US 20080139388A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2008/0139388 A1 Krohn et al. (43) Pub. Date: Jun. 12, 2008
(54) SYNERGISTIC INSECTICIDE MIXTURES (30) Foreign Application Priority Data
(76) Inventors: Peter-Wilhelm Krohn, Leverkusen Apr. 24, 2004 (DE) ...... 10 2004 0201145 (DE); Heika Hungenberg, Jul. 9, 2004 (DE) ...... 10 2004 033 289.4 Langenfeld (DE); Wolfgang Thielert, Odenthal (DE) Publication Classi?cation Correspondence Address: (51) Int. Cl. A01N 43/40 BAYER CROPSCIENCE LP (2006.01) Patent Department, 2 T .W. ALEXANDER DRIVE A01N 37/44 (2006.01) RESEARCH TRIANGLE PARK, NC 27709 A01P 7/04 (2006.01) (52) US. Cl...... 504/100; 514/357; 514/551; 514/341; (21) Appl. No .: 11/578,928 504/130 (22) PCT Filed: Oct. 14, 2005 (57) ABSTRACT (86) PCT No.: PCT/EP05/03924 The invention relates to insecticidal mixtures comprising methiocarb and at least one further known active compound § 371 (0X1), from the group of the neonicotinoids, and to the use of these (2), (4) Date: Dec. 13, 2007 mixtures for controlling animal pests and for seed dressing. US 2008/0139388 A1 Jun. 12, 2008
SYNERGISTIC INSECTICIDE MIXTURES [0006] The compounds mentioned are knoWn, for example, from “The Pesticide Manual”, 11”’ Edition, 1997, published by the British Crop Protection Council. [0001] The present invention relates to novel active com [0007] Thiamethoxam has the formula pound combinations comprising, as active compounds, methiocarb and a further active compound from the group of the neonicotinoids, Which combinations have very good 0 insecticidal properties. [0002] It is already knoWn that methiocarb (3,5-dimethyl 4-(methylthio)phenyl methylcarbamate) of the formula
0 H3C i >N O and is knoWn from EP A2 0 580 553. H [0008] Clothianidin has the formula
H S | H3C CH3 scH3 c1—
[0012] Nitenpyram has the formula to 1:100, preferably from 125:1 to 1:50 and particularly pref erably from 25: 1 to 1:5, Where in the ratios, as above, methio carb is alWays mentioned ?rst. HN/ CH3 [0022] Preferably, the mixtures mentioned above as being preferred do not contain any other insecticidally active com ponent. \ N)\/ N02 [0023] The active compound combinations, having good IDA CZHS| plant compatibility and favourable homeotherm toxicity, are 01 N suitable for controlling animal pests, in particular insects, arachnids and nematodes, encountered in agriculture, in for ests, in the protection of stored products and materials and in and is known from EP A2 0 302 389. the hygiene sector. They are preferably used as crop protec [0013] Imidacloprid has the formula tion compositions for foliar and soil treatment. [0024] They are effective against normally sensitive and resistant species and against all or individual stages of devel opment. The abovementioned pests include: C. / \ CHFFN H, [0025] From the order of the Isopoda, for example, Oniscus 0 Y asellus, Armadillidium vulgare, Porcellio scaber. From the order of the Diplopoda, for example, Blaniulus gullulalus. N02 From the order of the Chilopoda, for example, Geophilus carpophagus, Sculigera spp. From the order of the Symphyla, and is known from EP A10 192 060. for example, Sculigerella immaculala. From the order of the Thysanura, for example, Lepisma saccharina. From the order [0014] The ratio in Which the active compounds are of the Collembola, for example, Onychiurus armalus. From employed and the total amount of the mixture to be used the order of the Orthoptera, for example, Achela domeslicus, depend on the nature and the occurrence of the insects. For Gryllolalpa spp., Locusla migraloria migralorioides, Mel each application, the optimum ratios and total amounts to be anoplus spp., Schislocerca gregaria. From the order of the used can in each case be determined by test series. Blattaria, for example, Blalla orienlalis, Periplanela ameri [0015] A particularly preferred mixture according to the cana, Leucophaea maderae, Blattella germanica. From the invention comprises the active compounds methiocarb and order of the Dermaplera, for example, Foiy‘icula auricularia. clothianidin or methiocarb and imidacloprid. In these mix From the order of the Isoptera, for example, Reliculilermes tures, the Weight ratio of the respective active compounds is spp. From the order of the Phthiraptera, for example, Pedicu from 1000:1 to 1:100, preferably from 125:1 to 1:50 and lus humanus corporis, Haemalopinus spp., Linognalhus spp., particularly preferably from 25:1 to 1:5, Where in the ratios Trichodecles spp., Damalinia spp. From the order of the here and beloW methiocarb is alWays mentioned ?rst. Thysanoptera, for example, Hercinolhripsfemoralis, Thrips [0016] A further particularly preferred mixture according Zabaci, Thrips palmi, Frankliniella occidenlalis. From the to the invention comprises the active compounds methiocarb order of the Heteroptera, for example, Eurygasler spp., Dys and acetamiprid. In the mixture, the Weight ratio of the tWo dercus inlermedius, Piesma quadrala, Cimex leclularius, active compounds is from 1000:1 to 1:100, preferably from Rhodnius prolixus, Trialoma spp. From the order of the 125:1 to 1:50 and particularly preferably from 25:1 and 1:5. Homoplera, for example, Aleurodes brassicae, Bemisia [0017] A further particularly preferred mixture according Zabaci, Trialeurodes vaporariorum, Aphis gossypii, Bret/ico to the invention comprises the active compounds methiocarb ryne brassicae, Cryplomyzus ribis, Aphisfabae, Aphis pomi, and nitenpyram. In the mixture, the Weight ratio of the tWo Eriosoma lanigerum, Hyaloplerus arundinis, Phylloxera active compounds is from 1000:1 to 1:100, preferably from vaslalrix, Pemphigus spp., Macrosiphum avenae, Myzus spp., 125:1 to 1:50 and particularly preferably from 25:1 and 1:5. Phorodon humuli, Rhopalosiphum padi, Empoasca spp., [0018] A further particularly preferred mixture according Euscelis bilobalus, Nepholellix cincliceps, Lecanium corni, to the invention comprises the active compounds methiocarb Sal'sselia 0leae, Laodelphax slrialellus, Nilaparvala lugens, and dinotefuran. In the mixture, the Weight ratio of the tWo Aonidiella auranlii, Aspidiolus hederae, Pseudococcus spp., active compounds is from 1000:1 to 1:100, preferably from Psylla spp. From the order of the Lepidoptera, for example, 125:1 to 1:50 and particularly preferably from 25:1 and 1:5. Peclinophora gossypiella, Bupalus piniarius, Chemalobia [0019] A further particularly preferred mixture according brumala, Lilhocollelis blancardella, Hyponomeula padella, to the invention comprises the active compounds methiocarb Plulella xyloslella, Malacosoma neuslria, Euproclis chrysor and thiamethoxam. In the mixture, the Weight ratio of the tWo rhoea, Lymanlria spp., Bucculalrix Zhurberiella, Phyllocnis active compounds is from 1000:1 to 1:100, preferably from Zis cilrella, Agrolis spp., Euxoa spp., Fellia spp., Earias insu 125:1 to 1:50 and particularly preferably from 25:1 and 1:5. lana, Heliolhis spp., Mameslra brassicae, Panolis?ammea, [0020] A further particularly preferred mixture according Spodoplera spp., Trichoplusia ni, Carpocapsa pomonella, to the invention comprises the active compounds methiocarb Pieris spp., Chilo spp., Pyrausla nubilalis, Epheslia kueh and thiacloprid. In the mixture, the Weight ratio of the tWo niella, Galleria mellonella, Hneola bisselliella, ?nea pel active compounds is from 1000:1 to 1:100, preferably from lionella, Hofmannophilapseudosprelella, Cacoecia podana, 125:1 to 1:50 and particularly preferably from 25:1 and 1:5. Capua reliculana, Charisloneurafumlferana, Clysia ambig [0021] A particularly preferred mixture according to the uella, Homona magnanima, Torlrix viridana, Cnaphalocerus invention comprises the active compounds methiocarb and spp., Oulema oryzae. From the order of the Coleoptera, for clothianidin. In the mixture, Which is used for seed dressing, example, Anobium punclalum, Rhizoperlha dominica, the Weight ratio of the tWo active compounds is from 1000:1 Bruchidius obleclus, Acanlhoscelides obleclus, Hylolrupes US 2008/0139388 A1 Jun. 12, 2008
