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    The use of soforoliids and their derivatives in combination with pesticides as a plant protection adjuvant / additive and for the non-crop industrial scope The present invention relates to the use of soforolides as pesticide co-adjuvants as a tank mix additive and / or formulation additive for plant production and non-crop industrial purposes.
    公开号:BR112012007570B1
    申请号:R112012007570-5
    申请日:2010-08-30
    公开日:2019-05-07
    发明作者:Sabine Giessler-Blank；Martin Schilling；Oliver Thum；Ewald Sieverding
    申请人:Evonik Degussa Gmbh；
    IPC主号:
    专利说明:

    Descriptive Report of the Invention Patent for USE OF SOPHOROLIPIDS AND THEIR DERIVATIVES IN COMBINATION WITH PESTICIDES AS ADJUVANT / ADDITIVE FOR PLANT PROTECTION AND FOR THE NON-AGRICULTURAL INDUSTRIAL SECTOR, PROCESS FOR THE PREPARATION OF A FORM OF SOLUBILIZED SOILS AND SOILS. Description [001] The present invention relates to the use of soforolipids and their derivatives and compositions as a formulation additive and / or tank mix additive (also called adjuvant) for pesticides or mixtures of pesticides.
    [002] In the field of plant protection, in products for pest control and also in the non-agricultural industrial sector, for improving the biological effectiveness of such pesticides or mixtures of pesticides, so-called adjuvants or also adjuvants or additives are normally employed . Effectiveness is also often called effectiveness. The Pesticides Safety Directorate (PSD, from the executive level of Health and Safety Executive, a public non-governmental organization in Great Britain) defines an adjuvant as a substance that, in addition to water, is not exactly effective as a pesticide, but increases the effectiveness of a pesticide or supports it. (http://www.pesticides.gov.uk/approvals). These are added to the aqueous spray broth either immediately before application and spray (as tank mix additives), or are introduced directly into the pesticide formulations. The use of the word adjuvants in patents or in the literature is usually used as a synonym for the term surfactants or cross-linking agents, which however are far-reaching and can be interpreted as a generic term.
    [003] Based on the use advised here, it can be done
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    2/36 reference to the term adjuvarrte, since the function of soforolipids is better described with it. Soforolipids, as will be shown later, do not humidify / spread. In contrast to this, many of the crosslinkers or surfactants known in pesticides are distinguished by a very high spreading behavior, and belong to these for example trisiloxanes.
    [004] In practice, there are several active agricultural defensive substances that have an acceptable effectiveness only with the aid of adjuvants, that is, achieve a relevant effectiveness in practice. Adjuvants help to compensate for the deficiency of the active substances, such as the UV sensitivity of avermectins (they are destroyed by ultraviolet radiation) or the water instability of sulfonylureas. Newer active substances are generally not water-soluble and therefore, in order to be effective, on a target = target organism = plants, adjuvants for the aqueous spray broth are essential to compensate for poor wetting of road surfaces through what influence on the physics of aqueous solutions. In addition, adjuvants help to overcome technical application problems, such as small amounts of water expenditure, different water qualities and the tendency to higher application speeds. The increase in pesticide efficacy, as well as the compensation of deficiencies of agricultural defensive agents by adjuvants, is, in general, called the increase in the effectiveness of agricultural pesticides.
    [005] Non-specialists could suspect that all commercially available crosslinkers / surfactants (for example in the cosmetic sector or within the scope of household cleaning products) cause an increase in the effectiveness of pesticides. However, this is not the case, as has also been seen in many publications (see eg in Pesticide Formulation and Adjuvant
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    3/36
    Technology, edited by Chester L. Foy and David W. Pritchard. CRC Press LLC, 1996, pages 323-349).
    [006] So it is surprising and not obvious, the fact that soforolipids increase the effectiveness of pesticides, and therefore behave as adjuvants.
    [007] Some publications teach that certain glycolipids, such as rhamnolipids, can themselves have an intrinsic pesticidal efficacy (US 2005/0266036 or also Yoo DS, Lee BS, Kim EK (2005), Characteristics of microbial biosurfactant as an antifungal agent against plant pathogenic fungus, J Microbiol Biotechnol 15: 1164-1169). Therefore it can be seen that in this patent application non-adjuvants are described in the sense of the UK-PSD definition.
    [008] US 2005/0266036 A1 describes biological crosslinkers that are prepared by microbes, for use against pests, for example nematodes. Thus, crosslinkers or microorganisms that produce crosslinkers almost place biopesticides directly on pests to combat them. Examples are given only for the use of ramnolipids against houseflies, cockroaches and nematodes, as well as against fungal spores in pumpkins. The concentration of biological crosslinker used, in this case a ramnolipid, in the herbicides was very high, with 5% by weight in the spray broth. In such a used concentration, the active substances of pesticides are not used. For the most part (however, there are also other concentrations of application) about 1 l / ha of pesticide formulation (which contains a maximum of 500 g / L of active substance) is used with a water quantity of about 250 l / ha . This corresponds to a maximum concentration of about 0.4% by weight. However, in the aforementioned US patent application, no declaration is made
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    4/36 on selective and / or controlled pest control, with more relevant effectiveness in practice as well as for preventive action, that is, for protective effectiveness.
    [009] Preventive means that the pesticide / adjuvant combination is applied to the target organism, when the disease or the damaged organism has not yet occurred (prevention = application of protection before the occurrence of pests or diseases). Preventive uses are particularly important for fungicides, but also for insecticides and acaricides.
    [0010] In US 2005/0266036 A1 it is not clear whether ramnolipids also enhance the effectiveness of herbicides when they are used in a selective dosage (therefore as adjuvants). Selective dosages are those in which the glycolipid itself does not cause any control (damage) of the harmful organism (such as weeds, insects, fungi, or similar harmful organisms) [0011] In patent application US2005 / 0266036 it is described that the biotensoactive agents there Employees, especially ramnolipids, have a pesticidal efficacy due to their penetrating effectiveness in the cell wall. Such penetration-promoting agents are, in fact, often necessary for pesticides, to control harmful organisms that are already found in plant tissue, which is called curative efficacy. From the aforementioned patent application, however, it can in no way be deduced, and it is also not obvious, that glycolipids would also not act preventively in the effectiveness of pesticides, if they were combined with each other, or even if they were essentially perfected. In the field of pesticides, most of the time, contact agents, such as sulfur fungicide, are used to protect safety. These active substances act only for
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    5/36 contact, that is, pests must be contacted. For curative protection on the contrary, most active substances are used that act mostly systemically, for example, rimsulfurone (from the group of sulfonylureas) or epoxyconazole (from the group of fungicides triazole). Active substances of this type are absorbed by plants and transported by sap. Pests feed on the plants or sip them and thus ingest the agent.
    [0012] Synergy here means that the effectiveness of combining pesticides and adjuvants is greater than the additive effectiveness that would be expected from both individual components (see Colby's formula: Colby SR 1967. Calculating synergistic and antagonistic responses of herbicide combinations. Weeds 15: 20-22). No evidence of such synergistic efficacy is found in the prior art in conjunction with pesticides and soforolipids.
