanide.
  • Complex II electron transport inhibitors such as cyenopyrafen.
  • ryanodine receptor effectors such as diamides, e.g. Flubendiamide, chlorantraniliprole (Rynaxypyr), cyantraniliprole (Cyazypyr) and 3-bromo-N- ⁇ 2-bromo-4-chloro-6 - [(1-cyclopropylethyl) carbamoyl] phenyl ⁇ -1- (3-chloropyridin-2-yl ) - lH-pyrazole-5-c arb oxamide (b ek from WO2005 / 077934) or methyl 2- [3,5-dibromo-2 - ( ⁇ [3-bromo-l- (3-chloro-pyridine-2-yl) yl) -1-pyrazol-5-yl] carbonyl ⁇ amino) benzoyl] -1,2-dimethylhydrazinecarboxylate (known from WO2007 / 043677).
  • diamides e.
  • drugs with unknown mechanism of action such as azadirachtin, amidoflumet, benzoximate, bifenazate, quinomethionate, cryolites, cyflumetofen, dicofol, fluensulfone (5-chloro-2 - [(3,4,4-trifluorobut-3-en-l-yl) sulfonyl] -l, 3-thiazoles), flufenerim, pyridalyl and pyrifluquinazone; furthermore preparations based on Bacillus firmus (1-1582, BioNeem, Votivo) and the following known active compounds
  • the treatment of the plants and plant parts with the compositions according to the invention is carried out directly or by acting on their environment, habitat or storage space by the usual treatment methods, for example by dipping, (spraying) spraying, spraying, sprinkling, evaporating, atomizing, misting , (Ver) spreading, foaming, brushing, spreading, injecting, pouring (drenchen), drip irrigation and propagating material, especially in seeds, further by dry pickling, wet pickling, slurry pickling, encrusting, single or multi-layer wrapping, etc. It is also possible to dispense the active ingredients according to the ultra-low-volume method or to inject the active ingredient preparation or the active ingredient itself into the soil.
  • the active ingredient is generally applied in a surface concentration of 1 to 500 g / ha, preferably in a concentration of 1 to 250 g / ha, more preferably in a concentration of 2 to 100 g / ha and most preferably in one Concentration of 5 to 50 g / ha.
  • a preferred direct treatment of the plants is foliar application, i. the compositions of the invention are applied to the foliage, wherein the treatment frequency and the application rate can be matched to the infestation pressure of the respective pest.
  • plants and parts of plants can be treated.
  • plants are understood as meaning all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants).
  • Crop plants can be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including the plant varieties which can or can not be protected by plant breeders' rights.
  • Plant parts are to be understood as meaning all aboveground and subterranean parts and organs of the plants, such as shoot, leaf, flower and root, by way of example leaves, needles, stems, stems, flowers, bodies, fruits and seeds as well as roots, tubers and rhizomes.
  • the plant parts also include crops and vegetative and generative propagation material, such as cuttings, tubers, rhizomes, offshoots and seeds.
  • plants and their parts can be treated.
  • wild-type or plant species obtained by conventional biological breeding methods such as crossing or protoplast fusion
  • plant cultivars and their parts are treated.
  • transgenic plants and plant cultivars obtained by genetic engineering if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof are treated.
  • the term "parts” or “parts of plants” or “parts of plants” has been explained above.Propes of the respective commercially available or in use plant varieties are particularly preferably treated according to the invention.PV plants are understood as meaning plants with new properties ("traits”) Both have been bred by conventional breeding, by mutagenesis or by recombinant DNA techniques.
  • the treatment according to the invention may also give rise to superadditive ("synergistic") effects.
  • superadditive for example, reduced application rates and / or extensions of the spectrum of action and / or an increase in the effect of the substances and agents usable in the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering power facilitated harvest, acceleration of ripeness, higher crop yields, higher quality and / or higher nutritional value of the harvested products, higher shelf life and / or machinability of the harvested products, which exceed the actual expected effects.
  • the preferred plants or plant varieties to be treated according to the invention to be treated include all plants which, as a result of the genetic engineering modification, obtained genetic material which gives these plants particularly advantageous valuable properties ("traits").
  • traits are better plant growth, increased tolerance to high or low temperatures, increased tolerance to dryness or to bottoms salt, increased flowering, easier harvesting, acceleration of ripeness, higher crop yields, higher quality and / or higher nutritional value of the harvested products , higher shelf life and / or workability of the harvested products.
  • Further and particularly emphasized examples of such properties are an increased defense of the plants against animal and microbial pests, as against insects, mites, phytopathogenic fungi, bacteria and / or viruses as well as an increased tolerance of the plants against certain herbicidal active substances.
  • transgenic plants include the important crops such as cereals (wheat, rice), corn, soybean, potato, cotton, oilseed rape, beets, sugarcane and fruit plants (with the fruits apples, pears, citrus fruits and grapes), with corn, soybean Potato, cotton and oilseed rape are particularly emphasized.
