Active substance combinations

[0001] The present invention relates to new combinations of active substances which consist of known carboxamides and known active substances with insecticidal activity and are very well suited for controlling undesirable animal pests, such as insects or mites, as well as undesirable phytopathogenic fungi. [0002] Fungicidal properties of certain carboxamides are known, e.g.

N- [2- (1,3-dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide of WO 03/010149 and 3- (trifluoromethyl) -N- [2 - (1,3-dimethylbutyl) phenyl] -5-fluoro-1-methyl-1Hpyrazole-4-carboxamide from DE-A 103 03 589. The activity of these substances is good, but at lower doses it is insufficient in some cases.

[0003] Further, insecticidal and acaricidal properties of numerous phosphoric esters, carbamates, heterocyclic compounds, organocin compounds, benzoylureas and pyrethroids are known (see e.g. US 2,758,115, US 3,309,266, GB 1,181,657, WO 93/22297 A1, WO 93/10083 A1, DE 26 41 343 A1, EP 347 488 A1, EP 210 487 A1, US 3,264,177 and EP 234 045 A2). However, the activity of these compounds is also not satisfactory in all respects.

[0004] New combinations of active substances with very good fungicidal, insecticidal and / or acaricidal properties have now been found containing carboxamide of general formula (I) (group 1)

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and at least one active substance selected from the group consisting of (2.1.1) clothianidin (2.1.2) imidacloprid (2.1.3) thiacloprid (3.1.1) methiocarb (3.1.2) thiodicarb (4.1.1) betacyfluthrin (5.1.1) spinosad (6.2.1) fipronil (21.1.1) N²- [1,1-dimethyl-2- (methylsulfonyl) ethyl] -3-iodo-N¹- [2-methyl-4- [1,2,2,2-tetrafluoro-1- (trifluoromethyl) ethyl] phenyl] -1,2-benzenedicarboxamide (flubendiamide).

[0005] The fungicidal, insecticidal or acaricidal activity of the inventive combination is surprisingly much higher than the sum of the activities of the individual active substances. There is therefore a previously unforeseen synergistic effect, rather than complementing the action.

[0006] Formula (I) includes, as a component of a mixture, belonging to the group (1):

N- [2- (1,3-dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide (known from WO 03/010149) [0007] The combinations according to the invention contain, in addition to N - [2- (1,3-dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide (group 1), one or more, preferably one component from the group (2.1.1) clothianidin ( 2.1.2) imidacloprid (2.1.3) thiacloprid (3.1.1) methiocarb (3.1.2) thiodicarb (4.1.1) betacyfluthrin (5.1.1) spinosad (6.2.1) fipronil (21.1.1) N²- [1,1-dimethyl-2- (methylsulfonyl) ethyl] -3-iodo-N¹- [2-methyl-4- [1,2,2,2-tetrafluoro-1- (trifluoromethyl) ethyl] phenyl] -1,2-benzenedicarboxamide (i.e. flubendiamide, CAS number: 272451-65-7).

The combinations according to the present invention are listed in the table below.

Table 1

<td>Active substance from the group (1)</td><td>Active substance from groups (2) to (24)</td>

<td>(1-2) N- [2- (1,3-dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide</td><td>(2.1.1) clothianidin</td>

<td>(1-2) N- [2- (1,3-dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide</td><td>(2.1.2) imidacloprid</td>

<td>(1-2) N- [2- (1,3-dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide</td><td>(2.1.3) thiacloprid</td>

<td>(1-2) N- [2- (1,3-dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide</td><td>(3.1.1) methiocarb</td>

<td>(1-2) N- [2- (1,3-dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide</td><td>(3.1.2) thiodicarb</td>

<td>(1-2) N- [2- (1,3-dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide</td><td>(4.1.1) betacyfluthrin</td>

<td>(1-2) N- [2- (1,3-dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide</td><td>(5.1.1) spinosad</td>

<td>(1-2) N- [2- (1,3-dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide</td><td>(6.2.1) fipronil</td>

<td>(1-2) N- [2- (1,3-dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide</td><td>(21.1.1) flubendiamide</td>

[0008] The active substance combinations may also contain other fungicidal, acaricidal or insecticidal active ingredients.

[0009] If the active substances are present in the combinations according to the invention in certain weight proportions, they show a particularly synergistic effect. However, these weight proportions of active ingredients in active substance combinations can vary within a relatively wide range. In general, the combinations of the invention contain the active compounds of formula (I) and the additional component in the preferred mixing ratios given in the table below, the mixing ratios being based on the weight ratios.

[0010] The proportion should be understood as the substance of formula (I) (from group 1): a component of the mixture

Table 2: Mixing proportions

<td>Mixture component (group)</td><td>Favorable mixing ratio</td><td>Particularly favorable mixing ratio</td>

<td>(2.1) Chloronicotinyls / neonicotinoids</td><td>500: 1 to 1:50</td><td>125: 1 to 1:25</td>

<td>(3.1) Carbamate</td><td>500: 1 to 1: 1000</td><td>125: 1 to 1: 500</td>

<td>(4.1) Piretroid</td><td>500: 1 to 1:50</td><td>125: 1 to 1:25</td>

<td>(5.1) Spinosyn</td><td>500: 1 to 1:50</td><td>125: 1 to 1:25</td>

<td>(6.2) Fiprol</td><td>500: 1 to 1: 200</td><td>125: 1 to 1:50</td>

<td>(21) Phthalamide</td><td>500: 1 to 1:50</td><td>125: 1 to 1:25</td>

[0011] The active compound combinations of the invention exhibit strong microbicidal activity and can be used to control undesirable microorganisms such as fungi and bacteria in plant protection and material protection.

[0012] Fungicides may be used to control Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.

[0013] Bactericidal agents may be used to control Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.

[0014] For example, but not limited to its content, mention should be made of some of the causative agents of fungal and bacterial diseases that fall within the abovementioned parent concepts:

Diseases caused by powdery mildew, such as

Blumeria species, such as, for example, Blumeria graminis;

Podosphaera species, such as, for example, Podosphaera leucotricha;

Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;

Uncinula species, such as, for example, Uncinula necator;

Diseases caused by rust-causing agents, such as

Gymnosporangium species, such as, for example, Gymnosporangium sabinae

Hemileia species, such as, for example, Hemileia vastatrix;

Phakopsora species, such as, for example, Phakopsora pachyrhizi and Phakopsora meibomiae;

Puccinia species, such as, for example, Puccinia recondita;

Uromyces species, such as, for example, Uromyces appendiculatus;

Diseases caused by Oomyceten pathogens, such as

Bremia species, such as, for example, Bremia lactucae;

Peronospora species, such as, for example, Peronospora pisi or P. brassicae;

Phytophthora species, such as, for example, Phytophthora infestans;

Plasmopara species, such as, for example, Plasmopara viticola;

Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubensis;

Pythium species, such as, for example, Pythium ultimum;

Leaf diseases and leaf wilt caused by, e.g.

Alternaria species, such as, for example, Alternaria solani;

Cercospora species, such as, for example, Cercospora beticola;

Cladosporium species, such as, for example, Cladosporium cucumerinum;

Cochliobolus species, such as, for example, Cochliobolus sativus (conidial form: Drechslera, Syn: Helminthosporium);

Colletotrichum species, such as, for example, Colletotrichum lindemuthanium; Cycloconium species, such as, for example, Cycloconium oleaginum;

Diaporthe species, such as, for example, Diaporthe citri;

Elsinoe species, such as, for example, Elsinoe fawcettii;

Gloeosporium species, such as, for example, Gloeosporium laeticolor;

Glomerella species, such as, for example, Glomerella cingulata;

Guignardia species, such as, for example, Guignardia bidwelli;

Leptosphaeria species, such as, for example, Leptosphaeria maculans;

Magnaporthe species, such as, for example, Magnaporthe grisea;

Mycosphaerella species, such as, for example, Mycosphaerelle graminicola;

Phaeosphaeria species, such as, for example, Phaeosphaeria nodorum;

Pyrenophora species, such as, for example, Pyrenophora teres;

Ramularia species, such as, for example, Ramularia collo-cygni;

Rhynchosporium species, such as, for example, Rhynchosporium secalis;

Septoria species, such as, for example, Septoria apii;

Typhula species, such as, for example, Typhula incamata;

Venturia species, such as, for example, Venturia inaequalis;

Root and stem diseases caused by e.g.