    [0013] For use in plant protection, pest control and in the industrial or biological field, agricultural pesticides (hereinafter also called pesticides) or mixtures of pesticides are used. These can be, for example, herbicides, fungicides, insecticides, growth regulators, molluscicides, bactericides, viridicides, micronutrients, as well as biological defensive agents based on natural or living raw materials or worked or processed microorganisms. Active pesticide substances are listed, along with their fields of use, for example in "The Pesticide Manual ', 14th Edition, 2006, The British Crop Protection Council, biological active substances are indicated, for example, in' The Manual of Biocontrol Agents ', 2001, The British Crop Protection Council. The following pesticide will always be used as a collective term.
    [0014] As tank mix additives, alkoxylated trisiloxane surfactants are often used, which significantly lower the surface tension significantly
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    6/36 spray broth or water, than the organic surfactants used in the past, such as nonylphenolethoxylates. Trisiloxane surfactants have the general structure Me3SiO-SiMeR-OSiMe3, where the radical R represents a polyether radical. The use of super-spreadable trisiloxane surfactants, such as BREAK-THRU® S-240, Evonik Goldschmidt GmbH, in combination with a pesticide leads to an improvement in pesticide absorption by plants and, in general, an increase in their effectiveness or its effectiveness. US 6,734,141 describes that, for this increase in effectiveness, a small surface tension is responsible in particular and not necessarily the spreading. In most patents under the term surface tension, static surface tension is always understood. For example, in trisiloxanes the static surface tension is about 20 to 25 mN / m.
    [0015] Trisiloxane surfactants in many states, however, are classified as harmful to health, which in the registry as constituents of pesticides is evaluated as an exclusion criterion. Many tank mix additives, especially ethoxylated alcohols or alkyl polyglycosides, form foams when the spray broth is strongly agitated, which can eventually lead to problems in use in the field. In general synthetic cross-linkers to obtain registration as adjuvants by national authorities, have a duty to prove that they do not leave any residue in the soil. This waste problem, which in most countries consists only of active pesticide substances, is also increasingly used in traditional adjuvants. Biological crosslinkers, since they are already biologically decomposable, did not have this problem, which represented a strong advantage for this use.
    [0016] Glycolipids comprise a class of compounds
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    7/36 chemicals, which are composed of a hydrophilic carbohydrate and a part of hydrophobic lipid and, due to their amphiphilic nature, are surfactants, or have surfactant properties and therefore are also called biotensoactive or biosurfactant agents. Often these are hydroxylated fatty acids, which are linked by a glycosidic bond with a sugar radical. This class of compounds also belong to products of microbial metabolism. Examples here are ramnolipids (RL), soforolipids (SL) and mannosileritritollipids (MEL), which are respectively synthesized from bacteria (eg Pseudomonas aeruginosa), yeasts (eg Candida bombicola) or larger yeasts and fungi (eg. Candida antarctica and Pseudozyma aphidis).
    [0017] The biotechnological synthesis of such compounds has been known for a long time, and appropriate strains and fermentation conditions are researched in detail (eg Mukherjee, S. et al. - 2006, Towards Commercial Production Of Biosurfactants, Trends in Biotechnology, vol. 24, no. 11). In recent times, the interest of this class of compounds in the context of the discussion on sustainability, however, has increased sharply, since its preparation from renewable raw materials can occur under mild conditions.
    [0018] Basically, the corresponding microorganisms are made available here, during fermentation, as a hydrophilic substrate a metabolizable carbohydrate (eg a monosaccharide or a disaccharide), and as a hydrophobic substrate a hydrocarbon, a fatty alcohol, a fatty acid , a triglyceride or their respective mixtures, and are converted therewith into the corresponding target compound. Here the origin of both substrates can vary greatly, since the necessary elements of the target molecule can also be synthesized by
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    8/36 microorganism metabolism, with which a wide spectrum of hydrocarbon and hydrocarbon sources are accessible (K. Muthusamy et al. - 2008, Properties, Commerical Production And Applications, Current Science, vol. 94, No. 6, pages 736-747). Examples of possible hydrophobic substrates are long-chain hydrocarbons, vegetable or animal oils, or free fatty acids or fatty acid derivatives (compare with EP 1 953 237 A1, esters of various chain lengths etc.), as well as fatty alcohols . As a source of hydrophilic carbon, mainly glucose is used, however, other sugars, such as lactose and sucrose, are also often accepted, depending on the organism employed (von Boegart et al. - 2006, Microbial Production And Application Of Soforolipids, Applied Microbiology and Biotechnology, Vol. 76).
    [0019] Another possibility for structural diversification and an expansion of the functional properties associated with this, is the subsequent chemical or biochemical modification of microbially prepared glycolipids. Various processes are also described here, for example in US 2007/027106-A1 - Charged
    Soforolipids and Soforolipids Containing Compounds or in US 2005 / 164955A1 - Antifungal Properties of Various Form of
    Soforolipids or in Bisht, K.S. et al. - 1999, Enzyme-Mediated Regioselective Acylation Of SLs, The Journal Of Organic Chemistry, 64, pages 780-789; Azim, A. et al. - 2006, Amino Acid Conjugated Soforolipids, Bioconjugate Chemistry, 17, pages 1523-1529). A simple process is, for example, the base-catalyzed saponification or esterification of aliphatic alcohols of different chain lengths. An interesting process for preparing soforolipids with short hydrophobic radicals has been similarly disclosed recently in EP 1 953 237 A1. Here fatty acid analogs are fed
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    9/36 as hydrophobic substrates which, for example, contain amide, ester or double bonds and can subsequently be dissociated chemically, hydrolytically or ozonolytically to obtain shorter chain hydrophobic radicals.
    [0020] Reducing the water content in crude soforolipid products, for example by distillation, leads to technical problems during processing, since the products become very highly viscous. This problem can be solved by using low volatile polyols, which, at low concentrations, are viscosity reducers, see US 4,197,166 Dehydrating Purification Process For A Fermentation Product.
    [0021] In the technical literature, ramnolipids, trehaloselipids and soforolipids are known as surfactants as biological surfactants (Desai JD and Banat IM. „Microbial Production of Surfactants and their Commercial Potential. Microbiology and Molecular Biology Reviews, March 1997, pages 47-64.). So, for example, these are used for soil sanitation (see Ozlem Zenginyürrek's master's thesis, Izmir 2002, Izmir Institute of Technology: Title: Effects Of Biosurfactants On Remediation Of Soils Contaminated With Pesticides; or Food Technology And Biotechnology (2001) , 39 (4), 295-304). These disclosures also describe the decomposition of pesticides, for example, endosulfan or metolachlor in the soil. Here the biological crosslinkers are applied directly to the soil.
    [0022] Most of the time in the literature, as well as in the patents, ramnolipids are taken in the context of biological crosslinkers. However, these are characterized as hazardous to health and can cause serious damage to the eyes according to the safety data sheets.
    [0023] The trend in the agricultural field is more and more additives
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    10/36 and toxicologically harmless adjuvarrtes. Furthermore, the preparation of ramnolipids is hampered by the fact that, during fermentative production, strong foaming occurs, and so far an efficient biotechnological production is possible only with potential pathogenic strains of the genus Pseudomonas. Therefore, rhamnolipids in the context of this invention are no longer researched. [0024] MEL (Mannosyl Erythritol Lipide) are other lipids, which would be of interest as adjuvants. Since from a molecular point of view, however, they are very hydrophobic and, therefore, very little dispersible in water, their applicability would be limited to oil-based formulations, since a condition for use as a tank mix additive is that the molecules are soluble in water. MELs could therefore, preferably, be used in combination with co-active agents.
