USE OF POLYETERS AS CARRIER FOR ACTIVE INGREDIENTS

Abstract

The present invention relates to the use of compositions comprising at least one compound of the formula (I): R1O-[(C2H3R2)-O]n-H, wherein R1 is a monovalent aliphatic residue having 1 to 22, preferably 2 to 10, particularly preferred 3 to 4 carbon atoms, R2 independently is a hydrogen radical or a methyl residue, and n is a number from 1 to 300, preferably from 5 to 100, particularly preferred from 10 to 30, with the proviso that at least one residue R2 is a methyl residue, as a carrier for at least one active ingredient. The invention also relates to a method for storing the active ingredient in the carrier; to active ingredient compositions that contain the carrier and the active ingredient; to the use of these active ingredient compositions in the treatment of plants, in the treatment of seeds, in the treatment of soils, as biostimulant, as a probiotic food supplement or probiotic additive for animal feed; to methods for treating plants, seeds or soils using these active ingredient compositions; to the active ingredient compositions for use as probiotic drugs; and to plant protection products, biostimulants, probiotic food supplements, probiotic additives for animal feed or probiotic drugs that contain this active ingredient composition or that consist thereof.

Description

[0001] Use of polyethers as carriers for active ingredients

[0002] The present invention relates to the use of compositions comprising at least one polyether as a carrier for an active ingredient; methods for storing the active ingredient in the carrier; active ingredient compositions comprising both the carrier and the active ingredient; the use of these active ingredient compositions for the treatment of plants, for the treatment of seeds, for the treatment of soils, as a biostimulant, as a probiotic food supplement or probiotic feed additive; methods for treating plants, seeds or soils using these active ingredient compositions; these active ingredient compositions for use as a probiotic drug; and plant protection products, biostimulants, probiotic food supplements, probiotic feed additives or probiotic drugs containing or consisting of this active ingredient composition.

[0003] In agriculture, microorganisms are used for a variety of beneficial applications, such as biological pest control, biological plant strengthening, and biological soil improvement. Furthermore, compositions containing live microorganisms are also used for seed treatment. The area of ​​application is therefore primarily agriculture and forestry, including horticulture and fruit growing, as well as the cultivation of ornamental plants and the establishment and maintenance of lawns. In addition, compositions containing live microorganisms are also used as probiotics in food and feed or as probiotic medicines.

[0004] Biological pesticides – also known as biopesticides – are increasingly used in agriculture because they help replace or reduce the use of chemical pesticides, thereby reducing chemical pesticide residues in food. Biological pesticides offer an alternative when plant diseases and pests are resistant to chemical pesticides. Their use is increasingly promoted by current environmental legislation because they utilize natural regulatory mechanisms that have evolved over time and are therefore environmentally friendly. Biological pesticides are used, for example, as fungicides, insecticides, nematicides, or herbicides and are employed for the preventative treatment or curative control of plant diseases and pests.Biological active substances are listed, for example, in The Manual of Biocontrol Agents, 2001, The British Crop Protection Council. According to Article 2(1) of REGULATION (EC) No 1107 / 2009 OF THE EUROPEAN PARLIAMENT AND OF THE COUNCIL of 21 October 2009 concerning the placing of plant protection products on the market and repealing Council Directives 79 / 117 / EEC and 91 / 414 / EEC, plant protection products are defined as products in the form supplied to the user which consist of or contain active substances, safeners or synergists and are intended for one of the following uses: (a) to protect plants or plant products from harmful organisms or to prevent their action, insofar as the main purpose of these products is not considered to be for hygienic purposes rather than the protection of plants or plant products; (b) to influence the life processes of plants in a manner other than providing nutrients (e.g.,Growth regulators); c) to preserve plant products, insofar as these substances or products are not subject to special Community rules on preservatives; d) to destroy unwanted plants or parts of plants, with the exception of algae, unless the products are applied to the soil or water for the protection of plants; e) to inhibit or prevent unwanted growth of plants, with the exception of algae, unless the products are applied to the soil or water for the protection of plants.

[0005] Within the scope of the present invention, the aforementioned definition of the term "plant protection product" is preferably used. According to the preliminary definition of the European Biostimulants Industry Council (EBIC), biostimulants contain substances and / or microorganisms whose function, when applied to plants or in the rhizosphere, is to stimulate natural processes to improve nutrient uptake, nutrient efficiency, tolerance to abiotic stress, and the quality of crops / harvested products (http: / / www.biostimulants.eu / ). For example, the microorganisms Trichoderma spp., Pythium oligandrum, Bacillus spp., Pseudomonas spp., and Streptomyces spp. can induce reactions in plants that lead to increased resistance to pathogens or other stress factors, such as drought, poor nutrient supply, unfavorable pH values, and / or high salinity in the soil. The microorganisms Trichoderma spp., Penicillium bilaii, Azotobacter spp., Azotomonas spp., Azospirillum spp. and Rhizobium spp., for example, can lead to an improvement in nutrient availability in the soil or directly at the plant root.

[0006] The widespread use of microbiological agents for biological plant protection, biological plant strengthening, or biological soil improvement is currently hampered by their lower efficacy compared to many chemical products. This lower efficacy is due, for example, to insufficient survival of the microorganisms in the formulation during storage. In application, too little of the active ingredient may reach its target location on the plant or in the soil, where it may be rapidly degraded by environmental factors. However, these disadvantages can be mitigated by using a suitable carrier.

[0007] The biological plant protection product, which relies on microorganisms as its active ingredient, as well as the biostimulants, are typically diluted in water before application. These formulations can be, for example, solid formulations such as wettable powders (WP) or water-dispersible granules (WG), but also liquid formulations such as oil dispersions (OD), suspension concentrates (SC), or dispersion concentrates (DC).

[0008] The carrier brings the microorganisms into a manageable form so they can be dispersed and applied in water. Since many microorganisms, such as some genera of fungal conidia, are water-repellent, the carrier's primary function is to make them compatible with water. Furthermore, the formulation should ensure the microorganisms' survival during transport and storage. The carrier should also allow for application using sprayers. Aggregation of the microorganisms should be prevented to avoid nozzle clogging. Advantageously, the carrier should also contain substances that ensure the dispersion and distribution of the microorganisms in the water, as well as facilitate the application of the spray solution to plants or soil.

[0009] In practice, chemical and biological pesticides are diluted in water by the user before application. The pesticides are typically added to a tank containing water and stirred to create the spray solution. This spray solution is a ready-to-use dilution of the pesticides. For sowing agricultural land, these spray solutions are atomized over the plants to be treated. In this context, atomization means the formation of droplets through mechanical action on a liquid medium, preferably by rotating objects and / or by releasing pressure at small openings. The spray solution is preferably applied as a spray using nozzles. For sowing agricultural land, 100 to 1000 liters, ideally 100 to 400 liters, of spray solution per hectare are typically applied. However, these limits are exceeded in exceptional cases.The limits can therefore vary considerably. In so-called low-level applications, for example, very small quantities of up to 1.5 l / ha are sprayed, while very high quantities of up to 15,000 l / ha can be achieved when using the so-called lance technique. The atomization process can be carried out either from high altitudes, for example by spraying the solution from an aircraft, or from near ground level, for example by spraying the solution using a spray boom attached to a tractor. Other devices, such as spray lances or backpack sprayers, are also commonly used for applying the solution. The solution is typically sprayed onto the plants or soil at a predetermined dosage using a nozzle. The spray droplets should be well distributed on the plant or soil to ensure optimal effectiveness.

[0010] To improve the biological efficacy (also known as effectiveness) of chemical pesticides, it is common practice to use so-called "adjuvants," also referred to as "additives." Adjuvants are typically added to the aqueous spray solution shortly before application as a tank mix additive or integrated directly into pesticide formulations. Adjuvants are usually added in concentrations of 0.001% to 1% by volume of the spray solution. Adjuvants reduce the surface tension of water, ensuring improved adhesion and wetting of the spray droplets to the hydrophobic leaves of the plant, thus resulting in a broad and homogeneous distribution of the pesticide. They also improve the penetration and distribution of the active components of the spray solution into the soil. This increases biological efficacy.Adjuvants can also improve the efficacy of biological pesticides and, depending on the formulation, can be used as dispersants, emulsifiers, and wetting agents. However, they can be potentially cytotoxic to living microorganisms and are therefore rarely used in formulations containing live microorganisms. It is particularly advantageous if the adjuvant is not mixed with the biological agent during the preparation of the spray solution, but rather acts as a carrier for the biological agent.

[0011] The Pesticides Safety Directorate (PSD, the executive arm of the Health and Safety Executive (HSE), a non-governmental, public body in the UK) defines an adjuvant as a substance that, when mixed with water, is not itself an effective pesticide but enhances the effectiveness of a pesticide (https: / / www.hse.qov.uk / pesticides / pesticides-reqistration / applicant-quide / the-applicant-quide-adiuvan.htm). This definition is based on REGULATION (EC) No 1107 / 2009 OF THE EUROPEAN PARLIAMENT AND OF THE COUNCIL of 21 October 2009 concerning the placing of plant protection products on the market and repealing Council Directives 79 / 117 / EEC and 91 / 414 / EEC, Article 2(3)(d).Subsequently, substances or preparations consisting of adjuvants or preparations containing one or more adjuvants, in the form supplied to the user and placed on the market with the intention of being mixed by the user with a plant protection product to enhance its efficacy or other pesticidal properties, are called "additives." The terms "additives," "adjuvants," or "adjuvants" are used synonymously in this disclosure. Synthetic surfactants, such as ethoxylated alcohols, nonylphenol ethoxylates, alkyl polyglycosides, or polyether-modified trisiloxanes, are frequently used as adjuvants.

[0012] State-of-the-art plant protection products typically have several disadvantages. Generally, all biological plant protection products suffer from the fact that the biological active ingredients they contain, particularly microorganisms or microbial spores, lose their viability and / or germination capacity over time. These products often need to be stored at temperatures below 10°C to ensure acceptable viability and / or germination capacity for at least a few weeks. Generally, the survival rate of microorganisms in formulations increases with lower storage temperatures. For this reason, users typically store these formulations in a refrigerator or freezer. At these temperatures, the viscosity of liquid formulations is often so high that the plant protection products are difficult to handle, especially when dosing.Therefore, formulations should maintain the lowest possible viscosity even at low temperatures to ensure easy handling, pumping, and mixing. It is also desirable that precipitation does not occur (pour point). Furthermore, the emulsifiability / dispersibility of liquid pesticides is better the closer their viscosity is to that of the water used for the spray solution / tank mix. Solid formulations, such as water-based and water-based formulations, have the disadvantage that users are at risk of inhalation when measuring and mixing the concentrated powder or granules. Additionally, solid formulations dispersed in water often exhibit reduced wetting of hydrophobic surfaces. Solid formulations also have the disadvantage of dispersing poorly in water and potentially clogging spray nozzles.Furthermore, the solid and liquid formulations of the prior art often contain additives which, on the one hand, are intended to improve solubility or dispersibility in water and thus simplify the production of the spray solution, but on the other hand, impair the viability and / or germination capacity of biological agents.

