WO2008037486A2 - Suspension concentrates for improving root uptake of agrochemically active compounds - Google Patents

Abstract

It is possible to increase the uptake of active compounds from crop protection compositions using suitable adjuvants, and thus to improve the action of crop protection agents. The present invention describes suitable adjuvants, methods and compositions.

Description

Suspension concentrates for improving root uptake of agrochemically active compounds

The present invention relates to improving the biological action of agrochemical suspension concentrates in soil applications by increasing the uptake of the active compound by the root using suitable adjuvants, and to their use for controlling harmful insects.

This procedure has the advantage that, using the compositions according to the invention, it is possible to decrease the amount of active compound applied or, at an unchanged application rate, to achieve improved action. Additionally, it is possible to reduce water consumption to a minimum.

In this context, an adjuvant is a component which improves the biological action of the active compounds in the compositions according to the invention without for its part exhibiting a biological action. The adjuvants are preferably incorporated into the concentrated formulation of the agrochemically active compound (in-can formulation). These finished formulations help to avoid dosage errors and to improve user safety when applying agrochemical products.

Furthermore, compared to the application by the tank-mix method, the unnecessary use of packaging materials is avoided.

For controlling harmful organisms, agrochemically active compounds can be applied in various ways. In addition to fourier treatment, it is also possible to treat the culture substrate, for example by spraying onto the soil, watering, side-dressing, shower drenching, overhead drenching or application using an irrigation system (drip irrigation). The culture substrate may be soil, but can also be a special substrate based on, inter alia, peat mosses, cocoa fibres, stone wool, such as, for example, Grodan®, pummis, expanded clay, such as, for example, Lecaton® or Lecadan®, clay granules, such as, for example, Seramis®, foamed plastics, such as, for example, Baystrat®, vermiculite, perlite, synthetic soil, such as, for example, Hygromull®, or combinations of these substrates. Hereinbelow, all of these culture substrates are referred to as soil. In addition to a treatment of the culture substrate, a further relevant application form is the direct addition of the active compound to the aqueous phase surrounding the root, for example by the floating-box or paddy field method. By applying active compounds into or onto the soil and directly into the aqueous phase, harmful organisms living in the soil/water are brought into contact with the active compound, and the uptake of systemic active compounds by the roots is initiated.

Various formulations for improving the action of agrochemically active compounds in fourier are already known. Thus, DE-A 10 129 855 describes oil-based suspension concentrates which, by virtue of added penetrants, improve uptake via the cuticles of the leaves. Also known are water- based suspension concentrates improving fourier uptake. Thus, WO 05/036963 describes formulations of this type which, in addition to certain fungicides, also comprise at least one penetrant. The penetrants described in these formulations suitable for fourier application are defined in that they penetrate from the aqueous spray liquor and/or the spray coating into the cuticles of the plant, thus being able to increase the mobility of active compounds in the cuticles. A method described in the literature (Baur et al., 1997, Pesticide Science 51, 131-152) may be used for determining this property. Also known are the mechanisms describing the uptake of active compounds by the cuticles of the leaves. The following publications may be mentioned by way of example: Hull, H.M. (1970) Residue Reviews 31, 1-150; Hartley, G.S., Graham-Bryce, I.L. (1980) Academic Press, London; Price, C.E., Anderson, N.H. (1985) Pestic. Sci., 16, 369-377; Kirkwood, R.C. (1993) Pestic. Sci. 38, 93-102; Holloway, P.J., Rees, R.T., Stock, D. (eds.) Springer-Verlag, Berlin (1994); Schδnherr J., Baur P. (1994) Pesticide Sci. 42, 185-208. It is also known to use adjuvants for improving the mobility of active compounds in soil systems. Griffith and Miller (McMullan, P.M. (ed.) 1998, Adjuvants for Agrochemicals. Proceedings of the 5th International Symposium on Adjuvants for Agrochemicals (1998), Memphis, USA pp.233 - 239 and 291 - 297) describe that the addition of surfactants has an effect on the interaction between soil minerals and water, thus improving the penetration of water and the active compounds transported therewith. Various non-ionic surfactants are mentioned as being suitable for this purpose. Others describe how surfactants reducing the surface tension of the spray liquor improve soil penetrations. Howell (McMullan, P.M. (ed.) 1998, Adjuvants for Agrochemicals. Proceedings of the 5th International Symposium on Adjuvants for Agrochemicals (1998), Memphis, USA pp. 247 - 253) describes the effect of trisilane surfactants which reduce the static surface tension to less than 30 mN/m on the horizontal and vertical mobility of permethrin in various soil types. By improving the capillary effect, more and smaller pores of the soil are reached. A comparable mechanism is described by Chung (Pesticide Science (1993), 38 (2-3), pp. 250-252) for improving the action of atrazine by addition of adjuvants.

In contrast, the effect of adjuvants on the uptake of agrochemically active compounds via the root system has hitherto not been described. The literature likewise does not mention the uptake via the root system and the associated mechanisms (Plant roots Growth, activity and interactions with soils, Peter Gregory; Blackwell Publishing (2006)).

It is an object of the present invention to provide agrochemical compositions comprising adjuvants suitable for increasing the uptake of active compounds via the root system. Moreover, these compositions should be stable enough for storage and have good biological activity.

Thus, the present invention provides the use of suitable adjuvants for increasing the uptake of active compounds via the root system. Accordingly, the present invention also provides formulations comprising these adjuvants. The present invention also provides the use of these adjuvants or these agrochemical formulations for improving the action of agrochemical compositions in soil applications, for example by spraying onto the soil, watering, side-drenching, shower drenching, overhead drenching or application using an irrigation system (drip irrigation) and in the case of direct application in the water in the case of plants being in direct contact with the aqueous phase. The invention furthermore provides the use of these formulations for controlling soil-borne harmful organisms and fourier pests.

The present invention now provides novel suspension concentrates comprising

at least one agrochemical Iy active compound from the group of the insecticidal phthalic acid diamides which is solid at room temperature,

at least one adjuvant,

at least one non-ionic surfactant and/or at least one anionic surfactant,

at least one antifreeze agent and

one or more additives from the groups of the antifoams, the preservatives, the antioxidants, the spreading agents, the colorants and/or thickeners.

The suspension concentrates according to the invention are referred to as being aqueous because they comprise virtually no organic solvent, in any case less than 75 g/1.

Suitable non-ionic surfactants are all compounds of this type which are usually employed in agrochemical compositions. Polyethylene oxide/polypropylene oxide block copolymers, polyethylene glycol ethers of straight-chain alcohols, reaction products of fatty acids with ethylene oxide and/or propylene oxide, furthermore polyvinyl alcohol, polyvinylpyrrolidone, mixed polymers of polyvinyl alcohol and polyvinylpyrrolidone, mixed polymers of polyvinyl acetate and polyvinylpyrrolidone and also copolymers of (meth)acrylic acid and (meth)acrylic esters, furthermore alkyl ethoxylates and alkylaryl ethoxylates which may optionally be phosphated and may optionally be neutralized with bases, polyoxyamine derivatives and nonylphenol ethoxylates may be mentioned as being preferred.

Suitable anionic surfactants are all substances of this type which are usually employed in agrochemical compositions. Preference is given to alkali metal and alkaline earth metal salts of alkylsulphonic acids or alkylaryl sulphonic acids. A further preferred group of anionic surfactants or dispersants are salts of polystyrenesulphonic acids, salts of polyvinylsulphonic acids, salts of naphthalenesulphonic acid/formaldehyde condensates, salts of condensates of naphthalenesulphonic acid, phenolsulphonic acid and formaldehyde and also salts of ligninsulphonic acid.

Suitable antifreeze agents are all substances of this type which are usually employed in agrochemical compositions. Preference is given to urea, glycerol, propanediol and propylene glycol. Particularly preferably, the suspension concentrates according to the invention comprise an antifreeze agent from the group of the polyglycerols and polyglycerol derivatives. Polyglycerols and polyglycerol derivatives are described in DE-A 100 23 153. Very particular preference is given to the polyglycerols and polyglycerol derivatives under the trade name Synergen® GL.

