WO2022156882A1 - Formulations containing cyclodextrin and fatty acids for controlling and repelling insects with improved effect - Google Patents
Formulations containing cyclodextrin and fatty acids for controlling and repelling insects with improved effect Download PDFInfo
- Publication number
- WO2022156882A1 WO2022156882A1 PCT/EP2021/051051 EP2021051051W WO2022156882A1 WO 2022156882 A1 WO2022156882 A1 WO 2022156882A1 EP 2021051051 W EP2021051051 W EP 2021051051W WO 2022156882 A1 WO2022156882 A1 WO 2022156882A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- cyclodextrin
- acid
- composition
- solvent
- fatty acids
- Prior art date
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- 229920000858 Cyclodextrin Polymers 0.000 title claims abstract description 56
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- 238000009472 formulation Methods 0.000 title claims abstract description 30
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- INISTDXBRIBGOC-XMMISQBUSA-N tau-fluvalinate Chemical compound N([C@H](C(C)C)C(=O)OC(C#N)C=1C=C(OC=2C=CC=CC=2)C=CC=1)C1=CC=C(C(F)(F)F)C=C1Cl INISTDXBRIBGOC-XMMISQBUSA-N 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- 210000003437 trachea Anatomy 0.000 description 1
- 229940099259 vaseline Drugs 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
Classifications
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/02—Saturated carboxylic acids or thio analogues thereof; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/06—Unsaturated carboxylic acids or thio analogues thereof; Derivatives thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Definitions
- the invention relates to a composition for use as an insecticide or biocide containing (i) saturated or unsaturated fatty acids, their salts or esters and (11) a cyclodextrin or cyclodextrin derivative, wherein after dissolving (i) and (ii) in a solvent in the solution (ii) is in a molar ratio to (i) of less than 1 (i.e. the ratio (i):(ii) is 1:less than 1 (mole:mole)). Furthermore, the invention relates to a formulation containing this composition, which is used as an insecticide or biocide, and a method for protecting against insects, characterized in that the composition according to the invention is applied to the skin or to other surfaces or textiles.
- insects are considered pests of humans and animals because they are thought to be vectors of disease transmission. In addition, they can cause damage to agricultural products and are sometimes seen as a massive nuisance when staying outdoors. These insects include ants, cockroaches, bed bugs, sand fleas, dust mites, fleas, flies, lice, termites, wasps, ticks and most importantly mosquitoes. Many mosquitoes can transmit life-threatening diseases as so-called vectors. Aedes aegypti acts as a vector for dengue fever and yellow fever, Anopheles sspec. for malaria, Glossina sspec. for sleeping sickness and Culex sspec. for West Nile disease.
- the migratory stable fly poses a threat to cattle herds, as it not only reduces milk yield, but also transmits the causative agent of bovine teat atresia.
- Ticks are a worldwide parasite that feeds on the blood of many vertebrates. If the tick is infected with pathogens, a tick bite can be dangerous for humans.
- the virus disease TBE (tick-borne encephalitis) and the bacterium Borreliosis sspec. be transmitted . When bed bugs bite, they emit a substance that can cause severe allergic reactions. Cockroaches or cockroaches can transmit salmonella and mold spores, increasing the risk of gastrointestinal disease.
- insect repellents One way to avoid mosquito bites, ticks, bed bugs and other insects is to apply insect repellents to the skin. These substances can also be used to deter and eliminate insects on surfaces such as house interior walls, floors, terraces, etc. to be applied .
- An important representative of the insect repellents is DEET (diethyl toluamide), which has a wide range of effects, but can cause allergies, damage plastics, synthetic fibers and leather with its dissolving properties and generally cause irritation.
- Other repellents such as ethylbutyl acetylaminopropionate (IR 3535), I-caridin, para-menthane-3, 8-diol or certain essential oils are much more skin-friendly, but have a lower protective effect.
- Insecticides are also used to kill, drive away or inhibit insects such as ants, cockroaches, bed bugs, termites or similar pests.
- Important representatives of the classic synthetic insecticides are phosphoric acid esters, carbamates, neonicotinoids or pyrethroids. Despite their excellent effect, they can lead to strong resistances in the target organisms, are dangerous to humans and pets and can trigger allergies. Therefore, one is looking for alternative, less toxic active ingredients that can be used as insect repellents or insect repellents. Insecticides can be used to control pests.
- Naturally occurring fatty acids contain both polar (carboxylic acid groups) and non-polar (alkyl groups) structural components and are described as natural repellents for a large number of insects.
- Low molecular weight fatty acids are sufficiently volatile to evaporate from surfaces such as human skin. It has been found that fatty acids with 6 to 12 carbon atoms have a stronger repellent effect than DEET.
- fatty acids and their salts have a toxic effect on certain insects such as beetles, lice, cicadas, bugs, ants, cockroaches and the like. It is assumed that the fatty acids or their salts attach themselves to the cuticle of the insects in order to then be incorporated via the trachea. Apparently, the fatty acids and their salts can destroy the structure of the cell membranes inside the insect.
- Patent DE 698 17 595 T2 describes insect repellents which are based on a mixture of fatty acids.
- Steven R. Sims Topicical and Vapor Toxicity of Saturated Fatty Acids to the German Cockroach ( Dictyoptera : Blattellidae ), J. of Economic Entomology, pp. 758-763, 2014 ) conducted tests in 2014 measuring the effectiveness of saturated fatty acids against cockroaches .
- Junwei J. Zhu (Better than DEET Repellent Compounds Derived from coconut Oil , Nature Sei- entific Reports, p. 1453-1465, 2018) examined in 2018 the insect repellent effect of fatty acids, which were obtained from coconut oil as a cheap and toxicologically harmless alternative to synthetic active ingredients.
- fatty acids and their salts represent an ecologically justifiable alternative to classic insect repellents and insecticides.
- these are often not sufficiently effective compared to synthetic active substances, or do not remain at the site of action long enough to provide lasting benefit due to their high volatility .
- Cyclodextrins are cyclic oligosaccharides containing six (a-), seven (ß-), or eight , containing D-glucopyranose units connected to one another via a-(1,4)-bonds and which are obtained enzymatically from starch. Due to their ring-shaped molecular structure with a hydrophobic cavity, cyclodextrins can form reversible complexes with hydrophobic guest molecules. Due to the hydrophilic surface of the cyclodextrins, the water solubility of hydrophobic substances can be greatly improved with their help.
- WO 19/215645 and WO 20/084572 describe that pesticide-cyclodextrin complexes are particularly effective because they increase the solubility increase the potency of the pesticide, which improves bioavailability, which has been studied with the active substances tau-fluvalinate and prothioconazole.
- active ingredients are the classic active ingredients that are bad for beneficial insects, can induce resistance and are toxic to the environment.
- equimolar amounts or a molar excess of cyclodextrin were added to the active substances.
- WO 2018/050211 describes that it is advantageous for the effective action of a repellent based on a complex of cyclodextrin and DEET if the active substance is not completely complexed so that it is available in sufficient proportion in the ambient air.
- the disadvantage of this complex is that the classic insect repellent DEET has an irritating effect on many materials.
- US 2012/149564 A is directed to an insecticidal composition containing athranil diamide insecticides and cyclodextrin.
- This class of chemicals which is highly effective on insects and invertebrates, is a relatively new class of compounds that also affects beneficial insects. In addition, resistance can develop.
- An approved formulation based on this was classified as hazardous to bees. Despite the classification as slightly toxic for humans, individual cases of poisoning by, for example, chlorantraniliprole have been reported, so that there are also disadvantages in the use of complexes with athranil diamides.
- the object of the invention was to provide a composition containing an ecologically justifiable variant of a classic insecticide or biocide, ie an environmentally friendly active substance for combating insects, which can be used effectively in a formulation for controlling and repelling insects.
- This object was achieved in that a composition for use as an insecticide or biocide containing (i) saturated or unsaturated fatty acids, their salts or esters and (ii) a cyclodextrin or cyclodextrin derivative, wherein after dissolving (i) and (ii) in a solvent in the solution (ii) is present in a molar ratio to (i) of less than 1 (ie the ratio (i):(ii) is 1:less than 1 (mole:mole)).
- the composition is a mixture of components (i) and (ii).
- the saturated or unsaturated fatty acids, their salts or esters are the insecticide or biocide, i.e. (i) is the insecticidally active part and is therefore also referred to as the active ingredient part.
- the composition can be used as an insecticide or biocide, i.e. it is an environmentally friendly active ingredient for controlling insects and achieves an insecticidal effect.
- the composition can be spread directly as a powder or processed and applied in the form of pellets.
- the molar ratio of (i):(ii) according to the invention is achieved when the composition dissolves, for example in rainwater in rainwater or in morning dew water.
- the amount of (i) and (ii) to be used to achieve the molar ratio according to the invention results from their molecular weight and is therefore easy to calculate.
- the insect killing and repellent compositions containing cyclodextrin and fatty acids have improved efficacy and may be preferentially applied to the skin of humans or animals as well as for the treatment of textiles or surfaces. It was surprising that when using fatty acids, their salts or esters as the active substance, the cyclodextrins or cyclodextrin derivatives used could be added in a less than equimolar ratio to the active substance. This was particularly surprising for an environmentally friendly composition for use as an insecticide or biocide, which can thus be used effectively and cost-effectively, for example, in ecological agriculture, near children or directly on people.
- insecticide is a means of killing, repelling or inhibiting insects and their developmental stages.
- the term insecticide is used in agriculture and forestry.
- composition is used as an insecticide and more preferred that the composition is used as an insecticide and the insecticide is an insecticide, ie. H . a means of killing insects.
- a biocide is a non-agricultural and non-plant protection agent used to repel or kill insects.
- the term is used in particular for the protection of stored products and materials, in animal breeding including livestock farming, in the hygiene sector and in private households.
- the biocides include z. B. Disinfectants, rat poison or wood preservatives. Biocides are intended for that to protect human health and products, d . H . In comparison to insecticides, the type and place of use of biocides is different (on people or in their homes, in the fields or in greenhouses and storage).
- composition is used as a biocide and most preferred that the composition is used as a biocide and the biocide is an insecticide, ie. H . a means of killing insects.
- the composition is effective as an insect killer.
- both the insecticide and the biocide are agents for killing insects.
- agents that act as repellents, ie serve to deter and/or drive away insects, are not the subject of the invention.
- Repellents are a class of biocides that repel organisms without killing them. They are also interchangeably referred to as insect repellents. Repellents are often perceived by an organism via the sense of smell. But an oral intake of the active substance, ie an effect on the sense of taste, is possible and is found e.g. B. used to deter wild boar
- the insecticidal effect is defined as the application of a sample of about 2 ⁇ l with an active substance concentration of 1-2% to the surface of the cuticle, namely on the ventral side of the body between the pairs of legs of anesthetized crawling or flying insects belonging to the pests count, such as a cockroach.