    [0025] In PCT / US2005 / 046426 (WO2006 / 069175) soforolipids are described as antifungal agents, however not in the context of pesticides or non-crop application. Property as an antifungal agent is used in the cosmetic sector or in medicine (K. Kim et. Al.Journal of Microbiology and Biotechnology (2002), 12 (2), 235-241). In the cosmetic sector, biological crosslinkers are mostly used with emulsifiers for oil-in-water emulsions (I. van Bogaert et. Al; Appl. Microbiol Biotechnology (2007) 76: pages 23-34). Bogaert et al. they also report on the commercial use of biological crosslinkers, especially soforolipids, in household cleaning products.
    [0026] Pesticide formulations, which are most often diluted with water before spraying for usual application by nozzles, contain, in addition to the effective pesticidal components or treatment components (called active ingredient or also active substance), also other supporting actors, such as
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    11/36 example emulsifiers, thickeners, dispersion aids, antifreeze agents, defoamers, biocides and / or tense active substances; such materials are known to the formulation experts.
    [0027] The type of formulation is influenced by the culture plant, the place of cultivation, as well as by the user. Due to the diversity of the physicochemical properties of the various active substances pesticides, there are a large number of liquid, but also solid, formulations on the market. Due to the formulation additive, especially the adjuvant, certain usage properties are produced, such as retention, penetration, rain resistance and spreading behavior. Through a special formulation, it must be ensured that the smallest possible amount of active substance can be distributed homogeneously over a large surface (reducing application rates for the protection of the user and the environment), however guaranteeing, in addition, a capacity and maximum effectiveness.
    [0028] Types of formulation widely disclosed, indicated here for example only, are: suspension concentrates, capsule suspensions, emulsion concentrates, water-soluble concentrates, oil dispersions, suspoemulsions, water emulsions, water-dispersible granules or powders . The possible types and varieties of formulation should not be limited to those described here.
    [0029] Such active substances are often added to a tank with water as content, to dilute the concentrated formulation of the active substance before spraying and make it compatible with plants. Tank mix additives (also called additives or adjuvants) are added to the water in the same tank separately before or after the formulation of the active substance and are distributed under stirring with all the
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    12/36 called spray broth.
    [0030] Active ingredients (active substances) are those that in each country are allowed to protect plants against damage, or to prevent losses of production in a crop or to reduce them. Such active ingredients or active substances can be of the synthetic type, as well as of the biological type. Such active substances can also be extracts or natural materials, or antagonistically active organisms. They are also commonly called pesticides. In the present invention, the type of active substance is not important, since the use as a tank mixture additive is of a general nature and is not specifically related to the active substance. Pesticides, which are referred to in their field as pesticides include, for example, the following classes: acaricides (AC), algicides (AL), baits (AT), repellents (RE), bactericides (BA), fungicides (FU ), herbicides (HE), insecticides (IN), molluscicides against snails (MO), nematicides (NE), rodenticides (RO), sterilizers (ST), viridicides (VI), growth regulators (PG), plant toners ( PS), micronutrients (MI) and macronutrients (MA). These designations and places of use are known to the specialist. Active substances are used alone or in combinations with other active substances. Preferred pesticides are HB, FU, IN, PG, MI, and particularly HB, FU, IN. Such active substances or active ingredients are distributed commercially more generally produced (formulated), since they are manageable by users in just such a form, and can be applied after their dilution with water, for the most part.
    [0031] Some active substances or active organisms are, for example, listed in 'The Pesticide Manual', 14th Edition, 2006, The British Crop Protection Council, or 'The Manual of Biocontrol Agents ", 2004, The British Crop Protection Council. This application
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    However, patent 13/36 is limited not only to those active ingredients listed there, but also includes more modern active substances, not yet mentioned in the aforementioned monograph. A listing of the individual active substances and the formulations of those active substances is omitted here, as well as combinations of active substances with each other or with each other.
    [0032] Products with a natural character, or biological products are also indicated in any of the documents mentioned above. Plant nutrients and plant micronutrients, which in liquid preparation are applied in the most diverse forms alone or in combination with other nutrients, or in combination with agricultural defensive agents, are, for example, nitrogen, phosphate, potassium, calcium, magnesium, manganese , boron, copper, iron, selenium, cobalt and others, which are known under the name micronutrients.
    [0033] There is a need to promote biological substances, which are toxicologically harmless, are not environmentally dangerous according to EC Directive 1907/2006, strongly reduce the surface tension of water, are soluble in water or dispersible in water, and can be used as tank mix additives as well as formulation aids, to promote selective pesticide efficacy. Toxicologically harmless means, in the context of this invention, that the biological substances verified are, for example, biologically decomposable, have no negative toxicity on fish, toxicity on daphnia (water fleas) and / or toxicity on algae (therefore> 10 mg / L) and, do not cause any burning in the user's eyes. Preferred concentrations of use within the tank mix are between 0.001 - 3% by volume, preferably 0.01-0.5% by volume and particularly preferred below 0.1% by volume (about respectively also 0, 1% by weight) of the spray broth. This
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    14/36 means the same as 10-3,000 ml / ha, when normally 100 to 1,000 l of spray broth per ha is applied, and preferably an amount of adjuvant of 50-700 ml / ha, which are also added to the quantities corresponding spray broth regardless of the total water application rate per ha. As a formulation aid, this concentration should be recalculated in the pesticide concentrate and its amount of use in the field. The rate of adjuvant mentioned above corresponds to the concentration of use in the field.
    [0034] It is the task of the present invention, therefore, to find toxicologically harmless adjuvants, which enhance the pesticidal efficacy.
    [0035] The task is solved by the use of adjuvants / additives based on soforolipids.
    [0036] The object of the present invention is thus the use of adjuvants containing soforolipids, soforolipid preparations, as well as their derivatives, as the tank mixture additives themselves or as a formulation additive, as an emulsifier, dispersant, defoamer, or generally as a crosslinker respectively with the function of adjuvant for pesticides (plant protection) and / or for the non-crop industrial scope.
    [0037] Soforolipid esters can preferably be used as derivatives.
    [0038] Preferably the adjuvants according to the invention containing soforolipids reinforce the effect of pesticides and / or increase the efficiency, preferably by more than 10%, compared to a use without soforolipids and their preparations or derivatives, with the condition that the dosage range of the adjuvant is between 10-3,000 ml / ha, preferably between 30-1,000 ml / ha and particularly preferred between 50-700 ml / ha.
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    15/36 [0039] Pesticides and / or fungicides are preferred in the sense of pesticides and industrial agents for pest control selected, for example, from the group of herbicides, insecticides and / or growth regulators or their mixtures, or defensive agents agricultural, micronutrients as well as macronutrients, in particular when the combination of pesticide and adjuvant is used preventively.
    [0040] Thus, the use of soforolipids in pesticidal applications as tank mix additives or formulation aids is particularly preferred. Thus, adjuvants should develop little foam and therefore less than 80 mL of foam after 30 seconds according to the CIPAC MT 47 process and / or not cause any irritation in the user's eyes and / or reduce the surface tension of water to values below than 40 mN / m, based on a 0.1% aqueous solution of the adjuvant by weight.