Corticium species, such as, for example, Corticium graminearum;

Fusarium species, such as, for example, Fusarium oxysporum;

Gaeumannomyces species, such as, for example, Gaeumannomyces graminis;

Rhizoctonia species, such as, for example, Rhizoctonia solani;

Tapesia species, such as, for example, Tapesia acuformis;

Thielaviopsis species, such as, for example, Thielaviopsis basicola;

Ear and panicle diseases (including corn cobs) caused by e.g.

Alternaria species, such as, for example, Alternaria spp .;

Aspergillus species, such as, for example, Aspergillus flavus;

Cladosporium species, such as, for example, Cladosporium spp. Like Cladosporium cladosporioides;

Claviceps species, such as, for example, Claviceps purpurea;

Fusarium species, such as, for example, Fusarium culmonun;

Gibberella species, such as, for example, Gibberclla zeae;

Monographella species, such as, for example, Monographella nivalis;

Diseases caused by sunblinds, such as

Sphacelotheca species, such as, for example, Sphacelotheca reiliana;

Tillefia species, such as, for example, Tilletia caries;

Urocystis species, such as, for example, Urocystis occulta;

Ustilago species, such as, for example, Ustilago nuda;

Fruit rot caused by e.g.

Aspergillus species, such as, for example, Aspergillus flavus;

Botrytis species, such as, for example, Botrytis cinerea;

Penicillium species, such as, for example, Penicillium expansum and Penicillium purpurogenum;

Sclerotinia species, such as, for example, Scleroiinia sclerotiorum;

Verticilium species, such as, for example, Verticilium alboatrum;

Spoilage and wilting of seeds and ground parts, as well as seedling diseases caused by e.g.

Fusarium species, such as, for example, Fusarium culmorum;

Phytophthora species, such as, for example, Phytophthora cactorum;

Pythium species, such as, for example, Pythium ultimum;

Rhizoctonia species, such as, for example, Rhizoctonia solani;

Sclerotium species, such as, for example, Sclerotium rolfsii;

Cancer, growths and witches' brooms, caused by e.g.

Nectria species, such as, for example, Nectria galligena;

Wilt diseases caused by e.g.

Monilinia species, such as, for example, Monilinia laxa;

Leaf, flower and fruit deformations caused by e.g.

Taphrina species, such as, for example, Taphrina deformans;

Degenerative diseases of woody plants caused by e.g.

Esca species, such as, for example, Phaemoniella clamydospora;

Flower and seed diseases caused by e.g.

Botrytis species, such as, for example, Botrytis cinerea;

Plant tuber diseases caused by e.g.

Rhizoctonia species, such as, for example, Rhizoctonia solani;

Helminthosporium species, such as, for example, Helminthosporium solani;

Diseases caused by bacterial agents, such as

Xanthomonas species, such as, for example, Xanthomonas campestris pv. oryzae;

Pseudomonas species, such as, for example, Pseudomonas syringae pv. lachrymans;

Erwinia species, such as, for example, Erwinia amylovora.

[0015] Advantageously, the following soybean diseases can be controlled:

Fungal diseases on the leaves, stems, covers and seeds, which are caused, for example, by alteriarnoza (Alternaria spec. Atrans tenuissima), anthracnose (Colletotrichum gloeosporoides dematium var. truncatum), brown spot (Septoria glycines), soybean cerkosporosis (Cercospora kikuchii), leaf rust caused by Choanephora (Choanephora infundibulifera trispora (Syn.)), leaf spot caused by Dactuliophora (Dactuliophora glycines), mealwormworm caused by fungi of the genus Drechslera (Drechslera glycini), leaf spot and rust caused by Cercospora (Cercospora sojina), leaf blotch caused by Leptosphaerulin (Leptosphaerulin trifolii), leaf blotch caused by Phyllostica (Phyllosticta sojaecola), rust of pods and stems (Phomopsis sojae), powdery mildew (Microsphaera diffusa), fuchsia fever (Rhizoctonia solani), rust (Phakopsora pachyrhizi), scab (Sphaceloma glycines), leaf rust caused by Stemphylium (Stemphylium botryosum), corinosporosis (Corynespora cassiicola)

Fungal diseases on the roots and bases of the stems, the cause of which is e.g. black leaf blotch (Calonectria crotalariae), rot caused by Macrophomina (Macrophomina phaseolina), gangrene caused by Fusarium, gangrene of roots, pods and the root neck (Fusarium oxysporum, Fusarium orthoceras, Fusarium semitectum, Fusariumzis Mycusycytiscus) terrestris), rot caused by Neocosmospora (Neocosmopspora vasinfecta), rust of pods and stems caused by Diaporthe (Diaporthe phaseolorum), dry rot (Diaporthe phaseolorum var. caulivora), rot caused by Phytophthora (Phytophthora megasperma), brown root rot (Phialophora gregata), gangrene (Pythium aphanidermatum, Pythium irregulare, Pythium debaryanum, Pythium myriotylum, Pythium ultimatum, thyme vulgaris) (Sclerotinia sclerotiorum), shoot base rot (Sclerotinia rolfsii), black root rot (Thielaviopsis basicola).

[0016] Good tolerance by plants of the concentrations of the combination of active substances necessary to combat plant diseases allows these substances to be treated with whole plants (aerial parts and roots), harvests and seeds and soil. The active compound combinations of the invention can be used for foliar application or as a dressing agent.

[0017] Good tolerance by plants of the concentrations of active substances used, necessary to combat plant diseases, allows treatment of these substances with seeds. The active substances of the invention can be used as a mortar.

[0018] A large proportion of the damage caused by phytopathogenic fungi in crops arises as a result of their attack during seed storage and after sowing them into the soil, as well as during and immediately after germination. This phase is particularly critical because the roots and shoots of growing plants are particularly sensitive and minor damage can lead to the death of the whole plant. So it becomes especially important to protect the seed and the whole germinating plant by using the right agent.

[0019] The control of phytopathogenic fungi, which exhibit harmful effects on plants after germination, is achieved primarily by subjecting soil and aerial plant parts to plant protection products. When considering the possible impact of plant protection products on the environment and human and animal health, the aim is to reduce the amount of active substances used.

[0020] The method of controlling phytopathogenic fungi by affecting plant seeds has long been known and is constantly being improved. However, when processing seeds, a whole series of problems arise, the solution of which is not always satisfactory. Thus, it is desirable to develop methods for protecting seeds and germinating plants so that the need to introduce plant protection products after sowing or after germination of plants is eliminated or at least clearly limited. Then, it is desirable to optimize the amount of active substance used to the extent that the seeds and germinating plants are best protected against the attack of pathogenic fungi, but without damaging the plants themselves by the active substance used. In particular, seed treatment methods should take into account the innate fungicidal properties of transgenic plants so as to achieve optimal protection of seeds and germinating plants with minimal use of plant protection products.

[0021] The present invention therefore also relates in particular to a method for protecting seeds and germinating plants against attack by phytopathogenic fungi in which the seeds are treated with the agent of the invention.

[0022] The invention also relates to the use of the agents of the invention for treating seeds to protect seeds and germinating plants against attack by phytopathogenic fungi.