- the effect of the sample is determined as an LDso value within the next 24 hours, i. H . the dose is given in mg, the lethal effect of which relates to 50 percent of the observed population. The smaller the LDso value, the smaller the amount of sample that needs to be used for the insect to die.
- insecticidal effect or insecticidal action is used both for insecticides and for biocides.
- pests refers only to insects and is also referred to synonymously with harmful insects.
- the expression is a collective term for organisms that reduce the economic success of humans, be it as destroyers of cultivated plants, as food competitors or by destroying buildings.
- Agricultural pests field beetle, codling moth, aphids, leaf edge beetles, thrips, fruit shell moth, potato beetle, cherry fruit fly, May beetle, corn borer, plum moth, rhododendron cicada, seed owl, scale insects, gypsy moth, spider mite, grape berry moth , Walnut fruit fly, Whitefly, Western corn rootworm Forest pests: certain aphids, Blue pine borer, Bark beetle, Oak borer, Oak processiffy moth, Oak moth, Spruce spider sawfly, Common woodworm (often just referred to as the woodworm) , Large brown barkeater, Pine sawfly, Pine owl, Pine moth, Small spruce sawfly , nun, horse chestnut leaf miner, gypsy moth, sapwood beetle
- Wood pests woodworm beetle (often colloquially referred to as "woodworm"), house longhorn (often mistakenly confused with wood tick), sapwood beetle, termites
- a solvent also solvent or solvent is a substance that can dissolve or dilute gases, liquids or solids without chemical reactions occurring between the dissolved substance and the solvent. Water, alcohols or ketones can be used as solvents.
- composition for use as an insecticide or biocide contains an active ingredient (i) that belongs to the class of environmentally friendly active ingredients and thus also in organic farming and all products on humans or in contact with the People or who can be used in his vicinity.
- the effectiveness of (i) in the composition can be significantly improved, resulting in a reduction in the proportion of (i) (active ingredient proportion), a temporal extension of the effect and an improvement in the possible uses as an insecticide or biocide result.
- An advantage of the more effective effectiveness of the complexes from (i) and (ii) is, for example, that the application frequency can be lowered, which leads to a large saving in time and material.
- Example 1 proves that the complexation of fatty acids, such as in this case getanoic, nonanoic or decanoic acid, with methylated beta-cyclodextrin (M-ß-CD) brings about a significant improvement in insecticidal effectiveness compared to the corresponding free, non-complexed fatty acid.
- M-ß-CD methylated beta-cyclodextrin
- test result from example 2 shows a clear increase in the insect repellent effect by up to 40% when fatty acids are used together with cyclodextrins compared to the use of fatty acids without the addition of cyclodextrins. This result could be shown for three different fatty acids and two different cyclodextrin derivatives.
- the test results mentioned clearly show that the combination of cyclodextrins with fatty acids to improve the insecticidal effect has the advantage of being able either to reduce the amount of fatty acids used or to be able to maintain the effectiveness of the fatty acids over a longer period of time. It was surprisingly found that the amount of cyclodextrin used must be lower than the sum of the fatty acids.
- fatty acids cyclodextrin mixture offers an effective ecological alternative to conventional insecticides or biocides.
- fatty acids effectively as an insecticidal or biocidal active ingredient with cyclodextrins in insect control and defense means that an environmentally friendly composition that is non-toxic to both humans and animals, including pets, can be made available.
- the composition is characterized in that after dissolving (i) and (ii) in a solvent, the molar ratio of (i):(ii) in the solution is between 1:0.01 and 1:0.5 (mol: mol) lies. Particularly preferably, after dissolving (i) and (ii) in a solvent, the molar ratio of (i):(ii) in the solution is 1:0.025 to 1:0.05 (mol:mol), particularly preferably 1: 0.05 (mole : mole) .
- (ii) is selected from the group consisting of ⁇ -cyclodextrin, ⁇ - Cyclodextrin, y-cyclodextrin, hydroxypropyl-a-cyclodextrin, acetyl-a-cyclodextrin, hydroxypropyl-ß-cyclodextrin, hydroxypropyl-y-cyclodextrin, acetyl-ß-cyclodextrin, methyl-ß-cyclodextrin, acetyl-y-cyclodextrin and their mixtures.
- (ii) is particularly preferably a native cyclodextrin such as ⁇ -cyclodextrin, ⁇ -cyclodextrin, ⁇ -cyclodextrin or a mixture thereof, particularly preferably ⁇ -cyclodextrin and/or ⁇ -cyclodextrin.
- (ii) is a cyclodextrin derivative such as hydroxypropyl- ⁇ -cyclodextrin, acetyl- ⁇ -cyclodextrin, hydroxypropyl- ⁇ -cyclodextrin, hydroxypropyl- ⁇ -cyclodextrin, acetyl- ⁇ -cyclodextrin, methyl- ⁇ -cyclodextrin , Acetyl-y-cyclodextrin or mixtures thereof, it is particularly preferred that (ii) is hydroxypropyl-ß-cyclodextrin or methyl-ß-cyclodextrin.
- Saturated or unsaturated fatty acids, their salts or esters are used as insecticidal or biocidal active ingredients.
- the composition is preferably characterized in that (i) has a chain length of 6 to 20 carbon atoms. Particular preference is given to (i) being selected from the group consisting of hexanoic acid (C6, caproic acid), heptanoic acid (C7, enanthic acid), octanoic acid (C8, caprylic acid), nonanoic acid (C9, pelargonic acid), decanoic acid (CIO, capric acid) , undecanoic acid (Cll), dodecanoic acid (C12, lauric acid), their unsaturated representatives, their homologues and mixtures thereof.
- C6 hexanoic acid
- C7 heptanoic acid
- octanoic acid C8 caprylic acid
- nonanoic acid C9, pelargonic acid
- decanoic acid C
- (i) is particularly preferably caprylic acid (C8), pelargonic acid (C9), capric acid (CIO) or a mixture thereof, particularly preferably it is a mixture of a C8, C9 and ClO fatty acid in each case equal share.
- unsaturated representatives or homologues of the fatty acids mentioned can also be used.
- the composition is characterized in that after dissolving (i) and (ii) in a solvent, the percentage of each fatty acid in the solution is 1.5%.
- This preferred percentage level does not relate to the total concentration of (i) in the composition but to each individual fatty acid, ie where (i) is a mixture of for example three different fatty acids each is preferably present at a level of 1.5% .
- the dry composition can be used directly as an insecticide or biocide, for example by scattering the powder and dissolving in rainwater.
- the composition according to the invention can also serve as a basis for the production of a formulation.
- a further object of the invention is therefore a formulation containing the composition according to the invention, characterized in that it is used as an insecticide or biocide.
- a formulation may contain components such as solvents, surfactants, viscosity regulators, antifoams, preservatives, emulsifiers and/or other classes of active ingredients such as growth regulators.
- the aim of the formulation is to optimize the biological effect of the composition in the target organism and, at the same time, to bring the finished product into a form that can be used in technical equipment. In this way, not only the effectiveness but also, for example, the shelf life of the formulation should be optimized.
- the formulation is used to kill insects.
- the formulation additionally contains a solvent.
- a solvent is particularly preferred for the solvent to contain water.
- the solvent is particularly preferably an acetone-water mixture.
- composition according to the invention is produced in a manner known per se by combining all the components.
- Active substances can be used either in the form of a physical mixture with the cyclodextrins, or these in the form of cyclodextrin complexes, or be used as a combination of these two options.
- the fatty acid-cyclodextrin complexes can be produced by any of the methods known in the prior art, preferably by the co-precipitation process, the melting-in process or the paste process.
- the active substance is dissolved in a suitable solvent and added in the desired ratio to an aqueous solution of the cyclodextrin or cyclodextrin derivative heated to 20 to 70.degree. C., preferably to 50.degree.
- the solution is stirred for a period of 16 hours and then the solvent is removed.
- the residue is dried at 40° C.
- the solvent is preferably acetone, methanol or ethanol.
- the cyclodextrin or cyclodextrin derivative is placed in water and heated to 20 to 70.degree. C., preferably 50.degree.
- the active ingredient is added in portions and stirred at the stated temperature for 16 hours. Uncomplexed active substance is filtered off and the complex is isolated by freeze-drying.
- the cyclodextrin or the cyclodextrin derivative is mixed together with the active substance in the desired ratio and water is added in a proportion of 30 percent by weight of the two components.
- the resulting paste is kept in a closed glass vessel at 70° C. for a period of eight hours and mixed hourly with a spatula. After the eight hours, the paste is dried and for the further
- the fatty acid-cyclodextrin complex is then incorporated into the solution used as formulation, for example by dissolving the product from the co-precipitation, melting-in or paste process in the solution used as formulation while stirring at room temperature.
- the cyclodextrin complex can easily be produced as a physical mixture by metering the cyclodextrins into a formulation that already contains the active ingredients.
- a further object is a method for protecting against insects, characterized in that the composition, preferably the formulation, is applied to the skin or to other surfaces or textiles.
- the method according to the invention makes it possible to repel and control insects with a clear improvement in the effectiveness of the insect repellent and a clear prolongation of the duration of action of the insect repellent.
- cockroaches each (BioGenius, Technologiepark, Bergisch Gladbach) were placed in a 10 cm x 2 cm Petri dish, the sides of which were treated with a mixture of mineral oil and vaseline (ratio 1:3, Sigma Aldrich) to prevent the to avoid animals.
- the cockroaches were treated with carbon dioxide for 15 to 25 seconds until anesthetized and positioned ventral side up. 2 ⁇ l each of the formulations were applied to the area between the pairs of legs and the insects were examined within the next 24 hours.
- the mortality of the individual formulations was evaluated by determining the mean lethal dose LD50.
- the LDso value indicates the dose in mg whose lethal effect relates to 50 percent of the observed population.
- Example 2 Efficacy of fatty acids complexed with cyclodextrin to combat ants
- Example 2 The experiment described in Example 1 was repeated, with the difference that, to improve the effectiveness, hydroxypropylated beta-cyclodextrin (HP-ß-CD, Wacker Chemie AG, molecular weight 1542 g/mol) was used in a molar ratio of 1:0.5 (fatty acid : cyclodextrin) was added. The pure solvent mixture served as a control. tab . 2: Contact toxicity when using the formulations from Example 2. This formulation can also be applied to other pests such as ticks, beetles, lice, leaf hoppers and the like.