[0013] If plant protection products are based on oils as liquid carriers for the active ingredient, they generally need to be formulated with emulsifiers to allow them to emulsify / disperse in water. However, the use of emulsifiers increases the complexity of plant protection formulations, which is why the use of self-emulsifying oils is desirable. Another advantage of self-emulsifying oils is that the user can incorporate an adjuvant of their choice as a tank-mix additive, the effect of which does not interfere with the emulsifier in the plant protection formulation, yet still offers the benefits of an oil dispersion. Furthermore, emulsifiers and surfactants are often toxic to microorganisms, which is why the use of self-emulsifying oils is preferable. Additionally, surfactants and emulsifiers tend to form superstructures that can negatively affect viscosity.Furthermore, formulations containing surfactants or emulsifiers tend to foam when mixed or pumped in water. Therefore, the use of defoamers can be avoided when using self-emulsifying oil dispersions, offering economic advantages as well as benefits for the formulator. Due to the small number of components, there are fewer compatibility issues between the individual parts of the crop protection formulation. Oil dispersions also do not require preservatives, and for the formulator, they offer the advantage that, unlike emulsions, little to no effort is required to optimize parameters such as droplet size and stabilization. Additionally, oil dispersions exhibit little to no hydrolysis, as the formulation typically contains little or no water. The rheology of oil dispersions can usually be modified, if necessary, by additives such as...B. Silica particles, are added. Furthermore, oil dispersions contain no solvents, which reduces the risk of fire as well as the exposure of users and the environment to volatile substances.

[0014] Components / solvents minimized.

[0015] WO 2017 / 210512 A1 discloses a non-aqueous, non-oily liquid support for living microorganisms. The support is preferably selected from the group consisting of polyethylene glycol, glycerol, ethylene glycol, dipropylene glycol, propylene carbonate and their derivatives.

[0016] Mixtures. A mixture of polyethylene glycol and glycerin is described as particularly preferred. It has been shown that the storage stability of biological pesticides is low when polyethylene glycol or glycerin is used. Furthermore, the viscosity of both polyethylene glycol and glycerin is comparatively high at the low temperatures typical for storing biological pesticides, which complicates the dosage and handling of the pesticides. Some polyethylene glycols are also solid.

[0017] Paul et al. (International Journal of Biological Chemistry (2015), 9(2), 79-85; DOI:

[0018] 10.3923 / jibc.2015.79.85; “Long Term Preservation of Commercial Important Fungi in Glycerol at 4°C” investigated the survival rate of various microorganisms, including those for

[0019] Trichoderma species were observed in glycerin / water mixtures, and it was found that the survival rate of the organisms is optimal in pure glycerin at 4°C. However, as described above, the storage stability of biological pesticides is still low when using glycerin, and the viscosity of glycerin at the low temperatures typical for storing biological pesticides is comparatively high, which complicates the dosage and handling of the pesticides.

[0020] WO 2017 / 116837 A1 discloses compositions comprising microbial spores, one or more dispersants, one or more preservatives, and a non-aqueous liquid carrier. Polyethylene glycols or polypropylene glycols are specifically disclosed as carriers. The storage stability of biological plant protection products using polyethylene glycols or polypropylene glycols is low; furthermore, polyethylene glycols are either solid or exhibit increased viscosity at low temperatures, which complicates dosing and handling.

[0021] Therefore, there remains a need to provide carriers for active ingredients that offer significant advantages over the state of the art.

[0022] The object of the present invention was therefore to provide new carriers for active substances which overcome at least one disadvantage of the prior art.

[0023] The main task was to provide carriers for active ingredients that lead to improved storage stability of the active ingredient or plant protection product, that also allow for low viscosity at low temperatures and thus better dosing and handling of the plant protection product, and that are also self-emulsifiable or water-soluble and therefore easily dilutable with water.

[0024] Surprisingly, it was found that the use of compounds of formula (I) as carriers for plant protection agents solves this problem.

[0025] The problem of the present invention is therefore solved by the subject matter of the independent claims. Advantageous embodiments of the invention are specified in the dependent claims, the examples, and the description.

[0026] A first object of the present invention is therefore the use of a composition comprising at least one compound of formula (I),

[0027] R 1 0-[(C2H3R 2 )-0]nH Formula (I), where

[0028] R 1 a monovalent aliphatic residue with 1 to 22, preferably 2 to 10, in particular 3 to 4 carbon atoms;

[0029] R 2 each is independently a hydrogen radical or a methyl group, n is a number from 1 to 300, preferably from 5 to 100, in particular from 10 to 30, with the proviso that at least one group R 2 a methyl group, as a carrier for at least one active ingredient.

[0030] A further object of the present invention is a method for storing at least one active ingredient, wherein the at least one active ingredient is stored in a carrier. A further object of the present invention is a composition comprising:

[0031] (a) at least one compound of formula (I) and

[0032] (b) at least one active ingredient.

[0033] Another object of the present invention is the use of the composition according to the invention i) for the treatment of plants and / or ii) for the treatment of seeds and / or iii) for the treatment of soils and / or iv) as a biostimulant and / or v) as a probiotic food supplement and / or probiotic feed additive.

[0034] Another object of the present invention is accordingly a method for treating plants and / or seeds and / or soils using the composition according to the invention.

[0035] Another object of the present invention is the composition according to the invention for use as a probiotic drug.

[0036] Other objects of the present invention include, accordingly, plant protection products, biostimulants, probiotic food supplements, probiotic feed additives and probiotic pharmaceuticals containing or consisting of the composition according to the invention.

[0037] The use of a compound of formula (I) as a carrier for an active ingredient, as described in the invention, leads to improved storage stability of the active ingredient or the active ingredient composition. The compound of formula (I) also exhibits a sufficiently low viscosity even at low temperatures. This results in better metering and easier handling of the active ingredient composition or the plant protection product. Furthermore, the compound of formula (I) is self-emulsifiable or water-soluble and thus readily dilutable with water. The use of additional additives that improve the solubility or dispersibility of the active ingredient or active ingredient composition in the spray solution is therefore unnecessary. Accordingly, the active ingredient composition according to the invention also exhibits improved storage stability, is easier to meter, simpler to handle, and is readily soluble or readily dispersible in water.

[0038] The invention is described below by way of example, without the invention being limited to these exemplary embodiments. Where areas, general formulas, or compound classes are specified below, these are intended to include not only the corresponding areas or groups of compounds that are explicitly mentioned, but also all sub-areas and subgroups of compounds that can be obtained by removing individual values ​​(areas) or compounds. Any embodiment that can be obtained by combining areas / sub-areas and / or groups / subgroups, such as combinations of essential, optional, preferred, or other elements according to the invention, is also included.Preferably selected, further preferred, even more preferred, particularly preferred, or especially preferred areas / sub-areas and / or groups / subgroups are fully part of the disclosure of the present invention and are considered explicitly, directly, and unambiguously disclosed. Where documents are cited within the scope of this description, their content is deemed to be fully part of the disclosure of the present invention. Where mean values ​​are given below, they are numerical averages unless otherwise stated. Where measured values ​​or material properties are given below, they are measured values ​​or material properties measured at 25 °C and preferably at a pressure of 101,325 Pa (standard pressure) unless otherwise stated. Wherever molecules orMolecular fragments that have one or more stereocenters, or that can be distinguished into isomers due to symmetries, or that can be distinguished into isomers due to other effects, such as restricted rotation, are all possible isomers included in the present invention. Specific embodiments are defined below, so that features such as indices or structural components may be subject to limitations by the embodiment. For all features not affected by the limitation, the remaining definitions remain valid. The units [(C2H3R. 2The )-Oj in formula (I) can be statistically distributed. Statistical distributions can be block-based with any number of blocks and any sequence, or they can be randomized; they can also be alternating or form a gradient over the chain, if one exists; in particular, they can also form any combination of these, where groups of different distributions may follow one another. Formula (I) describes compounds that can be composed of repeating units, such as repeating fragments, blocks, or monomer units, and can have a molecular weight distribution. The frequency of the repeating units is indicated by the index n. The index n is the numerical mean over all repeating units and is to be considered the statistical mean (number mean).The index n and the range of values ​​of the specified index are therefore to be understood as the mean of the possible statistical distribution of the actual existing structures and / or their mixtures. Specific implementations may lead to restrictions on the statistical distributions. For all areas not affected by the restriction, the statistical distribution remains unchanged. Where documents are cited within the scope of this description, their content shall be considered to be entirely part of the disclosure of the present invention. According to the invention, a composition comprising at least one compound of formula (I) is provided.

[0039] R 1 0-[(C2H3R 2 )-0]nH Formula (I), where

[0040] R 1 a monovalent aliphatic residue with 1 to 22, preferably 2 to 10, in particular 3 to 4 carbon atoms,

[0041] R 2each is independently a hydrogen radical or a methyl group, n is a number from 1 to 300, preferably from 5 to 100, in particular from 10 to 30, with the proviso that at least one group R 2 a methyl group is used as a carrier for at least one active ingredient.

[0042] The composition to be used as a carrier, comprising at least one compound of formula (I), is also referred to simply as the carrier or carrier composition within the scope of this disclosure. A composition comprising the carrier and the active ingredient is also referred to as the active ingredient composition within the scope of this disclosure.

[0043] The carrier composition is preferably liquid. It enables the dissolution or dispersal of the active ingredient, particularly fungi and fungal spores. The active ingredient is therefore dissolved or dispersed within the carrier. The carrier also facilitates the dissolution or dispersal of the active ingredient in an aqueous composition, such as the spray solution.

[0044] The compound of formula (I) has a monocoordinate aliphatic residue R at its terminal. 1 with 1 to 22, preferably 2 to 10, particularly 3 to 4 carbon atoms. This results in significantly improved storage stability compared to polyethers that are exclusively OH-terminated. 1 It can be, for example, linear or branched, cyclic or non-cyclic, saturated or unsaturated. It is preferred that the residue R 1an alkyl radical, preferably a radical selected from the group consisting of methyl, ethyl, n-propyl, / so-propyl, n-butyl, / so-butyl, sec-butyl, fe / -butyl, n-pentyl (amyl), 2-pentyl (sec-pentyl), 3-pentyl; 2-Methylbutyl, 3-Methylbutyl (iso-Pentyl or iso-Amyl), 3-Methylbut-2-yl, 2-Methylbut-2-yl, 2,2-Dimethylpropyl (Neopentyl), Hexyl, Octyl, Decyl, Dodecyl, Myristyl, Stearyl, 2-Ethylhexyl, 2-Propylheptyl, 3,5,5-Trimethylhexyl, isononyl, isotridecyl, in particular an n-butyl radical.

