ES2351440T3 - COMBINATIONS OF ACTIVE PRINCIPLES. - Google Patents

Abstract

- Combinations of active ingredients with very good fungicidal, insecticidal and / or acaricidal properties that contain a carboxamide of formula (I) (Group I) and at least one active ingredient that is selected from the group consisting of (2.1.1) Clothianidine (2.1 .2) Imidacloprid (2.1.3) Thiacloprid (3.1.1) Metiocarb (3.1.2) Thiodicarb (4.1.1) Beta-ciflutrin (5.1.1) Espinosad (6.2.1) Fipronil (21.1.1) N 2 - [1,1-Dimethyl-2- (methylsulfonyl) ethyl] -3-iodo-N 1 - [2-methyl-4- [1,2,2,2-tetrafluoro-1 (trifluoromethyl) ethyl] phenyl] -1 , 2-benzenedicarboxamide (flubendiamide).

Description

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The present invention relates to new combinations of active ingredients that are constituted, on the one hand, by known carboxamides and, on the other hand, by known insecticidal active ingredients and are very suitable for combating unwanted animal pests such as insects or mites, as well as unwanted phytopathogenic fungi.

It is already known that certain carboxamides possess fungicidal properties: for example, N [2- (1,3-dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1 H -pyrazol-4-carboxamide by WO 03 / 010149 and 3- (tri-fluoromethyl) -N- [2- (1,3-dimethylbutyl) phenyl] -5-fluoro-1-methyl-1 H -pyrazol-4-carboxamide by DE-A 103 03 589. The effectiveness of these substances is good, but in some cases it leaves you wanting at low doses.

In addition, it is known that numerous esters of phosphoric acid, carbamates, heterocycles, organotin compounds, benzoylureas and pyrethroids possess insecticidal and acaricidal properties (see, for example, 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 effect of these substances is not satisfactory in all areas.

Now we have found new combinations of active ingredients with very good fungicidal, insecticidal and / or acaricidal properties that contain a carboxamide of general formula (I) (Group 1)

image 1

and at least one active ingredient that is selected from the group consisting of

(2.1.1) Clothianidine

(2.1.2) Imidacloprid

(2.1.3) Tiacloprid

(3.1.1) Metiocarb

(3.1.2) Thiodicarb

(4.1.1) Beta-ciflutrin

(5.1.1) Espinosad

(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). Surprisingly, the fungicidal, insecticidal or acaricidal effect of the combination of

active ingredients according to the invention is essentially greater than the sum of the effects of the active ingredients separately. Therefore, there is an unpredictable synergistic effect and not just an addition of effects.

Formula (I) comprises the mixing partners of Group (1):

N- [2- (1,3-Dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1 H -pyrazol-4-carboxamide (known from the document

WO 03/010149)

The combinations of active ingredients according to the invention contain, in addition to carboxamide (1-2) N- [2- (1,3-dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1H-pyrazole-4 -carboxamide (Group 1), one or more mixing partners, preferably one, of the group

(2.1.1) Clothianidine

(2.1.2) Imidacloprid 10 (2.1.3) Tiacloprid

(3.1.1) Metiocarb

(3.1.2) Thiodicarb

(4.1.1) Beta-ciflutrin

(5.1.1) Espinosad 15 (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 (ie, flubendiamide, CAS reg. no .: 27245165-7).

The combinations according to the invention are shown in the following table.

20 Table 1

Active principle of the Group (1)

Active principle of Groups (2) to (24)

(1-2) N- [2- (1,3-Dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1 Hpyrazol-4-carboxamide

(2.1.1) Clothianidine

(1-2) N- [2- (1,3-Dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1 Hpyrazol-4-carboxamide

(2.1.2) Imidacloprid

(1-2) N- [2- (1,3-Dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1 Hpyrazol-4-carboxamide

(2.1.3) Tiacloprid

(1-2) N- [2- (1,3-Dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1 Hpyrazol-4-carboxamide

(3.1.1) Metiocarb

(1-2) N- [2- (1,3-Dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1 Hpyrazol-4-carboxamide

(3.1.2) Thiodicarb

(1-2) N- [2- (1,3-Dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1 Hpyrazol-4-carboxamide

(4.1.1) Beta-ciflutrin

(1-2) N- [2- (1,3-Dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1 Hpyrazol-4-carboxamide

(5.1.1) Espinosad

Active principle of the Group (1)

Active principle of Groups (2) to (24)

(1-2) N- [2- (1,3-Dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1 Hpyrazol-4-carboxamide

(6.2.1) Fipronil

(1-2) N- [2- (1,3-Dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1 Hpyrazol-4-carboxamide

(21.1.1) Flubendiamide

Combinations of active ingredients may also contain other fungicidal, acaricidal or insecticidally active mixture components. When the active ingredients in the combinations of active ingredients according to the invention are present in certain weight ratios, the synergistic effect is especially clear.

5 However, the weight ratios of the active ingredients in the active ingredient combinations can vary over a relatively large range. In general, the combinations according to the invention contain an active principle of formula (I) and the mixing associates in the mixing ratios specified preferably in the following table, the mixing ratios being based on weight ratios.

10 The relationship should be understood as the active ingredient of formula (I) (Group 1): mixing partner. Table 2: Mix ratios

Mixing constituents (Group)

Preferred Mix Ratio Especially preferred mixing ratio

(2.1) Chloronicotinyl / neonicotinoid

500: 1 to 1: 50 125: 1 to 1: 25

(3.1) Carbamate

500: 1 to 1: 1000 125: 1 to 1: 500

(4.1) Pyrethroid

500: 1 to 1: 50 125: 1 to 1: 25

(5.1) Spinosyne

500: 1 to 1: 50 125: 1 to 1: 25

(6.2) Fiprol

500: 1 to 1: 200 125: 1 to 1: 50

(21) Phthalamide

500: 1 to 1: 50 125: 1 to 1: 25

The combinations of active ingredients according to the invention have a strong effect

microbicide and can be used in phytoprotection and in protection of materials to combat

Unwanted microorganisms such as fungi and bacteria.

15 Fungicides can be used in phytoprotection to combat plasmodioforomycetes, oomycetes, chytridiomycetes, zygomycetes, ascomycetes, basidiomycetes and deuteromycetes. Bactericides can be used in phytoprotection to combat pseudomonadiaceae,

rhizobiaceae, enterobacteriaceae, corinebacteriaceae and streptomycetaceae.

As an example, but not limiting, some disease pathogens can be mentioned

fungal and bacterial that are within the generic terms mentioned above: Diseases caused by pathogens of the powdery mildew, such as Blumeria species, such as Blumeria graminis; Podosphaera species, such as Podosphaera leucotricha; Sphaerotheca species, such as Sphaerotheca fuliginea; Uncinula species, such as Uncinula necator;

Diseases caused by rust pathogens, such as Gymnosporangium species, such as Gymnosporangium sabinae Hemileia species, such as Hemileia vastatrix; Phakopsora species, for example Phakopsora pachyrhizi and Phakopsora meibomiae; Puccinia species, such as Puccinia recondita or Puccinia triticina; Uromyces species, such as Uromyces appendiculatus;

Diseases caused by pathogens of the oomycete group, such as Bremia species, such as Bremia lactucae; Peronospora species, such as Peronospora pisi or P. brassicae; Phytophthora species, such as Phytophthora infestans; Plasmopara species, such as Plasmopara viticola; Pseudoperonospora species, such as Pseudoperonospora humuli or Pseudoperonospora cubensis; Pythium species, such as Pythium ultimum;