The compositions according to the invention optionally comprise further additives from the group of the antifoams, the preservatives, the antioxidants, the spreaders, the colorants and/or the thickeners.

Suitable antifoams are all substances usually employed for this purpose in agrochemical compositions. Preference is given to silicone oils and magnesium stearate.

Suitable preservatives are all substances of this type usually employed for this purpose in agrochemical compositions. Examples which may be mentioned are Preventol® (Lanxess AG) and Proxel®.

Suitable antioxidants are all substances which are usually employed for this purpose in agrochemical compositions. Examples which may be mentioned are: butylated hydroxytoluene (2,6-di-t-butyl-4-methylphenol, BHT), propyl gallate, octyl gallate, dodecyl gallate, butylated hydroxyanisol, propyl paraben, sodium benzoate and nordihydroguaiaretic acid. Preference is given to butylated hydroxytoluene (2,6-di-t-butyl-4-methylphenol, BHT).

Suitable spreaders are all substances which are usually employed for this purpose in agrochemical compositions. Preference is given to polyether- or organo-modifϊed polysiloxanes.

Suitable colorants are all substances which are usually used for this purpose in agrochemical compositions. Examples which may be mentioned are titanium dioxide, pigment-grade carbon black, zinc oxide and blue pigments and also permanent red FGR. Suitable thickeners are all substances of this type which are usually employed in agrochemical compositions. Preference is given to silicates (such as, for example, Atagel ® 50 from Engelhard) or xantan gum (such as, for example, Kelzane ® S from Kelko).

In the context of the present invention, an adjuvant is a substance which improves the uptake of agrochemically active compound via the root in the plant in the test system described below:

A representative number (more than 40) seeds of a selected crop plant (tomato plants, cultivar rentita) are sown individually in cavities of perforated polystyrene tablets filled with special peat culture substrate-based seeding soil. The tablets, which float, are then placed into containers filled with a nutrient solution based on 0.1% Bayfolan^® and cultivated at 25°C, 80% rel. atmospheric humidity and 12 hours of light (Na vapour lamps) until the desired plant size is reached. The solutions comprising the active compound and (potential) adjuvant are added directly to the nutrient solution of individual containers before the tablets are inserted. Twelve and nineteen days after the treatment, the tomato seedlings are harvested and extracted with acetonitrile: water in a ratio of 80:20 (v/v), and the content of imidacloprid and the relevant degradation products is determined quantitatively in a suitable manner using HPLC - MS/MS.

To this end, for example, the extracted samples are examined using an Applied Biosystems API4000 QTrap HPLC-MS/MS in the MRM mould. The HPLC system consists of an Agilent 1100 pump, column oven, degassing unit and a CTC-PAL autosampler. The samples are chromatographed on a Phenomenex GEMINI 3 μm column (length 50 mm, internal diameter 2.1 mm) in the reversed-phase mould using gradient elution (mobile phase consisting of acetonitrile/water/0.1% formic acid). MS conditions for the quantification: 256.1 > 209.2 (ESI+; imidacloprid) and 155.9 > 111.9 (ESI-; 6-CNA). The peak integrals were evaluated using an external standard and a calibration curve (required correlation coefficient r > 0.99). Matrix effects are taken into account by adding a known amount of analyte to an untreated sample. Quantification limit = 1 ng/ml for each analyte.

4 litres of nutrient solution are used per box. The concentration of imidacloprid is 0,1 μg of imidacloprid/ml of nutrient solution (0.1 ppm). The concentration of the adjuvants tested in the nutrient solution is between 2.5 μg/ml and 0.1 mg/ml (2.5 and 100 ppm).

As a control, the same test is carried out without any added potential adjuvant. When the adjuvants according to the invention are used, this test shows an active compound uptake which is increased by at least 20% compared to the control. In this test, the root of the plant is in contact only with the nutrient solution. This excludes that other properties of the adjuvants, such as distribution in the culture substrate, concentration profiles, etc., may have an effect on the uptake via the roots.

Moreover, it was found that the compositions according to the invention can be prepared by mixing the components with one another and, if required, grinding the suspension formed. Accordingly, the invention furthermore provides a process for preparing the compositions according to the invention, which comprises mixing

at least one agrochemically active compound from the group of the insecticidal phthalic acid diamides which is solid at room temperature,

- at least one adjuvant,

at least one non-ionic surfactant and/or at least one anionic surfactant,

at least one antifreeze agent and

one or more additives from the groups of the antifoams, the preservatives, the antioxidants, the spreading agents, the colorants and/or thickeners

and, if required, grinding the suspension formed.

It is extremely surprising that the suspension concentrates according to the invention have a positive effect on the uptake of agrochemically active compounds via the root system. Based on the properties of the plant root described in the literature, this was not to be expected.

It is also surprising that the adjuvants selected using the test system described cause comparable effects in the more complex soil or in other culture substrates.

It is furthermore surprising that the effects of the various adjuvants do not correlate with a lowering of the static surface tension of the spray liquor and consequently do not depend on the mobility in the soil.

Furthermore, it is surprisingly that the adjuvants which improve uptake via the root system do not necessarily increase uptake via the cuticles of the leaves, this being an indication of differing mechanisms of action.

It is furthermore surprising that the use of polyglycol as antifreeze agent shows a synergistic effect in combination with the adjuvants according to the invention, even through no effect on the uptake via the root system was found for polyglycol alone. Finally, it is extremely surprising that the suspension concentrates according to the invention have very good stability. The adjuvants used, like the dispersants of a water-based suspension concentrate, have surface-active properties, which normally results in competition with the dispersants. Especially at high storage temperature or after storage under changing temperature conditions, this results in the suspension concentrate being destabilized. The very good stability of the suspension concentrates according to the invention can be described, for example, by dispersant stability, particle size distribution or the viscosity of the formulations.

Preferred embodiments of the subject-matter of the invention are described below.

It is already known that phthalimides of the formula (II) have insecticidal action. This applies to the racemic form of the compounds (EP-A 1 006 107) and even more so to the (S)-configured enantiomers (WO 06/ 22225).

where

Hal represents chlorine, bromine or iodine,

* denotes a carbon atom in the R- or the S-confϊguration, preferably in the S- configuration.

The formula (II) comprises the following preferred active compounds:

(II-l): (S)-3-iodo-N¹-{2-methyl-4-[l,2,2,2- tetrafluoro- 1 (trifluoromethyl)ethyl]phenyl}- N²-(l-methyl-2- methylsulphonylethyl)phthalamide

(II-2): (S)-3-chloro-N^I-{2-methyl-4-[l,2,2,2- tetrafluoro-l-(trifluoromethyl)ethyl]phenyl}-N²- ( 1 -methyl-2-methylsulphonylethyl)phthalamide

(II-3): (S)-3-bromo-N¹-{2-methyl-4-[l, 2,2,2- tetrafluoro- 1 -(trifluoromethyl)ethyl]phenyl }-N²- (l-methyl-2-methylsulphonylethyl)phthalamide

Examples of adjuvants according to the invention which may be mentioned are especially the following substances and compositions, which are all commercially available:

(1-1) Terminally capped alkoxylated fatty alcohols and terminally capped alkoxylated straight- chain alcohols, commercially available, for example, in the product series Plurafac®; preference is given to ethoxylated and/or butoxylated fatty alcohols and terminally capped ethoxylated and/or butoxylated straight-chain alcohols (where, here and below, "terminally capped" is to be understood as meaning that the terminal hydroxyl groups are alkylated),

(1-2) tributylphenol polyglycol ethers having 10 to 15 EO units (where EO means ethylene oxide), commercially available, for example, in the product series Sapogenat ®,

(1-3) branched alkanol alkoxylates of the formula CH₃-(CH₂),-CH₂-O-(-CH₂-CH₂-O-)_u-H, in which t represents numbers from 9 to 10.5 and u represents numbers from 6 to 25 (preferably from 8 to 12) and t and u are average values, commercially available, for example, in the product series Lutensol ®,

(1-4) polyalkoxylated triglycerides, where the triglyceride is preferably of vegetable origin, commercially available, for example, in the product series Crovol ®,

(1-5) alkoxylated fatty amines, commercially available, for example, in the product series Armoblen®, (1-6) sodium laureth sulphate, commercially available, for example, in the product series Genapol ®,

(1-7) alkoxylated terpenes available, for example, in the product series Rhodoclean®,

(1-8) compositions comprising maize syrup, methylated soya oil and non-ionic emulsifier, commercially available, for example, in the product series Superb®.

