Pesticidal mixture, and use thereof

Abstract

The present patent application relates to a mixture comprising: - 30 to 90% by weight of at least one zeolite, - 1 to 30% by weight of at least one biodegradable oligosaccharide, - 5 to 30% by weight of at least one phyllosilicate, and - 0.001 to 10% by weight of at least one insecticidal agent.

Description

[0001] MIXTURE AND ITS USE

[0002] TECHNICAL AREA

[0003] The present invention relates to the field of plant protection products, in particular the protection of plants against insect pests.

[0004] BACKGROUND OF THE INVENTION

[0005] The use of insecticides has long been an effective method for controlling insect pests in agriculture and the home. In recent decades, research has focused intensively on developing new and improved insecticides to increase their effectiveness while minimizing environmental impact. The state of the art includes a wide variety of chemical and biological insecticides that exhibit different modes of action against various types of pests.

[0006] The application of insecticides is an important part of agriculture for effectively controlling pests and protecting crops. Various methods and technologies for applying insecticides have been developed in the past to maximize efficiency and effectiveness.

[0007] Various methods of applying insecticides are currently used, including spraying and spreading, injections, granulation, and fumigation. Each of these methods has its own advantages and disadvantages that must be considered. Spraying methods, for example, are widespread and effective, but can lead to environmental pollution and require precise dosage. Spreading methods, on the other hand, are easy to apply but less precise in their distribution. All these methods have in common that the insecticide is rapidly available after application and is therefore quickly removed from the field, primarily by environmental factors. This necessitates the continuous and / or high-dose application of insecticides, which in turn places a burden on the environment and on farmers.To minimize environmental impact and ensure sustainable pest control, delayed-release insecticides have been used for some time. These methods are primarily achieved through special coatings or encapsulation techniques. These techniques allow the insecticide to be encapsulated in such a way that it is released in a controlled manner, thus enabling it to exert its effect over a longer period. However, there are still some limitations to the application of these techniques that need to be overcome.

[0008] One of the biggest challenges in developing delayed-release insecticides is selecting the appropriate carrier material. The carrier material must not only ensure the controlled release of the insecticide, but also adapt optimally to environmental conditions to achieve an effective action. To minimize environmental impact, the carrier material should be biodegradable or neutral / inert to nature to prevent harm and ensure positive effects.

[0009] Another challenge lies in determining the optimal release rate of the insecticide. The release should be controlled to ensure continuous effectiveness while simultaneously avoiding overdosing. Techniques such as the use of nano- or microcapsules are needed to precisely control the release rate. However, nano- and microcapsules have the disadvantage of containing microplastics that can be released into the environment.

[0010] For the delayed release of insecticides, coated or uncoated particles containing the insecticide are most commonly used today. These particles are suspended in water and applied to the treatment area. The use of delayed-release insecticide particles has significant disadvantages, particularly in economic terms and due to the release of microplastics, as their production is complex and expensive. Furthermore, users lack the flexibility to influence the release rate and insecticide composition, as delayed-release insecticide particles are only available ready for application.

[0011] In US 10,624,337 B2, particles of fenbart are described, which, in addition to pheromones, include zeolite, oligosaccharides, or cyclic polysaccharides. These particles may also include layered silicates.

[0012] CN 107555517 A describes a pond disinfectant which includes, among other things, montmorillonite, zeolite, chitosan and copper sulfate.

[0013] CN 104430640 A of fenbart is a eucalyptus insecticide. Its production involves mixing and pulverizing, among other things, zeolite, montmorillonite, chitosan, tangerine peel, and garlic, and then mixing with water.

[0014] CN 103430721 A describes an aqueous composition containing, among other things, zeolite, chitosan, bentonite and eucalyptus oil.

[0015] CN 105660729 A describes a powder containing zeolite, sepiolite, carboxymethyl chitosan, nanozinc oxide and realgar.

[0016] WO 03 / 061383 of fenbart is a composition that can release an active ingredient in a controlled manner. In this process, a biologically active substance, which may be an insecticide, is mixed with zeolite and then with a coating solution that may contain polysaccharides.

[0017] CN 114631541 A describes a composition that may include, among other things, zeolite, bentonite, carboxymethylcellulose and pesticides.

[0018] It is an object of the present invention to provide a composition that overcomes the disadvantages of conventional means for the delayed release of compounds effective against insects, such as insecticides and pheromones.

[0019] SUMMARY OF THE INVENTION

[0020] The present invention therefore relates to a mixture, preferably a solid mixture, comprising

[0021] - 30 to 90 wt% of at least one zeolite ,

[0022] - 1 to 30 wt% of at least one biodegradable oligosaccharide, - 5 to 30 wt% of at least one layered silicate, and

[0023] - 0.001 to 10 wt% of at least one active ingredient effective against insects.

[0024] The composition or mixture according to the invention, preferably a solid mixture, can be applied to plants in suspension in water. As the water evaporates after application, microscopic / macroscopic capsules / droplets form on the leaves, for example, enclosing the active ingredients. This effect can be described as "post-encapsulation." This occurs through the interaction of the biodegradable oligosaccharides and the other components of the composition or mixture. This enables a controlled release of the active ingredient(s) contained therein.The rate of release of the active substances can be influenced by the proportions of the components of the mixture, in particular the zeolite, the at least one biodegradable oligosaccharide and the at least one layered silicate, and by environmental conditions such as temperature and humidity.