[0045] The compound of formula (I) has one or more divalent groups -[(C2H3R 2 )-Oj- on, where the remainder R 2 Each is independently either a hydrogen radical or a methyl group. In the case of the divalent groups -[(C2H3R 2 )-Oj- therefore refers to alkylenoxy groups. Is R 2 a hydrogen radical, i.e., in the case where: R 2 = H, the group is -[(C2H3R 2)-Oj- around a group -[(C2H4)-O]-, i.e. around a group -(CH2-CH2-O)-, i.e. around an ethyleneoxy group. If, on the other hand, R 2 a methyl group, i.e., in the case that: R 2 = CH3, the group is -[(C2H3R 2 )-0]- around a group -[(C2H3(CH3))-0]-, i.e., around a propylene oxy group. The propylene oxy group can each be independently present in the spatial orientations -(CH2-CH(CH3)-0)- or -(CH(CH3)-CH2-0)-, but preferably in the spatial orientation -(CH2-CH(CH3)-0)-, in the compound of formula (I), wherein the spatial orientation chosen in formula (I) is to be used as the basis for the compound of formula (I), i.e., a spatial orientation in which the R 1 The 0 group is bonded at the left end and the OH group at the right end of the compound of formula (I).

[0046] The index n is a number from 1 to 300, preferably from 5 to 100, and particularly from 10 to 30. For example, the index n is a number from 1 to 300, from 2 to 250, from 3 to 200, from 4 to 150, from 5 to 100, from 6 to 81, from 7 to 50, from 8 to 40, and / or from 10 to 30, with a narrower range being preferable to a wider range. For n > 300, the viscosity of the compound of formula (I) is significantly increased and therefore less suitable as a carrier, since the increased viscosity impairs the dosing and handling of the active ingredient composition.

[0047] It is preferred that for the compound of formula (I) 10% to 100%, preferably 20% to 80%, and particularly 40% to 60% of the residues R 2Methyl groups are present, with a maximum value of 100%. The proportion of propylene oxy groups relative to the total amount of alkylene oxy groups, i.e., the total amount of propylene oxy groups and ethylene oxy groups combined, is therefore from 10% to 100%, preferably from 20% to 80%, and particularly from 40% to 60%, with a maximum value of 100%. The number of propylene oxy groups divided by the total number of alkylene oxy groups, i.e., the total number of propylene oxy groups and ethylene oxy groups combined, is therefore from 10% to 100%, preferably from 20% to 80%, and particularly from 40% to 60%, with a maximum value of 100%.

[0048] 100%.

[0049] It has been shown that polyethers containing only ethyleneoxy units and no propylenoxy units exhibit high viscosity or are solid, especially at low temperatures, whereas polyethers containing only propylenoxy units and no ethyleneoxy units, or containing both ethyleneoxy and propylenoxy units, consistently exhibit low viscosity.

[0050] The following embodiments have proven to be particularly advantageous:

[0051] In a preferred embodiment of the invention, a compound of formula (I),

[0052] R 1 0-[(C2H3R 2 )-0]nH Formula (I), where R 1 a monovalent aliphatic residue with 2 to 10 carbon atoms, in particular an alkyl residue with 2 to 10 carbon atoms;

[0053] R 2Each is independently a hydrogen radical or a methyl group; n is a number from 2 to 250; with the proviso that 20% to 80% of the residues R 2 Methyl groups are used.

[0054] In a further preferred embodiment of the invention, a compound of formula (I),

[0055] R 1 0-[(C2H3R 2 )-0]nH Formula (I), where

[0056] R 1 a monovalent aliphatic residue with 2 to 10 carbon atoms, in particular an alkyl residue with 2 to 10 carbon atoms;

[0057] R 2 each is independently a hydrogen radical or a methyl group; n is a number from 5 to 100; with the proviso that 20% to 80% of the residues R 2 Methyl groups are used.

[0058] In a further preferred embodiment of the invention, a combination of the formula

[0059] (I),

[0060] R 10-[(C2H3R 2 )-0]nH Formula (I), where

[0061] R 1 a monovalent aliphatic residue with 3 to 4 carbon atoms, in particular an alkyl residue with 3 to 4 carbon atoms;

[0062] R 2 each is independently a hydrogen radical or a methyl group; n is a number from 6 to 81; with the proviso that 20% to 80% of the residues R 2 Methyl groups are used.

[0063] In a further preferred embodiment of the invention, a combination of the formula

[0064] (I),

[0065] R 1 0-[(C2H3R 2 )-0] n -H formula (I), where

[0066] R 1 a monovalent aliphatic residue with 3 to 4 carbon atoms, in particular an alkyl residue with 3 to 4 carbon atoms;

[0067] R 2each is independently a hydrogen radical or a methyl group; n is a number from 8 to 40; with the proviso that 20% to 80% of the residues R 2 Methyl groups are used. In a further preferred embodiment of the invention, a compound of the formula

[0068] (I),

[0069] R 1 0-[(C2H3R 2 )-0]nH Formula (I), where

[0070] R 1 a monovalent aliphatic residue with 3 to 4 carbon atoms, in particular an alkyl residue with 3 to 4 carbon atoms;

[0071] R 2 each is independently a hydrogen radical or a methyl group; n is a number from 10 to 30; with the proviso that 20% to 80% of the residues R 2 Methyl groups are used.

[0072] In a further preferred embodiment of the invention, a compound of formula (I) is used.

[0073] R 1 0-[(C2H3R 2)-0]nH Formula (I), where

[0074] R 1 is an n-butyl;

[0075] R 2 Each is independently a hydrogen radical or a methyl group; n is a number from 2 to 250; with the proviso that 20% to 80% of the residues R 2 Methyl groups are used.

[0076] In a further preferred embodiment of the invention, a compound of formula (I) is used.

[0077] R 1 0-[(C2H3R 2 )-0] n -H formula (I), where

[0078] R 1 is an n-butyl;

[0079] R 2 each is independently a hydrogen radical or a methyl group; n is a number from 5 to 100; with the proviso that 20% to 80% of the residues R 2 Methyl groups are used.

[0080] In a further preferred embodiment of the invention, a combination of the formula

[0081] (I),

[0082] R 1 0-[(C2H3R 2 )-0] n -H formula (I), where

[0083] R 1 is an n-butyl;

[0084] R 2 each is independently a hydrogen radical or a methyl group; n is a number from 6 to 81; with the proviso that 20% to 80% of the residues R 2 Methyl groups are used. In a further preferred embodiment of the invention, a compound of the formula

[0085] (I),

[0086] R 1 0-[(C2H3R 2 )-0]nH Formula (I), where

[0087] R 1 is an n-butyl;

[0088] R 2 each is independently a hydrogen radical or a methyl group; n is a number from 8 to 40; with the proviso that 20% to 80% of the residues R 2 Methyl groups are used.

[0089] In a further preferred embodiment of the invention, a combination of the formula

[0090] (I),

[0091] R 1 0-[(C2H3R 2 )-0]nH Formula (I), where

[0092] R 1 is an n-butyl;

[0093] R 2 each is independently a hydrogen radical or a methyl group; n is a number from 10 to 30; with the proviso that 20% to 80% of the residues R 2 Methyl groups are used.

[0094] In a further preferred embodiment of the invention, a compound of formula (I) is used.

[0095] R 1 0-[(C2H3R 2 )-0] n -H formula (I), where

[0096] R 1 is an n-butyl;

[0097] R 2 Each is independently a hydrogen radical or a methyl group; n is a number from 2 to 250; with the proviso that 40% to 60% of the residues R 2Methyl groups are used.

[0098] In a further preferred embodiment of the invention, a compound of formula (I) is used.

[0099] R 1 0-[(C2H3R 2 )-0] n -H formula (I), where

[0100] R 1 is an n-butyl;

[0101] R 2 each is independently a hydrogen radical or a methyl group; n is a number from 5 to 100; with the proviso that 40% to 60% of the residues R 2 Methyl groups are used. In a further preferred embodiment of the invention, a compound of the formula

[0102] (I),

[0103] R 1 0-[(C2H3R 2 )-0]nH Formula (I), where R 1 is an n-butyl;

[0104] R 2 each is independently a hydrogen radical or a methyl group; n is a number from 6 to 81; with the proviso that 40% to 60% of the residues R 2Methyl groups are used.

[0105] In a further preferred embodiment of the invention, a combination of the formula

[0106] (I),

[0107] R 1 0-[(C2H3R 2 )-0]nH Formula (I), where R 1 is an n-butyl;

[0108] R 2 each is independently a hydrogen radical or a methyl group; n is a number from 8 to 40; with the proviso that 40% to 60% of the residues R 2 Methyl groups are used.

[0109] In a further preferred embodiment of the invention, a combination of the formula

[0110] (I),

[0111] R 1 0-[(C2H3R 2 )-0] n -H formula (I), where R 1 is an n-butyl;

[0112] R 2each is independently a hydrogen radical or a methyl group; n is a number from 10 to 30; with the proviso that 40% to 60% of the R groups are 2 Methyl groups are used.

[0113] Carrier compositions containing or (essentially) consisting of compounds of formula (I) according to at least one of these three embodiments are characterized by a particularly good property profile. They lead to improved storage stability of the active ingredient, exhibit low viscosity even at low temperatures, thus enabling better dosing and handling of the active ingredient composition, and are also self-emulsifiable or water-soluble and therefore readily dilutable with water.

[0114] It is further preferred that the number-average molar mass of the at least one compound of formula (I) is at least 300 g / mol, more preferably at least 400 g / mol, preferably at least 800 g / mol, and in particular at least 1200 g / mol, wherein the number-average molar mass is preferably determined as described in the examples. It is further preferred that the number-average molar mass of the at least one compound of formula (I) is from 300 g / mol to 4500 g / mol, more preferably from 400 g / mol to 3000 g / mol, preferably from 800 g / mol to 2000 g / mol, and in particular from 1200 g / mol to 1500 g / mol, wherein the number-average molar mass is preferably determined as described in the examples. A number-average molar mass in the ranges specified above results in optimal viscosity at low temperatures (e.g., 0 °C), at which, in particular, biological

[0115] Plant protection products are frequently stored both at high temperatures and at room temperature (e.g., 25 °C), where chemical plant protection products in particular are stored. If the viscosity is too high, the active ingredient composition is difficult to dose and handle; if the viscosity is too low, undesirable separation of the dispersion phase and the dispersed phase can occur, for example, the active ingredient settling. The polarity, molecular weight, and hydrophobicity / hydrophilicity of compounds of formula (I) can be adjusted so that they are self-emulsifying or water-soluble in water and thus readily dilutable with water. It is preferred that the HLB value of the at least one compound of formula (I) is from 0.0 to 14.0, preferably from 3.0 to 10.0, and particularly from 7.0 to 9.5. "HLB" stands for hydrophilic lipophilic balance.The HLB value can be determined using various state-of-the-art methods and is a recognized measure of hydrophobicity / hydrophilicity. Preferably, the HLB value is determined according to Griffin's method (see C. Griffin: Classification of surface active agents by HLB, J. Soc. Cosmet. Chem. 1, 1949, pp. 311-326). In this method, the HLB value is calculated according to the formula... calculated, where m t The molar mass of the lipophilic part of a molecule is μ, and m is the molar mass of the entire molecule. The molar mass m h The hydrophilic part of a molecule is determined accordingly according to m h= m - mi. The molar masses are determined according to prior art methods, preferably by mass spectrometry. The determination of the lipophilic fraction and the hydrophilic fraction is also preferably carried out from the mass spectroscopic results using stoichiometric rules known to those skilled in the art. The molar masses can also be calculated from the molecular structure. In the case of compounds of formula (I), the mass of the hydrophilic fraction is calculated from the total mass of all groups -[(C2H3R 2 )-0]- with R 2 = H, i.e., from the total mass of all contained ethyleneoxy groups (oxyethylene groups).