Diseases due to leaf spots and leaf wilting caused by, for example, Alternaria species, such as Alternaria solani; Cercospora species, such as Cercospora beticola; Cladiosporum species, such as Cladiosporium cucumerinum; Cochliobolus species, such as Cochliobolus sativus (conidia form: Drechslera, sin .: Helminthosporium); Colletotrichum species, such as Colletotrichum lindemuthianum; Cycloconium species, such as Cycloconium oleaginum; Diaporthe species, such as Diaporthe citri; Elsinoe species, such as Elsinoe fawcettii;

Gloeosporium species, such as Gloeosporium laeticolor; Glomerella species, such as Glomerella cingulata; Guignardia species, such as Guignardia bidwelli; Leptosphaeria species, such as Leptosphaeria maculans; Magnaporthe species, such as Magnaporthe grisea; Mycosphaerella species, such as Mycosphaerella graminicola and M. fijiensis; Phaeosphaeria species, such as Phaeosphaeria nodorum; Pyrenophora species, such as Pyrenophora teres; Ramularia species, such as Ramularia collo-cygni; Rhynchosporium species, such as Rhynchosporium secalis; Septoria species, such as Septoria apii; Typhula species, such as Typhula incarnata; Venturia species, such as Venturia inaequalis;

Root and stem diseases caused by, for example, Corticium species, such as Corticium graminearum; Fusarium species, such as Fusarium oxysporum; Gaeumannomyces species, such as Gaeumannomyces graminis; Rhizoctonia species, such as Rhizoctonia solani; Tapesia species, such as Tapesia acuformis; Thielaviopsis species, such as Thielaviopsis basicola;

Spike and panicle diseases (including corn cobs) caused by, by example, Alternaria species, such as Alternaria spp .; Aspergillus species, such as Aspergillus flavus; Cladosporium species, such as Cladosporium cladosporioides; Claviceps species, such as Claviceps purpurea; Fusarium species, such as Fusarium culmorum; Gibberella species, such as Gibberella zeae; Monographella species, such as Monographella nivalis;

Diseases caused by ustilaginales, such as Sphacelotheca species, such as Sphacelotheca reiliana; Tilletia species, such as Tilletia caries;

Urocystis species, such as Urocystis occulta; Ustilago species, such as Ustilago nuda;

Fruit rot caused by, for example, Aspergillus species, such as Aspergillus flavus; Botrytis species, such as Botrytis cinerea; Penicillium species, such as Penicillium expansum and P. purpurogenum; Sclerotinia species, such as Sclerotinia sclerotiorum; Verticilium species, such as Verticilium alboatrum;

Seed rot and soil borne and wilting, as well as seedling diseases caused by, for example, Fusarium species, such as Fusarium culmorum; Phytophthora species, such as Phytophthora cactorum; Pythium species, such as Pythium ultimum; Rhizoctonia species, such as Rhizoctonia solani; Sclerotium species, such as Sclerotium rolfsii;

Carcinogenic diseases, gills and gnarled excrescences caused by, for example, Nectria species, such as Nectria galligena;

Withering diseases caused by, for example, Monilinia species, such as Monilinia laxa;

Deformations of leaves, flowers and fruits caused by, for example, Taphrina species, such as Taphrina deformans;

Degenerative diseases of woody plants caused by, for example, Esca species, such as Phaemoniella clamydospora;

Diseases of flowers and seeds caused by, for example, Botrytis species, such as Botrytis cinerea;

Diseases of plant tubers caused by, for example, Rhizoctonia species, such as Rhizoctonia solani;

Helminthosporium species, such as Helminthosporium solani;

Diseases caused by bacterial pathogens, such as Xanthomonas species, such as Xanthomonas campestris pv. oryzae; Pseudomonas species, such as Pseudomonas syringae pv. lachrymans; Erwinia species, such as Erwinia amylovora.

Preferably, the following diseases of soy beans can be combated:

Fungal diseases of leaves, stems, pods and seeds caused by, for example, leaf spot by Alternaria (Alternaria spec. Atrans tenuissima), anthracnose (Colletotrichum gloeosporoides dematium var. Truncatum), brown spot (Septoria glycines), leaf spot and wilting by Cercospora (Cercospora kikuchii), foliar wilting by Choanephora (Choanephora infundibulifera trispora (sin.)), Leaf spot by Dactuliophora (Dactuliophora glycines), woolly mildew (Peronospora manshurica), wilting by Drechslera (Drechsgera, Frochapora (Cerropora) sojina), leaf spot by Leptosphaerulina (Leptosphaerulina trifolii), leaf spot by Phyllostica (Phyllosticta sojaecola), wilting of pods and stems (Phomopsis sojae), powdery mildew (Microsphaera diffusa), leaf spot by Pyrenochaeta (Pyrenochaine), Pyrenochaeta aerial (Pyrenochaeta) foliage and tissue by Rhizoctonia (Rhizoctonia solani), rust (Phakopsora pachyrhizi, Phakopsora meibo miae), scabies (Sphaceloma glycines), leaf wilting by Stemphylium (Stemphylium botryosum), concentric spot (Corynespora cassiicola).

Fungal diseases of the roots and stem base caused by, for example, black root rot (Calonectria crotalariae), carbon rot (Macrophomina phaseolina), wilting or wilting, root rot and pod and neck rot by Fusarium (Fusarium oxysporum, Fusarium orthoceras, Fusarium semitectum, Fusarium equiseti), root rot by Mycoleptodiscus (Mycoleptodiscus terrestris), Neocosmospora (Neocosmopspora vasinfecta), pod and stem rot (Diaporthe phaseolumum (Diaporthe phaseol phaseol) Dialoheorol phaseol (Diaporthe phaseolumum) caulivora), rot by Phytophthora (Phytophthora megasperma), brown stem rot (Phialophora gregata), rot by Pythium (Pythium aphanidermatum, Pythium irregularulare, Pythium debaryanum, Pythium myriotylum, Pythium fall and talus decomposition) of seedlings by Rhizoctonia (Rhizoctonia solani), stem decomposition by Sclerotinia (S Clerotinia sclerotiorum), southern wilt by Sclerotinia (Sclerotinia rolfsii), root rot by Thielaviopsis (Thielaviopsis basicola).

The good tolerance on the part of the plants of the combinations of active principles in the concentrations necessary to fight diseases of the plants allows a treatment of the whole plant (aerial plant parts and roots), of seedlings and seeds, and of the soil. The combinations of active ingredients according to the invention can be used for application to the sheets or also as protective substances.

The good tolerance on the part of the plants of the active principles that can be used in the concentrations necessary to fight diseases of the plants allows a treatment of the seed. Therefore, the active ingredients according to the invention can be used as protective substances.

A large part of the damage caused by phytopathogenic fungi in crop plants is already caused by infestation of the seed during storage and after the introduction of the seed in the soil, as well as during and immediately after the germination of the plants . This phase is especially critical since the roots and shoots of the growing plant are especially sensitive and already a small damage can lead to the death of the entire plant. Therefore, there is an especially great interest in protecting the seed and the plant that will germinate through the use of suitable agents.

The fight against phytopathogenic fungi that damage plants after emergence is first carried out by treating the soil and aerial plant parts with phytosanitary products. Due to doubts regarding a possible influence of phytosanitary products on the environment and the health of human beings and animals, efforts are being made to reduce the amount of active ingredients applied.

It has long been known to fight phytopathogenic fungi by treating plant seeds and is subject to continuous improvement. However, the treatment of seeds results in a series of problems that cannot always be satisfactorily resolved. Thus, it is desired to develop a procedure to protect the seed and the plant that will germinate that makes the additional application of phytosanitary products unnecessary after sowing or after the emergence of the plants or at least clearly reduce it. In addition, it is desired to optimize the amount of active ingredient used to best protect the seed and plant that will germinate from infestation by phytopathogenic fungi, but without damaging the plant itself by the active principle used. Seed treatment procedures should also include, in particular, the intrinsic fungicidal properties of transgenic plants to achieve optimal protection of the seed and plant that will germinate with minimal product expenditure

Phytosanitary

Therefore, the present invention also especially relates to a method for protecting the seed and plants that will germinate from infestation by phytopathogenic fungi by treating the seed with an agent according to the invention.