[0025] It has been shown that the composition or mixture according to the invention enables a uniform distribution and adhesion of the ingredients to leaf surfaces. This is advantageous in that the release of the active ingredient(s) is distributed evenly both spatially and temporally. This controlled release of the active ingredients results in a long-lasting effect. This reduces the need for frequent applications and minimizes the overall consumption of plant protection products. The use of naturally occurring ingredients and the reduced amount of chemicals required make this technology more environmentally friendly compared to conventional plant protection methods. Active ingredient losses during application to plants are a common problem with known active ingredient formulations.Compared to previously known and used technologies, especially those using coated particles / capsules containing volatile active ingredients, the mixture according to the invention achieves a residual amount of the active ingredient of 50% or higher after application. Furthermore, the use of the mixture according to the invention exhibits a more uniform active ingredient release rate than previously known formulations, which typically lose the most active ingredient during or shortly after application to the plants. This allows the release rate of the active ingredient to be significantly extended.

[0026] Another aspect of the present invention relates to a kit comprising a) a container comprising at least one zeolite as defined herein, b) a container comprising at least one biodegradable oligosaccharide as defined herein, c) a container comprising at least one layered silicate as defined herein, and d) a container comprising at least one insecticidal active ingredient as defined herein.

[0027] To allow the user to vary the mixture according to the invention within the ranges defined above, the individual components of the mixture can be provided separately in containers. Alternatively, it is also possible for more than one component, e.g., two or three components, to be present in one container.

[0028] Another aspect of the present invention relates to a suspension comprising a mixture according to the invention.

[0029] The mixture according to the invention can also be in the form of a suspension. The suspension can comprise the mixture in a concentration that can be applied directly to plants. The suspension is suitable for ready-to-use applications. These suspensions are particularly, but not limited to, home applications where small quantities of the mixture according to the invention are required.

[0030] Another aspect of the present invention relates to a method for treating plants or parts of plants comprising the steps: a) mixing a mixture according to the invention with water in a weight ratio of 1:1 to 1:500 to produce an aqueous suspension, and b) applying the aqueous suspension from step a) to a plant or part of a plant.

[0031] BRIEF DESCRIPTION OF THE FIGURES

[0032] Fig. 1 shows the cross-section of a leaf on which the mixture according to the invention, mixed with water, was applied (A). After water evaporates, a matrix forms on the surface of the leaf in which the active ingredient to be released is embedded (B). The active ingredient is released slowly over time ("slow release").

[0033] Fig. 2 shows a comparison of two drug carriers (zeolite and bentonite) with regard to their drug retention capacity over time.

[0034] Fig. 3 shows a comparison of two compositions with and without a synergistic effect of the combination of layered silicates and biodegradable saccharides on the long-term release of active ingredients after application. The active ingredient content after application is shown in [wt.%] compared to the initial concentration up to 56 days, as shown in Example 4.

[0035] DESCRIPTION OF THE EXECUTION FORMS

[0036] "Mixture" or "solid mixture," as used here, refers to a mixture of various chemical compounds, solids, and the like, which can be separated by physical methods. It is preferably a heterogeneous or homogeneous mixture, wherein the individual components of the mixture may be present in different concentrations and compositions. The components of a mixture can exhibit different physical and chemical properties, which makes it possible to separate them by various separation methods. For the purposes of the present invention, the at least one zeolite, the at least one biodegradable oligosaccharide, the at least one layered silicate, and the at least one active ingredient effective against insects are present in the mixture as individual components that can be separated from one another physically."Biodegradable oligosaccharides," as used here, are natural or synthetic polymers consisting of a chain of sugar building blocks that can be naturally broken down by microorganisms or enzymes. Biodegradable oligosaccharides can be made from various sugar building blocks such as glucose, fructose, galactose, or other monosaccharides. Oligosaccharides are short-chain carbohydrate compounds consisting of three to ten linked monosaccharide units connected by glycosidic bonds. The oligosaccharide can have linear or branched structures.The use of biodegradable oligosaccharides in the mixture according to the invention is particularly advantageous because, after suspension in water and subsequent application to plants, they are able to form a matrix on the plant surface through water evaporation, into which the other components of the mixture according to the invention can be embedded. Especially in combination with at least one silica and / or at least one salt thereof, a matrix can be produced that releases active substances into the environment over a long period. Since the oligosaccharides used according to the invention are biodegradable, they are broken down into their monosaccharides by existing microorganisms over time and / or utilized in other ways.

[0037] "Active agents effective against insects," as used here, include compounds of synthetic or natural origin that can be used to control insects. These active ingredients can be, among others, synthetic chemical compounds, natural plant extracts, or biological agents such as bacteria or fungi. The selection of the appropriate active ingredient depends, among other things, on the type of insect to be controlled. The active ingredients can kill, repel, or confuse insects so that they can no longer reproduce.

[0038] “At least one”, as used here, comprises at least two, at least three, at least four and at least five. “At least one” also includes one, two, three, four, five, six, seven, eight, nine and ten. The mixture according to the invention preferably comprises 35 to 85 wt%, more preferably 40 to 80 wt%, more preferably 40 to 75 wt%, and more preferably 40 to 70 wt% of the at least one zeolite.

[0039] The mixture according to the invention preferably comprises 1 to 25 wt% of the at least one biodegradable oligosaccharide.

[0040] The mixture according to the invention preferably comprises 5 to 25 wt% of the at least one layered silicate.

[0041] The mixture according to the invention preferably comprises 0.001 to 9 wt%, more preferably 0.001 to 8 wt%, of the at least one active ingredient effective against insects.

[0042] "% by weight", as used here, refers to the entire mixture, such that it comprises no more than 100% by weight of the ingredients. That is to say, the mixture according to the invention comprises the above-mentioned quantities of ingredients in the appropriate proportions to achieve a total of 100% by weight.