[0023] Further, the invention relates to seeds which have been treated with the agent according to the invention for protection against phytopathogenic fungi.

[0024] One of the advantages of the present invention is that, based on the special systemic properties of the agent of the invention, the effect of this agent on seeds protects against phytopathogenic fungi not only the seeds themselves but also the plants germinating from them. In this way, direct application of the product to crops at the time of sowing and shortly afterwards can be avoided.

[0025] A further advantage should be considered that the mixtures according to the invention can also be used in particular on seeds of transgenic plants.

[0026] The agents of the invention can be used to protect the seeds of any species that occur in agriculture, greenhouse farming, forests and horticulture. This is especially true for cereal seeds (such as wheat, barley, rye, millet and oats), corn, cotton, soybean, rice, potatoes, sunflower, beans, coffee, beets (e.g. sugar and fodder beets), peanuts, vegetables (like tomatoes, cucumbers, onions and lettuce), grass and ornamental plants. Effects on cereal seeds (such as wheat, barley, rye and oats), corn and rice are of particular importance.

[0027] Within the framework of the present invention, it is possible to act on the seeds with the agent according to the invention itself or with its appropriate formulation. It is beneficial to treat the seeds in a state in which there is no damage as a result of the impact on the seeds. Generally, the seed can be treated at any time between harvest and sowing. Usually seeds are used for this, which have been separated from the rest of the plant and freed from cobs, scales, peduncles, sheaths, wool or fruit pulp. Thus, for example, seeds that have been harvested, cleaned and dried to a moisture level below 15 wt.% Can be used. Alternatively, it is also possible to use seeds which, after drying, e.g. have been treated with water and then dried again.

[0028] In general, when treating seeds, care must be taken that the amounts of the agent according to the invention and / or other additives used are selected so as not to affect the germination of the seeds or to harm the plants germinating from them. This must first and foremost be considered for active substances, which may exhibit phytotoxic effects at certain doses.

[0029] The agents according to the invention can be used directly, i.e. without admixture of other ingredients and without dilution. In principle, it is preferable to treat the seeds with an agent in the form of a suitable formulation. Suitable formulations and methods of treatment for seeds are known to those skilled in the art and are e.g. described in the following documents: US 4,272,417 A, US 4,245,432 A, US 4,808,430 A, US 5,876,739 A, US 2003/0176428 A1, WO 2002/080675 A1, WO 2002 / 028186 A2.

[0030] The active compound combinations of the invention also show a strong strengthening effect on plants. They are therefore suitable for mobilizing the plant’s own defense against the attack of undesirable microorganisms.

[0031] In the context of the mentioned context, the term strengthening substances (immunity-inducing substances) should be understood to mean such substances that are able to stimulate the plant's defense system in such a way that treated plants achieve far-reaching resistance to these microorganisms in the event of subsequent inoculation with undesirable microorganisms.

[0032] In the present case, undesirable microorganisms are understood as meaning phytopathogenic fungi, bacteria and viruses. The substances of the invention can also be used to protect plants against the attack of said pests after a given period of time. Protection is carried out over a period of time lasting generally from 1 to 10 days, preferably from 1 to 7 days after the active substances have been applied to the plants.

[0033] Good tolerance by the plants of the combinations of active substances in the concentrations necessary to combat plant diseases allows the aboveground parts of plants, harvests and seeds and soil to be exposed to these substances.

[0034] The active compound combinations of the invention can be used with particularly good results to combat cereal diseases, e.g. against Puccinia species and vine, fruit and vegetable diseases, e.g. Botrytis, Venturia and Alternaria species.

[0035] The active compound combinations of the invention can also be used to increase harvest yield. In addition, they are low toxic and the plants show good tolerance towards them.

[0036] The active compound combinations of the invention can also be used as herbicides in specific concentrations and doses in order to obtain beneficial effects on plant growth as well as to control animal pests.

[0037] All plants and parts of plants can be treated with the substances of the invention. Plants are understood to include all plants and plant populations, such as desirable and undesirable wild plants or plant crops (including naturally occurring plant crops). Plant crops can be plants which have been obtained by conventional breeding and optimization methods or by biotechnological and genotechnological methods or by a combination of these methods, including transgenic plants and plant species for which intellectual property rights protection is or is not applicable. Plant parts should be understood as all above-ground and underground parts and organs of plants, such as shoots, leaves, flowers and roots, for example, leaves, needles, stems, stems, flowers, fruit pulp, fruits and seeds, as well as roots, tubers and rhizomes. Parts of plants also include harvest, as well as vegetative and reproductive material, for example cuttings, tubers, rhizomes, shoots and seeds.

[0038] The effect of the active substance combination on plants and plant parts is obtained in accordance with the invention either directly or by influencing their surroundings, location or storage room in accordance with customary methods, e.g. by immersion, spraying, evaporation, spraying, scattering, lining, and in the case of reproductive material - especially seeds - in addition by covering with one or more layers.

[0039] When protecting materials, a combination of the active substances of the invention can be used to protect technical materials against attack and destruction by undesirable microorganisms.

[0040] In this context, technical materials should be understood as inanimate materials adapted for technical use. For example, the materials that should be protected from exposure to and destruction by microorganisms using the combination of active substances of the invention may be adhesives, adhesives, paper and cardboard, textiles, leather, wood, coating agents, plastic objects, cooling lubricants and other materials that may be attacked or destroyed by microorganisms. Protected materials also include components of industrial equipment, such as the cooling water circuit, which can be damaged by bacterial growth. Within the scope of the present invention, as technical materials, mention should be made primarily of binders, adhesives, paper and cardboard, leather, wood, coating agents, plastic objects, cooling lubricants and heat transfer fluids, especially wood.

[0041] As microorganisms that can affect the decomposition or transformation of technical materials, mention should be made of bacteria, fungi, yeast, algae and slime molds. The active substances of the invention preferably counteract fungi, in particular molds, fungi causing color change and decomposing wood (Basidiomycetene), as well as slime molds and algae.

[0042] For example, the following species of microorganisms should be mentioned:

Alternaria, like Alternaria tenuis,

Aspergillus, like Aspergillus niger,

Chaetomium, like Chaetomium globosum,

Coniophora, like Coniophora puetana,

Lentinus, like Lentinus tigrinus,

Penicillium, like Penicillium glaucum,

Polyporus, like Polyporus versicolor,

Aureobasidium, like Aureobasidium pullulans,

Sclerophoma, like Sclerophoma pityophila,

Trichoderma, like Trichoderma viride,

Escherichia, like Escherichia coli,

Pseudomonas, like Pseudomonas aeruginosa,

Staphylococcus, like Staphylococcus aureus.

[0043] Furthermore, the active compound combinations of the invention also show very good antimicotic activity. They have a very broad antimicotic spectrum of action, especially against dermatophytes and yeasts, molds and dimorphic fungi (e.g. against Candida species, such as Candida albicans, Candida glabrata), as well as Epidermophyton floccosum, Aspergillus species, such as Aspergillus niger and Aspergillus fumigatus, Trichophyton species, as Trichophyton mentagrophytes, Microsporon species, such as Microsporon canis. The above list of species in no way exhausts the possible mycotic spectrum, but is only of an explanatory nature.

[0044] Combinations of active substances can be used as such, in the form of their use forms or the use forms prepared from them, such as ready-to-use solutions, suspensions, sprayable powders, pastes, soluble powders, dusting agents and granules. Application is carried out in the usual way, e.g. by pouring, spraying, spraying, scattering, dispersing, rubbing, lubrication, etc. Furthermore, it is possible to introduce active substances by the ultra-low-volume method or to inject into the soil a preparation of the active substance or the active substance itself. Plant seeds can also be treated with the substance.