- HP-ß-CD Wacker Chemie AG, molecular weight 1542 g/mol
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Abstract
The invention relates to a composition for use as insecticide or biocide, containing (i) saturated or unsaturated fatty acids, salts or esters thereof, and (ii) a cyclodextrin or cyclodextrin derivative, wherein, after (i) and (ii) are dissolved in a solvent, (ii) is present in the solution in a molar ratio to (i) of less than 1 (that is, the ratio of (i) : (ii) is 1 : less than 1 (mol : mol)). The invention also relates to a formulation containing this composition, which is used as insecticide or biocide, and to a method for repelling insects, characterized in that the composition or formulation according to the invention is applied to the skin or to other surfaces or textiles.
Description
Cyclodextrin und Fettsäuren enthaltende Formulierungen zur Kontrolle und Abwehr von Insekten mit verbesserter Wirksamkeit Insect control and repellent formulations containing cyclodextrin and fatty acids with improved efficacy
Die Erfindung betrifft eine Zusammensetzung zur Verwendung als Insektizid oder Biozid enthaltend (i) gesättigte oder ungesättigte Fettsäuren, deren Salze oder Ester und (11) ein Cyclodextrin oder Cyclodextrin-Derivat, wobei nach Lösen von (i) und (ii) in einem Lösungsmittel in der Lösung (ii) in einem molaren Verhältnis zu (i) von weniger als 1 vorliegt (d.h. das Verhältnis (i) : (ii) beträgt 1 : weniger als 1 (Mol : Mol) ) . Des Weiteren betrifft die Erfindung eine Formulierung enthaltend diese Zusammensetzung, die als Insektizid oder Biozid verwendet wird, sowie ein Verfahren zum Schutz vor Insekten, dadurch gekennzeichnet, dass die erfindungsgemäße Zusammensetzung auf die Haut oder auf andere Oberflächen oder Textilien aufgetragen wird . The invention relates to a composition for use as an insecticide or biocide containing (i) saturated or unsaturated fatty acids, their salts or esters and (11) a cyclodextrin or cyclodextrin derivative, wherein after dissolving (i) and (ii) in a solvent in the solution (ii) is in a molar ratio to (i) of less than 1 (i.e. the ratio (i):(ii) is 1:less than 1 (mole:mole)). Furthermore, the invention relates to a formulation containing this composition, which is used as an insecticide or biocide, and a method for protecting against insects, characterized in that the composition according to the invention is applied to the skin or to other surfaces or textiles.
Viele Insekten werden als Schädlinge für Menschen und Tiere betrachtet, da sie als Vektoren zur Übertragung von Krankheiten gelten. Zusätzlich können sie Schäden an landwirtschaftlichen Produkten verursachen und teils als massive Belästigung bei einem Aufenthalt im Freien angesehen werden. Zu diesen Insekten werden Ameisen, Kakerlaken, Bettwanzen, Sandflöhe, Staubmilben, Flöhe, Fliegen, Läuse, Termiten, Wespen, Zecken und vor allem Mücken gezählt. Viele Mücken können als sogenannte Vektoren lebensbedrohende Krankheiten übertragen. So fungiert Aedes aegypti als Vektor für das Dengue Fieber und das Gelbfieber, Anopheles sspec. für Malaria, Glossina sspec. für die Schlafkrankheit und Culex sspec. für die West-Nil-Krankheit. Die Wanderstechfliege stellt eine Gefahr für Rinderherden dar, da sie nicht nur die Milchleistung reduziert, sondern auch zusätzlich noch den Erreger der Rinderzitzenatresie überträgt. Zecken sind ein weltweit verbreiteter Parasit, der sich vom Blut zahlreicher Wirbeltiere ernährt. Ist die Zecke mit Krankheitserregern infiziert, kann ein Zeckenstich für Menschen gefährlich werden.
Dabei können die Virus-Krankheit FSME ( Frühsommer-Meningoenzephalitis ) , sowie das Bakterium Borreli ose sspec . übertragen werden . Bettwanzen sondern beim Stechen einen Stof f ab, der starke allergische Reaktionen verursachen kann . Kakerlaken oder Schaben können Salmonellen und Schimmelsporen übertragen und damit das Risiko für Magen-Darm-Erkrankungen erhöhen . Many insects are considered pests of humans and animals because they are thought to be vectors of disease transmission. In addition, they can cause damage to agricultural products and are sometimes seen as a massive nuisance when staying outdoors. These insects include ants, cockroaches, bed bugs, sand fleas, dust mites, fleas, flies, lice, termites, wasps, ticks and most importantly mosquitoes. Many mosquitoes can transmit life-threatening diseases as so-called vectors. Aedes aegypti acts as a vector for dengue fever and yellow fever, Anopheles sspec. for malaria, Glossina sspec. for sleeping sickness and Culex sspec. for West Nile disease. The migratory stable fly poses a threat to cattle herds, as it not only reduces milk yield, but also transmits the causative agent of bovine teat atresia. Ticks are a worldwide parasite that feeds on the blood of many vertebrates. If the tick is infected with pathogens, a tick bite can be dangerous for humans. The virus disease TBE (tick-borne encephalitis) and the bacterium Borreliosis sspec. be transmitted . When bed bugs bite, they emit a substance that can cause severe allergic reactions. Cockroaches or cockroaches can transmit salmonella and mold spores, increasing the risk of gastrointestinal disease.
Eine Möglichkeit , um Mückenstiche , Zecken, Bettwanzen und andere Insekten zu vermeiden, stellt die Applikation von Insektenabwehrmitteln auf der Haut dar . Auch können diese Substanzen zur Abschreckung und Beseitigung von Insekten auf Oberflächen wie beispielsweise Hausinnenwänden, Böden, Terrassen etc . aufgetragen werden . Ein wichtiger Vertreter der Insektenabwehrmittel stellt DEET ( Diethyl toluamid) dar, das zwar ein weites Wirkungsspektrum aufweist , j edoch Allergien hervorrufen, mit seinen Löseeigenschaften Kunststof fe , Kunstfasern und Leder beschädigen und ganz generell Rei zungen erzeugen kann . Weitere Abwehrmittel wie Ethylbutylacetylaminopropionat ( IR 3535 ) , I- caridin, para-Menthan-3 , 8-diol oder auch bestimmte Ätherische Öle sind wesentlich hautverträglicher, haben dafür aber eine geringere Schutzwirkung . One way to avoid mosquito bites, ticks, bed bugs and other insects is to apply insect repellents to the skin. These substances can also be used to deter and eliminate insects on surfaces such as house interior walls, floors, terraces, etc. to be applied . An important representative of the insect repellents is DEET (diethyl toluamide), which has a wide range of effects, but can cause allergies, damage plastics, synthetic fibers and leather with its dissolving properties and generally cause irritation. Other repellents such as ethylbutyl acetylaminopropionate (IR 3535), I-caridin, para-menthane-3, 8-diol or certain essential oils are much more skin-friendly, but have a lower protective effect.
Weiterhin werden zur Abtötung, Vertreibung oder Hemmung von Insekten wie beispielsweise Ameisen, Kakerlaken, Bettwanzen, Termiten oder ähnliche Schädlinge Insektenvernichtungsmittel verwendet . Wichtige Vertreter der klassischen synthetischen Insekti zide stellen Phosphorsäureester, Carbamate , Neonicotinoide o- der auch Pyrethroide dar . Trotz ihrer hervorragenden Wirkung können sie zu stark ausgeprägten Resistenzen bei den Zielorganismen führen, sind gefährlich gegenüber Menschen und Haustieren und können Allergien auslösen .
Daher ist man auf der Suche nach alternativen, weniger gi ftigen Wirkstof fen, die als Insektenabwehrmittel bzw . Insektenvernichtungsmittel zur Eindämmung von Schädlingen verwendet werden können . Insecticides are also used to kill, drive away or inhibit insects such as ants, cockroaches, bed bugs, termites or similar pests. Important representatives of the classic synthetic insecticides are phosphoric acid esters, carbamates, neonicotinoids or pyrethroids. Despite their excellent effect, they can lead to strong resistances in the target organisms, are dangerous to humans and pets and can trigger allergies. Therefore, one is looking for alternative, less toxic active ingredients that can be used as insect repellents or insect repellents. Insecticides can be used to control pests.
Gesättigte und ungesättigte Fettsäuren und deren Sal ze , sowie Ester sind seit langem als umweltfreundliche Wirkstof fe zur Bekämpfung von Schädlingen bekannt . Natürlich vorkommende Fettsäuren enthalten sowohl polare ( Carbonsäuregruppen) , als auch nicht polare (Alkylgruppen) Strukturbestandteile und werden als natürliche Abwehrmittel für eine Viel zahl von Insekten beschrieben . Fettsäuren mit einem geringen Molekulargewicht sind ausreichend flüchtig, um von Oberflächen wie der menschlichen Haut zu verdampfen . Es wurde gefunden, dass Fettsäuren mit 6 bis 12 Kohlenstof f atomen eine stärkere Abwehrwirkung aufweisen als DEET . Saturated and unsaturated fatty acids and their salts, as well as esters, have long been known as environmentally friendly active ingredients for controlling pests. Naturally occurring fatty acids contain both polar (carboxylic acid groups) and non-polar (alkyl groups) structural components and are described as natural repellents for a large number of insects. Low molecular weight fatty acids are sufficiently volatile to evaporate from surfaces such as human skin. It has been found that fatty acids with 6 to 12 carbon atoms have a stronger repellent effect than DEET.
Weiterhin wurde festgestellt , dass Fettsäuren und ihre Sal ze auf bestimmte Insekten wie Käfer, Läuse , Zikaden, Wanzen, Ameisen, Schaben und ähnliche eine toxische Wirkung aufweisen . Man geht davon aus , dass sich die Fettsäuren oder ihre Sal ze an der Cuticula der Insekten anlagern, um dann über die Tracheen inkorporiert zu werden . Of fenbar können die Fettsäuren und ihre Sal ze innerhalb des Insekts den Aufbau der Zellmembranen zerstören . Furthermore, it was found that fatty acids and their salts have a toxic effect on certain insects such as beetles, lice, cicadas, bugs, ants, cockroaches and the like. It is assumed that the fatty acids or their salts attach themselves to the cuticle of the insects in order to then be incorporated via the trachea. Apparently, the fatty acids and their salts can destroy the structure of the cell membranes inside the insect.