[0043] The zeolite used according to the invention can be of natural or synthetic origin, preferably of natural origin. Due to their chemical properties and structure, zeolites are able, among other things, to bind and release substances effective against insects in a delayed manner. The bonding between the different molecules and the zeolite surface can occur, among other things, through electrostatic bonds, cation bonds, hydrogen bonds, hydrophilic absorption, and interactions with porous surfaces. It is assumed that these interactions can occur in different forms depending on the type of molecules involved.

[0044] In combination with at least one biodegradable oligosaccharide and at least one layered silicate, it is surprisingly possible to further delay and make the release of the active ingredient more constant. According to a preferred embodiment of the present invention, the at least one zeolite is selected from the group consisting of a zeolite of Strunz class 9. GE ("tablets with 4-4-1-1 structural units") and of Strunz class 9. GD ("chains of five-membered rings").

[0045] The Strunz mineral classification is a defined and established classification in materials science, especially in mineralogy, and is described accordingly in all textbooks (H. Strunz and EH Nickel, Strunz Mineralogical Tables, 2001, 9th edition, E. Schweizerbart ' see Verlagsbuchhandlung, Stuttgart).

[0046] According to a further preferred embodiment of the present invention, the at least one zeolite is selected from the group consisting of a zeolite of Strunz class 9.GE.05 (heulandite-type zeolite), a zeolite of Strunz class 9.GD.10 (chabazite-type zeolite) and a zeolite of Strunz class 9.GD.35 (mordenite-type zeolite).

[0047] According to a further preferred embodiment of the present invention, the at least one zeolite is selected from the group consisting of heulandite-Ca, heulandite-K, heulandite-Na, heulandite-Sr, clinoptilolite-Ca, clinoptilolite-K and clinoptilolite-Na, wherein clinoptilolite is particularly preferred.

[0048] According to a preferred embodiment of the present invention, the at least one zeolite has a particle size D98 of less than 30 pm, preferably from 0.1 to 25 pm, more preferably from 0.2 to 20 pm, more preferably from 0.2 to 15 pm, more preferably from 0.5 to 12 pm, more preferably from 1 to 10 pm, more preferably from 2 to 8 pm.

[0049] It has been shown that it can be advantageous for the zeolites used to have a specific size or not exceed a certain size. Using zeolites with a D98 particle size of less than 30 pm has the advantage that they can be finely dispersed in the resulting matrix and also offer a large surface area, allowing the insecticidal active ingredients to bind efficiently and in sufficient quantities. Furthermore, larger particles cannot be sprayed effectively, as they can clog the spray cans.

[0050] “Particle size,” as defined here, can be determined from the particle size distribution. The particle size distribution can be determined using a variety of techniques. For the purposes of the present invention, the particle size is determined using a laser diffraction system according to ISO 13320. The D98 value is determined from the particle size distribution from a volume-based or a numerical representation. In the present application, all “dx” values ​​refer to the volume-based representation, i.e., to the particle diameter at “x” vol.% in the cumulative distribution (e.g., a D98 value of 30 gm means that 98 vol.% of the particles have a diameter smaller than 30 gm). The D50 value according to the invention is to be understood as the “mean particle size” and is determined from the particle size distribution. A D50 value of 5 gm means, for example, that 50 vol. -% of the particles have a diameter smaller than 5 gm.The particle size distribution can be determined by laser diffraction analysis according to ISO 13320 or CIPAC MT 187, e.g., using the CILAS 715 particle size analyzer. In particular, the particle size distribution of particles with a diameter of less than 30 g / m can be measured by laser diffraction analysis according to ISO 13320 using the CILAS 715 particle size analyzer.

[0051] According to a further preferred embodiment of the present invention, the at least one zeolite has a particle size D50 of less than 5 gm, preferably of 0.1 to 5 gm, more preferably of 0.5 to 5 gm, more preferably of 1 to 5 gm, more preferably of 1 to 4 gm.

[0052] According to a particularly preferred embodiment of the present invention, the at least one layered silicate has a particle size D98 of less than 300 gm, preferably of less than 250 gm, more preferably of 0.1 to 300 gm, more preferably of 0.1 to 250 gm, more preferably of 0.2 to 60 gm.

[0053] These particle sizes are particularly suitable because they improve the uniform distribution in solid mixtures and suspensions, thus preventing segregation, among other things. Furthermore, such particles can be applied using sprayers without clogging the nozzles.

[0054] According to a preferred embodiment of the present invention, the at least one layer silicate is selected from the group consisting of a layer silicate according to the Strunz classification (9th edition) of group 9 EC (“layer silicates (phyllosilicates) with mica sheets, composed of tetrahedral and octahedral networks”).

[0055] According to a further preferred embodiment of the present invention, the at least one layered silicate is selected from the group consisting of a layered silicate according to the Strunz classification (9th edition) of group 9. EC. 40 (montmorillonite group) and a layered silicate of group 9. EC. 45 (saponite group).

[0056] The zeolites and / or layered silicates used according to the invention can be of natural or artificial origin. Methods for obtaining both natural and artificial zeolites and / or layered silicates are well known to those skilled in the art.

[0057] According to a preferred embodiment of the present invention, the at least one biodegradable oligosaccharide comprises at least one modification.

[0058] At least one biodegradable oligosaccharide may be chemically modified. Methods for the chemical modification of oligosaccharides are well known to experts. Through chemical modification, oligosaccharides can achieve improved stability or degradability, better solubility, improved rheological properties, and / or increased binding capacity for insecticidal agents.

[0059] According to a particularly preferred embodiment of the present invention, the modification is selected from the group consisting of alkylation, preferably methylation, acetylation, sulfation and phosphorylation, wherein methylation is particularly preferred.

[0060] According to a further preferred embodiment of the present invention, the at least one biodegradable oligosaccharide is selected from the group of cyclodextrins.