[0045] When the active compound combinations of the invention are used as fungicides, the amounts used can vary widely depending on the mode of application. When used on parts of plants, the amounts of active substance used are generally between 0.1 and 10,000 g / ha, preferably between 10 and 1,000 g / ha. When treated with seeds, the amounts of active substance used are generally between 0.01 and 50 g per kg of seed, preferably between 0.01 and 10 g per kg of seed. When applied to soil, the amounts of active substance used are generally between 0.1 and 10,000 g / ha, preferably between 1 and 5,000 g / ha.

[0046] Said plants can be particularly advantageously treated with the active compound mixtures according to the invention. The preferred ranges given above for the active substances or mixtures also apply to these plants. Particular attention should be given to the effect on plants with the compounds or mixtures mentioned in this text.

[0047] The active compound combinations of the invention can also be used to control animal pests, preferably arthropods and nematodes, especially nematodes and insects, which are found in agriculture, veterinary medicine, in forests, in the protection of warehouses and materials, as well as in the hygiene sector. They exhibit action against both normally sensitive and resistant species, as well as against all or particular stages of development. The above-mentioned pests include:

Isopoda, e.g. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.

From the Diplopoda row, e.g. Blaniulus guttulatus.

From the order of Chilopoda, e.g. Geophilus carpophagus, Scutigera spp.

From the order of Symphyla, e.g. Scutigerella immaculata.

From the order of Thysanura, for example Lepisma saccharina.

From the order of Collembola, e.g. Onychiurus armatus.

From the order of the Orthoptera, e.g. Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus spp., Schistocerca gregaria.

From the Blattaria row, e.g. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica.

From the order of Dermaptera e.g. Forficula auricularia.

From the order of the Isoptera, e.g. Reticulitermes spp.

From the order of the Phthiraptera e.g. Pediculus humanus corporis, Haematopinus spp., Linognathus spp., Trichodectes spp., Damalinia spp.

From the order of Thysanoptera, e.g. Hercinothrips femoralis, Thrips tabaci, Thrips palmi, Frankliniella occidentalis.

From the order of the Heteroptera, e.g. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.

From the order of the Homoptera zB Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigiphpppos, Macros Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp.

From the Lepidoptera order e.g. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella xylostella, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberielista, Phyllocotta, Phyllocotta. spp., Mamestra brassicae, Panolis flammea, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia administered, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana, Cnaphalocerus spp., Oulema oryzae.

From the order of the Coleoptera e.g. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa ​​decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachza sphis. sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica, Lissorhoptrus oryzophilus.

From the order of the Hymenoptera, e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.

From the order of Dipter, e.g. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca ., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa, Hylemyia sppp, .

From the order of the Siphonaptera e.g. Xenopsylla cheopis, Ceratophyllus spp.

From the Arachnida class, e.g. Scorpio maurus, Latrodectus mactans, Acarus siro, Argas spp., Omithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., , Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp., Hemitarsonemus spp., Brevipalpus spp.

[0048] Plant nematodes include, for example, Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xphin ., Bursaphelenchus spp.

[0049] Depending on their specific physical and / or chemical properties, the active substance combinations can be converted into ordinary formulations, such as solutions, emulsions, spray powders, suspensions, powders, foams, dusting powders, pastes, soluble powders, granulates, aerosols, suspension and emulsion concentrates, plastics and natural materials impregnated with the active substance, microcapsules in polymer materials and in seed covering materials, as well as utility forms for producing hot or cold fog using the ultra-low-volume method.

[0050] These dosage forms are obtained in a known manner, e.g. by mixing the active substances with a diluent, i.e. a liquid solvent and / or a solid carrier, optionally with the use of surfactants, also emulsifying and / or dispersing agents and / or production agents. foam.

[0051] When using water as the diluent, organic solvents can also be used, for example, as auxiliaries. As liquid solvents, in fact, aromatic compounds such as xylene, toluene or alkylnaphthalene, chloroaromatic compounds and chlorinated aliphatic hydrocarbons such as chlorobenzene, chloroethylene or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol as well as their ethers and esters, ketones as acetone, methyl ethyl ketone or cyclohexanone, highly polar solvents such as dimethylformamide and dimethyl sulfoxide as well as water.

[0052] As solid supports are considered:

for example. ammonium salts and ground natural rocks, such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic, such as high dispersion silica gel, alumina and silicates; as solid carriers for granules are taken into account: e.g. crushed and fractionated natural rocks, such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours, as well as granules from organic materials, such as sawdust, shell flour coconuts, corn on the cob and tobacco stalks; as emulsifying and / or foaming agents, e.g. nonionic and anionic emulsifiers, such as polyhydroxyethylene fatty acid esters, polyhydroxyethylene fatty alcohol ethers, e.g., alkylaryl polyglycol ether, alkyl sulfonates, alkyl sulfates, aryl sulfonates as well as protein hydrolysates; as dispersing agents, for example, post-sulphite lignin lyes and methyl cellulose are included.

[0053] Adhesion enhancing agents, such as carboxymethyl cellulose, natural and synthetic, powdered, granular or latex-like polymers, such as acacia, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids such as cephalin and lecithin and synthetic phospholipids may be used in the dosage forms. Mineral and vegetable oils may be further auxiliaries.

[0054] Colored substances such as inorganic pigments, e.g. iron oxide, titanium oxide, Berlin blue and organic dyes, such as alizarin, azo and metal phthalocyanine dyes, and trace food substances such as iron, manganese, boron, copper, cobalt salts can be used , molybdenum and zinc.

[0055] The dosage forms generally contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90%.

[0056] The active compound combinations of the invention may exist in commercially available dosage forms as well as in application forms made from these dosage forms, in the form of mixtures with other active substances such as insecticides, attractants, sterilizing substances, insecticides, acaricides, nematocides, fungicides, plant growth regulators or herbicides. Insecticides include, for example, phosphoric acid esters, carbamates, carbonic acid esters, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms and others.

[0057] Mixtures with other known active substances, such as herbicides or fertilizers and growth regulators are also possible.

[0058] The active compound combinations of the invention may further occur, when used as insecticides, in commercially available formulation as well as in application forms made from these formulation, in mixtures with synergists. Synergists are compounds that increase the activity of the active substance, although the synergist added does not have to be active.

[0059] The content of active substance in the application forms made from commercially available dosage forms can vary widely. The active substance concentration in the application forms can be from 0.0000001 to 95% by weight, preferably between 0.0001 and 1% by weight.

[0060] The application proceeds according to one of the methods adapted to the given application form.

[0061] When used against pests that threaten hygiene or pests in warehouses, the active substance combinations have an excellent residual effect on wood and clay, as well as good stability in an alkaline environment on limed surfaces.

[0062] The active substance combinations of the invention act not only against plant pests, warehouse pests, hygiene-threatening pests, but also in veterinary medicine, against animal parasites (external parasites), such as ticks, mites, flies (prickly and licking), parasitic larvae flies, lice, lice and fleas. These parasites include:

From the order of Anoplurida e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.

From the order of Mallophagida and the subordinates Amblycerina and Ischnocerina e.g. Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp.

From the order Diptera, the orders of Nematocerina and Brachycerin e.g. 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 spp., Hippobosca spp., Lipoptena spp., Melophagus spp.

From the order of Siphonapterida e.g. Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.

From the order of Heteropterida e.g. Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.

From the Blattarida row, e.g. Blatta orientalis, Periplaneta americana, Blattela germanica, Supella spp.

From the Acaria (Acarida) subclass, orders of Meta- and Mesostigmata, e.g. 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., Stemostoma spp., Varroa spp.

From the order of Actinedida (Prostigmata) and Acaridida (Astigmata) e.g. 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.