bajulus, Agelaslica alni, Leplinolarsa decemlineala, Phae example, oranges, grapefruits, limes, lemons, kumquats, tan don cochleariae, Diabrolica spp., Psylliodes chrysocephala, gerines and satsumas, nuts such as, for example, pistachios, Epilachna variveslis, Alomaria spp., Oryzaephilus Surina almonds, Walnuts and pecan nuts, tropical fruits such as, for mensis, Anlhonomus spp., Silophilus spp., Oliorrhynchus sul example, mango, paW-paW, pineapple, dates and bananas, calus, Cosmopoliles sordidus, Ceulhorrhynchus assimilis, and grapes) and vegetables (comprising leaf vegetables such Hyperaposlica, Dermesles spp., Trogoderma spp., Anlhrenus as, for example, endives, corn salad, Florence fennel, lettuce, spp., Allagenus spp., Lyclus spp., Meligelhes aeneus, Plinus cos lettuce, SWiss chard, spinach and chicory for salad use, spp., Niplus hololeucus, Gibbium psylloides, Tribolium spp., cabbages such as, for example, cauli?ower, broccoli, Chinese Tenebrio molilor, Agrioles spp., Conoderus spp., Melolonlha leaves, Brassica oleracea (L.) convar. acephala var. sabellica melolonlha, Amphimallon solslilialis, Costelylra Zealandica, L. (curly kale, feathered cabbage), kohlrabi, Brussels sprouts, Lissorhoplrus oryzophilus. From the order of the red cabbage, White cabbage and savoy cabbage, fruit veg Hymenoptera, for example, Diprion spp., Hoplocampa spp., etables such as, for example, aubergines, cucumbers, capsi Lasius spp., Monomorium pharaonis, Vespa spp. From the cums, table pumpkins, tomatoes, courgettes and sWeetcom, order of the Diptera, for example, Aedes spp., Anopheles spp., root vegetables such as, for example celeriac, Wild turnips, Culex spp., Drosophila melanogasler, Musca spp., Fannia carrots, including yelloW cultivars, Raphanus salivus var. spp., Calliphora erylhrocephala, Lucilia spp., Chrysomyia niger and var. radicula, beetroot, scorZonera and celery, spp., Culerebra spp., Gaslrophilus spp., Hyppobosca spp., legumes such as, for example, peas and beans, and vegetables Slomoxys spp., Oeslrus spp., Hypoderma spp., Tabanus spp., from the Allium family such as, for example, leeks and Tannia spp., Bibio horlulanus, Oscinella?’il, Phorbia spp., onions). The combinations according to the invention are Pegomyia hyoscyami, Ceralilis capilala, Dacus oleae, ?pula particularly suitable for treating the seed of maiZe and sun paludosa, Hylemyia spp., Liriomyza spp. From the order of ?oWer. the Siphonaptera, for example, Xenopsylla cheopis, Ceralo [0029] The treatment according to the invention of the phyllus spp. Aus der Klasse der Arachnida, for example, plants andplant parts With the active compound combinations Scorpio maurus, Lalrodeclus maclans, Acarus siro, Argus is carried out either directly or by treating their environment, spp., Ornilhodoros spp., Dermanyssus gallinae, Eriophyes habitat or storage space by the customary treatment methods, ribis, Phyllocoplrula oleivora, Boophilus spp., Rhipiceph for example by dipping, spraying, vaporiZing, misting, broad alus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., casting, painting on and, in the case of propagation material, Psoroples spp., Chorioples spp., Sarcoples spp., Tarsonemus in particular seeds, furthermore by coating With one or more spp., Bryobia praeliosa, Panonychus spp., Telranychus spp., layers. Hemilarsonemus spp., Brevipalpus spp. [0030] The mixtures according to the invention, in particu [0026] The plant-parasitic nematodes include, for example, lar also the combination of the active ingredients imidaclopid Pralylenchus spp., Radopholus similis, Dilylenchus dipsaci, and methiocarb and of clothianidin and methiocarb, are par Elenchulus semipenelrans, Helerodera spp., Globodera ticularly suitable for the treatment of seeds. Thus, most of the spp., Meloidogyne spp., Aphelenchoides spp., Longidorus damage to crop plants Which is caused by pests occurs as early spp., Xiphinema spp., Trichodorus spp., Bursaphelenchus as When the seed is infested during storage and after the seed spp. is introduced into the soil, and during and immediately after [0027] All plants and plant parts can be treated in accor germination of the plants. This phase is particularly critical dance With the invention. Plants are understood as meaning, since the roots and shoots of the groWing plants are particu in the present context, all plants and plant populations, such as larly sensitive and even minor damage can lead to the death of desired and undesired Wild plants or crop plants (including the Whole plant. Protecting the seed and the germinating plant naturally occurring crop plants). Crop plants may be plants by the use of suitable compositions is therefore of particularly Which can be obtained by conventional breeding and optimi great interest. Zation methods or by biotechnological and genetic engineer [0031] The control of pests by treating the seed of plants has ing methods or by combinations of these methods, including been knoWn for a long time and is the subject of continuous the transgenic plants and including the plant varieties capable improvements. HoWever, the treatment of seed entails a series or not capable of being protected by plant breeders’ rights. of problems Which cannot alWays be solved in a satisfactory Plant parts are understood as meaning all above-ground and manner. Thus, it is desirable to develop methods for protect subterranean parts and organs of the plants, such as shoot, ing the seed and the germinating plant Which dispense With leaf, ?oWer and root, examples Which may be mentioned the additional application of crop protection products after being leaves, needles, stalks, stems, ?oWers, fruiting bodies, planting or after emergence of the plants. It is furthermore fruits and seeds, and also roots, tubers and rhiZomes. The desirable to optimiZe the amount of active compound plant parts also include harvested material and vegetative and employed in such a Way as to provide optimum protection for generative propagation material, for example cuttings, tubers, the seed and the germinating plant from attack by