[0061] Oligosaccharides, particularly cyclodextrins, can improve the chemical stability of active ingredients (such as pheromones) by protecting them from biotic degradation, abiotic degradation by heat, light, and oxidation. Many pheromones are poorly water-soluble, which can limit their application. Oligosaccharides, especially cyclodextrins, can improve the solubility of these compounds in aqueous solutions. According to a further preferred embodiment of the present invention, the cyclodextrin is alpha-cyclodextrin, beta-cyclodextrin, or gamma-cyclodextrin, preferably beta-cyclodextrin.

[0062] According to a preferred embodiment of the present invention, the at least one active ingredient effective against insects is a semiochemical, an insecticide or a repellent.

[0063] The active ingredients used according to the invention can be of different chemical natures and have different effects on insects. Preferably, however, the active ingredient is a semiochemical, an insecticide, or a repellent, with semiochemicals being particularly preferred.

[0064] According to a further preferred embodiment of the present invention, the semiochemical is effective on arthropods, preferably on Insecta, Arachnida and / or Diplopoda.

[0065] According to a preferred embodiment of the present invention, the semiochemical is effective on Lepidoptera and Coleoptera.

[0066] According to a further preferred embodiment of the present invention, the semiochemical is a pheromone, preferably a sex pheromone.

[0067] According to a further preferred embodiment of the present invention, the sex pheromone is selected from the group consisting of (Z)-9-tetradecenyl acetate, (Z)-11-hexadecenyl acetate, (Z)-7-dodecenyl acetate, (E)-7-dodecenyl acetate, (Z)-11-tetradecenyl acetate, (E)-11-tetradecenyl acetate, (E)-8-dodecenyl acetate, (Z)-8-dodecenyl acetate, 8-methyldecan-2-yl propionate, (E, E)-8,10-dodecadien-1-ol and (E, Z)-7,9-dodecadienyl acetate, (Z)-9-hexadecenal, (Z)-11-hexadecenal, (Z)-13-He- xadecenal .

[0068] The active ingredients used according to the invention can be produced by various methods. These substances can be produced synthetically, biotechnologically using yeast, or by a combination of both methods, allowing for flexible adaptation to specific requirements and scalability. Regardless of the production method, care is taken to ensure that the active ingredients can be used in various formulations. They are effective both as single active ingredients and in mixtures ("blends") with other active or inactive components. To ensure optimal efficacy and safety, a purity level of at least 50% is targeted, with higher purity levels being preferred. This high purity not only supports the efficacy and tolerability of the active ingredients but also the consistency and predictability of their effects on the target organisms.

[0069] According to a further embodiment of the present invention, the active substances that can be used against insects include not only naturally occurring insecticides and repellents, but also synthetically produced compounds or compounds developed by other technological processes. These can consist of a wide range of chemical compounds that can be used effectively to control or repel insects. Preferably, in addition to the aforementioned natural options such as pyrethrins, neem oil, orange oil, and cinnamon oil, the range of active substances also includes synthetic analogs and newly developed molecules that exhibit specific mechanisms of action against insects.

[0070] The active substances according to the invention can therefore be produced by both biotechnological and chemical-synthetic processes. The choice of production method can be made based on cost-benefit analyses, environmental compatibility, raw material availability, and regulatory requirements. The option of using biological active substances remains, but offers additional flexibility to meet changing market conditions and technological developments.

[0071] According to a further preferred embodiment of the present invention, the mixture has the form of a powder, a granulate or a combination thereof.

[0072] The mixture can be in various forms, with powders, granules, or a combination thereof being particularly preferred. The mixture according to the invention can contain various particles of different sizes and shapes. Powders are fine particles that are loosely connected and offer a high surface area. Granules, on the other hand, consist of coarser particles that are more tightly connected. The combination of both forms enables optimal mixing properties and applicability of the material.

[0073] According to a preferred embodiment of the present invention, the composition has a water content of less than 20 wt%, preferably less than 15 wt%, more preferably less than 10 wt%, more preferably less than 8 wt%, more preferably less than 5 wt%, more preferably less than 4 wt%, more preferably less than 3 wt%, more preferably less than 2 wt%, more preferably less than 1 wt%.

[0074] The mixture according to the invention preferably contains as little water as possible in order to ensure good shelf life of the mixture and to reduce or even prevent clumping of the individual components.

[0075] Another aspect of the present invention relates to a kit comprising a) a container comprising at least one zeolite as defined above, b) a container comprising at least one biodegradable oligosaccharide as defined above, c) a container comprising at least one layered silicate as defined above, and d) a container comprising at least one insecticidal active ingredient as defined above.

[0076] The components of the mixture according to the invention can also be included separately in a kit. In this case, the kit comprises several containers, each containing one component of the mixture according to the invention. This is particularly advantageous because it allows the user to vary the weight ratios within the mixture according to the invention. By varying the weight ratios of the individual components, it is possible, among other things, to influence the release rate of the active ingredient as well as the total amount of active ingredient to be released. Depending on the active ingredient or combination of active ingredients, more or less of the active ingredient(s) is required.

[0077] Another aspect of the present invention relates to a suspension comprising a mixture according to the invention and water.

[0078] The mixture according to the invention is suspended in water or an aqueous solution before its use as a plant protection product, for example. The resulting suspension is then applied to the plants or plant parts.

[0079] The suspension according to the invention can additionally contain additives capable of improving certain properties of the product, such as adhesion, distribution, wetting, and other properties that are particularly advantageous when applying the suspension to plants or plant parts. Wetting and adhesion agents are particularly preferred additives that enable even better wetting and adhesion to the target surfaces of the plants.