[0116] It was also surprisingly found that the viscosity and dilution (self-emulsifying ability and water solubility, respectively) of the support can be specifically adjusted by mixing different polyethers. It is therefore preferred that at least one compound (A) and at least one different compound (B) are used, wherein both the at least one compound (A) and the at least one compound (B) are compounds of formula (I), and wherein the HLB value of the at least one compound (A) is from 0.0 to 10.0, preferably from 0.0 to 3.0, in particular from 0.0 to 3.0, and the HLB value of the at least one compound (B) is from 2.0 to 15.0, preferably from 4.0 to 14.0, in particular from 8.0 to 13.0.

[0117] The combination of a compound (A) with HLB = 0, which has only oxypropylene units and no oxyethylene units, and a compound (B) with HLB > 0, which has both oxyethylene units and oxypropylene units, shows particularly advantageous properties as a support.

[0118] It is preferred that the carrier predominantly contains the at least one compound of formula (I). It is therefore preferred that the mass fraction of the at least one compound of formula (I) is at least 90%, preferably at least 95%, and in particular at least 99%, based on the total mass of the carrier, with a maximum value of 100%. Thus, it is preferred that the mass fraction of all compounds of formula (I) is at least 90%, preferably at least 95%, and in particular at least 99%, based on the total mass of the carrier, with a maximum value of 100%.

[0119] It is particularly advantageous if the composition used as a carrier consists (essentially) of the at least one compound of formula (I), i.e., if the mass fraction of the at least one compound of formula (I) is 100%, i.e., corresponds to the maximum value. It is therefore preferred that the mass fraction of all compounds of formula (I) is 100%, i.e., corresponds to the maximum value.

[0120] Methods for the preparation of compounds of formula (I) are known to those skilled in the art. The compounds of formula (I) are preferably prepared by reacting hydroxy-functional compounds of formula R. 1 -OH, where R 1 as defined in formula (I), with propylene oxide (PO) and optionally additionally ethylene oxide (EO). This reaction is an alkoxylation reaction of R 1 -OH with PO and, if necessary, additionally EO. The hydroxy functional compounds used have the formula R. 1-OH refers to aliphatic, monofunctional alcohols with 1 to 22, preferably 2 to 10, and particularly 3 to 4 carbon atoms. The hydroxy-functional compounds of formula R 1The -OH group forms the initiator (starting compound) for the alkoxylation reaction with the alkylene oxide(s), i.e., PO and optionally EO. The alkylene oxides add to the initiator. In this process, the alkylene oxides are added to the OH group in a polyaddition reaction, with ring opening and preferably in the presence of a suitable catalyst. This leads to the formation of the compounds of formula (I) according to the invention. The alkylene oxides can be added either individually in pure form, alternately in any dosage sequence, or simultaneously in a mixture. This determines the sequence of the oxyalkylene units or alkylenoxy units as repeating units in the resulting polyether chain. The process allows the construction of polyether chains characterized by their targeted and reproducible production with respect to structure and molar mass.The sequence of the repetition units can be varied within wide limits by the order in which the alkylene oxides are added. The molar mass of the compound of formula (I) can be varied within wide limits and can be precisely and reproducibly controlled via the molar ratio or the mass ratio of the alkylene oxides with respect to the starter R. 1 -OH can be controlled. The composition of compounds of formula (I) can therefore be adjusted by stoichiometry. For example, the reaction product of 296 g (4 mol) n-butanol, 870 g (15 mol) propylene oxide and 660 g (15 mol) ethylene oxide is a compound of formula R 1 0-[(C2H3R 2 )-0]nH with n = 7.5 and R 1 = n-Butyl, where 50% of the residues are R 2 Methyl groups are present. The HLB value of this compound is 7.2. The relationship between dosage and product structure is known to those skilled in the art.

[0121] For the alkoxylation reaction, i.e. the conversion of compound R1 -OH with PO and optionally additional EO, in principle all alkoxylation catalysts known to those skilled in the art can be used, e.g., basic catalysts such as alkali hydroxides like NaOH and KOH, alkali metal alkoxides such as sodium methoxide and potassium methoxide, amines, guanidines, amidines, phosphorus compounds such as triphenylphosphine, and also acidic and Lewis acidic catalysts such as SnCU, SnCL, SnF₂, BF₃ and BF₃ complexes, as well as double metal cyanide (DMC) catalysts, in particular those containing zinc hexacyanocobaltate(III). Preferably, the DMC catalysts described in US 5,158,922, US 20030119663, WO 01 / 80994 are used. The catalysts can be amorphous or crystalline.

[0122] After completion of the alkoxylation reaction, a secondary reaction preferably follows to complete the conversion. This secondary reaction can be carried out, for example, by continuing the reaction under controlled conditions (i.e., maintaining the temperature and pressure) without adding any reactants. Preferably, the secondary reaction is performed while mixing the reaction mixture, particularly by stirring.

[0123] Unreacted alkylene oxides and any other volatile components can be removed after the alkoxylation reaction, for example, by vacuum distillation, steam or gas stripping, or other deodorization methods. The reaction product is preferably neutralized with an acid such as lactic acid, acetic acid, propionic acid, or phosphoric acid, and the resulting salts are optionally removed by filtration. In principle, any suitable reactor type that allows the reaction and its heat of reaction to be controlled can be used for the alkoxylation reaction. The reaction can be carried out continuously, semi-continuously, or in batches using standard process engineering techniques and can be flexibly adapted to the existing production equipment.In addition to conventional stirred tank reactors, gas-phase jet loop reactors with internal heat exchanger tubes, as described in WO 01 / 062826, can also be used. Furthermore, gas-phase-free loop reactors can be employed.

[0124] The mean molar mass (number-average molar mass Mn or mass-average molar mass Mw) and polydispersity Mw / Mn of the compounds according to formula (I) can be determined via the molar ratio of the alkylene oxides to the starter R used. 1-OH is adjustable within wide limits. It is preferred that the number-average molar mass of the at least one compound of formula (I) is from 300 g / mol to 4500 g / mol, more preferably from 400 g / mol to 3000 g / mol, preferably from 800 g / mol to 2000 g / mol, and particularly from 1200 g / mol to 1500 g / mol, wherein the number-average molar mass is preferably determined as described in the examples. It is further preferred that the polydispersity Mw / Mn is from 1.0 to 3.0, preferably from 1.02 to 2.0, and particularly from 1.03 to 1.6, wherein the polydispersity is preferably determined as described in the examples. The compounds according to formula (I) are liquid, pasty, or solid, depending on their composition and molar mass.

[0125] The carrier may contain additional components that differ from the at least one compound of formula (I). For example, the carrier may contain defoamers, such as those selected from the group of water-insoluble, hydrophobic compounds. Examples of defoamers include silicone oils, organomodified siloxanes, mineral oils, vegetable oils, and modified vegetable oils. Furthermore, the carrier may contain solids that influence the rheological properties, such as silicic acid. Antioxidants may also be included. Additionally, biocides may be present, provided they do not impair the active ingredient.The product may also contain water-absorbing substances to further improve storage and, if necessary, dilution with water during subsequent use, to facilitate handling, to provide additional humactant properties, and / or to prevent the crystallization of active substances. Other components may be dispersing additives containing so-called anchoring groups for solids, such as sulfonates, phosphates, aromatic groups, and hydroxyl groups. The dispersing additives should preferably not be surfactants. For the reasons discussed above, surfactants, as additional components different from the at least one compound of formula (I), should preferably not be included in the carrier. For the purposes of this disclosure, surfactants are understood to be surface-active substances which, when present in a concentration of 0.5 wt.-% mixed with water at a temperature of 20°C and left to stand at the same temperature for one hour a) yields a transparent or translucent liquid or a stable emulsion without separation of insoluble substances and b) reduces the surface tension of the water to 4.5x10. -2 Reduce to N / m (45 dyn / cm) or less.

[0126] This corresponds to the definition of surfactants according to customs tariff heading 3402 (European Union). Surface tension can be determined, for example, using a tensiometer that measures surface tension via the shape of a hanging drop (pendant drop method, drop contour analysis). The OCA 25 model (DataPhysics) is a suitable tensiometer.

[0127] It is preferred that the at least one active ingredient is selected from the group consisting of chemical active ingredients and biological active ingredients, preferably selected from the group consisting of chemical and microbiological active ingredients, and in particular selected from the group of microbiological active ingredients.

[0128] It is further preferred that the at least one active ingredient is selected from the group of biological active ingredients, in particular microbiological active ingredients.

[0129] It is further preferred that at least one active ingredient is selected from the group of biological active ingredients, in particular microbiological active ingredients.

[0130] It may therefore be preferable that the at least one active ingredient is selected exclusively from the group of biological active ingredients, in particular microbiological active ingredients. In this case, it is therefore preferable that the at least one active ingredient is not selected from the group of chemical active ingredients.

[0131] Alternatively, it may be preferred that at least one active ingredient is selected from the group of biological active ingredients, in particular microbiological active ingredients, and optionally at least one additional active ingredient is selected from the group of chemical active ingredients.

[0132] It is further preferred that the active ingredient has an effect directed against a specific pathogen, preferably a plant pathogen, and preferably an antagonistic and / or hyperparasitic effect. The active ingredient is preferably a plant protection agent that acts in crop plants to cure, alleviate, or prevent diseases or pest infestations, or as a biostimulant.

[0133] It is preferred that the at least one active ingredient is selected from the group consisting of acaricides (AC), bactericides (BA), fungicides (FU), herbicides (HE), insecticides (IN), nematicides (NE), growth regulators (PG), plant strengtheners (PS), biostimulants, inoculates, and their mixtures; preferably from the group consisting of fungicides (FU), herbicides (HE), insecticides (IN), biostimulants, and their mixtures; and in particular from the group consisting of fungicides (FU), herbicides (HE), insecticides (IN), and their mixtures. Some of these active ingredients are listed, for example, in The Manual of Biocontrol Agents, 2001, The British Crop Protection Council, and in The Pesticide Manual, 14th edition, 2006, The British Crop Protection Council. However, the present invention is not limited to these active ingredients.

[0134] It is further preferred that at least one additional active ingredient from the group of fertilizers is included, preferably selected from the group consisting of NPK fertilizers and micronutrients, wherein the micronutrients particularly preferably contain the elements K, Mg, Mn, Zn and / or Fe.

[0135] Particularly preferred is the combination of at least one active ingredient selected from the group consisting of fertilizers and biostimulants with at least one further active ingredient selected from the group consisting of fungicides (FU), herbicides (HE) and insecticides (IN).