The active compound combinations according to the present invention are suitable for controlling arthropods found in farmed animals, such as cows, sheep, goats, horses, pigs, donkeys, camels, buffaloes, rabbits, chickens, turkeys, ducks, geese, bees, and others domestic animals such as dogs, cats, home-bred birds, aquarium fish, as well as in so-called experimental animals such as hamsters, guinea pigs, rats and mice. The control of these arthropods should reduce the number of fatal accidents and prevent the reduction of productivity (production of meat, milk, wool, skins, eggs, honey, etc.), as a result of which - by using the active substance combination according to the present invention - breeding of animals can be cheaper and simpler.

The use of the active compound combination according to the present invention takes place in veterinary medicine according to known methods by enteral administration in the form of e.g. tablets, capsules, beverages, liquids, granules, pastes, bolus, feed-through methods, suppositories, by parenteral administration, e.g. . injections (intramuscular, subcutaneous, intravenous, intraperitoneal and other), using implants, through the nose, through the skin - for example, by dipping or bathing (bathing), spraying (sprays), pouring (general and local), washing, powdering, and also by means of durable, active substances containing elements adapted to body parts, such as collars, ear and tail earrings, headbands, bridles, marking devices, etc.

[0065] The active substance combinations according to the present invention (e.g. powders, emulsions, liquid formulations) when used for cattle, birds, pets etc. can be used directly at a concentration of active substances from 1 to 80% by weight or as chemical bath liquid diluted 100 to 10,000 times.

[0066] In addition, it has been found that the active compound combinations of the present invention have a strong insecticidal effect on insects that destroy technical materials.

[0067] By way of example and above all, but not limited to the following list, the following insects should be mentioned:

Beetles like Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctusticussillum, Tryptodendron spec. Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. Dinoderus minutus.

Hymenoptera like Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur.

Termites like Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus.

Bristletails like Lepisma saccharina.

[0068] In the presented context, technical materials are considered to be inanimate materials, in particular plastics, adhesives, binders, paper and cardboard, leather, wood, wood processing products and impregnating agents.

[0069] In particular, the preferred materials to be protected against insects are primarily wood and wood processing products.

[0070] Wood and wood processing products that can be protected by the active substance combinations according to the present invention or mixtures containing them are understood to mean, for example: construction timber, beams, sleepers, bridge parts, platforms, wooden vehicles, crates, pallets, containers, telephone poles, paneling, wooden window frames and doors, plywood, chipboards, woodwork elements or wooden products generally applicable in the construction of houses or in carpentry.

[0071] The active compound combinations according to the present invention can be used as such in the form of concentrates or as generally known dosage forms such as powders, granules, solutions, suspensions, emulsions or pastes.

[0072] Said dosage forms can be prepared in known manner, e.g. by mixing the active substances with at least one diluent or solvent, emulsifier, dispersing and / or binding or fixing agent, hydrophobic, optionally drying and UV stabilizing agent, or dyes and pigments, as well as other auxiliaries.

[0073] The compositions or concentrates used for the protection of wood and wood processing products contain the active substance according to the present invention in a concentration of 0.0001 to 95% by weight, in particular 0.001 to 60% by weight.

[0074] The amounts of the agent or concentrate used depend on the type of insects, their occurrence and the environment. Optimal amounts can be determined by a series of tests. In general, however, a sufficient ratio of active substance to protected material is from 0.0001 to 20% by weight, preferably from 0.001 to 10% by weight. As the diluent and / or solvent is an organic solvent or mixture of solvents and / or oily or oily, a hardly volatile organic solvent or mixture of solvents and / or a polar organic solvent or mixture of solvents and / or water and optionally an emulsifier and / or wetting agent.

[0075] Oily or oily solvents with an evaporation number over 35 and a flash point above 30 ° C, preferably above 45 ° C are preferably used as organic solvents. Suitable mineral oils or their aromatic fractions or solvents containing mineral oils, primarily ligroin, gasoline and / or alkylbenzene, are used as such sparingly volatile, water-insoluble, oily or oily solvents.

It is preferred to use available mineral oils with a boiling range from 170 to 220 ° C, ligroins with a boiling range from 170 to 220 ° C, spindle oil with a boiling range from 250 to 350 ° C, kerosene or aromatic compounds with a boiling range from 160 to 280 ° C, turpentine oil, etc.

[0077] In a preferred embodiment, liquid aliphatic hydrocarbons with a boiling range from 180 to 210 ° C or a high boiling mixture of aliphatic and aromatic hydrocarbons with a boiling range from 180 to 220 ° C are used and / or spindle oil and / or monochloronaphthalene, preferably α -monochloronaftalen.

[0078] Hardly volatile, oily or oily organic solvents with an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C, may be partially replaced by readily volatile and medium volatile organic solvents, provided that the solvent mixture also has an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C and that the combination of active substances is soluble or emulsifiable in this solvent mixture.

[0079] According to a preferred embodiment, part of the solvent or solvent mixture or polar organic solvent or solvent mixture is replaced by another solvent or solvent mixture. Aliphatic organic solvents containing hydroxyl, ester and ether groups, e.g. glycol ethers and the like, are preferably used.

[0080] As organic binders, known, soluble or dispersed or emulsifiable in water and / or organic solvents used, synthetic resins and / or oil-binding binders used in the present invention, in particular binders consisting of or containing resin acrylic, vinyl, e.g. polyvinyl, polyester, polycondensation or polyaddition acetate, polyurethane, alkyd or modified alkyd, phenolic, hydrocarbon resin such as indenocoumarone, silicone, drying vegetable and / or drying oils and / or physically drying binding agents based on natural and / or synthetic resins.

[0081] The synthetic resin used as a binder can be used in the form of an emulsion, suspension or solution. Bitumen and bituminous substances up to a content of 10% by weight may also be used as the binder. In addition, dyes, pigments, dehydrating agents, odor improvers and corrosion inhibitors or anti-corrosive agents can be used.

[0082] According to the invention, it is preferred to incorporate at least one alkyd resin or modified alkyd resin and / or drying vegetable oil into the preparation or concentrate as an organic binder. Alkyd resins with an oil content exceeding 45% by weight, preferably 50 to 68% by weight, are preferred for use according to the invention.

[0083] Said binder can be completely or partially replaced by a fixing agent (mixture of fixing agents) or a plasticizer (mixture of plasticizers). These additives should counteract the volatilization of the active substances as well as crystallization or precipitation from the solution. Preferably, 0.01 to 30% of the binder remains (based on 100% of the binder used).

[0084] The plasticizers belong to the chemical class of phthalic acid esters, such as dibutyl phthalate, dioctyl phthalate or benzyl butyl phthalate, phosphoric acid esters, like tributyl phosphate, adipic acid esters, di- (2-ethylhexyl) adipate, stearic acid esters, like stearate butyl and amyl stearate, oleic acid esters such as butyl oleate, ethers such as glycerol ethers or high molecular weight glycol ethers, glycerol esters as well as paratoluene sulfonic acid esters.

[0085] Fixatives are chemically derived from polyvinyl vinyl ethers such as polyvinyl methyl ether or ketones such as benzophenone, ethylene benzophenone.

[0086] As the solvent or diluent, first of all, water is considered, optionally in admixture with one or more of the abovementioned organic solvents or diluents, emulsifiers and dispersing agents.

[0087] Particularly effective wood protection is achieved with large-scale impregnation methods, e.g. vacuum methods, double vacuum methods and pressure methods.

[0088] The active substance combinations according to the present invention can also be successfully used to protect against the fouling of objects in contact with seawater or saltwater, in particular parts of ships, screens, nets, structures, wharf facilities and signal devices.

[0089] Fouling by sedentary oligosperms, such as gonorrhea, as well as shells and Ledamorpha species (barnacles) and various Lepas and Scalpellum species or by Balanidae species, such as Balanus or Pollicipes species, increases vessel resistance and increases energy consumption , and as a result of the more frequent use of dry dock resulting from the above, the operating costs increase significantly.