    [0041] A synergistic effect of the adjuvant with the pesticide is preferred. The effectiveness of the pesticidal efficacy of these preferred compositions and according to the invention is thus greater than the effectiveness of the pesticide or adjuvant alone or its additive effect, whereas in a preferred embodiment the adjuvant alone, itself, does not present any effect. pesticidal efficacy within the scope of use concentration. This synergistic effect occurs preferably in a concentration range and a ratio of the amount of active substance pesticide to adjuvant from 1: 120 to 30: 1, preferably 1: 100 to 20: 1, very particularly preferred from 1:75 to 4 :1. This concentration range refers to the use as an additive to the tank mixture as well as as a formulation additive.
    [0042] Preferably used as pesticides, herbicides and / or fungicides and their mixtures. Particularly preferred are herbicides or fungicides, particularly preferred fungicides of
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    16/36 contact, such as, for example, sulfur and / or systemic fungicides of the triazole class and / or systemic herbicides of the sulfonylurea group, as well as mixtures of these and other pesticides. [0043] In a preferred embodiment, adjuvants / additives can be used together with other co-surfactants, for example carboxylic acids. As carboxylic acids, preferably alkaline acids with straight, saturated alkyl chain, with 6 to 10 carbon atoms or, preferably, octanic acid (caprylic acid), nonanic acid, decanic acid (capric acid), oleic acid or their mixtures.
    [0044] Adjuvants can be used as additives in pesticidal formulations, such as suspension concentrates, capsule suspensions, emulsion concentrates, water-soluble concentrates, oil dispersions, suspoemulsions, water emulsions, water-dispersible granules or powders , in addition to other additives such as dispersants, emulsifiers, thickeners and defoamers with an adjuvant content of 1% by weight to 99% by weight, preferably in the range of 1.5% by weight to 60% by weight, and is particularly preferred from 1.9 to 30% by weight.
    [0045] Another object of the invention are compositions containing soforolipids and at least one active substance pesticide, and in a preferred embodiment the soforolipid itself does not have any pesticidal effect.
    [0046] Another object of the invention are compositions of soforolipids and active pesticidal substances, where the pesticidal effectiveness and effectiveness of the composition is greater than the sum of the effectiveness of the individual components. Here the effectiveness is both relative to the total quantity as well as relative quantities. Optimal effectiveness is aimed at a proportion of the amount of active substance pesticide to adjuvant from 1: 100 to
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    17/36
    20: 1, preferably from 1:75 to 4: 1.
    [0047] The compositions object of the invention contain soforolipids, which can be prepared by fermentative processes. Due to the heterogeneous composition of the educts (for example mixtures of fatty acids) and the limited selectivity of the microbial biosynthesis apparatus, the substances do not appear as pure compounds, but as natural mixtures.
    [0048] Soforolipids according to the objects of this invention can therefore also include soforolipid preparations and compositions that can be introduced and used after fermentative preparation, without further purification.
    [0049] Soforolipids according to that definition, or soforolipid preparations, may contain, for example, the educts of the fermentation process, such as, for example, fatty acids and carbohydrates that served as substrates for microorganisms, such as also, for example water and other natural, in particular, organic impurities. Certain forms of soforolipids are not pH stable. In this way, for example, a basic catalysis, a deacetylation or a lactone opening can occur with formation of the analogous acid form.
    [0050] In a preferred embodiment of the invention, soforolipids and their derivatives are used, as well as soforolipid preparations as constituents of adjuvants / additives in plant protection and / or in the non-crop environment.
    [0051] Soforolipids are, relative to the dry mass, in a purity> 30% by weight, preferably> 65% by weight (m / m), particularly preferred> 80% by weight (m / m). Adjuvants can contain from 1 to 100% by weight of the soforolipids themselves, their derivatives, or soforolipid preparations.
    [0052] The content of soforolipids, their derivatives or preparations
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    18/36 of soforolipids in the adjuvant is, relative to the dry mass, preferably greater than 30% by weight, and in particular greater than 60% by weight.
    [0053] As hydrophobic substrate for the fermentation preparation, hydrocarbons, fatty acids, fatty acid esters and / or fatty alcohols can be used, preferably triglycerides, such as tallow, sunflower oil, rapeseed oil, thistle oil, are preferably used. soybean oil, palm oil, palm kernel oil, coconut oil, olive oil, or mixtures thereof, in addition to the hydrophilic substrate.
    [0054] The fraction of soforolipids in the adjuvant can be purified or unpurified, or:
    i) be present as a mixture of lactone and acid form with an acid fraction of 10 to 100% by weight, preferably <60% by weight, particularly preferred <20% by weight or ii) consist of a fraction> 90% by weight of the lactone form, which can be solubilized by adjusting the pH value between 6 and 8, or iii) as methylester or ethylester with a content of 1 to 100% by weight, preferably> 50% by weight and in particular > 90% by weight (w / w) of the corresponding ester.
    [0055] Surprisingly it was found that the lactone form of soforolipids can also be solubilized by the fatty acids existing in the fermentation or additionally added at a pH value of 6-8.
    [0056] Particularly surprising is that clear systems were obtained here, since at pH 6 neither the lactone form of the soforolipid nor the fatty acids alone are clearly „soluble. Clearly "soluble" here means that at least one visibly real solution is obtained, which however can also be present as a fine emulsion. However, it is emphasized that the optionally present emulsion is not dissociated again in phases
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    19/36 individual.
    [0057] Another object of the invention is, therefore, also a process for the preparation of a solubilized form of soforolipid lactone, in which the lactone form is solubilized in the solution by the presence of fatty acids by adjusting the pH value in 6- 8, as well as the solutions or emulsions so prepared. The pH value can be adjusted by adding inorganic bleaches, such as sodium bleach, or by other additions of fatty acid, depending on whether the pH value should be raised or reduced.
    [0058] As fatty acids can be mentioned fatty acids not fully reacted during fermentation and / or in addition, can be added. Fatty acids correspond to the acid components of triglycerides used as substrates, selected from the group of tallow, sunflower oil, rapeseed oil, thistle oil, soybean oil, palm oil, palm kernel oil, coconut oil, soybean oil , or also short to medium carboxylic acids with a chain length of 6 to 22 carbon atoms. Preferred examples of fatty acids already present or added are nonanic acid (pelargonic acid), decanic acid (capric acid), dodecanic acid (lauric acid), tetradecanic acid (myristic acid), hexadecanic acid (palmitic acid), octadecanic acid (stearic acid) ), octadecanic acid (oleic acid) or mixtures thereof.
    [0059] In a preferred embodiment the adjuvant containing soforolipid presents, in a 0.1% aqueous solution, a surface tension <40 mN / m.
    [0060] The adjuvant may contain, in addition to soforolipid and optionally organic and inorganic solvents, preferably water, and other additives known to the skilled person.
    [0061] Soforolipids can also be added with acids
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    20/36 organic or oils, preferably those mentioned above, and the mixtures obtained are then used as mixing constituents for tank mix additives.
    [0062] Another object of the invention is the use of soforolipids in formulations of pesticides respectively with the function of emulsifier, dispersant, defoamer or in general as a crosslinker.
    [0063] In a particularly preferred embodiment of the present invention, soforolipid preparations are employed, which contain the soforolipids of formula 1 or 1a,
    [0065] R 1 and R 2 independently of each other are either H or an acetyl group and, [0066] R 3 is H, a methyl group, an ethyl group or a hexyl group, [0067] R 4 independently of each other is an organic group
    Petition 870190029347, of 03/27/2019, p. 23/48
    21/36 saturated or unsaturated, bivalent / double-bonded, branched or unbranched, preferably a hydrocarbon group with 1-28 carbon atoms, which optionally can be interrupted by amine groups, ester groups, amide groups, or thioester groups, and in addition it is preferably at least monounsaturated, [0068] R 5 is H or a methyl group, [0069] with the proviso that the total number of carbon atoms in the groups R 4 and R 5 does not exceed the number 29 and preferably 12 to 20, and in particular 14 to 16.
