Patent Application
20120009238
The present invention is related to a method for the pesticidal treatment of crops which have a final growth height of at least 140 cm, comprising the treatment with an encapsulated pesticide at a growth height of the crop of up to 120 cm. The invention further relates to a composition comprising an encapsulated pesticide and a composition comprising a mixture of an encapsulated pesticide and a non-encapsulated, additional pesticide. Finally, the invention also relates to a use of an encapsulated pesticide for the pesticidal treatment of crop which has a final growth height of at least 140 cm at a growth height of the crop of less than 120 cm. Combinations of preferred embodiments with other preferred embodiments are within the scope of the present invention.
WO 2008/059053 discloses a method for increasing the dry biomass of a plant by treating a plant with a pesticide, e.g. pyraclostrobin. Suitable plant is corn. The plants are treated in the growing stage BBCH 30 to 70.
WO 2008/155097 discloses a method for improving the growth of a plant comprising applying to a plant microcapsules, which themselves comprise a polymeric shell and a core comprising a dispersed solid active ingredient. A suitable active ingredient are strobilurins and suitable plants are corn or sunflowers.
WO2008/021800 discloses a process for delaying or preventing the crystallization of a material having the tendency to crystallize in the aqueous phase, which comprises making certain capsules of said material. Suitable material are fungicides, such as pyraclostrobin. The capsules comprise urea formaldehyde prepolymers.
The technical information bulletin “Headline® Fungicide Corn” (published by BASF Corporation in 2008) discloses, that the Headline® fungicide (an emulsifiable concentrate of pyraclostrobin) may be applied to corn in the vegetative stages VE to V10 or in VT stage or later. As optimal application timing in corn VT through R2 stages or prior to the onset of disease is disclosed.
Pesticides are often commercially formulated as concentrates, emulsions or suspensions. Despite their various advantages, in some cases their use has some disadvantages: The optimal application timing for some pesticide is at a rather late growth stage, in which the plants are higher than 120 cm. For example, it recommended to apply emulsion concentrates of pyraclostrobin to corn at VT (corresponds to BBCH GS 55) through R2 (corresponds to BBCH GS 71) growth stage for the best yield response. This is only possible by rather expensive aerial application or special stilted tractors, because a ground application by usual tractors would result in damage to the crops after they have grown to a height of about 80 to 120 cm.
Object of the present invention was to develop a method for treating crops with pesticides, which avoids the problems associated with the state of the art. Such a method should be applicable by ground treatment with standard equipment at an earlier growth stage, whilst still delivering a yield benefit equivalent to the optimum timing which is at a later growth stage. Another object was to develop a pesticidal composition, which is useful for said method.
The object was solved by a method for the pesticidal treatment of crops which have a final growth height of at least 140 cm, comprising the treatment with an encapsulated pesticide at a growth height of the crop of up to 120 cm.
The term “final growth height” refers to the average highest growth height of a certain crop. Typically, this growth height is reached at the time of harvest. This final growth height is well known in literature (Carter, Jack F. (Ed.), “Sunflower Science and Technology”. Madison/Wis.: American Society of Agronomy, 1978. (Agronomy; volume 19); Cheers, Gordon. “Botanica: das Abc der Pflanzen: 10.000 Arten in Text und Bild”. Cologne: Könemann 1998; Cramer, Nils. “Raps: Anbau und Verwertung”. Stuttgart: Ulmer, 1990; Sprecher v. Bernegg, Andreas: “Tropische und subtropische Weltwirtschaftspflanzen, ihre Geschichte, Kultur und volkswirtschaftliche Bedeutung. Teil 1 (XV): Stärke-und Zuckerpflanzen” 1929; Zscheischler, Johannes: “Handbuch Mais: Umweltgerechter Anbau, wirtschaftliche Verwertung”. 4. Ed. Frankfurt/M.: DL.). The final growth height is usually determined in the absence of any growth regulators and refers to the growth height under average, natural conditions. In cases where the final growth height depends on local conditions, the final growth height refers to growth height in this local area.
Suitable crops which have a final growth height of at least 140 cm are well known. Typical examples are (final growth height in brackets) corn (200-300 cm), sunflower (up to 500 cm), oilseed rape (up to 200 cm), sugar cane (300-400 cm), sorghum (up to 500 cm) or miscanthus (up to 350 cm). Some crops species might be comprised of varieties, which have a final growth stage of less than 140 cm and of varieties, which have a final growth stage of at least 140 cm. According to the present invention only those varieties fall within the scope of the present invention, which have a final growth height of at least 140 cm.
Preferred crops are corn, sunflower, oilseed rape, sugar cane, sorghum or miscanthus. More preferred are corn, sunflower and oilseed rape, more preferably corn and sunflower, and most preferably corn. In another preferred embodiment, preferred crops are varieties of corn, sunflower, oilseed rape, sugar cane, sorghum or miscanthus, which have a final growth height of at least 140 cm, preferably of at least 160 cm.
The term “crops” is to be understood as including plants which have been modified by breeding, mutagenesis or genetic engineering including but not limiting to agricultural biotech products on the market or in development. Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination. Typically, one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant. Such genetic modifications also include but are not limited to targeted post-transtional modification of protein(s), oligo- or polypeptides e.g. by glycosylation or polymer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties.
Plants that have been modified by breeding, mutagenesis or genetic engineering, e.g. have been rendered tolerant to applications of specific classes of herbicides, such as hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors; acetolactate synthase (ALS) inhibitors, such as sulfonyl ureas (see e.g. U.S. Pat. No. 6,222,100, WO 01/82685, WO 00/26390, WO 97/41218, WO 98/02526, WO 98/02527, WO 04/106529, WO 05/20673, WO 03/14357, WO 03/13225, WO 03/14356, WO 04/16073) or imidazolinones (see e.g. U.S. Pat. No. 6,222,100, WO 01/82685, WO 00/026390, WO 97/41218, WO 98/002526, WO 98/02527, WO 04/106529, WO 05/20673, WO 03/014357, WO 03/13225, WO 03/14356, WO 04/16073); enolpyruvylshikimate-3-phosphate synthese (EPSPS) inhibitors, such as glyphosate (see e.g. WO 92/00377); glutamine synthetase (GS) inhibitors, such as glufosinate (see e.g. EP-A 242 236, EP-A 242 246) or oxynil herbicides (see e.g. U.S. Pat. No. 5,559,024) as a result of conventional methods of breeding or genetic engineering. Several cultivated plants have been rendered tolerant to herbicides by conventional methods of breeding (mutagenesis), e.g. Clearfield® summer rape (Canola, BASF SE, Germany) being tolerant to imidazolinones, e.g. imazamox. Genetic engineering methods have been used to render cultivated plants such as soybean, cotton, corn, beets and rape, tolerant to herbicides such as glyphosate and glufosinate, some of which are commercially available under the trade names RoundupReady® (glyphosate-tolerant, Monsanto, U.S.A.) and LibertyLink® (glufosinatetolerant, Bayer CropScience, Germany).
Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more insecticidal proteins, especially those known from the bacterial genus Bacillus, particularly from Bacillus thuringiensis, such as δ-endotoxins, e.g. CryIA(b), CryIA(c), CryIF, CryIF(a2), CryIIA(b), CryIIIA, CryIIIB(b1) or Cry9c; vegetative insecticidal proteins (VIP), e.g. VIP1, VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, e.g. Photorhabdus spp. or Xenorhabdus spp.; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins; toxins produced by fungi, such Streptomycetes toxins, plant lectins, such as pea or barley lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroid oxidase, ecdysteroid-IDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase; ion channel blockers, such as blockers of sodium or calcium channels; juvenile hormone esterase; diuretic hormone receptors (helicokinin receptors); stilben synthase, bibenzyl synthase, chitinases or glucanases. In the context of the present invention these insecticidal proteins or toxins are to be understood expressly also as pre-toxins, hybrid proteins, truncated or otherwise modified proteins. Hybrid proteins are characterized by a new combination of protein domains, (see, e.g. WO 02/015701). Further examples of such toxins or genetically modified plants capable of synthesizing such toxins are disclosed, e.g., in EP-A 374 753, WO 93/007278, WO 95134556, EP-A 427 529, EP-A 451 878, WO 03/18810 and WO03/52073. The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e.g. in the publications mentioned above. These insecticidal proteins contained in the genetically modified plants impart to the plants producing these proteins tolerance to harmful pests from all taxonomic groups of athropods, especially to beetles (Coeloptera), two-winged insects (Diptera), and moths (Lepidoptera) and to nematodes (Nematoda). Genetically modified plants capable to synthesize one or more insecticidal proteins are, e.g., described in the publications mentioned above, and some of which are commercially available such as YieldGard® (corn cultivars producing the Cry1Ab toxin), YieldGard® Plus (corn cultivars producing Cry1Ab and Cry3Bb1 toxins), Starlink® (corn cultivars producing the Cry9c toxin), Her-culex® RW (corn cultivars producing Cry34Ab1, Cry35Ab1 and the enzyme Phosphinothricin-N-Acetyltransferase [PAT]); NuCOTN® 33B (cotton cultivars producing the Cry1Ac toxin), Bollgard® I (cotton cultivars producing the Cry1Ac toxin), Bollgard® (cotton cultivars producing Cry1Ac and Cry2Ab2 toxins); VIPCOT® (cotton cultivars producing a VIP-toxin); NewLeaf® (potato cultivars producing the Cry3A toxin); BtXtra®, NatureGard®, KnockOut®, BiteGard®, Protecta®, Bt11 (e.g. Agrisure® CB) and Bt176 from Syngenta Seeds SAS, France, (corn cultivars producing the Cry1Ab toxin and PAT enyzme), MIR604 from Syngenta Seeds SAS, France (corn cultivars producing a modified version of the Cry3A toxin, c.f. WO 03/018810), MON 863 from Monsanto Europe S. A., Belgium (corn cultivars producing the Cry3Bb1 toxin), IPC 531 from Monsanto Europe S. A., Belgium (cotton cultivars producing a modified version of the Cry1Ac toxin) and 1507 from Pioneer Overseas Corporation, Belgium (corn cultivars producing the Cry1F toxin and PAT enzyme).
Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the resistance or tolerance of those plants to bacterial, viral or fungal pathogens. Examples of such proteins are the so-called “pathogenesis-related proteins” (PR proteins, see, e.g. EP-A 392 225), plant disease resistance genes (e.g. potato cultivars, which express resistance genes acting against Phytophthora infestans derived from the mexican wild potato Solanum bulbocastanum) or T4-lysozym (e.g. potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Erwinia amylvora). The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e.g. in the publications mentioned above.
Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the productivity (e.g. bio mass production, grain yield, starch content, oil content or protein content), tolerance to drought, salinity or other growth-limiting environmental factors or tolerance to pests and fungal, bacterial or viral pathogens of those plants.
Furthermore, plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve human or animal nutrition, e.g. oil crops that produce healthpromoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e.g. Nexera® rape, DOW Agro Sciences, Canada).
Furthermore, plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve raw material production, e.g. potatoes that produce increased amounts of amylopectin (e.g. Amflora® potato, BASF SE, Germany).
Usually, the treatment with an encapsulated pesticide is done at a growth height of the crop of less than 120 cm, preferably less than 115 cm, more preferably, less than 110 cm, even more preferably, less than 100 cm. Typically, the treatment with an encapsulated pesticide is done at a growth height of the crop of higher than 10 cm, preferably higher than 30 cm, and more preferably higher than 50 cm. The farmer can easily determine the growth height of the crop by measuring the growth height from the ground to the top of the crop by a measuring tape. Typically, at least 70%, preferably at least 80% and more preferably at least 90% of the crop plants on a field, which has to be treated, will show the aforementioned growth height.
The term “growth stage” refers to the growth stages as defined by the BBCH Codes in “Growth stages of mono- and dicotyledonous plants”, 2nd edition 2001, edited by Uwe Meier from the Federal Biological Research Centre for Agriculture and Forestry. The BBCH codes are a well established system for a uniform coding of phonologically similar growth stages of all mono- and dicotyledonous plant species. In some countries related codes are known for specific crops. Such codes may be correlated to the BBCH code as exemplified by Harell et al., Agronomy J., 1998, 90, 235-238. Corn is often classified in vegetative stages [VE (emergence), V1 (first leaf), V2 (second leaf), V3 (third leaf), V(n) (nth leaf), VT (tasseling)] and reproductive stages [R1 (silking), R2 (blister), R3 (milk), R4 (dough), R5 (dent), R6 (physiological maturity)].
In a preferred embodiment the crop is corn, which is treated at its growth stage BBCH 10 to 51; sunflower, which is treated at its growth stage BBCH 10 to BBCH 69; oilseed rape, which is treated at its growth stage BBCH 10 to 69; sorghum, which is treated at its growth stage BBCH 10 to 51; or sugar cane, which is treated at its growth stage BBCH 11 to 49.
More preferred, crop is corn, which is treated at its growth stage BBCH 13 to 39; sunflower, which is treated at its growth stage BBCH 13 to BBCH 57; oilseed rape, which is treated at its growth stage BBCH 13 to 59; sorghum, which is treated at its growth stage BBCH 13 to 39; or sugar cane, which is treated at its growth stage BBCH 29 to 49.
Even more preferred, crop is corn, which is treated at its growth stage BBCH 30 to 39; sunflower, which is treated at its growth stage BBCH 37 to BBCH 55; oilseed rape, which is treated at its growth stage BBCH 30 to 59; sorghum, which is treated at its growth stage BBCH 30 to 39; or sugar cane, which is treated at its growth stage BBCH 31 to 39.
In an preferred embodiment corn is usually treated at its growth stage BBCH 10 (First leaf through coleoptile) to 51 (Beginning of tassle emergence), preferably 13 (Third leaf unfolded) to 39 (9 or more nodes detectable), especially 30 (Beginning of stem elongation) to 39 (9 or more nodes detectable), and most preferably 32 (2 nodes detectable) to 39 (9 or more nodes detectable). In another preferred embodiment, corn is treated at a growth height of up to 120 cm, preferably up to 115 cm, more preferably up to 100 cm.
In an another preferred embodiment sunflower is usually treated at its growth stage BBCH 10 (Cotyledons completely unfolded) to 69 (End of flowering), preferably 13 (Third leaf unfolded) to 59 (Ray florets visible between the bracts), more preferably 37 (7 visibly extended internodes) to 55 (Inflorescence separated from youngest foliage leaf) and especially at 39 (9 or more visibly extended internodes) to 53 (Inflorescence separating from youngest leaves, bracts distinguishable from foliage leaves). In another preferred embodiment, sunflower is treated at a growth stage at a crop height of up to 120 cm, preferably up to 100 cm, more preferably up to 80 cm.