The invention also relates to the use of the agents according to the invention for the treatment of seeds to protect the seed and the plants that will germinate from phytopathogenic fungi.

In addition, the invention relates to seeds that, to protect them from phytopathogenic fungi, were treated with an agent according to the invention.

One of the advantages of the present invention is that, due to the special systemic properties of the agents according to the invention, the treatment of the seed with these agents not only protects the phytopathogenic fungus seed itself, but also the plants resulting therefrom. after the rise. In this way, the direct treatment of the crop can be suppressed at the time of sowing or shortly thereafter.

Likewise, it is also considered advantageous that the mixtures according to the invention can also be used especially in transgenic seeds.

The agents according to the invention are suitable for seed protection of any species of plants that are used in agriculture, in the greenhouse, in forestry or in gardening. In this regard it is especially cereal seed (such as wheat, barley, rye, millet and oats), corn, cotton, soy, rice, potatoes, sunflower, beans, coffee, beets (for example, sugar beet and fodder beet) , peanut, vegetables (such as tomato, cucumber, onions and lettuce), grass and ornamental plants. Of special importance is the treatment of cereal seed (such as wheat, barley, rye and oats), corn and rice.

Within the framework of the present invention, the agent according to the invention is applied alone or in a suitable formulation on the seed. Preferably, the seed is treated in a state in which it is so stable that no damage can occur during treatment. In general, seed treatment can be done at any time between harvest and planting. Normally, seed that was separated from the plant and released from ears, husks, stems, wrap, wool or pulp is used. Thus, for example, seed that was harvested, cleaned and dried to a moisture content of less than 15% by weight can be used. Alternatively, seed can also be used which, after drying, was treated, for example, with water and then dried again.

In general, in the treatment of the seed it should be taken into account that the quantity of the agent according to the invention and / or other additives applied on the seed is chosen in such a way that the germination of the seed is not influenced or the plant is not damaged resulting from it. This should be taken into account especially in active ingredients that may show phytotoxic effects at certain doses.

The agents according to the invention can be applied directly, that is, without containing other components and without having to be diluted. It is generally preferred to apply the agents on the seed in the form of a suitable formulation. The expert knows appropriate formulations and procedures for the treatment of seeds and are described, for example, 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.

The combinations of active ingredients according to the invention also have a potent invigorating effect on plants. In this regard, they are suitable for mobilizing the defenses of the plants themselves against infestation by unwanted microorganisms.

By invigorating substances of the plants (resistance inducers) it is understood in the present context those substances that can stimulate the immune system of the plants in such a way that the treated plants develop in the subsequent inoculation with unwanted microorganisms a broad resistance against these microorganisms .

In the present case, unwanted microorganisms should be understood as fungi, bacteria and phytopathogenic viruses. The substances according to the invention can also be used to protect plants within a certain period of time after treatment against infestation by the mentioned pathogenic organisms. The period of time within which protection is provided generally lasts from 1 to 10 days, preferably 1 to 7 days, after treatment of the plants with the active ingredients.

The good tolerance on the part of the plants of the combinations of active ingredients in the concentrations necessary to combat plant diseases allows a treatment of aerial plant parts, seedlings and seeds, and the soil.

In this regard, the combinations of active ingredients according to the invention can be used with especially good results for combating cereal diseases such as, for example, against Puccinia species and diseases in viticulture, fruit growing and vegetable cultivation, such as , against Botrytis, Venturia or Alternaria species.

The combinations of active ingredients according to the invention are also suitable for increasing the crop. In addition, they are less toxic and have a good tolerance on the part of the plants.

The combinations of active ingredients according to the invention can also be used in certain concentrations and doses, as herbicides to influence plant growth, as well as to combat animal parasites. Optionally, they can also be used as intermediates and precursors for the synthesis of other active ingredients.

According to the invention, all plants and plant parts can be treated. In this regard, plants are understood as all plants and plant populations, such as desired and unwanted wild plants or crop plants (including crop plants of natural origin). Cultivation plants can be plants that can be obtained by conventional cultivation and optimization procedures or by biotechnological and genetic procedures or combinations of these procedures, including transgenic plants and including plant varieties that can be protected or may not be protected by protection rights of species. Vegetable parts should be understood as all the aerial and underground parts and organs of the plants, such as bud, leaf, flower and root, listing, by way of example, leaves, acicles, stems, trunks, flowers, fruiting bodies, fruits and seeds, as well as roots, tubers and rhizomes. The crop also belongs to the plant parts, as well as the vegetative and generative multiplication material, for example layers, tubers, rhizomes, cuttings and seeds.

The treatment of plants and plant parts according to the invention with the combinations of active ingredients is carried out directly or by action on their environment, habitat or storage space according to the usual treatment procedures, for example, by immersion, spraying, gasification, nebulized, spread, paint and, in the case of the multiplication material, especially of seeds, also by coating with one or several layers.

In the protection of materials, the combinations of active ingredients according to the invention can be used to protect industrial materials from infestation and destruction by unwanted microorganisms.

Industrial materials should be understood in this context as non-living materials that have been prepared for use in the art. By way of example they can be industrial materials, which must be protected by the active ingredients according to the invention from microbial modification or destruction, adhesives, glues, paper and cardboard, textile products, leather, wood, coating materials and plastic articles, lubricants of refrigeration and other materials that can be attacked or broken down by microorganisms. Within the framework of the materials to be protected, it is also possible to mention parts of production plants, for example, cooling water circuits that can be damaged by the multiplication of microorganisms. Within the framework of the present invention, as industrial materials, adhesives, glues, paper and cardboard, leather, wood, coating materials, cooling lubricants and heat transfer liquids, especially wood, are preferably mentioned.

As microorganisms that can cause decomposition or modification of industrial materials, for example, bacteria, fungi, yeasts, algae and mucilaginous organisms can be mentioned. The active ingredients according to the invention preferably act against fungi, especially molds, wood coloring fungi and wood destroyers (basidiomycetes), as well as against mucilaginous organisms and algae.

As an example, microorganisms of the following genera can be mentioned: Alternaria, as Alternaria tenuis, Aspergillus, like Aspergillus niger, Chaetomium, like Chaetomium Globesum, Coniophora, like Coniophora puetana, Lentinus, like Lentinus tigrinus, Penicillium, like Penicillium glaucum, Polyporus, like Polyporus versicolor, Aureobasidium, such as Aureobasidium pullulans, Sclerophoma, such as Sclerophoma pityophila, Trichoderma, as Trichoderma viride, Escherichia, like Escherichia coli, Pseudomonas, such as Pseudomonas aeruginosa, Staphylococcus, such as Staphylococcus aureus. In addition, the combinations of active ingredients according to the invention also have

Very good antifungal effects. They have a very broad spectrum of antifungal action, especially against dermatophytes and blastomycetes, molds and diphasic fungi (for example, against Candida species such as Candida albicans, Candida glabrata), as well as Epidermophyton floccosum, Aspergillus species such as Aspergillus niger and Aspergillus fumigatus, Trychophyton species as Trychophyton mentagrophytes, Microsporon species such as Microsporon canis and audouinii. The list of these fungi does not represent at all a limitation of the recordable fungal spectrum, but only clarifies.

The combinations of active ingredients can be applied as such, in the form of their formulations or the application forms prepared therefrom as solutions, suspensions, wettable spray powders, pastes, soluble powders, dusting products and ready-to-use granules . The application is carried out as usual, for example, by irrigation, atomization, spraying, dusting, dusting, foaming, painting, etc. Furthermore, it is possible to produce the active ingredients according to the ultra-low volume process or to inject the active ingredient preparation or the active ingredient itself into the soil. The seed of the plants can also be treated.