    [0070] The organic group R 4 can be a carbon chain, which can be optionally broken down by heteroatoms such as N, S, O and thus is also interrupted by amine groups, ether groups, ester groups, amide groups or thioester groups.
    [0071] Other objects of the invention are described by the claims, whose content of disclosure is an integral part of that description.
    [0072] In the examples indicated below, the present invention is described by way of examples, without the invention, whose range of applications results from the general description and claims, being interpreted as being limited to the embodiments mentioned in the examples.
    [0073] Scopes, numerical values, general formulas or classes of compounds are indicated below, and these should not only cover those areas that are explicitly mentioned, but also all partial scopes and numerical values and partial groups of compounds, which can be obtained by selecting individual values (scopes) or compounds. EXAMPLES:
    CHECKED MATERIALS:
    [0074] The verified soforolipids are described by the following
    Petition 870190029347, of 03/27/2019, p. 24/48
    22/36 general formula 1 and / or 1a.
    [0075] The preparation of the crude product occurred through fermentation with the yeast Candida bombicola based on the substrate glucose, sunflower oil, rapeseed oil or olive oil (containing as fatty acid fraction mainly oleic acid).
    [0076] The growth medium contained the following constituents:
    - 10 g / L glucose ((D) + glucose * 1H20)
    - 7.5 g / L YNB (Yeast Nitrogen Base)
    - 2 g / L yeast extract [0077] 1.1 l of the medium was autoclaved in a fermenter with 2 l of working volume and inoculated with a pre-culture that is in the exponential phase of the same medium. The temperature was adjusted to 30 ° C. PO2 was maintained by gasification with air and relative saturation of 30% through rotation speed, however, the rotation speed was never less than 200 rpm. During the biomass formation phase the pH value dropped to 3.5 and was maintained at this value by the addition of NaOH. After the end of the biomass formation phase (consumption of glucose present, characterized by an increase in pO2, or a decrease in pCO2), the product formation phase was started by adding 150 g of the respective oil, 200 ml of a solution 750 g / L glucose and 10 ml of a 150 g / L yeast extract solution. The end of the product formation phase was characterized by a further increase in pO2. After the end of the fermentation the product was autoclaved, thus the crude product phase was deposited. The crude product phase was washed with water and then with hexane. Then the product phase was extracted with ethyl acetate and then the solvent was removed in vacuo. This resulted in a largely anhydrous product, which corresponds to the dry mass according to the invention. The analysis by means of HPLC-MS and NRM resulted that the product in
    Petition 870190029347, of 03/27/2019, p. 25/48
    23/36 a large part consists of the lactone form of the double acetylated soforolipid with glycosidically bound fatty acid (main constituent: soforolipid-lactone 65-80% by weight, fatty acid 1-16% by weight, glycerin 1-3% by weight).
    TABLE 1: Adjuvants checked in an overview
    SLL Soforolipid = dry mass (solid) SLM Soforolipid methylester (solid) SLS Acid form of soforolipid (solid) SLL-SLS Lactone form of soforolipid mixed with acid form, 50% in water SLLF Mixture of 30% SLL + 30% H2O + 20% nonanic acid +20% propylene glycol
    [0078] Standard adjuvant as a comparative substance: BREAKTHRU® S 240 (alkoxylated trisiloxane from Evonik Goldschmidt GmbH) [0079] In table 1, various derivatives of the fermented-prepared SLL soforolipids, which were tested in greenhouse tests, are shown.
    [0080] The course of the derivatization steps was verified by NMR analysis.
    [0081] SLL: The SLL corresponds to the dry mass of the fermentation process and forms a solid, whose content of soforolipids is> 80% by weight and which is mainly in the lactone form of soforolipid (> 90% by weight).
    [0082] SLM: For the synthesis of methylester or ethylester SLL was dissolved in methanol or ethanol as a solvent and esterified by adding NaOCH3 and NaOCH2CH3 (pH = 12) at a temperature of 60 ° C for 3 h. Then the solution was removed in vacuo. A slightly viscous product was obtained, which can be made by freezing and subsequent crushing to form a powder with a water solubility> 50% by weight (m / m).
    Petition 870190029347, of 03/27/2019, p. 26/48
    24/36 [0083] SLS: To a 60 wt% aqueous suspension of the SLL soforolipid was added 5 wt% of the solid NaOH pellet. After that, it was stirred for 30 minutes at a temperature of 50 ° C to obtain the deacetylated acid form of the soforolipid by saponification. Then the product was extracted by adding HCl to a pH value of 3 and the product was extracted with ethyl acetate. After the removal of ethyl acetate, a triturable residue was obtained in a powder, which is soluble in water> 50% by weight.
    [0084] SLL-SLS: It was done here as in SLS, however only 1/10 of the NaOH was added, with which only a partial hydrolysis of the lactone form was produced. This mixed form was solubilized with water to form a solution with a content of about 50% by weight.
    PHYSICAL PROPERTIES:
    a) Foam behavior and surface tension:
    [0085] For the structures in question the behavior of the foam (according to the CIPAC MT 47 process) and the static surface tension were measured in 0.1% by weight of the aqueous solutions (in the preparation of soforolipid since it was present as an adjuvant) . The surface tension of 0.1% by weight solutions was measured using a bubble pressure tensiometer from SITA Messtechnik GmbH, Sita online t 60 device; SITA online version 2.0. The duration of residence time of the bubbles of static surface tension was 30 ms. The measurement deviation was around 0.4 - 1% of the indicated mN / m values. Measurements were performed at an ambient temperature of 22 ° C. The indicated values are average values of 3 measurements.
    [0086] According to the CIPAC definition, “non-foaming” products are those that only produce a 5 ml foam in the measuring flask by the indicated process. As „little foamy
    Petition 870190029347, of 03/27/2019, p. 27/48
    25/36 are defined here then those values <80 ml after 30 seconds.
    b) Scattering measurements:
    [0087] The spreading properties are determined using a pipette and a biaxially oriented polypropylene laminate (FORCO OPPB AT-OPAL from 4P Folie Forchheim in Germany). A drop of an aqueous solution containing 0.1% by weight of the adjuvant, with a volume of 50 microliters, was placed on the laminate. The droplet diameter was measured after one minute. If the drop has not spread in a circular shape, the average value of the longest and shortest axes is calculated. The measurements were carried out in a laboratory air-conditioned at 21.5 ° C and 60% relative humidity.
    TABLE 2: Physical properties of adjuvants / additives according to the invention compared to synthetic Trisiloxan BREAKTHRU® S240.
    BREAK-THRU® S240 * SLM SLS SLL-SLS50% by weight in water SLL Static surface tension [mN / m] 21.1 38.6 39.5 39.8 35.2 Foam in ml(after 30 s) 220 80 80 70 60 Scattering [mm] 70 8 9 8 10
    * = Comparative substance- Organomodified trisiloxane
    Evaluation of the results of table 2:
    [0088] Surprisingly, when compared with the comparative substance BREAK-THRU ® S240, only a small spread is recognizable for the compositions according to the invention. However, the foaming of the formulations according to the invention has been noticeably reduced.