In another preferred embodiment oilseed rape is usually treated at its growth stage BBCH 10 (Cotyledon completely unfolded) to 69 (End of flowering), preferably 13 (Third leaf unfolded) to 59 (First petals visible), more preferably 30 (Start of stem extension) to 59 (first petals visible) and especially at 50 (flower buds present) to 59 (first petals visible). In another preferred embodiment, oilseed rape is treated at a growth stage at a crop height of up to 120 cm, preferably up to 100 cm, more preferably up to 80 cm.
In an another preferred embodiment sugar cane is usually treated at its growth stage BBCH 11 (first leaf unfolded) to 49 (harvestable vegetative plant parts have reached final size), preferably 29 (end of tillering) to 49 (harvestable vegetative plant parts have reached final size), more preferably 31 (beginning of shooting, 1 node detectable) to 39 (end of shooting, stem reached final length) and especially at 31 (beginning of shooting, 1 node detectable) to 37 (shooting, 7 nodes detectable). In another preferred embodiment, sugar cane is treated at a growth stage at a height of up to 120 cm, preferably up to 100 cm, more preferably up to 80 cm.
In an another preferred embodiment sorghum is usually treated at its growth stage BBCH 10 (First leaf through coleoptile) to 51 (Beginning of tassle emergence), preferably 13 (Third leaf unfolded) to 39 (9 or more nodes detectable), especially (Beginning of stem elongation) to 39 (9 or more nodes detectable), and most preferably 35 (5 nodes detectable) to 39 (9 or more nodes detectable). In another preferred embodiment, sorghum is treated at a growth stage at a crop height of up to 120 cm, preferably up to 100 cm, more preferably up to 80 cm.
The term “pesticide” refers to at least one pesticide selected from the group of fungicides, insecticides, nematicides, herbicides, safeners and or growth regulators. Also mixtures of pesticides from two or more of the aforementioned classes may be used. An expert is familiar with such pesticides, which might be found in the Pesticide Manual, 14th Ed. (2006), The British Crop Protection Council, London.
Suitable fungicides are
A) strobilurins
Preferably, the encapsulated pesticide comprises at least one of the aforementioned pesticides. More preferably, the encapsulated pesticide comprises a fungicide, a safeners and/or a growth regulator. Even more preferred, the encapsulated pesticide comprises a fungicide, and/or a growth regulator. Especially preferred, the encapsulated pesticide comprises a fungicide, such as a strobilurin, a triazole or a carboxamide. The encapsulated pesticide comprises most especially preferred pyraclostrobin or a 1-methylpyrazol-4-ylcarboxanilide of the formula I, preferably pyraclostrobin. In case the encapsulated pesticide comprises a growth regulator, the growth regulator is preferably an ethylene biosynthesis inhibitor which blocks the conversion of ACC into ethylene, an inhibitors of the action of ethylene, salicylic acid, azibenzolar-S-methyl, prohexadione-Ca, trinexapac-ethyl, cyclopropene and its derivatives, more preferably salicylic acid, azibenzolar-S-methyl, prohexadione-Ca, trinexapac-ethyl or 1-methylcyclopropene.
In another preferred embodiement, the encapsulated pesticide has a solubility in an aromatic hydrocarbon solvent (preferably in an an aromatic hydrocarbon with a distillation range 232-278° C., e.g. Aromatic® 200 from Exxon) at 20° C. of at least 5 g/l, more preferably at least 50 g/l, even more preferably at least 150 g/l, especially preferred at least 200 g/l and most preferred at least 300 g/l.
In a preferred embodiment, the method according to the invention comprises the treatment with a mixture of an encapsulated pesticide and a non-encapsulated, additional pesticide. The additional pesticide may be selected from the aforementioned pesticides. The non-encapsulated, additional pesticide may be present in a dissolved, suspended and/or emulsified form. Preferably, the non-encapsulated, additional pesticide is present in a dissolved form. The non-encapsulated, additional pesticide may comprise a fungicide, a herbicide, an insecticide or a growth regulator. A suitable fungicide may be a strobilurin, a triazole or a carboxamide, more preferably a triazole. A suitable herbicide may be an amino acid derivative, a cyclohexanedione, an imidazolinone, or dicamba, preferably glyphosate, glufosinate, cycloxydim, an imidazolinone or dicamba. A suitable insecticide may be a pyrethroid or a nicotinic receptor agonists/antagonists compound, more preferably a pyrethroid, especially alpha-cypermethrin. A suitable growth regulator may be chlormequat chloride, mepiquat chloride, salicylic acid, azibenzolar-S-methyl, prohexadione-Ca, trinexapac-ethyl, cyclopropene and its derivatives, more preferably chlormequat chloride, salicylic acid, azibenzolar-S-methyl, prohexadione-Ca, trinexapac-ethyl or 1-methylcyclopropene.
In a more preferred embodiement, the encapsulated pesticide comprises a fungicide and the non-encapsulated, additional pesticide comprises a fungicide, wherein the fungicides might be identical or different. Preferably, the encapsulated pesticide comprises a strobilurin or a carboxamide, and the non-encapsulated, additional pesticide comprises a triazole or a carboxamide. In an especially preferred embodiment, the encapsulated pesticide comprises pyraclostrobin, and the non-encapsulated, additional pesticide comprises epoxiconazol, metconazol, boscalid or a 1-methylpyrazol-4-ylcarboxanilide of the formula I. In another especially preferred embodiment, the encapsulated pesticide comprises a 1-methylpyrazol-4-ylcarboxanilide of the formula I, and the non-encapsulated, additional pesticide comprises epoxiconazol or metconazol. In an especially preferred embodiment, the encapsulated pesticide comprises pyraclostrobin, and the non-encapsulated, additional pesticide comprises epoxiconazol, metconazol, boscalid or fluxapyroxad.
In another more preferred embodiement, the encapsulated pesticide comprises pyraclostrobin and the non-encapsulated, additional pesticide comprises glyphosate, glufosinate, dicamba, imazamox, imazapyr, or imazethapyr.
In yet another more preferred embodiement, the encapsulated pesticide comprises pyraclostrobin and the non-encapsulated, additional pesticide comprises chlormequat chloride, mepiquat chloride, mepiquat pentaborate or prohexadione-Ca.
In yet another more preferred embodiement, the encapsulated pesticide comprises pyraclostrobin and the non-encapsulated, additional pesticide comprises alphacypermethrin or fipronil.