In the use of the combinations of active ingredients according to the invention as fungicides, the doses may vary within a wide range depending on the type of application. In the treatment of plant parts, the doses of active substance are generally between 0.1 and

10,000 g / ha, preferably between 10 and 1,000 g / ha. In the treatment of the seed, the doses of active ingredient are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 10 g per kilogram of seed. In soil treatment, the doses of active ingredient are generally between 0.1 and 10,000 g / ha, preferably between 1 and 5,000 g / ha.

The aforementioned plants can be treated according to the invention especially advantageously with the active ingredient mixtures. The preferred ranges specified above in the active ingredients or mixtures are also valid for the treatment of these plants. Especially noteworthy is the treatment of plants with the compounds or mixtures specially cited herein.

The combinations of active ingredients according to the invention are also suitable for combating animal pests, preferably arthropods and nematodes, especially nematodes and insects that appear in agriculture, animal health, forestry, in the protection of stored products and materials, as well as in the hygienic sector. They are effective against normally sensitive and resistant species, as well as against all stages of development or stages of individual development. To the harmful organisms mentioned above belong:

From the order of the isopods, for example Oniscus asellus, Armadillidium vulgare, Porcellio scaber From the order of the diplópodos, for example Blaniulus guttulatus. From the order of chilopods, for example Geophilus carpophagus, Scutigera spp. From the order of the syphilids, for example Scutigerella immaculata. From the order of the tisanuros, for example Lepisma saccharina. From the order of the colébolo for example Onychiurus armatus. From the order of the orthoptera, for example Acheta domesticus, Gryllotalpa spp., Locusta migratory migratory, Melanoplus spp., Schistocerca gregaria. From the order of the Blatarios, for example Blatta orientalis, Periplaneta americana, Leucophaea Maderae, Blattella Germanica. Of the order of the dermápteros, for example Forficula auricularia. From the order of the isoptera, for example Reticulitermes spp. From the order of the gyropathians, for example Pediculus humanus corporis, Haematopinus spp., Linognathus spp., Trichodectes spp., Damalinia spp. From the order of the thysanoptera, for example Hercinothrips femoralis, Thrips tabaci, Thrips Palmi, Frankliniella accidentalis. From the order of the heteroptera, for example Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp. From the order of homoptera, for example Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp.,

Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp. From the order of the lepidoptera, for example Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella xylostella, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis 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 podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana, Cnaphalocerus spp., Oulema oryzae. From the order of the beetles, for example Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus 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, for example Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp. From the order of the diptera, for example Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., 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 spp., Liriomyza spp. From the order of siphonaptera, for example Xenopsylla cheopis, Ceratophyllus spp. From the class of arachnids, for example Scorpio maurus, Latrodectus mactans, Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa,

Panonychus spp., Tetranychus spp., Hemitarsonemus spp., Brevipalpus spp.

To parasitic plant nematodes belong, for example, Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinemaod spp., Xiphinemaod spp. spp., Bursaphelenchus spp.

The combinations of active ingredients can be converted according to their respective physical and / or chemical properties in the usual formulations such as solutions, emulsions, powders for spraying, suspensions, powders, foams, dusting powders, pastes, soluble powders, granules, aerosols, suspension-emulsion concentrates, natural and synthetic substances impregnated in active ingredients, very fine escapsulations in polymeric substances and in coating materials for seeds, as well as formulations for cold mist and hot mist of ULV.

These formulations are prepared in a known manner, for example, by mixing the active ingredients with diluents, that is, liquid solvents and / or solid supports, if necessary with the use of surfactants, i.e. emulsifiers and / or dispersing agents and / or foaming agents.

In the case of using water as a diluent, for example, organic solvents can also be used as auxiliary solvents. Liquid solvents include essentially: aromatic compounds such as xylene, toluene or alkylnaphthalenes, chlorinated aromatic compounds and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol, as well as their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, as well as water.

Solid supports include: for example, ammonium salts and natural mineral powders such as kaolins, clay soils, talc, crete, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic mineral powders such as highly dispersed silicic acid, aluminum oxide and silicates As solid supports for granules are considered: for example, broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite, as well as synthetic granules of inorganic and organic flours, as well as granules of organic material such as sawdust, shells of coconut, corn cobs and tobacco stalks; as emulsifiers and / or foaming agents are considered: for example, non-ionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example, alkylaryl polyglycol ethers, alkyl sulphonates, alkyl sulfates, arylsulfonates, as well as hydrolysates of proteins; as dispersing agents are considered: for example, bleach

residual sulfite with lignin and methylcellulose.

Adherent agents such as carboxymethyl cellulose, natural and synthetic polymers, powdered, granulated or latex-shaped, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids, such as cephalin and lecithins, and synthetic phospholipids. Other additives can be mineral and vegetable oils.

Dyes can be used as inorganic pigments, for example iron oxide, titanium oxide, ferrocyanide blue, and organic dyes such as alizarin, azoic and metal phthalocyanine dyes, and trace elements such as iron, manganese, boron, copper, cobalt salts, molybdenum and zinc

The formulations generally contain between 0.1 and 95% by weight of active ingredient, preferably between 0.5 and 90%.

The combinations of active ingredients according to the invention can be presented in the usual commercial formulations, as well as in the forms of application prepared from these formulations mixed with other active ingredients such as insecticides, attractants, sterilizers, bactericides, acaricides, nematicides, fungicides , growth regulating substances or herbicides. Insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenyl ureas, substances produced by microorganisms, among others.

Also possible a mixture with other known active ingredients, such as herbicides or with fertilizers and growth regulators.

The active ingredients according to the invention can also be presented in the use as insecticides in their usual commercial formulations, as well as in the forms of application prepared from these formulations mixed with synergists. Synergists are compounds through which the effect of active ingredients is increased without the added synergist must itself be actively effective.

The content of active ingredient of the forms of application prepared from the usual commercial formulations may vary over wide ranges. The concentration of active ingredient of the application forms can be from 0.0000001 to 95% by weight of active ingredient, preferably between 0.0001 and 1% by weight.

The application is carried out in a usual way adapted to the forms of application.

In the application against harmful sanitary organisms and stored products, the combinations of active ingredients stand out for an excellent residual effect on wood and clay, as well as for a good alkaline stability on whitewashed bases.

The combinations of active ingredients according to the invention not only act against the

harmful organisms in vegetables, sanitary ware and stored products, but also in the field of veterinary medicine against animal parasites (ectoparasites), such as common ticks, feather ticks, scabies mites, thrombidiforms, flies (choppers and suckers), larvae of parasitic flies, lice, hair lice, feather lice and fleas. To these parasites belong:

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

From the order of the pituitary and amblyceous suborders, as well as ischnóceros, by example, Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp.

On the order of the dipterans and the suborders of the nematopores, as well as the brachyceres, 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 ssp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp., Melophagus spp. From the order of siphonaptera, for example, Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp. From the order of the heteroptera, for example, Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp. From the order of the Blatarios, for example, Blatta orientalis, Periplaneta americana, Blattela Germanica, Supella spp.

Of the subclass of the mites (accharides) and of the orders of the metastigmados, as well as the mesostigmados, 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 actinédidos (prostigmados) and acarídidos (astigmados), 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 combinations of active ingredients according to the invention are also suitable for combating arthropods that infest agricultural animals, such as cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese , bees, other domestic animals, such as dogs, cats, domestic birds, aquarium fish, as well as so-called experimental animals, such as hamsters, guinea pigs, rats and mice. When fighting these arthropods, cases of death and decreased performance (in meat, milk, wool, skins, eggs, honey, etc.) should be avoided, so that by using the combinations of active ingredients according to the invention a possible Animal husbandry cheaper and easier.