pests, but rhiZomes, slips and seeds. Without damaging the plant itself by the active compound [0028] What may be emphasiZed in this context is the par employed. In particular, methods for the treatment of seed ticularly advantageous effect of the compositions according should also take into consideration the intrinsic insecticidal to the invention With regard to their use in cereal plants such properties of transgenic plants in order to achieve optimum as, for example, Wheat, oats, barley, spelt, triticale and rye, but protection of the seed and the germinating plant With a mini also in maiZe, sorghum and millet, rice, sugar cane, soya mum of crop protection products being employed. beans, sun?owers, potatoes, cotton, oilseed rape, canola, [0032] The present invention therefore in particular also tobacco, sugar beet, fodder beet, asparagus, hops and fruit relates to a method for the protection of seed and for the plants (comprising pome fruit such as, for example, apples protection of plants, in particular of germinating plants, from and pears, stone fruit such as, for example, peaches, nectar attack by pests, by treating the seed With a composition ines, cherries, plums and apricots, citrus fruits such as, for according to the invention. The invention likeWise relates to US 2008/0139388 Al Jun. 12, 2008
the use of the compositions according to the invention for the [0038] Within the scope of the present invention, the com treatment of seed for protecting the seed and the resulting position according to the invention is applied to the seed plants from pests. Furthermore, the invention relates to seed either alone or in suitable formulation. Preferably, the seed is Which has been treated With a composition according to the treated in a state in Which it is stable enough to avoid damage invention so as to afford protection from pests. during treatment. In general, the seed may be treated at any [0033] One of the advantages of the present invention is that point in time betWeen harvest and soWing. The seed usually the particular systemic properties of the compositions accord used has been separated from the plant and freed from cobs, ing to the invention mean that treatment of the seed With these shells, stalks, coats, hairs or the ?esh of the fruits. compositions not only protects the seed itself, but also the [0039] When treating the seed, care must generally be taken resulting plants after emergence, from pests. In this manner, that the amount of the composition according to the invention the immediate treatment of the crop at the time of soWing or applied to the seed and/or the amount of further additives is shortly thereafter can be dispensed With. chosen in such a Way that the germination of the seed is not [0034] A further advantage is the synergistically increased adversely affected, or that the resulting plant is not damaged. insecticidal activity of the compositions according to the This must be borne in mind in particular in the case of active invention in comparison With the respective individual active compounds Which can have phytotoxic effects at certain compound, Which exceeds the total of the activity of the tWo application rates. active compounds When applied individually. This makes [0040] The compositions according to the invention can be possible an optimiZation of the amount of active compound applied directly, that is to say Without further components and employed. Without having been diluted. As a rule, it is preferable to apply [0035] Furthermore, it must be considered as advantageous the composition to the seed in the form of a suitable formu that the mixtures according to the invention can also be lation. Suitable formulations and methods for the treatment of employed in particular in transgenic seed, the plants arising seed are knoWn to the skilled Worker and are described, for from this seed being capable of expressing a protein directed example, in the folloWing documents: U.S. Pat. No. 4,272, against pests. By treating such seed With the compositions 417 A, U.S. Pat. No. 4,245,432 A, U.S. Pat. No. 4,808,430 A, according to the invention, certain pests can be controlled U.S. Pat. No. 5,876,739 A, US 2003/0176428 A1,WO 2002/ merely by the expression of the, for example, insecticidal 080675 Al, WO 2002/028186 A2. protein, and, surprisingly, the result in addition is a synergis [0041] The active compound combinations can be con tically complemented activity With the compositions accord verted into the customary formulations, such as solutions, ing to the invention, Which, again, increases the ef?cacy of the emulsions, Wettable poWders, suspensions, poWders, dusts, protection against attack by pests. pastes, soluble poWders, granules, suspoemulsion concen [0036] The compositions according to the invention are trates, natural and synthetic materials impregnated With suitable for protecting seed of any plant variety as already active compounds and microencapsulations in polymeric mentioned above Which is employed in agriculture, in the materials. greenhouse, in forests, in horticulture or in viticulture. In [0042] These formulations are produced in a knoWn man particular, this takes the form of seed of maiZe, peanut, ner, for example by mixing the active compounds With canola, oilseed rape, poppy, soya beans, cotton, beet (for extenders, that is, liquid solvents and/ or solid carriers, option example sugarbeet and fodder beet), rice, sorglum and millet, ally With the use of surfactants, that is, emulsi?ers and/or Wheat, barley, oats, rye, sun?oWer or tobacco. The composi dispersants and/or foam formers. tions according to the invention are likeWise suitable for treat [0043] If the extender used is Water, it is also possible to ing the seed of fruit plants and vegetables as already men use, for example, organic solvents as auxiliary solvents. Suit tioned above. The treatment of the seed of maiZe, soya beans, able liquid solvents are essentially: aromatics, such as xylene, cotton, Wheat and canola or oilseed rape is of particular toluene or alkylnaphthalenes, chlorinated aromatics or chlo importance. Thus, for example, the mixture according to the rinated aliphatic hydrocarbons, such as chlorobenZenes, chlo invention Which comprises the active compound methiocarb roethylenes or methylene chloride, aliphatic hydrocarbons, and imidacloprid or clothianidin and methiocarb is particu such as cyclohexane or paraf?ns, for example mineral oil larly suitable for treating the seed of maiZe and the seed of fractions, mineral and vegetable oils, alcohols, such as sun?ower. butanol or glycol and ethers and esters thereof, ketones, such [0037] As already mentioned above, the treatment of trans as acetone, methyl ethyl ketone, methyl isobutyl ketone or genic seed With a composition according to the invention is cyclohexanone, strongly polar solvents, such as dimethylfor also of particular importance. This takes the form of seed of mamide and dimethyl sulphoxide, and Water. plants Which, as a rule, comprise at least one heterologous [0044] Suitable solid