The method of the present invention is particularly suitable for controlling the following plant diseases:
Albugo spp. in sunflowers (e.g. A. tragopogonis) and rape (A. candida); Alternaria spp. rape (A. brassicola or brassicae) and sunflowers (A. helianth), Bipolaris and Drechslera spp. (teleomorph: Cochliobolus spp.), e.g. Southern leaf blight (D. maydis) or Northern leaf blight (B. zeicola) on corn, Aureobasidium zeae (syn. Kabatiella zeae) on corn, Botrytis cinerea (teleomorph: Botryotinia fuckeliana: grey mold) on rape, Cercospora spp. (Cercospora leaf spots) on corn (e.g. Gray leaf spot: C. zeae-maydis), sugar cane, (e.g. C. sojina or C. kikuchii); Cladosporium herbarum on corn; Cochliobolus (anamorph: Helminthosporium of Bipolaris) spp. (leaf spots) on corn (C. carbonum), Colletotrichum (teleomorph: Glomerella ) spp. (anthracnose) on corn (e.g. C. graminicola: Anthracnose stalk rot); Drechslera (syn. Helminthosporium, teleomorph: Pyrenophora) spp. on corn, Epicoccum spp. rape (e.g. E. cruciferarum); Exserohilum (syn. Helminthosporium) spp. on corn (e.g. E. turcicum); Fusarium (teleomorph: Gibberella) spp. (wilt, root or stem rot) on various plants, such as F. moniliforme, F. proliferatum, F. subglutinans, F. verticillioides and F. zeae (Fusarium graminearum) on corn; Gaeumannomyces graminis (take-all) on corn; Helminthosporium spp. (syn. Drechslera, teleomorph: Cochliobolus) on corn; Macrophomina phaseolina on corn; eyespot on corn (Kabatiella zeae); Peronospora spp. (downy mildew) rape (e.g. P. parasitica); Phoma lingam (root and stem rot) on rape and Phoma macdonaldii on sunflowers; Phomopsis spp. on sunflowers; Physoderma maydis (brown spots) on corn; Plasmodiophora brassicae (club root) on rape; Plasmopara spp., P. halstedii on sunflower, Puccinia helianthi in sunflower, Pythium spp. (damping-off) on corn, rape and sunflowers; Rhizoctonia spp. corn, rape; Sclerotinia spp. (stem rot or white mold) on field crops, such as rape and sunflowers (e.g. S. sclerotiorum); Setosphaeria spp. (leaf blight) on corn (e.g. S. turcicum, syn. Helminthosporium turcicum); Sphacelotheca spp. (smut) on corn, (e.g. S. reiliana: head smut); Stenocarpella macrospore on corn; Urocystis spp. e.g. corn (e.g. U. maydis: corn smut) and sugar cane; and Verticillium spp. (wilt) on various plants, such as field crops, e.g. V. dahliae on rape, Puccinia spp. in corn (P. sorghi and P. polysora), sunflower (P. helianthi), sugarcane (P. kuehnii and P. melanocephela). In another embodiment, the present invention is specifically suitable to control Sclerotinia sclerotiorum and Alterneria brassicae in oilseed rape.
The method according to the invention may be used for improving the health of the crop. The term “plant health” is to be understood to denote a condition of the plant and/or its products which is determined by several indicators alone or in combination with each other such as yield (e.g. increased biomass and/or increased content of valuable ingredients), plant vigor (e.g. improved plant growth and/or greener leaves (“greening effect”)), quality (e.g. improved content or composition of certain ingredients), tolerance to abiotic and/or biotic stress and production efficiency (increased harvesting efficiency). The above identified indicators for the health condition of a plant may be interdependent or may result from each other.
The encapsulated pesticide may be formulated in an agrochemical composition. An agrochemical composition comprises a pesticidal effective amount of a pesticide. The term “effective amount” denotes an amount of the pesticide, which is sufficient for controlling harmful pests on cultivated and which does not result in a substantial damage to the treated plants. Such an amount can vary in a broad range and is dependent on various factors, such as the fungal species to be controlled, the treated cultivated plant, the climatic conditions and the specific pesticide used.
The agrochemical compositions may also comprise auxiliaries which are customary in agrochemical compositions. The auxiliaries used depend on the particular application form and active substance, respectively. Examples for suitable auxiliaries are solvents, solid carriers, dispersants or emulsifiers (such as further solubilizers, protective colloids, surfactants and adhesion agents), organic and anorganic thickeners, bactericides, anti-freezing agents or anti-foaming agents.
Suitable solvents are water, organic solvents such as mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, glycols, ketones such as cyclohexanone and gamma-butyrolactone, fatty acid dimethylamides, fatty acids and fatty acid esters and strongly polar solvents, e.g. amines such as Nmethylpyrrolidone.
Suitable surfactants (adjuvants, wtters, tackifiers, dispersants or emulsifiers) are alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, such as ligninsulfonic acid. (Borresperse® types, Borregard, Norway) phenolsulfonic acid, naphthalenesulfonic acid (Morwet® types, Akzo. Nobel, U.S.A.), dibutylnaphthalene-sulfonic acid (Nekal® types, BASF, Germany), and fatty acids, alkylsulfonates, alkylarylsulfonates, alkyl sulfates, laurylether sulfates, fatty alcohol sulfates, and sulfated hexa-, hepta- and octadecanolates, sulfated fatty alcohol glycol ethers, furthermore condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, polyoxy-ethylene octylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether, tristearylphenyl polyglycol ether, alkylaryl polyether alcohols, alcohol and fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquors and proteins, denatured proteins, polysaccharides (e.g. methylcellulose), hydrophobically modified starches, polyvinyl alcohols (Mowiol® types, Clariant, Switzerland), polycarboxylates (Sokolan® types, BASF, Germany), polyalkoxylates, polyvinylamines (Lupasol® types, BASF, Germany), polyvinylpyrrolidone and the copolymers thereof.
Examples for thickeners (i.e. compounds that impart a modified flowability to compositions, i.e. high viscosity under static conditions and low viscosity during agitation) are polysaccharides and organic and anorganic clays such as Xanthan gum (Kelzan®, CP Kelco, U.S.A.), Rhodopol® 23 (Rhodia, France), Veegum® (R. T. Vanderbilt, U.S.A.) or Attaclay® (Engelhard Corp., NJ, USA). Bactericides may be added for preservation and stabilization of the composition. Examples for suitable bactericides are those based on dichlorophene and benzylalcohol hemi formal (Proxel® from ICI or Acticide® RS from Thor Chemie and Kathon® MK from Rohm & Haas) and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones (Acticide® MBS from Thor Chemie). Examples for suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin. Examples for anti-foaming agents are silicone emulsions (such as e.g. Silikon® SRE, Wacker, Germany or Rhodorsil®, Rhodia, France), long chain alcohols, fatty acids, salts of fatty acids, fluoroorganic compounds and mixtures thereof.
Various types of oils, wetters, adjuvants, herbicides, bactericides, other fungicides and/or pesticides may be added to the pesticide or the compositions comprising them, 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. Adjuvants which can be used are in particular polyether modified polysiloxanes such as Break Thru® S 240; fatty alcohol alkoxylates such as Plurafac® LF 120 (BASF) and Lutensol® ON 30 (BASF); EO/PO block polymers, e.g. Pluronic® RPE 2035 and Genapol B alcohol ethoxylates such as Lutensol XP 80®; dioctyl sulfosuccinate sodium such as Leophen RA®, polyvinylalcohols, such as Plurafac® LF 240 (BASF). Especially preferred adjuvants are fatty alcohol alkoxylates and polyether modified polysiloxanes.
The treatment of crop with an encapsulated pesticide may be done by applying said pesticide by ground or aerial application, preferably by ground application. Suitable application devices are a predosage device, a knapsack sprayer, a spray tank or a spray plane. Preferably the treatment is done by ground application, for example by a predosage device, a knapsack sprayer or a spray tank. The ground application may be done by a user walking through the crop field or with a motor vehicle, preferably with a motor vehicle. Such motor vehicles may have standard ground clearance, such as up to 100 cm, preferably up to 85 cm, especially up to 70 cm. Usually, 50 to 500 liters of the ready-to-use spray liquor are applied per hectare of agricultural useful area, preferably 80 to 400 litres. The amounts of pesticides applied are usually, depending on the kind of effect desired, from 0.001 to 3 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.
The method according the invention often helps to avoid areal application of the pesticides. Thus, the method according to the invention is useful for the treatment of crops outside closed buildings (such as greenhouses) and/or outside artificial growth pots (such as growth pots made of plastic, peat pots, seedling trays). Preferably, the crops grow directly in cropping soil of farmland. This means, the crops do not grow inside artificial growth pots.