The application of the combinations of active ingredients according to the invention occurs in the veterinary sector in a known manner by means of enteral administration in the form of, for example, tablets, capsules, watering cans, sprays, granules, pastes, boluses, of the process through food , of ovules, by parenteral administration, such as by injections (intramuscular, subcutaneous, intravenous, intraperitoneal, among others), implants, by nasal application, by dermal application in the form of, for example, immersion or bath (food immersion), spraying (spraying), spillage (back pouring “Pour-on and Spot-on”), washing, dusting, as well as with the help of molded bodies containing active ingredients, such as necklaces, ear marks, tail marks , limb bands, muzzles, marking devices, etc.

In the case of application for livestock, poultry, pets, etc., combinations of active ingredients can be applied as formulations (eg, powders, emulsions, agents that can flow) that contain the active ingredients in an amount from 1 to 80% by weight, directly or after a dilution of 100 to 10,000 times or used as a chemical bath.

Furthermore, it was found that the combinations of active ingredients according to the invention show a high insecticidal effect against insects that destroy industrial materials.

By way of example and with preference, but without limitation, the following insects should be mentioned:

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

Heminoptera such as 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.

Tisanuros like Lepisma saccharina.

Industrial materials are understood in this context as non-living materials, such as plastics, adhesives, glues, paper and cardboard, leather, wood, wood processing products and coating materials.

In a particularly preferred way, in the case of the material to be protected from insect infestation, it is wood and wood processing products.

By wood and wood processing products, which can be protected by the agent according to the invention or the mixtures containing it, for example: construction timber, wooden beams, railway sleepers, bridge parts, piers , wooden vehicles, boxes, pallets, containers, telephone poles, wooden walls, windows and wooden doors, plywood, particle boards, carpentry work or wood products that find use in a very general way in the construction of buildings or in the construction carpentry.

Combinations of active ingredients can be applied as such, in the form of concentrates or general customary formulations such as powders, granules, solutions, suspensions, emulsions or pastes.

The aforementioned formulations can be prepared in a manner known per se, for example by mixing the active ingredients with at least one solvent or diluent, emulsifier, dispersant and / or binder or fixing agent, water repellent, if necessary, desiccants and UV stabilizers and, where appropriate, dyes and pigments, as well as other processing aids.

The insecticidal agents or concentrates used for the protection of wood and carpentry materials contain the active ingredient according to the invention in a concentration of 0.0001 to 95% by weight, especially 0.001 to 60% by weight.

The amount of agents or concentrates used depends on the species and the origin of the insects and the environment. The optimum amount of use can be determined respectively in the application by series of tests. However, it is generally sufficient to use 0.0001 to 20% by weight, preferably 0.001 to 10% by weight of active ingredient, based on the material to be protected. The solvent and / or diluent serves as a solvent or mixture of organic chemical solvents and / or a solvent or mixture of oily or low volatile organic chemical solvents of the oily type and / or a solvent or mixture of polar organic chemical solvents and / or water and , if necessary, an emulsifier and / or crosslinker.

As organic chemical solvents, preferably oily or oily type solvents with an evaporation rate greater than 35 and a flash point above 30 ° C, preferably above 45 ° C are used. As oily and oil-insoluble, water-insoluble, low volatile solvents of this type are used the corresponding mineral oils or their fractions of aromatic compounds or solvent mixtures containing mineral oils, preferably diluting gasoline, petroleum and / or alkylbenzene.

Advantageously, mineral oils with a boiling range of 170 to 220 ° C, diluting gasoline with a boiling range of 170 to 220 ° C, spindle oil with a boiling range of 250 to 350 ° C, petroleum or aromatic compounds are used boiling range of 160 to 280 ° C, turpentine essence and the like.

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

Low-volatile oily or oily organic solvents with an evaporation rate greater than 35 and a flash point above 30 ° C, preferably above 45 ° C, may be partially replaced by light or moderately volatile organic chemical solvents with provided that the solvent mixture also has an evaporation rate greater than 35 and a flash point above 30 ° C, preferably above 45 ° C, and that the insecticide-fungicide mixture is soluble or can be emulsified in this mixture of solvents

According to a preferred embodiment, a part of the solvent or mixture of organic chemical solvents or a solvent or mixture of polar aliphatic organic chemical solvents is replaced. Preferably, aliphatic organic chemical solvents containing hydroxyl and / or ester and / or ether groups, such as glycol ether, ester or the like, are used.

Within the framework of the present invention, synthetic resins known per se which can be diluted in water and / or soluble in the used organic chemical solvents or which can be dispersed or emulsified and / or binder drying oils, especially compound binders, are used as organic chemical binders by or containing an acrylate resin, a vinyl resin, for example polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin such as coumarone-indene resin, silicone resin, drying and / or drying vegetable oils and / or physically drying binders based on a natural and / or synthetic resin.

The synthetic resin used as a binder can be used in the form of an emulsion, dispersion or solution. As binders, bitumen or bituminous substances up to 10% by weight can also be used. Additionally, dyes, pigments, hydrophobic agents can be used,

odor correctors and inhibitors or known anticorrosive agents and the like.

Preferably, according to the invention, at least one alkyd resin or modified alkyd resin and / or a drying vegetable oil is contained in the agent or in the concentrate. According to the invention, alkyd resins with an oil content of more than 45% by weight, preferably 50 to 68% by weight, are preferably used.

The aforementioned binder may be completely or partially replaced by a (a) (mixture of) fixing agent (s) or a (a) plasticizer (s) mixture. These additives must prevent volatilization of the active substances, as well as crystallization or precipitation. Preferably they replace 0.01 to 30% of the binder (based on 100% of the binder used).

The plasticizers come from the chemical classes of phthalic acid esters such as dibutyl, dioctyl or benzylbutyl phthalate, phosphoric acid esters such as tributyl phosphate, adipic acid esters such as di- (2-ethylhexyl) adipate, stearates such as stearate. amyl butyl or stearate, oleates such as butyl oleate, glycerin ethers or high molecular weight glycol ethers, glycerin esters, as well as p-toluenesulfonic acid ester.

The fixing agents are chemically based on polyvinyl alkyl ethers, such as polymethyl ether, or ketones such as benzophenone, ethylene benzophenone.

As solvent or diluent, water is also especially considered, if necessary in admixture with one or more of the above-mentioned organic chemical solvents or diluents, emulsifiers and chemical dispersants.

Especially effective wood protection is achieved by industrial impregnation procedures, for example vacuum, double vacuum or pressure procedures.

Likewise, the combinations of active ingredients according to the invention can be used to protect against encrustation of objects, especially of ship hulls, sieves, networks, civil works, wharf installations and signaling installations that are in contact with sea or salt water. .

Inlays by sessile oligochaetes, such as serpulids, as well as by bivalves and species of the group of ledamorphs (barnacles), such as different species of Lepas and Scalpellum, or by species of the group of balanomorphs (balances), such as species of Balanus or Pollicipes , increase the resistance to friction of ships and as a result lead to an increase in energy consumption and also a clear increase in operating costs due to frequent dry dock stays.

In addition to seaweed inlays, for example Ectocarpus sp. and Ceramium sp., especially it is of special importance the encrustation by sessile entomóstracos groups, that are included under the name of cirripedios (crayfish).

It has now been surprisingly found that combinations of active ingredients

according to the invention they have an excellent antifouling effect (antifouling).