[0080] According to a preferred embodiment of the present invention, the weight ratio between the mixture and the water is 1:1 to 1:500, preferably 1:1 to 1:400, even more preferably 1:1 to 1:300, even more preferably 1:1 to 1:250, even more preferably 1:1 to 1:200, even more preferably 1:1 to 1:150, even more preferably 1:1 to 1:100.

[0081] The appropriate ratio of mixture to water can depend on the application. For example, this ratio can be between 1:5 and 1:10 when used in drones and aircraft, between 1:20 and 1:50 when used in row crops, and between 1:100 and 1:500 in viticulture and fruit growing.

[0082] It has been shown that a suspension in which the weight ratio between the mixture and the water is 1:1 to 1:500 is particularly suitable for producing the mixture according to the invention.

[0083] Another aspect of the present invention relates to a method for treating plants or parts of plants comprising the steps of: a) mixing a mixture according to the invention with

[0084] Water in a weight ratio of 1:1 to 1:500, preferably 1:1 to 1:400, even more preferably 1:1 to 1:300, even more preferably 1:1 to 1:250, even more preferably 1:1 to 1:200, even more preferably 1:1 to 1:150, even more preferably 1:1 to 1:100, for the preparation of an aqueous suspension, and b) applying the aqueous suspension from step a) to a plant or a part of a plant.

[0085] The aqueous suspension used to treat plants or plant parts may also contain organic solvents.

[0086] In step a) of the process according to the invention, additives as described above can also be added. These additives are preferably added in known quantities. It is advantageous to mix the additives with the mixture according to the invention before application in order to influence the properties of the suspension depending on the situation and / or application.

[0087] According to a preferred embodiment of the present invention, 1 to 1000 liters of the aqueous suspension are applied per hectare.

[0088] According to a further preferred embodiment of the present invention, the aqueous suspension is applied to the plants or the plant part by spraying, preferably with a drone.

[0089] Methods for dispensing and applying the aqueous suspension according to the invention are well known to those skilled in the art. The present invention is illustrated in more detail by reference to the following embodiments and examples, without, however, being limited to these.

[0090] EXAMPLES

[0091] EXAMPLE 1:

[0092] Influence of using zeolites as the main component in the composition on the long-term release rate of active ingredients after application.

[0093] In this experiment, two formulations with different natural core carriers were compared: “Composition 1” was based on the core carrier “LNZ” from the zeolite group. It contained 95 wt% finely ground natural zeolite (>50% clinoptilolite content) with a d98 value of less than 10 pm, combined with 5 wt% (Z)-11-tetradecenyl acetate (an active ingredient from the sex pheromone group).

[0094] “Composition 2” was based on the core carrier “Bent” from the group of layered silicates. It contained 95% by weight of finely ground natural bentonites (>80% montmorillonites) with a d98 value of less than 55pm, combined with 5% by weight (Z)-11-tetradecenyl acetate (an active ingredient from the group of sex pheromones).

[0095] Based on these compositions, aqueous suspensions were prepared using a 1:50 ratio of mixture ("Composition 1" or "Composition 2") to water. These suspensions were then applied to the inert surface using a sprayer. Samples were taken and analyzed according to the established methods.

[0096] Using GC / MS, the residual content of the active ingredient after application was measured on specific days and expressed as a percentage of the initial concentration (100%) (see Fig. 2).

[0097] Table 1: Influence of core carrier on drug retention after application. Drug content after application compared to initial amount [wt. -%]

[0098] EXAMPLE 2:

[0099] Influence of the use of laminar flow agents or biodegradable oligosaccharides on the short-term release rate of active ingredients after application.

[0100] “Composition 3” was based on the core carrier “LNZ” from the zeolite group. It contained 99 wt% finely ground natural zeolites (>80% clinoptilolite content) with a d98 value of less than 10 pm, combined with 1 wt% 8-methyldecan-2-yl propionate (an active ingredient from the group of sex pheromones).

[0101] In this example, the influence of additional additives on “Composition 3” and the loss of the active ingredient during the application process, which impairs the effectiveness of the composition according to the invention, was analyzed.

[0102] In this experiment, additive 1 from the saponin group (GAS 12173-47-6) with a d98 value of less than 200 pm and additive 2 from the group of biodegradable oligosaccharides (GAS 7585-39-9) were added to composition 3 in different proportions.

[0103] The main objective was to reduce the loss of active ingredient during the application process by at least 50% through the use of additional components.

[0104] Based on these compositions 3-9, aqueous suspensions were prepared using a product-to-water ratio of 1:50. These suspensions were then applied to the inert surface using a sprayer. Samples were taken and analyzed according to the prescribed methods.

[0105] Using GC / MS, the residual concentration of the active ingredient after application was measured on specific days and expressed as a percentage of the initial concentration (100%).

[0106] Surprisingly, it was found that the addition of additive 1 increased the remaining amount of the active ingredient after application by 28% (19%). Further investigations with the addition of additive 2 from the group of biodegradable oligosaccharides showed that it could also increase the remaining amount of the active ingredient by 35% (26%) compared to composition 3 (see Table 2).

[0107] Table e 2 : Influence of Addi ti v 1 and Addi ti v 2 on the short-term active ingredient retention in compositions 3-9 after application [wt. -%] .

[0108] EXAMPLE 3:

[0109] Synergistic influence of the combination of layered silicates and biodegradable oligosaccharides on the short-term release rate of active ingredients after application.

[0110] The “composition^!” was based on the core carrier “LNZ” from the zeolite group. “Composition_3” contains 99 wt% finely ground natural zeolite (>50% clinoptilolite content) with a d98 value of less than 10 pm, combined with 1 wt% 8-methyldecan-2-yl propionate (an active ingredient from the group of sex pheromones);

[0111] In this example, the synergistic effect of the combination of additional additives 1 and 2 on “composition_3” and the loss of the active ingredient during the application process were analyzed.