In dem Patent DE 698 17 595 T2 werden Insektenvertreibungsmittel beschrieben, die auf einem Gemisch aus Fettsäuren beruhen . Steven R . Sims ( Topical and Vapor Toxicity of Saturated Fatty Acids to the German Cockroach ( Dictyoptera : Blattellidae ) , J . of Economic Entomology, S . 758-763 , 2014 ) hat 2014 Tests durchgeführt , bei denen die Wirksamkeit von gesättigten Fettsäuren gegenüber Kakerlaken gemessen wurde . Junwei J . Zhu (Better than DEET Repellent Compounds Derived from Coconut Oil , Nature Sei-
enti fic Reports , S . 1453- 1465 , 2018 ) untersuchte 2018 die insektenabwehrende Wirkung von Fettsäuren, die als günstige und toxikologisch bedenkenlose Alternative zu synthetischen Wirkstof fen aus Kokosöl gewonnen wurden . Patent DE 698 17 595 T2 describes insect repellents which are based on a mixture of fatty acids. Steven R. Sims (Topical and Vapor Toxicity of Saturated Fatty Acids to the German Cockroach ( Dictyoptera : Blattellidae ), J. of Economic Entomology, pp. 758-763, 2014 ) conducted tests in 2014 measuring the effectiveness of saturated fatty acids against cockroaches . Junwei J. Zhu (Better than DEET Repellent Compounds Derived from Coconut Oil , Nature Sei- entific Reports, p. 1453-1465, 2018) examined in 2018 the insect repellent effect of fatty acids, which were obtained from coconut oil as a cheap and toxicologically harmless alternative to synthetic active ingredients.
Insofern stellen Fettsäuren und ihre Sal ze eine ökologisch vertretbare Variante zu klassischen Insektenabwehrmitteln und Insekti ziden dar . Jedoch sind diese gegenüber synthetischen Wirkstof fen oft nicht ausreichend wirksam, bzw . verbleiben aufgrund ihrer hohen Flüchtigkeit nicht lange genug am Wirkort , um einen dauerhaften Nutzen zu erzielen . In this respect, fatty acids and their salts represent an ecologically justifiable alternative to classic insect repellents and insecticides. However, these are often not sufficiently effective compared to synthetic active substances, or do not remain at the site of action long enough to provide lasting benefit due to their high volatility .
Cyclodextrine sind cyclische Oligosaccharide , die sechs (a- ) , sieben ( ß- ) oder acht
, über a- ( 1 , 4 ) -Bindungen miteinander verbundene D-Glucopyranoseeinheiten enthalten und die enzymatisch aus Stärke gewonnen werden . Aufgrund ihrer ringförmigen Molekülstruktur mit einem hydrophoben Hohlraum können Cyclodextrine reversible Komplexe mit hydrophoben Gastmolekülen bilden . Aufgrund der hydrophilen Oberfläche der Cyclodextrine lässt sich mit ihrer Hil fe die Wasserlöslichkeit von hydrophoben Substanzen stark verbessern . Gleichzeitig besteht die Möglichkeit dazu, die Flüchtigkeit von volatilen Substanzen durch Komplexbildung mit Cyclodextrinen deutlich zu verringern, eine verzögerte Freisetzung zu erzielen, sowie Stabilitäten von labilen Substanzen zu verbessern . Auf Basis der nativen Cyclodextrine wurden zahlreiche Derivate mit unterschiedlichen Eigenschaften entwickelt . So weisen beispielsweise das Methyl- ß- Cyclodextrin und das Hydroxypropyl- ß-Cyclodextrin eine um ein Viel faches gesteigerte Wasserlöslichkeit gegenüber dem nativen ß-Cyclodextrin auf . Das gleiche tri f ft auf Derivate des a- und y-Cyclodextrins zu . Cyclodextrins are cyclic oligosaccharides containing six (a-), seven (ß-), or eight , containing D-glucopyranose units connected to one another via a-(1,4)-bonds and which are obtained enzymatically from starch. Due to their ring-shaped molecular structure with a hydrophobic cavity, cyclodextrins can form reversible complexes with hydrophobic guest molecules. Due to the hydrophilic surface of the cyclodextrins, the water solubility of hydrophobic substances can be greatly improved with their help. At the same time, it is possible to significantly reduce the volatility of volatile substances by forming complexes with cyclodextrins, to achieve delayed release and to improve the stability of unstable substances. Numerous derivatives with different properties have been developed on the basis of native cyclodextrins. For example, the methyl-β-cyclodextrin and the hydroxypropyl-β-cyclodextrin have a water solubility that is many times higher than that of the native β-cyclodextrin. The same applies to derivatives of a- and y-cyclodextrin.
WO 19/215645 und WO 20/ 084572 beschreiben, dass Pesti zid-Cyclo- dextrin-Komplexe besonders ef fektiv sind, da sie die Löslich-
keit des Pestizids erhöhen, was die Bioverfügbarkeit verbessert, was an den Wirkstoffen Tau-Fluvalinat und Prothioconazol untersucht wurde. Bei diesen Wirkstoffen handelt es sich um die klassischen Wirkstoffe, die schlecht für Nutzinsekten sind, Resistenzen auslösen können und toxisch gegenüber der Umwelt sind. Zu diesem Zweck wurden die Wirkstoffe äquimolar oder mit einem molaren Überschuss Cyclodextrin versetzt. WO 19/215645 and WO 20/084572 describe that pesticide-cyclodextrin complexes are particularly effective because they increase the solubility increase the potency of the pesticide, which improves bioavailability, which has been studied with the active substances tau-fluvalinate and prothioconazole. These active ingredients are the classic active ingredients that are bad for beneficial insects, can induce resistance and are toxic to the environment. For this purpose, equimolar amounts or a molar excess of cyclodextrin were added to the active substances.
WO 2018/050211 beschreibt, dass es für die effektive Wirkung eines Repellents auf Basis eines Komplexes aus Cyclodextrin und DEET von Vorteil ist, wenn der Wirkstoff nicht komplett komple- xiert vorliegt, um in ausreichendem Anteil in der Umgebungsluft zur Verfügung zu stehen. Dieser Komplex hat den Nachteil, dass das klassische Insektenabwehrmittel DEET auf viele Materialien reizend wirkt. WO 2018/050211 describes that it is advantageous for the effective action of a repellent based on a complex of cyclodextrin and DEET if the active substance is not completely complexed so that it is available in sufficient proportion in the ambient air. The disadvantage of this complex is that the classic insect repellent DEET has an irritating effect on many materials.
Ebenso ist US 2012/149564 A auf eine insektizide Zusammensetzung gerichtet, die Athranil-Diamid-Insektizide und Cyclodextrin enthält. Bei dieser für Insekten und Wirbellose hochwirksamen chemischen Klasse handelt es sich um eine relativ neue Wirkstoff gruppe, die ebenso Nutzinsekten betrifft. Zusätzlich können Resistenzen entstehen. Eine zugelassene Formulierung auf dieser Basis wurde als bienengefährlich eingestuft. Trotz der Einstufung als wenig giftig für den Menschen wurden einzelne Fälle von Vergiftung durch beispielsweise Chlorantraniliprol bekannt, so dass auch bei Komplexen mit Athranil-Diamiden Nachteile in der Verwendung bestehen. Likewise, US 2012/149564 A is directed to an insecticidal composition containing athranil diamide insecticides and cyclodextrin. This class of chemicals, which is highly effective on insects and invertebrates, is a relatively new class of compounds that also affects beneficial insects. In addition, resistance can develop. An approved formulation based on this was classified as hazardous to bees. Despite the classification as slightly toxic for humans, individual cases of poisoning by, for example, chlorantraniliprole have been reported, so that there are also disadvantages in the use of complexes with athranil diamides.
Aufgabe der Erfindung war es, eine Zusammensetzung enthaltend eine ökologisch vertretbare Variante eines klassischen Insektizids oder Biozids, d.h. einen umweltfreundlichen Wirkstoff zur Bekämpfung von Insekten bereitzustellen, der effektiv in einer Formulierung zur Kontrolle und Abwehr von Insekten eingesetzt werden kann.
Diese Aufgabe wurde dadurch gelöst, dass eine Zusammensetzung zur Verwendung als Insektizid oder Biozid enthaltend (i) gesättigte oder ungesättigte Fettsäuren, deren Salze oder Ester und (ii) ein Cyclodextrin oder Cyclodextrin-Derivat, wobei nach Lösen von (i) und (ii) in einem Lösungsmittel in der Lösung (ii) in einem molaren Verhältnis zu (i) von weniger als 1 vorliegt (d.h. das Verhältnis (i) : (ii) beträgt 1 : weniger als 1 (Mol : Mol) ) zur Verfügung gestellt wird. The object of the invention was to provide a composition containing an ecologically justifiable variant of a classic insecticide or biocide, ie an environmentally friendly active substance for combating insects, which can be used effectively in a formulation for controlling and repelling insects. This object was achieved in that a composition for use as an insecticide or biocide containing (i) saturated or unsaturated fatty acids, their salts or esters and (ii) a cyclodextrin or cyclodextrin derivative, wherein after dissolving (i) and (ii) in a solvent in the solution (ii) is present in a molar ratio to (i) of less than 1 (ie the ratio (i):(ii) is 1:less than 1 (mole:mole)).
Die Zusammensetzung ist eine Mischung der Komponenten (i) und (ii) . Die gesättigten oder ungesättigten Fettsäuren, deren Salze oder Ester sind das Insektizid oder Biozid, d.h. (i) ist der insektizid-wirkende Anteil und wird deshalb auch als Wirkstoffanteil bezeichnet. The composition is a mixture of components (i) and (ii). The saturated or unsaturated fatty acids, their salts or esters are the insecticide or biocide, i.e. (i) is the insecticidally active part and is therefore also referred to as the active ingredient part.
Die Zusammensetzung kann als Insektizid oder Biozid verwendet werden, d.h. sie ist ein umweltfreundlicher Wirkstoff zur Bekämpfung von Insekten und erzielt einen insektiziden Effekt. Zu diesem Zweck kann die Zusammensetzung direkt als Pulver ausgestreut werden oder in Form von Pellets verarbeitet und ausgebracht werden. In diesem Fall wird das erfindungsgemäße molare Verhältnis von (i) : (ii) dann erreicht, wenn sich die Zusammensetzung löst, beispielsweise bei Regen im Regenwasser oder im Morgentauwasser. The composition can be used as an insecticide or biocide, i.e. it is an environmentally friendly active ingredient for controlling insects and achieves an insecticidal effect. For this purpose, the composition can be spread directly as a powder or processed and applied in the form of pellets. In this case, the molar ratio of (i):(ii) according to the invention is achieved when the composition dissolves, for example in rainwater in rainwater or in morning dew water.