carriers are: gene Which governs the expression of a polypeptide With in for example ammonium salts and ground natural minerals, particular insecticidal properties. In this context, the heter such as kaolins, clays, talc, chalk, quartz, attapulgite, mont ologous genes in transgenic seed may be derived from micro morillonite or diatomaceous earth, and ground synthetic min organisms such as Bacillus, Rhizobium, Pseudomonas, Ser erals, such as ?nely divided silica, alumina and silicates; ralia, Trichoderma, Clavibacler, Glomus or Gliocladium. suitable solid carriers for granules are: for example crushed The present invention is particularly suitable for the treatment and fractionated natural rocks such as calcite, marble, pum of transgenic seed Which comprises at least one heterologous ice, sepiolite and dolomite, and synthetic granules of inor gene originating from Bacillus sp. and Whose gene product ganic and organic meals, and granules of organic material shoWs activity against the European corn borer and/or the such as saWdust, coconut shells, maiZe cobs and tobacco corn root Worm. It is particularly preferably a heterologous stalks; suitable emulsi?ers and/or foam formers are: for gene derived from Bacillus Zhuringiensis. Here, too, the com example nonionic and anionic emulsi?ers, such as polyoxy bination according to the invention is particularly suitable for ethylene fatty acid esters, polyoxyethylene fatty alcohol the seed of maiZe. ethers, for example alkylaryl polyglycol ethers, alkylsulpho US 2008/0139388 A1 Jun. 12, 2008
nates, alkyl sulphates, arylsulphonates and protein hydroly copper hydroxide, copper naphthenate, copper oxychloride, sates; suitable dispersants are: for example lignosulphite copper sulphate, copper oxide, oxine-copper and Bordeaux Waste liquors and methylcellulose. mixture, mancopper, mancoZeb, maneb, meferimZone, [0045] Tacki?ers such as carboxymethylcellulose and mepanipyrim, mepronil, metalaxyl, metconaZole, methasul natural and synthetic polymers in the form of poWders, gran focarb, methfuroxam, metiram, metomeclam, metsulfovax, ules or latices, such as gum arabic, polyvinyl alcohol and mildiomycin, myclobutanil, mycloZolin, nickel dimeth polyvinyl acetate, and natural phospholipids, such as cepha yldithiocarbamate, nitrothal-isopropyl, nuarimol, ofurace, lins and lecithins, and synthetic phospholipids can be used in oxadixyl, oxamocarb, oxolinic acid, oxycarboxim, oxy the formulations. Other possible additives are mineral and fenthiin, paclobutraZole, pefuraZoate, penconaZole, pencycu vegetable oils. ron, phosdiphen, pimaricin, piperalin, polyoxine, polyox [0046] It is possible to use colorants such as inorganic orim, probenaZole, prochloraZ, procymidon, propamocarb, pigments, for example iron oxide, titanium oxide and Prus propanosine-sodium, propiconaZole, propineb, pyraZophos, sian Blue, and organic dyestuffs, such as aliZarin dyestuffs, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur, quincona aZo dyestuffs and metal phthalocyanine dyestuffs, and trace Zole, quintoZene (PCNB), sulphur and sulphur preparations, nutrients such as salts of iron, manganese, boron, copper, tebuconaZole, tecloftalam, tecnaZene, tetcyclacis, tetracona cobalt, molybdenum and Zinc. Zole, thiabendaZole, thicyofen, thi?uZamide, thiophanate [0047] The formulations in general comprise betWeen 0.1 methyl, thiram, tioxymid, tolclofos-methyl, tolyl?uanid, tri and 95% by Weight of active compound, preferably betWeen adimefon, triadimenol, triaZbutil, triaZoxide, trichlamide, 0.5 and 90%. tricyclaZole, tridemorph, tri?umiZole, triforine, triticonaZole, [0048] Preferably, the active compound combinations uniconaZole, validamycin A, vincloZolin, viniconaZole, according to the invention comprise no further active com Zarilamid, Zineb, Ziram pounds apart from methiocarb and the neonicotinoids men tioned. and Dagger G, OK-8705, OK-880l, ot-(l,l-dimethylethyl) [0049] If appropriate, the active compound combinations [3-(2 -phenoxyethyl)- l H-l ,2,4-triaZole-l -ethanol, ot-(2,4 according to the invention, in commercially available formu dichlorophenyl)- [3-?uoro- [3-propyl- l H- l ,2,4-triaZole- l - lations and in the use forms prepared from these formulations, ethanol, ot-(2,4-dichloro-phenyl)-[3-methoxy-0t-methyl-lH can be present in a mixture With other knoWn active com 1,2,4-triazole-l-ethanol, ot-(5 -methyl-l ,3-dioxan-5-yl)-0t pounds such as insecticides, attractants, sterilants, bacteri [[4-(tri -?uoromethyl)phenyl]methylene] - l H-l ,2,4-triaZole cides, acaricides, nematicides, fungicides, groWth regulators l-ethanol, (5 RS,6RS)-6-hydroxy-2,2,7,7-tetra-methyl-5 - or herbicides. The insecticides include, for example, phos (l H- l ,2,4-triazol- l -yl)-3 -octanone, (E)-0t-(methoxyimino) phoric esters, carbamates, carboxylic esters, chlorinated N-methyl-2-phenoxyphenyl-acetamide, l -isopropyl hydrocarbons, phenylureas, substances produced by micro {Z-methyl-l -[ [[ l -(4 -methylphenyl)ethyl]amino]carbonyl] organisms, and the like. propyl}carbamate l-(2,4-dichlorophenyl)-2-(lH-1,2,4-tria [0050] Examples of especially advantageous components Zol-l -yl)ethanone O-(phenylmethyl)oxime, l -(2-methyl-l - naphthalenyl)- l H-pyrrole-2,5 -dione, l-(3 ,5 - in the mixtures are the folloWing: dichlorophenyl)-3-(2-propenyl)-2,5-pyrrolidinedione, Fungicides: l -[(diiodomethyl)sulphonyl]-4-methylbenZene, l -[[2-(2,4 dichlorophenyl)- l ,3 -dioxolan-2-yl]methyl] - l H-imidaZole, [0051] aldimorph, ampropylfos, ampropylfos-potassium, l-[ [2-(4-chlorophenyl)-3-phenyloxiranyl]methyl] - l H- l ,2,4 andoprim, anilaZin, aZaconaZole, aZoxystrobin, benalaxyl, triaZole, l -[ l - [2-[(2,4-dichlorophenyl)methoxy]phenyl] benodanil, benomyl, benZamacril, benZamacryl-isobutyl, ethenyl] - l H-imidaZole, l-methyl-5 -nonyl-2-(phenylm bialaphos, binapacryl, biphenyl, bitertanol, blasticidin-s, bro ethyl)-3-pyrrolidinol, 2',6'-dibromo-2-methyl-4' muconaZole, bupirimate, buthiobate, calcium polysulphide, tri?uoromethoxy-4'-tri?uoromethyl- l ,3 -thiaZole- 5 -carbox capsimycin, captafol, captan, carbendaZim, carboxin, car anilide, 2,2-dichloro-N-[l -(4-chlorophenyl)ethyl] -l -ethyl vone, quinomethionate, chlobenthiaZon, chlorfenaZole, chlo 3-methylcyclopropanecarboxamide, 2,6-dichloro-5 roneb, chloropicrin, chlorothalonil, chloZolinate, cloZylacon, (methylthio)-4-pyrimidinyl thiocyanate, 2,6-dichloro-N-(4 cufraneb, cymoxanil, cyproconaZole, cyprodinil, cypro tri?uoromethylbenZyl)-benZamide, 2,6-dichloro-N-[[4 furam, debacarb, dichlorophen, diclobutraZol, diclo?uanid, (tri?uoromethyl)phenyl]methyl]benZamide, 2-(2,3 ,3 - diclomeZin, dicloran, diethofencarb, difenoconaZole, dime triiodo -2 -propenyl)-2H-tetraZole, 2-[(l -methylethyl) thirimol, dimethomorph, diniconaZole, diniconaZole-M, sulphonyl] -5 -(trichloromethyl)-l ,3 ,4-thiadiaZole, 2-[ [6 dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, deoxy-4-O-(4 -O-methyl- [3-D-glycopyrano SYD-(X-D dodemorph, dodine, draZoxolon, ediphenphos, epoxicona glucopyrano syl] amino] -4 -methoxy- l H-pyrrolo-[2,3-d] Zole, etaconaZole, ethirimol, etridiaZole, famoxadon, fenapa