[0136] Preferably, the active ingredient increases resistance and / or stress tolerance and / or nutrient availability in plants. It is preferred that the (biological or microbiological) active ingredient is selected from the group consisting of microorganisms, organs of microorganisms, and mixtures thereof. It is particularly preferred that the microorganism is alive and / or active.

[0137] For the purposes of this disclosure, microorganisms include bacteria, fungi, algae, protozoa and viruses.

[0138] The microorganisms can therefore be selected from the group consisting of bacteria, fungi, algae, protozoa, viruses, and mixtures thereof. Preferably, the microorganism is selected from the group consisting of fungi and bacteria.

[0139] Preferably, the microorganism is not selected from the group of viruses, in particular not from the group consisting of viruses, algae and protozoa.

[0140] Preferably, the (biological or microbiological) active ingredient is selected from the group consisting of fungi, fungal organs, bacteria, bacterial organs and mixtures thereof.

[0141] Preferably, the (biological or microbiological) active ingredient is selected from the group consisting of fungi, fungal organs and their mixtures.

[0142] It is still preferred that the fungal organs be selected from the group consisting of spores, conidia, blastospores, chlamydospores, sclerotia, hyphal segments and their mixtures.

[0143] Further preferably, the (biological or microbiological) active ingredient is selected from the group consisting of the fungi Ampelomyces quisqualis, Aureobasidium pullulans, Beauveria bassiana, Beauveria brongniartii, Candida oleophila, Clonostachys rosea, Coniothyrium minitans, Gliocladium catenulatum, Gliocladium virens, Isaria fumosorosea, Isaria spp., Laetisaria arvalis, Lecanicillium lecanii, Lecanicillium muscarium, Metarhizium anisopliae, Myrothecium verrrucaria, Metarhizium riley (Nomuraea rileyi), Paecilomyces lilacinus, Phlebiopsis gigantea, Phoma macrostoma, Purpureocillium lilacinus, Pythium oligandrum, Talaromyces fiavus, Teratospema oligociadum, Trichoderma asperellum, Trichoderma atroviride, Trichoderma gamsii, Trichoderma hamatum, Trichoderma harzianum, Trichoderma koningii, Trichoderma reesei, Trichoderma spp., Verticillium biguttatum, their fungal organs and mixtures of these fungi and / or fungal organs.

[0144] The (biological or microbiological) active ingredient selected from the group consisting of the fungi Ampelomyces quisqualis, Aureobasidium pullulans, Beauveria bassiana, Candida oleophila, Clonostachys rosea, Coniothyrium minitans, Gliocladium virens, Isaria fumosorosea, Lecanicillium muscarium, Metarhizium anisopliae, Myrothecium verrrucaria, Metarhizium rileyi (Nomuraea rileyi), Purpureocillium lilacinus, Phlebiopsis gigantea, Trichoderma asperellum, Trichoderma atroviride, Trichoderma gamsii, Trichoderma hamatum, Trichoderma harzianum, Trichoderma koningii, Trichoderma reesei, their fungal organs and mixtures of these fungi and / or fungal organs is particularly preferred.

[0145] The use of the following fungi with antagonistic and / or hyperparasitic effects against certain plant pathogens is particularly preferred: Ampelomyces quisqualis, Beauveria bassiana, Beauveria brongniartii, Clonostachys rosea, Coniothyrium minitans, Gliocladium catenulatum, Isaria spp., Laetisaria arvalis, Lecanicillium lecanii, Lecanicillium muscarium, Metarhizium anisopliae, Metarhizium rileyi (Nomuraea rileyi), Paecilomyces lilacinus, Phoma macrostoma, Pythium oligandrum, Talaromyces flavus, Teratosperma oligociadum, Trichoderma spp. and Verticillium biguttatum.

[0146] Fungi that improve nutrient availability in the soil or increase the resistance of plants to stress factors (including pathogens and pests) are preferably used: Penicillium bilaii, Trichoderma spp. and all species that can be classified as mycorrhizal fungi.

[0147] (Microbiological) active substances selected from the group consisting of fungi, fungal organs and their mixtures are particularly suitable for use as plant protection products or plant protection active substances, for use as biostimulants and / or for the treatment of seeds.

[0148] It is preferred that the (biological or microbiological) active ingredient is a bacterium or a mixture of different bacteria.

[0149] It is still preferred that the bacterium or mixture of various bacteria be selected from the group consisting of Azospirillum brasilense, Azotobacter chroococcum, Bacillus amyloliquefaciens, Bacillus firmus, Bacillus licheniformis, Bacillus mycoides, Bacillus pumilus, Bacillus subtilis, Bacillus thuringiensis, Bradyrhizobium spp., Burkholderia spp., Chromobacterium subtsugae, Gluconacetobacter spp., Pseudomonas chlororaphis, Pseudomonas fluorescens, Pseudomonas syringae, Rhizobium spp., Streptomyces griseoviridis, Streptomyces lydicus, and their mixtures. These compositions are particularly suitable for use as plant protection products, biostimulants, and / or seed treatment.

[0150] It is further preferred that the bacterium or mixture of different bacteria is selected from the group consisting of Lactobacillus gasseri, Lactobacillus paracasei, Lactobacillus plantarum, Lactobacillus crispatus, Lactobacillus casei, Lactobacillus animalis, Lactobacillus rhamnosus, Lactobacillus pentosus, Lactobacillus reuteri, Lactococcus lactis, Bacillus pumilus, Bacillus licheniformis, Bacillus coagulans, Bacillus cereus, Bacillus subtilis, Bacillus amyloliquefaciens, Clostridium butyricum, Enterococcus faecium, Streptococcus faecium, Lactobacillus acidophilus, Lactobacillus salivarius, Lactobacillus fermentum, Lactobacillus johnsonii. Lactobacillus helveticus, Streptococcus thermophiles, Pediococcus acidilactici, Bifidobacterium lactis, Bifidobacterium adolescentis, Bifidobacterium lactobacillus, Bifidobacterium animalis, Bifidobacterium longum, Bifidobacterium infantis and their mixtures.These compositions are particularly suitable for use as a probiotic in food and / or animal feed.

[0151] It is still preferred that the (biological or microbiological) active ingredient be selected from the group consisting of lactobacilli, bifidobacteria, Enterococcus faecalis, Enterococcus faecium, and the yeasts Saccharomyces boulardii and Saccharomyces cerevisiae and their mixtures. These compositions may, for example, be suitable for use as a probiotic drug. The efficacy of probiotic drugs is relatively well researched for some diseases and applications. These include various chronic inflammatory bowel diseases, various diarrheal diseases, chronic constipation, prevention of allergies and infections in premature infants, prevention of atopic dermatitis, infections of the throat, nose, and ears, urinary tract infections, and dental caries.

[0152] It is also preferred that the (biological or microbiological) active ingredient be a virus or a mixture of different viruses, preferably selected from the group of baculoviruses, and more preferably from the genera nucleopolyhedrovirus and granulovirus. In a preferred embodiment of the composition, the virus CpGV (Cydia pomonella granulovirus) is selected as the microbiological active ingredient. This virus is used, for example, to protect against codling moth caterpillars in fruit growing. In another preferred embodiment of the composition, the virus HearNPV (Helicoverpa armigera nucleopolyhedrovirus) is selected as the microbiological active ingredient. This virus is specifically effective against the larvae of the cotton bollworm and is used, for example, to protect cotton plants.

[0153] It is still preferred that the (biological or microbiological) active ingredient is a mixture of the above-mentioned microorganisms and / or their organs.

[0154] It is particularly preferred that the at least one (biological or microbiological) active ingredient is selected from the group consisting of Trichoderma harzianum, Bacillus amyloliquefaciens, Beauveria bassiana, Metarhizium rileyi (Nomuraea rileyi), Metarhizium anisopliae, Clonostachys rosea, Aureobasidium pullulans, Coniothyrium minitans and their organs; wherein the organs are preferably selected from the group consisting of spores, conidia, blastospores, chlamydospores, sclerotia and hyphal segments.

[0155] It is further preferred that the at least one (biological or microbiological) active ingredient comprises or consists of spores, preferably fungal spores and / or bacterial spores, in particular spores of Trichoderma harzianum and / or of Bacillus amyloliquefaciens and / or of Beauveria bassiana and / or of Metarhizium rileyi (Nomuraea rileyi) and / or of Metarhizium anisopliae and / or of Clonostachys rosea and / or of Aureobasidium pullulans and / or of Coniothyrium minitans.

[0156] It is even more preferred that at least one (biological or microbiological) active ingredient is selected from the group consisting of Trichoderma harzianum and spores of Trichoderma harzianum.

[0157] It is even more preferred that the at least one (biological or microbiological) active ingredient comprises or consists of spores of Trichoderma harzianum.

[0158] It is particularly preferred that the at least one (biological or microbiological) active ingredient is spores of Trichoderma harzianum.

[0159] It is also preferred that the microbiological agent comprises vegetative cells, in particular vegetative cells of Pseudomonas fluorescens and / or Pseudomonas chlororaphis.

[0160] By adjusting the water activity, the viability and / or germination capacity of the contained microbial active ingredient is increased, and thus also its shelf life. The water activity (activity of water, a wWater activity (aw) is a thermodynamic parameter. It measures the amount of water available for chemical, biochemical, and microbial reactions in samples such as aqueous solutions and foods, and can also be used to characterize the composition of carriers and active ingredients. Water activity is expressed as the aw value and is defined as the ratio of the water vapor pressure above the sample (p) to the water vapor pressure of pure water (po) at the same temperature, aw = p / po. The water activity corresponds to 1 / 100 of the relative equilibrium humidity (RAH). The relative equilibrium humidity is also referred to as equilibrium relative humidity (ERH). Pure water has an aw value of 1, and any addition of water-binding substances lowers the aw value below 1.It is preferred that the a-value of the carrier composition is less than 0.4, preferably less than 0.3, and in particular less than 0.25. Water or aqueous.

[0161] Solutions are generally unsuitable for use as carriers for microbiological agents due to their high water activity. Methods for determining the ac value are known to those skilled in the art. The ac w The a-value is preferably determined as follows: To determine the water activity of a sample, the relative humidity is measured directly above the sample after moisture equilibrium has been reached (water vapor partial pressure differential). The equilibrium relative humidity (ERH) is measured in % relative humidity and is related to the a-value as follows: a = ERH / 100. The LabMaster-aW neo from Novasina was used to determine the water activity of the compositions.

[0162] The compounds of formula (I) may contain small amounts of water (for example, due to synthesis or absorption of atmospheric moisture during storage). It can therefore be advantageous to adjust, and in particular reduce, the water content and thus the water activity. This can be achieved, for example, by means of a thermal separation process. Thermal separation processes are known to those skilled in the art and include all processes based on establishing a thermodynamic phase equilibrium. Preferred thermal separation processes are selected from the group consisting of distillation, rectification, adsorption, crystallization, extraction, absorption, drying, and freezing; methods of distillation and rectification are particularly preferred. Drying agents such as molecular sieves, e.g., zeolites, can also be used for drying.It is preferred that the at least one active ingredient is a combination of at least one biological and at least one chemical active ingredient, preferably a combination of at least one microbiological active ingredient and at least one chemical active ingredient.