Suitable for the methods according to the invention are compositions comprising

at least one active compound selected from the group of the insecticidal phthalic acid diamides,

at least one adjuvant,

- at least one non-ionic surfactant and/or at least one anionic surfactant,

at least one antifreeze agent and

one or more additives from the groups of the antifoams, the preservatives, the antioxidants, the spreading agents, the colorants and/or the thickeners.

In a preferred embodiment, compositions according to the invention comprise:

- at least one active compound from the group of the insecticidal phthalic acid diamides,

at least one substance or composition selected from the group consisting of (1-1) to (1-8),

at least one non-ionic surfactant and/or at least one anionic surfactant,

at least one antifreeze agent and

one or more additives from the groups of the antifoams, the preservatives, the antioxidants, the spreading agents, the colorants and/or thickeners.

The compositions according to the invention comprise

generally from 1 to 60% by weight of one or more of the agrochemically active compounds which may be used according to the invention, preferably from 5 to 50% by weight and particularly preferably from 10 to 30% by weight,

- generally from 1 to 50% by weight of at least one adjuvant according to the invention, preferably from 2 to 30% by weight and particularly preferably from 5 to 20% by weight, generally from 1 to 20% by weight of at least one non-ionic and/or at least one anionic surfactant, preferably from 2.5 to 10% by weight,

generally from 1 to 20% by weight of antifreeze agent, preferably from 5 to 15% by weight,

generally from 0.1 to 20% by weight of additives from the groups of the antifoams, the preservatives, the antioxidants, the spreading agents, the colorants and/or thickeners, preferably from 0.1 to 15% by weight.

In general, preference is given to certain combinations of active compounds and adjuvants listed in the table below, where each combination is preferred per se:

The suspension concentrates according to the invention are prepared by mixing the particular ratios desired of the components with one another. The components may be mixed with one another in any order. Expediently, the solid components are employed in a finely ground state. However, it is also possible to subject the suspension formed after mixing of the components initially to a coarse grinding then to a fine grinding so that the mean particle size is below 20 μm. Preferred are suspension concentrates in which the solid particles have a mean particle size of from 1 to 10 μm.

When carrying out the process according to the invention, the temperatures may be varied within a certain range. In general, the process is carried out at temperatures between 10⁰C and 60⁰C, preferably between 15⁰C and 40⁰C. Suitable for carrying out the process according to the invention are customary mixers and grinders employed for producing agrochemical formulations.

The compositions according to the invention are formulations which are stable even after prolonged storage at elevated temperatures or in the cold, since no crystal growth is observed. By dilution with water, they can be converted into homogeneous spray liquors.

The application rate of the compositions according to the invention can be varied within a relatively wide range. It depends on the agrochemically active compounds in question and their content in the compositions.

The compositions of the invention, in combination with good plant tolerance, favourable toxicity to warm-blooded animals and high compatibility with the environment, are suitable for protecting plants and plant organs, for increasing the harvest yields, for improving the quality of the harvested material and for controlling animal pests, more particularly insects, arachnids, helminths, nematodes and molluscs, which are encountered in agriculture, in horticulture, in animal husbandry, in forests, in gardens and leisure facilities, in the protection of stored products and materials and in the hygiene sector. They may be preferably employed as crop protection agents.

They are active against normally sensitive and resistant species and against all or some stages of development. The abovementioned pests include:

From the order of the Anoplura (Phthiraptera), for example, Damalinia spp., Haematopinus spp., Linognathus spp., Pediculus spp., Trichodectes spp.

From the class of the Arachnida, for example, Acarus siro, Aceria sheldoni, Aculops spp., Aculus spp., Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Chorioptes spp., Dermanyssus gallinae, Eotetranychus spp., Epitrimerus pyri, Eutetranychus spp., Eriophyes spp., Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Latrodectus mactans, Metatetranychus spp., Oligonychus spp., Ornithodoros spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Scorpio maurus, Stenotarsonemus spp., Tarsonemus spp., Tetranychus spp., Vasates lycopersici.

From the class of the Bivalva, for example, Dreissena spp.

From the order of the Chilopoda, for example, Geophilus spp., Scutigera spp.

From the order of the Coleoptera, for example, Acanthoscelides obtectus, Adoretus spp., Agelastica alni, Agriotes spp., Amphimallon solstitialis, Anobium punctatum, Anoplophora spp., Anthonomus spp., Anthrenus spp., Apogonia spp., Atomaria spp., Attagenus spp., Bruchidius obtectus, Bruchus spp., Ceuthorhynchus spp., Cleonus mendicus, Conoderus spp., Cosmopolites spp., Costelytra zealandica, Curculio spp., Cryptorhynchus lapathi, Dermestes spp., Diabrotica spp., Epilachna spp., Faustinus cubae, Gibbium psylloides, Heteronychus arator, Hylamorpha elegans, Hylotrupes bajulus, Hypera postica, Hypothenemus spp., Lachnosterna consanguinea, Leptinotarsa decemlineata, Lissorhoptrus oryzophilus, Lixus spp., Lyctus spp., Meligethes aeneus, Melolontha melolontha, Migdolus spp., Monochamus spp., Naupactus xanthographus, Niptus hololeucus, Oryctes rhinoceros, Oryzaephilus surinamensis, Otiorrhynchus sulcatus, Oxycetonia jucunda, Phaedon cochleariae, Phyllophaga spp., Popillia japonica, Premnotrypes spp., Psylliodes chrysocephala, Ptinus spp., Rhizobius ventralis, Rhizopertha dominica, Sitophilus spp., Sphenophorus spp., Sternechus spp., Symphyletes spp., Tenebrio molitor, Tribolium spp., Trogo- derma spp., Tychius spp., Xylotrechus spp., Zabrus spp.

From the order of the Collembola, for example, Onychiurus armatus.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Diplopoda, for example, Blaniulus guttulatus.

From the order of the Diptera, for example, Aedes spp., Anopheles spp., Bibio hortulanus, Calliphora erythrocephala, Ceratitis capitata, Chrysomyia spp., Cochliomyia spp., Cordylobia anthropophaga, Culex spp., Cuterebra spp., Dacus oleae, Dermatobia hominis, Drosophila spp., Fannia spp., Gastrophilus spp., Hylemyia spp., Hyppobosca spp., Hypoderma spp., Liriomyza spp., Lucilia spp., Musca spp., Nezara spp., Oestrus spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Stomoxys spp., Tabanus spp., Tannia spp., Tipula paludosa, Wohlfahrtia spp.

From the class of the Gastropoda, for example, Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Succinea spp.

From the class of the helminths, for example, Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., Ascaris lubricoides, Ascaris spp., Brugia malayi,

Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp., Cooperia spp., Dicrocoelium spp, Dictyocaulus filaria, Diphyllobothrium latum, Dracunculus medinensis, Echinococcus granulosus, Echinococcus multilocularis, Enterobius vermicularis, Faciola spp., Haemonchus spp.,

Heterakis spp., Hymenolepis nana, Hyostrongulus spp., Loa Loa, Nematodirus spp., Oesophagostomum spp., Opisthorchis spp., Onchocerca volvulus, Ostertagia spp., Paragonimus spp., Schistosomen spp., Strongyloides fuelleborni, Strongyloides stercoralis, Stronyloides spp.,

Taenia saginata, Taenia solium, Trichinella spiralis, Trichinella nativa, Trichinella britovi, Trichinella nelsoni, Trichinella pseudopsiralis, Trichostrongulus spp., Trichuris trichuria, Wuchereria bancrofti.

It is further possible to control protozoa, such as Eimeria.