  • Traits which are particularly emphasized are the increased defense of the plants against insects by toxins which are formed in the plants, in particular those which are produced by the genetic material from Bacillus thuringiensis (for example by the genes CrylA (a), CrylA (b), CrylA (c), CryllA, CrylllA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CrylF and combinations thereof) are produced in the plants (hereinafter "Bt plants”). Traits also highlight the increased resistance of plants to fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins.
  • SAR systemic acquired resistance
  • Traits which are furthermore particularly emphasized are the increased tolerance of the plants to certain herbicidally active compounds, for example imidazolinones, sulfonylureas, glyphosate or phosphinotricin (eg "PAT" gene).
  • the desired intrinsic Traits conferring genes may also be present in combinations with each other in the transgenic plants.
  • “Bt plants” are maize varieties, cotton varieties, soybean varieties and potato varieties which are sold under the trade names YIELD GARD® (eg corn, cotton, soy), KnockOut® (eg corn), Star Link® (eg maize), Bollgard ® (cotton), Nucotn® (cotton) and NewLeaf® (potato).
  • herbicide-tolerant plants are maize varieties, cotton varieties and soybean varieties, which are sold under the trade names Roundup Ready® (tolerance to glyphosate eg corn, cotton, soy), Liberty Link® (tolerance to phosphinotricin, eg rapeseed), IMI® (tolerance to Imidazolinone) and STS® (tolerance to sulfonylureas eg corn).
  • Herbicide-resistant (conventionally grown on herbicide tolerance) plants are also the varieties marketed under the name Clearfield® (eg corn) mentioned. Of course, these statements also apply to future or future marketed plant varieties with these or future developed genetic traits.
  • the forest stock includes trees for the production of wood, pulp, paper and products made from parts of the trees.
  • crops refers to crops used as plants for the production of food, feed, fuel or for technical purposes.
  • crops that can be treated with the compositions of the invention include, for.
  • the following plant species turf, vines, cereals, for example wheat, barley, rye, oats, rice, maize and millet; Beets, for example sugar beets and fodder beets; Fruits, such as pome fruit, stone fruit and soft fruit, such as apples, pears, plums, peaches, almonds, cherries and berries, eg.
  • Particularly suitable target crops are the following plants: cotton, eggplant, turf, pome fruit, stone fruit, berry fruit, corn, wheat, barley, cucumber, tobacco, vines, rice, cereals, pear, beans, soybeans, oilseed rape, tomatoes, peppers, melons , Cabbage, potato and apple.
  • compositions according to the invention are suitable for plant tolerance, favorable warm-blood toxicity and good environmental compatibility for protecting plants and plant organs, for increasing crop yields, improving the quality of the crop and for controlling animal pests, in particular insects, arachnids, helminths, nematodes and molluscs that are found in agriculture, horticulture, livestock, forestry, gardens and recreational facilities, in supplies and materials, and in the hygiene sector.
  • the invention also relates to the compositions according to the invention for use in the method for controlling undesired animal pests, in which the composition according to the invention is preferably applied to the undesired animal pests and / or their habitat.
  • the above mentioned pests include:
  • Pests from the strain Arthropoda, especially from the class Arachnida eg Acarus spp., Aceria sheldoni, Aculops spp., Aculus spp., Amblyomma spp., Amphitetranychus viennensis, Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa , Centruroides spp., Chorioptes spp., Dermanyssus gallinae, Dermatophagoides pteronyssius, Dermatophagoides farinae, Dermacentor spp., Eotetranychus spp., Epitrimerus pyri, Eutetranychus spp., Eriophyes spp., Halotydeus destructor, Hemitarsonemus spp., Hyalomma spp., Ixodes spppp
  • Anoplura eg Damalinia spp., Haematopinus spp., Linognathus spp., Pediculus spp., Ptirus pubis, Trichodectes spp.
  • Attagenus spp. Bruchidius obtectus, Bruchus spp., Cassida spp., Cerotoma trifurcata, Ceutorrhynchus spp., Chaetocnema spp., Cleonus mendicus, Conoderus spp., Cosmopolites spp., Costelytra zealandica, Ctenicera spp., Curculio spp., Cryptorhynchus lapathi , Cylindrocopturus spp., Dermestes spp., Diabrotica spp., Dichocrocis spp., Diloboderus spp., Epilachna spp., Epitrix spp., Faustinus spp., Gibbium psylloides, Hellula and alis, Heteronychus arator, Heteronyx spp., Hylamorpha elegans, Hylot
  • Lucilla spp. Lutzomia spp., Mansonia spp., Musca spp., Nezara spp., Oestrus spp., Oscinella frit, Pegomyia Spp., Phlebotomus spp., Phorbia spp., Phormia spp., Prodiplosis spp., Psila rosae, Rhagoletis spp., Sarcophaga spp., Simulium spp, Stomoxys spp., Tabanus spp., Tannia spp., Tetanops spp., Tipula spp ..