Die zum Erreichen des erfindungsgemäßen molaren Verhältnisses einzusetzende Menge an (i) und (ii) ergibt sich aus deren Molekulargewicht und ist daher einfach zu berechnen. So kann beispielsweise das molare Verhältnis von (i) : (ii) = 0,5 : 1 eingestellt werden, indem x Gramm (i) und 2y Gramm (ii) gemischt werden, wenn (i) ein Molekulargewicht von x g/mol besitzt und (ii) ein Molekulargewicht von y g/mol besitzt. The amount of (i) and (ii) to be used to achieve the molar ratio according to the invention results from their molecular weight and is therefore easy to calculate. For example, the molar ratio of (i):(ii) = 0.5:1 can be adjusted by mixing x grams of (i) and 2y grams of (ii) when (i) has a molecular weight of x g/mol and (ii) has a molecular weight of y g/mol.
Die Cyclodextrin und Fettsäuren enthaltenden Zusammensetzungen zum Abtöten und zur Abwehr von Insekten haben eine verbesserte Wirksamkeit und können bevorzugt zur Applikation auf der Haut
von Menschen oder Tieren sowie zur Behandlung von Textilien o- der auch von Oberflächen verwendet werden . Dabei war es überraschend, dass bei Verwendung von Fettsäuren, deren Sal ze oder Ester als Wirkstof f , die eingesetzten Cyclodextrine oder Cyclodextrin-Derivate in einem geringeren als äquimolaren Verhältnis zum Wirkstof f zugegeben werden konnten . Dies war insbesondere überraschend für eine umweltfreundliche Zusammensetzung zur Verwendung als Insekti zid oder Biozid, die damit ef fektiv und kostengünstig beispielsweise in der ökologischen Landwirtschaft , in der Nähe von Kindern oder direkt am Menschen eingesetzt werden kann . In Kenntnis des Stands der Technik war es besonders überraschend, dass die ef fektive Wirkung der Zusammensetzung in diesem Konzentrationsverhältnis direkt über die Oberfläche wirksam ist , dass also auch bei der Wirkung über die Oberfläche ein besonders guter Ef fekt erzielt wird, wenn der Cyclodextrin-Anteil im molaren Unterschuss eingesetzt wird und dadurch vermutlich ein Teil der Substanz unkomplexiert vorliegt . The insect killing and repellent compositions containing cyclodextrin and fatty acids have improved efficacy and may be preferentially applied to the skin of humans or animals as well as for the treatment of textiles or surfaces. It was surprising that when using fatty acids, their salts or esters as the active substance, the cyclodextrins or cyclodextrin derivatives used could be added in a less than equimolar ratio to the active substance. This was particularly surprising for an environmentally friendly composition for use as an insecticide or biocide, which can thus be used effectively and cost-effectively, for example, in ecological agriculture, near children or directly on people. Knowing the state of the art, it was particularly surprising that the effective effect of the composition in this concentration ratio is effective directly on the surface, so that a particularly good effect is also achieved with the effect on the surface if the cyclodextrin proportion is used in the molar deficiency and thus presumably a part of the substance is present in uncomplexed form.
Ein Insekti zid ist ein Mittel zur Abtötung, Vertreibung oder Hemmung von Insekten und deren Entwicklungsstadien . Der Begri f f Insekti zid wird in der Land- und Forstwirtschaft verwendet .An insecticide is a means of killing, repelling or inhibiting insects and their developmental stages. The term insecticide is used in agriculture and forestry.
Es ist bevorzugt , dass die Zusammensetzung als Insekti zid verwendet wird und besonders bevorzugt , dass die Zusammensetzung als Insekti zid verwendet wird und es sich beim Insekti zid um ein Insektenvernichtungsmittel handelt , d . h . ein Mittel zum Abtöten von Insekten . It is preferred that the composition is used as an insecticide and more preferred that the composition is used as an insecticide and the insecticide is an insecticide, ie. H . a means of killing insects.
Ein Biozid ist ein Mittel zur Abwehr oder zum Abtöten von Insekten, das nicht in der Agrarwirtschaft und nicht im Pflanzenschutz eingesetzt wird . Der Begri f f wird insbesondere zum Vorrats- und Materialschutz , in der Tierzucht inklusive der Nutztierhaltung, im Hygienebereich und in privaten Haushalten verwendet . Zu den Bioziden zählen z . B . Desinfektionsmittel , Rattengi fte oder Hol zschutzmittel . Biozide sind dafür gedacht , die
Gesundheit und die Produkte des Menschen zu schützen, d . h . im Vergleich zu Insekti ziden ist bei Bioziden die Art und der Ort der Verwendung unterschiedlich ( am Menschen bzw . in seinem Haus - auf dem Feld bzw . im Gewächshaus und Lager ) . A biocide is a non-agricultural and non-plant protection agent used to repel or kill insects. The term is used in particular for the protection of stored products and materials, in animal breeding including livestock farming, in the hygiene sector and in private households. The biocides include z. B. Disinfectants, rat poison or wood preservatives. Biocides are intended for that to protect human health and products, d . H . In comparison to insecticides, the type and place of use of biocides is different (on people or in their homes, in the fields or in greenhouses and storage).
Es ist bevorzugt , dass die Zusammensetzung als Biozid verwendet wird und besonders bevorzugt , dass die Zusammensetzung als Biozid verwendet wird und es sich beim Biozid um ein Insektenvernichtungsmittel handelt , d . h . ein Mittel zum Abtöten von Insekten . It is preferred that the composition is used as a biocide and most preferred that the composition is used as a biocide and the biocide is an insecticide, ie. H . a means of killing insects.
Es ist besonders bevorzugt , dass die Zusammensetzung als Mittel zum Abtöten von Insekten wirksam ist . In diesem Fall handelt es sich sowohl beim Insekti zid, als auch beim Biozid um Mittel zum Abtöten von Insekten . In diesem besonders bevorzugten Fall sind Mittel , die als Repellents wirken, also der Abschreckung und/oder Vertreibung von Insekten dienen, nicht Gegenstand der Erfindung . It is particularly preferred that the composition is effective as an insect killer. In this case, both the insecticide and the biocide are agents for killing insects. In this particularly preferred case, agents that act as repellents, ie serve to deter and/or drive away insects, are not the subject of the invention.
Repellents stellen eine Produktklasse der Biozide dar, die Organismen abschrecken, ohne sie zu töten . Sie werden synonym auch als Insektenabwehrmittel bezeichnet . Repellents werden von einem Organismus häufig über den Geruchssinn wahrgenommen . Aber auch eine orale Aufnahme des Wirkstof fs , also eine Wirkung über den Geschmackssinn ist möglich und findet z . B . bei der Vergrä- mung von Wildschweinen Anwendung Repellents are a class of biocides that repel organisms without killing them. They are also interchangeably referred to as insect repellents. Repellents are often perceived by an organism via the sense of smell. But an oral intake of the active substance, ie an effect on the sense of taste, is possible and is found e.g. B. used to deter wild boar
Der insekti zide Ef fekt ist definiert als Aufbringen einer Probe von etwa 2 pl mit einer Wirkstof f konzentration von 1-2 % auf die Oberfläche der Cuticula und zwar auf die ventrale Körperseite zwischen den Beinpaaren von betäubten kriechenden oder fliegenden Insekten, die zu den Schädlingen zählen, wie beispielsweise einer Schabe . Die Wirkung der Probe wird als LDso-Wert innerhalb der nächsten 24 Stunden bestimmt , d . h . es wird die Dosis in mg angegeben, deren letaler Ef fekt sich auf 50 Prozent der beobachteten Population bezieht . Je kleiner der LDso-Wert ist ,
desto geringer ist die Probenmenge, die eingesetzt werden muss, damit das Insekt stirbt. The insecticidal effect is defined as the application of a sample of about 2 μl with an active substance concentration of 1-2% to the surface of the cuticle, namely on the ventral side of the body between the pairs of legs of anesthetized crawling or flying insects belonging to the pests count, such as a cockroach. The effect of the sample is determined as an LDso value within the next 24 hours, i. H . the dose is given in mg, the lethal effect of which relates to 50 percent of the observed population. The smaller the LDso value, the smaller the amount of sample that needs to be used for the insect to die.
Der Begriff insektizider Effekt bzw. insektizide Wirkung wird im Rahmen dieser Erfindung sowohl für Insektizide, als auch für Biozide verwendet. In the context of this invention, the term insecticidal effect or insecticidal action is used both for insecticides and for biocides.
Der Begriff Schädlinge bezieht sich im Rahmen dieser Erfindung nur auf Insekten und wird synonym auch mit Schadinsekten bezeichnet. Der Ausdruck ist eine Kollektivbezeichnung für Organismen, die den wirtschaftlichen Erfolg des Menschen schmälern, sei es als Zerstörer von Kulturpflanzen, als Nahrungskonkurrent oder durch Zerstörung von Bauwerken. In the context of this invention, the term pests refers only to insects and is also referred to synonymously with harmful insects. The expression is a collective term for organisms that reduce the economic success of humans, be it as destroyers of cultivated plants, as food competitors or by destroying buildings.
Zu den Schädlingen werden unter anderem gezählt: Agrarschädlinge: Ackerbohnenkäfer, Apfelwickler, Blattläuse, Blattrandkäfer, Fransenf lügler (Thripse) , Fruchtschalenwickler , Kartoffelkäfer, Kirschfruchtf liege, Maikäfer, Maiszünsler, Pflaumenwickler, Rhododendron-Zikade, Saateule, Schildläuse, Schwammspinner, Spinnmilbe, Traubenwickler, Walnussfruchtfliege, Weiße Fliege, Westlicher Maiswurzelbohrer Forstschädlinge: bestimmte Blattläuse, Blauer Kiefernprachtkäfer, Borkenkäfer, Eichenprachtkäfer, Eichen-Prozessionsspinner , Eichenwickler, Fichtengespinstblattwespe, Gemeiner Holzwurm (oft nur als Nagekäfer bezeichnet) , Großer Brauner Rindenfresser, Kiefernbuschhornblattwespe, Kieferneule, Kiefernspanner, Kleine Fichtenblattwespe, Nonne, Rosskastanienminiermotte, Schwammspinner, Splintholzkäfer Among the pests are counted, among others: Agricultural pests: field beetle, codling moth, aphids, leaf edge beetles, thrips, fruit shell moth, potato beetle, cherry fruit fly, May beetle, corn borer, plum moth, rhododendron cicada, seed owl, scale insects, gypsy moth, spider mite, grape berry moth , Walnut fruit fly, Whitefly, Western corn rootworm Forest pests: certain aphids, Blue pine borer, Bark beetle, Oak borer, Oak processionary moth, Oak moth, Spruce spider sawfly, Common woodworm (often just referred to as the woodworm) , Large brown barkeater, Pine sawfly, Pine owl, Pine moth, Small spruce sawfly , nun, horse chestnut leaf miner, gypsy moth, sapwood beetle
Vorratsschädlinge: Deutsche Schabe, Getreideplattkäfer, Kleidermotte, Kornkäfer, Mehlmotte Storage pests: German cockroach, flat grain beetle, clothes moth, grain weevil, flour moth
Holzschädlinge : Gemeiner Nagekäfer (umgangssprachlich oft als „Holzwurm" bezeichnet) , Hausbock (oft fälschlich mit dem Gemeinen Holzbock verwechselt) , Splintholzkäfer, TermitenWood pests: woodworm beetle (often colloquially referred to as "woodworm"), house longhorn (often mistakenly confused with wood tick), sapwood beetle, termites
Weitere Materialschädlinge: Larven der Speckkäfer, Braune Wegameise
Ein Lösungsmittel (auch Lösemittel oder Solvens) ist ein Stoff, der Gase, Flüssigkeiten oder Feststoffe lösen oder verdünnen kann, ohne dass es dabei zu chemischen Reaktionen zwischen gelöstem Stoff und lösendem Stoff kommt. Als Lösungsmittel können Wasser, Alkohole oder Ketone eingesetzt werden. Other material pests: larvae of the bacon beetle, brown garden ant A solvent (also solvent or solvent) is a substance that can dissolve or dilute gases, liquids or solids without chemical reactions occurring between the dissolved substance and the solvent. Water, alcohols or ketones can be used as solvents.