From the order of the Heteroptera, for example, Anasa tristis, Antestiopsis spp., Blissus spp., Calocoris spp., Campylomma livida, Cavelerius spp., Cimex spp., Creontiades dilutus, Dasynus piperis, Dichelops furcatus, Diconocoris hewetti, Dysdercus spp., Euschistus spp., Eurygaster spp.,

Heliopeltis spp., Horcias nobilellus, Leptocorisa spp., Leptoglossus phyllopus, Lygus spp.,

Macropes excavatus, Miridae, Nezara spp., Oebalus spp., Pentomidae, Piesma quadrata,

Piezodorus spp., Psallus seriatus, Pseudacysta persea, Rhodnius spp., Sahlbergella singularis, Scotinophora spp., Stephanitis nashi, Tibraca spp., Triatoma spp.

From the order of the Homoptera, for example, Acyrthosipon spp., Aeneolamia spp., Agonoscena spp., Aleurodes spp., Aleurolobus barodensis, Aleurothrixus spp., Amrasca spp., Anuraphis cardui, Aonidiella spp., Aphanostigma piri, Aphis spp., Arboridia apicalis, Aspidiella spp., Aspidiotus spp., Atanus spp., Aulacorthum solani, Bemisia spp., Brachycaudus helichrysii, Brachycolus spp., Brevicoryne brassicae, Calligypona marginata, Carneocephala fulgida, Ceratovacuna lanigera, Cercopidae, Ceroplastes spp., Chaetosiphon fragaefolii, Chionaspis tegalensis, Chlorita onukii, Chromaphis juglandicola, Chrysomphalus ficus, Cicadulina mbila, Coccomytilus halli, Coccus spp., Cryptomyzus ribis, Dalbulus spp., Dialeurodes spp., Diaphorina spp., Diaspis spp., Doralis spp., Drosicha spp., Dysaphis spp., Dysmicoccus spp., Empoasca spp., Eriosoma spp., Erythroneura spp., Euscelis bilobatus, Geococcus coffeae, Homalodisca coagulata, Hyalopterus arundinis, Icerya spp., Idiocerus spp., Idioscopus spp., Laodelphax striatellus, Lecanium spp., Lepidosaphes spp., Lipaphis erysimi, Macrosiphum spp., Mahanarva fimbriolata, Melanaphis sacchari, Metcalfiella spp., Metopolophium dirhodum, Monellia costalis, Monelliopsis pecanis, Myzus spp., Nasonovia ribisnigri, Nephotettix spp., Nilaparvata lugens, Oncometopia spp., Orthezia praelonga, Parabemisia myricae, Paratrioza spp., Parlatoria spp., Pemphigus spp., Pere- grinus maidis, Phenacoccus spp., Phloeomyzus passerinii, Phorodon humuli, Phylloxera spp., Pinnaspis aspidistrae, Planococcus spp., Protopulvinaria pyriformis, Pseudaulacaspis pentagona, Pseudococcus spp., Psylla spp., Pteromalus spp., Pyrilla spp., Quadraspidiotus spp., Quesada gigas, Rastrococcus spp., Rhopalosiphum spp., Saissetia spp., Scaphoides titanus, Schizaphis graminum, Selenaspidus articulatus, Sogata spp., Sogatella furcifera, Sogatodes spp., Stictocephala festina, Tenalaphara malayensis, Tinocallis caryaefoliae, Tomaspis spp., Toxoptera spp., Tri- aleurodes vaporariorum, Trioza spp., Typhlocyba spp., Unaspis spp., Viteus vitifolii.

From the order of the Hymenoptera, for example, Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp. From the order of the Isopoda, for example, Armadillidium vulgare, Oniscus asellus, Porcellio scaber.

From the order of the Isoptera, for example, Reticulitermes spp., Odontotermes spp.

From the order of the Lepidoptera, for example, Acronicta major, Aedia leucomelas, Agrotis spp., Alabama argillacea, Anticarsia spp., Barathra brassicae, Bucculatrix thurberiella, Bupalus piniarius, Cacoecia podana, Capua reticulana, Carpocapsa pomonella, Cheimatobia brumata, Chilo spp., Choristoneura fumiferana, Clysia ambiguella, Cnaphalocerus spp., Earias insulana, Ephestia kuehniella, Euproctis chrysorrhoea, Euxoa spp., Feltia spp., Galleria mellonella, Helicoverpa spp., Heliothis spp., Hofmannophila pseudospretella, Homona magnanima, Hyponomeuta padella, Laphygma spp., Lithocolletis blancardella, Lithophane antennata, Loxagrotis albicosta, Lymantria spp., Malacosoma neustria, Mamestra brassicae, Mocis repanda, Mythimna separata, Oria spp., Oulema oryzae, Panolis flammea, Pectinophora gossypiella, Phyllocnistis citrella, Pieris spp., Plutella xylostella, Prodenia spp., Pseudaletia spp., Pseudoplusia includens, Pyrausta nubilalis, Spodoptera spp., Thermesia gemmatalis, Tinea pellionella, Tineola bisselliella, Tortrix viridana, Trichoplusia spp.

From the order of the Orthoptera, for example, Acheta domesticus, Blatta orientalis, Blattella germanica, Gryllotalpa spp., Leucophaea maderae, Locusta spp., Melanoplus spp., Periplaneta americana, Schistocerca gregaria.

From the order of the Siphonaptera, for example, Ceratophyllus spp., Xenopsylla cheopis.

From the order of the Symphyla, for example, Scutigerella immaculata.

From the order of the Thysanoptera, for example, Baliothrips biformis, Enneothrips flavens, Frankliniella spp., Heliothrips spp., Hercinothrips femoralis, Kakothrips spp., Rhipiphorothrips cruentatus, Scirtothrips spp., Taeniothrips cardamoni, Thrips spp.

From the order of the Thysanura, for example, Lepisma saccharina.

The phytoparasitic nematodes include, for example, Anguina spp., Aphelenchoides spp., Belonoaimus spp., Bursaphelenchus spp., Ditylenchus dipsaci, Globodera spp., Heliocotylenchus spp., Heterodera spp., Longidorus spp., Meloidogyne spp., Pratylenchus spp., Radopholus similis, Rotylenchus spp., Trichodorus spp., Tylenchorhynchus spp., Tylenchulus spp., Tylenchulus semipenetrans, Xiphinema spp.

If appropriate, the compositions according to the invention can, at certain concentrations or application rates, also be used as herbicides, safeners, growth regulators or agents to improve plant properties, or as microbicides, for example as fungicides, antimycotics, bactericides, viricides (including agents against viroids) or as agents against MLO (Mycoplasma-like organisms) and RLO (Rickettsia-like organisms).

The compositions of the invention can in addition to the abovementioned agrochemical active compounds comprise other active compounds as mixing partners, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth-regulating substances, herbicides, safeners, fertilizers or semiochemicals.

Particularly favourable mixing partners are, for example, the following:

Fungicides: Inhibitors of nucleic acid synthesis

benalaxyl, benalaxyl-M, bupirimate, chiralaxyl, clozylacon, dimethirimol, ethirimol, furalaxyl, hymexazol, mefenoxam, metalaxyl, metalaxyl-M, ofurace, oxadixyl, oxolinic acid

Inhibitors of mitosis and cell division

benomyl, carbendazim, diethofencarb, ethaboxam, fuberidazole, pencycuron, thiabendazole, thiophanate-methyl, zoxamide

Inhibitors of respiratory chain complex I

diflumetorim

Inhibitors of respiratory chain complex II

boscalid, carboxin, fenfuram, flutolanil, furametpyr, furmecyclox, mepronil, oxycarboxin, penthiopyrad, thifluzamide

Inhibitors of respiratory chain complex HI

azoxystrobin, cyazofamid, dimoxystrobin, enestrobin, famoxadone, fenamidone, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, pyraclostrobin, picoxystrobin, trifloxystrobin

Decouplers

dinocap, fluazinam

Inhibitors of ATP production fentin acetate, fentin chloride, fentin hydroxide, silthiofam

Inhibitors of amino acid biosynthesis and protein biosynthesis

andoprim, blasticidin-S, cyprodinil, kasugamycin, kasugamycin hydrochloride hydrate, mepanipyrim, pyrimethanil