  • Dysaphis spp. Dysmicoccus spp., Empoasca spp., Eriosome spp., Erythroneura spp., Euscelis bilobatus, Ferrisia spp., Geococcus coffeae, Hieroglyphus spp., Homalodisca coagulata, Hyalopterus arundinis, Icerya spp., Idiocerus spp., Idioscopus spp., Laodelphax striatellus, Lecanium spp., Lepidosaphes spp., Lipaphis erysimi, Macrosiphum spp., Mahanarva spp., Melanaphis sacchari, Metcalfiella spp., Metopolophium dirhodum, Monellia costalis, Monelliopsis pecanis, Myzus spp., Nasonovia ribisnigri
  • Hymenoptera From the order of Hymenoptera, for example, Acromyrmex spp., Athalia spp., Atta spp., Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Solenopsis invicta, Tapinoma spp., Vespa spp.
  • Conopomorpha spp. Conotrachelus spp., Copitarsia spp., Cydia spp., Dalaca noctuides, Diaphania spp., Diatraea saccharalis, Earias spp., Ecdytolopha aurantium, Elasmopalpus lignosellus, Eidana saccharina, Ephestia spp., Epinotia spp., Epiphyas postvittana Etiella spp., Eulia spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Feltia spp., Galleria mellonella, Gracillaria spp., Grapholitha spp., Hedylepta spp., Helicoverpa spp., Heliothis spp., Hofmannophila pseudospretella
  • Perileucoptera spp. Phtho rimaea spp., Phyllocnis citrella, Phyllonorycter spp., Pieris spp., Platynota stultana, Plodia interpunctella, Plusia spp., Plutella xylostella, Prays spp., Prodenia spp., Protoparce spp., Pseudaletia spp., Pseudoplusia includens, Pyrausta nubilalis, Rachiplusia nu, Schoenobius spp., Scirpophaga spp., Ontario segetum, Sesamia spp., Sparganothis spp., Spodoptera spp., Stathmopoda spp., Stomopteryx subsecivella, Synanthedon spp., Tecia solanivora, Thermesia gemmat
  • Orthoptera for example, Acheta domesticus, Blatta orientalis, Blattella germanica, Dichroplus spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Melanoplus spp., Periplaneta spp., Pulex irritans, Schistocerca gregaria, Supella longipalpa.
  • Siphonaptera eg Ceratophyllus spp., Ctenocephalides spp., Tunga penetrans, Xenopsylla cheopis.
  • Thysanoptera e.g. Anaphothrips obscurus, Baliothrips biformis, Drepanothris reuteri, Enneothrips hevens, Frankliniella spp., Heliothrips spp., Hercinothrips femoralis, Rhipiphorothrips cruentatus, Scirtothrips spp., Taeniothrips cardamoni, Thrips spp.
  • Anaphothrips obscurus e.g. Anaphothrips obscurus, Baliothrips biformis, Drepanothris reuteri, Enneothrips hevens, Frankliniella spp., Heliothrips spp., Hercinothrips femoralis, Rhipiphorothrips cruentatus, Scirtothrips spp., Taeniothrips cardamoni, Thrips spp.
  • Zygentoma for example, Lepisma saccharina, Thermobia domestica. e.g. Lepisma saccharina, Thermobia domestica.
  • Pests from the strain Mollusca, especially from the bivalve class, e.g. Dreissena spp. From the class Gastropoda, e.g. Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Pomacea spp., Succinea spp.
  • Gastropoda e.g. Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Pomacea spp., Succinea spp.
  • Animal parasites from the strains Plathelminthes and Nematoda, in particular from the class of helminths e.g. Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp., Cooperia spp., Dicrocoelium spp, Dictyocaulus filaria, Diphyllobothrium latum, Dracunculus medinensis , Echinococcus granulosus, Echinococcus multilocularis, Enterobius vermicularis, Faciola spp., Haemonchus spp., Heterakis spp., Hymenolepis nana, Hy
  • Loa Loa Nematodirus spp. , Oesophagostomum spp., Opisthorchis spp., Onchocerca volvulus, Ostertagia spp., Paragonimus spp., Schistosomen spp, Strongyloides fuelleborni, Strongyloides stercoralis, Stronyloides spp., Taenia saginata, Taenia solium, Trichinella spiralis, Trichinella nativa, Trichinella britovi, Trichinella nelsoni Trichinella pseudopsiralis, Trichostrongulus spp., Trichuris trichuria, Wuchereria bancrofti.