[0112] Additive 1 from the saponin group with GAS 12173-47-6 with a d98 value of less than 200 pm was combined in different proportions with additive 2 from the group of biodegradable oligosaccharides with GAS 7585-39-9 and added to composition 3.

[0113] Based on these new compositions 10-17, aqueous suspensions were prepared using a product-to-water ratio of 1:50. These suspensions were then applied to the inert surface using a sprayer. Samples were taken and analyzed according to the prescribed methods.

[0114] Using GC / MS, the residual concentration of the active ingredient after application on specific days was measured and expressed as a percentage of the initial concentration (100%). Subsequently, the synergistic effects between additives 1 and 2 with composition 3 were investigated. Surprisingly, it was found that a combination of the identified additives can increase the residual amount of the active ingredient after application to up to 80% (see Table 3).

[0115] Table 3: Synergistic influence of additive 1 and additive

[0116] 2 on the short-term retention of active ingredients in the context-

[0117] Settlements 3 r 10-17 after application [wt%] .

[0118] EXAMPLE 4:

[0119] Synergistic influence of the combination of layered silicates and biodegradable oligosaccharides on the long-term release of active ingredients after application.

[0120] The next experiment was conducted to investigate and confirm the long-term retention effect of the active ingredient caused by the synergistic combination of additives 1 and 2. For this experiment, a comparison was made between "Composition_3" and "Composition_14".

[0121] For this purpose, an aqueous suspension was prepared for each composition, using a product-to-water ratio of 1:50. These suspensions were then applied to the inert surface using a sprayer. Samples were taken according to the prescribed methods and analyzed for residual amounts of active ingredient by GC / MS.

[0122] The data obtained surprisingly show better retention of active ingredients when using the synergistic interaction of additives 1 and 2. It was found that a combination of the identified additives has a synergistic effect and can ensure the slow release of the active ingredient after application compared to a composition without these additives (see Table 4).

[0123] Table 4: Active ingredient content after application compared to the initial concentration after 56 days in [wt. %] (see Fig. 3)

[0124] EXAMPLE 5:

[0125] Influence of the use of biodegradable oligosaccharides or modified biodegradable oligosaccharides on the short-term release rate of active ingredients after application.

[0126] The “composition^!” is based on the core carrier “LNZ” from the zeolite group. “Composition_3” contains 99 wt% finely ground natural zeolite (>80% clinoptilolite content) with a d98 value of less than 10 pm, combined with 1 wt% 8-methyldecan-2-yl propionate (an active ingredient from the group of sex pheromones);

[0127] In this example, the positive influence of biodegradable oligosaccharides or modified biodegradable oligosaccharides and their synergistic effects in combination with layered silicates on the loss of the active ingredient during the application process was analyzed.

[0128] Compositions 18-25 containing 2 wt% of different biodegradable oligosaccharides or modified biodegradable oligosaccharides were produced.

[0129] Based on these new compositions 03, 05, 18-25, aqueous suspensions were prepared using a product-to-water ratio of 1:50. These suspensions were then applied to the inert surface using a suitable method. Samples were taken and analyzed according to the prescribed methods.

[0130] Using GC / MS, the residual content of the active ingredient after application was measured and expressed as a percentage of the initial concentration (100%).

[0131] Table 5: Influence of biodegradable oligosaccharides or modified biodegradable oligosaccharides on the short-term release rate of active ingredients after application in weight percent of the initial amount.

[0132] Subsequently, the synergistic effects between proposed oligosaccharides and layered silicates were investigated. Additive 3 from the saponin group, with the chemical formula: (Ca, Na) 0.3 (Mg, Fe) 3 (Si, Al) 4O10 (OH) 2 • 4H2O, and a d98 value of less than 500 pm, was added at a rate of 20 wt.% to compositions 05, 18-25, resulting in compositions 26-34.

[0133] Surprisingly, it was found that a combination of the identified additives has a synergistic effect and was able to increase the remaining amount of the active ingredient after application to up to 70% (see Table 6).

[0134] Table 6: Synergistic influence of additive 3 and biodegradable oligosaccharides or modified biodegradable oligosaccharides on the short-term release rate of active ingredients after application in weight percent of the initial amount.

[0135] EXAMPLE 6

[0136] Influence of using zeolites as the main component in the composition on the long-term release rate of active ingredients after application.

[0137] In this experiment, several formulations with different potential active ingredient carriers were compared:

[0138] The “Composition 35” was based on the core carrier “LNZ” from the zeolite group. It contains 95% by weight of finely ground natural zeolite (>90% clinoptilolite content), combined with 5% by weight of a substance found in certain plants with CAS number 89-82-7. Due to its properties, this substance is increasingly used as a repellent or insecticide.

[0139] The “Composition 36” was based on the core carrier containing 95% by weight of finely ground natural mineral from group 5 “Carbonates and Nitrates” according to Strunz Systematics (9th edition) with CAS number 13397-26-7, combined with 5% by weight of substance CAS number 89-82-7.

[0140] The “Composition 37” was based on phyllosilicate as a core support. It contains 95 wt. percent finely ground (d98 value of less than 50 pm) natural mineral from the montmorillonite group (>80% montmorillonite), combined with 5 wt. percent of substance CAS number 89-82-7.

[0141] The “Composition 38” was based on the core carrier consisting mainly of finely ground fossil remains of diatoms, combined with 5% by weight of substance CAS number 89-82-7.

[0142] The “Composition 39” was based on the core carrier “4A”. It contains 95% by weight of finely ground synthetic zeolite with a cubic crystal structure and a uniform pore size of approximately 4 angstroms, combined with 5% by weight of substance CAS number 89-82-7.