Inhibitors of signal transduction

fenpiclonil, fludioxonil, quinoxyfen

Inhibitors of lipid and membrane synthesis

chlozolinate, iprodione, procymidone, vinclozolin

ampropylfos, potassium-ampropylfos, edifenphos, etridiazole, iprobenfos (EBP), isoprothiolane, pyrazophos

tolclofos-methyl, biphenyl

iodocarb, propamocarb, propamocarb hydrochloride, propamocarb-fosetylate

Inhibitors of ergosterol biosynthesis

fenhexamid,

azaconazole, bitertanol, bromuconazole, cyproconazole, diclobutrazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, etaconazole, fenarimol, fenbuconazole, fluquinconazole, flurprimidole, flusilazole, flutriafol, furconazole, furconazole-cis, hexaconazole, imazalil, imazalil sulphate, imibenconazole, ipconazole, metconazole, myclobutanil, nuarimol, oxpoconazole, paclobutrazole, penconazole, pefurazoate, prochloraz, propiconazole, prothioconazole, pyrifenox, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole, triforine, triticonazole, uniconazole, voriconazole, viniconazole,

aldimorph, dodemoφh, dodemoφh acetate, fenpropidin, fenpropimorph, spiroxamine, tridemoφh,

naftifme, pyributicarb, terbinafine

Inhibitors of cell wall synthesis

benthiavalicarb, bialaphos, dimethomoφh, flumoφh, iprovalicarb, mandipropamid, polyoxins, polyoxorim, validamycin A Inhibitors of melanin biosynthesis

capropamid, diclocymet, fenoxanil, phthalid, pyroquilon, tricyclazole

Resistance inductors

acibenzolar-S-methyl, probenazole, tiadinil

Multisite

captafol, captan, chlorothalonil, copper salts such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulphate, copper oxide, oxine-copper and Bordeaux mixture, dichlofluanid, dithianon, dodine, dodine free base, ferbam, folpet, fluorofolpet, guazatine, guazatine acetate, iminoctadine, iminoctadine albesilate, iminoctadine triacetate, mancopper, mancozeb, maneb, metiram, metiram zinc, propineb, sulphur and sulphur preparations containing calcium polysulphide, thiram, tolylfluanid, zineb, ziram

Further fungicides

amibromdol, benthiazole, bethoxazin, capsimycin, carvone, quinomethionate, chloropicrin, cufraneb, cyflufenamid, cymoxanil, dazomet, debacarb, diclomezine, dichlorophen, dicloran, difenzoquat, difenzoquat metilsulphate, diphenylamine, ferimzone, fiumetover, flusulfamide, fluopicolide, fluoroimide, fosetyl-aluminium, fosetyl-calcium, fosetyl-sodium, hexachlorobenzene, 8-hydroxyquinoline sulphate, irumamycin, methasulfocarb, metrafenone, methyl isothiocyanate, mildiomycin, natamycin, nickel dimethyl dithiocarbamate, nitrothal- isopropyl, octhilinone, oxamocarb, oxyfenthiin, pentachlorophenol and salts, 2-phenylphenol and salts, piperalin, propanosine-sodium, proquinazid, pyribencarb, pyrrolnitrin, quintozene, tecloftalam, tecnazene, triazoxide, trichlamide, valiphenal, zarilamid,

2-(2- { [6-(3-chloro-2-methylphenoxy)-5-fluoropyrimidin-4-yl]oxy} phenyl)-2- (methoxyimino)-N-methylacetamide,

2-[[[[l-[3-(l-fluoro-2-phenylethyl)oxy]phenyl]ethylidene]amino]oxy]methyl]-alpha- (methoxyimino)-N-methyl-alpha-benzacetamide,

cis- 1 -(4-chlorophenyl)-2-( 1 H- 1 ,2,4-triazol- 1 -yl)cycloheptanol,

1 -[(4-methoxyphenoxy)methyl]-2,2-dimethylpropyl- 1 H-imidazole- 1 -carboxylic acid,

2,3,5,6-tetrachloro-4-(methylsulphonyl)pyridine,

2-butoxy-6-iodo-3-propylbenzopyranon-4-one, 2-chloro-N-(2,3-dihydro- 1 , 1 ,3-trimethyl- 1 H-inden-4-yl)-3-pyridinecarboxamide,

3,4,5-trichloro-2,6-pyridinedicarbonitrile,

3,4-dichloro-N-(2-cyanophenyl)isothiazole-5-carboxamide (isotianil)

3-[5-(4-chlorophenyl)-2,3-dimethylisoxazolidin-3-yl]pyridine,

5-chloro-6-(2,4,6-trifluorophenyl)-N-[( IR)- 1,2,2- trimethylpropyl] [ 1 ,2,4]triazolo[ 1 ,5-a]pyrimidine-7-amine,

5-chloro-7-(4-methylpiperidin- 1 -yl)-6-(2,4,6-trifluorophenyl)[ 1 ,2,4]triazolo[ 1 ,5-a]pyrimidine,

5-chloro-N-[(lR)-l,2-dimethylpropyl]-6-(2,4,6-trifluorophenyl) [l,2,4]triazolo[l,5- a]pyrimidine-7-amine,

methyl 2-[[[cyclopropyl [(4-methoxyphenyl)imino]methyl]thio]methyl]-alpha-

(methoxymethylene) benzacetate,

methyl l-(2,3-dihydro-2,2-dimethyl-lH-inden-l-yl)-lH-imidazole-5-carboxylate,

N-(3',4'-dichloro-5-fluorobiphenyl-2-yl)-3 -(difluoromethyl)- 1 -methyl- 1 H-pyrazole-4- carboxamide,

N-(3-ethyl-3,5,5-trimethylcyclohexyl)-3-formylamino-2-hydroxy benzamide,

N-(4-chloro-2-nitrophenyl)-N-ethyl-4-methylbenzenesulphonamide,

N-(4-chlorobenzyl)-3-[3-methoxy-4-(prop-2-yn-l-yloxy)phenyl]propanamide,

N-[(4-chlorophenyl)(cyano)methyl]-3-[3-methoxy-4-(prop-2-yn-l- yloxy)phenyl]propanamide,

N-(5-bromo-3-chloropyridin-2-yl)methyl-2,4-dichloronicotinamide,

N-[l-(5-bromo-3-chloropyridin-2-yl)ethyl]-2,4-dichloronicotinamide,

(2S)-N-[2-[4-[[3-(4-chlorophenyl)-2-propynyl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2- [(methylsulphonyl)amino] butanamide,

N-{(Z)-[(cyclopropylmethoxy)imino][6-(difluoromethoxy)-2,3-difluorophenyl]methyl}-2- benzacetamide,

N-{2-[l,l'-bi(cyclopropyl)-2-yl]phenyl}-3-(difluoromethyl)-l-methyl-lH-pyrazole-4- carboxamide, N-{2-[3-chloro-5-(trifluoromethyl)pyridin-2-yl]ethyl}-2-(trifluoromethyl)benzamide,

N-ethyl-N-methyl-N'-{2-methyl-5-(trifluoromethyl>4-[3- (trimethylsilyl)propoxy]phenyl}imidoform amide,

O-[l -[(4-methoxyphenoxy)methyl]-2,2-dimethylpropyl]- 1 H-imidazole- 1 -carbothioic acid,

2-amino-4-methyl-N-phenyl-5-thiazolecarboxamide,

2,4-dihydro-5-methoxy-2-methyl-4-[[[[l-[3-(trifluoromethyl)phenyl]ethylidene]amino]oxy] methyl]phenyl]-3H-l,2,4-triazol-3-one (CAS No. 185336-79-2),

N-tό-methoxy-S-pyridinylJcyclopropane carboxamide,

Bactericides:

bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulphate and other copper preparations.