    Evaluation of the use technique:
    Petition 870190029347, of 03/27/2019, p. 28/48
    26/36 [0089] For the use of substances as a formulation additive, only physical / chemical compatibility with other formulation agents is important, which verifies the biological effectiveness of a substance as an adjuvant, however, always first alone therefore as a mixture additive tank. Therefore, as a basis for this invention, the verification of biological efficacy is verified through tests of the tank mixture in an oven. Next, greenhouse tests are described, which serve to determine the biological improvement of the effect of pesticides with the addition of adjuvants in plant protection. From the large number of pesticides, for example, epoxiconazole and sulfur fungicides were selected, as well as the herbicide rimsulfurone. To discover the synergism of the adjuvant, the following tests were performed (see tables 5-7)
    a) Adjuvant without addition of pesticide
    b) use of the pesticide alone
    c) Pesticide plus adjuvant.
    [0090] To be able to assess a synergy, the results of c should be better than the sum of a and b, see also „Colby formula.
    [0091] In the tests, which are represented in tables 3 and 4, only the influence of the most different adjuvants on the effectiveness of the pesticide was tested.
    Test layout for curative tests:
    [0092] In a greenhouse the barley variety „Ingrid (3 plants in each pot) was sown in vegetable soil„ Frustosol. Three weeks later the leaves about 10-15 cm in length from the plants were inoculated with fresh conifers of the Mehltau Blumeria graminis f. sp. hordei (Rasse A6) through an inoculation tower. Two days later they were sprayed with a broth of
    Petition 870190029347, of 03/27/2019, p. 29/48
    27/36 spray, which contained the fungicide Opus® (125 g / L epoxiconazole) from BASF. The specialist knows such tests as curative tests. The amount of spray water was 250 l / ha. The fungicide dosage was 10 mL / ha. The dosage of adjuvants varied between 50-125 ml (or g) / ha. In adjuvants / additives diluted in water (such as SLL-SLS) the dosage is related to the content of active ingredient. This amount corresponded to about 0.0025 - 0.5% by weight of the adjuvant / additive in the spray broth, which is comparable with standard adjuvants such as BREAK-THRU® S240.
    [0093] Table 3 shows the results of the comparison between BREAK-THRU® S240 and the soforolipid SLL with the same concentrations. Thus, it appears that the dosage should be between 50-100 mL / ha and that a concentration of SLLs greater than 50 g / ha does not produce any increase in the effect. Since there were no experiments in relation to an optimal dosage of soforolipids, as a basis for other tests, for the preparations of soforolipids and their derivatives, therefore, 75 mL / ha and 75 g ai (of active substance) / ha were taken as base (see tables 5-7). In some cases the adjuvants / additives were also sprayed without fungicides, to check whether the adjuvants / additives alone would show a biological effect. After the spray film was dry, 8 cm long leaf segments were cut from the treated plants and also from the totally untreated plants and, for each variant, 15 leaves were placed separately in Petri dishes with benzimidazole-agar (0 , 5% agar added to 40 ppm benzimidazole after sterilization). After 14 days of incubation time at room temperature, the leaves were affected with oids (Erysiphales), estimating the content of leaves infected by the surface. This experimental design is familiar to the specialist.
    [0094] The effectiveness of adjuvant alone, pesticide alone
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    28/36 (therefore of fungicides or herbicides) and the pesticide / adjuvant combination, is calculated by the specialist in a known way, in comparison with an untreated control sample, but inoculated with oid fungus and expressed as% of disease control.
    Test arrangement for preventive tests:
    [0095] The cultivation of plants (barley) took place in the greenhouse in exactly the same way as in the curative test. Plants about 3 weeks old were sprayed for the preventive trial with spray broths, which contained the active substance sulfur (Microthiol WG 80% sulfur from Stahler) as fungicides, either alone or in combination with adjuvants / additives. In addition, the adjuvant was also applied, for testing in relation to synergy, alone in the spray broth, therefore without sulfur. The sulfur dosage was 1000 ppm / L, the adjuvants were used in different dosages (for the dosages see the results in the tables). The amount of spray broth was 250 l / ha, so that the concentrations of adjuvant in the spray broth were at most 0.1%; the sulfur dosage was 250 g / ha. After drying the spray broths, 8 cm long leaf segments were cut from the treated plants and also from the totally untreated ones and placed for each variant separately 15 leaves on benzimidazole-agar in Petri dishes (0.5% agar was added at 40 ppm benzimidazole after sterilization). The next day the plants were inoculated with fresh conidia of the fungus oid Blumeria graminis f. sp. hordei (Rasse A6) through an inoculation tower. Such a test arrangement is known to the skilled person as a prevention test, because the plants were protected by fungicides before inoculation with the fungi. After 10 days of incubation time at room temperature, the involvement of the
    Petition 870190029347, of 03/27/2019, p. 31/48
    29/36 leaves with oids were observed, and the surface content of infected leaves was assessed. This experimental design is current for the specialist.
    [0096] The efficacy of the adjuvant alone, the pesticide alone (therefore fungicides or herbicides) and the pesticide / adjuvant combination was calculated, in a manner known to the expert, compared to a control sample inoculated with oids but not treated, and expressed % of disease control. Tests for determining the improvement of the biological effect of a herbicide:
    [0097] In the greenhouse, the grass Poa pratense was grown in pots. As soon as the plants reached a height of about 5-7 cm, they were sprayed with a spray broth containing the herbicide Cato® (DuPont, with 500 g / kg of rimsulfurone). The amount of spray water was 200 l / ha. This was also done in other variants, in which the spray broth in addition to Cato ® also contained several adjuvants. For reproducibility, 3 vessels were also treated per test member. The dosage of the pesticide was 10 g / ha. As a standard commercial adjuvant, Trisiloxan BREAK-THRU® S240 from Evonik Goldschmidt GmbH was added with 50 and 100 mL / ha. The dosage of soforolipids was between 50-250 ml or g / ha, that is, the concentration of use in the spray broth varied from 0.025 to 0.1% by weight. This was aimed at, to find an optimal concentration of use. Table 4 shows the comparative results between BREAK-THRU ® S240 and the soforolipid SLL in equal concentrations. Here it is seen that the dosage should be between 50-100 mL / ha and that no increase in effect is obtained with a SLL concentration greater than 50 g / ha. Since experiments in relation to an optimal dosage of soforolipids are not available, as a basis for further tests with the preparations of soforolipids and their
    Petition 870190029347, of 03/27/2019, p. 32/48
    30/36 derivatives were used 75 mL / ha or 75 g a.i. (of active substance) / ha (see tables 5-7). Since the dose is always calculated with the active content, it is used in SLL-SLS in general 150 mL / ha, which corresponds to 75 mL or g / ha of SLLs. Thus the different adjuvants for the preparation of soforolipids are comparable to each other. This concentration of active substance is only achieved in the SLLF with the use of 250 mL / ha of the adjuvant. The effect of the treatments was evaluated 14, 20 or 30 days after application using procedures known to the specialist. Here the damage of plants with herbicide treatment is compared with untreated plants and the effectiveness of spray treatment is subjected to comparison with untreated plants. Efficacy was determined per member for each of the 3 vessels in the assay. The average value was calculated and indicated as a percentage of effect in the result tables.