Wie oben bereits ausgeführt, ist es von besonderem Vorteil, dass die Zusammensetzung zur Verwendung als Insektizid oder Biozid einen Wirkstoff (i) enthält, der zur Klasse der umweltfreundlichen Wirkstoffe zählt und damit auch im Bioanbau und allen Produkten am Menschen bzw. im Kontakt mit dem Menschen o- der in seiner Nähe eingesetzt werden kann. As already stated above, it is of particular advantage that the composition for use as an insecticide or biocide contains an active ingredient (i) that belongs to the class of environmentally friendly active ingredients and thus also in organic farming and all products on humans or in contact with the People or who can be used in his vicinity.
Durch die Zugabe von (ii) lässt sich die Wirksamkeit von (i) in der Zusammensetzung deutlich verbessern, was eine Absenkung des Anteils von (i) (Wirkstoff anteil ) , eine zeitliche Ausdehnung des Effekts sowie eine Verbesserung der Einsatzmöglichkeiten als Insektizid oder Biozid zur Folge hat. Ein Vorteil der effektiveren Wirksamkeit der Komplexe aus (i) und (ii) ist z.B., dass die Applikationsfrequenz abgesenkt werden kann, was zu einer großen Einsparung an Zeit und Material führt. By adding (ii), the effectiveness of (i) in the composition can be significantly improved, resulting in a reduction in the proportion of (i) (active ingredient proportion), a temporal extension of the effect and an improvement in the possible uses as an insecticide or biocide result. An advantage of the more effective effectiveness of the complexes from (i) and (ii) is, for example, that the application frequency can be lowered, which leads to a large saving in time and material.
Beispiel 1 belegt, dass die Komplexierung von Fettsäuren wie in diesem Fall Getan-, Nonan- oder Decansäure mit methyliertem beta-Cyclodextrin (M-ß-CD) verglichen mit der entsprechenden freien, nicht komplexierten Fettsäure eine deutliche Verbesserung der insektiziden Wirksamkeit bewirkt. Example 1 proves that the complexation of fatty acids, such as in this case getanoic, nonanoic or decanoic acid, with methylated beta-cyclodextrin (M-ß-CD) brings about a significant improvement in insecticidal effectiveness compared to the corresponding free, non-complexed fatty acid.
Das Testergebnis aus Beispiel 2 zeigt eine deutliche Steigerung der insektenabwehrenden Wirkung um bis zu 40%, wenn Fettsäuren zusammen mit Cyclodextrinen verwendet werden verglichen mit dem Einsatz von Fettsäuren ohne Zugabe von Cyclodextrinen. Dieses Ergebnis konnte für drei verschiedene Fettsäuren und zwei verschiedene Cyclodextrin-Derivate gezeigt werden.
Aus den genannten Testergebnissen geht klar hervor, dass die Kombination von Cyclodextrinen mit Fettsäuren zur Verbesserung der insektiziden Wirkung den Vorteil aufweist, entweder die Einsatzmenge der Fettsäuren absenken zu können oder aber die Wirksamkeit der Fettsäuren über einen längeren Zeitraum aufrecht erhalten zu können. Dabei wurde überraschend festgestellt, dass die Einsatzmenge des Cyclodextrin gegenüber der Summe der Fettsäuren tiefer sein muss. Denn nur so kann offenbar sichergestellt werden, dass eine ausreichend große Menge an Fettsäure ab dem Zeitpunkt der Applikation unkomplexiert zur Verfügung steht, um einen unmittelbaren Effekt hervorrufen zu können. Die restliche, noch komplexiert vorliegende Menge an Fettsäure wird erst durch das Einwirken der Feuchtigkeit allmählich freigesetzt, wodurch es zu einer nachhaltigen Verstärkung des Effektes kommt. The test result from example 2 shows a clear increase in the insect repellent effect by up to 40% when fatty acids are used together with cyclodextrins compared to the use of fatty acids without the addition of cyclodextrins. This result could be shown for three different fatty acids and two different cyclodextrin derivatives. The test results mentioned clearly show that the combination of cyclodextrins with fatty acids to improve the insecticidal effect has the advantage of being able either to reduce the amount of fatty acids used or to be able to maintain the effectiveness of the fatty acids over a longer period of time. It was surprisingly found that the amount of cyclodextrin used must be lower than the sum of the fatty acids. Apparently, this is the only way to ensure that a sufficiently large amount of fatty acid is available uncomplexed from the time of application in order to be able to produce an immediate effect. The remaining amount of fatty acid, which is still present as a complex, is only gradually released through the effects of moisture, which leads to a lasting intensification of the effect.
Zusammengefasst bietet die Verwendung eines Fettsäure-Cyclo- dextrin-Gemisches eine wirksame ökologische Alternative zu herkömmlichen Insektiziden oder Bioziden. Dadurch, dass es möglich war, Fettsäuren als insektiziden bzw. bioziden Wirkstoff mit Cyclodextrinen effektiv in der Insektenbekämpfung und -abwehr einzusetzen, kann eine umweltfreundliche und sowohl für Menschen als auch für Tiere einschließlich Haustieren ungiftige Zusammensetzung zur Verfügung gestellt werden. In summary, the use of a fatty acid cyclodextrin mixture offers an effective ecological alternative to conventional insecticides or biocides. The fact that it was possible to use fatty acids effectively as an insecticidal or biocidal active ingredient with cyclodextrins in insect control and defense means that an environmentally friendly composition that is non-toxic to both humans and animals, including pets, can be made available.
Bevorzugt ist die Zusammensetzung dadurch gekennzeichnet, dass nach Lösen von (i) und (ii) in einem Lösungsmittel das molare Verhältnis von (i) : (ii) in der Lösung zwischen 1 : 0,01 und 1 : 0,5 (Mol : Mol) liegt. Insbesondere bevorzugt beträgt nach Lösen von (i) und (ii) in einem Lösungsmittel das molare Verhältnis von (i) : (ii) in der Lösung 1 : 0,025 bis 1 : 0,05 (Mol : Mol) , im speziellen bevorzugt 1 : 0,05 (Mol : Mol) . Preferably, the composition is characterized in that after dissolving (i) and (ii) in a solvent, the molar ratio of (i):(ii) in the solution is between 1:0.01 and 1:0.5 (mol: mol) lies. Particularly preferably, after dissolving (i) and (ii) in a solvent, the molar ratio of (i):(ii) in the solution is 1:0.025 to 1:0.05 (mol:mol), particularly preferably 1: 0.05 (mole : mole) .
Bevorzugt ist die Zusammensetzung dadurch gekennzeichnet, dassThe composition is preferably characterized in that
(ii) ausgewählt ist aus der Gruppe bestehend a-Cyclodextrin, ß-
Cyclodextrin, y-Cyclodextrin, Hydroxypropyl-a-Cyclodextrin, Acetyl-a-Cyclodextrin, Hydroxypropyl-ß-Cyclodextrin, Hydroxypropyl- y-Cyclodextrin, Acetyl-ß-Cyclodextrin, Methyl-ß-Cyclo- dextrin, Acetyl- y-Cyclodextrin und deren Gemische. Besonders bevorzugt handelt es sich bei (ii) um ein natives Cyclodextrin wie a-Cyclodextrin, ß-Cyclodextrin, y-Cyclodextrin oder deren Mischung, insbesondere bevorzugt um a-Cyclodextrin und/oder ß- Cyclodextrin . Wenn es sich bei (ii) um ein Cyclodextrin-Derivat wie Hydroxypropyl-a-Cyclodextrin, Acetyl-a-Cyclodextrin, Hydro- xypropyl-ß-Cyclodextrin, Hydroxypropyl-y-Cyclodextrin, Acetyl- ß-Cyclodextrin, Methyl-ß-Cyclodextrin, Acetyl- y-Cyclodextrin o- der deren Gemische handelt, ist es besonders bevorzugt, dass es sich bei (ii) um Hydroxypropyl-ß-Cyclodextrin oder Methyl-ß- Cyclodextrin handelt. (ii) is selected from the group consisting of α-cyclodextrin, β- Cyclodextrin, y-cyclodextrin, hydroxypropyl-a-cyclodextrin, acetyl-a-cyclodextrin, hydroxypropyl-ß-cyclodextrin, hydroxypropyl-y-cyclodextrin, acetyl-ß-cyclodextrin, methyl-ß-cyclodextrin, acetyl-y-cyclodextrin and their mixtures. (ii) is particularly preferably a native cyclodextrin such as α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin or a mixture thereof, particularly preferably α-cyclodextrin and/or β-cyclodextrin. When (ii) is a cyclodextrin derivative such as hydroxypropyl-α-cyclodextrin, acetyl-α-cyclodextrin, hydroxypropyl-β-cyclodextrin, hydroxypropyl-γ-cyclodextrin, acetyl-β-cyclodextrin, methyl-β-cyclodextrin , Acetyl-y-cyclodextrin or mixtures thereof, it is particularly preferred that (ii) is hydroxypropyl-ß-cyclodextrin or methyl-ß-cyclodextrin.