[0163] Preferred chemical active ingredients or classes of active ingredients are strobilurins, carboxamides, triazoles, benzophenones, morpholines, neonicotinoids, sulfonylureas, growth regulators, total herbicides and their combinations.

[0164] It is further preferred that the chemical active ingredient be selected from the group consisting of azoxystrobin, pyraclostrobin, isopyrazam, epoxyconazole, difenoconazole, metrafenone, fenpropimorph, thiamethoxam, rimsulfuron, dicamba, glyphosate and their combinations.

[0165] The use of the carrier composition according to the invention preferably leads to an improvement in the handling and dosing of the active ingredient composition, since the carrier composition preferably has a viscosity of less than 1 Pa s at 25 °C and preferably a viscosity of less than 10 Pa s at 0 °C.

[0166] It is therefore preferred that the support composition has a viscosity of less than 1 Pa s at 25 °C and a viscosity of less than 10 Pa s at 0 °C. Preferably, the viscosity is determined as described in the examples.

[0167] The use of the carrier composition according to the invention preferably leads to an increase in the storage stability of the (biological or microbiological) active ingredient. Preferably, the storage stability is determined as described in the examples. It is therefore further preferred that the proportion of viable spores or vegetative cells after storage at 40 °C after 28 days is at least 1%, more preferably at least 2%, and particularly at least 3%, based on the initial value. Preferably, the proportion of viable spores or vegetative cells is determined as described in the examples.

[0168] Another object of the present invention is therefore a method for storing at least one active ingredient, wherein the at least one active ingredient is stored in a carrier.

[0169] Another object of the invention is a composition (also referred to in the present disclosure as an active ingredient composition) comprising:

[0170] (a) at least one compound of formula (I) and

[0171] (b) at least one active ingredient.

[0172] The above statements apply to the carrier (the carrier composition), which consists of at least one compound of formula (I) and at least one active ingredient. All definitions,

[0173] The embodiments and explanations that apply to the use according to the invention also apply mutatis mutandis to the composition according to the invention.

[0174] (active ingredient composition) as well as for the inventive method and for other objects of the present invention and vice versa.

[0175] It is preferred that the active ingredient composition consists (essentially) of components (a) and (b).

[0176] It is further preferred that the mass fraction of the carrier, based on the total mass of the active ingredient composition, is from 40% to <100%, preferably from 70% to <99.999%, and in particular from 80% to 99.99%.

[0177] It is further preferred that the mass fraction of the at least one active ingredient (i.e., all active ingredients together) in relation to the total mass of the active ingredient composition is from >0% to 60%, preferably from 0.001% to 30%, and in particular from 0.01% to 20%.

[0178] It is therefore preferred that the mass fraction of the carrier, based on the total mass of the active ingredient composition, is from 40% to <100%, preferably from 70% to <99.999%, and in particular from 80% to 99.99%, and that the mass fraction of the at least one active ingredient (i.e., all active ingredients combined), based on the total mass of the

[0179] The active ingredient composition is >0% to 60%, preferably 0.001% to 30%, and in particular 0.01% to 20%. It is therefore preferred that the mass fraction of all compounds of formula (I), based on the total mass of the active ingredient composition, is 40% to <100%, preferably 70% to <99.999%, and in particular 80% to 99.99%, and / or that the mass fraction of all active ingredients, based on the total mass of the active ingredient composition, is >0% to 60%, preferably 0.001% to 30%, and in particular 0.01% to 20%.

[0180] Preferably, the a-value of the active ingredient composition is less than 0.4, preferably less than 0.3, and in particular less than 0.25. The a-value is preferably determined in the same way as for the carrier.

[0181] It is further preferred that the active ingredient composition is in liquid form, for example, as an oil dispersion (OD), dispersion concentrate (DC), or suspension concentrate (SC). This has the advantage of making the composition easy to handle. However, it is also possible for the active ingredient composition to be in solid form, for example, as a water-dispersible powder (WP) or water-dispersible granules (WG). It is particularly preferred, however, that the active ingredient composition is in the form of an oil dispersion (OD).

[0182] The active ingredient composition is obtained by mixing the active ingredient with the carrier. It is preferred that the active ingredient is dissolved and / or suspended and / or dispersed in the carrier.

[0183] When using a microbiological active ingredient, the active ingredient is preferably cultivated beforehand on a suitable nutrient medium using methods known per se, such as submerged fermentation or solid-state fermentation. Preferably, the cultivated microorganism is processed by suitable separation, drying, milling, and / or dispersion methods. Following cultivation, the microorganism and / or its preferred parts are preferably separated from the culture medium. In a particularly preferred embodiment, the culture medium colonized by the microorganism (especially in the case of solid culture media) is dried beforehand. In another embodiment, the microorganism or its preferred parts can be dried after separation from the culture medium, for example, using freeze-drying or spray-drying methods.After separation and, if necessary, drying, the microorganism and / or its organs are suspended and / or dispersed in the carrier. It is further preferred that the microorganism, preferably selected from the group of fungi, is prepared by milling and / or dispersion processes. In this process, after cultivation, and before the separation of the microorganism and / or its preferably used organs, the cultured substrate is prepared by a suitable dispersion process, or after drying, by a suitable milling process. Preferably, the microorganism or its preferably used organs are then subsequently separated / isolated by methods known per se, such as sieving, filtration, air classification, decantation, and / or centrifugation.Preferably, the active ingredient composition is prepared by mixing the at least one microorganism and / or its organs into the carrier, preferably in a mixing vessel using a stirrer. This preferably yields a liquid active ingredient composition, such as an oil dispersion (OD), suspension concentrate (SC), or dispersion concentrate (DC). By selecting suitable compounds of formula (I) and / or using appropriate viscosity regulators, the viscosity can be adjusted so that no or at least only reduced separation of the mixed-in microorganisms is observed in the liquid formulation, preferably an OD, SC, or DC formulation.

[0184] The active ingredient composition is preferably diluted with water in a spray tank to create a spray solution for application to plants or on or in the soil. Preferably, the mass fraction of water, based on the total mass of the spray solution, is 80% to 99.99%, more preferably 90% to 99.9%, and particularly 95% to 99%. However, the mass fraction can also be higher or lower, depending on the application rate of the at least one active ingredient. It is preferred to spray the solution with a maximum of 1000 liters, preferably 50 liters to 600 liters, and particularly 100 liters to 400 liters of water per hectare, depending on the application rate of at least one active ingredient and on the type and number of plants.

[0185] A further object of the present invention is the use of the active ingredient composition according to the invention for the treatment of plants and / or seeds and / or soils and / or its use as a biostimulant. A further object of the present invention is accordingly a method for treating plants and / or seeds and / or soils with and / or using the active ingredient composition according to the invention. Preferably, the active ingredient composition according to the invention is used as a plant protection product, plant strengthener, or soil improver; it is particularly preferred that the active ingredient composition according to the invention be used for plant protection. It is therefore preferred that the active ingredient composition according to the invention is a plant protection product.The active ingredient composition according to the invention is particularly preferred if the at least one active ingredient is selected from the group of biological active ingredients, in particular microbiological active ingredients, and is used as a biological plant protection product, biological plant strengthener or biological soil improver; this active ingredient composition according to the invention is particularly preferred for use in biological plant protection.

[0186] When used for plant protection, seed treatment, and / or as a biostimulant, the active ingredient composition is preferably mixed into the soil, watered in, or applied to / on the plant or seed. Depending on the intended application, the active ingredient composition is optionally diluted with water to the required application concentration. The active ingredient compositions according to the invention are preferably used as a formulation, preferably as a plant protection formulation, for spray solutions. The mass fraction of the carrier, based on the total mass of the spray solution, is preferably from 0.001% to 1%, more preferably from 0.01% to 0.5%. The spray solution is preferably applied to / on the plant via an irrigation system selected from the group consisting of micro-irrigation systems, sprinkler systems, and drip systems.

[0187] Plant protection formulations are usually diluted with water before being sprayed on plants or plant parts using nozzles. In addition to the active ingredient, they may contain other excipients such as emulsifiers, dispersing agents, antifreeze, defoamers, biocides, and surfactants. Emulsifiers or surfactants, unless they are compounds of formula (I), are preferably not included. Active ingredients, especially fungicides, insecticides, and nutrients, can also be applied to plant seeds using various methods, either alone or in combination with the excipients mentioned above. These methods are also called seed treatment methods. Seed treatment with fungicides and insecticides can protect plants from diseases and insect infestations in the early stages of growth.

[0188] Plant protection formulations can also be applied to plants using pollinating insects, such as bumblebees or honeybees. The composition may be mixed with water to apply it to the plants.

[0189] The application concentration is diluted. Preferably, however, the composition is used undiluted. The dispersal of chemical pesticides by means of pollinating insects is described, for example, in WO 2011026983 A1. Biological pesticides can also be dispersed in a similar manner. It is advantageous if the pollinators are not impaired or harmed by the active ingredient or the composition. If biocides are used in the formulations, they are selected so that they do not harm any microorganisms that may be contained in the composition according to the invention. This means that the microorganisms in the formulation are only minimally or not at all impaired in their viability and / or germination capacity.

[0190] An active ingredient composition containing conidia of Paecilomyces lilacinus as a microbiological agent can be used for the biological control of plant-parasitic nematodes. When using spores of Talaromyces flavus, the preparation can be used to control Verticillium dahliae, a pathogen that causes economically significant wilt in cotton. Compositions containing spores of Metarhizium rileyi (Nomuraea rileyi) can be used to control the caterpillars of various harmful butterfly species, such as Helicoverpa armigera and Spodoptera exigua. The application of the composition using conidia of PenicilHum bilaii increases the availability of mineral phosphorus in the soil.

[0191] Preferred agricultural applications for these active ingredient compositions include arable farming, horticulture and ornamental plant cultivation, viticulture, and cotton cultivation. Fruit and vegetable cultivation is particularly favored. Preferred fruits include pome fruits, stone fruits, berries, and nuts. Preferred vegetables include root vegetables, shoot vegetables, tuber vegetables, bulb vegetables, leafy vegetables, leafy greens, leafy salads, seed vegetables, and fruiting vegetables.

[0192] In the case of the use of the active ingredient composition i) for the treatment of plants and / or ii) for the treatment of seeds and / or iii) for the treatment of soils and / or iv) as a biostimulant, the active ingredient composition is preferably used as a formulation for spray solutions, wherein the mass fraction of the carrier composition is 0.001% to 1% in relation to the total mass of the spray solution.