Insecticides/acaricides/nematicides:

Acetylcholine esterase (AChE) inhibitors

Carbamates, for example alanycarb, aldicarb, aldoxycarb, allyxycarb, aminocarb, bendiocarb, benfuracarb, bufencarb, butacarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, cloethocarb, dimetilan, ethiofencarb, fenobucarb, fenothiocarb, formetanate, furathiocarb, isoprocarb, metam-sodium, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, promecarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb, triazamate

Organophosphates, for example acephate, azamethiphos, azinphos (-methyl, -ethyl), bromophos-ethyl, bromfenvinfos (-methyl), butathiofos, cadusafos, carbophenothion, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos (-methyl/-ethyl), coumaphos, cyanofenphos, cyanophos, chlorfenvinphos, demeton-S-methyl, demeton-S-methylsulphone, dialifos, diazinon, dichlofenthion, dichlorvos/DDVP, dicrotophos, dimethoate, dimethylvinphos, dioxabenzofos, disulfoton, EPN, ethion, ethoprophos, etrimfos, famphur, fenamiphos, fenitrothion, fensulfothion, fenthion, flupyrazofos, fonofos, formothion, fosmethilan, fosthiazate, heptenophos, iodofenphos, iprobenfos, isazofos, isofenphos, isopropyl O-salicylate, isoxathion, malathion, mecarbam, methacrifos, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion (-methyl/-ethyl), phenthoate, phorate, phosalone, phosmet, phosphamidon, phosphocarb, phoxim, pirimiphos (-methylAethyl), profenofos, propaphos, propetamphos, prothiofos, prothoate, pyraclofos, pyridaphenthion, pyridathion, quinalphos, sebufos, sulfotep, sulprofos, tebupirimfos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, triclorfon, vamidothion

Sodium channel modulators / voltage-dependent sodium channel blockers

Pyrethroids, for example acrinathrin, allethrin (d-cis-trans, d-trans), beta-cyfluthrin, bifenthrin, bioallethrin, bioallethrin-S-cyclopentyl isomer, bioethanomethrin, biopermethrin, bioresmethrin, chlovaporthrin, cis-cypermethrin, cis-resmethrin, cis-peπnethrin, clocythrin, cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin (alpha-, beta-, theta-, zeta-), cyphenothrin, deltamethrin, empenthrin (lR-isomer), esfenvalerate, etofenprox, fenfluthrin, fenpropathrin, fenpyrithrin, fenvalerate, flubrocythrinate, flucythrinate, flufenprox, flumethrin, fluvalinate, fubfenprox, gamma-cyhalothrin, imiprothrin, kadethrin, lambda-cyhalothrin, metofluthrin, permethrin (cis-, trans-), phenothrin (IR- trans-isomer), prallethrin, profluthrin, protrifenbute, pyresmethrin, resmethrin, RU 15525, silafluofen, tau-fluvalinate, tefluthrin, terallethrin, tetramethrin (IR isomer), tralomethrin, transfluthrin, ZXI 8901, pyrethrins (pyrethrum)

DDT

Oxadiazines, for example indoxacarb

Semicarbazone, for example metafiumizon (BAS3201)

Acetylcholine receptor agonists/antagonists Chloronicotinyls, for example acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, nithiazine, thiacloprid, thiamethoxam,

Nicotine, bensultap, cartap

Acetylcholine receptor modulators

Spinosyns, for example spinosad and spinetoram

GABA-controlled chloride channel antagonists

Organochlorines, for example camphechlor, chlordane, endosulfan, gamma-HCH, HCH, heptachlor, lindane, methoxychlor

Fiprols, for example acetoprole, ethiprole, fipronil, pyrafluprole, pyriprole, vaniliprole

Chloride channel activators

Mectins, for example abamectin, emamectin, emamectin-benzoate, ivermectin, lepimectin, milbemycin

Juvenile hormone mimetics,

for example diofenolan, epofenonane, fenoxycarb, hydroprene, kinoprene, methoprene, pyriproxifen, triprene

Ecdysone agonists/disruptors

Diacylhydrazines, for example chromafenozide, halofenozide, methoxyfenozide, tebufenozide

Chitin biosynthesis inhibitors Benzoylureas, for example bistrifluron, chlofluazuron, diflubenzuron, fluazuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, penfluron, teflubenzuron, triflumuron

Buprofezin

Cyromazine

Oxidative phosphorylation inhibitors, ATP disruptors

Diafenthiuron

Organotin compounds, for example azocyclotin, cyhexatin, fenbutatin-oxide

Oxidative phosphorylation decouplers acting by interrupting the H-proton gradient

Pyrroles, for example chlorfenapyr

Dinitrophenols, for example binapacryl, dinobuton, dinocap, DNOC, meptyldinocap

Site-I electron transport inhibitors

METI's, for example fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad, tolfenpyrad

Hydramethylnon

Dicofol

Site-II electron transport inhibitors Rotenone

Site-Ill electron transport inhibitors

Acequinocyl, fluacrypyrim

Microbial disruptors of the insect gut membrane

Bacillus thuringiensis strains

Lipid synthesis inhibitors

Tetronic acids, for example spirodiclofen, spiromesifen

Tetramic acids, for example spirotetramat, cis-3-(2,5-dimethylphenyl)-4-hydroxy-8-methoxy-l- azaspiro [4.5 ] dec-3 -en-2-one

Carboxamides, for example flonicamid

Octopaminergic agonists, for example amitraz

Inhibitors of magnesium-stimulated ATPase,

Propargite

Nereistoxin analogues, for example thiocyclam hydrogen oxalate, thiosultap-sodium

Ryanodine receptor agonists,

Benzodicarboxamides, for example flubendiamide Anthranilamides, for example Rynaxypyr (3-bromo-N-{4-chloro-2-methyl-6-[(methylamino)carbonyl]- phenyl}-l-(3-chIoropyridin-2-yI)-lH-pyrazole-5-carboxamide)

Biologicals, hormones or pheromones

azadirachtin, Bacillus spec, Beauveria spec, codlemone, Metarrhizium spec, Paecilomyces spec, thuringiensin, Verticillium spec.

Active compounds with unknown or unspecific mechanisms of action

Fumigants, for example aluminium phosphide, methyl bromide, sulphuryl fluoride

Antifeedants, for example cryolite, flonicamid, pymetrozine

Mite growth inhibitors, for example clofentezine, etoxazole, hexythiazox

Amidoflumet, benclothiaz, benzoximate, bifenazate, bromopropylate, buprofezin, chinomethionat, chlordimeform, chlorobenzilate, chloropicrin, clothiazoben, cycloprene, cyflumetofen, dicyclanil, fenoxacrim, fentrifanil, flubenzimine, fiufenerim, flutenzin, gossyplure, hydramethylnone, japonilure, metoxadiazone, petroleum, piperonyl butoxide, potassium oleate, pyridalyl, sulfluramid, tetradifon, tetrasul, triarathene, verbutin

A mixture with other known active compounds, such as herbicides, fertilizers, growth regulators, safeners, semiochemicals, or else with agents for improving the plant properties, is also possible.

When used as insecticides, the compositions according to the invention can furthermore be present in their commercially available formulations and in the use forms, prepared from these formulations, as a mixture with synergistic agents. Synergistic agents are compounds which increase the action of the active compounds present in the compositions according to the invention, without it being necessary for the synergistic agent added to be active itself. When used as insecticides, the compositions according to the invention can furthermore be present in their commercially available formulations and in the use forms, prepared from these formulations, as a mixture with inhibitors which reduce degradation of the agrochemically active compound present after use in the environment of the plant, on the surface of parts of plants or in plant tissues.

The active compound content of the use forms prepared from the commercially available formulations can vary within wide limits. The active compound concentration of the use forms can be from 0.00000001 to 95% by weight of active compound, preferably between 0.00001 and 1% by weight.

The compounds are employed in a customary manner appropriate for the use forms.

All plants and plant parts can be treated in accordance with the invention. Plants are to be understood as meaning in the present context all plants and plant populations such as desired and undesired wild plants or crop plants (including naturally occurring crop plants). Crop plants can be plants which can be obtained by conventional plant breeding and optimization methods or by biotechnological and genetic engineering methods or by combinations of these methods, including the transgenic plants and including the plant cultivars protectable or not protectable by plant breeders' rights. Plant parts are to be understood as meaning all parts and organs of plants above and below the ground, such as shoot, leaf, flower and root, examples which may be mentioned being leaves, needles, stalks, stems, flowers, fruit bodies, fruits, seeds, roots, tubers and rhizomes.

The plant parts also include harvested material, and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, offshoots and seeds.