    Table 3: Comparison of the increase in the effect of different adjuvants on fungicides (14 days after application)
    Fungicide with10 mL / ha Adjuvant Code Dose ofAdjuvant / ha It is made (%) Opus® without 0 46% Opus® BREAK-Thru® S240 50 mL / ha 91% Opus® BREAK-Thru® S240 100 mL / ha 96% Opus® SLL 50 g / ha 99% Opus® SLL 100 g / ha 98%
    Table 4: Comparison of the increase in the effect of different adjuvants in herbicides (30 days after application)
    Herbicide Crosslinker Code Crosslinker dose It is made 10 g / ha / there is (%) Cato® without without 53% Cato® BREAK-THRU® S240 50 mL / ha 70% Cato® BREAK-THRU® S240 100 mL / ha 80%
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    31/36
    Herbicide Crosslinker Code Crosslinker dose It is made 10 g / ha / there is (%) Cato® SLL 100 g / ha 60% Cato® SLL 200 g / ha 73%
    [0098] In tables 5-7 for the SLLF, a dosage is selected, which makes it possible, on the one hand, to compare the amount of adjuvant in proportion with other soforolipids (SLM or SLS) - among them we can understand the concentration of 125 mL / ha - and on the other hand, however, also a high concentration of adjuvant, with which the amount of soforolipid active substance of 75 g / ha there is then comparable. This means that 250 mL / ha of SLLF with 75 g / ha in SLM can be compared, or 150 mL / ha of the SLL-SLS, which in this case also contains 75 g / ha there.
    TABLE 5: Comparison of different adjuvant derivatives and mixtures in curative fungicide tests (14 days after application)
    Fungicide Adjuvant Code Adjuvant dose / ha It is made (%) - BREAK-THRU®S240 50 mL / ha 2% - SLL-SLS 150 mL / ha (= 75 g / haa.i. of the SLL) 5% - SLLF 250 mL / ha (= 75 g / haa.i. of the SLL) 6% 10 mL / ha Opus® without - 38% 10 mL / ha Opus® BREAK-THRU®S240 50 mL / ha 69% 10 mL / ha Opus® SLM 75 g / ha 77% 10 mL / ha Opus® SLM 125 g / ha 67% 10 mL / ha Opus® SLS 75 g / ha 50%
    Petition 870190029347, of 03/27/2019, p. 34/48
    32/36
    Fungicide Adjuvant Code Adjuvant dose / ha It is made (%) 10 mL / ha Opus® SLS 125 mL / ha 63% Opus® SLL-SLS 150 mL / ha (= 75 g / haa.i. of the SLL) 44% 10 mL / ha Opus® SLLF 67.5 mL / ha (= 18.7 g / ha a.i. des SLL) 45% 10 mL / ha Opus® SLLF 125 mL / ha (= 37.5 g / ha a.i. des SLL) 58% 10 mL / ha Opus® SLLF 250 mL / ha (= 75 g / haa.i. of the SLL) 93%
    * a.i. = active ingredient = Active content of active substance [0099] From Table 5 it can be seen that an increase in the dose of SLM does not bring with it a high effectiveness. This has already been shown in Table 3. It is possible to compare the dosage of BREAK-THRU® S240 (which is indicated in this commercial product by the permitted dosage label) of 50 ml / ha and that of soforolipids of 75 g / ha ai .
    TABLE 6: Comparison of different adjuvant products and mixtures in preventive fungicide tests (10 days after application)
    Fungicide Adjuvant Code Adjuvant dose / ha It is made(%) Without BREAK-THRU®S240 50 mL / ha 8% Without SLL-SLS 150 mL / ha (= 75 g / ha a.i.SLL) 9% Without SLLF 250 mL / ha (= 75 g / ha a.i.SLL) 7% Sulfur 250 g / ha without - 46% Sulfur 250 g / ha BREAK-THRU®S240 50 mL / ha 68%
    Petition 870190029347, of 03/27/2019, p. 35/48
    33/36
    Fungicide Adjuvant Code Adjuvant dose / ha It is made(%) Sulfur 250 g / ha SLM 75 g / ha 99% Sulfur 250 g / ha SLM 125 g / ha 90% Sulfur 250 g / ha SLS 75 g / ha 77% Sulfur 250 g / ha SLS 125 mL / ha 77% Sulfur 250 g / ha SLL-SLS 150 mL / ha (= 75 g / ha a.i.SLL) 85% Sulfur 250 g / ha SLL-SLS 250 mL / ha (= 125 g / ha a.i. of SLL) 65% Sulfur 250 g / ha SLLF 67.5 ml / ha (= 18.7 g / ha a.i.SLL) 64% Sulfur 250 g / ha SLLF 125 mL / ha (= 37.5 g / ha a.i.SLL) 75% Sulfur 250 g / ha SLLF 250 mL / ha (= 75 g / ha a.i.SLL) 91%
    TABLE 7: Increase in the effect of several adjuvant products in herbicides (20 days after application)
    Herbicide CodeAdjuvant Dose ofAdjuvant / ha It is made(%) without BREAK Thru®S240 50 mL / ha 0% without SLL-SLS 150 mL / ha (= 75 g / ha a.i. of SLL) 0% without SLLF 250 mL / ha (= 75 g / ha a.i. of the SLL) 0% Cato® 10 g / ha without73% Cato® 10 g / ha S240 50 mL / ha 91% Cato® 10 g / ha SLL-SLS 150 mL / ha (= 75 g / ha a.i. of SLL) 86% Cato® 10 g / ha SLLF 250 mL / ha (= 75 g / ha a.i. of the SLL) 88%
    Conclusions:
    Petition 870190029347, of 03/27/2019, p. 36/48
    34/36 [00100] The verified adjuvants / additives, in particular soforolipids alone or in combination with nonanic acid as a co-surfactant, improve, with selective dosing, the effectiveness of pesticides, especially fungicides and herbicides significantly, especially when its application alone is compared to that with the addition of pesticide (synergy). If adjuvants / additives alone are verified almost as biopesticides, as claimed in US 2005/0266036 (tables 5-7), then they have no effect on the control of fungal diseases and on the verified selective dosages or to control or regulate growth of plants (see Table 5: SLL-SLS or SLLF alone showed only irrelevant 5% to 6% effect, which can be caused by fluctuations in the test). From here it can be concluded that soforolipids, as long as they are not used in combination with pesticides, do not have any pesticidal effect.
    [00101] Due to the results listed, one can speak of synergistic effects between soforolipids and pesticides, and there is always a synergy when the observed effect of the mixture exceeds that of the sum of the individual effects. This is the case for substances that the invention is based on. So for example see Table 6. Soforolipid SLL-SLS alone showed 9% effectiveness, pesticide alone 46%, and meanwhile the effectiveness of the combination due to synergism was 85%. Synergy is normally calculated using the COLBY formula, see Colby S.R. 1967. Calculating synergistic and antagonistic responses of herbicide combinations, Weeds 15: 20-22.
    [00102] Colby's formula describes the expected effect:
    [00103] Expected effect (%) = x + y, or, when the sum of the percentages of effects> 100%, according to the formula:
    Petition 870190029347, of 03/27/2019, p. 37/48
    35/36
    Expected effect (%) = X + Y - ΛΦΪ
    100 [00104] where X is the effect (%) of the pesticide alone and Y is the effect (%) of the adjuvant alone.