[0193] A further aspect of the present invention is the use of the active ingredient composition as a probiotic food supplement and / or probiotic feed additive. The active ingredient compositions can be used as a probiotic in food and / or feed. Probiotic food and / or feed typically contain bacteria and / or fungi as the microbial active ingredient. Examples of probiotic foods include yogurt preparations, kefir preparations, sour milk preparations, and lacto-fermented vegetables. The microbial active ingredient exerts a health-promoting effect in the intestine. The use of the active ingredient composition as a probiotic food supplement and / or probiotic feed additive is subject to the condition that the at least one active ingredient it contains is suitable for use as a probiotic food supplement or probiotic feed additive.

[0194] Another object of the present invention is an active ingredient composition according to the invention for use as a probiotic drug.

[0195] For the active ingredient composition for use as a probiotic medicinal product, the requirement is that at least one of the active ingredients contained is suitable for use as a probiotic medicinal product.

[0196] According to the use of the active ingredient composition according to the invention, further objects of the present invention also include plant protection products, biostimulants, probiotic food supplements, probiotic feed additives and probiotic pharmaceuticals containing or consisting of the active ingredient composition according to the invention.

[0197] All definitions, embodiments and explanations that apply to the use according to the invention or to the composition (active ingredient composition) according to the invention also apply mutatis mutandis to the plant protection products, biostimulants, probiotic food supplements, probiotic feed additives and probiotic drugs according to the invention.

[0198] The carrier compositions or active ingredient compositions have numerous advantages:

[0199] One advantage is the improved shelf life of microorganisms through the use of the carrier composition, or the improved shelf life of the active ingredient composition. In particular, the active ingredient composition can be stored at room temperature for many weeks. This simplifies transport and storage. Storage and transport of the composition preferably take place in airtight containers such as bottles, bags, canisters, or drums. The increased shelf life leads, in particular, to an increase in biological activity.

[0200] Furthermore, the active ingredient composition, particularly in the form of a dispersion concentrate, a suspension concentrate or an oil dispersion, demonstrates improved viability and / or germination capacity compared to the state of the art.

[0201] A further improvement over the state of the art is that the microorganisms and / or their organs remain viable and / or capable of germination for significantly longer in the ready-to-use aqueous dilutions than in the aqueous dilutions based on the state of the art.

[0202] Formulations of fungal spores can, for example, be premixed with water to accelerate germination and reduce the infection time (see HD Burges: Formulation of Microbial Biopesticides, Springer, 1998). Similarly, some manufacturers of microbial products (e.g., Remedier® from Isagro, Naturalis® from CBC Europe, FZB24 from ABiTEP GmbH) recommend activating the spores in the formulation before spraying. To do this, the formulation is diluted in a smaller volume of water in a container (by a factor of 3 to 50) and left to stand for 2 to 24 hours before spraying. Since the microorganisms are particularly sensitive during this phase, it is advisable to use a biocompatible carrier composition in the formulation that does not adversely affect the microorganisms.The active ingredient composition according to the invention is characterized by a higher survival rate of the contained microorganisms at room temperature or slightly elevated temperatures. It is therefore easy to store and transport and does not require refrigeration to ensure that a sufficiently high concentration of viable microorganisms reaches the target location on the plant or in the soil. In the ready-to-use aqueous dilutions, the carrier compositions and active ingredient compositions according to the invention do not impair the germination or growth of the microorganisms at the target location.

[0203] Another advantage is that the carrier facilitates the dispersion of the active ingredient in an aqueous composition, such as the spray solution.

[0204] A further advantage is that the carrier is self-emulsifying or water-soluble, or can be made self-emulsifying or water-soluble. The carrier is therefore easily dilutable with water, or can be made dilutable. The carrier composition and the active ingredient composition can be easily dispersed or even dissolved in water. The dilutability, i.e., the self-emulsifying ability or water solubility, is preferably determined as described in the examples. Self-emulsifying or water-soluble, and thus dilutable, carriers or active ingredient compositions can be dispersed or dissolved in water without significant shear stress. Self-emulsifying carriers spontaneously form emulsion droplets, preferably with an average size of less than 400 pm, more preferably less than 200 pm, and particularly less than 100 pm.The size of the emulsion droplets can be determined, for example, by laser diffraction, either using laser diffraction systems or by computer-aided image analysis of high-resolution, static images of the spray mist. The size of the emulsion droplets is preferably measured by laser diffraction, particularly preferably using the Malvern MasterSizer 3000. The carrier dissolves or disperses readily in water and forms a clear solution or a milky emulsion when mixed with water in a mass ratio of 100:100 to 0.0001:100. Since efficiency enhancers for plant protection products are generally water-soluble to improve the effectiveness of plant protection products from aqueous spray solutions, it is surprising, in light of the prior art, that similar effects can also be achieved with self-emulsifying compositions.The self-emulsifying effect can be achieved in particular by specifically adjusting the hydrophobicity / hydrophilicity of the compound of formula (I). In the case of tank-mix formulations, for example, this results in a sufficiently homogeneous distribution of the compound of formula (I) in the spray solution even during the tank-mixing process. This facilitates the preparation of spray solutions. Furthermore, the good incorporability and the associated homogeneous distribution during the spraying process prevent clogging of the spray nozzles.

[0205] Another advantage is that the compound of formula (I) exhibits a sufficiently low viscosity even at low temperatures. This leads to better dosing and easier handling of the plant protection product.

[0206] A further advantage is the biodegradability of many compounds of formula (I), the carrier, and the composition comprising the carrier and the (biological or microbiological) active ingredient. The biodegradability is preferably determined according to the OECD 301 F method. More preferably, the biodegradability is determined according to OECD 301 F after 28 days at 22 °C.

[0207] Another advantage is that the adhesion and retention of sprays / spray solutions containing the carrier composition or the active ingredient composition is improved, even on plant surfaces that are difficult to wet.

[0208] A further advantage is the excellent compatibility of compounds of formula (I) with common adjuvants and defoamers. Suitable adjuvants and defoamers are known to those skilled in the art and are available, for example, under the trade names BREAK-THRU® (Evonik).

[0209] Industries AG), SURFYNOL® (Evonik Industries AG) and TOMADOL® (Evonik Industries AG) are commercially available. Particularly good compatibility is demonstrated with BREAK-THRU® S 301 and BREAK-THRU® S 255. A further advantage is that the viscosity, rheology and / or the

[0210] The sedimentation behavior of the dissolved active ingredient can be easily adjusted by adding silica. Suitable silicas are known to those skilled in the art and are commercially available, for example, under the trade name AEROSIL® (Evonik Industries AG). The following examples describe the present invention by way of example, without limiting the invention, the scope of which is evident from the entire description and the claims, to the embodiments mentioned in the examples.

[0211] Examples

[0212] Measurement methods and test procedures for polydispersity, mass-averaged molar mass (Mw) and number-averaged molar mass (Mn):

[0213] To determine the polydispersity, the mass-mean molar mass (Mw) and the number-mean molar mass (Mn), GPC measurements were carried out under the following measurement conditions: column combination SDV 1000 / 10000 A (length 65 cm), temperature 30 °C, THF as mobile phase, flow rate 1 ml / min, sample concentration 10 g / l, Rl detector, evaluation against polypropylene glycol standard.

[0214] Acid number: The acid number was determined using a titration method in accordance with DIN EN ISO 2114.

[0215] Hydroxyl number (OH number): Hydroxyl numbers were determined according to the method DGF CV 17 a (53) of the German Society for Fat Science. Samples were acetylated with acetic anhydride in the presence of pyridine, and the consumption of acetic anhydride was determined by titration with 0.5 N potassium hydroxide in ethanol against phenolphthalein. Viscosity:

[0216] The viscosity of the liquid under test (carrier without spores) was determined using an Anton Paar MCR 302 rheometer. A 50 mm diameter plate was used as the measuring geometry. The measurement was performed at a shear rate of 10 s⁻¹. _1 The temperature was measured. The measurement temperature was regulated to 25°C and 0°C using a Peltier element.

[0217] Preparation of the compositions with Trichoderma harzianum as the active ingredient and a carrier, and determination of storage stability: Spores of the fungus Trichoderma harzianum, obtained in powder form from Rhizo-Mic UG, were used as the active ingredient. According to elemental analysis, the powder contained approximately 75 wt% S1O2 in addition to the spores. The content of viable spores was 1.97 x 10 9Spores / g powder. The compositions containing the carrier and spores of Trichoderma harzianum were prepared as follows: 3 g and 6 g of the spore-containing powder, respectively, were weighed into a 50 mL sterile centrifuge tube (50 mL tube from Greiner Bio-One GmbH) and overlaid with 27 g and 24 g of carrier, respectively, to obtain 30 g of the composition containing the carrier and spores of Trichoderma harzianum. The mixture was mixed for 30 seconds on a vortex shaker (lab dancer from ika). After homogenization with a spatula, the compositions were mixed again for 30 seconds on a vortex shaker after a waiting period of 15 minutes. The prepared compositions were incubated for four weeks at 40 °C. The number of colony-forming units (CFU) was determined immediately after preparation (baseline) and again after 4 weeks.The colony-forming unit (CFU) count is a measure of the number of spores that were able to germinate and form colonies before and after storage. To determine the colony-forming unit (CFU) count using the plate method, 1.0 g of the sample material was diluted with sterile physiological saline solution (0.9 wt% NaCl in water) in a decimal dilution series up to the 10th dilution. -8 diluted. The three dilution levels were 10 -6 , 10 -7 and 10 -8(1.0 mL each) were plated onto ready-to-use culture medium (Compact Dry YM for yeasts and molds or Compact Dry Total Count from Nissui Pharmaceutical Co., Ltd.). The fungal spores were incubated for three days at 25°C. Plates showing 10 to 100 CFU were evaluated. Table 3 shows the percentage of colony-forming units (in CFU / g) relative to the initial value, as a measure of the survival rate and / or storage stability of the composition. The results presented are arithmetic means of three determinations.

[0218] Dilution (self-emulsifying / water solubility):

[0219] A 400 mL beaker was filled with 200 mL of tap water. One mL of the liquid to be tested (a carrier without spores) was drawn into a 2.5 mL plastic pipette and dispensed into the water from approximately ten centimeters above the water level with firm pressure on the pipette. After about ten seconds, the beaker was picked up and swirled three times clockwise by hand to check the further distribution. After swirling, the mixture should be homogeneously white (milky) or clear. The mixture was left to stand for 60 minutes and then re-evaluated for homogeneity (creaming / fat globules). If the mixture remained homogeneously white, it was self-emulsifiable; if it remained clear, it was water-soluble. The evaluation was performed by three experienced laboratory staff members. Dilution (self-emulsifiability / water solubility) was tested at 20°C to 22°C.