[0090] In addition to growing by algae, for example by Ectococus and Ceramium species, growing by the subclass of sedentary Entomostrac called Cirripedia is particularly important.

[0091] It has surprisingly been found that the active compound combinations according to the present invention have an excellent anti-fouling effect.

[0092] By using the active compound combination of the present invention, the use of heavy metal compounds such as e.g. bis (trialkyltin) sulfides, tributyltin laurate, tri-n-butyltin chloride, copper (I) oxide, triethyltin chloride, tri-n-butyl (2-phenyl) -4-chlorophenoxy) -tin, tributyltin oxide, molybdenum disulfide, oxide antimony, polymeric butyl titanate, phenylbispyridinobismuth chloride, tri-n-butyltin fluoride, manganese ethylene bis (dithiocarbamate), zinc dimethyl (dithiocarbamate), zinc ethylene bis (dithiocarbamate), copper and zinc salts with 2-pyridine N-oxide bisimethyldithiocarbamoyl zinc ethylene bistiocarbamate, zinc oxide, copper (I) ethylene bisithiocarbamate, copper thiocyanate, copper naphthenate and tributyltin halides, or reduce their concentrations.

[0093] The ready-to-use anti-fouling paints may optionally contain other active substances, in particular anti-algae agents, fungicides, herbicides, anti-molluscs as well as other anti-fouling agents.

[0094] As components of the combination for anti-fouling agents according to the present invention, the following are particularly suitable:

Anti-algae agents such as 2-tert-butylamino-4-cyclopropylamino-6-methylthio-1,3,5-triazine, dichlorophen, diuron, endotal, fentin acetate, isoproturon, metabenztiazuron, oxyfluorfen, quinoclamine and terbuthrin;

Fungicides such as S, S-cyclohexyl benzothiophene-2-carboxamide, dichlofluanide, fluorfolpet, 3-iodo-2-propinyl butyl carbamate, tolylfluanid and azoles, such as azaconazole, cyproconazole, epoxiconazole, proponazole, hexonazole anti-mollusc agents such as fentin acetate, metaldehyde, methiocarb, niclosamide, thiodicarb and trimethacarb;

or traditional anti-fouling agents such as 4,5-dichloro-2-octyl-4-isothiazolin-3-one, diiodomethylparatrylsulfone, 2- (N, N-dimethylthiocarbamoylthio) -5-nitrotiazil, potassium, sodium and zinc N-oxide salt 2-pyridine thiol, pyridine triphenylborate, tetrabutyl distanoxane, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, 2,4,5,6-tetrachlorisophthalic acid nitrile, tetramethylthiuram disulfide and 2,4,6-trichlorophenylmaleic acid imide.

[0095] The anti-fouling agents used contain the active compound combinations according to the present invention in a concentration of 0.001 to 50% by weight, in particular 0.01 to 20% by weight.

[0096] Anti-fouling agents according to the present invention contain other conventional ingredients as described, for example, by Ungerer in Chem. Indium. 1985; 37, 730-732 and Williams, Antifouling Marine Coatings, Noyes, Park Ridge, 1973.

[0097] Anti-fouling coating agents contain, in addition to anti-algae agents, fungicides, anti-mollusks and combinations of bactericidal active substances according to the present invention, in particular binders.

[0098] Examples of known binders are polyvinyl chloride in a solvent system, chlorinated rubber in a solvent system, acrylic resins in a solvent system especially in a water-containing system, a copolymer of vinyl chloride with vinyl acetate in the form of a water-containing suspension or in the form of a solution in an organic solvent system , rubbers based on butadiene, styrene, acrylonitrile, drying oils such as linseed oil, ester resins or modified hard resins in combination with tar or bitumen, asphalt as well as epoxy compounds, small amounts of chlorinated rubber, chlorinated polypropylene and vinyl resin.

[0099] The coating agents optionally also contain inorganic pigments, organic pigments or dyes, especially those which are insoluble in sea water. The coating agents may then contain materials such as rosin to allow controlled release of the active ingredients. The coating agents can then contain plasticizers, rheology modifiers as well as other customary ingredients. The compounds of the present invention or the aforementioned mixtures may also be included in self-cleaning systems of organisms growing on them.

[0100] Combinations of active substances are also suitable for controlling animal pests, especially insects, arachnids and mites, found indoors, such as flats, factory halls, offices, vehicle cabins etc. They can be used to combat these pests in the form of insecticides intended for home use. They are active against sensitive and resistant species, as well as against all stages of development. These pests include:

From the order of Scorpionidea, e.g. Buthus occitanus.

From Acarina, e.g. Argas persicus, Argas reflexus, Bryobia ssp., Dermanyssus gallinae, Glyciphagus domesticus, Omithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi, Neutrombicula autumnalis, Dermatophagoides pteronissimus.

From the order of Araneae, e.g. Aviculariidae, Araneidae.

From the order of Opiliones, e.g. Pseudoscorpiones chelifer, Pseudoscorpiones cheiridium, Opiliones phalangium.

From the order of Isopoda, e.g. Oniscus asellus, Porcellio scaber.

From the Diplopoda row, e.g. Blaniulus guttulatus, Polydesmus spp.

From the order of Chilopoda, e.g. Geophilus spp.

From the order of Zygentom, e.g. Ctenolepisma spp., Lepisma saccharina, Lepismodes inquilinus.

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

Saltatoria, e.g. Acheta domesticus.

From the order of Dermaptera e.g. Forficula auricularia.

From the order of Isoptera, e.g. Kalotermes spp., Reticulitermes spp.

From the order of Psocoptera, e.g. Lepinatus spp., Liposcelis spp.

From the order of Colepter, e.g. 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 Diptera, e.g. Aedes aegypti, Aedes albopictus, Aedes taeniorhynchus, Anopheles spp., Calliphora erythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culex pipiens, Culex tarsalis, Drosophila spppca, Fanos sarophila sp. , Simulium spp., Stomoxys calcitrans, Tipula paludosa.

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

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

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

From the Anoplura order, e.g. Pediculus humanus capitis, Pediculus humanus corporis, Phthirus pubis.

From the order of Heteroptera, e.g. Cimex hemipterus, Cimex lectularius, Rhodinus prolixus, Triatoma infestans.

[0101] Application is by the use of aerosols, by means of non-pressure spraying devices, e.g. pumps and spraying devices, automatic fog machines, steam generators, foams, gels, vaporizers with a cellulose or plastic vaporizer plate, liquid, gel and membrane vaporizers, propeller vaporizers, relatively non-passive vaporizing systems, paper saturated with antimole active substance , antimolar pouches and antimolar gels in the form of granules or dust, scattered baits or bait traps.

[0102] The present invention can be applied to all plants and parts thereof. Plants are understood to mean all plants and plant populations, both desirable and undesirable, wild growing or cultivated (including naturally occurring plant crops). Plant crops can be plants obtained by customary breeding and optimization methods or by biotechnological and gene methods or by a combination of these methods, including transgenic plants and including those that are protected or unprotected by species protection laws. Plant parts should be understood as above-ground and underground plant parts and organs, such as shoots, leaves, flowers and roots, e.g. leaves, needles, stems, stems, flowers, fruits and seeds as well as roots, tubers and rhizomes are exchanged. Plant parts also include harvests, both vegetative and those used for propagation, for example cuttings, tubers, rhizomes, shoots and seeds.

[0103] The active substances on plants and their parts which are the subject of the invention can be carried out directly or by means of usual methods on the surroundings, environment or room, e.g. by immersion, spraying, evaporation, spraying, sprinkling, lubrication, and in the case of reproductive material, especially seeds , also by covering with one or more layers. As previously mentioned, all plants and parts thereof can be subjected to the methods of the present invention. In a preferred embodiment, the plants and their parts, occurring in the wild or as species and genera obtained by conventional breeding methods, such as crossing or combination of protoplasts, are treated. In a further preferred embodiment, transgenic plants and their parts and their types are subjected to gene treatment methods, possibly in combination with conventional methods (genetic modified organisms). The term 'parts' or 'parts of plants' or 'plant parts' has been explained above.