Als insektizide bzw. biozide Wirkstoffe werden gesättigte oder ungesättigte Fettsäuren, deren Salze oder Ester eingesetzt. Bevorzugt ist die Zusammensetzung dadurch gekennzeichnet, dass (i) eine Kettenlänge von 6 bis 20 Kohlenstoff atomen besitzt. Besonders bevorzugt ist (i) ausgewählt aus der Gruppe bestehend aus Hexansäure (C6, Capronsäure) , Heptansäure (C7, Önanth- säure) , Octansäure (C8, Caprylsäure) , Nonansäure (C9, Pelargon- säure) , Decansäure (CIO, Caprinsäure) , Undecansäure (Cll) , Dodecansäure (C12, Laurinsäure) , deren ungesättigten Vertreter, deren Homologe und deren Gemische. Besonders bevorzugt handelt es sich bei (i) um Caprylsäure (C8) , Pelargonsäure (C9) , Caprinsäure (CIO) oder deren Mischung, insbesondere bevorzugt handelt es sich um eine Mischung einer C8-, C9- und ClO-Fett- säure in jeweils gleichem Anteil. Weiterhin können auch ungesättigte Vertreter oder Homologe der genannten Fettsäuren verwendet werden. Saturated or unsaturated fatty acids, their salts or esters are used as insecticidal or biocidal active ingredients. The composition is preferably characterized in that (i) has a chain length of 6 to 20 carbon atoms. Particular preference is given to (i) being selected from the group consisting of hexanoic acid (C6, caproic acid), heptanoic acid (C7, enanthic acid), octanoic acid (C8, caprylic acid), nonanoic acid (C9, pelargonic acid), decanoic acid (CIO, capric acid) , undecanoic acid (Cll), dodecanoic acid (C12, lauric acid), their unsaturated representatives, their homologues and mixtures thereof. (i) is particularly preferably caprylic acid (C8), pelargonic acid (C9), capric acid (CIO) or a mixture thereof, particularly preferably it is a mixture of a C8, C9 and ClO fatty acid in each case equal share. Furthermore, unsaturated representatives or homologues of the fatty acids mentioned can also be used.
In einer bevorzugten Aus führungs form ist die Zusammensetzung dadurch gekennzeichnet, dass nach Lösen von (i) und (ii) in einem Lösungsmittel der prozentuale Gehalt jeder Fettsäure in der
Lösung 1,5% beträgt. Dieser bevorzugte prozentuale Gehalt bezieht sich nicht auf die Gesamtkonzentration von (i) in der Zusammensetzung, sondern auf jede einzelne Fettsäure, d.h. wenn (i) ein Gemisch beispielsweise von drei verschiedenen Fettsäuren ist, liegt bevorzugt jede in einem Anteil von 1,5% vor. In a preferred embodiment, the composition is characterized in that after dissolving (i) and (ii) in a solvent, the percentage of each fatty acid in the solution is 1.5%. This preferred percentage level does not relate to the total concentration of (i) in the composition but to each individual fatty acid, ie where (i) is a mixture of for example three different fatty acids each is preferably present at a level of 1.5% .
Wie oben bereits beschrieben, kann die trockene Zusammensetzung direkt als Insektizid oder Biozid verwendet werden, z.B. durch Ausstreuen des Pulvers und Lösen in Regenwasser. Die erfindungsgemäße Zusammensetzung kann auch als Basis für die Herstellung einer Formulierung dienen. Ein weiterer Gegenstand der Erfindung ist daher eine Formulierung enthaltend die erfindungsgemäße Zusammensetzung, dadurch gekennzeichnet, dass sie als Insektizid oder Biozid verwendet wird. Zusätzlich zur Zusammensetzung kann eine Formulierung Komponenten wie beispielsweise Lösungsmittel, Tenside, Viskositätsregler, Antischaummittel, Konservierungsmittel, Emulgatoren und/oder andere Wirkstoffklassen wie Wachstumsregulatoren enthalten. Mit der Formulierung soll die biologische Wirkung der Zusammensetzung im Zielorganismus optimiert werden und gleichzeitig soll das Fertigprodukt in eine gerätetechnisch anwendbare Form gebracht werden. So soll nicht nur die Wirksamkeit, sondern auch z.B. die Haltbarkeit der Formulierung optimiert werden. As described above, the dry composition can be used directly as an insecticide or biocide, for example by scattering the powder and dissolving in rainwater. The composition according to the invention can also serve as a basis for the production of a formulation. A further object of the invention is therefore a formulation containing the composition according to the invention, characterized in that it is used as an insecticide or biocide. In addition to the composition, a formulation may contain components such as solvents, surfactants, viscosity regulators, antifoams, preservatives, emulsifiers and/or other classes of active ingredients such as growth regulators. The aim of the formulation is to optimize the biological effect of the composition in the target organism and, at the same time, to bring the finished product into a form that can be used in technical equipment. In this way, not only the effectiveness but also, for example, the shelf life of the formulation should be optimized.
Es ist bevorzugt, dass die Formulierung zum Abtöten von Insekten verwendet wird. It is preferred that the formulation is used to kill insects.
In einer bevorzugten Aus führungs form enthält die Formulierung zusätzlich ein Lösungsmittel. Für das Lösungsmittel gilt die oben gegebene Definition, wobei es besonders bevorzugt ist, dass das Lösungsmittel Wasser enthält. Insbesondere bevorzugt ist das Lösungsmittel ein Aceton-Wasser-Gemisch. In a preferred embodiment, the formulation additionally contains a solvent. The definition given above applies to the solvent, it being particularly preferred for the solvent to contain water. The solvent is particularly preferably an acetone-water mixture.
Die Herstellung der erfindungsgemäßen Zusammensetzung erfolgt in an sich bekannter Weise durch Kombination aller Komponenten.
Dabei können Wirkstof fe entweder in Form einer physikalischen Mischung mit den Cyclodextrinen verwendet , bzw . diese in Form von Cyclodextrinkomplexen, bzw . als Kombination dieser beiden Möglichkeiten eingesetzt werden . The composition according to the invention is produced in a manner known per se by combining all the components. Active substances can be used either in the form of a physical mixture with the cyclodextrins, or these in the form of cyclodextrin complexes, or be used as a combination of these two options.
Die Herstellung der Fettsäure-Cyclodextrin-Komplexe kann durch alle im Stand der Technik bekannten Methoden erfolgen, vorzugsweise erfolgt sie durch das Co-Precipitation Verfahren, dem Melting- In Prozess oder dem Pasten Verfahren . The fatty acid-cyclodextrin complexes can be produced by any of the methods known in the prior art, preferably by the co-precipitation process, the melting-in process or the paste process.
Beim Co-Precipitation Verfahren wird der Wirkstof f in einem geeigneten Lösemittel gelöst und in dem gewünschten Verhältnis zu einer auf 20 bis 70 ° C, vorzugsweise auf 50 ° C erwärmten wässrigen Lösung des Cyclodextrin oder Cyclodextrin Derivats zugegeben . Die Lösung wird über einen Zeitraum von 16 Stunden gerührt und anschließend das Lösemittel entfernt . Der Rückstand wird bei 40 ° C getrocknet . Bei dem Lösemittel handelt es sich vorzugsweise um Aceton, Methanol oder Ethanol . In the co-precipitation process, the active substance is dissolved in a suitable solvent and added in the desired ratio to an aqueous solution of the cyclodextrin or cyclodextrin derivative heated to 20 to 70.degree. C., preferably to 50.degree. The solution is stirred for a period of 16 hours and then the solvent is removed. The residue is dried at 40° C. The solvent is preferably acetone, methanol or ethanol.
Beim Melting- In Prozess wird das Cyclodextrin oder Cyclodextrin Derivat in Wasser vorgelegt und auf 20 bis 70 ° C, vorzugsweise 50 ° C erwärmt . Der Wirkstof f wird portionsweise zugegeben und 16 Stunden bei der genannten Temperatur gerührt . Nicht komplexierter Wirkstof f wird abfiltriert und der Komplex durch Gefriertrocknung isoliert . In the melting-in process, the cyclodextrin or cyclodextrin derivative is placed in water and heated to 20 to 70.degree. C., preferably 50.degree. The active ingredient is added in portions and stirred at the stated temperature for 16 hours. Uncomplexed active substance is filtered off and the complex is isolated by freeze-drying.
Beim Pastenverfahren werden das Cyclodextrin oder das Cyclodextrin Derivat zusammen mit dem Wirkstof f in dem gewünschten Verhältnis vermengt und Wasser in einem Anteil von 30 Gewichtsprozent der beiden Komponenten zugegeben . Die dabei entstandene Paste wird über einen Zeitraum von acht Stunden bei 70 ° C in einem geschlossenen Glasgefäß gehalten und stündlich mittels eines Spatels durchmischt . Nach Ablauf der acht Stunden wird die Paste getrocknet und für die weitereIn the paste method, the cyclodextrin or the cyclodextrin derivative is mixed together with the active substance in the desired ratio and water is added in a proportion of 30 percent by weight of the two components. The resulting paste is kept in a closed glass vessel at 70° C. for a period of eight hours and mixed hourly with a spatula. After the eight hours, the paste is dried and for the further
Anwendung vermahlen .
Anschließend wird der Fettsäure-Cyclodextrin-Komplex in die als Formulierung dienende Lösung eingearbeitet , beispielsweise indem das Produkt aus dem Co-Precipitation- , Melting- In- oder dem Pasten-Verf ahren unter Rühren bei Raumtemperatur in der als Formulierung dienenden Lösung aufgelöst wird . application grind . The fatty acid-cyclodextrin complex is then incorporated into the solution used as formulation, for example by dissolving the product from the co-precipitation, melting-in or paste process in the solution used as formulation while stirring at room temperature.
Darüber hinaus kann der Cyclodextrin-Komplex ganz einfach als physikalische Mischung durch Zudosierung der Cyclodextrine zu einer die Wirkstof fe bereits enthaltenden Formulierung erzeugt werden . In addition, the cyclodextrin complex can easily be produced as a physical mixture by metering the cyclodextrins into a formulation that already contains the active ingredients.
Eine Kombination aus Cyclodextrin-Komplexen mit physikalischen Mischungen ist ebenfalls möglich . A combination of cyclodextrin complexes with physical mixtures is also possible.
Ein weiterer Gegenstand ist ein Verfahren zum Schutz vor Insekten, dadurch gekennzeichnet , dass die Zusammensetzung, bevorzugt die Formulierung, auf die Haut oder auf andere Oberflächen oder Textilien aufgetragen wird . A further object is a method for protecting against insects, characterized in that the composition, preferably the formulation, is applied to the skin or to other surfaces or textiles.