The term “encapsulated pesticide” refers to any type of capsule, which comprises a core and an encapsulation material, wherein the core comprises at least one pesticide. Preferably, the core comprises at least one pesticide and at least one organic solvent (examples of organic solvents are given below). In an especially preferred embodiement, the core comprises at least one pesticide dissolved in at least one organic sok vent. Typically, at least 80 wt %, preferably at least 90 wt %, of the pesticide in the core is dissolved in the organic solvent(s) at 25° C. The encapsulation material of the encapsulated pesticide comprises preferably a polyurethane or poly(meth)acrylate.
Poly(meth)acrylate is a known encapsulation material, for example from WO 2008/071649, EP 0 457154 or DE 10 2007 055 813. Usually, the poly(meth)acrylate comprises C1-C24 alkyl esters of acrylic and/or methacrylic acid, acrylic acid, methacrylic acid, and/or maleic acid in polymerized form. More preferably, the poly(meth)acrylate comprises methyl methacrylate and methacrylic acid. The poly(meth)acrylate may also comprise in polymerized form one or more difunctional or polyfunctional monomers. The poly(meth)acrylate may further comprise other monomers.
More preferrably, the poly(meth)acrylate polymer is synthesized from
The capsules comprise usually a capsule core of a pesticide and a capsule wall of polymer. The capsule core is composed predominantly—to an extent of more than 95% by weight—of pesticide. Depending on the temperature the capsule core may be either solid or liquid.
The protective colloid is generally incorporated into the capsule wall and is therefore likewise a constituent of the capsule wall. Generally speaking, the surface of the polymer has the protective colloid, more particularly. Thus it is possible for there to be up to 10% by weight, based on the total weight of the microcapsules, of protective colloid.
The average particle size of the capsules (z-average by means of light scattering; preferably a D4,3 average) is 0.5 to 50 μm, preferably 0.5 to 8 μm, more preferably 1 to 5 μm, and especially 1 to 3 μm. In another preferred embodiment, the average particle size D90 of the capsules (determined by means of light scattering is 0.5 to 50 μm, preferably 1 to 15 μm, more preferably 3 to 9 μm, and especially 4.5 to 7.5 μm. The weight ratio of capsule core to capsule wall is generally from 50:50 to 95:5. Preference is given to a core/wall ratio of 70:30 to 93:7.
The poly(meth)acrylate of the capsule wall comprise generally at least 30%, in a preferred form at least 40%, in a particularly preferred form at least 50%, more particularly at least 60%, with very particular preference at least 70%, and also up to 100%, preferably not more than 90%, more particularly not more than 85%, and, with very particular preference, not more than 80%, by weight, of at least one monomer from the group comprising C1-C24 alkyl esters of acrylic and/or methacrylic acid, acrylic acid, methacrylic acid, and maleic acid (monomers I), in copolymerized form, based on the total weight of the monomers.
Furthermore the poly(meth)acrylate of the capsule wall comprises preferably at least 10%, preferably at least 15%, preferentially at least 20%, and also, in general, not more than 70%, preferably not more than 60%, and with particular preference not more than 50%, by weight, of one or more difunctional or polyfunctional monomers (monomers II), in copolymerized form, based on the total weight of the monomers. In another preferred embodiment, the poly(meth)acrylate of the capsule wall comprises preferably at least 10%, preferably at least 15%, and also, in general, not more than 50%, preferably not more than 40% by weight, of one or more polyfunctional monomers (monomers II), in copolymerized form, based on the total weight of the monomers.
Additionally, the poly(meth)acrylate may comprise up to 40%, preferably up to 30%, more particularly up to 20%, by weight, of other monomers III, in copolymerized form. The capsule wall is preferably synthesized only from monomers of groups I and II.
Suitable monomers I are C1-C24 alkyl esters of acrylic and/or methacrylic acid and also the unsaturated C3 and C4 carboxylic acids such as acrylic acid, methacrylic acid, and also maleic acid. Suitable monomers I are isopropyl, isobutyl, sec-butyl, and tert-butyl acrylates and the corresponding methacrylates, and also, with particular preference, methyl, ethyl, n-propyl, and n-butyl acrylates and the corresponding methacrylates. In general the methacrylates and methacrylic acid are preferred.
According to one preferred embodiment the microcapsule walls comprise 25% to 75% by weight of maleic acid, methacrylic acid and/or acrylic acid, more particularly methacrylic acid, based on the total amount of the monomers I, in copolymerized form.
Suitable monomers II are difunctional or polyfunctional monomers. By difunctional or polyfunctional monomers are meant compounds which have at least two nonconjugated ethylenic double bonds. Contemplated primarily are divinyl monomers and polyvinyl monomers. They bring about crosslinking of the capsule wall during the polymerization. In another preferred embodiment, suitable monomers II are polyfunctional monomers.
Suitable divinyl monomers are divinylbenzene and divinylcyclohexane. Preferred divinyl monomers are the diesters of diols with acrylic acid or methacrylic acid, and also the diallyl and divinyl ethers of these diols. Mention may be made, by way of example, of ethanediol diacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, methallylmethacrylamide, allyl acrylate, and allyl methacrylate. Particular preference is given to propanediol, 1,4-butanediol, pentanediol, and hexanediol diacrylates and the corresponding methacrylates.
Preferred polyvinyl monomers are the polyesters of polyols with acrylic acid and/or methacrylic acid, and also the polyallyl and polyvinyl ethers of these polyols, trivinylbenzene and trivinylcyclohexane. Particular preference is given to trimethylolpropane triacrylate and trimethacrylate, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, pentaerythritol triacrylate, and pentaerythritol tetraacrylate, and also their technical mixtures.
Monomers III contemplated are other monomers, different than the mononers I and II, such as vinyl acetate, vinyl propionate, vinylpyridine, and styrene or α-methylstyrene. Particular preference is given to itaconic acid, vinylphosphonic acid, maleic anhydride, 2-hydroxyethyl acrylate and methacrylate, acrylamido-2-methylpropanesulfonic acid, methacrylonitrile, acrylonitrile, methacrylamide, N-vinylpyrrolidone, N-methylolacrylamide, N-methylolmethacrylamide, dimethylaminoethyl methacrylate, and diethylaminoethyl methacrylate.
The preparation process of the microcapsules is what is called an in situ polymerization. The principle of microcapsule formation is based on the preparation of a stable oilin-water emulsion from the monomers, a free-radical initiator, the protective colloid, and the lipophilic substance to be encapsulated. Subsequently the polymerization of the monomers is triggered by heating and is controlled, if appropriate, by further increase in temperature, the resulting polymers forming the capsule wall which encloses the lipophilic substance. This general principle is described, for example, in DE A 101 39 171, expressly incorporated by reference.
Capsules with encapsulation material comprising a polyurethane are well known and can be prepared by analogy to prior art. They are preferably prepared by an interfacial polymerization process of a suitable polymer wall forming material. Interfacial polymerization is usually performed in an aqueous water-in-oil emulsion or suspension of the core material containing dissolved therein at least one part of the polymer wall forming ma-terial. During the polymerization, the polymer segregates from the core material to the boundary surface between the core material and water thereby forming the wall of the microcapsule. Thereby an aqueous suspension of the microcapsule material is obtained. Suitable methods for interfacial polymerization processes for preparing microcapsules containing pesticide compounds have been disclosed in prior art, e.g. U.S. Pat. No. 3,577,515, U.S. Pat. No. 4,280,833, U.S. Pat. No. 5,049,182, U.S. Pat. No. 5,229,122, U.S. Pat. No. 5,310,721, U.S. Pat. No. 5,705,174, U.S. Pat. No. 5,910,314, WO 95/13698, WO 00/10392, WO 01/68234, WO 03/099005, EP 619,073 or EP 1,109,450, to which full reference is made.