  • Plant pests from the strain Nematoda, ie plant parasitic nematodes, in particular Aphelenchoides spp., Bursaphelenchus spp., Ditylenchus spp., Globodera spp., Heterodera spp., Longidorus spp., Meloidogyne spp., Pratylenchus spp., Radopholus similis, Trichodorus spp. , Tylenchulus semipenetrans, Xiphinema spp .. Subphylum: protozoa
  • protozoa such as Eimeria
  • Eimeria protozoa
  • Solvesso 200 ND is a mixture of aromatic C10-C14 hydrocarbons, which is preferably depleted in naphthalene
  • 124.6 g of cyclohexanone are first 38.4 g of phospholane PE 169 (Phospholan PE 169 is an alcohol ethoxylate phosphate ester, CAS No. 216383-01-6, AkzoNobel) and 19.2 g of sapogenate T 30 (sapogenate T 30 is an ethoxylated tributylphenol, CAS No. 9046-09-7, from Clariant ) dissolved with stirring.
  • Luvitec K 90 is a Polyvinylpyrrohdon, CAS No. 9003-39-8, from BASF
  • methylparaben 0.1 g
  • propylparaben 0.19 g
  • Silfoam SRE is a defoamer based on polydimethylsiloxane from Wacker
  • Rhodorsil 416 Rhodorsil 416 is also a defoamer based on polydimethylsiloxane from Rhodia
  • 102.1 g of glycerol as antifreeze Add 394.0 g of water with vigorous stirring with a rotator.
  • the result is an emulsion in water with a droplet size distribution D 90 ⁇ 2 ⁇ and D 50 ⁇ 1.5 ⁇ .
  • the density at 20 ° C is 1.05 kg / L.
  • the size of the emulsion droplets was determined by laser diffraction [method according to CIPAC MT 187 described in CIPAC Handbook Volume K, Analysis of Technical and Formulated Pesticides, W. Dobrat and A. Martijn, eds. (2003), ISBN 0 902951 15 7, page 153 ff .; Measuring instrument: Malvern Mastersizer S with dispersion unit QS, measuring medium water, 2000 measuring operations]. In this way, the following batches of the same formulation were prepared, which may differ in the droplet size distribution:
  • Proxel GXL Proxel GXL is an approx. 20% solution of 1,2-benzisothiazolin-3-one as the sodium salt in aqueous dipropylene glycol instead of the biocides methyl- and propylparaben. Manufacturer for example Arch Chemicals
  • Preventol D7 Preventol D7 is a 1.5% solution of a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one in Ratio 3: 1, manufacturer for example Lanxess) use.
  • deltamethrin EW 075 (batch number 2010-002529), which was tested in the examples below, was obtained according to this protocol, except that 71.4 g (instead of 95.4 g) of deltamethrin and 418.6 g of water (instead of 394.0 g) used.
  • a defined amount of deltamethrin is dissolved in a defined amount of solvent with stirring and heating (50-70 ° C) and treated with a defined amount of isocyanate compound. Furthermore, an aqueous solution of a defined amount of Tanemul PS 1 6 (Tanemul PS 16 is a tristyrylphenol ethoxylate from Tanatex), Mowiol 26-88 (Mowiol 26-88 is a 1% aqueous solution of partially saponified polyvinyl acetate, manufacturer Clariant) and Silfoam SRE (Silfoam SRE is a defoamer based on polydimethylsiloxane from Wacker).
  • Tanemul PS 1 6 Tanemul PS 16 is a tristyrylphenol ethoxylate from Tanatex
  • Mowiol 26-88 Mowiol 26-88 is a 1% aqueous solution of partially saponified polyvinyl acetate, manufacturer Clariant
  • the organic phase is then mixed with vigorous stirring with a rotator system into the aqueous phase and emulsified until the desired droplet size is reached.
  • a rotator system into the aqueous phase and emulsified until the desired droplet size is reached.
  • the defined amount of amine compound or aqueous ammonia solution is added and the mixture with gentle stirring (standard laboratory stirrer, about 200 revolutions / minute) within 60 minutes to 70 ° C heated.
  • Baykanol SL is a condensation product of a 1.5-fold sulfonated ditolyl ether isomer mixture with 0.64 equivalents of formaldehyde and sodium sulfate, supplier Lanxess ) or alternatively with Morwet D 425 (Morwet D 425 is a condensate of naphthalenesulfonate sodium salt and formaldehyde, manufacturer AkzoNobel), an aqueous Kelzan pre-solution (Kelzan pre-solution is a 2% aqueous solution of xanthan gum, which is still about 0.15 % Proxel GXL, 0.08% Preventol D7 and 0.025% ammonia) as well as defined amounts of Proxel GXL (Proxel GXL is an approximately 20% solution of 1,2-benzisothiazolin
  • Preventol D7 is a 1.5% solution of a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazoline -3-on in the ratio 3: 1, manufacturer for example Lanxess).
  • Table 1 summarizes the individual CS formulations as well as the respective average particle size and the calculated wall thickness.
  • the size of the microcapsules suspended in water was determined by laser diffraction [method according to CIPAC MT 187 described in CIPAC Handbook Volume K, Analysis of Technical and Formulated Pesticides, W. Dobrat and A. Martijn, Ed. (2003), ISBN 0 902951 15 7 , Page 153 ff; Measuring device: Malvern Mastersizer S with dispersing unit QS, measuring medium water, 2000 measuring operations] and is typically between 1 D and 15 ⁇ .