[0220] Carriers used:

[0221] Commercially available raw materials: Examples 1 to 8 were selected as potential carriers from commercially available raw materials (see Table 1). Examples 2 to 8 are linear, OH-terminated polyethers. Table 1: Commercially available raw materials as carriers (PEG: poly(ethylene glycol), PPG:

[0222] Poly(propylene glycol), EO: ethylene oxide or ethylene oxy, PO: propylene oxide or propylene oxy) 1 Examples of synthesis not according to the invention:

[0223] In addition, the following polyethers were produced as potential carriers (examples 9 to 18):

[0224] Synthesis of examples 9 to 14 and 16 to 18:

[0225] In a 3-liter autoclave, allyl alcohol or n-butanol was used as the starting alcohol, and sodium methoxide or potassium methoxide as the base was placed under nitrogen and heated to 80–90 °C with stirring. The reactor was evacuated to an internal pressure of 400 mbar to remove any volatile components by distillation. Propylene oxide (PO) and / or ethylene oxide (EO) were continuously added over 6 hours at 110–120 °C and a maximum absolute reactor internal pressure of 4.0 bar, while cooling and stirring. A 60-minute post-reaction at 110–120 °C was followed by degassing. Volatile components such as residual propylene oxide or ethylene oxide were distilled off under vacuum. The polyether was neutralized with phosphoric acid. Water was removed by distillation under vacuum at <30 mbar and 100 °C. The low-viscosity and colorless polyether was cooled to below 80 °C and drained through a filter.The amounts of starting alcohol, sodium methoxide, ethylene oxide (EO) and / or propylene oxide (PO) used, as well as the characterization of the polyethers obtained, can be found in Table 2.

[0226] Synthesis of Example 15: In a 3-liter autoclave, 80.0 g of butanol and 11.3 g of sodium methoxide (as a base) were placed under nitrogen and heated to 80–90 °C with stirring. The reactor was evacuated to an internal pressure of 400 mbar to remove any volatile components by distillation. 2210 g of propylene oxide were continuously added over 11 hours at 115 °C and a maximum reactor internal pressure (absolute) of 4.0 bar, while cooling and stirring. A 60-minute post-reaction at 110–120 °C was followed by degassing. Volatile components, such as residual propylene oxide, were distilled off under vacuum. The polyether was neutralized with phosphoric acid. Water was removed by distillation under vacuum at <30 mbar and 100 °C. The low-viscosity, colorless polyether was cooled to below 80 °C and filtered. The product had an OH number of 32.2 mg KOH / g.GPC has a mass-averaged molar mass Mw of 1835 g / mol and a polydispersity Mw / Mn of 1.10 (see Table 2).

[0227] Table 2: Preparation and characterization of the polyethers of examples 9 to 18 (EO: ethylene oxide or ethyleneoxy, PO: propylene oxide or propylenoxy): 1] not according to the invention 2] according to the invention 3] Proportion of residues R 2 with R 2 = CH3 in the compound according to formula (I) given in % = molar fraction of PO relative to the total amount of PO and EO = n(PO) / (n(PO) + n(EO)), with n(PO) = m(PO) / M(PO) and n(EO) = m(EO) / M(EO) as well as M(PO) = 59.08 g / mol and M(EO) = 44.05 g / mol 4] Index n according to formula (I) = mean chain length = mean number of repeat units 5] calculated according to HLB = 20 (1 -m / m) = 20 = 20 m / m = 20 m(EO) / [m(starting alcohol)+m(EO)+m(PO)]

[0228] Application-related testing:

[0229] Examples 1 to 18 were tested for their suitability as carriers. The viscosity of the carrier was tested as a measure of its handling / dosage / pourability, the proportion of viable spores after storage as a measure of the storage stability of a carrier-active ingredient composition, and the dilution (self-emulsifiability or water solubility) of the carrier. Low viscosity results in good pourability and easy dosing. A high proportion of viable spores indicates high storage stability. High self-emulsifiability or water solubility, i.e., good dilution, facilitates the preparation of the spray solution. The results for examples 1 to 18 are summarized in Table 3.

[0230] Table 3: Results of the application-related testing of examples 1 to 18.

[0231] [1] not according to the invention

[0232] [2]according to the invention

[0233] [6] represented as a percentage of colony-forming units of Trichoderma harzianum (in CFU / g) relative to the starting value

[0234] [7] Experiments were conducted with 90 wt% carrier and 10 wt% spore powder.

[0235] [8] Experiments were conducted with 80 wt% carrier and 20 wt% spore powder.

[0236] In contrast to non-inventive examples 1 to 9, examples 10 to 18 according to the invention exhibit a viscosity of less than 1 Pa s at 25 °C and less than 10 Pa s at 0 °C (in each case measured as pure substance without spores) and, when used as a carrier for spores of Trichoderma harzianum, result in a percentage of colony-forming units (in CFU / g) relative to the initial value when stored at 40 °C to values ​​exceeding 3%. The carriers 10 to 18 according to the invention are easily handled / dosed / pourable at both 25 °C and 0 °C and, compared to the non-inventive carriers, exhibit storage stability improved by at least a factor of 10. Storage stability is greatly reduced in the case of the doubly OH-terminated polyethers (see examples 2 to 8) compared to the singly OH-terminated polyethers (see examples 10 to 12, 14 to 18).Polyethers containing only oxyethylene units (= ethyleneoxy units) and no oxypropylene units (= propylenoxy units) exhibit high viscosity, especially at low temperatures, or are even solid (see Examples 2 to 4 and 9). In contrast, polyethers containing only oxypropylene units and no oxyethylene units, or both oxyethylene and oxypropylene units, consistently exhibit low viscosity. Their water dilution is generally sufficient. Polyethers with a low molar mass show somewhat improved water dilution. This is particularly evident when comparing Example 17 with Example 18, which differ only in their molar mass. Furthermore, binary mixtures (mass ratio 1:1) of some of the above examples were also investigated with regard to their viscosity and dilution. The results are summarized in Table 4.Table 4: Results of the application-related testing of binary mixtures (mass ratios 1:1).

[0237] The viscosity and self-emulsifying properties of the support can therefore be specifically adjusted by mixing different polyethers. For example, the mixture of the polyether from Example 15 with one of the polyethers from Examples 10, 12, or 14 exhibits lower viscosity and better self-emulsifying properties than the polyether from Example 15 alone.

Claims

Patent claims 1. Use of a composition comprising at least one compound of the formula (I), R 1 0-[(C2H3R 2 )-0]nH Formula (I), where R 1 a monovalent aliphatic residue with 1 to 22, preferably 2 to 10, in particular 3 to 4 carbon atoms, R 2 each is independently a hydrogen radical or a methyl group, n is a number from 1 to 300, preferably from 5 to 100, in particular from 10 to 30, with the proviso that at least one group R 2 a methyl group, as a carrier for at least one active ingredient.

2. Use according to claim 1, characterized in that the remainder R 1 an alkyl group, preferably a group selected from the group consisting of methyl, ethyl, n-propyl, / so-propyl, n-butyl, / so-butyl, sec-butyl, te / -butyl, n-pentyl (amyl), 2-pentyl (sec-pentyl), 3-pentyl; 2-Methylbutyl, 3-Methylbutyl ( / so-Pentyl or / so-Amyl), 3-Methylbut-2-yl, 2-Methylbut-2-yl, 2,2-Dimethylpropyl (Neopentyl), Hexyl, Octyl, Decyl, Dodecyl, Myristyl, Stearyl, 2-Ethylhexyl, 2-Propylheptyl, 3,5,5-Trimethylhexyl, isononyl, isotridecyl, in particular an n-butyl radical.

3. Use according to one of claims 1 or 2, characterized in that 10% to 100%, preferably 20% to 80%, in particular 40% to 60% of the residues R 2 These are methyl groups.

4. Use according to any one of claims 1 to 3, characterized in that the number-average molar mass of the at least one compound of formula (I) is from 400 g / mol to 3000 g / mol, preferably from 800 g / mol to 2000 g / mol, and in particular from 1200 g / mol to 1500 g / mol.

5. Use according to any one of claims 1 to 4, characterized in that the HLB value of the at least one compound of formula (I) is from 0.0 to 14.0, preferably from 3.0 to 10.0, and in particular from 7.0 to 9.

5.

6. Use according to any one of claims 1 to 5, characterized in that the at least one active ingredient is selected from the group consisting of chemical active ingredients and biological active ingredients, preferably from the group consisting of chemical and microbiological active ingredients, and in particular from the group consisting of microbiological active ingredients.

7. Use according to any one of claims 1 to 6, characterized in that the at least one active ingredient is selected from the group of microorganisms consisting of Trichoderma harzianum, Bacillus amyloliquefaciens, Beauveria bassiana, Metarhizium rileyi, Metarhizium anisopliae, Clonostachys rosea, Aureobasidium pullulans, Coniothyrium minitans and their organs, wherein the microorganisms or their organs are preferably selected from the group consisting of spores, conidia, blastospores, chlamydospores, sclerotia and hyphal segments. 8.Use according to any one of claims 1 to 7, characterized in that the at least one active ingredient comprises or consists of spores, preferably fungal spores and / or bacterial spores, in particular spores of Trichoderma harzianum and / or of Bacillus amyloliquefaciens and / or of Beauveria bassiana and / or of Metarhizium rileyi and / or of Metarhizium anisopliae and / or of Clonostachys rosea and / or of Aureobasidium pullulans and / or of Coniothyrium minitans.

9. Use according to any one of claims 1 to 8, characterized in that the at least one active ingredient comprises or consists of spores of Trichoderma harzianum.

10. Use according to any one of claims 1 to 9, characterized in that the at least one active ingredient is selected from the group consisting of acaricides (AC), bactericides (BA), fungicides (FU), herbicides (HE), insecticides (IN), nematicides (NE), growth regulators (PG), plant strengtheners (PS), biostimulants, inoculates and their mixtures; preferably from the group consisting of fungicides (FU), herbicides (HE), insecticides (IN), biostimulants and their mixtures; in particular from the group consisting of fungicides (FU), herbicides (HE), insecticides (IN) and their mixtures.

11. Use according to any one of claims 1 to 10, characterized in that the at least one active ingredient is a combination of at least one biological and at least one chemical active ingredient, preferably a combination of at least one microbiological active ingredient and at least one chemical active ingredient.

12. Method for storing at least one active ingredient, characterized in that the at least one active ingredient is stored in a carrier, in each case according to the specifications of one of claims 1 to 11.

13. Composition comprising: (a) at least one compound of formula (I) and (b) at least one active ingredient according to each of claims 1 to 12.

14. Composition according to claim 13, characterized in that the mass fraction of all compounds of formula (I) based on the total mass of the active ingredient composition is from 40% to <100%, preferably from 70% to <99.999%, in particular from 80% to 99.99%, and / or the mass fraction of all active ingredients based on the total mass of the active ingredient composition is from >0% to 60%, preferably from 0.001% to 30%, in particular from 0.01% to 20%.

15. Use of the composition according to one of claims 13 or 14 i) for the treatment of plants and / or ii) for the treatment of seeds and / or iii) for the treatment of soils and / or iv) as a biostimulant and / or v) as a probiotic food supplement and / or probiotic feed additive.

16. Method for treating plants and / or seeds and / or soils using the composition according to one of claims 13 or 14.

17. Composition according to claim 13 or 14 for use as a probiotic medicinal product.

18. Plant protection product, biostimulant, probiotic food supplement, probiotic A feed additive or probiotic medicinal product containing or consisting of a composition according to one of claims 13 or 14.