Suitable wall forming materials for polyurethane capsules include preferably 2- or 3-component systems such as
Preferably, the polyurethane comprises polyfunctional isocyanate (also called polyisocyanate) and polyfunctional amine (also called polyamine) in polymerized form.
It is also known, that an isocyanate group may react with water to a carbamic acid group, which in turn may eliminate carbon dioxide to yield finally an amine group.
In a further embodiment, the 2-component system polyfunctional isocyanate/polyfunctional amine may be prepared by reacting the polyfunctional isocyanate with water. In a very preferred embodiment of the present invention the polymeric wall material is a polyurethane. In general, polyurethane is formed by reacting a polyisocyanate, having at least two isocyanate groups with a polyamine having at least two primary amino groups, optionally in the presence of a polyfunctional acid chloride, to form a polyurea wall material. Polyisocyanates may be used individually or as mixtures of two or more Polyisocyanates. Polyisocyanates which are suitable for use include di- and triisocyanates, wherein the isocyanate groups are attached to an aliphatic or cycloaliphatic moiety (aliphatic isocyanates) or to an aromatic moiety (aromatic isocyanates). Examples of suitable aliphatic diisocyanates include tetramethylene diisocyanate, pentamethylene diisocyanate and hexamethylene diisocyanate as well as cycloaliphatic isocycantates such as isophoronediisocyanate, 1,4-bisisocyanatocyclohexane and bis-(4-isocyanatocyclohexyl)methane. Suitable aromatic isocyanates include toluene diisocyanates (TDI: a mixture of the 2,4- and 2,6-isomers), diphenylmethene-4,4′-diisocyanate (MDI), polymethylene polyphenyl isocyanate, 2,4,4′-diphenyl ether triisocyanate, 3,3′-dimethyl-4,4′-diphenyl diisocyanate, 3,3′-dimethoxy-4,4′-diphenyl diisocyanate, 1,5-naphthylene diisocyanate and 4,4′,4″-triphenylmethane triisocyanate. Also suitable are higher oligomers of the aforementioned diisocyanates such as the isocyanurates and biurethes of the aforementioned diisocyanates and mixtures thereof with the aforementioned diisocyanates.
In another preferred embodiment, the polyisocyanate is an oligomeric isocyanates. Such oligomeric isocyanates may comprise above mentioned aliphatic diisocyanates and/or aromatic isocyanates in oligomerized form. The oligomeric isocyanates have an average functionality in the range of 2.0 to 4.0, preferably 2.1 to 3,2, an more preferably 2.3 to 3.0. Typically, these oligomeric isocyanates have a viscosity (determined according to DIN 53018) in the range from 20 to 1000 mPas, more preferably from 80 to 500 mPas and especially from 150 to 320 mPas. Such oligomeric isocyanates are commercially available, for example from BASF SE under the tradenames Lupranat®M10, Lupranat® M20, Lupranat® M50, Lupranat® M70, Lupranat® M200, Lupranat® MM103 or from Bayer AG as Basonat® A270.
Also suitable are adducts of diisocyanates with polyhydric alcohols, such as ethylene glycol, glycerol and trimethylolpropane, obtained by addition, per mole of polyhydric alcohol, of a number of moles of diisocyanate corresponding to the number of hydroxyl groups of the respective alcohol and mixtures thereof with the aforementioned diisocyanates. In this way, several molecules of diisocyanate are linked through urethane groups to the polyhydric alcohol to form high molecular weight polyisocyanates. A particularly suitable product of this kind, DESMODUR® L (Bayer Corp., Pittsburgh), can be prepared by reacting three moles of toluene diisocyanate with one mole of 2-ethylglycerol (1,1-bismethylolpropane). Further suitable products are obtained by addition of hexamethylene diisocyanate or isophorone diisocyanate with ethylene glycol or glycerol.
Preferred polyisocyanates are isophorone diisocyanate, diphenylmethane-4,4′-diisocyanate, toluene diisocyanates. In another embodiement, preferred polyisocyanates are oligomeric isocyanates.
Suitable polyamines within the scope of this invention will be understood as meaning in general those compounds that contain two and more amino groups in the molecule, which amino groups may be linked to aliphatic or aromatic moieties. Examples of suitable aliphatic polyamines are α,ω-diamines of the formula H2N—(CH2)n—NH2, wherein n is an integer from 2 to 6. Exemplary of such diamines are ethylenediamine, propylene-1,3-diamine, tetramethylenediamine, pentamethylenediamine and hexamethylenediamine. A preferred diamine is hexamethylenediamine.
Further suitable aliphatic polyamines are polyethylenimines of the formula H2N—(CH2—CH2—NH)n—H, wherein n is an integer from 2 to 5. Representative examples of such polyethylenimines are diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pen-taethylenehexamine. Further suitable aliphatic polyamines are dioxaalkane-α, ω-diamines, such as 4,9-dioxadodecane-1,12-diamine of the formula H2N—(CH2)3O—(CH2)4O(CH2)3—NH2.
Examples of suitable aromatic polyamines are 1,3-phenylenediamine, 2,4- and 2,6-toluenediamine, 4,4′-diaminodiphenylmethane, 1,5-diaminonaphthalene, 1,3,5-triaminobenzene, 2,4,6-triaminotoluene, 1,3,6-triaminonaphthalene, 2,4,4′-triaminodiphenyl ether, 3,4,5-triamino-1,2,4-triazole and 1,4,5,8-tetraminoanthraquinone. Those polyamines which are insoluble or insufficiently soluble in water may be used as their hydrochloride salts.
Polyamines, such as those mentioned above may be used individually or as mixtures of two or more polyamines.
The relative amounts of each complementary wall-forming component will vary with their equivalent weights. In general, approximately stoichiometric amounts are preferred, while an excess of one component may also be employed, especially an excess of polyisocyanate. The total amount of wall-forming components approximately corresponds to the total amount of polymeric wall forming materials.
The invention also relates to a composition comprising an encapsulated pesticide, wherein the pesticide is a strobilurin and the encapsulation material of the encapsulated pesticide comprises polyurethane. Such a composition is especially suited for the method according to the invention and the use according to the invention. Preferably, the strobilurin is azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoximmethyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyribencarb, trifloxystrobin. More preferably, the strobilurin is pyraclostrobin. Suitable polyurethane encapsulation material and its preparation is as described above. Typically, the polyurethane comprises polyfunctional isocyanate and polyfunctional amine in polymerized form. Preferred polyisocyanates are isophorone diisocyanate, diphenylmethane-4,4′-diisocyanate, and toluene diisocyanates. In another preferred embodiment, the polyisocyanate comprises an aromatic polyisocyanate, such as toluene diisocyanates (TDI: a mixture of the 2,4- and 2,6-isomers), diphenylmethene-4,4′-diisocyanate (MDI), preferably MDI. In another preferred embodiment, the polyisocyanate comprises an oligomeric isocyanate, which are described above. Preferred polyfunctional amines are aliphatic polyamines, such as α,ω-diamines of the formula H2N—(CH2)n—NH2, wherein n is an integer from 2 to 6. Examples of such diamines are ethylenediamine, propylene-1,3-diamine, tetramethylenediamine, pentamethylenediamine and hexamethylenediamine. A preferred diamine is hexamethylenediamine.