By using the combinations of active ingredients according to the invention, the use of heavy metals can be dispensed with, for example, in bis- (trialkyltin) sulphides, tri-n-butyl tin laurate, tri-n-butyl chloride -Tin, copper (I) oxide, triethyl-tin chloride, trin-butyl- (2-phenyl-4-chloro-phenoxy) -tin, tributyl-tin oxide, molybdenum disulfide, antimony oxide, titanate polymeric butyl, phenyl- (bispyridin) -bismuth chloride, tri-n-butyltin fluoride, manganese ethylenebistiocarbamate, zinc dimethyldithiocarbamate, zinc ethylenebistiocarbamate, zinc and copper salts of 2-pyridine-thiol-1-oxide, bisdimethyldithiocarbamoyl zinc zinc ethylene bistiocarbamate, zinc oxide, copper (I) ethylene bisdithiocarbamate, copper thiocyanate, copper naphthenate and tributyl tin halides or the concentration of these compounds be reduced decisively.

Antifouling paints ready for application may still contain, where appropriate, other active ingredients, preferably algaecides, fungicides, herbicides, molluscicides or other antifouling active ingredients.

Preferably, as combination components for the antifouling agents according to the invention, suitable are:

Algicides such as 2-tert-butyl-amino-4-cyclopropylamino-6-methylthio-1,3,5-triazine, dichlorophen,

diuron, endotal, phentine acetate, isoproturon, metabenzthiazuron, oxyfluorfen, quinoclamine and

terbutrine;

fungicides such as S, benzo [b] thiophenecarboxylic acid cyclohexylamide dioxide,

diclofluanide, fluorfolpet, 3-iodo-2-propynyl butylcarbamate, tolylfluanide and azoles such as

azaconazole, ciproconazole, epoxiconazole, hexaconazole, metconazole, propiconazole and

tebuconazole;

molluscicides such as phentine acetate, metaldehyde, methiocarb, niclosamide, thiodicarb and

trimetacarb;

or common anti-fouling active ingredients such as 4,5-dichloro-2-octyl-4-isothiazolin-3-one, diiodomethylparatrilsulfone, 2- (N, N-dimethylthiocarbamoylthio) -5-nitrotiazyl, potassium, copper, sodium and zinc salts of 2-Pyridyntiol-1-oxide, pyridine-triphenylborane, tetrabutyldiestannoxane, 2,3,5,6-tetrachloro-4 (methylsulfonyl) -pyridine, 2,4,5,6-tetrachloro-phosphononitrile, tetramethylthiuram disulfide and 2,4,6-trichlorophenylmaleinimide .

The antifouling agents used contain the combinations of active ingredients according to the invention in a concentration of 0.001 to 50% by weight, especially 0.01 to 20% by weight.

The antifouling agents according to the invention also contain the usual constituents as described, for example, in Ungerer, Chem. Ind. 1985, 37, 730-732 and Williams,

Antifouling Marine Coatings, Noyes, Park Ridge, 1973.

The antifouling coating agents contain especially binders, in addition to the active substances algicides, fungicides, molluscicides and insecticides according to the invention.

Examples of recognized binders are polyvinyl chloride in a solvent system, chlorinated rubber in a solvent system, acrylic resins in a solvent system, especially in an aqueous system, vinyl chloride / vinyl acetate copolymer system in in the form of aqueous dispersions or in the form of organic solvent systems, butadiene / styrene / acrylonitrile rubbers, drying oils, such as flaxseed oil, resin esters or modified hardened resins in combination with pitch or bitumen, asphalt, as well as epoxy compounds, small amounts of chlorinated rubber, chlorinated polypropylene and vinyl resins.

If necessary, the coating agents also contain inorganic pigments, organic pigments or dyes, which are preferably insoluble in seawater. In addition, the coating agents may contain materials such as rosin to enable a controlled release of the active ingredients. In addition, the coatings may contain plasticizers, modifying agents that influence rheological properties, as well as other common constituents. The compounds according to the invention or the aforementioned mixtures can also be incorporated into self-polishing antifouling systems.

Combinations of active ingredients are also suitable for fighting animal pests, especially insects, arachnids and mites, which may be present in enclosed spaces, such as homes, factory buildings, offices, car cabins, among others. They can be used to combat these harmful organisms in household insecticide products. They are effective against sensitive and resistant species, as well as against all stages of development. To these harmful organisms belong:

From the order of the scorpions, for example, Buthus occitanus. From the order of acarins, 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 spiders, for example, avicular, araneides. From the order of opilions, for example, Pseudoscorpiones chelifer, Pseudoscorpiones Cheiridium, Opiliones phalangium. From the order of the isopods, for example, Oniscus asellus, Porcellio scaber. From the order of the diplomapods, for example, Blaniulus guttulatus, Polidesmus spp. From the order of chilopods, for example, Geophilus spp. From the order of the zigentomos, for example, Ctenolepisma spp., Lepisma saccharina,

Lepismodes inquilinus. From the order of the Blatarios, 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 grasshoppers, for example, Acheta domesticus. From the order of the dermápteros, for example, Forficula auricularia. From the order of the isoptera, for example, Kalotermes spp., Reticulitermes spp. From the order of the psocopters, for example, Lepinatus spp., Liposcelis spp. From the order of the beetles, 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, Typula 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 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 anoplides, for example, Pediculus humanus capitis, Pediculus humanus corporis, Phthirus pubis. From the order of the heteroptera, for example, Cimex hemipterus, Cimex lectularius, Rhodinus prolixus, Triatoma infestans.

The application is carried out in aerosols, non-pressure spraying means, for example, pump and spray aerosols, automatic fog distributors, thermal nebulizers, foams, gels, evaporation products with cellulose or plastic evaporation tablets, liquid evaporators , gel and membrane evaporators, propellant-driven evaporators, energy-free or passive evaporation systems, anti-pill papers, anti-moth sacks and anti-moth gels, such as granules or powders, in dispersal baits or bait points.

According to the invention, all plants and plant parts can be treated. In this regard, plants are understood as all plants and plant populations, such as wild plants or desired and unwanted cultivated plants (including crop plants of natural origin). Cultivation plants can be plants that can be obtained by conventional cultivation and optimization procedures or by biotechnological and genetic procedures or combinations of these procedures, including transgenic plants and including plant varieties that can be protected or may not be protected by protection rights of species. Vegetable parts should be understood as all the aerial and underground parts and organs of the plants, such as bud, leaf, flower and root, citing as an example leaves, acicles, stems, trunks, flowers, fruiting bodies, fruits and seeds, as well as roots, tubers and rhizomes. The crop also belongs to the plant parts, as well as the vegetative and generative multiplication material, for example layers, tubers, rhizomes, cuttings and seeds.

The treatment of plants and plant parts according to the invention with the active ingredients is carried out directly or by action on their environment, habitat or storage location according to the usual treatment procedures, for example, by immersion, dusting, gasification, fogging, spreading, coating and, in the case of the multiplication material, especially of seeds, also by wrapping one or several layers. As already mentioned above, according to the invention all plants and their parts can be treated. In a preferred embodiment, plant species and plant varieties of wild origin are treated or obtained by conventional biological cultivation procedures, such as crossing or fusion of protoplasts, as well as their parts. In another preferred embodiment, transgenic plants and plant varieties are treated, which were obtained by genetic procedures, where appropriate together with conventional procedures (genetically modified organisms), and their parts. The terms "parts" or "parts of plants" or "plant parts" were explained above.

According to the invention, plants of the vegetable varieties are respectively treated, which are usually commercially available or are in use.