[0143] Based on these compositions, aqueous suspensions were prepared using a product-to-water ratio of 1:2.5. These suspensions were then applied to the inert surface using a suitable method. Samples were taken according to the prescribed methods.

[0144] Using GC / MS, the residual concentration of the active ingredient after application was measured on specific days and expressed as a percentage of the initial concentration (100%).

[0145] Table 7: Influence of core carrier on drug retention (CAS number 89-82-7) after administration. Drug content after administration compared to initial amount [wt. -%]

[0146] Subsequently, the synergistic effects with additives from the group of layered silicates were investigated.

[0147] In this experiment, the following additives were added to composition 35:

[0148] • Composition 40. Additive 4 Layer silicate from the saponite group with a chemical formula:

[0149] (Ca, Na) 0.3 (Mg, Fe ) 3 ( Si , Al ) 4O10 (OH) 2 • 4H2O with a d98 value of less than 500 pm was added in a proportion of 33 wt.%.

[0150] • Composition 41. Additive 5 Layered silicate from the saponite group; finely ground (d98 value of less than 50 pm) natural mineral from the montmorillonite group (>80% montmorillonite) added in a proportion of 50 wt.%.

[0151] • Composition 42. Additive 5 Layered silicate from the saponite group; finely ground (d98 value of less than 50 pm) natural mineral from the montmorillonite group (>80% montmorillonite) added at a proportion of 33 wt.%

[0152] • Composition 43. Additive 4 Layered silicate from the saponin group with a chemical formula:

[0153] (Ca, Na) o.3 (Mg, Fe ) 3 ( Si , Al ) 4O10 (OH) 2 • 4H2O with a d98 value of less than 500 pm was added in a proportion of 25 wt.% and additive 5 phyllosilicate from the saponite group; finely ground (d98 value of less than 50 pm) natural mineral from the montmorillonite group (>80% montmorillonite) in a proportion of 25 wt.%.

[0154] Based on these compositions, aqueous suspensions were prepared using a product-to-water ratio of 1:2.5. These suspensions were then applied to the inert surface using a suitable method. Samples were taken according to the prescribed methods.

[0155] Using GC / MS, the residual concentration of the active ingredient after application was measured on specific days and expressed as a percentage of the initial concentration (100%).

[0156] Table 8: Synergistic effect of additive 4 and additive 5 on long-term drug retention (CAS number 89-82-7) after administration compared to initial amount [wt. %]. Surprisingly, it was found that a combination of the identified additives has a synergistic effect and can ensure slow release after administration (see Table 8).

[0157] EXAMPLE 7

[0158] Influence of oligosaccharides (additive N) vs. polysaccharides (additive O) in combination with layered silicates from the saponite group on the short-term release rate of (Z)-11-tetradecenyl acetate after application

[0159] This experiment investigated how different additives from the oligosaccharide and polysaccharide groups, in combination with layered silicates and the core carrier "LNZ" from the zeolite group, influence the short-term retention of an active ingredient after application. Additive B (GAS 7585-39-9) was used as the oligosaccharide, and Additive 0 (GAS 9012-76-4) was used as the polysaccharide. Two fractions of a synthetic 2:1 layered silicate with low layer charge from the saponite group (GAS 1319-41-1) were used: Additive S 63 with a d g8 -value < 63 pm and additive S350 with a d g8 -Value of 350 pm .

[0160] All formulations were based on a fixed proportion of:

[0161] • 49% by weight of core carrier “LNZ” from the group of zeolites (>90% clinoptilolite, d g8 < 10 pm)

[0162] • 1 wt% (Z) - 11-Tetradecenyl acetate (sexual pheromone, GAS 35153-32-5)

[0163] The remaining 50% by weight consisted of the respective additives (see Table 9). Compositions 44-47 were prepared on this basis.

[0164] Aqueous suspensions with a product-to-water ratio of 1:50 were prepared from these compositions. These suspensions were then applied to the inert surface using a suitable method. After drying, samples were taken according to the prescribed methods. The residual active ingredient content was analyzed by GC / MS on days 0, 1, and 3 (Table 9). Additionally, a wet sieve test was performed using a 75-pm sieve to assess dispersibility (Table 10).

[0165] Table 9: Influence of additives B / 0 and particle size of layered silicates (S63 / S250) on short-term drug retention [ (Z) -11-Tetradecenyl acetate] after administration [wt. %]

[0166] Table 10: Influence of additives on sediment formation [%

[0167] Residue on 75g sieve]

[0168] The composition_44 (Additive N + Additive S63) showed the highest retention with 72.3% remaining active ingredient on day 3 and simultaneously 0.0% residue in the sieve test.

[0169] The composition of zung_46 (Additive 0 + Additive S63) showed 63.8% retention on day 3 with moderate sedimentation (9.0%).

[0170] The use of coarse-grained phyllosilicate (additive S250) significantly reduced retention in both cases (composition_45 : 58.5%, composition_47 : 46.2%) and led to increased sediment formation (17.0% and 26.5% respectively).

[0171] Surprisingly, it was found that the combination of oligosaccharide (additive N) and finely divided layered silicate (additive S63) significantly slows down the drug release while exhibiting excellent dispersibility.

[0172] The results show that Additive N (oligosaccharide) represents an advantageous alternative to conventional polysaccharides (Additive 0), particularly in combination with finely divided layered silicates from the saponite group. The combination of Additive N + S63 exhibits clear advantages with regard to both short-term retention and formulation stability.

Claims

REQUIREMENTS:

1. mixture comprising - 30 to 90 wt% of at least one zeolite, - 1 to 30 wt% of at least one biodegradable oligosaccharide , - 5 to 30 wt% of at least one layered silicate, and - 0.001 to 10% by weight of at least one active ingredient effective against insects.