Treatment according to the invention of the plants and plant parts with the compositions is carried out by watering.

As already mentioned above, it is possible to treat all plants and their parts according to the invention. In a preferred embodiment, wild plant species and plant cultivars, or those obtained by conventional biological breeding methods, such as crossing or protoplast fusion, and parts thereof, are treated. In a further preferred embodiment, transgenic plants and plant cultivars obtained by genetic engineering methods, if appropriate in combination with conventional methods

(Genetically Modified Organisms), and parts thereof are treated. The terms "parts", "parts of plants" and "plant parts" have been explained above.

With particular preference, plants of the plant cultivars which are in each case commercially available or in use are treated according to the invention. Plant cultivars are to be understood as meaning plants having novel properties ("traits") which have been obtained by conventional breeding, by mutagenesis or by recombinant DNA techniques. They can be cultivars, bio- and genotypes.

Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, vegetation period, diet), the treatment according to the invention may also result in superadditive ("synergistic") effects. Thus, for example, reduced application rates and/or expansions of the activity spectrum and/or a boost to the activity of the compounds and compositions which can be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, higher quality and/or higher nutritional value of the harvested products, better keeping properties and/or processability of the harvested products are possible, which exceed the effects which were actually to be expected.

The transgenic plants or plant cultivars (obtained by genetic engineering) which are preferably to be treated according to the invention include all plants which, by virtue of the genetic modification, received genetic material which imparts particularly advantageous, useful traits to these plants. Examples of such traits are better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, higher quality and/or a higher nutritional value of the harvested products, better keeping properties and/or processability of the harvested products. Further and particularly emphasized examples of such traits are a better defence of the plants against animal and microbial pests, such as against insects, mites, phytopathogenic fungi, bacteria and/or viruses, and also increased tolerance of the plants to certain herbicidally active compounds. Examples of transgenic plants which may be mentioned are the important crop plants, such as cereals (wheat, rice), maize, soya beans, potatoes, sugar beet, tomatoes, peas and other vegetable varieties, cotton, tobacco, oilseed rape and also fruit plants (with the fruits apples, pears, citrus fruits and grapes), and particular emphasis is given to maize, soya beans, potatoes, cotton, tobacco and oilseed rape. Traits that are emphasized in particular are increased defence of the plants against insects, arachnids, nematodes and slugs and snails by virtue of toxins formed in the plants, in particular those formed in the plants by the genetic material from Bacillus thuringiensis (for example by the genes CryΙA(a), CryΙA(b), CryΙA(c), CryllA, CrylllA, CryIIIB2, Cry9c, Cry2Ab, Cry3Bb and CryIF and also combinations thereof) (referred to hereinbelow as "Bt plants"). Traits that are also particularly emphasized are the increased defence of the plants against fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins. Traits that are further particularly emphasized are the increased tolerance of the plants to certain herbicidally active compounds, for example imidazolinones, sulphonylureas, glyphosate or phosphinotricin (for example the "PAT" gene). The genes which impart the desired traits in question can also be present in combination with one another in the transgenic plants. Examples of "Bt plants" which may be mentioned are maize varieties, cotton varieties, soya bean varieties and potato varieties which are sold under the trade names YIELD GARD® (for example maize, cotton, soya beans), KnockOut® (for example maize), StarLink® (for example maize), Bollgard® (cotton), Nucotn® (cotton) and NewLeaf® (potato). Examples of herbicide-tolerant plants which may be mentioned are maize varieties, cotton varieties and soya bean varieties which are sold under the trade names Roundup Ready® (tolerance to glyphosate, for example maize, cotton, soya beans), Liberty Link® (tolerance to phosphinotricin, for example oilseed rape), IMI® (tolerance to imidazolinones) and STS® (tolerance to sulphonylureas, for example maize). Herbicide-resistant plants (plants bred in a conventional manner for herbicide tolerance) which may be mentioned include the varieties sold under the name Clearfield® (for example maize). Of course, these statements also apply to plant cultivars which have these genetic traits, or genetic traits still to be developed, and which will be developed and/or marketed in the future.

The plants listed can be treated according to the invention in a particularly advantageous manner with the compositions of the invention. The preferred ranges stated above for the compositions also apply to the treatment of these plants. Particular emphasis is given to the treatment of plants with the compositions specifically mentioned in the present text.

The compositions according to the invention act not only against plant, hygiene and stored product pests, but also in the veterinary medicine sector against animal parasites (ecto- and endoparasites), such as hard ticks, soft ticks, mange mites, leaf mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, feather lice and fleas. These parasites include:

From the order of the Anoplurida, for example, Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp..

From the order of the Mallophagida and the suborders Amblycerina and Ischnocerina, for example, Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp..

From the order of the Diptera and the suborders Nematocerina and Brachycerina, for example, Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus s snpnp., F HTiinpnpoohbnossccaa s snpnp., T L.iinpnonptteennaa s snpnp., M Meellnonphhaagcmucs s snpnp.

From the order of the Siphonapterida, for example, Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp..

From the order of the Heteropterida, for example, Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp..

From the order of the Blattarida, for example, Blatta orientalis, Periplaneta americana, Blattela germanica, Supella spp..

From the subclass of the Acari (Acarina) and the orders of the Meta- and Mesostigmata, for example, Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp., Varroa spp..

From the order of the Actinedida (Prostigmata) and Acaridida (Astigmata), for example, Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., Laminosioptes spp..

The compositions according to the invention are also suitable for controlling arthropods which infest agricultural productive livestock, such as, for example, cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese and bees, other pets, such as, for example, dogs, cats, caged birds and aquarium fish, and also so-called test animals, such as, for example, hamsters, guinea pigs, rats and mice. By controlling these arthropods, cases of death and reduction in productivity (for meat, milk, wool, hides, eggs, honey etc.) should be diminished, so that more economic and easier animal husbandry is possible by use of the compositions according to the invention.

The compositions according to the invention are used in the veterinary sector and in animal husbandry in a known manner by enteral administration in the form of, for example, tablets, capsules, potions, drenches, granules, pastes, boluses, the feed-through process and suppositories, by parenteral administration, such as, for example, by injection (intramuscular, subcutaneous, intravenous, intraperitoneal and the like), implants by nasal administration, by dermal use in the form, for example, of dipping or bathing, spraying, pouring on and spotting on, washing and powdering, and also with the aid of moulded articles containing the active compound, such as collars, ear marks, tail marks, limb bands, halters, marking devices and the like.

When used for cattle, poultry, pets and the like, the compositions of the formula (I) can be used as formulations (for example powders, emulsions, free-flowing compositions), which comprise the active compounds in an amount of 1 to 80% by weight, directly or after 100 to 10 000-fold dilution, or they can be used as a chemical bath.

It has furthermore been found that the compositions according to the invention also have a strong insecticidal action against insects which destroy industrial materials.

The following insects may be mentioned as examples and as preferred - but without any limitation:

Beetles, such as Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthes rugicollis, Xyleborus spec. Tryptodendron spec. Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. Dinoderus minutus;

Hymenopterons, such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur;

Termites, such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus;

Bristletails, such as Lepisma saccharina.

Industrial materials in the present connection are to be understood as meaning non-living materials, such as, preferably, plastics, adhesives, sizes, papers and cardboards, leather, wood and processed wood products and coating compositions. The ready-to-use compositions may, if appropriate, comprise further insecticides and, if appropriate, one or more fungicides.

With respect to possible additional additives, reference may be made to the insecticides and fungicides mentioned above.

The compositions according to the invention can likewise be employed for protecting objects which come into contact with saltwater or brackish water, such as hulls, screens, nets, buildings, moorings and signalling systems, against fouling.

Furthermore, the compositions according to the invention, alone or in combination with other active compounds, may be employed as antifouling agents

In domestic, hygiene and stored-product protection, the compositions are also suitable for controlling animal pests, particularly insects, arachnids and mites, which are found in enclosed spaces such as, for example, dwellings, factory halls, offices, vehicle cabins and the like. They can be employed alone or in combination with other active compounds and auxiliaries in domestic insecticide products for controlling these pests. They are active against sensitive and resistant species and against all developmental stages. These pests include:

From the order of the Scorpionidea, for example, Buthus occitanus.