  • Table la Detailed formulations of various deltamethrin CS formulations (formulation component b) or aqueous suspension of the microcapsules c))
  • Table lb Detailed formulations of various deltamethrin CS formulations (formulation component b) or aqueous suspension of microcapsules c))
  • the CS formulations listed in Table Ia and Ib are stable for weeks at temperatures between -5 and +54 ° C.
  • Genagen 4166 mixture of octanoic acid and decanoic acid dimethylamide, manufacturer Clariant
  • IPDI isophorone diisocyanate, manufacturer Bayer MaterialScience
  • MDI V20 diphenylmethane-4,4'-diisocyanate (MDI) with isomers and higher functional homologs,
  • deltamethrin in Solvesso 200 ND at 20 ° C is about 11 g deltamethrin / 100 g Solvesso 200 ND, increases with increasing temperature and decreases with decreasing temperature. From supersaturated solutions, deltamethrin also crystallizes acicularly without the addition of seed crystals, i. For example, cooling the approximately 17% solution of deltamethrin in Solvesso 200 ND from 50 ° C. to room temperature called in the course of production of batch 2009-008323 CS 075 causes fine needles to precipitate within several minutes. In this context, it should be mentioned that the melting point of deltamethrin is about 100 ° C and thus the lattice energy is quite high.
  • an aliquot i.e., a first part
  • a very polar solvent mixture e.g., acetonitrile, 2-propanol, and tetrahydrofuran
  • an aliquot (ie a second portion) of the microcapsules suspended in water is treated with n-heptane to leave the capsules intact and to dissolve only unencapsulated deltamethine present in the aqueous suspension (CS formulation) in the n-heptane phase Content of deltamethrin in the n-heptane phase with HPLC. From the thus determined deltamethrin content (total content / content of non-encapsulated deltamethrin present), the content of deltamethrin encapsulated in the microcapsules can be determined simply by calculation.
  • deltamethrin was present only in traces, unencapsulated (ie "1% by weight of the total content), while the total content was the theoretical value in the aqueous suspension, ie aqueous phase + microcapsules , (100 or 75 g / L) corresponds.
  • the proportion of encapsulated deltamethrin is> 99% by weight (about 100% by weight) of the total amount used.
  • the concentration of deltamethrin in the microcapsules is calculated by dividing the amount of encapsulated deltamethrin found by the amount of solvent used (Solvesso 200). The values are given in the last line of Tables Ia and Ib.
  • deltamethrin CS formulation (formulation component b)) and a defined amount of deltamethrin EW formulation (formulation component a)) are combined with water or Mowiol 26-88 (Mowiol 26-88 is a 1% aqueous Solution of partially saponified polyvinyl acetate, manufacturer eg Clariant) and then an aqueous Kelzan preliminary solution (Kelzan preliminary solution is a 2% aqueous solution of xanthan gum, which still contains about 0.15% Proxel GXL, 0.08% Preventol D7 and 0.025% ammonia contains) added. Finally, if appropriate, the desired pH is adjusted with aqueous ammonia.
  • Kelzan 2% aqueous solution of xanthan gum containing about 0. 15% Proxel GXL, 0.08% Preventol D7 and 0.025%
  • IPDI isophorone diisocyanate, manufacturer Bayer MaterialScience
  • MDI V20 diphenylmethane-4,4'-diisocyanate with isomers and higher functional homologs
  • the desired proportion of formulated product is mixed with water to the desired concentration.
  • Barley plants (Hordeum vulgare), which are populated with a mixed population of the large cereal aphid (Sitobion avenae), are sprayed with the application solution in the desired concentration.
  • the effect is determined in%. 100% means that all aphids have been killed; 0% means that no aphids have been killed.
  • the deltamethrin commercial product Decis® Expert EC 100 used as a comparison differs from the deltamethrin ZW formulations according to the invention in that it contains no deltamethrin-containing microcapsules.
  • the lack of water content in the Decis ® Expert EC 100 compared to the EW formulation (which is part of the ZW formulation according to the invention) is compensated by the addition of water during the production of the spray solution.
  • the desired proportion of formulated product is mixed with water to the desired concentration.
  • Maize plants (Zea maidis) are sprayed with the application solution in the desired concentration and, after the coating has dried on, are infested with the armyworm ⁇ Spodoptera frugiperda).
  • the effect is determined in%. 100% means that all caterpillars have been killed; 0% means that no caterpillars have been killed.
  • the desired proportion of formulated product is mixed with water to the desired concentration.
  • Maize plants (Zea maidis) are sprayed with the application solution in the desired concentration and, after the coating has dried on, are infested with the armyworm ⁇ Spodoptera frugiperda).
  • the milling rate is determined in%. 100% means that the plant was protected from frass; 0% means that the plant was not protected from frass.
  • the desired proportion of formulated product is mixed with water to the desired concentration.