The composition comprising an encapsulated pesticide, wherein the pesticide is a strobilurin and the encapsulation material of the encapsulated pesticide comprises polyurethane preferably comprises 10 to 450 g/l encapsulated strobilurin, 50 to 450 g/l organic solvent, 1 to 100 g/l surfactant (nonionic and/or anionic surfactant), and water up to 1.0 l. More preferably, said composition comprises 100 to 350 g/l encapsulated strobilurin, 150 to 400 g/l organic solvent, 10 to 60 g/l surfactant, and water up to 1.0 l. In another preferred embodiment, the composition comprises 10 to 300 g/l polyisocyanate and 0.5 to 30 g/l polyamine. More preferably, said composition comprises 50 to 150 g/l polyisocyanate and 1 to 10 g/l polyamine. Examples for suitable organic solvent are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives. Preferably, the core of the encapsulated pesticide comprises at least one strobilurine and at least one organic solvent (such as aliphatic, cyclic and aromatic hydrocarbons). In an especially preferred embodiment, the core of the encapsulated pesticide comprises at least one strobilurine dissolved in at least one organic solvent. Suitable surfactans are as listed above. Preferably, a mixture of at least two different surfactants is used. More preferably, the surfactant is a mixture of a non-ionic and ionic surfactant. Said composition may also comprise auxiliaries which are customary in agrochemical compositions. Examples for suitable auxiliaries are solvents, solid carriers, dispersants or emulsifiers (such as further solubilizers, protective colloids, surfactants and adhesion agents), organic and anorganic thickeners, bactericides, anti-freezing agents or anti-foaming agents. Suitable examples of such auxiliaries are as listed above.
The invention also relates to a composition comprising an encapsulated pesticide, wherein the pesticide is a pesticide, which is dissolved in at least one organic solvent, and the encapsulation material of the encapsulated pesticide comprises polyurethane. Such a composition is especially suited for the method according to the invention and the use according to the invention. The organic solvent is preferably an aprotic organic solvent, more preferably mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives. Most preferred organic solvents preferably an aliphatic, cyclic and aromatic hydrocarbons. Preferably, the pesticide, which is dissolved in at least one organic solvent is a strobilurin, such as azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyribencarb, trifloxystrobin. More preferably, the strobilurin is pyraclostrobin. Suitable polyurethane encapsulation material and its preparation is as described above. Typically, the polyurethane comprises polyfunctional isocyanate and polyfunctional amine in polymerized form. Preferred polyisocyanates are isophorone diisocyanate, diphenylmethane-4,4′-diisocyanate, and toluene diisocyanates. In another preferred embodiment, the polyisocyanate comprises an aromatic polyisocyanate, such as toluene diisocyanates (TDI: a mixture of the 2,4- and 2,6-isomers), diphenylmethene-4,4′-diisocyanate (MDI), preferably MDI. In another preferred embodiment, the polyisocyanate comprises an oligomeric isocyanate, which are described above. Preferred polyfunctional amines are aliphatic polyamines, such as α,ω-diamines of the formula H2N—(CH2)n—NH2, wherein n is an integer from 2 to 6. Examples of such diamines are ethylenediamine, propylene-1,3-diamine, tetramethylenediamine, pentamethylenediamine and hexame-thylenediamine. A preferred diamine is hexamethylenediamine.
The composition comprising an encapsulated pesticide, wherein the pesticide is a pesticide, which is dissolved in at least one organic solvent, and the encapsulation material of the encapsulated pesticide comprises polyurethane preferably comprises 10 to 450 g/l encapsulated pesticide (e.g. a strobilurin), 50 to 450 g/l organic solvent, 1 to 100 g/l surfactant (nonionic and/or anionic surfactant), and water up to 1.0 l. More preferably, said composition comprises 100 to 350 g/l encapsulated pesticide (e.g. strobilurin), 150 to 400 g/l organic solvent, 10 to 60 g/l surfactant, and water up to 1.0 l. In another preferred embodiment, the composition comprises 10 to 300 g/l polyisocyanate and 0.5 to 30 g/l polyamine. More preferably, said composition comprises 50 to 150 g/l polyisocyanate and 1 to 10 g/l polyamine. Examples for suitable organic solvent are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives. Preferably, the core of the encapsulated pesticide comprises at least one strobilurine and at least one organic solvent (such as aliphatic, cyclic and aromatic hydrocarbons). Suitable surfactans are as listed above. Preferably, a mixture of at least two different surfactants is used. More preferably, the surfactant is a mixture of a non-ionic and ionic surfactant. Said composition may also comprise auxiliaries which are customary in agrochemical compositions. Examples for suitable auxiliaries are solvents, solid carriers, dispersants or emulsifiers (such as further solubilizers, protective colloids, surfactants and adhesion agents), organic and anorganic thickeners, bactericides, anti-freezing agents or anti foaming agents. Suitable examples of such auxiliaries are as listed above.
The invention further relates to a composition comprising a mixture of an encapsulated pesticide and a non-encapsulated, additional pesticide, wherein the encapsulated pesticide comprises a strobilurin or a carboxamide, and the non-encapsulated, additional pesticide comprises a triazole or a carboxamide. Such a composition is especially suitable for the method according to the invention and the use according to the invention. In a preferred embodiment, the encapsulated pesticide comprises pyraclostrobin, and the non-encapsulated, additional pesticide comprises epoxiconazol, metconazol, boscalid or a 1-methylpyrazol-4-ylcarboxanilide of the formula I. In another preferred embodiment, the encapsulated pesticide comprises a 1-methylpyrazol-4-ylcarboxanilide of the formula I, and the non-encapsulated, additional pesticide cornprises epoxiconazol or metconazol. Usually, the encapsulation material of the encapsulated pesticide comprises polyurethane or poly(meth)acrylate. Suitable polyurethane or poly(meth)acrylate is as described above. Preferably, the core of the encapsulated pesticide comprises at least one pesticide and at least one organic solvent (such as aliphatic, cyclic and aromatic hydrocarbons). In an especially preferred embodiment, the core of the encapsulated pesticide comprises at least one pesticide dissolved in at least one organic solvent. The composition preferably comprises 10 to 450 g/l encapsulated pesticide, 50 to 450 g/l organic solvent, 1 to 100 g/l surfactant (nonionic and/or anionic surfactant), and water up to 1.0 l. More preferably, said composition comprises 100 to 350 g/l encapsulated pesticide, 150 to 400 g/l organic solvent, 10 to 60 g/l surfactant, and water up to 1.0 l. In another preferred embodiment, the composition comprises 10 to 300 g/l polyisocyanate and 0.5 to 30 g/l polyamine. More preferably, said composition comprises 50 to 150 g/l polyisocyanate and 1 to 10 g/l polyamine. Said composition may also comprise auxiliaries which are customary in agrochemical compositions. Examples for suitable auxiliaries are surfactants, solvents, solid carriers, dispersants or emulsifiers (such as further solubilizers, protective colloids, surfactants and adhesion agents), organic and anorganic thickeners, bactericides, anti-freezing agents or anti-foaming agents. Suitable examples of such auxiliaries are as listed above. Suitable surfactans are as listed above. Preferably, a mixture of at least two different surfactants is used. More preferably, the surfactant is a mixture of a non-ionic and ionic surfactant.
The invention also relates to a use of an encapsulated pesticide for the pesticidal treatment of crop which has a final growth height of at least 140 cm at a growth height of the crop of up to 120 cm. Preferably, the crop is corn, sunflower, oilseed rape, sugar cane, sorghum or miscanthus. In another preferred embodiement, said use is for pescticidal treatment by ground application. Suitable pesticides, encapsulation materials, final growth height, growth heights of the crop and pesticidal treatments are as described above.