pyrimidine-5 -carbonitrile, 2-aminobutane, 2-bromo -2 nil, fenarimol, fenbuconaZole, fenfuram, fenitropan, fenpi (bromomethyl)pentanedinitrile, 2-chloro -N- (2,3 -dihydro-l , clonil, fenpropidin, fenpropimorph, fentin acetate, fentin l ,3 -trimethyl- l H-inden-4 -yl)-3-pyridinecarboxamide, hydroxide, ferbam, ferimZon, ?uaZinam, ?umetover, ?uoro 2-chloro -N- (2,6-dimethylphenyl)-N- (isothiocyanatomethyl) mid, ?uquinconaZole, ?urprimidol, ?usilaZole, ?usulfamide, acetamide, 2-phenylphenol (OPP), 3,4-dichloro- l -[4-(dif ?utolanil, ?utriafol, folpet, fosetyl-aluminium, fosetyl-so luoromethoxy)phenyl] - l H-pyrrole-2,5 -dione, 3 ,5 -dichloro dium, fthalide, fuberidaZole, furalaxyl, furametpyr, furcar N-[cyano [( l -methyl-2 -propynyl)oxy] -methyl]benZamide, bonil, furconaZole, furconaZole-cis, furmecyclox, guaZatine, 3 -( l , l -dimethylpropyl-l -oxo)- l H-indene-2 -carbonitrile, hexachlorobenZene, hexaconaZole, hymexaZole, imaZalil, 3 -[2-(4 -chlorophenyl)-5 -ethoxy-3-isoxaZolidinyl]pyridine, imibenconaZole, iminoctadine, iminoctadine-albesilate, imi 4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-1H noctadine-triacetate, iodocarb, ipconaZole, iprobenfos (IBP), imidaZole-l -sulphonamide, 4-methyltetraZolo[ l ,5 -a] iprodione, irumamycin, isoprothiolane, isovaledione, quinaZolin-5 (4H) -one, 8-(1,l-dimethylethyl)-N-ethyl-N kasugamycin, kresoxim-methyl, copper preparations such as: propyl- l ,4-dioxaspiro [4 .5] decane-2 -methanamine, US 2008/0139388 A1 Jun. 12, 2008
8-hydroxyquinoline sulphate, N-2-[(phenyl-amino)carbo cythrinate, ?ucycloxuron, ?ucythrinate, ?ufenoxuron, ?uten nyl] -9H-Xanthene-9-carbohydraZide, bis-(1-methylethyl)-3 - Zine, ?uvalinate, fonophos, fosmethilan, fosthiaZate, methyl-4-[(3 -methylbenZoyl) -oxy] -2,5 -thiophene dicar fubfenprox, furathiocarb, granulosis Viruses, halofenoZide, boxylate, cis-1-(4-chlorophenyl)-2-(1H-l,2,4-triaZol-1-yl) HCH, heptenophos, hexa?umuron, heXythiaZoX, hydroprene, cycloheptanol, cis-4- [3 -[4-(1,1-dimethylpropyl)phenyl-2 imidacloprid, indoxacarb, isaZofos, isofenphos, isoxathion, methylpropyl] -2,6-dimethylmorpholine hydrochloride, ethyl ivermectin, nuclear polyhedrosis Viruses, lambda-cyhalo [(4 -chlorophenyl)aZo] cyanoacetate, potassium hydro gencar thrin, lufenuron, malathion, mecarbam, metaldehyde, metha bonate, sodium methanetetrathiolate, methyl 1 -(2,3 -dihydro midophos, Melharhizium anisopliae, Melharhizium ?a 2,2-dimethyl-1H-inden-1-yl)-1H-imidaZole-5 -carboXylate, methyl N-(2,6-dimethylphenyl) -N- (5 -isoXaZolylcarbonyl) voviride, methidathion, methiocarb, methomyl, DL-alaninate, methyl N- (chloroacetyl)-N-(2,6-dimethyl methoXyfenoZide, metolcarb, metoXadiaZone, mevinphos, phenyl) -DL-alaninate, N- (2,3 -dichloro -4 -hydroxyphenyl) milbemectin, monocrotophos, naled, nitenpyram, nithiaZine, 1 -methylcyclohexanecarboxamide, N- (2,6 novaluron, omethoate, oxamyl, oxydemethon M, Paecilomy dimethylphenyl) -2 -methoXy-N-(tetrahydro-2-oxo -3 - ces fumosoroseus, parathion A, parathion M, permethrin, furanyl)acetamide, N- (2,6-dimethylphenyl) -2 -methoXy-N phenthoate, phorate, phosalone, phosmet, phosphamidon, (tetrahydro-2-oxo -3 -thienyl)acetamide, N- (2 -chloro -4 phoxim, pirimicarb, pirimiphosA, pirimiphos M, profenofos, nitrophenyl) -4 -methyl-3 -nitrob enZene sulphonamide, N- (4 - promecarb, propargite, propoxur, prothiofos, prothoate, cycloheXylphenyl)-1 ,4, 5, 6-tetrahydro-2-pyrimidineamine, pymetroZine, pyraclofos, pyresmethrin, pyrethrum, pyrida N- (4 -hexylphenyl) -1 ,4 , 5 ,6 -tetrahydro -2 -pyrimidineamine, ben, pyridathion, pyrimidifen, pyriproxyfen, quinalphos, rib N- (5 -chloro -2 -methylphenyl) -2 -methoXy-N-(2 -oxo-3-ox avirin, salithion, sebufos, sila?uofen, spinosad, spirodi aZolidinyl)acetamide, N- ((6 -methoxy)-3-pyridinyl)cyclo clofen, spiromesifen, sulfotep, sulprofos, tau-?uvalinate, propanecarboxamide, N-[2,2,2-tri-chloro-1-[(chloracetyl) tebufenoZide, tebufenpyrad, tebupirimiphos, te?ubenZuron, amino]ethyl]benZamide, N- [3 -chloro -4,5 -bis-(2 te?uthrin, temephos, temivinphos, terbufos, tetrachlorvin propynyloxy)phenyl] -N' -methoxymethaneimidamide, phos, theta-cypermethrin, thiacloprid, thiamethoxam, thi sodium N-formyl-N-hydroxy-DL-alaninate, 0,0-diethyl [2 apronil, thiatriphos, thiocyclam hydrogenoxalate, thiodicarb, (dipropyl-amino)-2-oxoethyl]ethylphosphoramidothioate, thiofanox, thuringiensin, tralocythrin, tralomethrin, triarath O-methyl S-phenyl phenylpropylphosphoramido-thioate, ene, triaZamate, triaZophos, triaZuron, trichlophenidine, S-methyl 1,2,3-benZothiadiaZole-7-carbothioate, spiro[2H] trichlorfon, tri?umuron, trimethacarb, Vamidothion, Vanilip [1-benZopyran-2,1'(3'H)-iso-benZofuran]-3'-one. role, Verlicillium lecanii, Yl 5302, Zeta-cypermethrin, Zola profos, Bactericides: and also (1R-cis)-[5-(phenylmethyl)-3-furanyl]-methyl [0052] bronopol, dichlorophen, nitrapyrin, nickel dimeth 3-[(dihydro-2-oXo-3 (2H)-furanylidene)-methyl]-2,2-dim yldithiocarbamate, kasugamycin, octhilinone, furancarboxy ethylcyclopropanecarboxylate, (3-phenoxyphenyl)methyl lic acid, oxytetracyclin, probenaZole, streptomycin, teclofta 2,2,3,3-tetramethyl-cyclopropanecarboxylate, 1-[(2-chloro 5 -thiaZolyl)methyl] tetrahydro-3 ,5 -dimethyl-N-nitro -1 ,3 ,5 - lam, copper sulphate and other copper preparations. triaZine-2(1H)-imine, 2-(2-chloro-6-?uorophenyl)-4-[4-(1, 1 -dimethylethyl)phenyl] -4,5 -dihydro -oxaZole, lnsecticides/Acaricides/Nematicides: 2-(acetyloxy) -3 -dodecyl-1,4-naphthalenedione, 2-chloro-N [0053] abamectin, acephate, acetamiprid, acrinathrin, [[ [4 -(1 -phenylethoxy)phenyl] -amino] carbonyl] benZamide, alanycarb, aldicarb, aldoxycarb, alpha-cypermethrin, alpha 2-chloro-N-[[[4-(2,2-dichloro-1,1-di?uoroethoxy)phenyl] methrin, amitraZ, avermectin, AZ 60541, aZadirachtin, amino]-carbonyl]benZamide, 3-methylphenyl propylcar aZamethiphos, aZinphosA, aZinphos M, aZocyclotin, Bacillus bamate, 4-[4-(4-ethoxyphenyl)-4-methylpentyl]-1-?uoro-2 popilliae, Bacillus sphaericus, Bacillus sublilis, Bacillus Zhu phenoxybenZene, 4-chloro-2-(1,1-dimethylethyl)-5 - [[2-(2, ringiensis, baculoViruses, Beauveria bassiana, Beauveria 6-dimethyl-4-phenoxyphen-oxy)ethyl]thio]-3 (2H) Zenella, bendiocarb, benfuracarb, bensultap, benZoXimate, pyridaZinone, 4-chloro-2-(2-chloro-2-methylpropyl)-5-[(6 betacy?uthrin, bifenaZate, bifenthrin, bioethanomethrin, bio iodo-3 -pyridinyl) -methoXy] -3 (2H) -pyridaZinone, 4 -chloro - permethrin, BPMC, bromophos A, bufencarb, buprofeZin, 5-[(6-chlor-3-pyridinyl)methoXy]-2-(3,4-dichlorophenyl)-3 butathiofos, butocarboxim, butylpyridaben, cadusafos, car (2H)-pyridaZinone, Bacillus Zhuringiensis strain EG-2348, baryl, carbofuran, carbophenothion, carbosulfan, cartap, N-[2-benZoyl-1-(1,1-dimethylethyl)]-benZohydraZide, 2,2 chloethocarb, chlorethoxyfos, chlorfenapyr, chlorfenvin dimethyl-3 -(2,4-dichlorophenyl) -2 -oxo- 1 -oxaspiro [4 .5] dec phos, chlor?uaZuron, chlormephos, chlorpyrifos, chlorpyri 3-en-4-yl butanoate, N-[3-[(6-chloro-3 -pyridinyl)methyl]-2 fos M, chlovaporthrin, cis-resmethrin, cis-permethrin, clo