Depending on the plant species or plant varieties, their habitat and growth conditions (soils, climate, periods of vegetation, food), through the treatment according to the invention may also appear effects ("synergistic") added. Thus, for example, decreased doses and / or extensions of the spectrum of action and / or a reinforcement of the effect of the substances and agents that can be used according to the invention are possible, better plant growth, more developed root system, greater resistance of the plant species or plant variety, increased sprout growth, increased plant vitality, high tolerance compared to high or low temperatures, high tolerance to dryness or water content or salts in the soil, high capacity to flower, facilitated collection, acceleration of maturity, greater harvests, larger fruits, larger plant size, greener leaf color, earlier flowers, higher quality and / or greater nutritional value of the collected products, higher concentration of sugar in the fruits, greater conservation capacity and / or machinability of the collected products, which exceed the effects that are really expected.

To the preferred transgenic plants or varieties (obtained by genetic engineering) that are to be treated according to the invention belong all the plants that were obtained by means of the genetic modification of genetic material, which gives these plants especially advantageous valuable properties ("traits") . Examples of such properties are better plant growth, high tolerance compared to high or low temperatures, high dryness tolerance

or to the content of water or salts in the soil, high capacity to flourish, facilitated harvesting, acceleration of maturity, greater harvests, higher quality and / or greater nutritional value of the collected products, greater conservation capacity and / or machinability of collected products. Other examples and especially prominent of such properties are a high phytoprotection against animal and microbial pests, such as against insects, mites, plant pathogenic fungi, bacteria and / or viruses, as well as a high phytotolerance to certain herbicidal active principles. Examples of transgenic plants are important crop plants such as cereals (wheat, rice), corn, soybeans, potatoes, cotton, rapeseed, as well as fruit plants (with apples, pears, citrus fruits and grapes), especially rice, corn, soy, potato, cotton and rapeseed. The properties ("traits") especially highlight the high phytoprotection against insects by toxins that form in plants, especially those that are generated in plants (then "Bt plants") by the genetic material of Bacillus thuringiensis (for example, through the genes CryIA (a), CryIA (b), CryIA (c), CryllA, CrylIIA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CrylF, as well as their combinations). The properties ("traits") also highlight the high phytoprotection compared to certain herbicidal active ingredients, for example imidazolinones, sulfonylureas, glyphosates or phosphinothricin (for example, the "PAT" gene). The genes that respectively confer the desired properties ("traits") may also be present in combinations with each other in transgenic plants. Examples of “Bt plants” include corn varieties, cotton varieties, soy varieties and potato varieties that are marketed under the trade names YIELD GARD® (for example, corn, cotton, soybeans), KnockOut® (for example , corn), StarLink® (for example, corn), Bollgard® (cotton), Nucotn® (cotton) and NewLeaf® (potatoes). Examples of herbicide-tolerant plants include corn varieties, cotton varieties and soy varieties that are marketed under the trade names Roundup Ready® (glyphosate tolerance, for example, corn, cotton, soy), Liberty Link® (tolerance to phosphinothricin, for example rapeseed), IMI® (tolerance to imidazolinones) and STS® (tolerance against sulfonylureas, for example corn). As herbicide resistant plants (conventionally cultivated with herbicide tolerance), varieties marketed under the Clearfield® designation (for example, corn) are also mentioned. Obviously, these statements also serve for plant varieties developed in the future or that will reach the market in the future with these genetic properties or genetic properties developed in the future ("traits").

The plants mentioned can be treated according to the invention especially advantageously with the active ingredient mixtures according to the invention. The preferred ranges specified above in the mixtures are also valid for the treatment of these plants. Especially noteworthy is the treatment of plants with the mixtures specially cited in this text.

The good insecticidal, acaricidal and fungicidal effect of the combinations of active ingredients according to the invention can be deduced from the following examples. While the active ingredients separately have weaknesses in their effect, the combinations show an effect that overcomes a simple sum of effects.

There is a synergistic effect on insecticides, acaricides and fungicides provided that the insecticidal or fungicidal effect of combinations of active ingredients is greater than the sum of the effects of the active ingredients applied separately.

The insecticidal, acaricidal or fungicidal effect that can be expected from a given combination of two active ingredients can be calculated according to S.R. Colby ("Calculating Synergistic and Antagonistic Responses of Herbicide Combinations", Weeds 1967, 15, 20-22) as follows:

Yes

X

means the degree of elimination, expressed in% of the untreated control, when using the principle

active A at a dose of m g / ha or at a concentration of m ppm,

Y

means the degree of elimination, expressed in% of the untreated control, when using the principle

active B at a dose of n g / ha or at a concentration of n ppm, and

AND

means the degree of elimination, expressed in% of the untreated control, when using the principles

assets A and B at doses of m and n g / ha or at a concentration of m and n ppm,

So

image 1

If the actual degree of insecticide, acaricide or fungicide removal is greater than calculated, Then the combination is more than additive in its elimination, that is, there is a synergistic effect. In this case, the degree of elimination actually observed must be greater than the value calculated at from the aforementioned formula for the expected degree of elimination (E). Examples Example A

Trial with Myzus persicae

Solvent: 7 parts by weight of dimethylformamide Emulsifier: 2 parts by weight of alkylaryl polyglycol ether To prepare an active ingredient preparation in an appropriate manner, mix 1 part in

5 weight of active ingredient with the specified amounts of solvent and emulsifier and the concentrate is diluted with water containing emulsifier to the desired concentration.

Cabbage leaves (Brassica oleracea), which are heavily infested by the green peach aphid (Myzus persicae), are treated by immersion in the active ingredient preparation of the desired concentration. After the desired time the elimination in% is determined. To this

10 respect, 100% means that all aphids were removed; 0% means that it means that no aphids were removed. The determined disposal values are calculated according to the Colby formula (see sheet 1).

In this test, for example, the following combination of active ingredients according to the present application shows synergistically enhanced efficacy compared to the active ingredients applied separately: Table A

Insects harmful to plants: Test with Myzus persicae

Active ingredients Concentration of

Degree of elimination in% active substance in ppm

after d Hall. *

Calc. **

d *** (1-2) N- [2- (1,3-Dimethylbutyl) phenyl] -5-fluoro-1,3

100 0 6

dimethyl-1H-pyrazol-4-carboxamide

(6.2.1) Fipronil 100

65

6 (1-2) N- [2- (1,3-Dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1 H -pyrazol-4-carboxamide + (6.2.1)

100 + 100 85

65

6 fipronil (1: 1) (1-2) N- [2- (1,3-Dimethylbutyl) phenyl] -5-fluoro-1,3

100 0 6

dimethyl-1H-pyrazol-4-carboxamide

(3.1.1) Metiocarb 100

0

6 (1-2) N- [2- (1,3-Dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1 H -pyrazol-4-carboxamide + (3.1.1)

100 + 100 25

0

6 metiocarb (1: 1)

* Hall. = effect found ** Calc. = effect calculated according to Colby's formula *** d = evaluation after the specified number of days Example B

Trial with Phaedon cochleariae

Solvent: 7 parts by weight of dimethylformamide Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

5 To prepare an active ingredient preparation in an appropriate manner, 1 part by weight of active ingredient is mixed with the specified amounts of solvent and emulsifier and the concentrate is diluted with water containing emulsifier to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by immersion in the active ingredient preparation of the desired concentration and covered with beetle larvae of radish 10 leaves (Phaedon cochleariae) while the leaves are still wet.

After the desired time the elimination in% is determined. In this regard, 100% means that all beetle larvae were removed; 0% means that no beetle larvae were removed.