There are several advantages of the present invention: The crops may be treated earlier then usual whist still providing the yield equivalent to the optimum timing which is later in growth stage. Thus, the crop plants are smaller at the time of application and may be treated not only by aerial application, but also from the ground by standard equipment. Fewer applications, especially in corn, allow more economic and less time consuming crop protection. The farmer can use his own equipment so there is a cost saving and application timing can be decided by the grower. There is a limit on the area that can be treated via aerial application equipment due to numbers of planes available to treat crops, particularly in the USA. Aerial application is not an option in most countries around the world, so at present growers have to apply at a less optimum timing to gain access to the crop with conventional equipment resulting in yield responses, which are less than could be achieved with a later application timing. Another advantage is that less damage is caused to crop by treating at an earlier growth stage, in which the crop plants are smaller. The compositions according to the invention are especially advantageous for the method and the use according to the invention, because they allow the aforementioned advantages of said method. The compositions according to the invention show also very good draining properties when drained out of their packagings, thus allowing a safe and efficient handling for the farmers. The compositions according to the invention, especially the composition comprising the encapsulated pesticide, allow the encapsulation of very high concentrations of pesticides, resulting in a high pesticide loading of the composition.
The inventive examples below give further illustration of the invention, which is not, however, restricted to these examples.
The four PMMA capsules of Table 1 were prepapred using the concentration [g/l] as summarized in Table 1. The water phase comprising water, protective colloid and sodium nitrite was prepared. The oil phase was prepared by dissolving pyraclostrobin in Solvesso 200 at elevated temperatur and added to the water phase while stirring. Next the monomers MMA, MAS, BDA and PETIA were added. The two phase mixture was stirred at 70° C. for 30 minutes and cooled down to 50° C. To the resulting emulsion tert-butyl perpivalate was added while stirring and heated within 2 h up to 70° C. and afterwards 1.5 h at 85° C. Next, tea-butyl hydroperoxide and ascorbic acid were added within 60 min while cooling down to 20° C. The particle size was determined as z-average by means of light scattering on a Malvern Mastersizer. The residue after evaporation was determined by heating the capsules for 2 h at 105° C. and subsequently 1 h at 130° C. The solid content was determined by heating the capsule suspension for 2 h at 105° C. Further details about the preparation of the PMMA capsules CWF and CXF are described in EP 09177493.5 (especiylla in Example 8).
The suspension of PU capsules of Table 2A and 2B were prepared using the concentration [g/l; referring to the concentration in the overall suspension] as summarized in Table 2. The water phase comprising water, protective colloid (e.g. Mowiol, Culminal, dispersant) was prepared under nitrogen atmosphere. Under intensive stirring a mixture of the diisocyanate and the pyraclostrobin dissolved in Solvesso were added and dispersed in the aqueous phase for 15 min at 40° C. Next, the diamine was added within 1 h while stirring and heating for 1 h at 60° C. and 2 h at 80° C. The particle size was determined as z-average by means of light scattering on a Malvern Mastersizer.
The capsules listed in Table 2B had an particle size of D90 4.0 to 6.0 μm and D4,3 of 2.0 to 2.5 μm. The residue after evaporation was determined by heating the capsules for 2 h at 105° C. and subsequently 1 h at 130° C. The solid content was determined by heating the capsule suspension for 2 h at 105° C.
Corn was grown in 15 different fields in USA. The corn was planted around April to Mai 2008. The fields were treated with 150 g/ha pyraclostrobin from Example 1 by spraying at a growth stage V8 to V10 (corresponds to BBCH 32/35; growth height approximately 100 to 115 cm). For comparison, each field was partly untreated and partly treated with Headline® at VT to R1 (corresponds to BBCH 55 to 61; growth height approximately 200 to 250 cm) The corn was harvested at maturity and the grain yield of the crop was determined. Table 1 lists the mean yield calculated as percent of untreated of 13 field trials, wherein the untreated control corresponds to 100% yield.
The field trials showed that the early treatment of corn with encapsulated pesticide results in a similar yield as the conventional treatment with non-encapsulated pesticide at a later growth stage of corn.
a)not according to the invention
The corn was grown as described in Example 2. The crop was naturally infested with the fungi Puccinia sorghi (PUCCSO), Cercospora zea maydis (CERCZM) and Physoderma maydis (PHYOMA) during the vegetation period. The corn was treated with 150 g/ha pyraclostrobin from Example 1 at growth stage V8 to V10 (BBCH 32/35; growth height approximately 100 to 120 cm) by a CO2 sprayer. For comparison, the fields were partly untreated and partly treated with Headline® at growth stage VT/R1 (BBCH 55/61; growth height approximately 200 to 250 cm). The level of infestation was determined at growth stage R4 to R5 (BBCH 75/82) by estimating the infected leaf area of ten randomly selected plants per plot. The efficacy was calculated according to Abbolt's formular [E=1−infect control/infect treatment*100]. Table 2 lists the mean level of efficacy of the 4 field trials for Puccinia sorghi control, 14 field trials for Cercospora zeae-maydis control, and 3 field trials for Physoderma zeae-maydis control.
The field trials showed that the early treatment of corn with encapsulated pesticide results in a similar fungi control as the conventional treatment with non-encapsulated pesticide at a later growth stage of corn.
a) not according to the invention
Corn was grown in 3 different fields in Germany and France. The corn was planted in May 2008. The fields were treated with 110 g/ha pyraclostrobin from Example 1 by spraying at a growth stage BBCH 32/34 (growth height approximately 80 to 115 cm). In addition, 110 g/ha pyraclostrobin was applied as the PU-1 formulation in a tank mix with 40 g of metconazole fungicide as the commercial formulation Caramba®. For comparison, each time the field was partly untreated and partly treated with 110 g/ha Headline® by spraying at the growth stage BBCH 55/57 (tassel emergence; growth height approximately 175 to 200 cm). The corn was harvested at maturity and the grain yield of the crop was determined. Table 3 lists the mean yield calculated as percent of untreated of the three field trials, wherein the untreated control corresponds to 100%.
The field trials showed that the early treatment of corn with encapsulated pesticide results in a similar yield as the conventional treatment with non-encapsulated pesticide at a later growth stage of corn.
a) not according to the invention
The corn was grown as described in Example 4. The corn crop showed natural infestation with the fungi Helminthosporium turgidum in a trial in France at the growth stage 73 to 82. The corn was treated with 110 g/ha pyraclostrobin from Example 1 by spraying at growth stage BBCH 32/34 (growth height approximately 80 to 115 cm). In addition, 110 g/ha pyraclostrobin was applied as the PU-1 formulation in a tank mix with 40 g of metconazole fungicide as the commercial formulation Caramba®. For comparison, the fields were partly untreated and partly treated with Headline® by spraying at growth stage BBCH 55/57 (growth height approximately 175 to 200 cm). The level of infestation was determined by estimating the infected leaf area of ten randomly selected plants per plot. The efficacy was calculated according to Abbott's formular [E=1−infect control/infect treatment*100]. Table 4 lists the mean efficacy of the field trial in France.
The field trials showed that the early treatment of corn with encapsulated pesticide results in a better fungal control even as the conventional treatment with non-encapsulated pesticide at a later growth stage of corn.
a) not according to the invention
| Number | Date | Country | Kind |
|---|---|---|---|
| 09158960.6 | Apr 2009 | EP | regional |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP2010/053148 | 3/12/2010 | WO | 00 | 9/19/2011 |
| Number | Date | Country | |
|---|---|---|---|
| 61161959 | Mar 2009 | US |