[0104] It is particularly preferred to treat plants of the species commercially available or used according to the present invention.

[0105] Actions according to the present invention may also have extra-synergistic ("synergistic") effects depending on the plant species or species, place and conditions of growth (soil, climate, growing season, nutrition). Thus, it is possible, for example, to reduce the consumption and / or extend the scope of action and / or strengthen the activity of the compounds and agents used according to the present invention, improve development, increase tolerance to higher and lower temperatures, increase tolerance to drought, due to the increased content of water or salt in soil, increase flowering, facilitate harvesting, accelerate ripening, higher harvest, higher quality and / or higher nutritional value of harvested products, higher durability and better storage and / or processing properties that exceed the expected results.

[0106] Transgenic plants (obtained by genetic engineering techniques), preferably treated with the present invention, include plants or plant species obtained by means of technological genetic modification of genetic material that exhibit particularly valuable properties (traits). Examples of such properties are: better development, increased tolerance to elevated and reduced temperatures, increased tolerance to drought, to increased water or salt content in soil, increased flowering, facilitated harvesting, accelerated ripening, higher harvest, higher quality and / or higher nutritional value collected products, higher durability and better properties during storage and / or processing that exceed the expected effects. Further and excellent examples of such properties are: increased plant protection against animal and microbial pests such as insects, mites, plant disease fungi, bacteria and / or viruses, as well as increased plant tolerance to certain herbicides. As examples of transgenic crops, cereals (wheat, rice), corn, soybean, potatoes, cotton, tobacco, rapeseed, as well as fruit trees (with apples, pears, citrus fruits and grapes) are mentioned, with corn deserving special mention. soybeans, potatoes, cotton, tobacco and oilseed rape. As properties (features) deserve special mention: increased defense of plants against insects, arachnids, nematodes and snails by plant toxins, especially those that were produced in plants by Bacillus Thuringiensis (e.g. by the CryIA (a) genes, CryIA ( b), CryIA (c), CryIIA, CryIIIA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CrylF as well as a combination thereof (hereinafter referred to as "Bt plants"). As properties (features) deserve special mention: increased defense of plants against fungi, bacteria and viruses through systemically acquired resistance (SAR), systemin, phytoalexins, elicitors, as well as resistance genes and properly manifested proteins and toxins. As properties (features) deserve special mention: increased tolerance of plants to certain herbicides, for example imidazolinones, sulfonylureas, glyphosphate or phosphinothricin (e.g. the PAT gene). In a given case, the desired properties (features) of the added gene in transgenic plants can also occur as a result of interconnections. Examples of "Bt plants" include corn, cotton, soybean and potato, which are sold under the trade names YIELD GARD® (e.g. corn, cotton, soybean, KnockOut® (e.g. corn), StarLink® (e.g. Corn), Bollgard® (cotton), Nucotn® (cotton) and NewLeaf® (potatoes). Examples of plants that tolerate herbicides well include corn, cotton and soybean, which are sold under the trade names Roundup Ready® (glyphosphate tolerance, e.g. corn, cotton, soybean), Liberty Link® (phosphinothricin tolerance, e.g. rapeseed), IMI® (imidazolinone tolerance) and STS® (sulfonylurea tolerance, e.g. corn). As herbicide resistant plants (conventionally grown) mention should be made of the species sold under the name Clearfeld® (e.g. maize). It goes without saying that these statements are also valid for future or future plant species with these or future developed properties (traits).

[0107] The plants listed can according to the present invention be particularly advantageously treated with the active compound combinations according to the invention. The advantages described above when discussing the combinations also apply to their effects on these plants. It is especially beneficial to act on the combinations of plants specially highlighted in the submitted text.

[0108] The beneficial insecticidal, acaricidal and fungicidal action of the active compound combinations of the present invention is supported by the examples below. While individual active substances show poor activity, they combine to give an effect that outweighs the sum of their activity.

[0109] A synergistic effect occurs with insecticides, acarids and fungicides whenever the activity of the active substance combination is higher than the sum of the activities of the individual active substances used.

[0110] The insecticidal, acaricidal and fungicidal activity expected for a given combination of the two active substances can be calculated from the following formula which

SR Colby, Weeds 15 (1967), 20-22:

When

X is the degree of mortality expressed in% of the control sample, not treated with the active substance, using substance A in mg / ha or in concentration m ppm,

Y is the mortality rate expressed in% of the untreated control sample when substance B is used at ng / ha or at a concentration of n ppm and

E is the mortality rate expressed in% of the control sample, not treated with the active substance, using substances A and B in quantities of ming / ha or in a concentration of min ppm, then

E = X + Y - XY / 100 [0111] If the actual rate of mortality is higher than calculated, then the combination is more active than it results from additivity, i.e. there is a synergistic effect. In this case, the actually observed mortality rate must be higher than the expected mortality rate (E) calculated from the quoted formula.

Examples

Example A

Test for Myzus persicae [0112] solvent: 7 parts by weight of dimethylformamide, emulsifier:

parts by weight of alkylaryl polyglycol ether [0113] To prepare a suitable preparation of active substance, 1 part of active substance is mixed with the given amount of solvent and emulsifier and diluted with water containing the emulsifier to obtain the desired concentration.

[0114] Cabbage leaves (Brassica oleracea) heavily infested by peach aphids (Myzus persicae) are treated with the preparation of the active substance of the selected concentration by immersion. After the selected time, the mortality rate is determined. A 100% result means that all aphids have been killed, a 0% result means none. Detected mortality rates are inserted into Colby's formula (see page 1).

[0115] In this test, for example, the following active substance combinations prepared according to the present invention show a synergistic increase in activity compared to the individual active substances used:

Table A.

Insects harmful to plants: test for Myzus persicae

<td rowspan="2">Active substances</td><td rowspan="2">Active substance concentration in ppm</td><td colspan="3">Mortality rate in% after d</td>

<td>knew. *</td><td>calc. **</td><td>d ***</td>

<td>(1-2) N- [2- (1,3-dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide</td><td> 100</td><td> 0</td><td></td><td> 6</td>

<td>(6.2.1) fipronil</td><td> 100</td><td> 65</td><td></td><td> 6</td>

<td>(1-2) N- [2- (1,3-dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide + (6.2.1) fipronil (1: 1)</td><td> 100 + 100</td><td> 85</td><td> 65</td><td> 6</td>

<td>(1-2) N- [2- (1,3-dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide</td><td> 100</td><td> 0</td><td></td><td> 6</td>

<td>(3.1.1) methiocarb</td><td> 100</td><td> 0</td><td></td><td> 6</td>

<td>(1-2) N- [2- (1,3-dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide + (3.1.1) methiocarb (1: 1)</td><td> 100 + 100</td><td> 25</td><td> 0</td><td> 6</td>

<td colspan="5">* Knew. = activity found ** calculated. = activity calculated according to Colby's formula *** d = evaluation carried out after the given number of days</td>

Example B

Test for Phaedon cochleariae [0116] solvent: 7 parts by weight of dimethylformamide emulsifier:

parts by weight of alkylaryl polyglycol ether [0117] To prepare a suitable preparation of active substance, 1 part of active substance is mixed with the given amount of solvent and emulsifier and diluted with water containing the emulsifier to obtain the desired concentration.

[0118] Cabbage leaves (Brassica oleracea) are treated with the preparation of active substance of the selected concentration by immersion and planted with larvae of the horseradish duck (Phaedon cochleariae) while the leaves are still moist.