In this test, the following combination of active ingredients according to the present application 15 showed a synergistically reinforced efficacy compared to the active ingredients applied separately: Table B

Insects harmful to plants: Test with Phaedon cochleariae

Active ingredients Concentration of active substance in ppm Degree of elimination in% after d Hall. * Calc. ** d ***

(1-2) N- [2- (1,3-Dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1 H -pyrazol-4-carboxamide 100 0 6 (2.1.1) Clothianidine 0.8 0 6 ( 1-2) N- [2- (1,3-Dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1 H -pyrazol-4-carboxamide + (2.1.1) clothianidine (125: 1) 100 + 0, 8 30 0 6 (1-2) N- [2- (1,3-Dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1 H -pyrazol-4-carboxamide 100 0 6 (2.1.2) Imidacloprid 0, 8 40 6 (1-2) N- [2- (1,3-Dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1 H -pyrazol-4-carboxamide + (2.1.2) imidacloprid (125: 1) 100 + 0.8 80 40 6 (1-2) N- [2- (1,3-Dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1 H -pyrazol-4-carboxamide 100 0 6

(5.1.1) Espinosad

0.8 80 6

(1-2) N- [2- (1,3-Dimethylbutyl) phenyl] dimethyl-1 H -pyrazol-4-carboxamide spinosad (125: 1)

5-fluoro-1,3 + (5.1.1) 100 + 0.8 100 80 6

(1-2) N- [2- (1,3-Dimethylbutyl) phenyl] dimethyl-1H-pyrazol-4-carboxamide

5-fluoro-1,3 100 0 4

(3.1.2) Thiodicarb

100 0 4

(1-2) N- [2- (1,3-Dimethylbutyl) phenyl] dimethyl-1 H -pyrazol-4-carboxamide thiodicarb (1: 1)

5-fluoro-1,3 + (3.1.2) 100 + 100 twenty 0 4

* Hall. = effect found ** Calc. = effect calculated according to l *** d = evaluation after no.

a specified Colby's formula of days only

Example C

Essay with Plutella xylostella

Solvent: 7 parts by weight of dimethylformamide Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

5 To prepare an active ingredient preparation in an appropriate manner, 1 part by weight of active ingredient is mixed with the specified amounts of solvent and emulsifier and the concentrate is diluted with water containing emulsifier to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by immersion in the preparation of active ingredient of the desired concentration and covered with caterpillars of the cabbage moth (Plutella xylostella) 10 while the leaves are still wet. After the desired time the elimination in% is determined. In this respect, 100% means that all tracks were removed; 0% means that no caterpillar was removed. In this test, the following combination of active ingredients according to the present application showed synergistically enhanced efficacy compared to the active ingredients applied separately: Table C

Harmful insects for plants: Test with Plutella xylostella

Active principles

Concentration of Degree of elimination in%

active substance in ppm

after d

Hall.*

Calc. ** d ***

(1-2)

N- [2- (1,3-Dimethylbutyl) phenyl] 5-fluoro-1,3100 fifteen 6

dimethyl-1H-pyrazol-4-carboxamide

(2.1.1) Clothianidine

twenty twenty 6

(1-2) N- [2- (1,3-Dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1 H -pyrazol-4-carboxamide + (2.1.1) clothianidine (5: 1)

100 + 20 65 32 6

(1-2) N- [2- (1,3-Dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1 H -pyrazol-4-carboxamide

100 0 6

(2.1.2) Imidacloprid

4 twenty 6

(1-2) N- [2- (1,3-Dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1 H -pyrazol-4-carboxamide + (2.1.2) imidacloprid (25: 1)

100 + 4 40 twenty 6

* Hall. = effect found ** Calc. = effect calculated according to Colby's formula *** d = evaluation after the specified number of days

Example D

Botrytis cinerea assay (in vitro) / microtiter plates

The microassay is performed in microtiter plates with potato dextrose broth (PDB) as a liquid experimental medium. The application of the active ingredients is carried out with p.a. industrial

5 dissolved in acetone. For inoculation a spore suspension of Botrytis cinerea is used. After 5 days of incubation in the dark and with stirring (10 Hz), the light transmission in each filled cavity of the microtiter plates is determined with the help of a spectrophotometer.

In this respect, 0% means a degree of action that corresponds to the growth in controls, while a degree of action of 100% means that no growth of 10 fungi is observed.

From the following table it is clear that the effect of the combination of

active ingredients according to the invention is greater than calculated, that is, there is an effect

synergistic

Table D

Botrytis cinerea assay (in vitro) / microtiter plates

Active principles

Concentration of Degree of elimination in%

active substance in ppm

after d

Hall.*

Calc. ** d ***

(1-2)

N- [2- (1,3-Dimethylbutyl) phenyl] -5-fluoro-1,3

3

16 5

dimethyl-1H-pyrazol-4-carboxamide

(2.1.2) Imidacloprid

3 3 5

(1-2)

N- [2- (1,3-Dimethylbutyl) phenyl] -5-fluoro-1,3 3 + 3 29 19 5

dimethyl-1H-pyrazol-4-carboxamide + (2.1.2) imidacloprid (1: 1)

* Hall. = effect found ** Calc. = effect calculated according to Colby's formula *** d = evaluation after the specified number of days

Example E

Assay with Alternaria mali (in vitro) / microtiter plates

The microassay is performed in microtiter plates with potato dextrose broth (PDB) as a liquid experimental medium. The application of the active ingredients is carried out with p.a. industrial

5 dissolved in acetone. For inoculation a spore suspension of Alternaria mali is used. After 4 days of incubation in the dark and with stirring (10 Hz), the light transmission in each filled cavity of the microtiter plates is determined with the help of a spectrophotometer.

In this respect, 0% means a degree of action that corresponds to the growth in controls, while a degree of action of 100% means that no growth of 10 fungi is observed.

From the following table it is clear that the effect of the combination of

active ingredients according to the invention is greater than calculated, that is, there is an effect

synergistic

Table E

Assay with Alternaria mali (in vitro) / microtiter plates

Active ingredients Concentration of

Degree of elimination in% active substance in ppm

after d Hall. *

Calc. **

d *** (1-2) N- [2- (1,3-Dimethylbutyl) phenyl] -5-fluoro-1,3

3 48 4

dimethyl-1H-pyrazol-4-carboxamide

(2.1.1) Clothianidine 3

8

4 (1-2) N- [2- (1,3-Dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1 H -pyrazol-4-carboxamide + (2.1.1)

3 + 3 58

53

4 clothianidine (1: 1)

* Hall. = effect found ** Calc. = effect calculated according to Colby's formula *** d = evaluation after the specified number of days

5

10

fifteen

twenty

25

30

33

Claims (6)

1.-Combinations of active ingredients with very good fungicidal, insecticidal and / or acaricidal properties that contain a carboxamide of formula (I) (Group I) image 1 and at least one active ingredient that is selected from the group consisting of (2.1.1) Clothianidine (2.1.2) Imidacloprid (2.1.3) Tiacloprid (3.1.1) Metiocarb (3.1.2) Thiodicarb (4.1.1) Beta-ciflutrin (5.1.1) Espinosad (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). 2.-Combinations of synergistic active ingredients that contain a combination of active ingredients according to claim 1. 3. Use of combinations of active ingredients according to one of claims 1 to 2 to combat unwanted animal pests, as well as unwanted phytopathogenic fungi. 4. Procedure for combating unwanted animal pests, as well as unwanted phytopathogenic fungi, characterized in that combinations of active ingredients according to one of claims 1 to 2 are allowed to act on harmful organisms and / or their habitat. 5. Method for preparing combinations of active ingredients, characterized in that a combination of active ingredients according to one of claims 1 to 2 is mixed with surfactants and / or diluents. 6.-Use of combinations of active ingredients according to claim 1 for seed treatment. 7. Use of combinations of active ingredients according to claim 1 for the treatment of transgenic plants. 8. Use of combinations of active ingredients according to claim 1 for the treatment of seed of transgenic plants. 9.-Seed that was treated with a combination of active ingredients according to claim 1. 10. Procedure for combating unwanted animal pests, as well as unwanted phytopathogenic fungi, characterized in that the combinations of active ingredients according to claim 1 are applied to unwanted animal pests, as well as unwanted phytopathogenic fungi and / or their habitat and / or seed