  • Cabbage plants (Brassica oleracea) are sprayed with the application solution in the desired concentration and, after the coating has dried, are populated with larvae of the cabbage moth ⁇ Plutella xylostella).
  • the effect is determined in%. 100% means that all caterpillars have been killed; 0% means that no caterpillars have been killed.
  • the desired proportion of formulated product is mixed with water to the desired concentration.
  • Paprika plants Capsicum annuum are sprayed with the application solution in the desired concentration and, after certain time intervals, are populated with larvae of the weevil (Spodoptera exigua).
  • the effect is determined in%. 100% means that all caterpillars have been killed; 0% means that no caterpillars have been killed.
  • Table D1 Spodoptera exigua on paprika
  • the desired proportion of formulated product is mixed with water to the desired concentration.
  • Capsicum plants (Capsicum annuum) are sprayed with the application solution in the desired concentration and irrigated after the coating has dried on with different amounts of water.
  • the effect is determined in%. 100% means that all caterpillars have been killed; 0% means that no caterpillars have been killed.
  • the desired proportion of formulated product is mixed with water to the desired concentration.
  • Maize plants (Zea maidis) are sprayed with the application solution in the desired concentration and, after the coating has dried on, are infested with the armyworm ⁇ Spodoptera frugiperda).
  • the effect is determined in%. 100% means that all caterpillars have been killed; 0% means that no caterpillars have been killed.
  • the desired proportion of formulated product is mixed with water to the desired concentration.
  • Barley plants (Hordeum vulgare), which are populated with a mixed population of the large cereal aphid (Sitobion avenae), are sprayed with the application solution in the desired concentration.
  • the effect is determined in%. 100% means that all aphids have been killed; 0% means that no aphids have been killed.

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  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Environmental Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Toxicology (AREA)
  • Chemical & Material Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Manufacturing Of Micro-Capsules (AREA)

Abstract

L'invention concerne une formulation de deltaméthrine qui contient une émulsion aqueuse et/ou des microcapsules, selon laquelle tant l'émulsion aqueuse que les microcapsules contiennent de la deltaméthrine.
PCT/EP2011/064826 2010-09-03 2011-08-29 Formulations contenant de la deltaméthrine WO2012028583A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US37985110P 2010-09-03 2010-09-03
EP10175209 2010-09-03
EP10175209.5 2010-09-03
US61/379,851 2010-09-03

Publications (1)

Publication Number Publication Date
WO2012028583A1 true WO2012028583A1 (fr) 2012-03-08

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PCT/EP2011/064826 WO2012028583A1 (fr) 2010-09-03 2011-08-29 Formulations contenant de la deltaméthrine

Country Status (2)

Country Link
AR (1) AR082830A1 (fr)
WO (1) WO2012028583A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103070166A (zh) * 2012-12-26 2013-05-01 南通联农农药制剂研究开发有限公司 一种微囊悬浮-水乳剂zw及其制备方法
CN103563892A (zh) * 2013-10-14 2014-02-12 广东中迅农科股份有限公司 一种甲氨基阿维菌素苯甲酸盐的水基化新剂型
CN109337032A (zh) * 2018-09-28 2019-02-15 韶关市合众化工有限公司 一种聚醚醚酮低聚物改性聚氨酯固化剂
WO2021094598A1 (fr) * 2019-11-13 2021-05-20 Jesmond Holding Ag Combinaison de phénothrine encapsulée et de pralléthrine émulsifiée
CN112841184A (zh) * 2021-01-28 2021-05-28 常州大学 一种大黄素甲醚微囊缓释剂及其制备方法

Citations (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0238184A1 (fr) 1986-02-07 1987-09-23 The Wellcome Foundation Limited Compositions pesticides
WO1990009103A1 (fr) 1989-02-17 1990-08-23 Roussel-Uclaf Nouvelles emulsions aqueuses concentrees, leur procede de preparation et leur application dans le domaine pesticide