    [00105] Soforolipids caused increases in the effects of pesticides, in particular fungicides, which are comparable with commercial standards (such as BREAK-THRU® S240), or the commercial standard, usually even with an equal dosage can be higher ( Tab. 3). This is surprising, since soforolipids do not show, like BREAK-THRU® S240, a super-widespread effect or strongly reduce surface tension.
    [00106] The application rate of soforolipids or their derivatives is 10 - 3000 ml or gram per hectare, preferably 50700 ml or g / ha. This corresponds to the application rates of commercially available adjuvants, commercially obtainable in agriculture.
    [00107] All soforolipid derivatives are effective, some however more than others. Thus soforolipid methyl esters (SLM) are more effective than NaOH hydrolyzed soforolipids (SLS), both with contact pesticides (sulfur) as well as with systemically effective pesticides (epoxiconazoles).
    [00108] The efficacy of soforolipids in certain cases, in which in binary systems the effect of pesticides can only be insufficiently improved, can be increased above the proportional by co-surfactants, such as, for example, nonanic acid. Thus the soforolipid (SLL-SLS) at 75 g ai / ha of active substance content achieved a small increase in efficacy together with the systemic fungicide Opus® (Table 5) (44% more adjuvant fungicide compared to 38% fungicide alone) , together with nonanic acid (SLLF), however with the same active content of soforolipid, also at a dosage of 250 mL / ha
    Petition 870190029347, of 03/27/2019, p. 38/48
    36/36 produced a 93% increase in effect. In a herbicide assay (Table 7) the combination of herbicide and soforolipid / nonanic acid showed values comparable with soforolipid alone.
    [00109] Since these soforolipids and their derivatives have no fungicidal or herbicidal effects in the dosages used, one can speak of synergies between biological surfactants to increase the effect of pesticides and to name the soforolipids themselves as adjuvants, according to the definition of the PSD.
    权利要求:
    Claims (11)
    [1]
    1. Use of Soforolipids of Formula (s) 1 and / or 1a, in which
    R 1 and R 2 , independently of each other, are H or an acetyl group;
    R 3 is H, a methyl, ethyl or hexyl group;
    R 4 , independently of each occurrence, is a divalent, branched or unbranched organic, saturated or unsaturated group;
    R 5 is H or a methyl group, with the proviso that the total number of carbon atoms in the groups R 4 and R 5 does not exceed the number 29;
    said use being characterized by the fact that it is as a constituent of tank mix additives, in each case, with the function of the adjuvant, and the dosage range of the soforolipids falls
    Petition 870190029347, of 03/27/2019, p. 40/48
    [2]
    2/4 between 10 and 3000 mL / ha, and, as pesticides, contact fungicides, and / or systemic herbicides selected from the group of sulfonylureas, and / or systemic fungicides selected from the triazole class are used.
    2. Use, according to claim 1, characterized by the fact that the soforolipids and the pesticide act together synergistically.
    [3]
    3. Use, according to claim 2, characterized by the fact that the combination of soforolipids and pesticide acts synergistically in a ratio of the amount of active substance pesticide to soforolipids from 1: 120 to 30: 1.
    [4]
    4. Use according to any one of claims 1 to 3, characterized by the fact that soforolipids are used as additives in pesticidal formulations, such as suspension concentrates, capsule suspensions, emulsion concentrates, water-soluble concentrates, dispersions in oil, suspoemulsions, water emulsions, granules dispersible in water or powders, in addition to other additives in quantities of 1% by weight to 99% by weight.
    [5]
    5. Use, according to claim 4, characterized by the fact that soforolipids are used in an amount of 1.5% by weight to 60% by weight.
    [6]
    6. Use, according to claim 1, characterized by the fact that it is in formulations of agricultural defensive products, such as emulsifiers, dispersants, defoamers or as crosslinkers.
    [7]
    7. Composition, characterized by the fact that it comprises:
    (a) Soforolipids of Formula (s) 1 and / or 1a,
    Petition 870190029347, of 03/27/2019, p. 41/48
    3/4 in which
    R 1 and R 2 , independently of each other, are H or an acetyl group;
    R 3 is H, a methyl, ethyl or hexyl group;
    R 4 , independently of each occurrence, is a divalent, branched or unbranched organic, saturated or unsaturated group;
    R 5 is H or a methyl group, with the proviso that the total number of carbon atoms in the groups R 4 and R 5 does not exceed the number 29; and (b) a pesticidal active ingredient with the proviso that component (a) has no pesticidal efficacy, and with the proviso that, as pesticides, contact fungicides and / or systemic herbicides selected from the group of sulfonylureas, and / or selected systemic fungicides
    Petition 870190029347, of 03/27/2019, p. 42/48
    4/4 of the class of triazoles.
    [8]
    8. Composition according to claim 7, characterized by the fact that the content of the soforolipids in the adjuvant is, relative to the dry mass, greater than 30% by weight.
    [9]
    9. Composition according to claim 8, characterized by the fact that the fraction of soforolipids, in the adjuvant, in purified or unpurified form, (i) is present, as a mixture of lactone and acid form, with an acidic fraction of 10% to 100% by weight, or (ii) is present as methyl ester or ethyl ester, with a fraction of 1% to 100% by weight of the respective ester.
    [10]
    10. Process for preparing a solubilized form of lactone from soforolipids, characterized by the fact that the form of lactone is brought to the solution by fatty acids present by adjusting the pH value between 6-8, with the proviso that fatty acids are selected from the group of nonanic acid (pelargonic acid), decanic acid (capric acid), dodecanic acid (lauric acid), tetradecanic acid (myristic acid), hexadecanic acid (palmitic acid), octadecanic acid (stearic acid) and octadecanic acid ( oleic acid).
    [11]
    11. Composition according to claims 7 to 9, characterized by the fact that the fraction of soforolipids, in purified or unpurified form, consists of a fraction of> 90% by weight of the lactone form solubilized by the process, as defined in claim 10.
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    US20160249604A1|2016-09-01|
    KR101760532B1|2017-07-31|
    JP5699153B2|2015-04-08|
    NZ598963A|2014-02-28|
    ES2544266T3|2015-08-28|
    JP2013505906A|2013-02-21|
    EP2482647A1|2012-08-08|
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    CN102548398A|2012-07-04|
    AU2010300168B2|2015-03-19|
    US9351485B2|2016-05-31|
    MX2012003495A|2012-05-29|
    BR112012007570A2|2015-09-15|
    DK2482647T3|2015-08-24|
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    法律状态:
    2016-10-25| B25A| Requested transfer of rights approved|Owner name: EVONIK DEGUSSA GMBH (DE) |
    2017-03-01| B07A| Technical examination (opinion): publication of technical examination (opinion)|
    2019-03-12| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|
    2019-04-09| B09A| Decision: intention to grant|
    2019-05-07| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 30/08/2010, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 30/08/2010, OBSERVADAS AS CONDICOES LEGAIS |
    优先权:
    申请号 | 申请日 | 专利标题
    DE102009045077.7|2009-09-29|
    DE102009045077A|DE102009045077A1|2009-09-29|2009-09-29|Use of sophorolipids and their derivatives in combination with pesticides as adjuvant / additive for crop protection and industrial non-crop sector|
    PCT/EP2010/062600|WO2011039014A1|2009-09-29|2010-08-30|Use of sophorolipids and derivatives thereof in combination with pesticides as adjuvant/additive for plant protection and the industrial non-crop field|
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