From the order of the Acarina, for example, Argas persicus, Argas reflexus, Bryobia ssp., Dermanyssus gallinae, Glyciphagus domesticus, Ornithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi, Neutrombicula autumnalis, Dermatophagoides pteronissimus, Dermatophagoides forinae.

From the order of the Araneae, for example, Aviculariidae, Araneidae.

From the order of the Opiliones, for example, Pseudoscorpiones chelifer, Pseudoscorpiones cheiridium, Opiliones phalangium.

From the order of the Isopoda, for example, Oniscus asellus, Porcellio scaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus, Polydesmus spp.

From the order of the Chilopoda, for example, Geophilus spp.

From the order of the Zygentoma, for example, Ctenolepisma spp., Lepisma saccharina, Lepismodes inquilinus.

From the order of the Blattaria, for example, Blatta orientalies, Blattella germanica, Blattella asahinai, Leucophaea maderae, Panchlora spp., Parcoblatta spp., Periplaneta australasiae, Periplaneta americana, Periplaneta brunnea, Periplaneta fuliginosa, Supella longipalpa.

From the order of the Saltatoria, for example, Acheta domesticus.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example, Kalotermes spp., Reticulitermes spp.

From the order of the Psocoptera, for example, Lepinatus spp., Liposcelis spp.

From the order of the Coleoptera, for example, Anthrenus spp., Attagenus spp., Dermestes spp., Latheticus oryzae, Necrobia spp., Ptinus spp., Rhizopertha dominica, Sitophilus granarius, Sitophilus oryzae, Sitophilus zeamais, Stegobium paniceum.

From the order of the Diptera, for example, Aedes aegypti, Aedes albopictus, Aedes taeniorhynchus, Anopheles spp., Calliphora erythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culex pipiens, Culex tarsalis, Drosophila spp., Fannia canicularis, Musca domestica, Phlebotomus spp., Sarcophaga carnaria, Simulium spp., Stomoxys calcitrans, Tipula paludosa.

From the order of the Lepidoptera, for example, Achroia grisella, Galleria mellonella, Plodia interpunctella, Tinea cloacella, Tinea pellionella, Tineola bisselliella.

From the order of the Siphonaptera, for example, Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis.

From the order of the Hymenoptera, for example, Camponotus herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis, Paravespula spp., Tetramorium caespitum.

From the order of the Anoplura, for example, Pediculus humanus capitis, Pediculus humanus corporis, Pemphigus spp., Phylloera vastatrix, Phthirus pubis.

From the order of the Heteroptera, for example, Cimex hemipterus, Cimex lectularius, Rhodinus prolixus, Triatoma infestans. In the field of domestic insecticides, they are used alone or in combination with other suitable active compounds, such as phosphoric esters, carbamates, pyrethroids, neonicotinoids, growth regulators or active compounds from other known classes of insecticides.

Determination of the efficiency of various adjuvants for root uptake of imidacloprid - examples of adjuvants according to the invention

45 seeds of tomato plants, Sorte Rentita, were sown individually into the cavities of perforated polystyrene tablets filled with special seeding soil based on peat culture substrate. The floats were then placed into containers with nutrient solution based on 0.1% Bayfolan^® and cultivated at 25°C, 80% rel. atmospheric humidity and 12 hours of light until the desired plant size was reached. Before the tablets were introduced, the appropriate solutions were added directly to the nutrient solution of individual boxes. Twelve and nineteen days after the treatment, tomato seedlings were harvested and extracted, and the imidacloprid content was analysed by HPLC -MS/MS.

Adjuvants according to the invention are defined as those substances which increased uptake by more than 20%, compared to the control.

Table 1: Improvement of imidacloprid uptake in tomato plants after addition of 0.008 mg of imidacloprid and 8 mg of adjuvant per plant. When mixtures were added, the amount was in each case 8 mg.

Claims

Patent Claims

1. Method for controlling animal pests by applying an agrochemical composition comprising at least one agrochemical Iy active compound from the group of the insecticidal phthalic acid diamides to the culture substrate of a plant, characterized in that a compositipn comprising at least one adjuvant is applied.

2. Method according to Claim 1 for controlling animal pests by applying an aqueous suspension concentrate having a content of organic solvents of less than 75 g/1 and comprising at least one agrochemically active compound from the group of the insecticidal phthalic acid diamides to the culture substrate of a plant, characterized in that a composition comprising at least one adjuvant is applied, the adjuvant being characterized in that it is capable of increasing the uptake of imidacloprid into the shoots of a tomato plant if the plant is cultivated in a soil-free system and the nutrient solution comprises 0.1 ppm of imidacloprid and 2.5 to 100 ppm of adjuvant.

3. Method according to Claim 1 or 2, characterized in that the adjuvant is selected from the group consisting of

terminally-capped alkoxylated fatty alcohols and terminally-capped alkoxylated straight-chain alcohols,

tributylphenol polyglycol ethers having 10 to 15 EO units (where EO means ethylene oxide),

branched alkanol alkoxylates of the formula CH₃-(CH₂)_rCH₂-O-(-CH₂-CH₂-O-)_u-H, in which t represents numbers from 9 to 10.5 and u represents numbers from 6 to 25 and t and u are average values,

polyalkoxylated triglycerides,

- alkoxylated fatty amines,

sodium laureth sulphate,

alkoxylated terpenes and

compositions comprising maize syrup, methylated soya oil and a non-ionic emulsifier.

4. Aqueous suspension concentrate having a content of organic solvent of less than 7.5% by weight for use in the soil, comprising:

- at least one agrochemically active compound from the group of the insecticidal phthalic acid diamides,

- at least one adjuvant selected from the group consisting of

terminally-capped alkoxylated fatty alcohols and terminally-capped alkoxylated straight-chain alcohols,

tributylphenol polyglycol ethers having 10 to 15 EO units (where EO means ethylene oxide),

- branched alkanol alkoxylates of the formula CH₃-(CH₂),-CH₂-O-(-CH₂-

CH₂-O-)_U-H, in which t represents numbers from 9 to 10.5 and u represents numbers from 6 to 25 and t and u are average values,

polyalkoxylated triglycerides,

alkoxylated fatty amines,

- sodium laureth sulphate,

alkoxylated terpenes and

compositions comprising maize syrup, methylated soya oil and a non-ionic emulsifier.

5. Composition according to Claim 4, comprising

- at least one non-ionic surfactant and/or at least one anionic surfactant,

one or more additives from the groups of the antifreeze agents, the antifoams, the preservatives, the antioxidants, the spreading agents, the colorants and/or the thickeners.

6. Composition according to Claim 4 or 5, comprising

- from 1 to 60% by weight of at least one agrochemically active compound from the group of the insecticidal phthalic acid diamides, from 1 to 50% by weight of at least one adjuvant,

from 1 to 20% by weight of at least one non-ionic surfactant and/or anionic surfactant,

from 1 to 20% by weight of antifreeze agent and

from 0.1 to 20% by weight of additives from the groups of the antifoams, the preservatives, the antioxidants, the spreading agents, the colorants and/or the thickeners.

7. Composition according to Claim 5, characterized in that it comprises at least one active compound selected from

8. Use of adjuvants for improving the action of crop protection agents comprising at least one active compound from the class of the insecticidal phthalic acid diamides in soil applications.

9. Use according to Claim 8, characterized in that at least one adjuvant selected from the group consisting of

terminally-capped alkoxylated fatty alcohols and terminally-capped alkoxylated straight-chain alcohols,

- tributylphenol polyglycol ethers having 10 to 15 EO units (where EO means ethylene oxide),

branched alkanol alkoxylates of the formula CH₃-(CH₂),-CH₂-O-(-CH₂-CH₂-O-)_u-H, in which t represents numbers from 9 to 10.5 and u represents numbers from 6 to 25 and t and u are average values,

- polyalkoxylated triglycerides,

alkoxylated fatty amines,

sodium laureth sulphate,

alkoxylated terpenes and

compositions comprising maize syrup, methylated soya oil and a non-ionic emulsifier,

is used.

10. Use according to Claim 8, characterized in that the improved action is achieved by increased uptake of the active compound by the roots.