thiaZolidinylidene]cyanamide, dihydro-2-(nitromethylene) cythrin, cloethocarb, clofenteZine, clothianidin, cyanophos, 2H-1,3-thiaZine-3 (4H)-carboxaldehyde, ethyl [2-[[1,6 cycloprene, cycloprothrin, cy?uthrin, cyhalothrin, cyhexatin, dihydro - 6-oxo -1 - (phenylmethyl) -4 -pyridaZinyl] oxy] ethyl] cypermethrin, cyromaZine, deltamethrin, demeton M, deme carbamate, N-(3,4,4-tri?uoro-1-oXo-3 -butenyl) glycine, ton S, demeton-5-methyl, diafenthiuron, diaZinon, dichlor N-(4-chloro-phenyl)-3-[4-(di?uoromethoxy)phenyl]-4,5-di VOS, di?ubenZuron, dimethoate, dimethylvinphos, diofeno hydro-4-phenyl- 1 H-pyraZole- 1 -carboxamide, N-methyl-N' lan, disulfoton, docusate sodium, dofenapyn, e?usilanate, (1 -methyl-2-propenyl)-1 ,2-hydraZinedicarbothioamide, emamectin, empenthrin, endosulfan, Enlomophlhora spp., N-methyl-N'-2-propenyl- 1 ,2-hydraZinedicarbothioamide, esfenvalerate, ethiofencarb, ethiprole, ethion, ethoprophos, 0,0-diethyl [2-(dipropylamino)-2-oxoethyl]ethylphos etofenprox, etoxaZole, etrimfos, fenamiphos, fenaZaquin, phoramido-thioate. fenbutatin oxide, fenitrothion, fenothiocarb, fenoxacrim, [0054] A mixture With other knoWn active compounds such fenoxycarb, fenpropathrin, fenpyrad, fenpyrithrin, fenpy as herbicides, or With fertilizers and growth regulators, is also roximate, fenvalerate, ?pronil, ?uaZinam, ?uaZuron, ?ubro possible. US 2008/0139388 A1 Jun. 12, 2008
[0055] When used as insecticides, the active compound [0064] Industrial materials in the present context are under combinations according to the invention in their commer stood as meaning non-live materials such as, preferably, plas cially available formulations and in the use forms Which are tics, adhesives, siZes, paper and board, leather, Wood, timber prepared from these formulations may furthermore be present products and paints. as a mixture With synergists. Synergists are compounds by [0065] The material Which is to be protected from insect Which the action of the active compounds is increased Without attack is very especially preferably Wood and timber prod it being necessary for the synergist added to be active itself. ucts. [0056] The active compound content of the use forms pre [0066] Wood and timber products Which can be protected by the composition according to the invention, or mixtures pared from the commercially available formulations can vary comprising it, are to be understood as meaning, for example: Within Wide ranges. The active compound concentration of [0067] Construction timber, Wooden beams, railWay sleep the use forms can amount to from 0.0000001 to 95% by ers, bridge components, jetties, vehicles made of Wood, Weight of active compound, preferably betWeen 0.0001 and boxes, pallets, containers, telephone poles, Wood lagging, 1% by Weight. WindoWs and doors made of Wood, plyWood, chipboard, join [0057] They are applied in a customary manner adapted to ery, or timber products Which quite generally are used in suit the use forms. house construction or building joinery. [0058] When applied against hygiene and stored-product [0068] The active compound combinations can be used as pests, the active compound combinations are distinguished such, in the form of concentrates or generally customary by outstanding residual action on Wood and clay and by good formulations such as poWders, granules, solutions, suspen stability to alkali on limed substrates. sions, emulsions or pastes. [0059] The active compound combinations according to [0069] The abovementioned formulations can be prepared in a manner knoWn per se, for example by mixing the active the invention are not only active against plant pests, hygiene compounds With at least one solvent or diluent, emulsi?er, pests and stored-product pests, but also, in the veterinary dispersant and/or binder or ?xative, Water repellant, if desired medicine sector, against animal parasites (ectoparasites) such desiccants and UV stabiliZers, and if desired colorants and as hard ticks, soft ticks, scab mites, harvest mites, ?ies (sting pigments and other processing auxiliaries. ing and licking), parasitic ?y larvae, lice, hair lice, bird lice [0070] The insecticidal compositions or concentrates used and ?eas. for protecting Wood and timber products comprise the active [0060] The active compound combinations according to compound according to the invention in a concentration of the invention are also suitable for controlling arthropods from 0.0001 to 95% by Weight, in particular 0.001 to 60% by Which infest agricultural productive livestock such as, for Weight. example, cattle, sheep, goats, horses, pigs, donkeys, camels, [0071] The amount of the compositions or concentrates buffaloes, rabbits, chickens, turkeys, ducks, geese, honey employed depends on the species and the abundance of the bees, other domestic animals such as, for example, dogs, cats, insects and on the medium. The optimal quantity to be caged birds, aquarium ?sh and What are knoWn as experimen employed can be determined in each case by test series upon tal animals, such as, for example, hamsters, guinea pigs, rats application. In general, hoWever, it Will su?ice to employ and mice. By controlling these arthropods, cases of death and from 0.0001 to 20% by Weight, preferably 0.001 to 10% by reduced productivity (of meat, milk, Wool, hides, eggs, honey Weight, of the active compound, based on the material to be and the like) should be diminished, so that more economic protected. and simpler animal husbandry is possible by using the active [0072] A suitable solvent and/or diluent is an organochemi compound combinations according to the invention. cal solvent or solvent mixture and/or an oily or oil-type orga [0061] The active compound combinations according to nochemical solvent or solvent mixture of loW volatility and/or the invention are applied in the veterinary sector in a knoWn a polar organochemical solvent or solvent mixture and/or manner by enteral administration in the form of, for example, Water and, if appropriate, an emulsi?er and/or Wetter. tablets, capsules, portions, drenches, granules, pastes, [0073] Organochemical solvents Which are preferably boluses, the feed-through method, and suppositories, by employed are oily or oil-type solvents With an evaporation parenteral administration, such as, for example, by injections number of above 35 and a ?ash point of above 30° C., pref (intramuscular, subcutaneous, intravenous, intraperitoneal erably above 45° C. Such oily and oil-type solvents Which are and the like), implants, by nasal administration, by dermal use insoluble in Water and of loW volatility and Which are used are in the form of, for example, dipping or bathing, spraying, suitable mineral oils or their aromatic fractions or mineral pouring on and spotting on, Washing, dusting, and With the aid oil-containing solvent mixtures, preferably White spirit, of active-compound-containing moulded articles such as col petroleum and/or alkylbenZene. lars, ear marks, tail marks, limb bands, halters, marking [0074] Mineral oils Which are advantageously used are devices and the like. those With a