Das erfindungsgemäße Verfahren ermöglicht die Abwehr und Bekämpfung von Insekten mit einer deutlichen Verbesserung der Wirksamkeit der Insektenschutzmittel und einer deutlichen Verlängerung der Wirkdauer der Insektenabwehrmittel . The method according to the invention makes it possible to repel and control insects with a clear improvement in the effectiveness of the insect repellent and a clear prolongation of the duration of action of the insect repellent.
Die folgenden Beispiele dienen der weiteren Erläuterung der Erfindung, ohne sie zu beschränken .
The following examples serve to explain the invention further without restricting it.
Beispiel 1 : Wirksamkeit von Fettsäuren im Komplex mit Cyclodextrin zur Bekämpfung von Kakerlaken Example 1 Efficacy of fatty acids in complex with cyclodextrin for controlling cockroaches
Zur Untersuchung der Wirksamkeit wurden die unten beschriebenen Formulierungen auf die Oberfläche der Cuticula von Kakerlaken appli ziert . Dazu wurden j eweils 10 Kakerlaken (BioGenius , Technologiepark, Bergisch Gladbach) in eine 10 cm x 2 cm große Petrischale gegeben, deren Seiten mit einem Gemisch aus Mineralöl und Vaseline (Verhältnis 1 : 3 , Sigma Aldrich) behandelt wurden, um ein Entweichen der Tiere zu vermeiden . Die Schaben wurden 15 bis 25 Sekunden lang mit Kohlendioxid behandelt bis sie betäubt waren und mit der ventralen Seite nach oben positioniert . Jeweils 2 pl der Formulierungen wurden auf den Bereich zwischen den Beinpaaren aufgetragen und die Insekten innerhalb der nächsten 24 Stunden untersucht . Dabei wurde die Mortalität der einzelnen Formulierungen durch Bestimmung der mittleren letalen Dosis LD50 bewertet . Der LDso_Wert gibt die Dosis in mg an, deren letaler Ef fekt sich auf 50 Prozent der beobachteten Population bezieht . To study the effectiveness, the formulations described below were applied to the surface of the cuticle of cockroaches. For this purpose, 10 cockroaches each (BioGenius, Technologiepark, Bergisch Gladbach) were placed in a 10 cm x 2 cm Petri dish, the sides of which were treated with a mixture of mineral oil and vaseline (ratio 1:3, Sigma Aldrich) to prevent the to avoid animals. The cockroaches were treated with carbon dioxide for 15 to 25 seconds until anesthetized and positioned ventral side up. 2 μl each of the formulations were applied to the area between the pairs of legs and the insects were examined within the next 24 hours. The mortality of the individual formulations was evaluated by determining the mean lethal dose LD50. The LDso value indicates the dose in mg whose lethal effect relates to 50 percent of the observed population.
Als Formulierungen dienten Lösungen mit j eweils 1 , 5% einer Fettsäure ( Sigma Aldrich) in einem Gemisch von Wasser und Aceton ( 50/ 50-Vol-% ) . Zur Verbesserung der Wirksamkeit wurde methyliertes beta-Cyclodextrin (M-ß-CD, Wacker Chemie AG, Molekulargewicht 1310 g/mol ) in einem molaren Verhältnis von 1 : 0 , 5 ( Fettsäure : Cyclodextrin) hinzugefügt . Als Kontrolle diente das reine Lösemittelgemisch .
Tab. 1: Kontakttoxizität bei Anwendung der Formulierungen aus Beispiel 1.
Solutions each containing 1.5% of a fatty acid (Sigma Aldrich) in a mixture of water and acetone (50/50% by volume) served as formulations. To improve the effectiveness, methylated beta-cyclodextrin (M-ß-CD, Wacker Chemie AG, molecular weight 1310 g/mol) was added in a molar ratio of 1:0.5 (fatty acid:cyclodextrin). The pure solvent mixture served as a control. Tab. 1: Contact toxicity when using the formulations from Example 1.
Beispiel 2: Wirksamkeit von Fettsäuren im Komplex mit Cyclodextrin zur Bekämpfung von Ameisen Example 2: Efficacy of fatty acids complexed with cyclodextrin to combat ants
Der in Beispiel 1 beschriebene Versuch wurde wiederholt mit dem Unterschied, dass zur Verbesserung der Wirksamkeit hydroxypro- pyliertes beta-Cyclodextrin (HP-ß-CD , Wacker Chemie AG, Molekulargewicht 1542 g/mol) in einem molaren Verhältnis von 1:0,5 (Fettsäure : Cyclodextrin) hinzugefügt wurde. Als Kontrolle diente das reine Lösemittelgemisch.
Tab . 2 : Kontakttoxi zität bei Anwendung der Formulierungen aus Beispiel 2 .
Diese Formulierung lässt sich auch auf andere Schädlinge wie Zecken, Käfer, Läuse , Zikaden und ähnliche anwenden .
The experiment described in Example 1 was repeated, with the difference that, to improve the effectiveness, hydroxypropylated beta-cyclodextrin (HP-ß-CD, Wacker Chemie AG, molecular weight 1542 g/mol) was used in a molar ratio of 1:0.5 (fatty acid : cyclodextrin) was added. The pure solvent mixture served as a control. tab . 2: Contact toxicity when using the formulations from Example 2. This formulation can also be applied to other pests such as ticks, beetles, lice, leaf hoppers and the like.
Claims
1. Zusammensetzung zur Verwendung als Insektizid oder Biozid enthaltend Claims 1. Composition for use as an insecticide or containing a biocide
(i) gesättigte oder ungesättigte Fettsäuren, deren Salze oder Ester und (i) saturated or unsaturated fatty acids, their salts or esters and
(ii) ein Cyclodextrin oder Cyclodextrin-Derivat wobei nach Lösen von (i) und (ii) in einem Lösungsmittel in der Lösung (ii) in einem molaren Verhältnis zu (i) von weniger als 1 vorliegt (d.h. das Verhältnis (i) : (ii) beträgt 1 : weniger als 1 (Mol : Mol) ) . (ii) a cyclodextrin or cyclodextrin derivative wherein upon dissolution of (i) and (ii) in a solvent in the solution (ii) is in a molar ratio to (i) of less than 1 (i.e. the ratio (i) : (ii) is 1:less than 1 (mole:mole)).
2. Zusammensetzung gemäß Anspruch 1 dadurch gekennzeichnet, dass diese als Mittel zum Abtöten von Insekten wirksam ist. 2. The composition of claim 1 characterized in that it is effective as an insect killer.
3. Zusammensetzung gemäß einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, dass nach Lösen von (i) und (ii) in einem Lösungsmittel das molare Verhältnis von (i) : (ii) zwischen 1 : 0,01 und 1 : 0,5 (Mol : Mol) liegt. 3. Composition according to one of claims 1 or 2, characterized in that after dissolving (i) and (ii) in a solvent the molar ratio of (i): (ii) is between 1: 0.01 and 1: 0, 5 (mole : mole).
4. Zusammensetzung gemäß einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass (ii) ausgewählt ist aus der Gruppe bestehend aus a-Cyclodextrin, ß-Cyclodextrin, y-Cyclodextrin, Hydroxypropyl-a-Cyclodextrin, Acetyl-a-Cyclodextrin, Hydro- xypropyl-ß-Cyclodextrin, Hydroxypropyl- Y_Cyclodextrin, Ace- tyl-ß-Cyclodextrin, Methyl-ß-Cyclodextrin, Acetyl- Y_Cyclo- dextrin und deren Gemische. 4. Composition according to any one of claims 1 to 3, characterized in that (ii) is selected from the group consisting of α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, hydroxypropyl-α-cyclodextrin, acetyl-α-cyclodextrin, hydro - xypropyl-ß-cyclodextrin, hydroxypropyl- Y _ cyclodextrin, acetyl-ß-cyclodextrin, methyl-ß-cyclodextrin, acetyl- Y _ cyclodextrin and mixtures thereof.
5. Zusammensetzung gemäß einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass (i) eine Kettenlänge von 6 bis 20 Kohlenstoff atomen besitzt. 5. Composition according to any one of claims 1 to 4, characterized in that (i) has a chain length of 6 to 20 carbon atoms.
6. Zusammensetzung gemäß einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass (i) ausgewählt ist aus der Gruppe be- stehend aus Hexansäure (C6, Capronsäure) , Heptansäure (C7,
Önanthsäure) , Octansäure (C8, Caprylsäure) , Nonansäure (C9, Pelargonsäure ) , Decansäure (CIO, Caprinsäure) , Undecansäure (Cll) , Dodecansäure (C12, Laurinsäure) , deren ungesättigten Vertreter, deren Homologe und deren Gemische. Zusammensetzung gemäß einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass nach Lösen von (i) und (ii) in einem Lösungsmittel der prozentuale Gehalt jeder Fettsäure in der Lösung 1,5% beträgt. Formulierung enthaltend eine Zusammensetzung gemäß einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass sie als Insektizid oder Biozid verwendet wird. Formulierung gemäß Anspruch 8 dadurch gekennzeichnet, dass diese zum Abtöten von Insekten verwendet wird. Formulierung gemäß einem der Ansprüche 8 oder 9, dadurch gekennzeichnet, dass sie zusätzlich ein Lösungsmittel enthält . Formulierung gemäß einem der Ansprüche 8 bis 10, dadurch gekennzeichnet, dass als Lösungsmittel Wasser eingesetzt wird . Verfahren zum Schutz vor Insekten, dadurch gekennzeichnet, dass eine Zusammensetzung gemäß einem der Ansprüche 1 bis 7 oder Formulierung gemäß einem der Ansprüche 8 bis 11 auf die Haut oder auf andere Oberflächen oder Textilien aufgetragen wird.
6. The composition according to any one of claims 1 to 5, characterized in that (i) is selected from the group consisting of hexanoic acid (C6, caproic acid), heptanoic acid (C7, enanthic acid), octanoic acid (C8, caprylic acid), nonanoic acid (C9, pelargonic acid), decanoic acid (CIO, capric acid), undecanoic acid (Cl1), dodecanoic acid (C12, lauric acid), their unsaturated representatives, their homologues and their mixtures. A composition according to any one of claims 1 to 6 characterized in that after dissolving (i) and (ii) in a solvent the percentage of each fatty acid in the solution is 1.5%. Formulation containing a composition according to any one of claims 1 to 7, characterized in that it is used as an insecticide or biocide. Formulation according to claim 8, characterized in that it is used to kill insects. Formulation according to one of claims 8 or 9, characterized in that it additionally contains a solvent. Formulation according to one of Claims 8 to 10, characterized in that water is used as the solvent. Method of protection against insects, characterized in that a composition according to any one of claims 1 to 7 or formulation according to any one of claims 8 to 11 is applied to the skin or to other surfaces or textiles.
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