2. Mixture according to claim 1, characterized in that the at least one zeolite is selected from the group consisting of a zeolite of Strunz class 9. GE and of Strunz class 9. GD.

3. Mixture according to claim 1 or 2, characterized in that the at least one zeolite is selected from the group consisting of a zeolite of Strunz class 9.GE.05 (heulandite-type zeolite), a zeolite of Strunz class 9.GD.10 (chabazite-type zeolite) and a zeolite of Strunz class 9.GD.35 (mordenite-type zeolite).

4. Mixture according to one of claims 1 to 3, characterized in that the at least one zeolite is selected from the group consisting of heulandite-Ca, heulandite-K, heulandite-Na, heulandite-Sr, clinoptilolite-Ca, clinoptilolite-K and clinoptilolite-Na.

5. Mixture according to one of claims 1 to 4, characterized in that the at least one zeolite has a particle size D98 of less than 30 pm, preferably of 0.1 to 25 pm, more preferably of 0.2 to 20 pm, more preferably of 0.2 to 15 pm, more preferably of 0.5 to 12 pm, more preferably of 1 to 10 pm, more preferably of 2 to 8 pm.

6. Mixture according to one of claims 1 to 4, characterized in that the at least one zeolite has a particle size D50 has a mass of less than 5 gm, preferably from 0.1 to 5 gm, more preferably from 0.5 to 5 gm, more preferably from 1 to 5 gm, more preferably from 1 to 4 gm.

7. Mixture according to one of claims 1 to 6, characterized in that the at least one layered silicate has a particle size D98 of less than 300 gm, preferably less than 250 gm, more preferably of 0.1 to 300 gm, more preferably of 0.1 to 250 gm, more preferably of 0.2 to 60 gm.

8. Mixture according to any one of claims 1 to 7, characterized in that the at least one layered silicate is selected from the group consisting of a layered silicate of Strunz group 9. EC.

9. Mixture according to claim 8, characterized in that the at least one layered silicate is selected from the group consisting of a layered silicate of Strunz class 9. EC.40 (montmorillonite group ) and a layered silicate of Strunz group 9. EC.45 (saponite group ).

10. Mixture according to any one of claims 1 to 9, characterized in that the at least one biodegradable oligosaccharide comprises at least one modification.

11. Mixture according to claim 10, characterized in that the modification is selected from the group consisting of alkylation, preferably methylation, acetylation, sulfation and phosphorylation.

12. Mixture according to one of claims 1 to 11, characterized in that at least one biodegradable oligosaccharide is selected from the group of cyclodextrins.

13. Mixture according to claim 12, characterized in that the cyclodextrin is alpha-cyclodextrin, beta-cyclodextrin or gamma-cyclodextrin, preferably beta-cyclodextrin.

14. Mixture according to any one of claims 1 to 13, characterized in that the at least one active ingredient effective against insects is a semiochemical, an insecticide or a repellent.

15. Mixture according to claim 14, characterized in that the semiochemical is effective on arthropods, preferably on Insecta, Arachnida and / or Diplopoda.

16. Mixture according to claim 14 or 15, characterized in that the semiochemical is effective on Lepidoptera and Coleoptera.

17. Mixture according to one of claims 14 to 16, characterized in that the semiochemical is a pheromone, preferably a sex pheromone.

18. Mixture according to claim 17, characterized in that the sex pheromone is selected from the group consisting of (Z)-9-tetradecenyl acetate, (Z)-11-hexadecenyl acetate, (Z)-ll-tetradecenyl acetate, (Z)-7-dodecenyl acetate, (E)-7-dodecenyl acetate, (E)-11-tetradecenyl acetate, (E)-8-dodecenyl acetate, (Z) -8-dodecenyl acetate, 8-methyldecan-2-yl propionate, (E,E)-8, 10-dodecadien-l-ol and (E, Z)-7, 9-dodecadienyl acetate, (Z)-9- hexadecenal, (Z)-11-hexadecenal, (Z)-13-hexadecenal.

19. Mixture according to any one of claims 14 to 18, characterized in that the insecticide is a synthetic or naturally occurring insecticide, preferably selected from the group consisting of pyrethrins, neem oil, orange oil and cinnamon oil.

20. Mixture according to one of claims 13 to 19, characterized in that the repellent is an insect repellent.

21. Mixture according to any one of claims 1 to 20, characterized in that the mixture has the form of a powder, a granulate or a combination thereof.

22. Kit comprising a) a container comprising at least one zeolite as defined in any one of claims 2 to 6, b) a container comprising at least one biodegradable oligosaccharide as defined in any one of claims 10 to 13, c) a container comprising at least one layered silicate as defined in any one of claims 7 to 9, and d) a container comprising at least one insecticidal active ingredient as defined in any one of claims 14 to 20.

23. Suspension comprising a mixture according to any one of claims 1 to 21 and water.

24. Suspension according to claim 23, characterized in that the weight ratio between the mixture and the water is 1:1 to 1:500, preferably 1:1 to 1:400, even more preferably 1:1 to 1:300, even more preferably 1:1 to 1:250, even more preferably 1:1 to 1:200, even more preferably 1:1 to 1:150, even more preferably 1:1 to 1:

100.

25. A method for treating plants or parts of plants comprising the steps of: a) mixing a mixture according to any one of claims 1 to 21 with water in a weight ratio of 1:1 to 1:500 to produce an aqueous suspension, and b) applying the aqueous suspension from step a) to a plant or part of a plant.

26. Method according to claim 25, characterized in that 1 to 1000 liters of the aqueous suspension are applied per hectare.

27. Method according to claim 25 or 26, characterized in that the aqueous suspension is applied to the plants or plant part by spraying, preferably with a drone.

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