[0119] After the selected time, the degree of mortality is determined. At the same time, a 100% result means that all larvae have been killed, a 0% result means none.

[0120] In this test, for example, the following active substance combinations prepared according to the present invention show a synergistic increase in activity compared to the individual active substances used:

Table B

<td colspan="5">Insects harmful to plants: test for Phaedon cochleariae</td>

<td rowspan="2">Active substances</td><td rowspan="2">Active substance concentration in ppm</td><td colspan="3">Mortality rate in% after d</td>

<td>knew. *</td><td>calc. **</td><td>d ***</td>

<td>(1-2) N- [2- (1,3-dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide</td><td> 100</td><td> 0</td><td></td><td> 6</td>

<td>(2.1.1) clothianidin</td><td> 0,8</td><td> 0</td><td></td><td> 6</td>

<td>(1-2) N- [2- (1,3-dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide + (2.1.1) clothianidin (125: 1)</td><td> 100 + 0,8</td><td> 30</td><td> 0</td><td> 6</td>

<td>(1-2) N- [2- (1,3-dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide</td><td> 100</td><td> 0</td><td></td><td> 6</td>

<td>(2.1.2) imidacloprid</td><td> 0,8</td><td> 40</td><td></td><td> 6</td>

<td>(1-2) N- [2- (1,3-dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide + (2.1.2) imidacloprid (125: 1)</td><td> 100 + 0,8</td><td> 80</td><td> 40</td><td> 6</td>

<td>(1-2) N- [2- (1,3-dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide</td><td> 100</td><td> 0</td><td></td><td> 6</td>

<td>(5.1.1) spinosad</td><td> 0,8</td><td> 80</td><td></td><td> 6</td>

<td>(1-2) N- [2- (1,3-dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide + (5.1.1) spinosad (125: 1)</td><td> 100 + 0,8</td><td> 100</td><td> 80</td><td> 6</td>

<td>(1-2) N- [2- (1,3-dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide</td><td> 100</td><td> 0</td><td></td><td> 4</td>

<td>(3.1.2) thiodicarb</td><td> 100</td><td> 0</td><td></td><td> 4</td>

<td>(1-2) N- [2- (1,3-dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide + (3.1.2) thiodicarb (1: 1)</td><td> 100 + 100</td><td> 20</td><td> 0</td><td> 4</td>

<td colspan="5">* Knew. = activity found ** calculated. = activity calculated according to Colby's formula *** d = evaluation carried out after the given number of days</td>

Example C

Test for Plutella xylostella. [0121] solvent: 7 parts by weight of dimethylformamide, emulsifier: 2 parts by weight of alkylaryl polyglycol ether [0122] To make a suitable preparation of active substance, 1 part of active substance is mixed with the amount of solvent and emulsifier given and diluted with water containing the emulsifier to obtain desired concentration.

[0123] Cabbage leaves (Brassica oleracea) are treated with the preparation of the active substance of the selected concentration by immersion and planted with caterpillars of the Phillipennis mantis (Plutella xylostella) while the leaves are still moist.

[0124] After the selected time, the degree of mortality is determined. A 100% score means that all caterpillars have been killed, a 0% score means none.

[0125] In this test, for example, the following active substance combinations prepared according to the present invention show a synergistic increase in activity compared to the individual active substances used:

Table C

<td colspan="5">Insects harmful to plants: test for Plutella xylostella</td>

<td rowspan="2">Active substances</td><td rowspan="2">Active substance concentration in ppm</td><td colspan="3">Mortality rate in% after d</td>

<td>knew. *</td><td>calc. **</td><td>d ***</td>

<td>(1-2) N- [2- (1,3-dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide</td><td> 100</td><td> 15</td><td></td><td> 6</td>

<td>(2.1.1) clothianidin</td><td> 20</td><td> 20</td><td></td><td> 6</td>

<td>(1-2) N- [2- (1,3-dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide + (2.1.1) clothianidin (5: 1)</td><td> 100 + 20</td><td> 65</td><td> 32</td><td> 6</td>

<td>(1-2) N- [2- (1,3-dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide</td><td> 100</td><td> 0</td><td></td><td> 6</td>

<td>(2.1.2) imidacloprid</td><td> 4</td><td> 20</td><td></td><td> 6</td>

<td>(1-2) N- [2- (1,3-dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide + (2.1.2) imidacloprid (25: 1)</td><td> 100 + 4</td><td> 40</td><td> 20</td><td> 6</td>

<td colspan="5">* Knew. = activity found ** calculated. = activity calculated according to Colby's formula *** d = evaluation carried out after the given number of days</td>

Example D

Botrytis cinerea (in vitro) / microtiter plate assay [0126] The microtest is performed on microtiter plates using potato dextrose medium (PDB) as the liquid sample medium. The active substance is used as the technical active ingredient dissolved in acetone. Botrytis cinerea spore suspension is used for inoculation. After 5 days of incubation in the dark and with shaking (10 Hz), the light transmittance in each well of the plate is determined using a spectrophotometer.

[0127] A degree of activity of 0% means an increase corresponding to an increase in control samples, and a degree of 100% means that no fungal growth is observed.

[0128] From the table below it is clear that the activity of the combination according to the invention found is greater than the calculated, i.e. there is a synergistic effect.

Table D

<td colspan="5">Botrytis cinerea test (in vitro) / on microtiter plates</td>

<td rowspan="2">Active substances</td><td rowspan="2">Active substance concentration in ppm</td><td colspan="3">Mortality rate in% after d</td>

<td>knew. *</td><td>calc. **</td><td>d ***</td>

<td>(1-2) N- [2- (1,3-dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide</td><td> 3</td><td> 16</td><td></td><td> 5</td>

<td>(2.1.1) clothianidin</td><td> 3</td><td> 3</td><td></td><td> 5</td>

<td>(1-2) N- [2- (1,3-dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide + (2.1.1) clothianidin (1: 1)</td><td> 3 + 3</td><td> 29</td><td> 19</td><td> 5</td>

<td colspan="5">* Knew. = activity found ** calculated. = activity calculated according to Colby's formula *** d = evaluation carried out after the given number of days</td>

Example E

Alternaria mali test (in vitro) / microtiter plates [0129] The microtest is performed on microtiter plates using potato dextrose medium (PDB) as the liquid sample medium. The active substance is used as the technical active ingredient dissolved in acetone. Alternaria mali spore suspension is used for inoculation. After 4 days of incubation in the dark and with shaking (10 Hz), the light transmission in each well of the plate is determined using a spectrophotometer.

[0130] An activity grade of 0% means an increase corresponding to an increase in control samples, and a degree of 100% means that no fungal growth is observed.

[0131] The table below clearly shows that the activity of the combination according to the invention found is greater than the calculated, i.e. there is a synergistic effect.

Table E

<td colspan="5">Test on Alternaria mali (in vitro) / on microtiter plates</td>

<td rowspan="2">Active substances</td><td rowspan="2">Active substance concentration in ppm</td><td colspan="3">Mortality rate in% after d</td>

<td>knew. *</td><td>calc. **</td><td>d ***</td>

<td>(1-2) N- [2- (1,3-dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide</td><td> 3</td><td> 48</td><td></td><td> 4</td>

<td>(2.1.1) clothianidin</td><td> 3</td><td> 8</td><td></td><td> 4</td>

<td>(1-2) N- [2- (1,3-dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide + (2.1.1) clothianidin (1: 1)</td><td> 3 + 3</td><td> 58</td><td> 53</td><td> 4</td>

<td colspan="5">* Knew. = activity found ** calculated. = activity calculated according to Colby's formula *** d = evaluation carried out after the given number of days</td>

Aleksandra Twardowska, PhD

Patent Attorney