boiling range of from 170 to 220° C., White spirit [0062] When used on livestock, poultry, domestic animals With a boiling range of from 170 to 220° C., spindle oil With and the like, the active compounds may be used as formula a boiling range of from 250 to 350° C., petroleum and aro tions (for example poWders, emulsions, ?oWables) Which matics With a boiling range of from 160 to 280° C., oil of contain the active compounds in an amount of from 1 to 80% turpentine, and the like. by Weight, either directly or after 100- to 10 000-fold dilution, [0075] In a preferred embodiment, liquid aliphatic hydro or they may be used as a chemical bath. carbons With a boiling range of from 180 to 210° C. or [0063] Moreover, it has been found that the active com high-boiling mixtures of aromatic and aliphatic hydrocarbons pound combinations according to the invention shoW a potent With a boiling range of from 180 to 220° C. and/ or spindle oil insecticidal action against insects Which destroy industrial and/or monochloronaphthalene, preferably ot-monochloro materials. naphthalene, are used. US 2008/0139388 A1 Jun. 12, 2008
[0076] The organic oily or oil-type solvents of loW volatil [0086] If appropriate, the ready-to-use compositions may ity and With an evaporation number of above 35 and a ?ash additionally also contain further insecticides and also, if point of above 300 C., preferably above 45° C., can be appropriate, one or more fungicides. replaced in part by organochemical solvents of high or [0087] The active compound combinations according to medium volatility, With the proviso that the solvent mixture the invention can at the same time be employed for protecting likeWise has an evaporation number of above 35 and a ?ash objects Which come into contact With saltWater or brackish point of above 300 C., preferably above 45° C., and that the insecticide/ fungicide mixture is soluble or emulsi?able in this Water, such as hulls, screens, nets, buildings, moorings and solvent mixture. signalling systems, from fouling. [0077] In a preferred embodiment, some of the orga [0088] Fouling by sessile Oligochaeta, such as Serpulidae, nochemical solvent or solvent mixture is replaced by an ali and by shells and species from the Ledamorpha group (goose phatic polar organochemical solvent or solvent mixture. Ali barnacles), such as various Lepas and Scalpellum species, or phatic organochemical solvents Which contain hydroxyl and/ by species from the Balanomorpha group (acorn barnacles), or ester and/or ether groups are preferably used, such as, for such as Balanus or Pollicipes species, increases the frictional example, glycol ethers, esters or the like. drag of ships and, as a consequence, leads to a marked [0078] Organochemical binders used for the purposes of increase in operation costs oWing to higher energy consump the present invention are the synthetic resins and/ or binding tion and additionally frequent residences in the dry dock. drying oils Which are knoWn per se and Which can be diluted [0089] Apart from fouling by algae, for example Eclocar in Water and/or dissolved or dispersed or emulsi?ed in the pus sp. and Ceramium sp., fouling by sessile Entomostraka organochemical solvents employed, in particular binders groups, Which come under the generic term Cirripedia (cir composed of, or comprising, an acrylate resin, a vinyl resin, riped crustaceans), is of particular importance. for example polyvinyl acetate, polyester resin, polyconden [0090] The active compound combinations according to sation or polyaddition resin, polyurethane resin, alkyd resin or modi?ed alkyd resin, phenol resin, hydrocarbon resin such the invention are also suitable for controlling animal pests, in as indene/coumarone resin, silicone resin, drying vegetable particular insects, arachnids and mites, Which are found in and/ or drying oils and/ or physically drying binders based on enclosed spaces such as, for example, dWellings, factory a natural and/ or synthetic resin. halls, o?ices, vehicle cabins and the like. They can be [0079] The synthetic resin employed as binder can be employed alone or in combination With other active com employed in the form of an emulsion, dispersion or solution. pounds and auxiliaries in domestic insecticide products for Bitumen or bituminous substances may also be used as bind controlling these pests. They are active against sensitive and ers, in amounts of up to 10% by Weight. In addition, colorants, resistant species and against all developmental stages. pigments, Water repellants, odour-masking agents, and [0091] Application in the ?eld of the domestic insecticides inhibitors or anticorrosive agents and the like, all of Which are can also be effected in combination With other suitable active knoWn per se, can be employed. compounds such as phosphoric esters, carbamates, pyre [0080] In accordance With the invention, the composition throids, groWth regulators or active compounds from other or the concentrate preferably comprises, as organochemical knoWn classes of insecticides. binders, at least one alkyd resin or modi?ed alkyd resin and/ or [0092] They are used as aerosols, pressure-free spray prod a drying vegetable oil. Alkyd resins Which are preferably used ucts, for example pump and atomiZer sprays, automatic fog in accordance With the invention are those With an oil content ging systems, foggers, foams, gels, evaporator products With of over 45% by Weight, preferably 50 to 68% by Weight. evaporator tablets made of cellulo se or polymer, liquid evapo [0081] Some or all of the abovementioned binder can be rators, gel and membrane evaporators, propeller-driven replaced by a ?xative (mixture) or plasticiZer (mixture). evaporators, energy-free, or passive, evaporation systems, These additives are intended to prevent volatiliZation of the moth papers, moth bags and moth gels, as granules or dusts, active compounds, and also crystalliZation or precipitation. in baits for spreading or in bait stations. They preferably replace from 0.01 to 30% of the binder [0093] When applying the active compound combinations (based on 100% of binder employed). according to the invention, the application rates can be varied [0082] The plasticiZers are from the chemical classes of the Within a substantial range, depending on the type of applica phthalic esters, such as dibutyl phthalate, dioctyl phthalate or tion. In the treatment of plant parts, the application rates of benZyl butyl phthalate, phosphoric esters such as tributyl active compound combinations are generally betWeen 0.1 and phosphate, adipic esters such as di-(2-ethylhexyl) adipate, 10 000 g/ha, preferably betWeen 10 and 1000 g/ha. stearates such as butyl stearate or amyl stearate, oleates such [0094] The good insecticidal action of the active compound as butyl oleate, glycerol ethers or higher-molecular-Weight combinations according to the invention can be seen from the glycol ethers, glycerol esters and p-toluenesulphonic esters. examples Which folloW. While the individual active com [0083] Fixatives are based chemically on polyvinyl alkyl pounds exhibit Weaknesses With regard to the action, the ethers such as, for example, polyvinyl methyl ether, or combinations demonstrate an action Which exceeds the ketones such as benZophenone and ethylenebenZophenone. simple summation of action. [0084] Other suitable solvents or diluents are, in particular, [0095] Formula for the calculation of the kill rate of a also Water, if appropriate as a mixture With one or more of the combination of tWo active compounds abovementioned organochemical solvents or diluents, emul [0096] The expected activity for a given combination of si?ers and dispersants. tWo active compounds can be calculated (cf. COLBY, S. R.; [0085] Particularly effective timber protection is achieved “Calculating Synergistic andAntagonistic Responses of Her by industrial-scale impregnating processes, for example the bicide Combinations”, Weeds 15, pages 20-22, 1967): vacuum, double-vacuum or pressure processes. if US 2008/0139388 A1 Jun. 12, 2008