US5049182A (en) 1989-02-03 1991-09-17 Ici Americas Inc. Single-package agricultural formulations combining immediate and time-delayed delivery
EP0539588A1 (fr) 1990-07-05 1993-05-05 Nippon Soda Co., Ltd. Derive d'amine
US5229122A (en) * 1986-02-07 1993-07-20 Burroughs Wellcome Co. Pesticidal compositions
WO1997006688A1 (fr) 1995-08-16 1997-02-27 Bayer Aktiengesellschaft Composition a action insecticide
WO1997044125A1 (fr) 1996-05-23 1997-11-27 Zeneca Limited Compositions microencapsulees
WO2000013504A1 (fr) 1998-09-05 2000-03-16 Bayer Aktiengesellschaft Formulations de microcapsules
WO2000013503A1 (fr) 1998-09-05 2000-03-16 Bayer Aktiengesellschaft Formulations de microcapsules
EP1339281A1 (fr) 2000-12-01 2003-09-03 Bayer CropScience S.A. Formulation emulsion huile dans l'eau d'insecticides
WO2003092378A1 (fr) * 2002-04-29 2003-11-13 Rothamsted Research Ltd Compositions et procedes pour inhiber ou reduire la resistance d'insectes a des insecticides
WO2005035486A1 (fr) 2003-10-02 2005-04-21 Basf Aktiengesellschaft 2-cyanobenzenesulfonamides destines a lutter contre les animaux nuisibles
WO2005077934A1 (fr) 2004-02-18 2005-08-25 Ishihara Sangyo Kaisha, Ltd. Anthranilamides, procédé pour la production de ceux-ci et agents antiparasitaires contenant ceux-ci
WO2006043635A1 (fr) 2004-10-20 2006-04-27 Kumiai Chemical Industry Co., Ltd. Dérivé de 3-triazolylphénylsulfide et insecticide/acaricide/nématicide incluant ledit dérivé au titre de principe actif
WO2006056433A2 (fr) 2004-11-26 2006-06-01 Basf Aktiengesellschaft Composes de 2-cyano-3-(halo)alcoxy-benzenesulfonamide destines au combat des parasites des animaux
WO2006089633A2 (fr) 2005-02-22 2006-08-31 Bayer Cropscience Ag Cetoenols cycliques substitues par spirocetal
WO2006100288A2 (fr) 2005-03-24 2006-09-28 Basf Aktiengesellschaft Composes a base de 2-cyanobenzenesulfonamide, destines au traitement des semences
WO2006129714A1 (fr) 2005-06-01 2006-12-07 Meiji Seika Kaisha, Ltd. Agent antiparasitaire
WO2007043677A1 (fr) 2005-10-14 2007-04-19 Sumitomo Chemical Company, Limited Dérivé d'hydrazide et son utilisation en tant que pesticide
WO2007057407A2 (fr) 2005-11-21 2007-05-24 Basf Se Procedes insecticides utilisant des derives de 3-amino-1,2-benzisothiazole
WO2007095229A2 (fr) 2006-02-10 2007-08-23 Dow Agrosciences Llc (6-haloalkylpyridin-3-yl)alkyl sulfoximines n-substituees insecticides
WO2007115646A1 (fr) 2006-03-31 2007-10-18 Bayer Cropscience Ag Composés énaminocarbonylés substitués utilisés comme insecticides
WO2007115643A1 (fr) 2006-03-31 2007-10-18 Bayer Cropscience Ag Composés énaminocarbonylés substitués
WO2007115644A1 (fr) 2006-03-31 2007-10-18 Bayer Cropscience Ag Composés énaminocarbonylés substitués
WO2007149134A1 (fr) 2006-06-23 2007-12-27 Dow Agrosciences Llc Procédé pour lutter contre des insectes résistant aux insecticides courants
WO2008067911A1 (fr) 2006-12-04 2008-06-12 Bayer Cropscience Ag Cétoénols spirocycliques substitués par le biphényle
WO2008104503A1 (fr) 2007-03-01 2008-09-04 Basf Se Mélanges actifs pesticides comprenant des composés aminothiazoline
WO2009000545A2 (fr) 2007-06-28 2008-12-31 Endura S.P.A. Méthode de modulation de la vitesse de libération d'ingrédients actifs micro-encapsulés

Patent Citations (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0238184A1 (fr) 1986-02-07 1987-09-23 The Wellcome Foundation Limited Compositions pesticides
US5229122A (en) * 1986-02-07 1993-07-20 Burroughs Wellcome Co. Pesticidal compositions
US5049182A (en) 1989-02-03 1991-09-17 Ici Americas Inc. Single-package agricultural formulations combining immediate and time-delayed delivery
WO1990009103A1 (fr) 1989-02-17 1990-08-23 Roussel-Uclaf Nouvelles emulsions aqueuses concentrees, leur procede de preparation et leur application dans le domaine pesticide
EP0539588A1 (fr) 1990-07-05 1993-05-05 Nippon Soda Co., Ltd. Derive d'amine
WO1997006688A1 (fr) 1995-08-16 1997-02-27 Bayer Aktiengesellschaft Composition a action insecticide
WO1997044125A1 (fr) 1996-05-23 1997-11-27 Zeneca Limited Compositions microencapsulees
WO2000013504A1 (fr) 1998-09-05 2000-03-16 Bayer Aktiengesellschaft Formulations de microcapsules
WO2000013503A1 (fr) 1998-09-05 2000-03-16 Bayer Aktiengesellschaft Formulations de microcapsules
EP1339281A1 (fr) 2000-12-01 2003-09-03 Bayer CropScience S.A. Formulation emulsion huile dans l'eau d'insecticides
WO2003092378A1 (fr) * 2002-04-29 2003-11-13 Rothamsted Research Ltd Compositions et procedes pour inhiber ou reduire la resistance d'insectes a des insecticides
WO2005035486A1 (fr) 2003-10-02 2005-04-21 Basf Aktiengesellschaft 2-cyanobenzenesulfonamides destines a lutter contre les animaux nuisibles
WO2005077934A1 (fr) 2004-02-18 2005-08-25 Ishihara Sangyo Kaisha, Ltd. Anthranilamides, procédé pour la production de ceux-ci et agents antiparasitaires contenant ceux-ci
WO2006043635A1 (fr) 2004-10-20 2006-04-27 Kumiai Chemical Industry Co., Ltd. Dérivé de 3-triazolylphénylsulfide et insecticide/acaricide/nématicide incluant ledit dérivé au titre de principe actif
WO2006056433A2 (fr) 2004-11-26 2006-06-01 Basf Aktiengesellschaft Composes de 2-cyano-3-(halo)alcoxy-benzenesulfonamide destines au combat des parasites des animaux
WO2006089633A2 (fr) 2005-02-22 2006-08-31 Bayer Cropscience Ag Cetoenols cycliques substitues par spirocetal
WO2006100288A2 (fr) 2005-03-24 2006-09-28 Basf Aktiengesellschaft Composes a base de 2-cyanobenzenesulfonamide, destines au traitement des semences
WO2006129714A1 (fr) 2005-06-01 2006-12-07 Meiji Seika Kaisha, Ltd. Agent antiparasitaire
WO2007043677A1 (fr) 2005-10-14 2007-04-19 Sumitomo Chemical Company, Limited Dérivé d'hydrazide et son utilisation en tant que pesticide
WO2007057407A2 (fr) 2005-11-21 2007-05-24 Basf Se Procedes insecticides utilisant des derives de 3-amino-1,2-benzisothiazole
WO2007095229A2 (fr) 2006-02-10 2007-08-23 Dow Agrosciences Llc (6-haloalkylpyridin-3-yl)alkyl sulfoximines n-substituees insecticides
WO2007115646A1 (fr) 2006-03-31 2007-10-18 Bayer Cropscience Ag Composés énaminocarbonylés substitués utilisés comme insecticides
WO2007115643A1 (fr) 2006-03-31 2007-10-18 Bayer Cropscience Ag Composés énaminocarbonylés substitués
WO2007115644A1 (fr) 2006-03-31 2007-10-18 Bayer Cropscience Ag Composés énaminocarbonylés substitués
WO2007149134A1 (fr) 2006-06-23 2007-12-27 Dow Agrosciences Llc Procédé pour lutter contre des insectes résistant aux insecticides courants
WO2008067911A1 (fr) 2006-12-04 2008-06-12 Bayer Cropscience Ag Cétoénols spirocycliques substitués par le biphényle
WO2008104503A1 (fr) 2007-03-01 2008-09-04 Basf Se Mélanges actifs pesticides comprenant des composés aminothiazoline
WO2009000545A2 (fr) 2007-06-28 2008-12-31 Endura S.P.A. Méthode de modulation de la vitesse de libération d'ingrédients actifs micro-encapsulés

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
"CIPAC Handbook", vol. K, 2003, article "Analysis of Technical and Formulated Pesticides", pages: 153 FF
"Nomenklatur in Catalogue of Pesticide Formulation Types and International Coding System, Technical Monograph No. 2", March 2002, CROPLIFE INTERNATIONAL
"The Pesticide Manual", 2006, BRITISH CROP PROTECTION COUNCIL
BJÖRN L. CHRISTENSEN: "Untersuchungen von ''Controlled Release''-Formulierungen und ihr Einfluß auf das Umweltverhalten von Fenamiphos anhand von Laborstudien und Modellrechnungen", DISSERTATION, 1997, pages 29

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103070166A (zh) * 2012-12-26 2013-05-01 南通联农农药制剂研究开发有限公司 一种微囊悬浮-水乳剂zw及其制备方法
CN103070166B (zh) * 2012-12-26 2015-03-04 南通联农农药制剂研究开发有限公司 一种微囊悬浮-水乳剂zw及其制备方法
CN103563892A (zh) * 2013-10-14 2014-02-12 广东中迅农科股份有限公司 一种甲氨基阿维菌素苯甲酸盐的水基化新剂型
CN109337032A (zh) * 2018-09-28 2019-02-15 韶关市合众化工有限公司 一种聚醚醚酮低聚物改性聚氨酯固化剂
WO2021094598A1 (fr) * 2019-11-13 2021-05-20 Jesmond Holding Ag Combinaison de phénothrine encapsulée et de pralléthrine émulsifiée
CN114727605A (zh) * 2019-11-13 2022-07-08 杰斯蒙德控股公司 胶囊化的苯醚菊酯和乳化的右旋丙炔菊酯的混合物
CN114727605B (zh) * 2019-11-13 2023-08-18 杰斯蒙德控股公司 胶囊化的苯醚菊酯和乳化的右旋丙炔菊酯的混合物
CN112841184A (zh) * 2021-01-28 2021-05-28 常州大学 一种大黄素甲醚微囊缓释剂及其制备方法

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