[0097] X?he kill rate, expressed in % of the untreated control, When employing active compound A at an appli TABLE A2 cation rate of m ppm, Plant-damaging insects [0098] Y?he kill rate, expressed in % of the untreated M22143 gersicae test control, When employing active compound B at an appli cation rate of n ppm, Concentration Kill Active compound in ppm in % after 1 day [0099] E?he kill rate, expressed in % of the untreated methiocarb 20 5 control, When employing active compounds A and B at clothianidin 0.16 0 application rates of m and n ppm, found* calc.** then methiocarb + clothianidin (125:1) 20 + 0.16 70 5
*found = activity found _ X x Y **calc. = activity calculated using Colby’s formula E _ X + Y - 100
TABLE A3 [0100] If the actual insecticidal kill rate is higher than the calculated one, the kill rates of the combination are superad Plant-damaging insects M22143 gersicae test ditive, i.e. a synergistic effect is present. In this case, the kill rate that is actually observed has to be higher than the value, Concentration Kill calculated using the formula above, for the expected kill rate Active compound in ppm in % after 1 day (E) methiocarb 20 5 thiacloprid 0.8 20 found* calc.** EXAMPLE A methiocarb + thiacloprid (25:1) 20 + 0.8 75 24 Myzus persicae Test *found = activity found **calc. = activity calculated using Colby’s formula [0101] Solvent: 7 parts by Weight of dimethylformamide Emulsi?er: 2 parts by Weight of alkylaryl polyglycol ether EXAMPLE B [0102] To produce a suitable preparation of active com pound, 1 part by Weight of active compound is mixed With the Plulella xyloslella Test stated amounts of solvent and emulsi?er, and the concentrate is diluted With emulsi?er-containing Water to the desired con Normally Sensitive Strain centration. [0103] Cabbage leaves (Brassica oleracea) Which are [0106] heavily infested by the green peach aphid (Myzus persicae) are treated by being dipped into the preparation of active compound of the desired concentration. Solvent: 7 parts by Weight of dimethylfonnalnide [0104] After the desired period of time, the kill in % is Emulsi?er: 2 parts by Weight of alkylaryl polyglycol ether determined. 100% means that all aphids have been killed; 0% means that none of the aphids have been killed. The deter mined kill rates are entered into Colby’s formula. [0107] To produce a suitable preparation of active com [0105] In this test, for example, the folloWing combination pound, 1 part by Weight of active compound is mixed With the of active compounds according to the present application stated amounts of solvent and emulsi?er, and the concentrate shoWs a synergistically enhanced activity compared to the is diluted With emulsi?er-containing Water to the desired con active compounds applied on their oWn (Tables A1 to A3): centration. [0108] Cabbage leaves (Brassica oleracea) are treated by TABLE A1 being dipped into the active compound preparation of the Plant-damaging insects desired concentration and are populated With caterpillars of M2143 gersicae test the diamond-back moth (Plulella xyloslella, normally sensi tive strain) While the leaves are still moist. Concentration Kill Active compound in ppm in % after 6 days [0109] After the desired period of time, the kill in % is determined. 100% means that all caterpillars have been methiocarb 100 50 acetalniprid 0.16 30 killed; 0% means that none of the caterpillars have been found* calc.* * killed. The determined kill rates are entered into Colby’s formula (see sheet 1). methiocarb + acetalniprid (625:1) 100 + 0.16 85 65 [0110] In this test, the folloWing combination of active *found = activity found compounds according to the present application shoWed a **calc. = activity calculated using Colby’s formula synergistically enhanced activity compared to the active com pounds applied on their oWn: US 2008/0139388 A1 Jun. 12, 2008
17. A composition according to claim 16 comprising a TABLE B synergistically effective amount of methiocarb and thiaclo prid. Plant-damaging insects 18. A composition according to claim 16 comprising a PZuleZZa xyZosleZZa (normally sensitive strain) test synergistically effective amount of methiocarb and thia Concentration Kill methoxam. Active compound in ppm in % after 3 days 19. A composition according to claim 16 comprising a synergistically effective amount of methiocarb and acetami methiocarb 20 0 prid. thiacloprid 20 0 20. A composition according to claim 16 comprising a found* calc.* * synergistically effective amount of methiocarb and niten methiocarb + thiacloprid (1:1) 20 + 20 35 0 pyram. 21. A composition according to claim 16 comprising a *found = activity found synergistically effective amount of methiocarb and dinotefu **calc. = activity calculated using Colby’s formula ran. 22. A composition according to claim 16 comprising a What is claimed is: synergistically effective amount of methiocarb, clothianidin, 1-15. (canceled) and imidacloprid. 16. A composition comprising a synergistically effective 23. A composition according to claim 16 Wherein the amount of Weight ratio of methiocarb to component (2) is between 100:1 and 1:50. (1) methiocarb of the formula 24.A method of protecting seeds and/orplants germinating therefrom comprising applying a composition according to 0 claim 16 to the seeds as a seed dressing. 25. A method according to claim 24 Wherein the composi H3C i tion is a synergistically effective mixture of imidacloprid and >N O methiocarb. H 26. A method according to claim 24 Wherein the composi tion is a synergistically effective mixture of clothianidin and methiocarb. 27. A method of controlling animal pests comprising allowing a composition according to claim 16 to act on the scn3 pests and/ or their habitat. 28.A process for preparing pesticides comprising mixing a composition according to claim 16 With one or more extend and ers and/or surfactants. (2) one or more compounds selected from the group con 29. Seed treated With a composition according to claim 16. sisting of thiacloprid, thiamethoxam, acetamiprid, nitenpyram, and dinotefuran. * * * * *